Ref. 547.7082 ZEC V.1lib3.dss.go.th/fulltext/c_book/540-549/547.7082ZECv1_V20.pdf · Physikalische...

Ref. 547.7082 ZEC V.1

CONTENTS

Neuere Richtungen der Glykosidsynthese. 1

I. Alkylglykosid-synthesen aus freiem Zucker und Alkohol mit chemischen Mitteln 1

II. Biochemische Synthesen 1

III. Synthesen aus Acetohalogenverbindungen 2

IV. Umwandlung von β-Glykosiden in ihre α-Form 2

V. Quecksilbersalz-methode 6

VI. Darstellung der Bioside der α-Reihe ohne Anwendung der Acetohalogen verbindungen 15

VII. Phenol-glykosid bzw. Phenol-biosid-synthesen nach HELFERICH, mit Hilfe von Zink

Hloid bzw. P-Toluol-sulfonsaure 18

Literaturverzeichnis 20

The Component Glycerides of Vegetable Fats. 24

I. Attempts to Isolate Individual Triglycerides from Fats by Crystallisation 25

II. Crystallisation of Hydrogenated or Brominated Fats 26

III. Quanthitative Studies of the Componet Glycerides in Natural Fats 27

References 50

Recent Advances in the Chemistry of the Sterols. 53

Stereochemistry of the Steroids 53

i-Cholesterol 60

Oxidation of Cholesterol 62

Bromination of Steroid Ketones 71

Ergosterol and its Photoisomerides 81

Phytosterols and Sterols of Lower Animals 91

References 94

Cozymase. 99

I. Biologische Institung der Cozymase 99

II. Darstellung und Eigenschaften der Cozymase 102

III. Konstitutionsermittlung 106

IV. Ist Cozymase ein phosphat-ubertragendes Coenzym? 115

V. Derivate der Cozymase 116

Nucleinsauren 121

I. Einleitung 121

II. Allgemeine Bedeutung 121

III. Konstitution der Nucleinsauren 125


Chlorophyll. 159

I. Die fruheren Arbeiten (1904-1913) 160

II. Die neueren Arbeiten (1927-1932) 168

III. Ergebnisse der Jahre 1932 bis Mitte 1938 184

IV. Bacterio-chlorophyll 222

V. Protochlorophyll 227

VI. Funktion und Zustand des Chlorophylls im Blatte 229

Verzeichnis der Chlorophyllsubstanzen 233


Anwendung physikalischer Methoden zur Erforschung von Naturstoffen: Form und Grobe dis-

Pergierter Molekule. Rontgenographie. 255

I. Bestimmung von Form und Grobe der Einzelmolekule im dispergierten Zustand 257

II. Die rontgenographische Untersuchung in festem Zustand 298


Namenverzeichnis 352

Sachverzeichnis 362

Ref. 547.7082 ZEC V.2

CONTENTS

Lignin. Von Professor I

I. Einleitung I

2. Verwandte Pflanzenstoffe 2

3. Zuslierung 3

4. Isolierung 4

5. Physikalische Eigenschaften 5

6. Analytische Unterlagen 6

7. Lignin als Derivat des Phenylpropans 7

8. Uber die Konstitution des Fichtenlignins 7

9. Funktionelle Derivate 10

10. Substitutionsprodukte 10

11. Unmittelbarer abbau 11

12. Abbau nach Aufschluβ mit Alkali 12

13. Abbau nach Aufschluβ mit Bisulfit. Ligninsulfonsaure 14

14. Abbau nach Aufschluβ mit Thioglykosaure 16

15. Abbau nach Aufschluβ mit Alkoholen und Mineralsauren 16

16. Abbau nach Aufschluβ mit Hydrazin, sowie mit Kalium in Ammoniak 18

17. Dehydro-diisoeugenol und seine Umwandlungsprodukte als Modelle 18

18. Andere Modelle 19

19. Coniferylalkohol als Modell 20

20. Schluβbetrachtung 21

Nachtrag 23


Flechtenstoffe. 27

A. Verbindungen der fettreihe 28

B. Verbindungen der Benzolreihe 33

Flavine. 61

A. Allgemeines 61

B. Die synthetischen Verfahren 75

C. Flavine als wasserstoff-ubertragende Cofermente 90


Chemistry of the iodine compounds of the thyroid. 103-129

The structure and synthesis of vitamin C (ascorbic acid) and its analogues. 132-156

Neuere Richtungen der Oligosaccharid-Synthese. 160-207

Chitin und seine Spaltprodukte. 212-240

Tabak-alkaloide. 248-292

La spectrochimie de fluorescence dans I’etude des produits biologiques. 301-336

Namenverzeichnis 342

Sachverzeichnis 352

Inhaltsverzeichnis.Seite

Bedeutung der Dien-Synthese filr Bi1dung .Aufbau und Erforschung

von Naturstoffen. Von Prof. Dr. 0. DIELS, Universitjtt Kiel I

Einleitung. Eigenart der Dien-Synthese I

I. Bedient sich die Natur der Dien-Synthese als Aufbaupcinzip ? 3

II. Kiinstliche Gewinnung von Naturprodukten durch DieD-Synthese 6I. Dien-Synthesen in der Reihe der Terpene und Campher 72. Dien-Synthesen in der Reihe des Cantharidins II3. Dien-Synthesen in der pyrrol-Reihe , 44. Dien-Synthese in der Lupinan-Reihe 17

III. Die Dien-Synthese als Hilfsmittel zur Erforschung von Naturprodukten 21Ausblick. 26

Literaturverzeichnis. 27

Biochemische Hydrierungen. Von Professor Dr. F. G. FISCHER. Univer.sitat Wiirzburg 30

I. Einleitung 30

II. Die Hydrierung der Athylenbindung ...; 31

A. Hydrierungen durch Hefe und Bakterien 32I. Primare Alkohole 322. Aldehyde. 343. Ketone. 354. Sekundare Alkohole 385. Ketosauren. 396. Stoffe mit konjugierten Doppelbilldungen 4°

7. Allgemeine Bemerkungen 42B. Hydrierungen im Tierkorper 45

I. Alkohole und Aldehyde 472. Ketone. 48

3. Allgemeine Bemerkungen 50C. Stereochemisches %U den Athylenhydrierungen 51

III. Hydrierungen in be80nderen Stoffgruppen 53

A. Steroide ~ ; 53I. Sterine 53. a);Die Hydrierung von Cholesterin zu Koprosterin 53.

b) Zur Frage der Bildung von Gallensauren aus Cholesterin 55.2. Ga1lensauren : 563. Steroide Hormone 59. a) Reduktionen mit Hefe 59. b) Hydrie-

rungen und Dehydrierungen mit Bakterien 62.

4. A1Igemeine Bemerkungen 65

IV Inhaltsverzeichnis

Seite

: b7

71

71

72

74

75

B. Fettsauren.., , , , IV. Die Fermentsysteme biochemischer Hydrierungen .

I. Die Carbonylhydrierung 2. Die Athylenhydrierung , 3. Die Hydrierung der Carbiminbindung. .., ., ...,

Literaturverzeichnis ,..,...:, ,.

Gallenfarbstoffe. Von J)ozentl)r. W.SIEDEL. TechnisCheHochschuleM(inchen 81

l..::inleitung , 81

II. Vorkommen der Gallenfarbstoffe. Bildung und Ausscheidung. R2I. Bildung des Bilirubins.. X22. Umwandlung des Hilirubins im Organismus S43. Zur Bilanz des Hlutfarbstoffwechsels X6

III. Vierkernige Gallenfarbstoff" (Bilirubinoide) 871. Bilirubin, Mesohilirubin. Dihydrobilirubin 1j7

Bilirubinsaur", Xanthobilirubinsaure XX

..Ni:ritkorper.' 91Neoxanthobilirubinsaure. Mesobilirubin-XiIl.1X 91Synthesen der Xantho-. Neoxantho-! 1so-neoxanthobilirubinsaure ;

Mesobilirubin-III:IX 9:!Nomenklatur der Bilirubinoide 96Synth,ese des Mesobilirubins-IX,IX 97Konstitution des Bilirubins. Dihydrobilirubin 9XFarbreaktionen des Bilirubins und Mesobilirubins '1'1Ober den physiko-chemischen Zustand d.es Bilirubins im Blut und Harn

101. a) Bilirubin-Albumin 101. b) .,Aktives.' Bilirubin 101;.

2 Ferrobilin, Glaukobilin. Biliverdin; Mechanismus der (~allenfarbstoff.bildung ro1;Ferrobilin. (;lat1kobilin rO1;

Biliverdin \Uteroverdin) 104Ober die Aufspaltung d~ Porphyrinringes zu Bilirubinoiden sowie tiber

die Konstitution derVerdoha.mochromogene und den Mechanismusder Bilirubinbildung a) Chemische Aufspaltung des Porphyrin-ringes 105. b) Physiologische Aufspaltung des Porphyrinringes 10S.c) Photochemische Aufspaltung des Porpflyrinringes 1O'J.

3. Bilipurpurine. Choleteline; Mechanismus derGMELINschen Reaktion. .~O'J4. Urobilinogen und Stereobilinogen 112

Urobilinogen (Mesobilirubinogen-IX.tX) 112

Stercobilinogen 113Nachweisreaktion fiir die Bili-chromogene 113Reaktionen zur \Jnterscheidung von Urobilinogen und Stercobilinogen 113

5. Urobilin, Stercobilin 114Na~hweisreaktion des Stercobilins und Urobilins 1 ISUnterscheidungsreaktion zwischen Urobilin und Stercobilin. 11S

(). Dihydro-mesobilirubin IlS7. Mesobiliviolin. Mesobilirh()(lin ; 11,>

Phykobiline, die Pigmente der Rotalgen; Mesobilierythrin. Mesobili-cyanin 121;

Typen der bis jetzt.bekannten Hilirubinoide (Tabelle 1) 12.1I-ichtabsorption un,1 Kon!!titution dt'r Bilirubinoide 124

Inhaltsverzeichnis-

v

SeiteIV. Zweikernige Gallenfarbstoffe , 125

I. Mesobilifuscin, Bilifuscin, Myobilin 125Mesobilifuscin 125Bilifuscin. 128

Myobilin 1292.. Pentdyopent 13°

V. Gallenfarbstoffe unbekannter Konstitution 1311. Porphobilinogen. 1312.. Rubrobilin 132

3. Biliprasin 1324. Bilihumin I3i

5.. Choleprasin 13J.6.. Bilinigrin, Dehydroxy-bilirubin 13J.

7.. Kopronigrin 1328. UrochromB , :.. 1329.. Xanthorubin 133

Literaturverzeichnis. I~~

The chemistry of the lipoids of the tubercle bacillus and certain

other microorganisms. l3y ProfessorR. J. ANDERSON, Yale Uni-versity. New Haven (Conn.). USA. 145

Introduction J45

Methods. 147Separation of the alcohol-ether soluble lipoids J48

Propertie& and composition of acid-fast bacterial phosphatide& J5OCleavage products of the phosphatides on. acid hydrolysis J52

The acetone-soluble fats of the acid-fast bacteria J56Saponification of the fats and sep"Tation of the cleavage products. 159The fatty acids. The solid saturated acids. J59

The liqui<l fatty acids. J59The reduced acids J()Q

Thc liquid saturatcd fatty acids 160

A(;i(l-fast bacterial waxe& J63Tllc wax fn)m thc human tubt-rclc bacillus. J64The Timothy b.lcilfus wax J()6Thc W.lX from the avian t\lbercle bacillus Ju7Thc W.lX of thc bovine tubercle bacillus J(J9Thc uns.lponifiable matter or neutral material J7J

Composition of leprosin J72Thc wax found in the alco1lol-ether extract of the human tubercle bacillus J73

Hi~1Icr alcohols in .lcid-fast bacleria J74

l)igmcl\ls in tubercle bacilli 177I'hthiocol 177Tht. oc.cllrt.ncl' (,{ ribofl.lvin in tubcrclc bacilli. J79Car(,tirn)i(! pigmcnts in acid-fast l>actcria IRo

l..irmly l)o\lI\(llipoi(ls of luberclc b.lcilli 1,;1I..imlly 1)()\1nd lipoid8 ih the.l.viantul>crcle bacillus J~4TII(~ (.lhcr-solublc constituents of t1ll' avian bound lipoids. IR5

Th(.firmlyu()\1I\(llipoi<lsofthl~lcprosvl>.lcillus IR.S

VI Inhaltsvcrzeichnis

Seite

187

.89

191

193

194

195

107

Are sterols metabolic products of acid-fast bacteria

The lipoids of Phytomonas tumefaciens. The lipoids of Lactobacillus acidQPll.ilus The phosphatide of.Lactobacil1us acidophilus. ..

Thc lipoids of yeast.. Thcyeast phosphatides R"ferenr""

J

203

203

2°5

207?r)

215218

220

222

227

22q

Recent work on the configuration and electronic structure of

molecules; with some applications to natural products. By

Professor LINUS PA ULING, California Institute of Technology, Pasadena

!California),USA. , ' Introduction. , , ., , ..'! , ! The electronic theory of valence for non-resonating molecules. Interatomic distances and bond angles in non-resonating organic molecules. .

l{estrictedrotation abbut single boi1ds The distances of non-bonded contact of atoms:. The structure of resonating molecules Resonance and molecular configuration The structure of the a.nthocyanidins Coplanarity of conjugated systems The effect of resonance on interatomic distances. Isomerism and structure of the car.otenoids References

Namenverzeichnis 2,6

Sachverzeichnis 2A"-

~

l'

"'

1

f

Inhaltsverzeichnis. Seite

Die Chemie der pflanzlichen Herzgifte, Krotengifte, Saponine und

Alkaloide der Steroidgruppe. Von RUDOLF TSCHESCHE, Berlin I

I. EinIeitung III. Die Herzgiftaglykone derCI3-Reihe 7.

III. Di6 Herzgiftaglykone der C1.-Reihe 6IV. Die Glykoside SV. Pie Kr~tengifte 17.

VI. Die Sapogenine der Steroidgruppe 1(,

VIl. Die Alkaloide der Steroidgruppe :J;1 .. h .;".lteraturverzelc nlS. Zur Bio:chemie der Vitamin B-Gruppe (Pantothensaure. und

Vitamin B6. Von THEODOR WIELAND und IRMEXTRAUT Low,Heidelberg J;~

8Die Pantothensa.ure. J;

I. Entdeckung 28

II. Bio1ogische Wirkungen , 29Ill. Konstitution 30IV. Synthesen. , 32

I. Synthesen von fJ-Alanin und seineIi Estern , 337.. Synthesen de's !X-Oxy-fJ.fJ-dimethyI-y-butyro1aktons.. 33

Spaltung des racemischen (X-Oxy-fJ.fJ-dimethyl-y-butyro1aktons in die

optischen Antipoden , 34

3. Verknilpfung der Spaltstilcke : 35

Anspaltung der racemischen Pantothensa.ure 37

...Bio10gische Synthese ; ..37.

V. Konstitutionsspezifita.t ; 38

I. Verbindungen mit unvera.nderter Laktonko!Uponente 387.. Verbindungen mit unvera.nderter fJ.Alaninkomponente 393. Verbindungen mit vera.nderter fJ-Alanin- und DioxySa.\N"ekomponente 42

VI. Nachweis und Bestimmung 42

Literaturverzeichnis. 43.

})as Vitamin B. ; 46I. Einleitung ; '.. 46

II. Physio1ogie. ; 46III. Vertra.glichkeit und Abbau im Tierkorper 48Iv. Mikroorganismen und Pflanzen ~ , 48

V. Vorkommen ; ..., ; 50VI. Iso1ierung , , 50

\I.II. Konstitution und Synthese 51VIII. Eigenschaften ; 54

IX. Nachweis und Bestimmungsmethoden 57

I. Bio1ogische Verfahren 577.. Chemische Verfahren , :.; 58

Literaturverzeichnis. ~. 60

I nhaltsverz.'ich nisIV

Scitc

64

65

io

i6

i6

i9

80

8'2

82

84

8-,

~7

8Q

8992939396')9

10[

10.5

109

109

III

I I. ;)

116

, ,x

121

122

125

131

136

137

13!3;

138

141

41

143

144

144

144

145

148

Pterine, Vori I{OBERT Pl'HH~IA:-;:-;, ~Iiinchcn"""""""""""",

[. Ptcrinsynthcsen """""""""""""""""""""",.,""

II, Eigenschaftcn urul [{eaktionen dcr l)eri\'ate desPteri\lin:;"""""",

[I I I~as Vorkomm"n cter Pterine in tler ;.;atl1r urul ihre ( ;e".innl1ng , , , , , , ,

I Schmetterlingl' """"""""""""""""""",.,:,"""

J. Andere Insekten, , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , .

3 \~'irbe[tiere"".." """,.,...,."..,.".""..."..;,...,.

.[V. Oie bio[ogische Bedeutung (ler l"terine , I. Insekten",.,."" ,."".".., ,',..,.

J. Saugetiere , , , , , , ..' , .., .., ..., ., ., , , ., , ., , , , ..

I.i te rat l1 rverzeich i:; ., , , , , , , , , , ..., , ., .., , .., ., , ..' .., ..

Die Biochemie der Virusarten. Von GERHARD SCHRAMM , Hl'rlin-1 )al\ll'm

[ , Ein[eitung , ..., ,. , ., ., ., ., , , , , ,

Definition des Virusbegriffe:;.,.., ,...,."""., [I. Bio[ogie der Viren,.,.., ".",..,."..,." " ,.

[. ()bersicht tiber tlie Viruskrankheiten,..,.,..,.", "" "

J.. J)ie Entstehungder Viren,.".., , """,..,.".., 3. Die Vbertragung , ., ., , , , ..., ., .., , , ., ., , 4. VerhaIten des' Virus im \Virt , , , , ..., , 5. Die Virusvermehrung .., , ..., ., , ..., , , , .., , 6, DieTumorbi[dung durch Viren...,..., ,."...,..,;,."..,...

7. Die Veranderlichkeit der Viren,."" " ,...""", [II. Methoden der Virusforschung.,..".,...,..,..,."., "".

[ , Biologische Meth(jtlen , , ., , , ..., .., .., , , , ,

J.. Die Reindarstellung der Virusarten, , , ,...

a) Chemische Verfahren , , .., ., , , ..., ., , .., , b) Die Ultrazentrifuge , '.' ., , , , , , ., , , .., ., , ., , ..., , .., .

c) Die E[ektrophorese.",;., , " ,.., 3. Die Prtifung auf Einheit[ichkeit , , 4. Die physika[isch-chemische Kennzeichnung der Virusarten a) Die elektronenmikroskopische Untersuchung , b) Bestimmung des Teilchendurchmessers durch Lltrafiltration. c) Bestimmung des MoIeku[argewichtes mit der {ltrazentrifuge d) Bestimmung der Gestalt der ~-iren "',."."..".,.,.,..,:.,.

e) Die e[ektrochemische Charakterisierung der Viien , ..., ., ., ..., ..

5.. Die sero[ogische Charakterisierung der Viren , , ., .,. .., ,. , .., a) Das Antigen. .., , .., .., , ., , , , .,'

b) Der Antikorper ...,. , , , " .., , ., , ., ,

c) Die Antigen-Antikorperreaktion , ,.""...

d) Feststellung der Verwandtschaft..., ,.., ".,.

e) Reinheitsprtifung und Na.chweis der ~-iren..,.,.., ,;.

f) Rtickschliisse auf die chemische Zusammensetzung der Vireri IV. Chemische Eigenschaften der ~..iren ,""

I. Zusammensetzung und chemisches ~..erha[ten , .., , ., a) Verhalten gegen physika[ische Einfltisse , .., , ., , .,. b) Verhalten gegen chemlsche Einwirkungen , .., c) Verhalten gegen Enzyme " , ,',...,..

I nhaitsverzeichni;; v

S,.jt,.

I ~.f

I~.j

I('~

~. Oie einzelnen Viru8arten , a) f)as T;\bakmoSaikvirl\s (jWa..mol. t{/.baci var. vutga..e) :'.. Vorkornmen 14'!. -Darstellung 150. Das Vcrhal.ten in I.bsl\n~ 15!

-GroUe und (;estalt 153. Elektrochemischc Eigensehalten 153

Zusarnrnensetzung 154. Str1lktur des Tabakrnosaikvirus 155.

b) Oie Varianten de8 Tabakmosaikvirus , Bi010gische Eigenschafte1\ 161. Serologischt'8 Verhalten 10.~.

GroUe und (~estalt 16(); -Chemisches Verhalten 106

c) Die Kartoffelviren Bi010gie der Kartoffelkrankhe1ten 108. f)a!; Kart()ffel-X-Virlls 1!"1

-Das Kartoffel-Y-Yirus 170

(

d) Das Tabakringfleckenvirus 17Q

e) Das Severe-Etch-Virus ~ 17r

f) Das Tomaten-Bushy-stunt-Virus '7'

g) Das Tabaknekrosevirus 'i3

h) Die Polyederviren der lnsekten li3

j) Das .Virus deF Maul- und Klauenseuche ; li5

k) Das Encephalornyelitisvirus der Maus r7!'

I) Das Virus der Kinde!"lahmung (Polyornyelitis) 177

m) Das Kaninchenpapillornvirus ;, 17~

n) Die E~ementarkorper der Vaccine , 180

0) Die Ba'kteriophagen 18;:

Literaturverzeichnis. ; ,!\~

Biologische Oxydationen. Von KARL BERNHARD 1Ind HAROLD

LINCKE. Ziirich ; I. Einleitung TI. Die einzelnen oxydativen Prozesse ; 1. Bildung von Hydroxylgruppen a) OH-Gruppen bei aliphatischen Verbindungen br OH-Gruppen bei aromatischen Verbindungen c) OH-Gruppen an hydrocyclischen Ringen d) OH-Gruppen an heterocyclischen Ringen ~. Bildung von Aldehydgruppen 3. Bildung von Carbonylgruppen a) Entstehung von Ketonen b) Ketosa.~ren aus Oxysa.uren ; c) Ketosa.uren aus Aminosa.uren 4. Bildung von Carboxyl-Gruppen a) Durch Desaminierung b) Durch oxydative Aufspaltung von Ringen. 1. Aromatische Ringe 210. -~. Hydrocyclische Ringe ~11.' -

3. Heterocyclische Ringe 212.

c) Aus MethylgI;uppen 1. Oxydation am ~nzolkern befindlicher CH3-Gruppen ~15. -

2. Methyloxydationen natiirlicher Fettsa.uren215. --3. Methyloxy-

dationen substituierter Fettsauren 2 r 7.

~-sta.ndige Gruppen 217; p-sta.ndlge Gruppen ~18 ; y: undE-standige

GruRPen !19

1X~

18H

190

1(!0

1',10

Iq1

1"-,,:1

1<)7

ly7

19'1

.I<)<)

!00

20!

204

!0,!

210

214

,,~

VI Inhalt"vf'rz"i,.hni"

," ",4 Methyloxydationen bei Polyencarbon!;auren 220. 5. Methyloxy-<iHtionen von Sauerstoffderivaten der Terpene 222.

~) Aliphat.ische Terpene 222; P) Methyloxydation cycli!;cher Ter-pene 224.

6. Met.hyloxydationen bei Steroid~n 22f.

t!) '\II!; OH-Gruppen ; l.l.7~) Aus CHO.:Gruppen 229f) Aus CO-Gruppen ; 230g) t~brige COOH-Bildungen 231

.'i. .I.)ehydrierungen l.31H) Entstehung doppelter Bindungen bei aliphatisch~n Verbindungen .231b) .I.)ehydrierungen ringformiger Verbint!ungen. 23~

]1]. I)ie Oxydation langerer C-Ketten bei bestehender COOH-Gruppe 239

I. Abbau normaler und substituierter Fettsauren (MoIiocarbonsauren) ..239a) Die {J-Oxydation: ". 240b) Multiple alternative Oxydation 24()c) (u-Oxydation...' , , 251

2. ~\bbau verzweigter Fettsaureketten (Monocarbonsauren) l.543. Abbau...vonDicarbonsauren ,..,., " l.57

a) .\llgemeines l.57b) Abbau unverzweigter Dicarbonsauren 258c) _\bb1i.u verzweigter Dicarbonsauren 261d) Abbau cyclischer Dicarbonsauren :.. 2h2

4. Abbau der Seitenkette alicyciischer Verbindungen .;. ...; 2(Y2

IV. Oxydation der Intermediarprodukte der Hauptnahrstoffe: Bio.1.ogischer Ab-bau der Brenztraubensaure. .Essigsaure und der p-Ketocarbonsa.uren 2b4I. .I.)er Abbau der Brenztraubensaure iiber d~n Citronensaurecyclus 266

a) Bildung und Abbau der Citronensa.ure nach KNOOP und MARTIUS. .266b) Der Citronensaurecyclus 267c) Bedeutqng desSzENT-GY~RGY1-Systems fiir den Citronensaurecyclus 268d) Abbau der Brenztraubensaure im Herzmuskel 269e) Abbau der Brenztraubensaure in der Leber 270

I. Bildu~g von Acetessigsaure aus Brenztraubensa.ure 27°. ~2.Bil-dung von (X-Ketoglutarsaure und der C,-Dicarbonsauren aus BTSin der Leber 272. ~ 3. _-\lIgemeine Bedeutung und Verlauf der Oxal-essigsaurebildung 275.

f) Abbau der Brenztraubensaure im Gehirn 2772. Abbau der Ca-Korper: Essigsaure. Acetaldehyd und Alkoh0l (BilduJ1g

der Citronensa.ure aus Essigsa.ure und Oxalessigsiiute) ., 282.

a) Im \\'armbliitlerorganismus 282b) Durch Hefe ' 283

c) Durch Schimmelpilze ;..., " 286d) Hemmende Wirkung zwelwertiger Kationen auf den Abbau der

Citronensa.ure , , ., ; 287e) Bemerkungen zur energetischen Koppelung , 287

3. Abbau der p-Ketocarbonsa.uren iiber denCitronensaure-Cyclus. (Bildungder Citronensaure aus p-Ketocarbonsauren und Oxalessigsaure) 290,,\ Ahh,,11 (l"r A(""t""";""ji,,rp ;n N;pr" llnn Hpr7m11"l-pl ?00

Inhaltsverzeichnis. VII

Seitec b) .-\bbau der {1-I\etocarbonsa.uren ({1-0xydativer Abb~u ~!er l;e.ttsa.u~~n) 290

C) Bemerkungen zur Koppelung des Kohlenhydrat- un(l-Fettsa.ure-

abbaus. ; 291

4. Intermedia.rprodukte der CitronenSa.Uresynthese 292

a.) Beim Abbau der Brenztraubensa.ure ...; : ~92

b) Versuche mitsignierter Oxalessigsa.ure und Trideuterioessigsa.ure zur

Kla.rung des KondensationSmechanismus 295

c) Zusammenfassende Betrachtungen tiber den ReaktionSVerlauf bei der

CitronenSa.urebildung 298

5. Bemerkungen zu den Einwa.nden gegen die Theorie des CitronenSa.Ure-

cyclus 3036. AIlgemeine Bemerkungen zur bakteriellen Ga.rung 306

7. Die PropionSa.Urega.rung ; 308

a) Bildung der C4-DicarbonSa.Uren ...; 309

b) Zur Bildung der C3-Korper (PropionSa.Ure. BTS und Milchs1j.ure) .310

C) BildungderEssigs~ure 315

8. Die Buttersa.ure- und Butanolga.rung 317

9. Abbau der Essigs~ure. CitronenSa.Ure und Acetessigsa.ure 318

a) Abbau der Essigsa.ure 318

b) Abbau derCitronenS~Ure 324

c) Abbau der Acetessigsa.ure durch B. coli. 329

10. SchluGbemerkung 331


~

Ober monomolekulare Filme an Wassergrenzflachen und iiber

Schichtfilme. Von H.J. TRURNIT, Heidelberg 347

Namen und Zeichen 347

Einleitung 348I. H-Filme. 352.

I. Einfache Erfahrungen an Wasseroberfllichen 3522. Methoden der Schubmessung 354

3. Anderung des.Yo1tapotentials 3564. Das thermodynamische und mo1ekulare Bild der Filme 358

a) Expansive Filme : 360b) Kondensierte Filme 364c) GedehnteFilme , 369

5. EinfluB des Substrates 37I6. Filme von Kettenmo1ekiilen mii Doppelbindung 3727. Filme von Sterinenund lihnlichen Verbindungen 3738. Filme von Kohlenhydraten und synthetischen Po1ymeren. 3769. Filme von anderen Stoffen 377

IO. Indicatorole 377II. Spreitungsmechanismus. Bewegung in Grenzfllichen 378I2. UltramikroSkopische Beobachtung 382

I3. .Viskositlit 382I4. Elektrische Leitfahigkeif.., 384I5. Verdampfung durch Filme hindurch 384I6. Mischfilme und Wechselwirkung 385I7. Reaktionen derFilme 390

Seitc

394

398

39()

4.00

401404407409410

410412

413413414415415

415

416417418420423

423427432432435439440442442

444445446447

18. l3eitI:age zu Probleml'n tler Physiologie und Pharmakol()gie

19. Ergebnisse anderer ljntersuchungen 20. I'ilme an der (;renze fl/fl .., 21. I'ilme an der Grenze f/fi II. K-Filme. 22. Hl;rstellung und Mcssung 23. Mechanische Eigenschaften 24. Elektrische Eigenschaften 25. P-Filme (~keleton films) 26. Untersuchungen mit Rontgen- und Elektronenstrahlen ...

a) Rontgenstrahlen b) Elektronenstrahlen /..

27~ Restfilme 28. K-Filme als Schutzschichten 29. Wirkung von UV-Licht auf K-Filme 3°. Verdampfung von K-Filmen 3I. S-Schichten m.. EiweiBfilme. 32. Unt~rsuchungstechnik 33. Allgemeine Eigen~chaften 34. Spreitungsmethoden 35. Das Spreiten 36. Spezielle Eigenschaften a) F/A- und L1V/A-Verhalten b) Abhangigkeit, der Spreitungsflache vom PH c) Spreitungsdauer. d) Dicke .der Filme, Mo1gewichtsbestimmungen e) Denaturierung f) Homogenitat der Filme :...

g) Elastizitat h) Kompressibilitat i) Viskositat 37. Spezielle Untersuchungen 38. Mischfilme .j 39. K-Filme , 40. Filme an der Grenze fest/fiiissig. (S-Schichten) 41. Reaktionen an Filmen : 42. Filmeander Grenzefi/fi' ~ 43. Struktur der Filme IV. Ausblick., T"iteraturverzeichnis.

457458

463

467

477Namenverzeichnis

492Sachverzeichnis

Inhaltsverzeichnis.

Contents. -Table des l}1atieres.

Carotinoid-epoxyde und furanoide Oxyde von Carotinoidfarb-stoffen. VonP. KARRER, Universit!!.t Ziirich I

I. Vorkommen, Konstitution und Pattialsynthesen der Carotinoid-epoxyde III. Die futanoid gebauten Carotinoid-epoxyde 6

III. Die Molekularsttuktur der Carotinoid-epoxyde 12IV. Biologische Bedeutung det Carotinoid-epoxyde 14

I Literaturverzeichnis 17

I Some Biochemical Aspects of Marine Carotenoids. By D. L. FoxJ

Scripps Institution of Oceanography of the University ofCalifornia, LaJo!la, California. ' 20

Introduction 21Marinemuds 21Marine animals in general. 23Protista. ; 24

Sponges 25Coelenterates 26Worms 27Echinoderms. 28Mollu$ks , 29

, Cru$taceans 30

Tunicates 3 IFishe$ 32Mammals 34Conclusions. 34Ref er en c e$ 36

Azulenes. By A. J. HAAGEN-SMIT, California I,nstitute of Technology.

Pasadena, California. 40

Introduction. 40

I$olationandpurification 41Physicalproperties 41Chemical properties. : 44Structure determination 45Nomenclature. 46Structure of naturally occuring precursors of azulenes 47Syn!hesis of Azulenes 49

Absorption spectra. 57~ Some bioche~ical aspects. 62

, Further possible types of azulenes 65"f Pharmacological properties ofazulenes 66..J References 67

Recent Advances in the Study of Component Acids and Com-ponent Glycerides of Natural Fats. By T. P. HILDITCH, The

, UnivetsityofLiverpool , Introduction: Discussion of the ..Rulp; of even distribution" 72

72

_:;'

Table des matiere...IV Inhalts""~zei,,hni~ -Contents.

Spectrophotometric determination of certain unsaturated higher fatty acids. .75Resolution of mixed fatty acids by crystallisation from solvents at low tem-

peratuces A6Partial resolution of mixed glycerides in natural fats by crystallisation from

solvents at low temperatures : ; 81The present state of knowledge of the glyceride structure of natural fats. .86

I. Fats with three (or at most four) major component acids. 86(a) Fats in which saturated acids predominate over unsaturati,d (oleic)

acids 86(by Fats in which oleic. linoleic and/or linolenic acids predominate. 87

2. Computation of component glycerides from the proportions of the com-ponent fatty acids in a fat 88

3. Fats with four or more component acids in similar proportions 89

4. Animal body fats rich in stearic acid and animal milk fats containingnotable proportions of butyric and/or other lower saturated acids. 90(a) Animal body fats. 90(b) Animal milk fats. 93

5. Synthesis and transformation by chemical means of mixed glycerides inthe laboratory. 95

References. 96

Enzymatically Synthesized Polysaccharides and Disaccharides.

By W. Z. HASSID and M. DOUDOROFF, The University of California,Berkeley, California 101

Introduction. 101Formation of starch and glycogen through the phosphorolytic condensation. .102Conditions affecting polysaccharide formation. 104Synthetic polysaccharides 106Arsenolysis and phosphorolysis of amylose and amylopectine.. 107Phosphorylase. 108The mechanism of dextran and levan formation. 109M~hanism of sucrose formation ; " 111Specificity of sucrose phosphorylase 115D-glucosido-D-xyloketoside, D-glucosido-L-araboketoside and D-glucosido-

L-sorboside 116/X-D-glucosido-L-arabinose LISFormation of sucrose and other disaccharides through exchange of glycosidic

linkages. 121

References. 123

Recent Developments in the Structural Problem of Cellulose. By

E. p ACS U, Princeton University. and The Textile Foundation. Princeton. .New Jersey 128

I. The linear structure of cellulose 128Introduction 128Critical review of the proofs supporting the linear structure of cellulose 13°

I. Nature and uniformity of the building units 130

2. Location and number of the free hydroxyl groups 13°

3. The chemical proof of the constitution of cellulose. 131

4. The polarimetric proof of the constitution of cellulose. 1325. The kinetic proof of the constitution of cellulose. T

vInhaltsverzeichnis. -Contents. -Table des matieres.

I

~

I.

,\

.:

~

1

'

I!;

t

\

t

6. The static proof of the constitution of cellulose. 134

1. The X-raypatternofcellulose.' 134

Molecular weight determination of cellulose. 135

A. Chemical..methods , .., 135

B. Physical methods. 138

Oxycellulose 140Hydrocellulose ; 144Conclusions regarding the linear structure of cellulose. 145

II. The laminated chain structure of cellulose 146

Theoryof eeter linkages 146Theory of blocked hydroxyl groups 150Theory of looping bonds 151Theory of acid-sensitive bonds and the principle of periodi6ty 155Theory ofacetallinkages in equi-distant open-chain units and the laminated

chain structure of cellulose..; , : 158

A. Heterogeneous and homogeneous degradation of cellulose in acidiC'media. '0 158

B. The co.ncept of,:limit hydrocellulose" 160

C. Proposed structure of cellulose 163

j Li::::~e:;e; ..~.. ~~~.~~~~ .;~~ .~~~~~~~~ '~f..;~~~r. ~~~~~~: .~~~:e~~~: 17°

Wisconsin. , 175

I. Occurrence, formationand detection : 175The state of lignin in wood 175Lignin-complexes in wood 179Formation, detection and estimation of lignin. 180

II. Isolation 9f ligniri 182

III. Properties and convers.ions of lignin 186Physical properties 186Various conversions. 188Vanillin from lignin. 192Oxidation, reduction and halogenation. 193Nitration 195Sulfonatiori 195Ethanolysis of wood and lignin 199Hydrogenation. , 200E~periments on the synthesis 0£ lignin and similar products. 208Decomposition 211

IV. The strqcture of lignin 213ERDTMAN'S concept of the lignin structure. 213FREUDENBERG'S concept 0£ the lignin structure. 217HIBBERT'S concept of the lignin structure. 217Conclusions. 224

I T:ee£~~::i:~~. .~.; .~~~ .~~~~~~~~.~~~ ..~~. .;~~~ .~~~~~~~ ..~; 225

V. DEULOFEU, Facultad de Ciencias Exactas, Fisicas y Naturales,

BuenosAires, Argentina 241

Introduction.. 241

-

VI I~t$v~rzeichBiS.;'-CQt1te~. ~ Tabl6des matier~~

~

i}

¥,~

:ff~.

1;;.

I. The b\\fagins ; " 242

Main representa,tives of tht1 b\\f9talin class. 246B\\fotalin 246

Marinob\\fagin ,. : 249Gamab\\fagin (gamab\\fotalin, gamab\\fogenin) : 249

Cinob\\fagin., 25°Cinob\\fotalin, B\\falin. 252

PSe\\do;.desacetyl-b\\fQ:tali~ 252.Pharmacology of the b\\fagins 253

,II. B\\fotoxins. 254\

Main representatives of the b\\fotoxin class. 255B\\fotoxin 255Arenob\\fotoXin , 256Gamab\\fotoxin 256Marjnob\\fotoxin. 256

Pharmacology ofthe bufptoxins 256

III. Basic constituents oftoad venom.s 257

Buiotenine 257Pharmacology of bufotenine 259Bufotenidine 259Pharmacology of bufotenidine 260Bufothionine , ; 26()D~hydro-bufotenine 261Pharmacology of dehydro-bufotenine , 261L-Adrenaline :.~ , 261

JV. Ster9ls ..., : 262

.V. Suberic acid 262

References. 262

Biochemistry of Fish Proteins. By E. GEIGER, The University ofSouthern Californi~! LoS Angeles, C~lifornia , ' ..267

Introduction. , , 267Composition of fish m\\s(:leprotein , 268

Amino a(:id content 0( fish muscle protein,..., , 272Nutritiveval1)e Qf fish protein ,.., , 275

,Feeding experiments 275.Evaluation of results 281

.Fish blood proteins. 284Fish collagens. 287Fish proteins wit~ enzyrnaticactivity , 289Proteins i~olat~ frornfish s~rm 289Pharmacologic~l effects of some histones and protamins. 291PI'oteins iSolated (rom female reproductive organs of fish. 294

References ,." ,.,. 294

Some Recent Developments in Chemical Genetics.

By G. ,W. BEADLE, California Institute of Technology. Pasadena,.California. ; , 300

Classical genetics. ; 300

Chemical genetics., , , 302

j

~

--.

IDhaltsverzeichnis. -Contents.- T{\ble des mB.tieres. .vu

~ ,.'

iii, "

Phenylalanine metabolism. 304

Antigen specificity. 306Hemophilia. : 307

Gene.directed specific reactions in other organisms. 308

Neurospora 310Nature and action of genes 317

Gene mutation 3.18

Universality of genes ,320

Cytoplasmic factors. 321

Genes and evolution. : ..324

Conclusions ,.3~6

References. 326

f

Infrared Spectroscopy in Structure Determination and its

Application to Penicillin. By R. S. RASMUSSEN, Shell Develop-ment Company, Emeryville, California 331

Introduction 331

I. Experimental methods. 332

I. Instruments. 332

2. The transmission curve , 3333. Absorption cells for vapor and liquid samples. 336

4. Solid samples. 337

II. Interpretation of infrared spectra 338"" I. General 338

;.lit," 341

3 3434. Comparison of ~ "cc -_.spectra. 344

III. General features of infrared spectra of organic compounds 345

I. Paraffin hydrocarbons 345

2. Cycloparaffins 3473. Olefins; bands associated with the carbon-carbon double bond. 3484. Conjugated carbon-carbon double bonds. 3545. Alkyl-benzenes; bands of aromatic ring systems. 3566. Acetylenes. 3617. Alkyl halides; the carbon-chlorine stretching band. 3618. Alcohols, phenols and ethers 3629. Amines, mercaptans and sulfides 364

10. Carbonyl compounds 364

a) Aldehydes. 367b) Ketones. 367

, c) Carboxylic esters "., , 36g

d) Carboxylic acids. , 370e) Salts of carboxylic acids 370f) Acid halides. 371g) Acid anhydrides 371

h) Amides of carboxylic acids 371

II. Carbonic acid derivatives 373

12. Compounds containing carbon-nitrogen double tonds 373

and frequencies

.1

;1'

.

13.. Nitriles , 373

14. Nitro c{)mpounds ,373

15. Sulfones.,a~d sulfonates ; 37f

16. More complicated structures 374

IV. Applications tQ structure determinations. 374

Penicillin : 376

V. Conclusion. 379

References. 380

Namenverzeichnis. Index of Names. Index des Auteurs. ,.. .381

Sachverzeichnis. Index of Subjects. Index des Matieres. 400

lnhal tsverzeichnis.

Contents. -Table des matieres.

J Some Biochemical and Nutritional Aspects in Fat Chemistry.

By H. J. DEUEL, JR. and S. M. GREENBERG, Department of Bio-chemistry and Nutrition, Universityof Southern California, Los Angeles. I

J. Introduction. 2

I. General Remarks on Fat Composition 2

a) Non-solvent Crystallization 4b) Crys:t3.l1iiation from Solvents 4c) Fractional Distillation 5

d) Chromatographic Separation 5e) Counter current Distribution 6f) Ultraviolet Spectroscopy 6g) Raman Spectroscopy 6h) Determination of Triglyceride Structure. 6

2. Composition of Substances Associated with Triglycerides 10

3. Factors Influencing the Composition of Fats. 12

II. Nutritional Evaluation of Fats in General 4

I. Functions of Fat in the Animal 4

2. The Digestibility of Fats 14

a) The Digestibility in Man of Vegetable and Animal Fats with MeltingPoints Below 5OoC 15

b) The Digestibility in Man of Vegetable and Animal Fats with MeltingPoints Above 50oC 16

c) Digestibility of Oleomargarines 18d) Digestibility of Polymerized Oils 18e) Digestibility of Fats in Animals Other than Man. 19f) Factors Influencing the Digestibility of Fats. 21

.g) Utilization of Fats Introduced Parenterally 23

3. The Rate of Absorption of Fats from the Gastrointestinal Tract ...23

4. Fats as Sources of "Essential" Fatty Acids. ~ 26

5. Fat-Vitamin Interrelationships 32

a) Thiamin and Fat. 32b) Riboflavin and Fat 34c) Pantothenic Acid and Fat 34d) pyridoxine (Vitamin Be) and Fat 35

-

IV Inhaltsverzeichnis. -Contents. :.- Table des matiere~

e) Niacin, Folic Acid, and Fat 36f) Biotin arid Fat. 36g) Fat-soluble Vitamins and Fats 38

6. Relation of Fat to ~otein Metabolism. , 39

7. Fats in Relation to Specific Dynamic Action of Foodstuffs. 41

8. Fats in Relation to Growth 43

9. Fats in Relation to Sexual Maturity ; 45

10. Fats in Relation to Pregnancy and Lactation. 45

II. Fats in Relation to Work Capacity and Sur,:ival. 47

12. Fats as Antithyrotoxic Agents 49

13. Optimum Fat Levels in the Diet 50

III. Comparison of the Nutritional Value of Animal and Vegetable Fats. ...51

I. General Remarks ~~ 51

2. The Comparative Amounts of Vitamins and Essential Fatty Acids in

Animal and Vegetable Fats : 52a) Vitamin A and Provitamin A .52b) Vitamin D 53c) Vitamin E 54d) Unsaturated Fatty Acid Content in Animal and Vegetable Fats. .54

3. Comparative Digestibility and Absorption of Animal and Vegetable Fats 57

4. Growth Tests with Vegetable and Anima1. Fats 57

a) Experiments with Normal Rats 57b) Experiments on Prematurely-Weaned Rats. 61c) Comparative Effectiveness of Animals Receiving Fats in a Restricted .

Diet 62d) Experiments on Rats Using Growth Hormones. 62e) Growth and Nutrition Experiments °~ Children 63

5. Pregnancy and Lactation Performance of Rats Receiving Animaland Vegetable Fats 63

6. Growth and Reproduction of Rats over Many Generations on a DietContaining a Vegetable Margarine 64

IV. Conclusions. 66

Referen ces. 67

878888

.90

9191919~

9~9798

10~

Odeurs et parfums des animaux. Par E. LE.DERER, Institut de bio-

logie physico-chimique, Paris. Introduction. R6le de l.odeur dans le regne animal Drogues anima1es uti1isees en parfumerie I. Produits d.excretion des glandes sebacees. 10 Musc et civette a) Le Musc b) La Civette c) La chimie des grands cycles d) Premieres syntheses de cetones macrocycliques e) Syntheses de la muscone f) Syntheses de la civettone

vlnhaltsverzeichnis. -Contents. -Table des matieres,

20' Constitution chimique et odeur musquee des substances macrocycliques 106

3° Musc americain 106

4° Autres animaux a. seCretion musquee 110

5° Substances soufrees des Mustelides et d.autres animaux. ...:. III

6° Castoreum 112

7° Suintine 118

8° Yacarol 119

II. Concretions intestinales 120

10 Ambre gris 120

Composition chimique de l.ambre gris 121Ambreine 123Biosynthese de l.ambreine et formation de l.ambre gris. 128Essais synthetiques dans la serie de l'ambreine 129

2° Bezoards i31

III. Substances odorantes de l.urine de Vertebre3 131

10 Derives de l.ionOne ~ 131

a) De l.urine de Lapin. 131b) De l.urine de Jumentgravide 132

2° Phenols de l'urine de Jument gravide. 135

3° Acides de l.urine deJument gravide 136

4° Le5 steroides odorants 137° D.

5 Ivers 141

IV. Feces 142

Hyraceum 142Conclusions. 143

Bibliographie 144

Vorkommen und biochemisches Verhalten der Chinone. Von

0. HoFFMANN-osTENHOF. I. Chemisches Laboratorium der Univ~rsita.tWien 154

Einleitung 154I. Natiirlich vorkommende Chinone 155

Das Vorkommen Von Chinonen im Mineralreich 155Chinone bakteriellen Ursprunges 156Durch Pilze erzeugte Chinone 157

Die Biosynthese Von Pilzchinonen 170Funktionder Pilzchinone 172

DurchFlechten erzeugte Chinone 173Von hoheren Pflanzen erzeugte Chinone. 173

Photosensibilisierende Chinone 178Biosynthese und Funktion der Chinone hoherer Pflanzen 179

Chinone tierischen Ursprungs 193

II. Biologische Wirkungen der Chinone 201

Wirkungen der Chinone gegeniiber Mikroorganismen 201Der Einflu6 der Chinone auf Vorga.nge bei der Zellteilung.. 209

Antimitotische Effekte 209Muta~ene Effekte 212

~

-

VI Inhaltsve];zeichnis. -Contents. -Table des matieres.

Wirkungen der Chinone auf tierische Organismen. 213Wirkung von Ch.inonen auf Invertebraten '. 213Wirkung von Chinonen auf Vertebraten. 214

Der m6g1iche Mechanismus einiger Chinonwirkungen. 216Wirkung der Chinone auf Enzyme 217

SchluBbem~rkung 242


J Cactus Alkaloids and Some Related Compounds, By L. RETI,,.. Atanor". Compania Nacional para la Industria Quimica. BuenoS Aires. 242

I. Introduction. 243

II. Historical 244

III. Occurrence of Alkaloids inCacti 247

List of Cactaceae from WhichAlkaloids Qf Known Structure Have Been

Isolated 247List of Cactaceae Which Contain Alkaloids of Undetermined Structure 249

lv. Location of the Alkaloids in Tissues of the Cacti.. 250

V. Extraction and Isolationof Cactus Alkaloids. 250

VI. The Chemistry of the Cactus Alkaloids and Some Related Natural Bases 252

A. ,8-Phenylethylamines 252

I. ,8-Phenylethylamine 252. -2. N-Methyl-,8-phenylethylamine 252.-3. Tyramine 253. -4. Hordenine 254. -5. Candicine 255. .:c- 6. 0-

Methyltyramine-N-methylcinnamide 756. -7. 3-Hydroxy-tyramine256. -8. Coryneine 257. -9. Mezcaline 257. -IO. N-Methy1mezcaline259. -II. N-Acetylmezcaline 259. -12. Trichocereine 259.

B. Tetrahydro-isoquino1ines , '... 260I. Anhala~ine 260.. -:-c- 2. Anha1inine 261.. -3. Anhalidine 261. -

4. Anhalonidine 261. -5. Pellotine 26I. -6. O-Methyl-d-anhaloni-dine 262. -7. Anhalonine 262. -8. Lophophorine 262.Structure and Synthesis of the Isoquinoline Bases Obtained fromAnhalonium lewinii 262Anhalonidine and Pellotine 262. -Anhalamine. Anhalidine andAnhalinine 263. -Anhalonine and Lophophorine 264. -9. Carnegine264. -10. Sa1soline 266. -II. Salsolidine 266. -12. Corypalline

267. -13. Hydrohydrastinine 267. -14. Hydrocotarnine 267.

VII. Biogenesis of the Cactus Alkaloids and rrheir Relation,ship to OtherNatural Products ,... 268

VIII. PharJllaCOlogical Effects of Cactus Alkaloids and Some Related, Naturally

Occurring Bases 276

Phenylethylamine, Tyramine, Hydroxy-tyramine 276. -Horde-nine 276. -Candicine 277. -Coryneine 277. -Mezcaline 277. -Trichocereine 278. -Anhalonine 279. -Anhalonidine 279. -

Pellotine 279. -Lophophorine 279. -Camegine 279. -Pi10-

cereine 279. -Salsoline 279.

R"f"r"n""" ..: 280

VIIInhaltsverzeichnis; -COntents. -Table des matieres.

J pl.ant Proteins. By J. BaNNER, California InstituteofTeGhno1ogy, Pasadena. 290

I. Introduction. ; 290

II. Proteins of Cereal Seeds ""., 291

III. Proteins of Seeds of Dicotyledenous Plants. 293

IV. The Leaf Proteins. 295

Preparation ~ 295Properties of the Chloroplastic .Protein. , 299The Cytoplasmic Proteins 301Cytoplasmic Proteins of Leaves in Relation toVirus Formation. 304

V. Proteins ofTissues Other than Leaves 306

VI. Conclusion. , 307

References. 307

Progres recents en spectrochimie de fluorescence des produits

biologiques. Par CH. DHERE, Universite de Geneve (Suisse) 311

I. Avant-propo$ 312

II. Hydroearbones (gllfcides) et glucosides. 313

Escorceine 313Rutine ' 315

III. Sterols et steroides 315

Reaction de SALKOWSKI 316Reaction de WINDAUS 3X7Steroides a. fonctions hormonales 319Reaction des steroides avec .1e sulfate dimethylique 319Hormones surrenales ...: 320Hormones sexuelles 321Reactions speciales 322

IV. Proteines (protides) et aminoacides 323

Reactions_§peciales 325

V. Pyrimrdines, purineS et pterines 326

pyrimidines et purines 326Pterines , 327

VI. Thiamine (aneurine), thiochrome et thiazol 331

VII. Adrenaline et adrenochrome 332

VIII. Alcaloides 333

IX. Polyphenols , 335

x. Derives de l'indol. 336

XI. Acide nicotinique et nicotylamide 337

XII. Uroerythrine (uroroseine) 338

XIII. Chlorophylles 338

XIV. Polyhydroxyanthraquinones et composes similaires 34°

xv. Lampyrine , 343

XVI. Car~ene, phytofluene etvitamine A : 344

XVII. peniGilline et streptomycine 344

Appendice: La topographie spectrale dans l'excitation des fluorescences

(Spectrofluorescence) 345

Bibliographie 349

Namenverzeichnis. Index of Names. Index des Auteurs.. 357


ki;~

~

'1lnhal tsverzeichnis.


Uber die Konstitution der Triterpene.Von 0. JEGER,.Laboratoriumfur organische Chemie, Eidg. Technische Hochschule,. Zurich. I

I. Einleitung 2

I. Einteilung der Triterpene 2

2. Bemerkungen zur Konstitutionsaufklarung 3

II. Squalen-Gruppe 5

Squalen " 5Ambrein 5

III. Tetracyclische Triterpene. 12

I. Kryptosterin-Gruppe ".. 13Vorkommen und Isolierung 13

Umwandlungen 13Abbaureaktionen 13a) Umwandlungen im Bezirke der Hydroxylgruppe 13b) Umwandlungen im Bezirke der reaktionstragen Doppelbindurigen

des Kryptosterins 13

2. Euphol und Butyrospermol " 4

3. Elemisaure-Gruppe 14

IV. Pentacyclische Triterpene ...; 15

I. fJ-Amyrin-Oleanolsaure-Gruppe 17Nomenklatur 19Vorkommen und Isolierung 19Umwandlungen 21Oleanolsa.ure 21

Echinocystsa.ure 24Umwandlungen in den Ringen C, D und E des fJ;.Amyrins 27

Erythrodiol 3tQuillajasa.ure, GeninA, Maniladiol 31

Gypsogenin, Hederagenin 3zSumaresinolsaure 36lX-Boswellinsa.ure 4°SojasapogenoleA, B, C und D 4°

Glycyrrhetinsa.ure 45Siaresinolsa.ure 45Germanicol 46Basseol 47

~

2. ~-Amyrin-Ursols1lure-Gruppe 47Nomenk1atur 48Vorkommen und Isolierung 48

~-Amyrin 49Brein 57

{J-Boswellins1lure 59Ursols1lure 59Uvaol 60

3. Lupeol- und Heterobetulin-Gruppe 6INomenklatur ., 6IVorkommen und Isolierung 6IUmwandlungsreaktionen 6ILupeo1. 62Betulin und Betulins1lure 65Heterobetulin 66

4. Nicht vo1lig aufgekl1lrte pentacyclische Triterpene 66Aescigenin ; ~ 66Bassias1lure 67Chinovas1lure ; 69

a) Dehydrierung 69b) Sekund1lre Hydroxylgruppe und deren Umgebung... 69c) Leicht abspa1tbare Carboxylgruppe 7°d) Ringe D und E. 7°Friede1in und Cerin 74

5. Stereochemie der pentacyclischen Triterpene 74I. {J-Amyrin-Oleanols1lure-Gruppe 742. ~-Amyrin-Ursols1lure-Gruppe 753. Lupeol- und Heterobetulin-Gruppe. 76

Litera£urverzeichnis. 76

.t

Konstitution, Konfiguration und Synthese digitaloider Aglykone

und Glykoside. Von H. HEUSSER, Laboratorium fur organischeChemie. Eidg. Technische Hochschule. Zurich. 87

I. Einleitung 88

II. Aglykone und Glykoside bekannter Konstitution 94

I. Digitoxigenin. 94

a) Konstitutionsaufk11i.rung 94b) Synthese von Abbauprodukten und Umwandlungen des Digitoxi-

genins in Desoxy-corticosteron 97c) Glykoside des Digitoxigenins 99

2. Uzarigenin 101a) Konstitutionsaufk11i.rung und Synthese von Abbauprodukten des

Uzarigenins 101b) Glykoside des Uzarigenins 106

c) aUo-Uzarigenin 1073. Gitoxigenin. 110

a) Konstitution und Synthese von Abbauprodukten des Gitoxigenins 110b) Glykoside des Gitoxigenins c) Oleandrigenin (16-Acetyl-gitoxigenin) ,

~

.

:~:1

4. Digoxigenin 115a) Konstitution des Digoxigenins und Synthesevon Abbauprodukten 115b) Glykoside des Digoxigenins 118

5. Sarmentogenin :' 118a) Konstitution des Sarmentogenins und Synthese von Abbauprodukten 118b) Glykoside des Sarmentogenins 120

6. Periplogenin 120a) Konstitution. 120b) Synthetische Arbeiten " 124c) Glykoside des Periplogenins 126

7. Konstitution der allQ-Aglykone; allo-Periplogenin 127

a) Konfigurationsbestimmung 127b) Glykoside des allQ-Periplogenins 129

8. Strophanthidin 130a) KonBtitution 130b) Synthetische Arbeiten und die Zusammenha.nge zwischen den

einzelnen Strophanthus-Glykosiden 133

c) Glykosidedes Strophanthidins 134d) allQ-Strophanthidin, Aglykon und Glykosid. 135

9. Strophanthidol, Aglykon und Glykoside , .136

III. Glykoside und Aglykone unbekannter Konstitution. : .I36

I. Ouabain 13.6

2. Antiaris-Glykoside 139

3. Calotropis-Gifte l40

4. Sarverosid und die Sarmentoside A und B l42

5. Adonitoxin. , l42

6. Glykoside des Pfaffenhiitchens, EvQnymus eu'.opaea l43

7. Nebenglykoside des Oleanders l44

8. Glykoside und Aglykone von CQ'.Qnilla glauca l46

9. Tanghinia-Glykoside l48

IV. t'rbersichtstabellen 15°


j Thyroxine and Related Compounds. By C. NIEMANN, Ca1iforniaInstitute of Technology, Pasadena, California. 167

Introduction. 167

I. The Relation Between Structure and Thyroxine-like Activity 168

I. Halogenated Thyronines 16~

2. Isomers of Thyroxine. 171

3. Thyroxine Derivatives 174

4. Homologs and Analogs of Thyroxine 175

5. General Remarks on Thyromimetic Activity. 178

II. The Synthesis of DL- and L-Thyroxine 179

III. Inhibition of the Action of Thyroxine by Structurally Related Compounds 187

Re,ferences 190

~j;

}

i

Penicillin and its Place in Science. By A. H. COOK, The BrewfugIndustry Resear~h Foundation, Nutfield (England) 193

Introduction. 193History of Penicillin and its Development. 194Some Biochemical and Microbiological Asp.ects of Penicillin. 196

Penicillin Assay Methods 196Dilution Assays. ; .196Penicillin Standards. 197The Cup-Plate Method 198Other Assays. 198

Production of Penicillin 200a) Culture media 201b) Productive mould strairis 203

The Structure of the Penicillins : 204Penicillin and Preparative Organic .Chemistry. 220

fJ-Lactams ; 220Thiazolidines , 223Oxazolones 225

The Synthesis of Penicillin 231Concluding Remarks. 239

Reference" 240

Sennosides A and B, the Active Principles of Senna. By A. STOLL

and B. BECKER, Chemische Fabrik vorm. Sandoz, Basel (Switzerland} 248

I. Historical 248

ll. General Considerations 25°

rn. I!!olation of the Senna Glucosides 251

IV. Determination of the Molecular Weights of the Senna Glucosides andtheir Aglucones 253

V. Elucidation of the Structure of Sennosides A and Band their Partial

Synthesis. , 254

I. Reductive Cleavage of the Sennosides and the Sennidins. 258

2. Investigation of the Meso-Compounds 262

3. Determination of the Position of the Anthrone Oxygen Atom. 264

4. The Relationship Between Sennoside A and Se~noside B 265

5. The Synthesis of Racemic Sennidin and Partial Synthesis of Sennosides Aand B. 267

VI. Pharmacological Observations 268

Refetences 26q

,1 Some Recent Developments in the Chemistry of Antibodies.By J. W. WILLIAMS, Department of Chemistry, The University ofWisconsin, Madison, Wisconsin 27°

Introduction. 27°

I. Concentration and Purification of Antibodies. 271'Fractionation bv Saltin~-Out 2'7~

VIIInhaltsverzeichnis. -Contents. -Table des matieres.

Fractionation by Organic Precipitant or Extractant. 274Purification of Antibodies 282

II. Characterization of the Antibody-Rich Protein Systems. ~'. 283

III. The Enzymatic Digestion of Serum .Globulins and the Characterizationof the Cleavage Products 290

IV. Immunological Studies with the Several y-Globulins. 296References. 300

Namenverzeichnis. Index of Names. Index des Auteurs. 306

SacRverzeichnis. Index of Subjects. Index des Matieres 316

Inhaltsverzeichnis.Contents. -Table des matieres.

I

j

t"

The Fine Structure of Cellulose. By A. FREY-WYSSLING and

K. MijHLETHALER, Pf1anzenphysiologisches' Institut, Eidg. TechnischeHochschule, Zurich. I

I. Plant Cell Wal1s 2

I. Identification of Cellulose 2a) Preparation of Cell Wal1s 2b) Reaction of Cellulose with Iodine 2c) The Behavior of Cellulose toward Direct Dyes and Basic Dyes 3

d) Dissolution of Cellulose 4e) X-ray Ana1ysis 4f) The Double Refraction Test 5

2. Ontogeny of Cell Wal1s 6a) Primary Cell Wal1s 6b) Secondary Cell Walls 8

II. Microfibrils ; 10

I. Occurrence of Microfibri1s 10a) Parallel Texture of Secondary Wal1s in Natural Fibers 10

b) Woven Texture of Primary Walls 13c) Cellulose S1imes 4d) Bacterial Cellulose 16

2. Internal Structure of Microfibrils 18a) No Visible Segmentation 18

b) Lamination. 19c) Crista1linity 20

d) Intermicellar Spaces 23

III. Conclusions. 24

References. 24

~

jBacterial Dextrans. By M. STACEY and C. R. RICKETTS, Chemistry

Department, The University, Birmingham 28

I. Introduction 28

II. Historical. 28

III. The genus Leuconostoc 29

I. Classification ,' 29

2. Growth Factors 29

~. Dextran Formation in Leuconostoc Cultures 30

~ '; .~ ~

3°

31

32

33

36

36

3738

39

40

41

43

43

4. Enzymic Synthesis of Dextran. .

5. Serologie of Leuconostoc. IV. Derivatives of Dextran. V. Structure of Dextrans VI. Physico-chemical Studies of Dextran

I. The Macro Molecule. 2. Partial Hydrolysis ,

3. Fractionation ,

4. Ultracentrifugal Studies. 5. Adsorption Analysis :. VII. Dextran in Blood Transfusion. :VIII. Conclusion References.

47

48

4949

5°5°515252

5353535556

5960606363

64

65

66

67

6767686970

I ,Sugar Phosphates. By L. F. LELQIR, lnstituto de investigaciones bio-quimicas. Buenos Aires Introduction. I. PTeparation of Sugar Phosphates Isolation from Natural Sources PTeparation of Synthetic Esters Phosphorylation 0£ the Hemiacetalic Hydroxyl. Phosphorylation 0£ Alcoholic Hydroxyls ...: Phosphorylation 0£ Sugar Anhydrides. Phosphorylations Followed by Group Migration. II. Determination 0£ the Structure 0£ Sugar Phosphates. The Identi£ication of the Carbohydrate Component. The Position 0£ the Phosphates Group. Periodate Oxidation The Structure 0£ Sugar Phosphates in Solution. III. Hydrolysis 0£ Phosphoric Esters Acid Hydrolysis 0£ Aldose-I-phosphates Acid Hydrolysis 0£ the Phosphates at the Alcoholic Groups. Alkaline Hydrolysis Inversion During Hydrolysis IV. The Acid Strength 0£ Sugar Phosphates. V. Methods 0£ Estimation aqd Identification. VI. The Coenzymatic Action ~£ Some Esters. , VII. Pentose Phosphates. Ribose Phosphates. Ribose-I-phosphate Desoxyribose-I-phosphate : \ Ribose-3-phosphate. ). Ribose-5-phosphate ,

.

Arabinose Phosphates 70

D-Arabinose-5-phosphate 7°

Xylose Phosphates 71D-Xylose-l-phosphate 71D-Xylose-5-phosphate 71

~II. Hexose Phosphates 7z

Glucose Phosphates. 7z

(X-D-Glucose-l-phosphate (CoRI Ester) 7zp-D-Glucose-l-phosphate 74(X-L-Glucose-l-phosphate 74Gl1icose-z-phosphate 74Glucose-3-phosphate 75Glucose-4-phosphate 75Glucose-5-phosphate 76Glucose-6-phosphate (ROBISON Ester) 76Glucose-I,6-diphosphate : 78

Galactose Phosphates : 79

(X-D-Galactose-I-phosphate 79p-Galactose-l-phosphate ,80Galactose-6-phosphate 80

Mannose Phosphates. 80Mannose-I-phosphate 80Mannose-6-phosphate 80

Fructose Phosphates 81Fructose-I-phosphate (ROBISON-TANKO Ester) 81Fructose-3-phosphate 8zFructose-6-phosphate (NEUBERG Ester) 8zFructose-I,6-diphosphate (HARDEN-YOUNG Ester). 8z

Tagatose Phosphate. 84D-Tagatose-6-phosphate 84

Sorbose Phosphates 84L-Sorbose-I-phosphate 84L-Sorbose-6-phosphate : 85

IX. Disaccharide Phosphates 85

Trehalose-monophosphate 85Malt.ose-l-phosphate 85Unidentified disaccharide-monophosphate 86

, X. Miscellaneous PhosphateEsters., 86

Methyltetrose-phosphate 86Ketoheptose-monophosphate 86

References 86

!j

j The Chemistry of Nucleotides. By G. W. KENNER, The UniversityChemical Laboratory, Cambridge 96

Introduction 97

I. Methods. , 98

I. Countercurrent Distribution 98

VI InhaItsverzeichDis. -Contents.~ Table des matieres.

2. Ion Exchange. '. 99

3. Paper Chromatography; : 101

4. Use of Physical Properties 102

5. Periodate Oxidation ; 10Z

II. Ribonucleosides 103

I. Isolation 103

2. Structure. 104

3. Synthesis 108a) pyrimidine Nucleosides 108

b) Purine Nucleosides 109c) Nicotinamide Nucleosides 115d) Benziminazole Nucleosides 116

III. Deoxyribonucleosides 117

I. Isolation 117

2. Structure 118

3. Synthesis ' 118

IV. Isolation and Structure of Nucleotides 119

I. Nucleotides derived from Phosphoric Acid 119

a) Adenylic Acids. 119b) Guanylic Acids. 122c) Cytidilyc and UridylicAcids IZZd) Nucleotide from Vitamin B1s 12Ze) Polynucleotides IZ2

Z. Monoa1kyl Esters of. Polyphosphoric Acids. Iz33. Dialkyl Esters of pyrophosphoric Acid. Iz3

a) Nicotinamide Nucleotide5" Iz3b) Flavin Nucleotides IZ5c) The Coenzyme of "Galactowaldenase" 1Z5

V. Synthesis of Nucleotides Iz5

I. Methods of Phosphorylation 1z6

Z. Nucleotides derived from Phosphoric Acid. 13°

a) 5'-Phosphates 130b) Z'- and 3'-Phosphates 131c) Dialkyl Esters of Phosphoric Acid 13z

3. Mononucleotides derived from Polyphosphoric Acids ..'.. 133

4. Dinucleotides derived from pyrophosphoric Acids. 135

References. ; 1~6

Die Veilchenriechstoffe. Von H. SCHINZ, Organisch-chemisches Labora-torium der Eidg. Technischen Hochschule, Zurich. I46

Einleitung , 147BegI:iff der Veilchenriechstoffe 147A11gemeirier Ve,]auf der Arbeiten uber die Veilchenriechstoffe 148

I. Die Jonone. 149Konstitution der Jonone 149Hvn,.;..,.nna n..,. Tnnnn..- I..I

In l1er. Seitenkette m~thylierte Jonofie 151Andere Untersuchungen an den Jononen , .152Vorkommen von Jononen und ihren Abkommlingen in ~aturprodukten 153

~f

rI

1

~

"

I i

!

~

1,iii!If

II. Die Irone. 155Gewinnung des Irons 155Arbeiten von TIEMANN und KRttGER 156Erste Synthesen auf Grund der Formel von TIEMANN und KRttGER. ..157

Tetrahydro-iron 158Diensynthesen auf Grund der TIEMANNschen Formel 159Richtige Bruttoformel des Irons 159Synthese eines 6-Methyl-jonons (Gemisch (¥ und fJ) 161Oxydativer Abbau des Irons mit Ozon und Chromsj!,ure; Hypothese der

7-Ringstruktur des Iran&c~.." 162

Ultraviolett-Spektrum des naturlichen Irons; Isomerisierungen. 164Synthesen "ironartiger" Ketone mit 7-Ring-struktur 164Abbau des Tetrahydro-irons; Beweis der 6-Ring-struktur 165"I-Iron ; 169

Weitere Nachweise des "I-Irons 17°Argumente von NAVES und Mitarbeitern zugunsten der 6-Ring-struktur

des Irons; RAMAN-Spektren 171Anwesenheit von (¥-Iron im naturlichen IrongeIriisch. 171(¥-, fJ- und "I-Iron aus genuineri undisomerisierten Gemischen von Natur-

Iron. 173Synthese von (:J::)-(¥- und (:J::)-fJ-Iron 174Infrarot-Spektren ~ 175Stereoisomerie-Moglichkeiten der Irone und Hydroirone ~6Stereoisomerie-(2,6)der Irone.; 177Stereoisomerie-(21,22) der Irone 178Vergleich der naturlichen und synthetischen Irone 179Dihydro-irone : 181

Tetrahydro-irone 183Weitere Ironsynthesen 185Andere Arbeiten mitIron 186

III. Die Riechstoffe des Veilchenblatter- und Veilchenbliitenols Veilchenblatterol Veilchenbliitenol. Svnthesen von Nonadienol und Nonadienal .187.187.188

.1891f!f"!

~.

IV. Geruch und Konstitution 190Empfindung und Charakterisierung der Gertiche. 19°Gleiche Gertiche bei Substanzen verschiedener chemiScher Konstitution 191Geruch und Konstitution innerhalb der einzelnen Korperklassen ,.. 192Geruch und Konstitution bei den Veilchenriechstoffen 193

v. Zur Biogenese der Veilchenriechstoffe 195Hypothese tiber die Biogenese der Terpenverbindungen im allgemeinen. 195Hypothesen tiber die Biogenese der Veilchenriechstoffe. 196

Literaturverzeichnis 198(11.

.

,

~~

VIII Inhaltsverzeichnis. -Contents. -Table des matieres.

~

f

Neuere Entwick1ungen auf dem Gebiete der Flechtenstoffe. Von

Y. ASAHINA, Research Institute of Natural Re~ources, Tokyo. 207

Einleitung 208

I. Verbindungen der Fettreihe 20~

I. Fettsa.uren und Laktone 20~

Proto1ichesterinsa.ure, Nephromopsinsaure, NephrosterinSa.ure. Nephro.steransa.ure. Caperatsa.ure, Rocel1$a.ure 209'

Rangiformsaure 209

2. Triterpenoide 210Zeorin 210-Leukotylin 211Urs01sa.ure 211

3. Zuckeralkoh01e 2IZ

II. Verbindungen der Benz01reihe : 2IZ

I. Pulvinsa.ure-Derivate 2IZVulpinsa.ure, Pinastrinsa.ure, Calycin 2IZ

2. Diphenylenoxyd-Derivate 2IZDidiymsa.ure. 2IZ

Strepsi1in 213Usninsaure 214Usnonsa.ure 216-Dihydro-Usninsa.ure, Tetrahydro-desoxy-usninsa.ure. 216-

Usn01sa.ure und Decarbusn01 217

.3. Xanthon-Derivate 2I~Lichexanthon 2I~

4. Depside. 220Depside der Orcin-Gruppe 220-

Lecanorba.Ure-Typus: Erythrin 220Olivetorsa.ure-Typus: Olivetonid 222Gyrophorsa.ure-Typus: Hiascinsa.ure. 222

Depside der .8-0rcin-Gruppe 223Nichtexistenz der Isosquamatsa.ure 22~

Hypothamn01sa.ure 223Barbat01sa.ure ; .224

5. Depsidone.. : 225Grundskelett des Depsidons 225-Depsidone der Orcin-Gruppe 225-

Vari01arsa.ure. 225-Psoromsa.ure 226-l¥- und .8-Methylather-salazinsa.ure 227

Chlorhaltige Depsidone 228Diploicin. 22S

Gangaleoidin 229Pannarin 2.29

6.'Anthrachinon- und Phen~nthrenchinon-Derivate 23LMagnesiumacetat a1s Reagens fiir P01yoxyanthrachinone. 23L

RhodoCladonsa.ure. 231

Thelephorsaure 23Z t

~

IXInhaltsverzeichnis. .-Content. --Table des matieres.

7. Stickstoffhaltige Substanzen 232Pikroroccellin 232

III. Biogenese der Flechtenstoffe 234

IV. Antibiotische Wirkung von Flechtenstoffen 238

V. MikrochemischerNachweis der Flechtenstoffe 239


t

II+

I

IJr

Lupinen-Alka1oide und verwandte Verbindungen. Von F. GALI-

NOVSKY, II. Chemisches Universita.ts1aboratorium, Wien : 24.5

I. Einleitung 245

II. Lupinen-Alkaloide bekannter Konstitution 246

I. Bemerkungen zur KonstitutionSaufkla.rung 246

2. Lupinin. 247

3. Anagyrin. 253

4. Spartein 254

5. Lupanin 2606. Oxylupanin 261

III. Lupinen-Alkaloide unbekannter Konstitution ,. 263

IV. Verwandte Alkaloide anderer PapilionaCeen oder Pflanzenfamilien. 264

I. Cytisin 265

2. Aphyllin und Aphyllidin 267

3. Weitere verwandte Alkaloide (fraglicher Konstitution) 268

V. Versuche einer zell-moglichen Synthese der Lupinen-Alkaloide 269

VI. Pharmako1ogie der Lupinen-Alkaloide 271

Literaturverzeichnis. : : 272

~

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i

Brechwurzel-Alkaloide. Von M. PAILER, II. Chemisches Universita.ts-laboratorium, Wien 278

I. Einleitung. 278Zur Geschichte 278

Verfalschungen. 279Hande1ss0rten. 280

II. Zusammenha.nge der einzelnen Brechwurzel-Alkaloide 280

IlI. Emetin 281

I. Konstitution 283

2. Rubremetin (Dehydroemetin) 292

3. Technische Gewinn~ng des Emetins 296

IV. Nebenalkaloide der Brechwurzel ; 297

I. Cephaelin. 297

2. Psychotrin und O-Methylpsychotrin 298

3. Emetamin 300

V. Nachweisreaktionen der Ipecacuanha-Alkaloide. 300

.

~

301

30Z

303

306

VI. Biogenetische Betrachtungen zur Konstitution des Emetins

VII. Therapeutische Verwendung des Emetins VIII. Synthesen von Substanzen mit Emetin-Wirksamkeit Literaturverzeichnis..

I.310

.310

.311

.312

.314

.316

.318

.318

.322

.326

.330

.330

.332

.333

.337

.339

X-Ray Diffraction Studies of Crystalline Amino Acids and Peptides.

By R. B. COREY, California Institute of Technology, Pasadena. Introduction. I. X-Ray Analysis of Crysta1s in General I. Outline of the X-Ray Method 2. The Trial Structure and the PATTERSON Diagram. 3. Refinement of the Structure II. Studies of Crystals of Amino Acids I. Glycine 2. DL-Alanine 3. L-Threonine. III.. Studies of Crystals of Peptides and Some Related Compounds. I. 2,5-Diketopiperazine. 2. .8-Glycylglycine 3. N-Acetylglycine. IV. Inferences Concerning Protein Structure. References.

J

j Some Aspects of Enzyme Chromatography. By L. ZECHMEISTER,

California Institute of Technology, Pasadena. and M. ROHDEWALD,Physiologisch-chemisches Institut der Universitat Bonn. 341

I. General Remarks on Enzyme Chromatography 34z

II. Methods. 344

Exchange Adsorption 344"Salting out" Adsorption 345

Chromatography of Enzymes on Filter Paper 345

Location of Enzyme Zones on the Column by Brushing with Color Reagents 348

The Treatment of Colored Enzymes and Colored Derivatives of Colorless

Enzymes 351

!II. Chromatography as a Step in the Purification of Enzymes. 353

IV. The Resolution of Enzyme Mixtures by Partial Adsorption. 354

Amylase and Maltase 355

Lichenase and Cellobiase 355

Cellulaseand Cellobiase~ 355

Cellobiase and Salicinase 355

Gentiobiase, Salicinase and Amygdalase 356

.B-Glucosidase, ~-Galactosidase and Chitinase. 356

~

Chitinase and Chitobiase 356

Chitinase, Chitobiase, (X- and p-Phenyl-N-acetyl-D-glucosaminase, and

Salicinase. 357

Tannase and Esterase 357

Tannase and p-Glucosidase ; 357

Phosphorylase, Phosphatase and Phosphoglucomutase 357

Dehydrogenases 358

Mono- and Diphenolase 358

Thiaminases 358

Dipeptidase and Amin<;>polypeptidase 358

Trypsin, Lipase, and Amylase 358

v. The Use of Enzymes in the Chromatographic Treatment of Other Sub-

stances. 359

References. 359

365Namenverzeichnis. Index of Names. Index des Auteurs.

Sachverzeichnis. Index of Subjects. Index des Matieres. . ..377

~

tInhal tsverzeichnis.

j .Cont~nts. -T~bl~ des matieres.

Synthet1sche Chemle der Carot1nolde. Von H. H. INHOFFEN und

H. SIEMER, Organisch-chemisches Institut der Technischen Hochschule,Braunschweig I

I. Allgemei1ie Ei1ileitung INomenklatur-Vorsch1ag und Ei1iteilung des Stoffes. 2

.Zur Stereochemie der Carotinoide 4Die m6g1ichen Stereoisomeren 6Spektrale Vera.nderungen durch t1'ans -cis-Isomerisierung 8"cis-peak"-Effekt 8

II. Synthesen von C8o- und C81-Kohlenwasserstoffen als Modellsynthesen. ..9

III. Bis-nor-methyl-p-carotin und 7,7'-Dihydro-p-Caroti1i 13

Bis-nor-methyl-p-caroti1i ; 137,7'-Dihydro-p-Caroti1i 16

IV. p-Caroti1i-Synthesen 19

p-Caroti1i-Synthesen CI8+C8+CI8 19.8-Caroti1i-Synthese cI8+cl+c1' 22

Stereoisomerisierungvon I5,I5'-mono-cis-p-Caroti1i. 26

p-Caroti1i-Synthese ~8+C.+CI8...; 27

V. Lycopi1i und el-Carotin 28

LyCOpi1i 28

el-Caroti1i 30

VI. Synthesen von h6heren Caroti1i-Homologen. 31

I6;If1!.Homo-p-Caroti1i 31Decapreno-p-caroti1i und Decapreno-el-caroti1i. 34

Dodecapreno-p-Caroti1i 35

JiteraturverzeiChnis JS

Synthesis and Properties of Vitamin A and Some Related Com-

pounds. By J. G. BAXTER, Distillation Products Industries. Rochester,New York , 41

Introduction 42

I. Synthesisof Yitami1i A , 43

I. Via Esters of fJ-Ionylideneacetic Acid 43Ethyl p-Ionylideneacetate and its p",-Unsaturated Isomer. 46

p-Ionylidene-ethan01 50CI8-Ketone 50

'.

-

IV

-

inhaltsverzeichnis.. -Contents.. -Table des mati~res.

Vitamin A Acid ethyl ester and its .B;'Y-Unsaturated .Isomer. 50

Vitamin A 5IIsomer of Vitamin A 5ISynthesis by WEND~R, SLATES, TRENNER and TISHLER 5I

.B-Ionylideneacetaldehyde 522. Synthesis of Vitamin A via Esters of .B-Ionyltdenecrotonic Acid. ...52

.B-Ionylidenecrotonic Acid 53C18-Ketone 53Vitamin A Aldehyde 56Vitamin A Acids. 56Vitamin A , ..., 57Synthesis by ScHwARZKOPF, CAHNMANN, LEWIS, SWIDINSKY and WUEST 57

3. Synthesis of Vitamin A via "C14-Aldehyde'.' 58Cu-Aldehyde 60AUylic Rearrangement ,.. 60

4. Synthesis of Vitamin A by Other Methods. 64

ll. Synthesis and Biplogical Activity of Some CompoUnds Related to Vitamin A 66Alcohols. , 66Estersand Ethers of Vitamin A :.. 74

~~~:::e~~..::::::::::::::::::::::::::::::::::::::::::::::::::: ;~Hydrocarbons. ..'. 77Vitamin A Acids. .~. ., 79Conclusions : 80

III. Relationship between Vitamin A and Carotenes. 80

References. 80

Les Antivitamines. Par P. MEUNIER, Laboratoire de chimie biol()giquede la Faculte des Sciences, Lyon , 88

Introduction. 88

I.Les antagonistes des vitamines hydrosolubles 90

10 Les antagonistes de la thiamine 90a) pyrithiamine 90b) Oxythiamine , 91

c) Homot4iamine-glycol , 9ld) Antagonistes de la thiamine de nature enzymatique: thiaminases

diverseS 92e) Antithiamines des f9ug"'res 93

2" Les antagonistes des flavines et de la vitamine B12 94

3° Les antagonistes de l'acide pantothenique 95

4Q Les antagonistes de lapyridoxine 95a) Activite vitaminique B6 95b) Constitution thimique des antivitamines B6 96c) Desoxypyridoxine. 96d) Methoxypyridoxine 97e) Autres antivitaminesB6 97

5° Les antagonistes de l'acide nic()tinique 98I

6° Les antagonistes de la biotin~ 98

7° Les antisulfamides lOO

~

~~

~~Inhaltsverzeicbnis.- COntents. -Table d~ matieres. V

8cr Les anti-acides f01iques '; 100

9° L.activite antisu1famide et antisu1fone de derives voisins ~ l.acidep-aminobenzoique :' 101

II. Les antagonistes des vitamines lipos01ubles 102° L . t .. t . AI an IVl amme 102

2° Les antivitamines E 103

3° Les antivitamines K 104.Bibliographie 1°7

/ Recent,1nvestigations on Ergot Alkaloids. By'A. STOLL, ChemischeFabrik Sandoz. Basle. Switzerland 14

I. Historical Introduction 114

II. The Structure of the Ergot Alkaloids 119

I. Introduction. 1192. The Structure of Lysergic Acid ; 1223. Structure of the Peptide Portion 134

III. The Individual Alkaloids of Ergot , 49

I. Ergobasine and Ergobasinine 492. Ergotamine and Ergotaminine : 1533. Ergosine and Ergosinine 1554. Alkaloids of the Ergotoxine Group 1565. Ergocristine and Ergocristinine 1596. Ergokryptine and Ergokryptinine 16I7. Ergocornine and Ergocorninine 162

IV. Partially Synthetic and Hydrogenated Derivatives of Ergot Alkaloids. 163

I. Partially Synthetic Derivatives of Lysergic Acid 1642. The Dihydro Derivatives of the Natural Alkaloids of Ergot. 167

References. 170

Die Alkaloide der Menispermaceae-Pflanzen. Von M. TOMITA,Pharmazeutisches Institut der Universitat Kyoto. 175

I. Einleitung , 17.6

II. Die in Menispermaceae a1ffgefundenen Alkaloide 177

A. Durch RONDO und seine Mitarbeiter untersuchte Pflanzen 177

B. Von nicht-japanischen Forschern untersuchte Pflanzen. 177

C. Pflanzen. in denen vo~ RONDO und MitarbeiterIl das Vorkommenvon Alkaloiden festgelegt wurde. ,..178

D. In der Literatur als alkaloidhaltig angegebene Pflanzen. 178

E. Aus Rohmaterialien des chinesischen Drogenmarktes isolierte Alkaloide 178

F. Nicht zu den Menispermaceae gehOrende, Biscoclaurin-Basen ent-haltende Pflanzen : 179Berberidaceae 179. -Anonaceae 179. -Magnoliaceae 179. -

Monimiaceae 179.r:. Tn r,1r"r.. ..nth"lt..n.. R;,."oclaurin-Alkaloide : 179

VI Inhaltsverzeichnis. 7- Contents. Table des matieres.

llI. Klassifizierung der Menispermaceae-Alkaloide I80

Systematik der :5iscoclaurin-:5asen I80

Gruppe I. :5asen mit einem Athersauerstoff I80

-Gruppe IIa. :5asen mit zwei Athersauerstoffen (Tetrandrin-Typus) I80

Gruppe II b. :5asen mit zwei Athersauerstoffen (IsoChondendrin-Typus) " , I80

Gruppe III a. :5asen mit drei Athersauerstoffen (Dip4enylendioxyd-

Typus) I80

Gruppe IIIb. :5asen mit drei Athersauerstoffen (Depsidan-Typus) I80

IV. Allgemeine Untersuchungsprinzipien der :5iscoclaurin-Alkaloide. I8I

I. Per~nganat~Oxydation des Alkaloides selbst oder seines HoFMANN-schen Abbauproduktes , I81

2. Ozon-Spaltungvon Methinbasen I82

3. Aufspaltung durch Natrium in fltissigem Ammoniak 184

V. Spezieller Teil : 186

I. :5enzylisochin01in-Typus ; I86Coclaurin 186. -Isococlaurin 187. -Magnocurarin 187. -'- Salicif01in-chlorid 188.

2. Phenanthropyridin-Typus 188Sinomenin 188. -Disinomenin 188. -Tuduranin 189. -Step~a-nin I89. -Crebanin 189. -Phanostenin I90. -Dicentrin I90.

3. :5erberin-Typus I90:5erberin I9°. -Palmatin I90. -C01umbamin I90. -Jatrorrhi-zin I90. -Sinactin I9I. ~

4. :5enzochin01izin-Typus I9IRotundin I91.

5. :5iscoclaurin-Typus. 1;92

Gruppe I. Dauricin I92. -Magn01in I92.. -Magn01amin 192. -

Aztequin I93.Gruppe IIa. :5erbamin I93. -Isotetrandrin I94. -Tetrandrin I94. -

Phaeanthin I95. -Cepharanthin I95.. -Oxyacanthin I95. -Re-pandin I97. -Daphnandrin I98. -Daphn01in (Trilobamin) I98. -Arom01in I98. -Epistephanin I99. -Hypoepistephanin 199.

Gruppe IIb. .IsoChondodendrin I99. -Cycleanin 200. -Protocu-ridin 200.. -Neoprotocuridin 20I.. -:5ebeerin20I. -Chondro-f01in 202. -Tubocurarinch10rid 202. -ChondoCUrin 202.

Gruppe lIIa. Trilobin 203. -Isotrilobin 204. -Menisarin 204. -Nor-menisarin 204. -Micranthin 205.

Gruppe IIIb. Insularin 205.

6. Strukturell ungekla.rte :5asen 207

7. Optische Isomerie der :5iscoclaurin-:5asen 2°7

8. Charakterisierung der :5isc6claurin-:5asen. 209

VI.. :5iogenetische :5etrachtungen tiber :5iscoclaurin-:5asen 209

VII. Medizinische Anwendungen , 2[3

Literaturverzeichnis ..., 214

,

VIIInhaltsverzeichnis. -Contents.. ~ Table des matieres.

Naturally Occurring Coumarins. By F. M. DEAN, The Universityr of Liverpool. Depa,rtment ot Organic Chemistry. 225

I. General Structural Features : 22Q

II. The Chelriistry of the Coumarin System. 229

Conversions and Degradation 229The Synthesis of Coumarins 235Theoretical Considerations 237

III. Occurrence, Isolation _~ndDetermination 239

Iy, Some Biochemical Properties, ,: 24°"

V. Simple Coumat:ins , 242Couma;in 242. -Dihydro-coumarin 243. -Umbelliferone 243. -

Het:~iarin 243. -Aesculetin244. -Scopoletin 245. -Fabiatrin 245.-Ayapin 245. -Citropten 245. -Daphnetin 246. -Fraxetin 247.-Fraxidin248. -Isofraxidin 249. -Fra~ino1249. -Eugenin 249.-5-Gerat;1oxy-7-methoxycoumarin 249.. Suberosin Z5°. -

Collinin 250. -Brayleyanin 25°, -Umbel1iprenin 251. -Toddalo-lactone 251; -Aculeatin 252. -Auraptene 252. -Ostruthin 253. -

Osthenol 254. .-Ostho1254. -Ammoresino1256. -Dicoumarol 257.

VI. Furanocoumarins .., , , , 257Psoralene260. -Angelicin 261. -Bergapten 262. -Bergapto1263. -

Isobergapten 264. -Xanthotoxin 264. -Xanthotoxo1265. -Sphon-din 265. -Sphondylin 265. -Isopimpinel1in 265. -Pimpinellin266. -Isoimperat.orin 266. -Oxypeucedanin 267. -Ostrutho1267. -

Imperatorin 268. -Bergamottin 269. -Phellopterin 269. -Byak-angelicol 27&. --.: Byakangelicin 27°. -Ferulin 271. -Nodakenetin

272. -Ma,rmesin 272. -Peucedanin 273. -Athamantin 275.

VII. Chromeno-lX-pyrones , , , 276

Xanthyletin27i- -Seselin 278: -Xanthoxyletin 278. -Luvangetin280. -Al1oxanthoxyletin 281. -Braylin 281.

VlII.3:4'"Benzc.oumarins 282

2' :3" -Dihydroxydibenz-lX-pyrone 282. -4: 6: 4' : 6'-Dihydroxydiphenicacid dilactone 282. -El1agic acid283. -4: 4'~Dihydroxy-6:6'-dimeth-oxydiphenic acid dilactone 284.

References. , 285

J The Biosynthesis of Proteins and Peptides, including Isotopic

Tracer Studies. By H. BORSOOK, California Institute of Technology.

Pasadena, California. 292


I. The Theory of Endogenous and Exogenous Protein Metabolism. ...2942. The Theory of Protein Metabolism as a Dynamic Steady State. ...294

a) Indirect Evidence. 294b) Direct Evidence. : 297c) Lability of Enzyme Proteins : 298

II. The Measurement of Protein Turnover. 299

Ill. Incorporation of Labeled Amino Acids in vivo 300

I. N15-labeled Amino Acids as Tracers 3°O

2. C14- and S85-labeled Amino Acids a~ Tracers. 303

a) In Normal Tissues. 303b) In Tumors. 3°5c) Influence of Hormones 305

d) Incorporation ~f Foreign Amino Acids. 308

IV. Incorporation of Labeled Amino Acids in vitro 309

I. Incorporation of Carbon Dioxide into Amino Acids. 310

2. Net Synthesis of Protein in vitro 3I2

3. Comparison of Incorporation 0£ AmiI.1o Aci4s: in vivo and in vitro. ..313

4. Amino Acid Incorporation in Different Cell Fractions. 313

5. The Nucleus, Amino Acid lncorporation, and the Maintenance of theAmino Acid Pattern in Proteins ; 314

6: Nucleic Acids, Protein Synthesis and Amino Acid Incorporation intoProteins 315

7. Normal, Foetal and Tumor Tissue , 315

8. Effect of Concentration of Labeled Amino Acid on its Rate of In-

corporation 3.159. Does Incorporation of One Amino A~id Require the Presence of Others ? 316

a) Feeding Experiments 316b) In viva Experiments with Single Labeled Amino Acids: 316c) In vitra Experiments with Labeled Amino Acids. 317

V. The Biological Significance of the High Lability of the Proteins in the Cell 319

VI. Mechanism of Peptide Bond Synthesis. :.. 319

T. Heats and Free Energies of Formation of Some Amino Acids and

Peptides (Solids} 319

2. Free Energies of Forrilation of Some Peptides in Aqueous Solution 320

3; The Effect of PH on the Free Energy Change in Peptide Formation 321

4. Peptide Synthesis by Proteases and Peptidases. : 322

a) Classification of Enzymatic Peptide Syntheses According to theSign and Magnitude of the Free Energy Change ( -L1F) 322

b) Peptide Syntheses where -LJF is Positive and Large. 323c) Peptide Syntheses where -L1Fis Small and the Peptide is Relatively

Insoluble. 325d) Plastein Formation. 327e) Peptide Synthesis in an Exchange Reaction during Hyd1:9lysis

(Transamidation and Transpeptidation). 328f) Peptide Synthesis from Amino Acid Esters. 333

.'j. Glutamo- and Asparto-Transferases. 334

6. Syntheses where -L1F is Negative and Large, Coupled with High

Energy Phosphate. 336a) Synthesis of Glutamine 336b) Sylithesis of Hippuric Acid : 337c) Synthesis of p-Aminohippuric Acid. 338d) Synthesis of Ornithuric Acids , 339e) Synthesis of Glutathione ~4.I

" , , ,,;;-~-~-Inhaltsverzeichriis; ?C6ntent$. 4;;Tabledes matieres,~ c "- -

cVII. Mechanism of Amino Acid Incoryoration ihtoProtein) 343

I. Effect of Inhibiiors 3432. Amino Acid 1ncorporation and Phosphorylation. 3463. Heat-Stable Co-factors for Amino Acid Incorporation. 3464. Is Amino Acid Incorporation Synthesis of Protein de novo or an Ex-

change? 3475. The Possibility of Peptides as Intermediates in Protein Synthesis. ..3486. The Linkage of Incorporated Amino Acids ...: 349

References. 352

The Enzymes of Nucleoside Metabolis~. By HERMAN M. KALCKAR,Cytophysiological Institute of the University, Copenhagen. 363

Introduction. 363

I. The Preparation of Nucleosides 364

II. The Enzymes of Nucleoside Metabolism.. 365

I. Purine Nucleoside Phosphorylase 3672. Pyrimidine Nucleoside Phosphorylase. 3723. Trans-N-Glycosidase 3724. Ribosidase 3745. Phosphoribomutase 3756. Degradation and Synth~is of Ribose-Phosphoric Esters. 3167. Nucleoside Deaminases 378

III. Phospho-Ribosides 381

I. Preparation and Properties of Ribose-I-phosphate 38I2. Enzymatic Synthesis (jfRibosides 3823. Preparation and Properties of Deoxyribose-I-phosphate 3854. Enzymatic Synthesis of Hypoxanthine Deoxyriboside 386

IV. Trans-N-Glycosidic Reactions 387I. Non-participation of Deoxyribose-I-Phosphate in Trans-N-glycosidic

Reactiong 3872. Trans-N-Glycosidic Reactions in the Deoxyribose N~cleoside Series. .3813.. Enzymatic Formation of New Deoxyribosides 3S8

V. Phosphorylation of Nucleosides 390

VI. Incorporation of Purines and pYrimidines into Nucleic Acids. 39IInviv() Studies with Labelled Purines 39I. -In vivo Studies withLabelled

pyrimidines 392.. -In vitro Studies with Labelled Purines 393. -Studies on the Amphibian and Echinoderm Egg 394. -Studies onMicro-organisms 394.

Reference" C1""'.."'.. , 395

J Nucleosides and Nucleotides as Growth Substances for Micro-organisms. By W. S.. McNuTT, Vanderbilt University, School ofMedicine, Department of Biochemistry, Nashville, Tennessee. 401

Introduction. 402

I. Nucleosides and Nucleotides of Ribose 405

I. Coenzyme I, '.Desamino.codehydrogenase I," Coenzyme II and Nicotin;.amide Riboside : 40.S

-

x Inhaltsverzeichnis. --Contents. -Table des niatieres.

2. Purine-Nucleosides and Nucleotides. ~o.s

a) Growth-promoting Activity : 4°.S

b) Growth-inhibiting Activity and the Ability to Reverse Growth-inhibition. 409

3. Nucleotides in the Nutrition of Lactobacillus gayonii 410

4. pyrimidine-Nucleosides and Nucleotides 411

a) Growth-promoting Activity 411

b) Growth-inhibiting Activity 412.s. The Biosynthesis of Ribosides and Ribonucleotides ~I3

A Comparison between Microorganisms and Higher Animals withRegard to Purine Precursors in Nucleic Acid Biosynthesis 413

6. Vitamin B12 417Microbiological Functions of Vitamin B12 418Different Forms of Vitamin B12 ,.419

II. Nucleosides and Nucleotides of Desoxyribose 420

I. The Biosynthesis of Desoxyribosides :... 421

Considerations of the Mode of Formation of the DesoxyribosidicLinkage. ...: 422

2. The Growth-promoting Activity of Desoxyribosides and Desoxyribo-

nucleotides. 424a} The Specificity of Certain Desoxyribosides in Eliciting the Growth-

response of Bacteria. , .424

b) The Non-specificity ofthe Natural Desoxyribosides in Promotingthe Growthof Certain Bacteria, 424

3. The Relationship of the Desoxyribosides, Vitamin B12, Reducing Agents,and the "Citroverum-Factor" in Supporting the Growth of Various

Microorganisms. 426Relationship between Certain Reducing Agents and Vitamin B12

Requirement 427The "Citrovorum Factor" ~31

References. 33

J Some Current Concepts of tbe Chemical Nature of Antigensand.Antibodies. By DAN H. CAMPBELL and N. BULMAN, CaliforniaInstitute of Technology, Pasadena, California. 443

I. Introduction. ~43

II. Antigens and Haptens ~45

I. Antigens 446

2. Haptens ~~9

III. Antibodies ~5 I

I. Chemical Composition of Antibodies ~5I

2.. Electrophoretic Properties of Antibodies. ~5z

3. Shape and size of Antibodies 453

4. Nature of Combining Sites : ~55

5. Purification of Antibodies ~6I

XId~Si Inatie:re$. t~,~..?j,;ti~,

-,Physical Nature o.f'.Antigen-AntibodyReactions 463

:i. The Properties of Specific Precipitates. 463

a) Composition. 463b) Formation and Specificity 465

c) 'Ageing' 4662. Thermodynamic Properties of Antigen-Antibody Reactions. 466

a) The Free Energy and Heat Changes in Antigen-Antibody Reactions 467

b) Differences in Free Energies of Combination. ; 468

3. Nature of the Force$ Involved 471

4.MatheInatical Interpretations of the Precipitin Reaction. 475

'5. A Note on the Use of Polyvalent Haptens 476

V. Conclusions. ; 477

References. 478



-

Inhaltsverzeichnis.Contents. ~ Table des matieres.

,

Anwendungen der Dien-Synthese fiir die Erforschung von

Naturstoffen. Von KURT ALDER und MARIANNE SCHUMACHER,Chemisches Institut der Universiti1t, Koln a. Rh. I

A. Allgemein er Teil.

Einleitung 2

I. Die philodiene Komponente 5

II. Die Dien-Komponente 8I. Diene 82. Die Tri- und Poly-ene 93. Die En-Synthese (indirekte substituierende AddItion) I I

nl. Der Retro-Dien-Zerfall 12

IV. Die Dien-Synthes~als stereochemisches Phanomen 4I. Dien-Synth~se und freie Drehbarkeit 142. Die sterischen Auswahlgesetze : 17

.V. Dien-Synthesen mit unsymmetrischen Addenden 21

VI. Dien-Synthese und Katalyse. Addition unter Bestrahlung. Anomalienin der Betatigung phikldiener Funktionen. Glutardialdehyd als Aus-gangsmaterial zur Synthese von achtgliedrigen Ringen. 23

B. Anwendungen.

VII. Synthetische Versuche zur Darstellung von Aldehyden des Cyclocitral-und Safranal.typus ' 27Verhalten hochmethylierter Butadiene bei Dien-Synthesen. 27

VIII. Dien-Synthesen zum Nachweis von konjugierten Doppelbindungs-systemen (Thebain, Muscarufin, Spilanthol) 34

IX. Dien-Synthesen in der Reihe der Fetts~uren 36I. Dienometrie 362. Si1ure von MANGOLD 363. IX- und fJ-Eli1ostearinsi1ure 404. En-Synthesen mit ().lsi1ure-methylester 435. Kombinierte En- und Dien-Synthesen mit Linol- und Lin<:>lens~ure 45

X. Dien-Synthesen inder Terpen-reihe 47I. Acyclische Terpene (Myrcen und Allo-ocimen) , 472. Analyse und Genese der Pyronene 513. Dien-Synthesen mit Menthadienen 534. Neue Wege in di~ Reihe desm- und des p-Menthans. : 55

5. Bicyclische Terpene 56a) Nor-bornylan, Nor-borneol, Nor-campher. 57b} Synthesea von natiirlichen bicyclischen Terpenen. 58c) Konfiguration der Campheralkohole 60d) Veral1gemeinerung. Ausblick 61

6. Di-terpene 67

XI. Steroide 69I. Charakterisierung von Ergosterin und seinen Isomeren. 6g2. Fraktionierte .Dien-Synthesen. Vitamin D2 und Tachysterin 723. Darstellung oestrogener Carbons1turen. Beitr1tge zur Konfiguration

von Equilenin und Oestron 754. Dien-Synthesen als Ausgangspunkt fiir Totalsynthesea von Steroiden 83

XII. Cantharidin-Synthese; das Cafestol 87

XIII. Dien- und En-Synthesen mit molekularem Sauerstoff 94Ascaridol-Synthese. Zur Frage der Entstehung von aromatischen

Kernen in Naturprodukten 94

XIV. Bedient sich die N atur derDien-Synthese als Aufbauprinzip ? 99

J ~~;::;::V~~::i::~ .~~ .~.~~~~;~.. .~~. ~: ~~~~: ;~l~~~~~~~ ~~~~i~~~ 101

ofBrook1yn.Brooklyn,NewYork 119

I. Introduction 119

II. Fundamental Aspects of Rubberiness 120

III. Structure a.nd Molecular Weight of Rubbery Polymers. 126

A. Natural Rubber 126

B. Synthetic Polyhydrocarbon Elastomers. 131I. Polyisobutylene and its Copolymers. 1322. Polybutadiene and Polyisoprene 1343. Polychloroprene 1374. Butadiene-Styrene Copolymers 1385. Butadiene-Acrylonitrile Copolymers. 1416. Synthetic Elastomers of Various Other Types. 142

a) Rubber Elastic Polyesters and Polyamides 142

b) Elastic Polyalkyl-siloxanes ,. 144c) Other Synthetic Elastomers 145

IV. Rubbery Materials in the Condensed State. 146

A. Crystallization of Polymers 146a) Natural Rubber , 146b) Polychloroprene 147c) Polybutadiene an4 Polyisoprene 47d) Polyisobutylene 147e) Other Rubbery Polymers 148

B. Transition Phenomena in Amorphous Polymers. 149

C. Crosslinked Amorphous Chain Networks. 153

V. Kinetic Theoryof Rubber Elasticity 154

A. Outline of the Theory : 154

B. Comparison with the Experiment 162

References. : 164

vInhaltsverzeichl1iS. -Contents. -Table des matieres.

~

I

~

Chimie des lipides bacteriens. Par J. ASSELINEAUet E. LEDERER,

Institut de biologie physico-chimique, Paris. 170

Introduction 172

I. Proprietes generales des lipides bacteriens. 172

II. Variations de la composition des lipides bacillaires. 174

Premiere Partie.

Chimie des constituants des lipides bacterien" 176

1. Substances hydroxylees 176

a) Octadecanol et eicosanol 176

b~ /X-et .B-Leprosols 176

c) Phtiocerol et substances apparentees 176

II. Acides gras ramifies 178

, a:) Acide (+) methyl-6 octanoique : ~ 178

b) Acide tuberculostearique 180

c) Acide lactobacillique 18S

d) Acide phytomonique : 186

e) Acides phtioiques: acides phtienoiques et acide mycolipenique-I ...188

f) Acide coryno-mycolique 194

g) Acidc coryno-mycolenique 196

h) Corynine 197

i) Acides mycoliques des Mycobacteries. 198

I. Constitution chimique. de l'acide /X-mycolique Test. 199

2. Acides .B-, y-et6-mycoliques Test 206

3. Inventaire des acides mycoliques 2°7A. Acides mycoliques de souches humaines 208. -B. Acidesmycoliques de souches bovines 211. -C. Acides mycoliquesde M.phlei 212. --D. Acides mycoliques de M. smegmatis 212.

.III. Biosynthese des acides gras de:s Bacteries. 213

Biosynthesedesacidesnormaux 213

Biosynthesedesacidesramifies 213

IV. Pigments lipo-solubles 217

I. Carotenoides 217

a) Carotenoides specifiques des Bacteries. 218I. Leprotene 218. -2. Rhodoviolascine 219. -3. Rhodopine 219.

-4. Rhodovibrine ;Z19. -5. Rhodopurpurine 220. -6. Flavo-rhodine 220. -7. Sarcinine et sarcinaxanthine 220.- 8. Bacterio-ruberines /X et .B 220.

b) Les carotenoides de diverses especes de Bacteries 221I. Mycobacteries 221. -2. Corynebacteries 221. -3. Actinomy-cetes 221. -4. RhodobacilIes photosynthetiques 222. -5. Sta-phylocoque~ 222. -6. Streptocoques 222. -7. Micrococcus 223.

c) Biosynthese des carotenoides des Bacteries 223

r.'

VI

2. NaphtoquinonesdesBact~ries 223

a) Vitamine ~ 224b) Homologue superieur de la vitamine K1 225c) PhtiOCOl 225d) Role biologique des naphtoquinones des Bacteries 226

Deuxieme Partie.

Composition chimique des lipides bacillaires 226

I. Mycobact~ries ; 226

a) Graissessolublesdansl'acetone 227

b) Phosphatides 229c) Cires A 230

~~~~:g::::::::::::::::::::::::::::::::::.::::::::::::::::::;~f) Cires D 233g) Autres preparations de lipo-polysaccharides complexes. iSOlees de

Mycobacteries : , 233h) Lipides fortement lies 237i) Acides gras des diverses fractions lipidiques 237j) Comparaison de la Composition des lipides de diff~rentes souches

de Mycobacteries 239k) Acido-resistance. 242

2. Co'.ynebacte'.ium diphthe'.iae 242

3. Lactobacillus acidoPhilus et L. a'.abinosus 245

4. Phytomonas tumefaciens 246

5.Bacilles du genre Bacillus 247

6. Brucella. 249

7. Esche'.ichia 250

8. Malleomyces mallei 251

9. Neisseriagono'.'.hoeae 252

10. Bacilles appartenant au genre Pseudomonas. 252

II. Bacilles appartenant au genre Salmonella~. ..~-.. 253

12. Azotobacte'. ch,.oococcum 253

13. Bacilles divers 254

14. Endotoxines 254

15. Membranes cellulaires 255

Troisieme Partie.

Proprietes biologiques des lipides bacillaires 2,56

Bibliographie. 256

J Syntheses of Cortisone. By G. ROSENKRANZ and F. SONDHEIMER,

SyntexS.A.,MexicoCity 27~

Introduction. 275

I. Syntheses of Cortisone from Bile Acids. 276

I. Conversion of Cholic to Desoxycholic Acid 277

2. Side-Chain Degradation 278

-


3. Introduction of Oxygen at C(ll) 282

a) From a ;,1ll-Ethylene by Addition of Hypobromous Acid (REICH-STEIN) : 282

b) From a C(lB) Ketone by Removal of the C(lB) Oxyge~Group froman Intermediate 11,12-Ketol (GALLAGHER) 294

c) From a ;,1ll-Ethylene or from a C(lB) Ketone by Addition of Halogento an Intermediate ;,1ll-3 (X,9(X-Oxide (KENDALL) 299

d) From a ;,19 (ll)-Ethylene by Oxidation of the 9(X,11 (X-Oxido-3(X-ol toa 3(X,9(X-Oxido-3 fJ-ol-II-one (HEYMANN and FlESER) 304

e) Froln a ;,19 (ll)-Ethylene by Oxidation with Potassium Permanganate

(SARETT; WALLIS) 306~ From a ;,17, 8 (ll)-Diene (FIESER; HEUSSER and jEGER; D]ERASSI

and ROSENKRANZ) , ,... 307

4. Formation of the Dihydroxyacetone Side-chairi and Introduction ofthe ;,14-3-Ketone Function ,..., ,., 310

a) Method Involvirig FISCHER Rearrangement of a Dihydroxy-aldehyde(REICHSTEIN) .'...' "' !...310

b) Method Involvirig Chromium Trioxide Oxidationbf a '7 ~,20,21-triol

21-Acetate.(SARETT) 312c) Method Inyolvirig Simultaneous Hydroxylation and Oxidation of

a ;,117 (BO)-21-ol Acetate (MmscHER) ,315

d) Method Involving Hydroxylationof a;,1l7 (20)-20-Cyano-21-olAcetate

(SARETT) 315e) Method InvolvirigHydroxylationof a;,1l7 (20)-2o-Bromo-21-olAcetate

(WAGNER and MOORE) , 319

f) Method Involvirig Reduction of the Oxide of a ;,1l6-20-One-21-o1Acetate (KENDALL) , 321

g) Methods for Introducirig the ;,14-Double Bond irito 4,5 fJ-Dihydro-cortisone Acetate (KENDALL) 322

h) Methods Involving the Introduction of the 17(X-Hydroxyl GroupPrior to that at C(Bl) (SARETT; GALLAGHER) 324

II. Syntheses of Co~isone from Steroids with Ring C Unsubstituted. 326

I. Introduction of Oxygen at C(ll) and Side-chairi Degradation. 327

a) Method Involvirig Hydration of a ;,17-9 (X,11 (X-Oxide (TISHLER;HEUSSER and jEGER) 328

b) Method Involving Oxidation of a ;,1~, 8 (ll)-Diene with Sodium Di-

chromate (FIESER) , 335c) Method Involvirig Interaction of a ;,17, 8 (U)-Diene with N-Bromo-

succiriimide (FIESER) 338d) Method Involvirig Oxidation of a ;,17, 8 {U)-Diene with Performic

Acid (STORK, ROSENKRANZ and D]ERASSI) .., 338

e) Utilization of ;,18-7-Ketones (D]ERASSI and ROSENKRANZ) , , 342

f) Method Involving Chemical Reduction of a;,18-11-One (SONDHEIMER,D]ERASSI and ROSENKRANZ; TISHLER) 344

2. Formation of the Dihydroxyacetone Side-chairi and Introduction ofthe;,14-3-Ketone Function 345

III. Synthesis of Cortisone from Sarmentogenin. , 349

IV. Synthesis of Cortisone from Hecogeniri 351

~

-'-' Table des matieres.

Syntheses of Cortisone 353

, I. Synthesis According to ROBINSON and CORNFORTH 353, 2. Synthesis According to WOODWARD, SONDHEI~ER and TAUB. 356

3. Alternative Synthesis Investigated by RoBINSON'o'. 362

4. Synthesis According to SARETT 363

VI. Biochemical Syntheses of Cortisone* 366

I. Oxygenation by Means of Adrenal Glands. 366

2. Microbiological Oxygenation 369

,VII. Syntheses of I7(X-Hydroxy-corticosterone 370

References 372

Addendum. 388

j Rauwolfia Alkaloids. By ASIMA CHATTERJEE (nee MOOKERJEE),

University College of Science and Tech~ology. Calcutta. 390

I. Iritroduction 390

II. TheAlkaloidofRauwolfiacanescens 393

Rauwolscine 393

The Pharmacology of Rauwolscine 400

III. The Alkaloids of Rauwolfia serpentina. 401

Ajmaline 402

tjmalinine 404

Ajmalicine. 405

Serpentinine .., 405

Serpentine 405

Reserpine 410

Rauwolfinine. 410

The Pharmacology of Rauwolfia serpentina 413

Pharm~cology of Reserpine 413

IV. The Alkaloids of Rauwolfia vomitoria and R. obscura. 414

~stonine 414

The Pharmacology of Rauwolfia vomitoria and R. obscura 415

V. The Alkaloids of Further Rauwolfia Species. 415

Rauwolfia caffra 415

The Pharmacology of Rauwolfine 415'- Rauwolfia heteroPhyUa , 415

!C The Pharmacology of R.heteroPhyUa 416

c' Rauwolfia natalensis , 416

~au1i(olfia mombasiana ' .416

,VI. Conclusions 416

~eferences 417

..i. This Chapter was written in collaboration 'with A. ZAFFARONI..

!" Inhaltsverzeichni$. .;..;:;<:ontents. ,Table des matierl!8.

JInsecticides Occurring in Higher Plants. By ~ FEINSTEIN and

M. JACOBSON , Division of Insecticide Investigations. Bureau of

Entomology and P1ant Quarantine, Ul1ited States Dept. 01 A.,griculture.

Beltsville. Maryland. 423

I. Introduction. ' 424

II. Nicotine and other Tobacco Alkaloids. 426I. General Remarks 4262. Origin of Nicotine, Anabasine and Nornicotine. ; 4283. Insecticidal Use. 4294. Analysis. ; 434

5. Toxicity. 435.

III. Rotenone and Related Compounds 436I.General Remarks 4362. Chemical Structure. 437

A. Rotenone 437

B. Deguelin 439C.. Tephrosin 440D. Toxicarol. 44IE. Sumatrol 442F. Malaccol 443G. Elliptone 443

3. Insecticidal Action. 444

4. Pharmacology 445IV. pyrethrum 447

L GeneralRemarks 4472. Chemical Structure. 4473. Toxicity and Phatmacology 4494. Synthetic Products. ; 450

V. Unsaturated Ispbutylamides 452I. Pellitorine ' 452

2.. Spilanthol 4533. Affinin 4534.. Herculin. 4535. Sanshool-1 arid Sanshool-II 4546. Scabrin 454

VI. Synergetic Effects 455I. Sesamin and Related Compounds 4552. Piperine. 456

VII. Essential Oils, Camphor, Turpentine; Fatty Oils. 457

VIII. Miscellaneous. 459I. Ryania speciosa 4592. TriPterygium wilfordii HOOK 460

3. Quassia 46I4. Sabadilla. 4625. Hellebore (Veratrum) 4636. Larkspur. 464

7. Mamey. 464References. 465


Sachverzeichnis. Index of Suhiect". Index des Matieres. AQA

Inhaltsverzeichnis.


j

\

i

Starch: Its Constitution, Enzymic Synthesis and Degradation.

By STANLEY PEAT, Department of Chemistry, University College ofNorth Wales, Bangor, Caernarvonshire I

I. Introduction. 2

II. Chemical Investigations 0{ the Basic Structure of Starch. 4

I. End-Group Assay 4

2. The Molecular Size of Starch 5

III. Amylose and Amylopectin 6

1. Separation. 6

2. Comparison of Properties : 8a) Solubility 8

b) Degree of Polymerisation 9c) Percentage of Non-reducing End-Groups ~d) Reaction with Iodine 9e) C~tallinity 10

3. The Amylose-Amylopectin Ratio 10

IV. Structure of Amylose 11

1.. Molecular Size. II

.2. Evidence from Amylolysis 13

3. Z-Enzyme 144. The Maltosaccharides : 16

V. Structure of Amylopectin 18

1. Molecular Size and Degree of Branching .18

2. Nature of the Branch Link 19

3, R-Enzyme, a Debranching Enzyme 23

4. Conformation of the Amylopectin Molecule. 24

VI. Enzymic Synthesis of Starch 25.I. Synthesispf Amylose 26

a) The Donor. 26b) The Acceptor. 26

c) The Enzyme 29

2. The Synthesis of Amylopectin 29a) Th~BranchingEnzyme 30b) The Mechanism of Branching 3°c) Substrate for Q-Enzyme 31d) Q-Enzyme, a Transglucosylase 32e) The Acceptor 32f) D-Enzyme. 33

References 34

~

IV Inhaltsverzeichnis. -Contents. -Table des matieres.

Neuere Ergebnisse auf dem Gebiete des Lignins und der Ver.bolzung. Von K. FREUDENBERG, Chemisches Institut der Universita.tHeidelberg. 43

I. Einleitung 43

II. Der Stoff : 44

III. Analyse und Reaktionen ; 46

IV. Abbau 49

V. Modellsubstanzen 51

VI. Optisches Verhalten 52

VII. Biosynthese des Lignins 55

VIII. Vorstufen der Ligninbildung. Die sekund~en Bausteine 60

IX. Verkniipfung der sekunda.ren Bausteine zum Lignin 64

X. Beziehu~g der natiirlichen Ligninarten untereinander und zum kiinst-lichen Lignin. ". 66

XI. Die Bindung des Lignins iIn Holze 67

XII. Der Vorgang der Verholzung 69

XIII, SchluBwort 74

Literaturverzeichnis. 75

Probleme und neuere Ergebnisse in der Vitamin D-Chemie.

Von H. H. INHOFFEN und K. BRUCKNER, Organisch-chemischesInstitut der Technjschen HoChschule Braunschweig 83

I. Pra.calcifer01, ein neues Isomeres in der Reihe der Bestrah1ungsproduktedes Ergosterins 83

II. Konstitution des Vitamins D2 und des Tachysterins 87

III. Zusammenfassung neuerer Einzelergebnisse aus der Chemie der Vitamineund Provitamine D ; 90

I. Neue Verbindungen des Vitamins D2 9°

2. Neuere Methoden zur Darstel1ung von Provitaminen und Vitaminen D 91

3. Neue Vitamine D und Beitra.ge zum Zusammenhang zwischen Kon-

stitution und physi010gischer Wirkung 93

IV. Ozon-Abbau des Vitamins D2; zugleich ein Beitrag zur Stereochemie der

Steroide 95

V. IsomeriSierung des Vi~mins D2 91

VI. Synthetische Versuche in der Vitamin D-Reihe 102

I. Modellversuche zur Darstel1ung Vitamin D-a.hnlicher Substanzen. ..102

2. Partia1synthese Von zwei neuen Isomeren des Vitamins D2. 108

3. Syntheseversuche des '.D-Hydrindan-Ringsystems .112

VII. Photodehydro-ergosterin 115

VIII. SCh1uBwort 118


~

,

.,--,-

I.

!

,..

~iI.I

I

.I~1;8verzeichnis. --Contellts. ~ Table des matieres. ,- ' V

,; ;, ; ,

Natiirlich vorkommende Chromone. (Mit Anhang iiDer weitere Eleb..therine-Inhaltsstoffe.) Von H. SCHMID, Chemisches Institut der Uni-versitiit Zurich. 124

I. Einleitung. 125

II. Pflanzlicher Ursprung und Isolierung der Chromone. 126

Ammi visnaga 126. -Peucedanum Ost'.utkium 127. -Eugeniaca'.yopkyllata 127. -Eleutke'.ine bulbosa 127. -Isolierung derChromone 127.

III. Konstitutionsermittlung der Chromone 127

I. Allgemeine Bemerkungen 127Abbau mit Alkali 127. -Reaktionen der 2.-stiindigen Methyl-gruppe 128. -Farbreaktionen 129. -Reaktion mit Carbonyl-reagenzien 129.

2. Spezieller Teil 129Chromone aus Eugenia ca'.yoPkyllata: Eugeni~ 129. -Eugenitin 130. -Isoeugenitin 131. -Isoeugenitol 131, -Urnlagerungen mit Jod-wassetstoffsii11re 13~. -ChroJIion aus Peucedanu~ Ost'.~tkium:Peucenin 131, -Chromone aus Ammi visnaga: Khellin 'I33. -Visnagin 134. -Visa:mminol 136. -Khellinol 136, -Kh~llolglucosid.Khellol 137. -Konstitution und U, V.-Absorptionsspektren von'Y-Benzopyrone~ 137. -Chromon ;tus Eleutke'.ine bulbosa: Eleutherinol138.

IV. Synthese der naturlichen Chromone und verwandter Verbindungen. ..4°

I. Allgemeine Bemerkungen 14°

2. Spezieller Teil 142

Chromo~e aus Eugenia ca'.yoPkyllata 42. -Peucenin 42. -Khellinund Khellinon 43. -Khellol 146. -Visnagin. Visnagin6n undverwandte Verbindungen 47. -Isovisnagin 48. -Al10visnagin 48.-Weitere Furo- und Dihydrofuro-chromone 15°.

V.Zur Biogenese der Chromone 150

VI. Pharmakologie und therapeutische Anwendung einiger Chrom(}ne. 154

Khellin 154. -Visnagin 155. -Khellol-glucosid 155. -Visammi-no1155, -Khellinol 155. -Visnagan 155. -Klinische Verwendungvon Khellin 155. .

VII. Z~sammenhiinge zwisch~n Kon&titution und. pharmakologischer Wirk-sariikeit von Chromonen , 156

Anhang: VIII. Weitere Inhaltsstoffe aus Eleutke'.ine bulbosa und einige damitverwandte Verbindungen 157

Eleutherol 158. -~-Sorinin und ~-Sorigenin 160. -.8-S0rinin und.8-S0rigenin 161. -Weitere nati1rliche Naphthaline 161. -EleJl.therine-chinone und Fusarubin: Eleutherin 162. -Isoeleutherin 165..-Allo-eleutherin 166, -Alloiso-eleutherin 166. -KonfigurativeZusammenhiinge 166. -Fusarubin 170. .

Litera turverzeichnis

VI Inhaltsverzeichnis. -Contents. -Table des matieres.

The Configuration of Polypeptide Chains in Proteins. By LINUS

PAULING and ROBERT B. COREY, California Institute of Technology,Pasadena.California I80

Introduction. I8I

r. The Dimensions of the Amide Group I82

I. The Amino Acids I82al The Crystal Structure of L-Hydroxyproline I82bl The Crystal Structure of DL-Serine I86

2. Simple Peptides and Related Substances. I88a) The Crystal Structure of ~-Glycyl-glycine. I88

.b) The Crystal Structure of N.N'-Diglycyl-L-cystine Dihydrate. I9°c) The Crystal Structure of Glycyl-L-asparagine I93d) The Crystal Structure of Glycyl-L-tryptophan Dihydrate. I95

3. The Configuration of the Amide Group. I96a) Dimensions of the Amide Group I96b) Effects of Resonance I99c) Properties of N-H. ., O Hydrogen Bonds. 200d) Estimations of Stabilization and Strain Energies. 202

II. Helical Configurations of Polypeptide Chains. 204

I. The (X Helix. , 2042. The yHelix and Other Helixes 207

III. Sheets of Polypeptide Chains 209

IV, The Structure of Fibrous Proteins 2I3

I. The Structure of the (X-Keratin Proteins 2I5..

a) Some Interpretatlons of the X-ray Pattern. 2I7b) The Occurrence of the (XHelix 220

A. Synthetic Polypeptides 220. -B. The (X-Keratin Proteins 222.2. The Structure of Silk and the fJ-Keratin Proteins. 2253. Collagen and Gelatin 227

V. The Structure of Globular Proteins 228

References. 234

Column Chromatography in the Study of the Structure of Pep-

tides and Proteins. By W. A. SCHROEDER, California Institute 0{Technology, Pasadena, California 240

IntrQduction 24I

I. The Separation of Ammo Acids and the Determination of the Amino Acid

Composition. of Peptides and Proteins. 242

I. Analytical Determination of Amino Acids by Chromatography. 242a) Separation of Amillo Acids on Starch. 242b) Separation of Amino Acids on Ion Exchange Resins 246c) Comparison and Discussion of Starch and Ion Exchange Methods 246d) Application of Starch and Ion Exchange Methods to the Analysis

of Peptides and Proteins , 250..2. Isolation of Amino Acids by Chromatography. 255

a) Method of HIRS, MOORE, and STEIN 256b) Method of PARTRIDGE and Collaborators. 258c) Miscellaneous Isolative Methods 260

3. Conclusions 260

.

VIIInhaltsverzeichDjs. -Contents. -Table des matieres.

.

~_.

II. The Deter~ination of Amino Acid Sequence in Proteins. The Identification ..

of Terminal Residues and the Separation and Identification of Peptides 261

I. Identification of N-Terminal Amino Acids. 262a) SANGER'S Method: The Use of 2.4-Dinitrofluorobenzene 262b) EDMAN'S Method : The Use of Phenylisothiocyanate. ~69c) Other Methods , : 271d) Conclusions ' 271

2. Identification of C-Terminal Amino Acids 272a) The SCHLACK and KUMPF Method 272b) The Carboxypeptidase Method 274c) Reduction Methods 275d) The Flydrazinolytic Method 275e) Conclusions. 276

3. The Separation and Identification of Peptides 276a) The Separation of Free Peptides 277b) The Separation of DNP-Peptides 281

.c) The Identification of Peptides 282'd) Conclusions. 282

III. The Separation and Purification of Proteins. 283

IV. Concluding Remarks 287

References 288

Porphyrins in Nature. By R. LEMBERG, Institute of Medical Research,The Royal North Shore Flospital, St. Leonards, Sydney. 299


II. The Structure of the Porphin Nucleus. 301

III. The Naturally Occurring Porphyrins 306

IV. Methods of Isolation, Separation, Identification and Estimation. 310

Isolation of Porphyrins from Natural Sources 3JO

Separation 310Solubility. 310FlCl-Method 311

Crystallisation 311Chromatography 311

Identification of Porphyrins 312

Absorption Spectra 312Fluorescence Spectra 34Estimation 34

V. Individual Porphyrins 34

Protoporphyrin '.IX" 34Mesoporphyrin ..IX" 316Deuteroporphyrin "IX" 316Flaematoporphyrin .'IX" 317

Chlorocruoroporphyrin 317Porphyrin a (Cytoporphyrin) 318

Cryptoporphyrins 320Mono-, Di-, and Tricarboxylic Porphyrins of Unknown Structure. .320

Coproporphyrins 320Porphyrins with five to seven Carboxyl Groups 323

VIII. lnhaltsverzeichnis. -Contents. -Table des matieres.

Uroporphyrins 323Colourless Precursors of Uroporphyrins 325Porphyrins derived from Chlorophyll 328

VI. The Biosynthesis of Porphyrins : 329

VII. The Biosynthesis of Chlorophyll ; 336

VIII. Porphyrins are not Intermediates in the Catabolism of Haem Compounds 337

References. : , 337

The Pteridines. By ADRIEN ALBERT, Department of Medical Chemistry,

The Australian National University. Canberra 350

I. Introduction. 35 I

II. Simple Mono- and Di-substituted Pteridines as Models for the Under-

standing of Naturally-occurring Pteridines 352

I. Solubility and Fusibility 352

2. Stability to Acids and Alkalis 355

3. Ionization; Metal-binding Properties. 356

4. Spectra 360

5. Chemical Reactions. 366

III. The Natura11y-occurring Pteridines (excluding the Folic Acid Series) ..366

I. Glossary of Synonyms , 367

2. The Xanthopterin Family: Xanthopterin, Chrysopterin. Erythropterin 367

Xanthopterin 367. -Chrysopterin 36g. -Erythropterin 36g.

3. The isoXanthopterin Family: isoXanthopterin. Ichthyopterin.Fluorescyanineand Leucopterin , 37°

iso~ant.hopterin 370. .,..". Ichthyopterin 370. -Fluorescyanine 37°.

-Leucopterin 371.4. Substances closely Related to the N atura11y-occurring Pteridines :

Pterorhodin. Urothion 37~

Pterorhodin 371. -Urothion 372.

IV. The Folic Acid Series 372

I. The Synthesis of Pteroylglutamic Acid ("PGA") 373

2. The Occurrence and Properties of Pteroylglutamic Acid. 377

3. Conjugates of Pteroylglutamic Acid ' 380

4. Rhizopterin 382

5. The Citrovorum Factor and Leucovorin. 382

6. New Members ofthe Folic Acid Series 385

V. Substances which are Presumably Pteridines 385

VI. Chromatography and other Techniques of Isolation and Purification. .388

VII; The Physiological Action of the Natural Pteridines. 389

The Simpler Pteridines : 389

The,FolicAcid Series 391

References. 392

Namenverzeichnis. Index of Names. Index des Auteurs.. 404

Sachverzeichnis. Index of Subiects. Index des Matieres..: 422

Inhaltsverzeichnis.


.j Sesquiterpenes and Diterpenes. By A. J. HAAGEN-SMIT, California

Institute of Technology, Pasadena, California. I

.Introduction. I

I. Sesquiterpenes 3

I. Acyclic Sesquiterpene~ 3

2. Bisabolene and Cadinene Type Sesquiterpenes. 3

3. Eudesmol Type Sesquiterpenes 6

4. Elemol 8

5. Eremophilone 86.Iresin 9

7.AzuleneTypeSesquiterpenes 10Synthesis and Properties of Azulenes. 12

8. Longifolene I4

9. Caryophyl1ene. , 16

10. .B-Caryophyl1ene Alcohol 17

I I. Humulene 18

I2.Cedrene 18

II. Diterpenes 20

I. Structure 20

2. Stereochemistry of the Diterpenes 23

III. The Biogenesis of Sesqui- and Diterpenes 26

Biogenesis and Nomenclature 28

References. 31

hetracyclic Triterpenes. By E. R. H. JONES and T. G. HALSALL,Department of Chemistry, The University of Manchester 44

I. Introduction. 45

II. Lanostane Type Group : 48

I. Lanosterol Group 48

Occurrence and Isolation 48Nomenclature 5°. -Interrelationship of Lanosterol, Agnosteroland their Dihydro-derivatives 51.

Structure of Lanosterol : 51Location of the~nert Double Bond 52. -The Side-chain andRing D 59.

IV Inhaltsverzeichms .'.

Conteats Thble desmatleres.

Stereochemistry of Lanosterol 62Rings A and B 62. -Rings C and D 63. -Side-chain Con-figuration 64. -Stereochemistry at C(8) and C(9) in Lanostane

Derivatives 64. -Lanost-7-enol 66.

Synthesis of Lanostenoi 672. Eburicoic Acid. 68

3. Polyporenic Acid A. 734. Polyporenic Acid C ; 8I

5. Tumulosic Acid (PoJyporenic Acid B) 88

.6. Pinicolic Acid A 92

7. Trametenolic Acid A 95

8. cycloArtenol 96

9. cycloLaudenol 99

III. Euphane Type Group 101

I. Euphol 10I

2. Butyrospermol I08

3. Tirucallol II2

4. Euphorbol I I4

5. The Acids of Manila Elemi Resin II6

IV. Compounds of 1Jnkno'Nn Structure I2I

References. I22

Neuere Vorstellungen auf dem Gebiete der Biosynthese der Steroide

und verwandter Naturstoffe. Von R. TSCHESCHE, Chemisches Staats-

institut der Universitat Hamburg 131

I. Einleitung. 131

II. Steroidbiogenese mit markierten Verbindungen. 132

I. Essigsaure als Baustein 132

2. Die Rolle des Squalens 136

III. Unsere Kenntnisse der biologischen Beziehungen der Steroide unter-

einander 139

I. Ein C21-Sterol als Vorstufe der Pflanzensterole mit 28 und 29 C-Atomen 139

2. Gibt es Unterschiede der Biosynthese von Steroiden bei Tieren und

Pflanzen ? 443. Ist ein C27-Sterol obligates Zwischenprodukt bei der Biogenese al1er

Steroide ? 45

4. Die C3o- und C31-Steroide I5I

IV. Die Hypothesen der Steroidbiogenese '. 153

I. Squa.len-Hypothese I53

2. Isosqualen-Hypothese 155

3. Hypothese von MIESCHER I55

4. Hypothese von TSCHESCHE und KORTE. 156

5. Neue Vorstellungen , 158

V. SchluJ3betrachtung I62

Literaturverzeichnis o 162

Some Biochemical Aspects of Fungal Carotenoids. ",By F. T. HAXO,

Scripps Institution of Oceanography of the University of California,

La Jolla, California. :: ..~ 16Q

169I. Introduction

171

174

175

176

177

178

178180

183184186.""

189

190

1Q1

II. Occurrence of Carotenoids in Fungi. I. Carotenes with Fonnula C40H68 2. Carotenoid Hydrocarbons more Saturated than C4oH68

3. Neutral Xanthophylls 4. Acidic Xanthophylls III. Carotenoid Formation in Fungi I. Interrelationships of the C4o-Polyenes a) Mutant Studies. b) Inhibitor Studies. ,

c) Studies of Light-Activated Carotenoid Synthesis. .

d) Temperature Stu<l"1es 2. Precursors of the C4o-Polyenes IV. Physiological Role of Fungal Carotenoids I. Carotenoids in Sexual and Reproductive Processes. .

2. Carotenoids as Ph9tosensitizers V. Conclusion.

19:References

/ The Pyrrolizidine Alkaloids. By F ..L. WARREN , Department of Chemistry,

University of Natal, Pietermaritzburg, South Africa. 198

I. Introduction: Origin, Occurrence and Nature of the pyrrolizidine Alkaloids 199

NatureofthePyrrolizidineAlkaloids 201

Isolation. 205

II. The Basic Hydrolysis Products 208

Retron~ine, Platynecine and Heliotridine as Derivatives of Heliotridane. .209

The Degradation of Heliotridane 211

The Structure of Retronecine and Platynecine 213

The Structure of Heliotridine 24

Monohydroxy-methylpyrrolizidines: Trachelanthamidine andSupinidine. .215

N-Oxides: Trachelanthidine and Isatinecine 216

Syntheses of Pyrrolizidine Bases 217

Stereochemistry and Syntheses of Heliotridane, Pseudo-heliotridane andtheir Derivatives. 22C

Trihydroxy-methylpyrrolizidine: Rosmarinecine. 222

Bases of Unknown Structure: Mikanecine, Hastanecine, Turneforcidine

and Otonecine ~-,

Summary9ftheStructuresoftheBases : 22:

224


~

III. The Acid Hydrolysis Products 225

C1o-Acids ; 225Isatinecic and Retronecic Acids 227Senecic. Integerrinecic and Usaramoensinecic Acids. 228Seneciphyllic and isoSeneciphyllic Acids. 23iRiddellic Acid. 233Sceleranecic and Sceleratinic Acids. 233Jaconecic Acid and the Neutral Lactone from Jaconine 235

C1o-Acids of Undetermined Structure 236Senecifolic, Squalinecic. Mikanecic, Grantianic and Hastanecic Acids 236

Monocrotalic and Dicrotalic Acids 236

Acids having Seven-Carbon Skeleton Structures. 240Trachelanthic Acid. 240Viridifloric Acid. 240Heliotrinic Acid. 241Lasiocarpic Acid. 243Acid from Makrotomine 243Acid from Trichodesmine 243

IV. The Structures of the Alkaloids 244

Alkaloids from Monohydroxy-methylpyrrolizidines 245

A. AlkaloidsofTrachelanthamidine..: 245Trachelanthamine , 245Viridiflorine 246Makrotomine 246

B. Alkaloids from Supinidine 246

Supinine 246.Base C. 246

C. Alkaloids from D-isoRetronecanol 246Lindelofine ,. 246Lindelofamine ~ , 246

Alkaloids from Heliotridine: Heliotrine, .Base G'. Lasiocarpine 247

C18-Alkaloids from Retr'onecine. Platynecine and Rosmarinecine 248Retrorsine. Isatidine 248Riddelliine 249Senecionine 251

Integerrimine 251Usaramoensine. 252

Platyphylline 252Rosmarinine. 252

Seneciphylline 252Grantianine 253Sarracine 254Sceleratine 254Senecifoline 254Alkaloids from Senecio brasiliensis 254

Monocrotaline. 254

Dicrotaline 256

TheAlkaloidsasN-Oxides , 256.

V. Pharmacology (with M. E. VON KLEMPERER) 257

References , 259

-

VII

Paper Chromatography in the Study of the Structure of Peptides and

.

.

I

)

7

S

.328References

Proteins. By E. 0. P. THOMPSON and A. R. THOMl"SON, Biochemistry

Unit, Wool Textile Research Laboratories, Commonwe::\Jth Scientific

and Industrial Research Organization, Melbourne. Au'1;tralia .,. , .27°

Introduction. 271

I. Principles of Paper Chromatography 274

II. Paper Chromatographic Techniques 276

I. Choice of Paper 276

2. Preparation of the Material for Chromatography 277

3. Application of the Material to the Paper. 278

4.EffectofpH ; 279

5. Apparatus. 2796. Solvents , 281

7. Drying of Chromatograms 287

8. Detection of Amino Acids, Peptides and Proteins on Paper. 288a) General Reagents 288b) Non;Specific Reagents ~ 290c) Specific Colour Reactions for Some Amino Acids and Peptides ..290

III. The Determination of the Amino Acid Composition of Peptides and Proteins 292

I. Qualitative Analysis 292

2. Quantitative Analysis 294a) Measurements Applied Directly on the Paper. 295b) Methods Involving Elution from the Paper after Reaction with a

Reagent. 297c) Methods Involving Elution from the Paper before Reaction. 299

IV. Identification of Terminal Sequences in Peptides and Proteins. 302

I. N-Terminal Sequences 303a) Dinitrofluorobenzene Method 303b) Isothiocyanate Method 308c) Other Methods.. ., 312

2. C-Terminal Sequences :.. 315

a) Carboxypeptidase Method. 315b) Reduction Methods 319c) Other Methods. 319

3. Conclusion. 321

V. The Determination of Amino Acid Sequences in Long Chain Polypeptides

and Proteins 32,

I. Separation of Component Chains 32'

2. Methods for the Partial Hydrolysis of Peptides and Proteins. 32:

3. Isolation and Purification of Peptides 32f

4. Deduction of Polypeptide Sequence from the Structure of Lower

Peptides 32:

VI. Concluding Remarks. 32:

Inhaltsverzeichnis.VIII-

-'- Contents. ~ Table des matieres.

Acides amines iodes et iodoproteines. Par JEAN RoGHE et RAYMOND

MICHEL, Biochimie generale et comparee, College de France, Paris. ..349

Introduction530

II. Les acides amines iodes 35I

I. Caracteres analytiques generaux des acides amines iodes ~ 35I

2. lodot~osines etiodohistidines 352

a) lodotyrosines 352

Io L-3-Monoiodotyrosine 352

2° L-3:5-Diiodotyrosine 353

b) .Iodohistidine~ 355

c) Reaction d.ioduration de laL-tyrosine, de la L-histidine et de leurs

derives. 3. lodothyronines et derives. a) lodothyronines ; Io Monoiodothyronines. 2° Diiodothyronines 3° Triiodothyronines 4 ° Thyroxine. b)Derives de la thyronine Iu Derives substitues sur les noyaux. 2° Derivessubstituessurlephenol 3° Modification de la liaison entre le3 deux noyaux c) Derives de la thyronine avec modifications de la chatne laterale. .

Io Acides amines et derives : 2°AcidesA .

d { .{ 11314. c1esamm"smarqu"spar a) lodotyrosines marquees. b) lodothyi-onines marQuees.

.356

.358

.359

.360

.361, 362

.363

.364

.364

.366

.367

.367

.367

368

, 371

371

.372

.373

.374

.374

.378

381

383

383

386

389

390

391

396

III. lodoproteines I. Proteines artificiellement iodees .: a) loduration des proteines et reactions de substitution. b) Formation de thyroxine au cours de l.ioduration des proteines .

c) Mecanisme chimique de formation de la thyroxine et de la 3 : 5 : 3'

triiodothyronine , 2. Thyroglobuline a) Preparation. b) Proprietes et composition en acides amines c) lode et acides amines iodes 3. Scleroproteines lodees a) Gorgonines et antipathines b) Spongines : Biblio~raphie.

.jn'.

JChemistry and Biochemistry of Snake Venoms. By KARL SLOTTA,

Caixa Posta14790, sao Paulo, Brazil 406

I. Introduction. ; P7

II. Snakes and Venoms 409

I. Zoological Classification of Poisonous Snakes. 409

2. Poison Apparatus .I2

3. Extraction of Venom 4I3

4. Drying and Conservation of Venom 44

III. The Action of Venoms 4

I. Pharmacological Activity 4I4

a) "Curare" Group 4I5b) Circulation Group. 416

c) Hemorrhagic Group .I7d) Toxic Value. 4I7

2. EnzymicActivity 4I9

IV. EJlzymesfromSnakeVenoms ~ 4z0

I. Esterases 420a) Phospholipase A(LecithinaseA) 20b) Phospholipases Band C 422

c) Phosphoesterases 422d) 5-Nucleotidase 424e) Adenosine triphosphatase(ATPase) 4z5

f) Ophio-cholinesterase(OChEase) 426

2. Carbohydrases: Hyaluronidase 426

3. Proteases 427

a) Proteinases 427

b) Peptidases 428c) Proteolytic Enzymes and Coagulation. 428

4. Oxidases. 429

a) Catalase .29b) Ophio-L-Amino Acid Oxidase (OAAO) 3°

5. InhibitingEnzymes 43I

V. Separation, Purification, and Crystallization of Biologically Active VenomConstituents 433

I. Non-proteins , 433

2. First Attempts to Separate Active Proteins. 433

3. The Active Principles from Naia Venoms. 435

a) Neurotoxin. 435 .b) Constitution of NeurotoxiIJ 437

c) Hemolysin. 439d) Properties and Composition of Crystalline Hemolysin 440e) Cholinesterase 44If) Cardiotoxin 44Ig) Inhibitor. 442

4. NeurotoXin from Bunga1'us fasciatu.. Venom. 443

x~~ -

Inhaltsverzeichnis. -'-- Contents. -'-- Table des matieres.

5 The Neurotoxic and CoagulatingPrinciples from Vip/Jra russ/Jllii Venom ..443

6. Active Proteins from CrQtalus t. t/Jrrificus Veno~ 444

a) Coagulin. " 444b) Preparation of Crotoxin 445c)Composition. C~enrical Properties and Homogeneity of Crotoxin ..446d) Bio1o~Cal Properties of Crotoxin 448e}The Structuie of Crotoxin 450

VI. Electrophoresis of Snake Venoms 451

jReferences 455

Gene Structure and Gene Action. By G. \\7. BEADLE, California Institute

of Technology, Pasadena, California ; 466

Introduction. 466

The Gene as a Biological Unit 466

The Chenristry of the Genetic Material 468

Transfornring Principles 469

The Genetics of Viruse~ 47°

The Structure of DNA 471

Gene Specificity 472

Gene Reproduction. 473

Gene Mutation. 473

Gene Function. 473

Genetics of Hemoglobin Structure 475

Genes and Enzymes 476

Genes and Aromatic Amino Acids 478

Summarizil1g Discussion , 480

References. ; 482

485

Sachverzeichnis. Index of Subjects. Index des Matieres 506

Namenverzeichnis. Index of Names. Index des Auteurs

.r,.

.ij,i

1

Inhaltsverzeichnis.


J Infrared Spectra of N~ral Products. By A. R. H. COLE, Department

of Chemistry, The University ofWestern Australia, Nedlands, Australia. ..I

I. Introduction. 2

ll. Methods. 3

I. General. 3

2. Instruments. 5a) Radiation Sources. 5

b)Cells 6c) Dispersing Systems. 6

d)Detectors 7e)Single-Beam ~pectrQmet~rs 9f)Double-Beam,SpecirQmeters, IIg)Diffraction Gratings 4h) Calibration. 4

3. Sampling Techniques. i5a)Solvents 16b) Size of Samples. 17c)Use of Polarized Radiation 22

III. Applications. 22

I. General. 22

a)Compound Comparison 23b) Structural Analysis. 25

2. Steroids and Terpenoids 27A. Steroids. 28

a)Hydroxyl Absorption 30b)C-H Stretching Absorption 33c)Carbonyl Absorption 35d)Ethylenic Dotible Bonds 40e) Methyl and Methylene Bending Vibrations. 42f)Bands in the "Fi.ngerRIjnt Region" 45

B. Terpenoids , 48C.Studies of Stereochemistry 53

a) Axial and EquatoriaI. Hydroxyl Groups. 53b) ~-Bromo-ketones 56

3. Application of Infrared Spectroscopy to the Structure and Configurationof Long-Chain Polyenes a) Mycomycin. b) Carotenoids IV. Conclusion. References.

..{

575758

60

60~

70

71

7171

72738085

8989919595969799

99100102

105105110

115

1I8

118

121

124

126

126

127

129

132

Gallotannine und El1agen-gerbstoffe. Von 0. TH. SCHMIDT, Organisch-

chemisches Institut der Universitat Heidelberg I. Einleitung II. Gallotannine: E1lagsaure-freie Gerbstoffe I. Hamameli-tannin 2. Chebulinsaure a) Chebulsaure ("Spaltsaure" CUHJ801J b) 3.6-Diga1loyl-glu(:ose. c) Neochebulinsaure und I,3.6-Triga1loyl-glucose III. E1lagen-gerbstoffe I. 1)bersi8ht 2. Corilagin. 3. Chebulagsaure a) Beschreibung und Analyse b) Hydrolyse mit Wasser; Neochebulagsaure (:) Zur Gesamtkonstitution 4. Hexaoxy-diphensaure. a) Darste1lung der optisch aktiven Hexamethoxy- und Hexabenzoxy-

diphensauren sowie der racemischen und aktiven Hexaoxy-diphen-

sauren b) Sterische Stabilitat der aktiven Formen c) Umwandlung in E1lagsaure; ,.Blume"-Birdung 5. Brevifolin und Brevifolin-carbonsii.ure a) Beschreibung und Analyse. Konstitution b) Synthesen des Trimethyl-brevifolins c) Zusammenhange zwischen Konstitution. sterischem Bau und Ultra-

violett-Spektrum 6. Dehydro-diga1lussaure 7. Valoneasaure a) Beschreibung und Analyse; Ultravioiett-Spektrum b) Alkali-Spaltung c) Valonea-xanthon. IV. Mogliche genetische Beziehungen I. Zur Bildung der Hexaoxy-diphenoyl-verbindungen 2. Zur Entstehung der Chebulsaure und Brevifolin-carbonsaure. 3. Zur Entstehung der verschiedenen Typen von hydrolysierbaren Gerb-

stoffen Literaturverzeichnis

Neuere Ergebnisse auf dem Gebiete der glykosidischen Herzgifte :

Grundlagen und die Aglykope. Von CH. TAMM, Organisch-chemische

AnstaltderUniversitatBasel 137

I. Einleitung 138

II. Die Isolierung von herzaktiven Glykosiden : 139

I. Isolierung von reinen Glykosiden und Aglykonen 14°

a) Herstellung der Rohextrakte I4ob) Trennung von Substanzgemischen 142

vInhaltsverzeichnis. -Contents. -Table des matieres.

2. Farbreaktionen 43a) Allgemeine Farbreaktionen 43b) Farbreaktionen fiir Cardeno1ide 44c) Farbreaktionen fiir Bufadien01ide. :.. 145

d) Quantitative Bestimmungsmethoden 145

3. Papierchromatographie 146a) Schwach polare Glykoside und Aglykone 46b) Stark p01are Glykoside und Aglykone 47

III. Die Konstitutionsermittlung 47

A. Abbaureaktionen 48

a) Glykosidspaltung 48I. Chemische Methoden.., 482. Enzymatische Methoden 151

b) DieKonstitution der Aglykone 152

I. Carden01ide. 153<X) Beweis des Kohlenstoffskeletts. 154fJ) Abbau der Aglykone zu Atiansa.uren 155y) Abspaltung der Hydroxylgruppe an C(14) 156

6) Stereochemie der Substituenten des Digitoxigenins (Grund-typ XIII) und seiner Isomeren 157

Digitoxigenin 1_;7. -Isogenine J58. -3-Epi-digitoxi-genin 160. -Uzarigenin 160. -Urezigenin 160.

e) Stellung und Konfiguration von zusatzlichen funktionellenGruppen. Weitere Aglykone bekannter Konstitution 161

Acovenosigenin A 161. -Periplogenin 162. -CorotoXi-genin 163. -Corog1aucigenin 163. -Strophanthidin 163. -

Strophanthid01 163. -Sarmentogenin 166. -II-Epi-sar-mentogenin 166. -Desarogenin 166. -Digoxigenin 167. -

Gitoxigenin 167- -Oleandrig~nin 167. -Gitaloxigenin 167.-Adonitoxigenin I67- -16-Monoanhydro-gitoxigenin 168.-Allostrophanthidin I69. -Allo-periplogenin I69.

C) Aglykone mit teilweise bekannter Konstitution 169

Adynerigenin I69. -Neriantogenin 172. -O.Acetyl-smalogenin 173. -Xysmalogenin 173. -Tanghini-genin I75. -3-Epi-tanghinigenin I75. -Abogenin I76. -

Allo-g1aucotoxigenin In -Sarmutogenin I78. -Caudo-genin 178. -Decogenin 178- -Acetyl-caulutogenin I78. -Sarverogenin I79. -Inertogenin 179. -Leptogenin 179. -

Chryseogenin 181. -Flavogenin 181. -Antiarigenin I8"Z.-al-Dihydro-antiarigenin 182. -Nigrescigenin 183. -

Ouabagenin 183.

2. Bufadien01ide 188

<X) Beweis des Kohlensto~fskeletts. I88

P) Abbau zu Atiansa.uren und einige Besonderheiten: Aglykonemit bekannterKonstitution 189

Bufalin 189. -Hellebrigenin (Bufotalidin) I89. -Te10-cinobufagin 189. -Gamabufota1in 189. -Bufotalin I89.-Bovogenin A 189. -Bovogen01 A I8g. -Scillarenin

190. -Scilliglaucosidin 190.

i

~

J1

2. Farbreaktionen 43a) Allgemeine Farbreaktionen 43b) Farbreaktionen fiir Cardenolide 44c) Farbreaktionen fiir Bufadienolide. , 145

d) Quantitative Bestimmungsmethoden 45

3. Papierchromatographie 46a) Schwach polare Glykoside und Aglykone 46b) Stark po1are Glykoside und Aglykone 47

III. Die Konstitutionsermittlung 47

A. Abbaureaktionen 48

a) Glykosidspaltung 148I. Chemische Methoden 482. Enzymatische Methoden 151

b) DieKonstitutionderAglykone 152I. Cardenolide. 153

a.) Beweis des Kohlenstoffskeletts. 154p) Abbau der Aglykone zu Atiansa.uren 1559'r Abspaltung der Hydroxylgruppe an C(14) 156

6) Stereochemie der Substituenten des Digitoxigenins (Grund-typ XIII) undseiner Isomeren..., 157

Digitoxigenin 157. -Isogenine 158. -3-Epi-digitoxi-genin 160. -Uzarigenin 160. -Urezigenin 160.

B) Stellung und Konfiguration Von zusatzlichen funktionellenGruppen. Weitere Aglykone bekannter Konstitution 161

Acovenosigenin A 161. -Periplogenin 162. -Corotoxi-genin 163. -Corog1aucigenin 163. -Strophanthidin 163. -Strophanthid01 163. -Sarmentogenin 166. ~ II-Epi-sar-mentogenin 166. -Desarogenin 166. -Dlgoxigenin 167. -

Gitoxigenin 167. -Oleandrigenin 167. -Gitaloxigenin 167.-Adonitoxigenin 167. -16-Monoanhydro-gitoxigenin 168.-Allostrophanthidin 169. -Allo-periplogenin 169. -

t.) Aglykone mit teilweise bekannter Konstitution 169

Adynerigenin 169. -Neriantogenin 172. -O-Acetyl-smalogenin 173. -Xysmalogenin 173. -Tanghini-genin 175. -3-Epi-tanghinigenin 175. -Abogenin 176. -

Allo-glaucotoxigenin 177- -Sarmutogenin 178. -Caudo-genin 178. -Decogenin 178. -Acetyl-caulutogenin 178. -,Sarverogenin 179. -Inertogenin 179. -Leptogenin 179. -

Chryseogenin 181. -Flavogenin 181. -Antiarigenin 182.-al-Dihydro-antiarigenin 182. -Nigrescigenin 183. -

Ouabagenin 183.

2.. Bufadienolide 188

a.) Beweis des Kohlenst?ffskeletts. 188

fJ) Abbau zu Atiansa.uren und einige Besonderheiten: Aglykonemit bekannterKonstitution 189

Bufalin 189. -Hellebrigenin (Bufotalidin) 189. -Telo-

cinobufagin 189. -Gamabufotalin 189.. -Bufotalin 189.-Bovogenin A 189. -Bovogen01 A 189. -Scillarenin

190. -Scilliglaucosidin 190.

.

Marinobuf(

194

195195196200202

214

216

y} Aglykone mit teilweise bekannter Konstitution

Artebufogenin 191. -Resibufogenin 192. -

genin 193. -Scillirosidin 193.

B. Teilsynthese der Aglykone IV. Tabellen Vorbemerkung zu den Tabellen 1-4 I. Cardenolide. 2. Bufadienolide 3. Cardenolid~Glykoslde 4. Bufadienolid-Glykoside Literaturverzeichnis

232

234

236

236

2,\6

240241

241241242243244

245245245

247247248

254254254254255

256256

258

/ Natural Tropolones and Some Related Troponoids. By TETSUO NOZOE.

Faculty of Science, Tohoku University, Sendai, Japan. I. Introduction. iI. Naturally Occurring Tropolones I. Terpenoid Tropolones a) Occurrence. b) Hinokitiol or fJ-Thujaplicin and Hinokitin. Studies on Hinokitiol 237. -Structure of fJ-Thujaplicin 239.

c) y-Thujaplicin d) IX,-Thujaplicin e) Nootkatin 2. Hydroxytropolone-carboxylic Acids a) Occurrence asMold Metabolites b) Stipitatic Acid. c) Puberulic Acid d) Puberulonic Acid. 3. Purpurogallin a) Possible Occurrence in Nature b) The StructureofPurpurogallin 4. Alkaloidal Tropolones a) Occurrence. b) Colchicine and Colchiceine The WINDAUS Formula 248. -Further Experimental Evidence 249.

-DEwAR's Colchicine Formula 25°. -Structure of Ring B 25I. -

The Tropolonic Nature of Ring C 25I. -Detailed Examination of

Ring C 252.

c) N-Formyl-desacetyl-colchicine d) Demecolcine orColchamine e) 2-Demethyl-colchicine and 3-Demethyl-colchicine. f) Colchicoside g) Substances ..1" and " J'.' (Lumicolchicines), and Substance '.D" ...

III. The Synthesis of.Troponoids I. Tropolones and Tropones Tropolone 256. -Tropolone-carboxylic Acid 257. -Tropone 257. -

Preparation of Tropolones from Tropones 257. .

2. Benzotropolones 3.4-Benzotropolone 258. -4,5-BenzQtropolone 258. -3,4,5,6-

Dibenzotropolone 258..

VII.;

Inha.ltsverzeichnis.-"-COntents. ,-- Table des JIlatieres.

3. Colchicine Analogs 259a) Approach to the Synthesis 259b) Styryl-tropolones :. 259c) Phenylethyl-tropolones and their Ring Closure. ;0. 260d) Phenylpropyl-tropolone and Derivatives. 260

4. Halotropones. 2605.3- and 4-Hydroxytropones 2616. Heterocyclic Troponoids 261

IV. Physical Properties and Fine Structure. , 262

I. General Considerations. w~2. Acidity and Complex Formation 262

3. UltraViolet Spectra 2634. Infrared Spectra ; 2655. X-Ray and ElectronDiffraction 266

6. Dipole Moments 267

7. Polarography. 267

V. Chemical Properties. 268

I. General Properties of Troponoid Rings. 268

a) Ketonic Properties 268b) Hydroxylic Function and Methyl Ethers. 268

c) Stability and Double Bond Character. 26gd) Oxidative DegI:adation of the Tropolone Ring. 27°e) Reduction of Tropolones 272

2. Cationoid and Free Radical Reactions. 2i3

a) General Considerations. 273b) Location of Substituents 274c) Steric Effect in Substitution ProCesses. 277d) Halogenation of Tropolones and 2-Aminotropones. 278

e) Benzotropolones 279f) 3- and 4-Hydroxytropones 279g) Free Radical Reactions. 279

3. Anionoid Substitution and Rearrangements. 279

a) General Considerations. 279b) Alkali and Alkoxides 281c) Ammonia and Amines 282

d) Sulfides, Mercaptides, and Cyanides. 283e) Anionic Substitution in Strong Acids 283f) GRIGNARD Reagents and Phenyllithium. 284g) Rearrangements with Alkali.Hypohalites or by Perhalogenation ..284h) Some Other marrangement Reactioris': z85

4. Formation of Azulenoid Compounds 286

a) 2-OXO-I,2-dihydro-1-Oxa-azulene 286b) 2-OXO-I,2-dihydro-I-aza-azulene and I-Aza-azulene 286

c) 2-OXO-I,2-dihydro-I-thia-3-\lza-azulene. 287d) 2-OXO-I,2-dihydro-I,3-diaza-azulene and I,3-Diaza-azulene 287e) 4,5-Imidazolo-tropone and 4,5-Triazolo-tropone 287f) Azulene. ; 288

VI. Biogenetical Problems and ConcluSion. 288

References 290

-Contents. Table des matieres.

JAlkaloids Related to Anthranilic Acid. By J. R. PRICE, Division of

Industrial Chemistry, Commonwealth &clentific and Industrial Research

Organization, Melbourne, Australia 30Z

I. Introduction. , , 303

II. Anthranilic Acid Derivatives 304

Damascenine 304

III. Simple Quinoline Derivatives 305

Echinopsine .., , 3°5

F1indersine , 305

Alkaloids of Angostura 307

Cusparine : 3°7

'Galipine 3°7

Galipoline 308

Cuspareine 308

Minor Alkaloids. 309

Alkaloids of Lunasia amara 31()

Quinoline Derivatives from Microorganisms 311

Cyclopenin 311

Viridicatin 311

Ps8udomonas Metabolites 31Z

IV. Acridine Alkaloids 31Z

Melicopicine 313

Evoxanthine 314

Melicopine 314

Melicopidine 314

Evoxanthidine 315

Xanthevodine 315

Acronycine 315

Xanthoxoline 316

V. Furoquinoline Alkaloids 317

Simple Furoquinolines 317

Dictamnine 118

Evolitrine Fagarine Skimmianine Kokusagine Maculine Maculosidine Kokusaginine Acronycidine Flindersiamine Furoquinoline isoPentane Ethers Evoxine Evolatine , Dimethyl-pyranofuroquinolines Medicosmine Acronidine VI. Quinazoline Alkaloids ArborineV"~;I';n..

323323324324324324325326326326327328328329

330331~~2

Febrifugine and isoFebrifugine

Evodiamine and Rutaecarpine

ViI. Quindoline Alkaloids. Cryptolepine References.

334337339339340

J Recent Developments in the Chemistry and Pharmacology of

Rauwolfia Alkaloids. By ASIMA CHATTERJEE and SATYESH

C. P AKRASHI, University College of Science and Technology, University

of Calcutta, India, and G. WERNER, Faculdade de Medicina de Ribereirao

Preto, UniversidadedeSaoPaulo 346

First Part: Chemistry of the Rauwolfia Alkaloids. 348


II. Thlj Alkaloids of R.canescens 349Rauwolscine. 350

The Structure of Rauwolscine 352The Stereochemistry of Yohimbme Alkaloids. 354Yohimbine. 354VI- Yohimbine. 355

Corynanthine 356{J- Yohimbine. 356

Serpine 356Alloyohimbine 356~- Yohimbine. 357

3-Epi-~-yohimbine , ..357The Stereochemistry of Rauwolscine 357

Reserpine. 359Deserpidine (Canescine, Recanescine) 359

The Stereochemistry of Deserpidine 361Aricine 363

Isoreserpinine 365Reserpiline and Isoreserpiline 365Ajmaline, Ajmalicine, Reserpinine and Sarpagme 366Raunescine and Isoraunescine 366

Serpentine. 366'I'-Reserpine 366

III. The Alkaloids of R.serpentina 366Methods of Isolation. 369

Ajmaline 36gIsoajmaline 374Ajma1inine 374Ajmalicine 375

The Stereochemistry of Ajmalicine 375

Reserpine. 376The Stereochemistry of Reserpine. 380Total Synthesis of Reserpine 387Structure-Action Relation i~ Reserpine. 387R ..

3 88escmnamme Sarpagine (Raupine) 390

Rauhimbine (Corynanthine) 390

Isorauhimbine. '. 391

Inhaltsverzeichnis.

-

x Table des matieres.Contents.

39139Z39Z39339339339539&39&39&399

399400401401401

40Z

40Z

405

408

408

40~

409

413-

413

41j.

415

421

421

421

422

42Z

Reserpinine Reserpiline Serpine Serpinine Yohimbine 3-Epi-(X-yohimbine Rauwolfinine Thebaine and Papaverine Reserpic Acid Methylester Serpentine. Serpentinine IV. The Alkaloids of R.vomitoria and R.obscura Alstonine RaumitoTine Seredine Rauvomitine V. The Alkaloids of R.heterophyUa VI. The A)kaloids of F\lrther Rauwolfia Species. R. hirsuta 402. -R. d8nsiflora 402. -R. perakensis 402. -R. inde-

cora 403. -R. micrantha 403. -R. tetraPhyUa 403. -Tetraphyllin

403. -Tetraphyllicine 403. -R. sellowii 404. -Ajmalidine 404. -

R. semperflorens 404. -R. caffra 405. -R. natalensis 405. -R.

mombasiana 405. -R. grandiflora 405. -R. cumminsi 405. -

R. verticiUata 405. -R. beddomei 405. -R. degneri 405.

VII. On the Biogenesis of the Rauwolfia Alkaloids $econd Pax:t: Pharmacology of the Rauwolfia Alkaloids. VIII. Historical Introduction IX. Pharmacological Effects of the R. serpentina Alkaloids. I. Alkaloid Mixtures. 2. Individual Alkaloids. a) Tertiary Ind{)line Alkaloids : b) Quaternary Anhydronium Bases c) Tertiary Indole Bases d) Other Alkaloids, not Classified Chemically. x. Pharmacological Effects of R. canescens Alkaloids. I. Rauwolscine 2. Deserpidine (Canescine) XI. The Pharmacological Action of Further Rauwolfia Species. I. ,R. caffra 4~2. --2."Jl'; ketetQjJhyUa 422. -3. R. vonntor~ 423.

-4. R. hirsuta 423. -5. R. seUowii 423.

XII. Concluding Remarks ; , ~ {

References.

423

424-

444

446447455455

Synthese von Peptiden. Von W. GRASSMANN und Eo'WUNSCH. Max.

Planck-Institut fiir EiweiB- und Lederforschung, Regensburg. Einleitung : I. Theoretische Grundlagen der Peptidsynthese ll. Methodische Voraussetzungen der Peptidsynthese A. Leicht abspaltbare cx-Amino-Schutzgruppen.

I. Die..Acyl-blockierung.. 455a) Carbamids1\.ureester (Urethane) 455

(X) Der ..Carbobenzoxy-rest 455P) Modifizierte ..Carbobenzoxy-reste.. 457y) Weitere leicht spaltbare Urethane. 457

b) Thio-urethane 458c) Der ..Formyl-rest 460d) Der ..Trif1uoracetyl-rest.. 460e) Die ..Lactam-Schutzgruppen.. 462

(X) Der 2-Nitrophenoxy-acetyl-rest 462. -P) Der (2-Nitro-4-

carbomethoxyphenyl-)-glycyl-rest 463. -'Y) Der ..Ch10r-

acetyl-(2-aminophenyl-)-glycyl-rest 463.f) Der ..Phthalyl-rest.. 464g) Salze der Carbamid- und Dithiocarbamids1\.ure 465h) Der Pyrr01idon-ring 466j) Der P-T01u01sulfonyl-(..ToSyl'.-)-rest 467

k) Phosphatamide 4682. Die ..Alkyl-b10ckierung.. 468

a) Mono- und Dibenzyl-aminos1\.uren 468

b) N-Trityl-aminos1\.uren 469c) Die .,SCHIFFSchen Basen.. 471

3. Die ..Ammonsalzbildung.. 471

B. Die nachtr1\.gliche Einfiihrung der (X-Aminogruppe 472

I. (X-Halogen-acyl-verbindungen 472

2. (X-Azido-acyl-verbindungen 472

3. (X-l\:eto-acyl-verbindungen 472

4. (X.p-Unges1\.ttigte Acyl-verbindungen 473

C. Leicht abspaltbare (X-Carbonsaure-Schutzgruppen... 474

i~ I. Ester und Alkalisalze 474

2. N'-Phenylhydrazide 476

3. N'-Carbobenzoxy-hydrazide 476

.AminoSauren und ihre Einbeziehung in die Syn-

477I. 477

2. Die w-Guanidogruppe 479

3. Die heterocyclischen Ringsysteme. 481

a) Imidazole. 481b) Indole. 482

4. Die alkoh01ischeHydroxylgruppe 482

5. Die phen01ische Hydroxylgruppe 484

6. Die Sulfhydrylgruppe 487

a) Das.,Cystin-verfahren 487b) Das ..S-Benzylather-verfahren.. 489

c) S-Aminoacyl-derivate ..: 490

7. Die ..Thioather.. ...' 490

8. Die w-Carboxylgruppe 491

a) Synthesen mit ungeichiitzter w-Carboxylgruppe : 491b) Synthesen mit veresterter w-Carboxylgruppe 491

c

l .,

r

l ..'

~

9. Die primare Carbonsaureamid-gruppe 492a) Synthesen mit ungeschiitzter -CONH2-gruppe 492b} Nachtraglicher Aufbau der --CONH2-gruppe 492

10. Aminozucker und Phosphorsaureester. 493

III. Methoden der Peptidkniipfung 494

E. Esterkondensationen 4941. Diketopiperazine und ihre Aufspaltung 494

2. Freie lineare Esterkondensation 494

3. Cyclische Esterkondensation 495

4. Systematische Esterkondensation 495

a) Energiereiche ,..O-Ester" 495b) Energiereiche ,.S-Ester" 496

F. O-Acyl-halbacetale 498

G. Gemischte Anhydride aus Acylaminosaure und anorganischen bzw.

organischen Sauren 499

1. Die "FISCHERSche Saurechlorid-methode" 499

2. Die ..CuRTIUSsche Azid-methode" 501

3. Anhydride der PhoSphorSaure 503

4. Anhydride der Phosphorigsaure 504

5. Anhydride der Arsenigsaure 505

6. Thiosauren 5067. Anhydride der Schwefel- und Schwefligsaure. , 507

8. Anhydride aliphatischer und aromatischer Carbonsauren 508

9. Anhydride der Kohlensaure 510a)Bisanhydride 510b) Anhydride der Mono-alkyl-kohlensaure 510

10. Die N(Im)-Acyl-imidaz01e 512

11. Das "Carbodiimid-Verfahren" 51312. Cyclische "innermo1ekulare" Anhydride ~.. 5r4

a) Die N-Carbonsaure-anhydride (Oxaz01id-2.5-dione) 514b) Die Mercapto-thiaz010ne (Thio-thiazolidone) 521c) Oxazo10ne und "Azlactone" 522d) N-Acyl-oxazo1idone 524e) Spezielle innermo1ekulare Anhydride. 524

H. Energiereiche "N-Derivate" der Aminosaureester 527

I. N-Carbonyl-aminosaureester ((X-Isocyanat-fettsaureester) 527

2. Phosphatamide 5283. N-Phosphorigsaure-derivate (Phosphitamide. -imide und PhoS-

phorazokorper} 529

4. Arsenitamide 536

J. Spezielle Umlagerungsreaktionen 536

1. Symmetrische ~-Trifluoracetyl-aminosaureanhydride 536~. O-((X-Aminoacyl)-salicylsauren bzw. -amide. 537


560

,83

Namenverzeichnis. Index of Namex. Index des Auteurs. .'. Sachverzeichnis. Index of Subjects. Index des Matieres.

.t

:,

Inhaltsverzeichnis.

Contents. -Table des matieres.i

,

1

.,j

~;iJ

9

,J

1

~

f

Acetylenverbindungen im Pflanzenreich. Von F. BOHLMANN und

H. J. MANNHARDT, Organisch-chemisches Institut der Technis<;h~n

HochschuleBraunschweig I. Einleitung II. Vorkommen und Isolierung III. Methoden der Konstitutionsaufkliirung. I. Chemische Methoden 2. Die Ultraviolettspektren 3. .Die yltrarot- und Ramanspektren 4. Weitere physikalische Untersuchungsmethoden IV. Synthetische Methoden V. EinzelneVerbindungen I. Acetylenverbindungen aus hoheren Pflanzen (Angiosperme1i) a) Carlinaoxyd b} Lachnophyllumester und Matricariaester Composit-Cumulen I I6.

c} Weitere C1o-Carbonsiiureester aus Compositen. Dehydro-matricariaester I8. -2,3-Dihydro-matricariaester I9.

d} Ester von Polyin-Alkoholen aus Compositen. Matricarianol I9. -C1a-Alkohol aus Carlina vulgaris 20.

e} Das Keton aus Artemisia vulgaris f} Kohlefiwasserstoffe aus Compositen C1a-Kohlenwasserstoff 22. -C1a-K6hlenwasserstoff aus

Coreopsis 24. -Centaur Xa 25.

g} Aromatische Acetylenverbindungen aus Compositen Phenyl-triin-Kohlenwasserstoff aus Coreopsis 25. -Ca-

pil1in 27.

h} Anacyclin Dehydro-anacyclin 29.

i} Farbstoffe aus Compositen 4Ioo-Pigment 31.

k} Inhaltsstoffe unbekannter Struktur. Centaur X-Verbindungen 32. -Lachnophyl10133.

I) Verbindungen aus Umbel1iferen Cicutoxin 33. -Cicutol 34. -Oenanthotoxin 35. -

Oenanthetol und Oenantheton 36.

m) Agropyren

i

38

-

IV

" ., .

InhaJtsverZelOhnlS. -Contents; -Table des matieres.

~

2. Acetylenverbindungen in Fetten und fetten Olen. ; 39

a) Taririnsaure 39

b) Ximeninsaure und 8-0xy.ximeninsaure. 40

c) Acetylenfettsauren des Isanools 42Isansaure 43. -Tsanolsaure 44.

3. Acetylenverbindungen aus niederen Pflanzen. 45

a) Mycomycin 46

b) Nemotinsaure und Ne1ll0tin 48bdyssin und Odyssinsaure 49.

c) Agrocybin 5°d) Verbind~ng~n aus ~titocy,be diatreta. 50

D.iatretiri I 50. -Diatretin 2 50.

e) Verbindungen aus Polyporus anthracophilus 51Matricarianol 51. -Matricariaester 52. -Decadien-diin-dicarbonsaure 52.

f) Junipal 52g) Verbindungen unbekannter Konstitution aus Pilzen , .53

Biformin 53. -DroSOphilin 53. -Quadrifidin 54.

VI. Gedanken zur Biogenese der natiirlichen Acetylene. 55

VII. Die Bedeutung der natiirlichen Acetylene fiir die Pflanzensystematik 60

VIII. SchluBbetrachtung 62

titeraturverzeichnis : 62

Neuere Ergebnisse auf dem Gebiete der glykosidischen Herzgifte:

Zucker und Glykoside. Von CH. TAMM, Organisch-chemische An-

stalt der Universitat Easel. 71

I. Einleitung 72

II. Konstitution und Nachweis der Zucker. 72

III. Teilsynthese von Glykosiden 74

IV. Verkniipfung der Zucker in den Glykosiden. 76

V. Die isolierten Glykoside, ihre Aglykone und Zucker 78

I. Allgemein~ Eemerkungen zu ihrer Konstitution 78

a) Die Aglykone. ...; :. 78Gitoxigenin .78. -3-Epi-oleandrigenin und 3-Epi-gitoxige-nin 79. -Tanghiferigenin 79. -Sarmutog~nin 80. -Caudo-genin 80. -Calotropagenin 80. -Sarverogenin 81. -Ouaba-genin 83. -Gomphogenin 85. -Diginatigenin 85. -Di-O-acetyl-englog~nin 8.'j. -Nicht aufgeklarte Aglykone undGlykoside 86.

b) Die Zucker-Komponel1ten der GlykoSid~. 88

2. Physio10gischeWirksamkeit 90

3. Verhalten im tierischen Stofiwechsel 91

VI. Eotanisch~ Verteilung der herzaktiven Glykoside : 91

I. Die glykosidhaltigen Pflanzenfamilien ; ;.,' 91c .

2. Verteilung der Herzglykoside in Pflanzenorganen ., ...'.:.:. 95

vlnhaltsverzeichnis.- Contents. -Table des matieres.

,

i

.~i

VII. Abbildungen , , , ..., , , , , .97

vnI. Tabellen ., , , , , , 102

I, Zucker der herzaktiven Glykoside " 0 ,. 102

2. Papierchromatographie der Zucker: RF-Werte , , .., :'. , , 104

3. Neue Aglykone und Glykoside. deren Konstitution vollstii.ndig oderteilweise gesichert ist, , , "",... 106

4. Glykoside mit unbekannter Konstitution: Carden01id- und Bufa-dienolid-Derivate...,." 0 ,., , ,"""'.. 108a) Cardenolid-D~rivate 108, --b) Bufadienolid-Derivate I 12.

5. Botanische Verteilung der herzaktiven Glykoside und Aglykone, , , ..14

6. Chemische Einteilung der Strophanthusarten ..., , ..., , ., , , .126

Literaturverzeichnis ., , ., , , , , , ' , , ., , ..127

Photodynamisch wirksame Pflanzenfarbstoffe. Von HANS BROCKMANN,

Organisch-chemisches Institut der Universitii.t GOttingen. ., ., .., 141

I. Der photodynamische Effekt..", ,..,.."" "...,.".,..,. r42

II. Durch photodynamisch wirksame Pflanzenfarbstoffe hervorgerufene Licht-schii.digungen , , .143

I~ Hypericismus , 143

2. Fagopyrismus , 145

III. Photodynamisch wirksame Farbstoffe der Hype1'icum-Arte~ i45

I. Hypericin, , 1.46Isolierung von Hypericin aus Hype1'icu~ hi1'sutum... 46

2. Konstitutionsaufklii.rung des Hypericins..o ,... 146Spektroskopische Identifizierung des Stammkohlenwasserstoffesmehrkerniger Oxy-chinone , ~, 148

3, Synthesen des Hypericins , : , 156Totalsynthese des Hypericins iiber I-Brom-emodin. 156Synthese des Proto-hypericins und Hypericins aus Emodin-anthron-(9) 161Partialsynthese des Proto-hypericins u~d :J;Iypericins aus Peni-

, cilliopsin , 164

4, Pseudo-hypericin ..., , , , , , , , , , .167Isolierung des Pseudo-hypericins ..,.." 168Konstitution des Pseudo-hypericins. ..., , , , ...168Pseudo-hypericin-Gehalt der zur Konsiitutionsaufklii.rung verwen-deten Hypericin-Prii.parate , ,..0,; ,.. 17°

5. Vorkommen von Hypericin und Pseudo-hypericin in Hype1'icum-Arten 171Gesamtgehalt an Hypericinfarbstoffen , ..., ,. 171Hypericin und Pseudo-hypericin in verschiedenen Hype1'icum-Arten 171

IV, Zur Biogenese der photodynamisch wirksamen Hype1'icum-Farbstoffe 172'

I. Vorstufen des Hypericins, , , ".".. 172Proto-hypericin , '.. 173

Hyperico-dehydro-dianthron 173Emodin-anthron-(9) , , 174

2. Vorstufen des Pseudo-hypericins ; 174

3, Z'ur Stereochemie des Hypericins ,..,., , , 175

4. Natives Proto.hypericin und Hypericin. , ...176Pharmak010gisches ,...;:...:..., ,... 177~

-

VI Inhaltsverzeichnis. -CoIitents. -Table des matieres.

...177

...178

...179

.., 181

...181

...182

.V. Photodynamisch wirksame Farbstoffe des Buchweizens Isolierung desFagopyrins Zur Konstitution des Fagopyrins Proto-fagopyrin VI. Zusammenfassung T.iterat11rverzeichnis

.\j

.\

/ Biosynthetic Relations of Some Natural Phenolic and Enolic Compounds.By A. J. BIRCH, Department of Organic Chemistry, The University of

Manchester 186

I; Introduction: Historical Survey and Premises. 186

II. Biosynthesis of Phenols and Enols from Acetic Acid. 188

I. StructuralEvidence 188

2. Evidence Based on Biological Experime~t 192

3. Uses of the Hypothesis in Structure Determination. 194

III. Extensions ot the Acetic Acid Hypothesis 197

I. Introduction of Oxygen, 198

2. Removal of Oxygen , , 198

3. Introduction of.Methyl and Isopentenyl and Related Groups. 200The Mycins ., 202

IV. Biosynthesis of C8-C3 Compounds 203

I. The Dehydroquinic Acid Route, 203

2, Lignin and its Congeners 204

3. Allyl- and Propenylbenzene Derivatives. 205

4. Flavonoids and Anthocya!:Iins 206

V. Some Other Natural Phenols 210

I. Terpenoid-derived Phenols 210

2. TrQpolones 211

VI. Conclusions. 212

References. 213

,1 The Aminochromes. By HARRY SOBOTKA, NORMAN BARSEL and

J. D. CHANLEY, Department of Chemistry, Mount Sinai Hospital, and

International Hormones, Inc., New York. 217

I. Chemistry. 217

Introduction. 217Structure and Preparation 219

Spectra 223Optical Activity : 223Pathway of Formation 224Halogenation. 227Rearrangements 228

Reduction. 231Oxidation. 233Aminochrome neriv"tiveB : 233 i

-


II. Physiology and Phar~acology 235

Induction of Hypoglycemia 236Hallucinogenic Effects ; 236Antipressor Effects ~ 236Hemostatic Action ' 237Therapeutic Use of Some Derivatives 238Conclusion. 238

"23q

Visual Pigments. By R. A. MORTON and G. A. J. PITT, Department of

Biochemistry. TheUniversityofLiverpool 244

I. Introduction ,.. 245

Rods andCones 245Early Work on Visual Purple 246PioneerWorkofHECHT ,..247RodandConeVision ,..249The Electrophysiological Approach. 25°Acceptable Criteria for Visual Pigments. 252

II. Vitamin A 253

Discovery and Preparation of Retinene. 254VitaminA2 and Retinene2 255

III.. Cis-trans Isomerism ofRetinenel 257

SynthesisofIsqmers 359Properties 9f Isomeric Retinenes and Vitamins A 263

IV. Rhodopsin. 265

PreparationofRodOuterSegments 266

ExtractionofRhodopsin 267Contaminants in Rhodopsin Solutions. 268

PurityofRhodopsinPreparations 27°Transient Orange and Indicator Yellow. 273Lumi- and Meta-rhodopsin 275

N-Retinylidene-opsin 279Retinene-Opsin Linkages 281SpectrosCopic Considerations 285

V. Porphyropsin 287

Visual Pigments of Fish 288Visual Pigments of Xenopus 293

VI. Other Retinenel-Pigments 295

VII. Cone Pigments. 296

Iodopsin. : 299

Cyanopsin 304

VIII. Iso-pigments 304

IX. Visual Pigment Chromophores : 306

References. 307

lnhaltsverJeichni8. -Contents.VIII Table des mamres.,

j

317

317

318

318319

320

320320323

323

325

326

326327327327328

329

330

332

332

The Carbon Cycle in Nature. By HARRISON BROWN, California Institute

of Technology, Pasadena, California I. Introduction. : II. Quantities of Reacting Si1bstances I. Water 2. Carbon. III. Rates of Photosynthesis and of Oxidation. I. Photosynthesis on Land 2. Photosynthesis in the Oceans 3. Respiration'and Oxidation IV. The Cycling of Carbon as Carbonate V. Carbon Deposited in the Sediments ' VI. The Evolution of the Present Carbon System. I. Carbon in the Universe 2. Carbon on the Primitive Earth 3. Carbonaceous Chondritic Meteorites. ~ .~, : 4. The Production of Oxygen 5. Early Production of Organic Chemical Compounds. VII. Variations in the Isotopic Composition of Carbon VIII. Variations in the Carbon Dioxide of the Air IX. Miscellaneous Aspects I. Carbon from the Depths 2. Atmospheric Methane. 3. Organic Material in Rainwater References


Sachverzeichnis. Index of Subjects. Index des Matieres.

334

345

Inhaltsverzeichnis.


Der Kohlenhydratstoffwechsel der Graser. Von H. H. SCHLUSACH,Chernisches Staatsinstitut, Universitat Hamburg. I

I. Einleitung I

II. Das Pf1anzenmaterial 2

III. Die Isolierun g der loslichen Kohlenhydrate 3~IV. Die analytischen Methoden 5

V. Die Konstitution der Polysaccharide der Graser. 7

VI. Die niedermolekularen Kohlenhydrate in den Grasern. 12

VII. Die Biogenese der Oligo- und Polysaccharide der Graser 14

VIII. Abwandlungen des Kohlenhydrat- und des EiweiBgehaltes im J;.auleeiner Vegetationsperiode 17

IX. Anwendungen auf die Grtinlandwirtsch;tft. 23


j Some in vitro Conversions 0£ Naturally Occurring Carotenoids.

By L. ZECHMEISTER, California Institute of Technology, Pasadena,

California. 3I

I. Introductory Remarks 32

normal and retro Strnctures 33. ~ Addition of Hydrogen to the.Chromophore 34. ~ Addition of Oxygen to Terminal DoubleBonds of the Chromophore 35.. ~ Lengthening of the Chromo-

phore 36.

II. Preparation and Conversions of Carotenoids by Means of N-BromoSUccin-

imide 36.

I. Dehydrogenation of Colorless Compounds to Carotenoid Pigments 37

Squalene 37. ~ PhytqenE? and Phytofluene 37.

2. Action of N-Bromosuccinimide on {J-Carotene 40

a) N-BromoSUccinimide and {J-Carotene in Carbon Tetrachloride

Solution. 40retro-Dehydrocarotene 40. ~ retro-Bisdehydrocarotene 4°. ~Anhydro-eschscholtzxanthin 41.. ~ 3,4,3',4'-Bisdehydro-{J-caro-tene AI. ~ ~.A-Dehvdro-B-carotene 42.

IV

b) N-Bromosuccinimide and p-Carotene in Ethanol-Containin?Chloroform Solution ; 42

Formation of Ketones 42. -4-Keto-3'.4'-dehydro..p-carotene 43.-4-Keto-p-carotene and 4.4'-Diketo-p-carotene 45. -Identi-fication of 4-Keto-p-carotene and 4.4'-Diketo-p-carotene withNatural Products 47. -Addendum 47.

3. Action ot N-Bromosuccinimide on ~-Carotene 48

3.4-Dehydro-~-carotene 48. /

4. Action of N-Bromosuccinimide on Lycopene 49

5. A<:tion of N-Btomosuccinimide on Cryptoxanthin. 49

6. Action of N:.Bromosuccinimide on Physaliene 49

rrr. Conversions of Carotenoids via their Boron Trifluoride Complexes. ...50

I. Cleavage Products of the p-Carotene-BF3 Complex. 51

2. Cleavage Products of the ~-Carotene-BF3 Complex. 52

3. Cleavage Products of the BF3 Complexes of Some DehydrogenatedCarotenes. 55

a) retro-Dehydrocarotene-BF3 55

b) 3.4-Dehydro-~-carotene-BF3 and 3.4-Dehydro-p-carotene-BFa 56

c) retro-Bisdehydrocarotene-BF3 57

4. Cleavage Products of the Lycopene-BF3 Complex. , 58

5. Cleavage Products of the y-Carotene-BF3 Complex. 60

6. Cleavage Product of the An1iydrovitamin A1-BF3 Complex. 61

IV. Dehydration and Dehydrogenation of Lutein. 62

V. Some Spectroscopic Observations ..., 63

Position of the Maxima 65. -Lengthening of the p-CaroteneChromophore 67. -Influence of the Spatial Configuration 70. -'-

Transition from normal to retro Structures 73. -SpectralCurves 75.

References ~~~t:~.- 16

/ The Chemistry of Podophyllum. By J. L. HARTWELL and

A. W. SCHRECKER, Laboratory of Chemical Pharmacology, National

Cancer Institute, National Institutes of Health, Public Health Service,

U. S. Department of Health, Education and Welfare, Bethesda, Maryland 83

I. History ,84

II. Preparation of Podophyllin 88

III. Composition of Podophyll4m , 88

IV. Other Sources of Podophyllum Lignans. 93

V. Isolation Plocedures 94

I. Isolation without Chromatography. 95

2. Adsorption Chromatography; 96

3. Partition Chromatography 97

..98

..98

..99

..108

..III

..119

VI. PodoJlhyllotoxin I.. Properties 2. Structure :0:'-: 3. The Apopicropodophyllins. 4. Stereo<;:hemistry 5. Synthetic Approaches. VII. Desoxypodophyllotoxin VIII. Dehydropodophyllotoxin.

~

121

123

IX. 4'-Dernethylpodophylloto~in. .

X. The Peltatins

124

126

XI. Sikkimotoxin 13°

XII. Lignan Glucosides 133

XIII. Ionic Derivatives of Podophyllotoxin and of the Peltatins 136

XIV. Flavonols 138

v.,Absorption Spectra. I. Ultraviolet Spectra. 2. Infrared Spectra. .139

.139

.143

XVI. Biological Actiol1 .. 143

XVll. Tables. 145

I. Well-characterized Compounds Isolated from Podophyllum Species 45

2. Solvates and Modifications of Podophyllotoxin. 146

3. Molecular Rotations of Compounds in the Conidendrin and Desoxy-podophyllo"toxin Series 46

4. Podophyllotoxin and Derivatives. 147

5. Desoxypodophyllotoxin and Derivatives. 150

6. 4'-Demethylpbdophyllotoxin and Derivatives. 150

7. Peltatins!1nd Derivatives 151

8. Sikkimotoxin and Derivatives 152

9. Lignan Glucosides and Derivatives. 152

10. Maximum Tolerated Doses (MTD) and Minimum Effective Doses

(MED) in.Mice Bearing Sarcoma37 153

II. Ionic Derivatives of Podophyllotoxin and of the Peltatins, andIntermediates 154

12. Flavonolsand Derivatives , , 155

13. Ultraviolet Absorption Maxima of Podophyllum Lignans and of Someof Their Derivatives : 156

References. I~7

/ X-ray Analysi~ and the Structure of Vitamin B12. By DOROTHY

CROWFOOT HODGKIN, University Museum, Oxford. 167.

I. Introduction , 167.

II. Some Characteristics of the X-ray Crystallographic Methods Applied tothe Analysis of VitaminB12 169

m. The Determination of the Structure of Vitamin B12 173

I. Preliminary Crystallographic Measurements and Observations. 173.

2. The Stages of Atom Identification 176a) The Cyanide Group 179b) The "Nucleotide" Group 17.9c) The Corrin Nucleus 183d) The Side-chains Attached to the Nucleus. 185e) The Propanolamine Groups 189

3. The Problem of Right and Wrong Atoms 194

4. The Refinement of the Atomic Positions. 195

5. The Absolute Configuration of the Moiecule. 196

6. The Chemical Formulae of Vitamin B12 and the Hexacarboxylic Acid 196

IV. The Chemical Reactions of Vitamin Bt2 202

V. Biochemical Problems Connected with the B12 Structure. 207

VI. The Crystal Structures of Vitamin B12 and the Hexacarboxylic Acid. ; 212

VII. Conclusion. 218

References. 218


Sachverzeichnis. Index of Subjects. Index des Matieres.

Inhaltsverzeichnis.


J Catechine. andere Hydroxy-flavane und Hydroxy-flavene. Von ~ARL

FREUDENBERG und KLAUS WEINGES, Chemisches Institut der Uni-

versita.t Heidelberg I

I. Altere Arbeiten. I

2. Die bekannten Hydroxy-flavane 2

3. Eigenschaften, Herstellung der Hydroxy-flavane 5

4. l(ondensation durch sauren 5

5. Hydroxy-flavene 9

6. Leucoanthocyanidin-hydrate. Acetate der PseudoanthoCyanidine rind de.r

Pseudoanth06yanidin-hydride. 12

.7. Oxydations- und Reduktionsiibergange in der C8C3C8-Reihe. 15

8. Cyanomaclurin 15

9. Catechin-3-gallat und Catechin-3-g1ucoSid. 17

10; Stereochemie der Catechine 18

II. Biogenese der C8CaC8-Gruppe 21


j Recent Progress in the Chemistry of the Aconite-Garrya Alkaloids.

By KAREL WIESNER and ZDENEK VALENT A, Department of Chemistry.

The University .of New Brunswick, Fredericton, N. B., Canada. 26

I. Introduction. 27

II. Garrya Alkaloids. 28

I. The Structure of Veatchine and Garryine 28Environment of the Nitrogen 28Structure of the Skeleton 3IStructure of the Oxoveatchine Dicarboxylic Acids 33StructuTe Assignment to Veatchine a:nd Garryine 35

2c The Stereochemistry of the Garrya Skeleton and its Influence onthe Properties of Garrya Alkaloids 36

3. The Structure of Cuauchichicine anII: Garryfoline .: 40

4. Configuration of the Secondary Hydroxyl Group in Veatchine andGarryfoline ~ 42

~ I.nhaltsverzeichnis. -Contents. ~ Table des matieres.

III. The Structure of Atisine 44

Original Degradation Work on Atisine 44Similarity of Atisine with the Garrya Alkaloids and the Deduction

of the Atisine Structure 45Some Confirmatory Evidence 47

IV. Biogenesis of Veatchine and Atisine and Consideration of the Stereo-chemistry of Atisine 50

V. The Structure of Ajaconine 53

VI. The Structure of Napelline 53

VII. The Chemistry of Hetisine 62

VIII. Lycoctonine and Delpheline 63

I. The Chemistry of Lycoctonine 64Oxidation Studies 65Skeletal Changes 69

2. The CheInistry of Delpheline 72Environment of the Nitrogen 72Transformations in the Demethylene Series. 74The Carbon Skeleton of Delpheline 79

3. Biogenesis of Lycoctonine and Delpheline 80

IX. The Chemistry of Delphinine 81

References. 87

J Structural Chemistry of Actinomycetes Antibiotics. By E. E. VAN

TAMELEN, Department of Chemistry, The University of Wisconsin,

Madison, Wisconsin. 90

Introduction 90

I. Actidione (Cycloheximide) 922. Actinomycins. 933. Actithiazic Acid. 944. Amicetin 95

5. Aureomycin (Chlorotetracycline) 986. Aureothricin and Thiolutin 1017. Azaserine. 1028. Chloromycetin (ChlQramphenicol) 103

9. Cycloserine (Oxamycin) 10410. Elaiomycin. 105II. Erythro~ycin ; 10612. Etamycin (Viridogrisein) 1()913. Magnamycin (Carbomycin) 116

4. Methymycin. 11315. Mycomycin 11516. Netropsin : 11617. Nocardamine 11818. Novobiocin. 118

19. Puromycin (Achromycin) X2120. Sarkomycin : 12321. Streptomycin. ., 12422. Terramycin 128

i l~

It"" "

23. Tetracycline ~3i24. Valinomycin. L32

References. :': ~32

J Protein Synthesis in Plants. By JAMES .BONNER, California Institute of

T~hnology, Pasadena. California ~39

I. Introduction. ~4O

II. Isolation of Microsomes ~4°

III. Structure of the Microsomes i43

IV. Role of the Microsomes in Protein Synthesis ~44

V. Biology of the Microsomes ~46

~. NuclearMicrosomes ~462. Origin of Microsomes ~473. Transfer of Microsomal RNA ~484. Synthesis of the Microsomal Components. ~495. Kinetics of Microsomal Labeling ~5~

VI. Protein Synthesis as a Catenary Sequence. ~53

~. Amino Acid Activation ~542. Transfer to Soluble RNA ~553. The Microsome as Acceptor of Amino Acid. ~574. Alternative Pathways of Peptide Synthesis. ~58

VII. Protein Synthesis in Mitochondria and Chloroplasts. ~6o

VIII. Protein Synthesis in Varied Plant Organs. ~6~

~. Developing Fruits and Seeds 16~2. Leaves. ~62

IX. Conclusion ~64

References. 164

~

I

J The Electron Gas Theory of the Color of Natural and Artificial Dyes :

Problems and Principles. By HANS KUHN, Physikalisch-Chemisches

Institut der Universitat Marburg a. d, Lahn. 169

I. Some Experimental Facts Concerning Color and Structure.. 17°

I. Polyacetylenes, Polyenes. Symmetrical Cyanine Dyes. and Some Similar

Compounds. 17°

2. Aza Derivatives of Symmetrical Cyanine Type Compounds. 175

3. Acridine Type Bridge Formation in Symmetrical Cyanine Type

Compounds. 1764. Some Other Types of Resonance Systems Causing Absorption of

Visible Light 178

II. Some General Principles and Postulates. 178

I. Light Quanta and the Einstein-Bohr Frequency Relation. 179

2. Wave Particle Duality of the Electron and the de Broglie Relationship 180

3. Standing Electron Waves. The Pauli Principle. : 180

4. The Chemical Bond; (1 and n Electron States. : 184

III. Quantum Mechanical Determination of the Position of the Absorption

Bands of Simple Dyes 190

I. A Simple Model of Symmetrical Cyanine Dyes 19°

2. A Simple Treatment of the Aza Derivatives of Symmetrical Cyanine

Type Compounds 194

References. 201


sachverzeichnis. Index of Subjects. Index des Matieres. 213

Inhaltsverzeichnis.


~

J Flavones and Isoflavones. By K. VENKATARAMAN, National Chemical

Laboratory, Poonit, India I

I. Introduction. 2

II. Structural Relations and Interconversions 4

III. OcGuqence in Plants. 6

Glycosides 6

Hydroxy~ation Patterns. 7

IV. Isolation ; 9

V. Color Reactions. 12

VI. Survey of Natural Flavones 14

Flavone. 5-Hydroxyflavone and Dihydroxyflavones 4Trihydroxyflavones , 15Tetrahydroxyflavones 16Pentahydroxyflavones 18

Hexahydroxyflavones 19Heptahydroxyflavones 20Furanoflavones 21

VII. Survey of Natural Isoflavones 22

Polycyclic Compounds Containing the Isoflavone or Isoflavanone

Nucleus 23

VIII. Absorption Spectra of Flavones and Isoflavones 25

Ultraviolet Spectra. 25Infrared Spectra. 28

IX. Determination of the Structure of Flavones and Isoflavones 28

Degradation of Isoflavones 33

X. Synt4esis of Flavones 34

XI. Synthesis of Isoflavones 41

XII. Synthesis of Flavone and Isoflavone Glycosides. 44

XIII. Biogenesis of Flavo~es and Isoflavones. 45

XIV. Physiological Properties of Flavones and Isoflavones 48

Flavones 48T"oflavones 50

IV / Inhaltsverzeichnis. COnten~ -Table des matieres.

xv. Tables 51

I. Visible Color and ;'max of Methanolic Solutions of some Flavonesafter Reduction with Mg and HCl 51

2. Trihydroxyf1avones and their Methyl Ethers 51

3. Tetrahydroxyf1avones and their Methyl Ethers. 52

4. Quercetin and its Derivatives : 53

5. Pentahydroxyf1avones other than Quercetin and their Methyl orMethylene Ethers. 54

6. Hexahydroxyf1avones and their Derivatives. 55

7. Natural Isof1avones 56

8. Ultraviolet Absorption Spectra of some. Naturally OccurringFlavones in Ethanol. 57

9. Ultraviolet Absorption Spectra of some Naturally OccurringIsof1avones in Ethanol 58

10. Hydroxyl and Carbonyl Frequencies of some Naturally OccurringFlavonoids 58

References 59

Fortschritte der Chemie der Vitamine D und ihrer Abkommlinge.

Von H. H. INHOFFEN und K. IRMSCHER, Organisch-chemisches Institut

der Technischen HoChschule Braunschweig 70

I. Konstitution der Vitamine D und ihrer Abkommlinge. 71

I. Vitamine D. 71

2. 5.6-t'.ans-VitamineD 72

3. iSO- Vitamine D. 75

4. Praecalciferole 76

5. Tachysterine 79

6. iso-Tachysterine 81

7. u- Tachysterin 82

8. Pyrotachysterin(e) 83

9; Suprasterine 83

10. Dihydro-Verbindungen 85

II. C(8)-Ketone 89

II. Neue Abbauprodl1kte der VitamineD 90

I. Die stereoisomeren 5,6-Dihydroxy-Vitarnine D8 90

2. Die t'.ans-C,D-Abbau-alkohole 90

3. Die Seitenketten-alkohole 91

4. Seitenketten-acetoxy-aldehyde , 92

5.. Das 8-Methyl-t'.ans-hydrindanol-(4)-on-(I) und die 8-Methyl-

hydrindandione 92

III. Photochemische Isomerisierung 93

IV. Thermische Isomerisierung 96

V. Chemische Isomerisierung : 98

VI. Ergebnisse von BARON, L~ BOULCH und RAour. 99

VII. Verschiedene Verbindungen : 102"

I. Atio-Analoga der Praecalcifer01e und der Vitamine D. 102

2. VitaminD-hom010ge Verbindung , 103

3. Strukturisomere Vitamin D-Verbindung 103

4. 9.10-Seco-D-Homo-Steroid-Verbindung 1045. VitaminDm ,., 105

VIII. Partialsynthesen 105

,; I. 3-Desoxy-14P-praecalcifer012 105

2. iso-Vitamin D2-methylather-C(2)-Epimerengemisch und iso-Tachy-sterin-methylather-C(8)-Epimerengemisch 106

3. 3-Desoxy-iso-tachysterine 107

4. 6.7-cis-iso-Tachysterin2-methylather-C(8)-Epimerengemisch. 107

IX. Tota1synthese des VitaminsD8 108

I. Das Hydrindansystem 109

2, Die Seitenkette 110

3. Trienchromophor. Epimeren-trennung, trans- cis-Isomerisierung ..116


Neuere Ergebnisse der Chemie pflanzlicher Bitterstoffe. Yon F. KORTE,

H. BARKEMEYER und I. KORTE, Chemisches lnstitut der Universitat

Bonn. 124

I. Einleitung 125

Der bittere Geschmack und die Bestimmung des Bitterwertes 126Therapeutische Verwendung der Bitterstoffe. 127W\rtschaftliche Bedeutung der Bitterstoffe. 128

II. Bitterstoffe der Gentianaceen 129

ciF I. Gentiopikrin. 130~ 2. Amarogentin 132

;-. 3. Loganin. : , 133

III. Bitterstoffe der Asclepiadaceen 135

I. Kondurangin 1352. Vincetoxin 137

IV. Bitterstoffe der Compositen 137

I. Absinthin und Anabsinthin 1382. Cnicin 1393. Lactucin und Lactucopikrin 1404. Tenulin 1445. Helenalin 1476. Alantolactone : 149

V. Bitterstoffe der Menispermaceen 151

I. Columbin 1512. Picrotoxinin (Picrotoxin) 155

VI. Bitterstoffe der Coriariaceen 161

Tutin und Coriamyrtin 161

VI Inhaltsverzeichnis. Contents. Table des matieres.

162162

165165

168168

173

17,

VII. Bitterstoffe der Urticaceen Hopfenbitterstoffe: Humulon. Lupulon, Humulinon

VIII. Bitterstoffe der Labiaten Marrubiin. IX. Bitterstoffe der Apocynaceen Plumierid X. Tabellen Literaturverzeichnis

Alkaloide aus Calebassencurare und siidamerikanischen Strychnosarten.

vonK. BERNAUER, Ch~misches Institut der Universitat Zurich. I83

I. Einleitung I84

II. Die Entwick1ung der Chemie der Calebassen-Alkaloide I86

III. Die Auftrennung des Cal~bassencurare in Einzelalkaloide I87

IV. Die Alkaloide sudamerikanischer Strychnosarten I89

" "

I. -obersicht I89

2. Die Alkaloide aus Strychnos toxifera :' I89

3. Die Alkaloide aus St1'. melinoniana BAILLON. I9O

4. Die Alkaloide aus Str. amazonica KRUK.. Str. macroPhylla und

Str. guianensis (AUBL.) MART I9I

5. Diabolin und Desacetyl-diabolin aus Str. diaboU SANDW. I9I

V. Die Elektronenspektren der Alkaloide aus Calebassencurare und

sudamerikanischen Strychnosarten , I9I

VI. Konstitution von Calebassen- und sudamerikanischen Strychnos-

Alkaloiden Vorbemerkung A. Alkaloide vom Yohimbin-Typus I. -obersicht 2. C-Mavacurin, C-Alkaloid-Y und C-Fluorocurin 3. Lochnerin und Lochneram 4. Melinonin-A 5. Melinonin-B 6. Melinonin.E 7. Melinonin-G B. Alkaloide vom Strychnin-Typus I. -obersicht 2. C-Fluorocurarin ..., 3. C-Dihydrotoxiferin 4. C-Toxiferin-I und Caracurin-V 5. C-Curarin-I. 6. C-Calebassin :. ~~v

7. Experimentelle Verknupfung und Systematik der Alkaloide vom

Strychnin- Typus 226

VII. Zur Biogenese der Alkaloide aus Calebassencurare und sudainerikanischen

Strvchnosarten :...u

194

194

195

195195200202202

204204

205

205207211

215218~~"

~~~

VIIInhaltsverzeichnis. -ContentS. -Table des matieres.

VIII. Zur Pharmakologie der Alkaloide aus Calebassencurare und sud-amerikanischen Strychnosarten 232

I. Allgemeines 2322. Der Maustest ~' 2333. Curare-Wirkung und Nebenwirkungen 2334. Resorption, Verteilung und Ausscheidung von Calebassen-

Alkaloiden. ..; 2345. Nachweis der FixieruRg des C-Curarins-I an den motorischen

~! Endplatten 234;;~-; 6. Kenstitution und Curare-Wirksamkeit 234

IX. Tabellen 236

I. Alkaloide aus Calebassencurare 2362. Strychnosarten, die Calebassen-Alkaloide fuhren. 2373. Aus sudamerikanischen Strychnosarten isolierte Alkaloide 238

~ 4. Cale.ba~sen- und S~rychnos-Alkaloi~e nach UV-Spektren geordnet 239, 5. Naturl1che Alkalolde vom Strychmn-Typus 240

Literaturverzeichnis 24I

"

/ Occurrence and Metabolism of Simple Indoles in Plants. By BRUCE

B. STOWE, The Biological Laboratories, Harvard University, Cambridge,

Massachusetts. 248

Introduction. 249

I. Volatile Indoles 250

I. Indole. 2502. Skatole (3-Methylindole) 254

II. Tryptophan and its Derivatives 255

I. L-Tryptophan [2-AIffinG-3-~-indole)-propionic Acid] 2552. L-Abrine (AInino-N-methyltryptophan) 259

3. L-Hypaphorine (Tryptophan Betaine) 2604. Malonyl-tryptophan 26I

III. Indole Bases and Some Related Compounds. 26I

.~ I. Gramine.[3-(Dimethy~aminome:hyl)-indole] 26I2. Tryptamme [3-(2-Ammoethyl)-mdole] 262

3. AInino-N-~ethyltrYi>tamine 2634. Amino-N.N-dimethyltryptamine and its N-Oxide 264

5. 5-Hydroxytryptamine [3-(2-Aminoethyl)-5-indolol] 2646. 5-Methoxy-aInino- N -methyl-tryptamine [3-(2-MethylaIninoethyl)-5-

methoxyindole] 265." 7. Bufotenine [3-(2-Dime1;hylaIninoethyl)-5-indolol] and its N-Oxide ...266

8. 5-Hydroxy-3-indoleacetic Acid 266

lV. Potential Precursors of 3-Indoleacetic Acid. 267. c I. 3-Indoleaceta1dehyde 267c 2. 3-Indoleacetonitrile 268

3. 3-Indolepyruvic Acid 270

4. Ascorbigen 272

V. 3-Indoleacetic Acid 273

Table des matieres.

VI. Products Formed from 3-Indoleacetic Acid. 277

I. 3-Indolealdehyde. 277

2. Ethyl 3-Indoleacetate 278

3. 3-Indoleacetamide. 278

4. 3-Indoleacetylaspartic Acid 279

VII. Some Other Indoles 280

I. 3-Indolecarboxylic Acid. 280

2. 3-Indoleglycolic Acid. 280

3. Indican ~8I

References 282

j Some Biochemical Aspects of Disease in Plants. By A. E. DIMOND,

The Connecticut Agricultural Experiment Station, New Haven, Connecticut 298


II. Abnormal Growth in Plant Disease 299

I. Ethylene Production and its Effects 299

2. Gibberellin 301

3. Crown Gall Induction. 3°4

III. Abnormal Metabolic Pathways in

IV. Abnormal Water Economy I. Lycomarasmin 2. fusaric Acid. 3. Pectic Enzymes. V. Conclusion References.

308

315

"TO

/ The Chemical Structure of the Normal Human Hemoglobins.

By W. A. SCHROEDER, California Institute of Technology, Pasad6na,California. 322


II. Nomenclature 324

III. The Hemoglobin Molecule as a Whole 326

1. Iron Content 326

2. The Molecular Weight 327

.3. The Shape of the Molecule 329

IV. The Prosthetic Group 330

V. The Linkage Between Heme and Globin. 331

VI. The Normal Human Hemoglobins 333

1. The Change in the Type of Hemoglobin in the Indiv:idual Human

as a Function of 4ge 334

2. Does an Embryonic Hemoglobin Actually Exist? 335

~~

VII. The Purity of Hemoglobin in Hemoglobin Preparations. 340

I. Isolation. :. 340

2. Effect of the Isolation Procedure on the Purity of HemoglobinPreparations. :- 340

3. Heterogeneity of Hemoglobin Preparations 341

4. Biological Significance of the Heterogeneity of HemoglobinPreparations ' ,., 347

VIII. Chemical Investigations of Hemoglobin, ., , , ., , , , , , , 348

I. Amino Acid Composition 349a) Adult Hemoglobin 349

b) FetaLHemoglobin 353c) Comparison of the Amino Acid Composition of Adult and Fetal

Hemoglobin. 3542. Sulfhydryl Groups 355

3. N-Terminal Amino Acid Residues and Sequences 357a) Adult Hemoglobin. 357b) Fetal Hemoglobin. 359

4. C-Terminal Amino Acid Residues 359

5. Investigation of Internal Sequences. 360

~ 6. The Insolub~e Residue from T~tic H~drolysates 365" 7. The Separatlon of the Polypeptlde Chams of Hemoglobm 365

IX. Discussion and Conclusions 368

.~ I. The Hemoglobin Molecule as a Whole .' 368

2. The Polypeptide Chains Themselves. 370

3. Final Remarks 371

References. 371

I Paleobiochemistry and Organic Geochemistry. By PHILIP H. ABELSON,

Geophysical Laboratory, Carnegie Institution of Washington, Washing-

ton.D.C 379

Introduction. 379

Major Constituents of Livi~g Matter 381

Preservation of Organic Substances 386

Organic Complexes of High Molecular Weight. 387

The Stability of Organic Substances 389

Organic Substances in Soils and Rocks 391

Amino Acids in Soils 391Peats and Coals. 392Amino Acids in Sediments 392Amino Acids in Shells and Calcareous Tests 393Amino Acids in Bone. : ...394

Lipides 396Carbohydrates. 398Carbohydrates in Fossils 3Q8

Porphyrins 398Precambrian Occurrences 399

The Perspective.; , 400

References. 400

J The Electron Gas Theory of the Color of Natural and"Artificial Dyes: ,,"

Applications and Extensions. By HANS KUHN. Physikalisch.Chemi- .

sches Institut der Universita.t Marburg a. d. Lahn 404""

I. Quantum Mechanical Determination of the Position of the AbsorptionBands of Simple Dyes with an Unbranched, a Ring-Shaped. or a BranchedElectron Gas. 405

I. A Simple Model of VitaminB12 405

2. A Simple Electron Gas Ring Model of the Phthalocyanines a1ld Benzo-

porphyrines. 4073. A Simple Model of Dyes with a Bra1lched Electron Gas. 41 I

rr. A Refined One-dimensional Model Considering Irregularities of Potentialalong the Chain (Wave Shape Potential Model) ~c.,c...tI8

,""I. Qualitative Discussion of Some Quantum Mechanical Aspects of '"~

Polyenes and Symmetrical Cyanines 418

2. A Quantitative Treatment of the Light Absorption of Polye1les 422

3. Treatment of the Light Absorption of Polyacetylenes 427

4. Wave Shape Potential Model of Cyanines, Aza-cyanines and Some

OtherDye Classes 427

5. A Simple Treatment of Polyenes, Polyacetylenes, and UnsymmetricalCyanines (Sine Curve Potential Model) 428

rrr. The Two-dimensional Electron Gas Model. 430

IV. Intensity and Structure of Absorption Bands. 434

I. Oscillator Strength of an Absorption Band. 434

2. Strncture of Absorption Bands 441

References. 445

Namenverzeichnis. Index of Names. Index des Auteurs. Sachverzeichnis. Index of Subjects. Index des Matieres. 452

470

~~~

~

Inhaltsverzeichnis.


I

2

4

4668

99

",

~i'

i,,~ .

Die Actinomycine. Von H. BROCKMANN, Organisch-chemi~hes. Institut

der Universitat GOttingen ,

I. Einleitung II. Gewinnung und Eigenschaften der Actinomycine I. Trennung von Actinomycingemischen. 2. Von StreptQmyces-Arten produzierte Actinomycingemische Die Actinomycingemische C, X und I ; Actinomycingemisch Z Actinomycin bildende Strept"myces-Arten ~ '. Identifizierung friiher beschriebener Actinomycingemische Actinomycingemische der dirigierten Biosynthese 3. Nomenklatur der Actinomycine Nomenk1atur nativer Actinomycingemische... , Nomenklaturreiner A.ctinomycine... 4. Eigenschaften und Aminosauregehalt ' reiner Actin6mycine .., I3

Physikalische Eigenschaften I3

Chemische Eigenschaften I4

Molekulargewicht I4

Aminosauregehalt. I5

III. Die Konstitution der Actinomycine I7

I. Die Konstitution des Chromophors ; I7

Despeptido-actinomycin ; I7

Konstitution des Despeptido-actinomycins ; I8

Synthese des Despeptido-actinomycins 20

Farbige Abbauprodukte der Saurehydrolyse. 2I

Actinocinin 24

Konstitution des Actinomycin-Chromophors. 26

Synthese des Actinomycin-Chromophors 28

Reaktionen des Actinomycin-Chromophors 29

2. Die Konstitution des Peptidteils 3I

Actinomycin Cs 33

Actinomycin ~ (I1;X1. D) 38

Actinomycin C2 ,... ;39

Actinomycin Xz , 40

Actinomycin Xop 4I

Actinomycin ~" ; 42

3. Struktur-Variationen des Peptidteils 42

IV. Derivate der Actinomycine; ; 46

I. Derivate. die durch Veranderung des Peptidteils entstehen 46

2. Derivate. die durch Veranderung des Chromophors entstehen. 47

Literaturverzeichnis : 48

,~

t

5656~R

66

687°74

Natiirlich vorkommende Nitroverbindungen. Von M. PAILER, II. Chemi

sches Institut der Universitat W~en ; ,

Einleitung I. Chloramphenicol. I. Isolierung und Konstitutionsermi1;tlung 2. Synthesen 3. Herstellung des Chloramphenicols au£ biologischem Wege 4. Bestimmung des Chloramphenicols II. p-Nitropropionsaure III. Aristolochiasauren. I. t)ber altere Arbeiten 2. Neuere Arbeiten zur Isolierung. Reindarstellung und Konstitutions

ermittlung 3. Konstitution der Aristolochiasaure-I. 4. Konstitution der Aristolochiasaure-II 0. ..

5. Weiteres Vorkommen von Aristolochiasauren und Isolierung unc

Charakterisierung von strukturell verwandten Natursto££en Literaturverzeichnis 77

78

83

84

84848587QO

9()

9()

97989900

10'l

102

Derives guanidiques biologiques. Par N GUYEN V AN THOAI et J. ROCHE

College de France, Biochimie generale et comparee. Paris. ; Introduction ,

I.. Structure et formation. 1. Structqre , 2. Nomenclature. 3. Formation par voie chimique 4. Biogenese. ,

a. Formation par amidination successive: cas de l'arginine 90- -

b- Formation par transformation d.autres composes guanidiques 92. -

c- Formation par transamidination 94.

II. Proprietes generales. 1. Basicite 2- Formation des sels 3. Stabilite et hydrolyse. 4. Cyclisation 5. Oxydation 6- Degradation biochimique a. Deguanidylation 99. -b. Desamidination totale 99. -c- Des

amidination partielle 100.

III. Methodes generales d'analyse et de preparation. 1. Reactions d'identifica1;ion et d~ dosage. ..'. .., a. Reaction au diacetyle lOZ. -b. Reaction a. l.iX-naphtol 102. -

c. Reaction au nitroi>russiate ferrique 102. -d- Reaction a. la nin

hydrine 103- !;

2- Chromatographie sur papier et sur colonne. Electrophorese. IV. Repartition des derivesguanidiques Conclusions Bibliographie 103

105107

107

vInhaltsverzeichnis.. -Contents. -'Table des matieres.

~

..',.,

.1

.

"

,d

.-

.~. VII. Biological Properties of isoThiocyanates and Their Parent Glucosides .155t

8

.

VIlI. Tables. :. I57

I. Crystalline isQThiocyanate Glucosides. Known at the End of I959 I57

2. Crystalline isQThiocyanate Glucoside Tetraacetates, Known at the

Eiid of I959. I583. isQThiocyanat~ Glucosides with Established Side-chains. Known at

the End of I959 I594. Molecular Rotations of Sulphoxide isQThiocyanates of Natural Origin,

Some Derivatives and Related C{)mpounds I6o

5. The Occurrence of isQThiocyanates or Their Parent Glucosid~s inSpecies of the Family Crucifefae I6I

6. The Occurrence of isQThiocya¥ates C?r Their Parent Glucosides inFamilies other than Cruciferae : I67

References. I69

,

-

11

-

j Naturally Derived isoThiocyanates (Mustard Oil~) and Their Parent

Glucosides. By ANDERS KJJER, Organic Chemical Laboratory, Royal

Veterinary and Agricultural College, Copenhagen. ::..,. I22

I. Introduction. I23

II. Historical Development :.. I23

III. Parent Glucosides I24

I. General Properties I24

2. Distribution in PlantTissues I26

3. Detection, Isolation, Separation and Determination. I27a. Paper Chromatography I27. -b. Isolation and SeparationMethods I28. -c. Quantitative Determination I29.

4. Chemical Structure ; I29a. Earlier Formulation I29. -b. Revised Structures I3I. -

c. Synthesis I34.

5. Individual Glucosides. I35

IV. Enzymic Hydrolysis. I36

I. Distribution of Myrosinase I36

2. Properties of Myrosinase I37

V. Naturally Derived isoThiocyanates I38

I. General Properties I38

2. Detection, Isolation, Separation and Determi1+ation .; I39a. Chromatographic Methods 139". -b. Isolation 4°. -c. Separa-

tion 40. -d. Quantitative Determination I4I.

3. Chemical Structure I4Ja. Saturated Alkyl isoThiocyanates I4I. -b. Unsaturated AlkylisoThiocyanates I42. -c. w-Methylthioalkyl isoThiocyanates andRelated Sulphoxides and Sulphones 44. -Stereochemistry 47. -

d. Aromatic isoThiocyanates I48. -e. Hydroxy-substituted iso-Thiocyanates I5°. -f. isoThiocyanates of Doubtful Structur~ I53.

VT R()t"ni{'"l Di"trihlltion of isoThiocyanate Glucosides I.S4

179

17918018118118z

183186

189

194

199

199z03

z03

zo3211

Z13

215

216

Z18

Die Farbst()ffe im Gefieder .derVogel. VGn QrTo V()LKER, ZOologisches

1;nstitut der Justus Liebig-Hochschule, Gie6en. ,,! ! ..

I. Einleitung II. Carotinoid.e(Lipochrome) I. Lutein (Xa;nthophyll) 2. Kanarienxanthophyll 3. Zeaxanthin , 4. Picofulyin 5. Astaxanthin bzw. Astacin 6. Rhodoxant.hin 7. Rote Carqtinoide unbekannter Struktur 8. Physiologisch~ G~ndl~gen der Carotinoid-Ablagerung III. Die gelben und roten Federfarbstoffe, der Papageien IV. Fluoreszierende. gelbe Federfarbstoffe I. Bei Papageien 2. Bei anderen Arten v. Pyrrolfarbst.offe I. Koproporphyrin 2. Turacin " 3. Pyrrolfarbstoffe im Stoffwechsel der Vogel VI. Chemisch ungeklarte Federpigmente VII. Riickblick. Literaturyerzeichnis

/v223

224226

229

2~2

23!5

2'!8

239

239

241

244

244

24"

249

155

6~

Cis.frans Isomeric Carotenoid Pigments. By L. ZECHME.ISTER, California

Institute of Technology, Pasadena, California. I. Introduction Nolllenc!ature Sollle Historical Relllar!1:s on Stereoisolllerislll of Polyenes. p. Nulllber and Types of cis Carotenoids. Steric Hindrance. III. Sollle Properties of cis Carotenoids I. Relative Stabilities. Sterically .Unhindered cis Forllls 238. -Sterically Hindered cis

Forllls 239. -Polycis Forn1s 239.

2. Melting Points. ..,. 3. Rotatory Power. 4. Relative Adsorption Affiniti~s IV. Cis-trans Isomerism and UV Spectra I. S(jme Remarks on the. Spectra of all-trans Carotenoids 2. Spectral Effect of trans- cis Isomerization in the Visible Region .

.

3. SPectral Effect of trans -cis Isomerizationin the Near Ultraviolet

Region: the cis-Peak : 4. A Theoretical Interpretation of Spectral PhenomeIia, EspeciaUy of

the cis-Peak Effect 'i. SDectra at Extremelv Low TemDeratures

VIIInhaltsverzeichnis. -Contents. --Table des matieres.

i

.

,~

~

v. Preparation of cis Carotenoids by Direct Rearrangementof the All-transForm; ~ , 264

I. Therm~l Methods of cis-trans Isomerization. ~'... 264(a) Spontaneous Rearrangement in Solution at Room Temperature 264(b) cis-trans Isomerization in Refluxed Solutions. 265(c) cis-trans Isomerization by Melting Crystals...; 265

2. Photochemical cis-trans Isomerization ih the Absente of Cat:a;Iysts ..2'68

3. cis-trans Isomerization by Iodine Catalysis, in t.ig~t ~ 269

4. cis-trans Isomerization by Acid Catalysis. ; 273

5. cis-trans Isomerization by Contact with Active Surfaces. 2736. cis-trans Isomerization via Boron Trifluoride Complexes. 274

7. Bio-stereoisomerization 274

VI. Preparation of cis Carotenoids by Total Synthesis. 274"c'c"y Cc

VII. Naturally Occurring cis and Polycis Carotenoids. 279I. Mono- and Dicis Carotenoids 279

2. Polycis Carotenoids 280Prolycopene 283. -Further Polycis Lycopenes 287. -Proneuro-

-sporene (Protetrahydrolycopene, Neoneurosporene P) 288. -Pro-y-carotene 29I.

VIII. Some General Remarks on Configurational Assignments. 29II. Stereoisomeric Types ' 29I

2. Number and Location of cis Double Bonds. 293

3. Configuration and Infrared Spectrum. 294

IX. Configurational Assignments in Certain Stereoisomeric Sets. 295I. Stereoisomeric Sets with Two Hydroaromatic Terminal Groups. ..295

" p-Carotene Set 295. -Cryptoxanthin Set 300. ,- Zeaxanthin~ Set 300. -Isozeaxanthin Set 30I. -Echinenone Set 30I.. -Can-I thaxanthin Set 30I. -p-Carotene Monoepoxide Set 3°3. -p-Caro.

tene Diepoxide Set 3°3. -3,4-Dehydro-p-carotene and 3,4,3',4'-Bisdehydro-p-carotene Sets 305. -I6,I6'-Homo-p-carotene Set 305. -r3,I3'-Bis-desmet4yl-p.ca,rot~ne Set 305.. -retrQ:-pehydrocaroteneSet 306. -(X-Carotene Set 306. -(X-Cryptoxanthin (Physoxanthin)Set 3°7. -Lutein Set 308. -Tr9llixanthin .Set 30/). -3,4-Dehydro-(X-carotene Set 308. :- Taraxanthin Set 308.

2. Stere9isomeric Sets with One Hydroaromatic and One AliphaticTerminal Group. 399y-Carotene Set 309. -Gazaniaxanthin Set 3IO. -CelaxanthinSet 3IO. -Capsanthin Set 3IO. -Torularh9din ~t 3II.

3. Stereoisomeric Sets with Two Aliphatic Terminal G~oups. 3IrLycopene Set 3II. -Neurosporene Set 3I4.- Phytofluene Set3I5.~Rhodoviolascin (Sprill9xanthin) Set 316. -Capsorubin Set 3I6. -'-Fucoxanthin Set 3i7.

4. Stereoisomeric Sets with Two Arolriatic Terminal Gr9ups. 3I8;," 1,18~Diphenyl-3;7,I2,I~-tetramethyl-9Ctadecanonaene Set 3.X8. -

Remeratene and IsOrenleratene Sets 3I9. -I,3.7,12,t6,18-Hexaphenyl-octadecanonaene Set 3I9. -..Naphthyl-carotene" Set 320.

I

Irihaltsverzeichnis. JContents..-

VIII Table des mat

x. Lower-m01ecular W!Jight Carotenoid-carboxylic Acids: Bixin and Crocetin 320Bixin Set 320. -Crocetin Set 327.

XI. Cis-trans Isomerism and Provitamin A Effect 0( Carotenoids. 33 I

References. 334

j The Gibberellins. By,P..W. BRIAN, JOHN FREDERICK GROVE and

J. MACMILLAN, Imperial Chemical Industries, Ltd., Akers Research

Laboratories, The Frythe, Welwyn, Hertfortshire, England. 35°

I. Introduction 35I

II. The Chemistry of the Gibberellins 352

I. General Remarks 352

2. Nomenclature 354

3. The Chemistry of Gibberellic Acid 355

A. Structure of Gibberene 356

B. Structure of Gibberic Acid 358(a) Gibberic Acid 358. -(b) epiGibberic Acid 364.

C. Structure alid Stereochemistry of alloGibberic. Acid. 365(a) alloGibberic Acid 365.. -(b) Absolute Configuration 369. -(c). epialloGibberic Acid 372. -

D. Structure and Stereochemistry of Gibberellic Acid. 374(a) Gibberellic Acid 374. -(b) Epimerisation at Position 2 inGibbanes 382. -(c) Rearrangement of Gibb-3-ene I- 4a Lactones385. -(d) Absolute Configuration 386. -(e) MiscellaneousReactionS of Ring A 388.

4. Biogenesis of the Gibberellins 389

III. Occurrence of Gibberellins in Higher Plants. 390

IV. Effects on Plant Growth and Development. 394

I. Stem Growth 394/

A. Day-neutral Annuals, etc. 395B. Herbaceous Plants Sensitive to Vemalisation or Photoperiod. ...395C. Photoperiod-controlled Growth of Woody Plants. 397D. Cell-extension or Cell-multiplication? 398E. Mode of Action Studies: Interactions with Auxins. 399F. Mode of Action Studies: Int~ractions with Light. 402G. Other Interactions 4°3

2. Leaf GroWth 4°4

3. Root Growth. 405

A. Root Extension 4°5B. Root Initiation on Stem Cuttings 405C. Development of Ro_°t-nodules on Legumin?us Plants. 405

4. Floweri~g. 466A. Rosette Plants Requiring Vernalisation or Long-days 406

B. Caulescent Plants Induced to Flower by Vernalisation or Long-dayPhotoperiods. : 406

C. Short-dav Plants. 407

Discu! 407

5. Fertilisation and Fruit Growth A. Pollen Growth B. Parthenocarpy C. Fruit-swelling 6. Seed Germination , A. Breaking of Dormancy B. Acceleration of Germination. 7. Effects on Lower Plants 8. Discussion. A. I:iormonal Interactions B. The R6le of the Gibberellins as Plant Hormones

V. Detection and Estimation of Gibberellins I. Bioassay. 2. Chemical and Physical Methods. References

453

456

462

.t6o;

466

j Selected Subjects in Sedimentation Analysis, with .Some Applicationsto Biochemistry. By J. W. WILLIAMS, Department of Chemistry,

The University of Wisconsin, Madison, Wisconsin. Glossary of Terms. Introduction I. Basic Theory. I. Charge Effects a) Diffusion b) Sedimentation. z. The Theory of Sedimentation Analysis. a) Conservation of Mass. The Continuity Equation. b) The Flow Equations. 3. Velocity Equation for Two-Component, Incompressible Systems and

Its Uses...: , , 4. The Differential Equation of the Ultracentrifuge and Its Solutions.

Two Components. , II. The Sedimentation Velocity Experiment and the Determination of

Molecular Weight. (Two-~omponent, Idealized Systems.). 1. Definition and Evaluation of the Sedimentation Coefficient. z. Molecular Weights from Sedimentation and Diffusion. 3. Molecular Weight Determination by Combination of Sedimentation

Coefficient and Intrinsic Viscosity :...

III. H6terogeneity and the Form of the Boundary Gradient Curve. 1. Boundary Spreading: Negligible Diffusion, Constant Sedimentation

Coefficient z. Boundary Spreading: Appreciable Diffusion, Constant Sedimentation

Coefficient

x Inhaltsverzeichnis. -Contents. -Table des matieres.

3. Boundary Spreading: Sharpening Effects of Concentration Dependenceof Sedimentation Coefficient 473

4. The Johnston-Ogston Effect 477

5. Protein-Protein Interactions 480

a) Monomer~Polymer Equilibria : 482b) Bimolecular Associations 484

c) Interconversion of Isomers 488,

IV. Three-Component Systems 489

I. Solvati9n : 489

2. Sedimentation Equilibrium in a Density Gradient. 492

References. ; 4.Q"

,"'

Structure and Immunological Specificity of Polysaccharides.

By MICHAEL HEIDELBERGER, College of Physicians and Surgeons,

Columbia University, New York, and Institute of Microbiology, Rutgers,

the State University, New Brunswick, New Jersey. .,.,~+~,~;t!c#;~,~~, 503


II. Chemistry of Capsular Polysaccharides of Pneumococcus and O-Poly-saccharides of.Salmonella 506

III. Cross-reactions of AntipneumoCOCCal Sera. 509

IV. Cross-reactions in Anti-Salmonella Sera. 517

V. Cross-reactions in Anti-Mycoplasma mycoides Serum. 518

VI. Conclusion 518

VII.Tables 519

I. Specific Capsular Polysaccharides of Pneumococcus and Polysaccharideii ~of Cross-reacting Microorganisms 519

2. Polysaccharides which Precipitate Antipneumococcal and Other Serato Strongly Moderately 520

-3. Cross-reactions of Polysaccharides of Microorganisms in Anti-

pneumococcal and Other Antisera 523

4. Cross-reactions of Animal and Plant Polysaccharides in Anti-

pneumococcal and Other Antisera 525

References. .; "2q

Namenverzeichnis. Index of Names. Index des Auteurs. Sachverzeichnis. Index of Subjects. Index des Matieres 537

557

t

Inhaltsverzeichnis.


i

J

J Medium-ring Terpenes. By F. SORM, Institute of Organic Chemistry and

Biochemistry, Czechoslovak Academy of Science, Prague I

I- Introduction. I

II. Terpenes Containing a Nine-Membered Carbon Ring. 3

I. Caryophyllene :- 3

2. The Betulenols 7

III. Terpenes Containing an Eleven-Membered Carbon Ring 8

Humulene and Zerumbone 8

IV. Terpenes Containing a Ten-Membered Carbon Ring II

I. Germacrone II

2- Lactones 15

Pyrethrosin I5. -Arctiopicrin 17- -Costunolide 18. -Bal-chanolide 19. -Isobalchanolide 19. -Hydroxybalchanolide 19. -

Acetylba:lchanolide 19. -Cnicin 2I. -Parthenolide 23. .-' Aristo-lactone 24. -Biogenetic Relationships 24.

V. Some Spectral Anomalies in Medium-ring Terpenes 25

References , 27~

j Recent Advances in the Chemistry of Azulenes and Natural Hydro-

azulenes. By TETSUO NOZOE and SHO ITo, Faculty .of Science,

Department of Chemistry, Tohoku University, Sendai, Japan. 32

I. Introduction. 33

II. Azulenes 34

I. Synthetic Methods 34

a) Syntheses with Dehydrogenation 34b) Syntheses without Dehydrogenation. 35c) Syntheses Starting from Troponoids and Heptafulvenes 36

2. Physical Properties 40

3. Chemical Properties 41

a) Electrophilic Substitutions 41b) Free Radical Reactions 44c) Nucleophilic Substitutions 44d) Arylideneazulenium Salts and Related Compounds. :. 45e) Formyl- and Some Other Acylazulenes 46f) Mannich Base. ; 48g) Amino- and Hydroxyazulenes : 49h) Ring Formation on the Azulene Nucleus. ,;0

..

"

I,~

4

III. Naturally Occurring Hydroazulenes 5z

I. Non-lactonic Hydroazulenes 53

a) Guaiol and Bulnesol 53b) Aromadendrene and Alloaromadendrene. 53c) Globulol. Ledol and Viridiflorol 55d) Palustrol 56

e) (X-Gurjunene 57f) Cyclocolorenone. 58g) Zierone 58

h) Tricyclovetivene. Tricyclovetivenol and Bicyclovetivenol. 58i)Hinesol , ' 59

j) Carotol and Daucol ..: : 60

2. Lactonic Hydroazulenes 61

a) Arlabsin. Absinthin and Anabsinthin 61b) Matrictn and Matricarin 64c) Lactucin 65

d) Cynaropicrin 67e) Helenalin. Isohelenalin, Neohelenalin. Tenulin. Balduilin, and

Mexicanin C 67f) Geigerin and Geigerinin 72g) Ambrosin and Damsin 74h) Parthenin. 75i) DehydrocostuS Lactone 76

3. Stereochemistry of Hydroazulenes 76

4. Azulene Precursors of Some Other Types. 78

Addendum. 79

IV. Tables. , 80

I. AzuleneDerivatives (since 1958) 80

2. Azulenium Salts and Other Related Polymethine Dyes. 105

References. 107

j Chemistry of the Natural Pyrethrins. By L. CROMBIE, Departmentof Chemistry, King's College (University of London), London, and

M. ELLIOTT, Department of Insecticides and Fungicides, Rothamsted

Experimental Station, Harpenden, Herts. 120


II. Nomenclature. 126

III. Isolation of Natural Rethrins 128

IV. Structure and Chemistry of Chrysanthemic and Pyrethric Acids. 129

V. Synthesis of Chrysanthemic and pyrethric Acids. 133

VI. Structure and Chemistry of pyrethrolone and Cinerolone. 137

pyrethrolone 137. -Ciner.olone I40.

VII. Synthesis of cis-pyrethrolone and cis-Cinerolone 141

VIII. Synthesis of pyrethrins and Cinerins 145

IX. Allethrin. 146

X. Biosynthesis of the pyrethrins and Cinerins 148

XI.. Synergists for Rethrins 148

XII. The Insecticidal Activity of Natural and Closely Related Synthetic

Rethrins 15°

References. 155

.

,

j Conformational Analysis of Steroids and Related Natural Products.

By D. H. R. BARTON and G. A. MORRISON, DepartmeI)tofChemistry,Imperial College of Science and Technology (University of London),London 165

I. Introduction ; 0 166

II. Definition of Conformation 167

III. The Existence of Preferred Conformations. 167

I. Acyclic Compounds 1672. Cyclohexane Derivatives 168

a) Boat and Chair Conformations 168b) Axial and Equatorial Bonds !69c) Auwers-Skita Rules 171d) Exceptions to the Usual Stability Relationships. 17Ze) Six-memberedRings Containing Trigonal Carbon Atoms. 175

3. Decalin Derivatives 176

4. Perhydroanthracenes and Perhydrophenanthrenes 1775. Steroids. 0 177

a) Relation between Configuration and Conformation. 178b) Stability of Ring Junction in Hydrindanones Incorporated into

Fused Ring Systems 1796. Triterpenoids 18z

IV. Conformational Analysis of Reactions Controlled by Steric Hindranceand Steric Compression 183

I. Axial and Equatorial Substituents 184a) Esterification of Alcohols and Carboxylic Acids, and Hydrolysis

of Esters 184b) Strengths of Acids and Amines 187c) Chromatographic Behaviour of Alcohols. 188d) Oxidation of Secondary Alcohols with Chromium Trioxide. 188e) Solvolysis ; 188

2. Reactivity of Carbonyl Groups 189a) Formation of Carbonyl Derivatives. 189b) Hydride Reduction of Carbonyl Groups. 189

3. Cis Addition to Double Bonds 191

V. Spectroscopic Correlations 193

I. Infrared Spectra 193a) G-O Vibrations : 194b) O-H Stretching Frequency ', 194c) C-Halogen Absorption 194d) G-D Stretching.Frequencies 194e)C=O Stretching Frequencies: : 194f) Intramolecular Hydrogen Bonding. 195

r

I~


2. Ultraviolet Spectra 195

3. Proton Magnetic Resonance Spectra. 196

4. Optical Rotatory Dispersion 197

VI. Effect of Conformation on Reactions with Stereochemically DemandingTransition States 199

I. Reactions Involving Four Coplanar Centres. ...; 199

a) Bimolecular Elimination 199b) Diaxial Electrophilic Addition 201c) Opening of Epoxide Rings 202d) Formation of Epoxide Rings, and Neighbouring Group Participation 205

e) 1,2-Diaxial Rearrangements 206f) Ring Contraction and Ring Expansion ~e~ctions 206

2.. Reactions Involving Coplanar Cyclic Transition States 208

3. Deamination Reactions 209

4. Bromination and Protonation of Enols. 209

VII. Preferred Boat Conformations 212

VIII. Conformational Driving Forces 216

IX. Conformational Transmission 217

I. Long Range Effects 217

2. Reflex Interactions 222

X. Carbanion Reduction Processes 223

References. 22"

J Biogenetic-type Syntheses of Natural Products. By E. E. VAN TAMELEN,Department of Chemistry, The University of Wisconsin, Madison, Wisconsin 242

Introduction. 243

I. Alkaloids. 248

I. Pyrrolidine and Piperidine Groups 248Hygrine, Cuscohygrine 248. ~ Isopelletierine 249. -Lobelanine,

Arecaidine 249. -Nicotine, Anabasine 250. -Atropine, Tropine,Tropinone 25I. -Pseudo-pelletierine, Meteloidine 252.

2. Quinolizidine Group. 252Lupinine 252. -Sparteine 253. -Cytisine, Anagyrine, Thermo-

psine 254.

3.Anthranilic Acid Group 255Amyl-quinolines 255. -Vasicine 256. -Arborine 256. -Acridonealkaloids 256.

4. Isoquinoline Group. 257Laudanosine, Berberine, Papaverine, Glaucine 258. -Norsalsoline,

Norlaudanosine, Benzyl-tetrahydroisoquinolines, Cryptopine, Cory-daline 259. ,

5. Indole Group. ; 260Yohimbine 260. -Eleagnine 26I. -Strychnine 26I. -Gramine 263.-Physostigmine 263. -Rutaecarpine 264. -Cryptolepine 264. -

Cinchonamine, Cinchonine 264. -Quinamine 265.

~

VII-

Inhaltsverzeichnis. -Contents. -Table des matieres.

i

.II. Terpenes 266

I. Syntheses Involving Polyene Cyclization ; 266

Geraniol, Geraniolenes, Ionones 266. -Limonene 266. -Farnesolderivatives, Farnesic acid 267. .

2. Conversions and Partial Synt~eses 269

Squalene 269. -Hopenone-I 27°. -Friedelin 271. -Glutinone 271.

-Lupeol, Ger~anicol 271.

3. Miscellaneous 271

!X-Terpinene, Ascaridol 271. -Santonin, Verbenone 271. -Lupulone.Humulone 272. -Iridomyrmecin 272.

III. Some Other Natural Products 273

I. Monosaccharides 273

Fructose, Sorbose, Xylose, Arabinose, Ribose 274. -N-Acetyl-neuraminic acid 274.

2. Porphyrins 274

Etioporphyrin 275. -?orphobilinogen, Uroporphyrinogen 275. -

Uroporphyrin-1II 275. -Chlorophyll 277.

3. Vitamins. ; 277Ergosterol, Vitamin Ds 277. -Riboflavin. LuInichrome 277. -

pyridoxin 278.4. Amino Acids and Peptides 278

Serine, Threonine, p-Hydroxyleucine 279. -Thyroxine 279. -Peptideformation 279. -Role of histidine residues 280. -Thioesters andamino acids 280. .

5. Phenol Oxidation Products 281

Hydroxyindoles 282. -Bufotenin 282. -Serotonin 282. -Xanthommatin 282. -Actinomycin antibiotics 283. -Usnic acid 283.-Griseofulvin 283. -Hypericin 284.

References. 280;

Der Kohlenhydratstoffwechsel im Roggen und Weizen. Von

H. H. SCHLUBACH, Physio1ogisch-Chemisches Institut der Universita.tMiinchen 291

I. Die loslichen Kohlenhydrate im Roggen und ihre Konstitution. 291

II. Die loslichen Kohlenhydrate im Weizen und ihre Konstitution. 301

III. Die Biogenese der Polyfructosane im Roggen und Weizen.. 307


Les phosphatases des vegetaux superieurs: repartition et action.

Par JEAN EMILE COURTOIS et ANDREA LINO, Laboratoire de Chimie.

Biologique, Faculte de Pharmacie de Paris. 316

Introduction 317

Definition 317. -Historique 318. -Classification generale des

phosphatases 319.

320

320

I. Les phosphomonoesterases I. Classification des principaux groupes dephosphomonoesterases. Bases de la classification 320. -Les principaux types de phospho.

monoesterases 32I.

2. Repartition dans les organes vegetaux. 323

a. Graines 323

Variations d'act;ivite selon l'origine botanique 323. -Purification

et champ d'action 324. -Phosphatase d' A.mandier 324. -Phospha-

tase de Moutarde-Blanche 326. -Son de Ble 328. -Influence

de la germination sur l'activite phosphatasique 329.

b. Feuilles c. Tubercules d. Racines, fleurs et fruits. 3. Phosphomonoesterases a action specifique caracteristique a. Les phytases Repartition 335. -Purification 337. -specificite 338.

b. Les osylphosphatases 4. Action des effecteurs a. Generalites b. Action des anions. Orthophosphates 34R. -Arseniates 348. -Fluorures 348. -

Molybdates 349. -Autres formateurs de complexes 35I.

c. Action des cations. ~ 5. Reversibilite d'action 6. Action transferante des phosphomonoesterases. II. Les phosphodiesterases III. Les pyrophosphatases ATPases et apyrases IV. R6le physiologique des phosphatases Conclusions Bibliographie. Namenver2eichnis. Index of Names. Index des Auteurs. Sachverzeichnis. Index of Subjects. Index des Matieres

33°

332

333

334

335

344

346

346

348

00 351

00 353

00 354

00 358

..359

.0 360

0. 360

, 0 363

.363

374

389

~

~

Inhaltsverzeichnis.


j Nitrogen-containing Metabolites of Fungi. By J. H.BIRKINSHAW and

C. E. STICKINGS, London School of Hygiene and Tropical Medicine,London- ; 1.

I. Introduction. I

II. Compounds Containing Acyclic Nitrogen. 2

I. Amines 22. Quaternary Ammonium Compounds 43: Nitro- and Nitroso-Compounds...; 6

4. Polyacetylenes COntaining Nltrogen 7

III. Oligopeptides 7

I.V. HeterocyclicNitrogen.Compounds 15

I. pyrrole Derivatives 152. Simple Indole Derivatives 153. Ergot Alkaloids : '174. pyridine Derivatives 215. Quinoline Derivatives. 22

6. Azanthracene Derivative 237. Phenoxazone Derivatives 238. Pyrazine Derivatives 249. Purine Derivatives 27

V. Heterocyclic Compounds Containing Sulphur as well as Nitrogen. 28

I. The Penicillins. 28

2. Other Metabolites COntaining Sulphur. 3°

VI. Concluding Remarks 32

References. 33

J Forschungen am Lignin. Von K. FREUDENBERG, Chemisches Institutder Universitat Heidelberg 4I

I. Einleitung 41

II. Ligninpraparate 42

I. Milled-Wood-Lignin nach BJORKMAN 422. Ligninpraparate anderer Herstellung 433. Berechnung der Ligninan8.1ysen :.. 44

.III. Die Abbausauren. 45

IV. Die destruktive Hydrierung des Lignins.. 48

V. Weitere Eigenschaften des Lignins 49

VI. Diep-Hydroxy-zimtalkohole 5°

VII. Die HerstellunEt des Dehvdrierungspolymerisates (DHl") 5°

~

---,!-:i!VI Inhaltsverzeichnis. -"- ('.l\nt"nt_q --. fable des matieres.

53

55

61

63

66

VIII. Vergleich des natiirlichen und des kiinstlichen Lignins. IX. Zwischenprodukte der Ligninbildung X. Zur Biochemie und iiber Versuche mit Isotopen XI. Die Wachstumsprinzipien des Lignins XII. Die Bindung des Lignins an die Kohlenhydrate. XIII. Bemerkungen zu den Entwiirfen eines Konstitutionsschemas des

Coniferenlignins XIV. Laubholzlignin. Humus Literaturverzeichni" ... 67

68

60

73

74

75

75

7.1

7';

7Q

80

82

84

84

84

85

8788

89

89

89

92

96

96TOT

Die Ubichinone (Coenzyme Q). Von 0. SCHINDLER, Forschungsinstitut

Dr.A.WanderA.-G., Bern I. Einleitung II. Isolierung und Vorkommen der Ubichinone I. Erste Beobachtungen zum Vorkommen von Ubichinon 2. Isolierung von Ubichinon aus verschiedenen tierischen Geweben

sowie Mikroorga~ismen a) Nachweis und Isolierung von Substanz SA (Ubichinon) durch

MORTON und Mitarbeiter b) Isolierungvon Ubichinon (Coenzym Q bzw.Coenzym Q275) durch

FOLKERS und Mitarbeiter c) Isolierung von Ubichinon (Coenzym Q bzw. Coenzym Q275) durch

GREEN, CRANE, HATEFI, LESTER, WIDMER und Mitarbeiter. 3. Isolierung und Nachweis von Ubichinon als Coferment III. Physikalisch-chemische Eigenschaften der Ubichinone I. Schmelzpunkte. 2. Papierchromatographisches Verhalten 3. UV-Absorptionsspektren 4. IR-Absorptionsspektren 5. Kernresonanzspektren IV. Ermittlung der ~onstitution der Ubichinone durch chemischen Abbau

I. Reduktive Methylierung und ansch1ieBender oxydativer Abbau ...

2. Reduktive Acetylierung und anschlieBende Ozonisierung V. Synthesen der Ubichinone VI. Umwandlungsprodukte der Ubichinone I. Chroman- und Chromen-Derivate von Ubichinon (Substanz SC) ...

2. Alkoxy-Homologe der Ub.ichinone VII. Biosynthese der Ubichinone VIII. Plastochinon (KOFLERS Chinon, Coenzym Q254) IX. Biochemische Bedeutung der Ubichinone. Bedeutung der Lipide fiir Electron-Transport-SystemeJ.,i tera t1l TVeTzei " h ni ~

".

~

Naturally Occurring Aromatic Derivatives of Monocyclic (X-pyrones.

By WALTER B. MORS, MAURO TAVEIRA MAGALHAES an:d OTTO

RICHARD GOTTLIEB, Ministerio da Agricultura, Instituto,de QuimicaAgricola. Riode Janeiro..., ~ 131

I. Introduction and Historical Development. 132

II. Structural Elucidation 133

I. (X-Pyrones not Methoxylated at C(4) 133

2. Partially Saturateq (at. 5.6) (X-Pyrones Methoxylated at C(4) 136

3. (X-pyrones Methoxylated at C(4) : 138

4. Characterization of (X- and 'Y-pyrones by Physical and ChemicalMethods 141

5. The Mechanism of Alkaline Hydrolysis. 143

III. Syntheses 144

I. Non-methoxylated (X-pyrones I44a) Phenylcoumalin I44. -b) Paracotoin 144.

2. (X-Pyrones Methoxylated at C(4) I45

a) Yangonin 145. -b) II-Methoxy-yangonin and 5,6-Dehydro-

met.hyst.icin 15°. -c) 5,6-Dehydrokawain 150. -d) 4-Methoxyphenyl-coumalin 15°. -e) Methoxyparacotoin 151. -f) Anibine 152.

3. Partially Saturated .(at 5,6) (X-Pyrones Methoxylated at C(4) 152Kawain 152. -Methysticin 152. -Dihydromethysticin 152. -

Dihydrokawain 152.

IV. Physical Properties 154

V. PharmacologicalProperties : 154

VI. Taxonomic Significance of the Distribution of (X-pyrones in Lauraceae 158

VII. Reflections on Biosynthesis and Phylogenesis. 158

Addendum ; J6o

References. 160

J Anthocvanins and their Sugar Components. By T. B. HARBORNE.

I-if

,

i

John Innes Institute, Bayfordbury, Hertford, Herts, England. 165


II. Isolation. : 168

III. Properties of Anthocyanins 169General Remarks 169Spectral Characteristics 17°

Chromatographic Properties 175Hydrolysis Products 176

Enzymic Degradation i77IV. Identification of Anthocyanins 178

V. Natural Occurrence 179Monosides. 179Biosides 182Triosides : 183

Acylated Anthocyanins. 184Anthocyanin-like Compounds 185

186

186

188

188

189

190

190

191

191

192

194

195

VI. Distribution of Anthocyanins ..

.Systematic Relations. Tissue Variatiol;l. ., Intraspecific Variation. VII. Anthocyanins and Plant Colour

Colour and Structure. Metal Complexes Copigmentation., Concentrati{)n VIII. Biosynthesis of Anthocyanins ..

IX.Conclusion , .

References ;...,

200

202

202

2042042042052062062°72°72°7

208

208208208

209210210211211212212212

2132!4214215

215

217217218218

Aminozucker, Synthesen und Vorkommen in Naturstoffen. Von

GERHARD BASCHANG, Max-Planck-Institut rur medizinische Forschung.

Heidelberg. und The Rockefeller Institute, New York. Verzeichnis der Abkiirzungen I. Einleitung. Nomenklatur. : II. Allgemeine Reaktionen von Aminozuckern. I. Acylierung 2. Glykosidierung 3. Hydrolyse der Glykosidbindung 4. Epimerisierung 5. Perjodatoxydation 6. Desaminierung 7. Methylierung. 8. Bestimmu:ngsmethoden Aminozucker 207. -Sialinsiiuren 208.

III. Synthesen von Aminozuckern I.. Aminoaldosen a) Cyanhydrinsynthese b) Halbhydrierung von Aminonitrilen c) Epoxyde und Ammoniak (Amine) d) Episulfide und Ammoniak e) Konfigurat.ionsumkehr f) Phenylthiourethan-Methode g) Verkiirzung der Zuckerkette h) Hydrazinolyse von Sulfonsiiureestern i) Epimerisierung von 2-Acetamino-zuckern k) Nitroolefine und Ammoniak 1) Dialdehyde und Nitromethan m) Dialdehyde und Phenylhydrazin n) Heyns-Carson-Umlagerung 0) Oxoglykoside und Phenylhydrazin 2. I-Amino-2-keto-zuckei" 3. Von Aminozuckern sich ableitende Verbindungen. Muraminsiiure (3-0-D-Lactyl-D-glucoSamin) D-Glucosamin- und D-Galaktosamin-uronsiiure N-Acetyl-neuraminsa.ure..

FIXInhaltsverzeichnis.. -Contents. -Table des matieres.

IV. Aminozucker-haltige Naturstoffe 2I9

I. Mono-, Di- und Trisaccharide 2tt)

a) Antibiotica ,: 2I9b) Nucleotide. 220

2. HOhere Oligosaccharide. 22 I

a) Oligosaccharide, aus Milch 22I

b) Ganglioside. , 224

3. Polysaccharide. 226

a) Polysaccharide von Invertebraten und Pilzen. 227Chitin 227. -Gala.ktosarnino&lykan 228.

b) Bakterienpolysaccharide 228Vi-Antigen 2z8Neuraminsaure-haltige Polysaccharide. 228I. Zellwandpolysaccharide228. -2. Somatische Polysaccharide 23°.

-3. Ka.pselpolysaccharide 23I.c) Ul:onsaure- und schwefelsaure-haltige Polysaccharide (Mucop6ly-

saccha.ride) 23IHyaluronsii.ure 232. -Chondroitin-4-su1fat, Chondroitin-6-su1fat undDermansu1fat 232. -Heparin 233.

d) Glykoproteine 233I. Submaxilla.ris-mucine 233. -2. Blutgruppensubstanzen (Fuco-mucine) 234. -3. Glykoproteine des Magens, aus Ascitesfliissig-keiten, aus Ham, aus Milch, aus Eik1ar 237 .-4. Plasmaproteine 240.-(Xl- und (X2-Glykoproteine 240. -Haptoglobine, Transferrine,Coeruloplasmine 24I. -Fetuin 242. -Thyreoglobulin 24Z. -

y-Globuline z4z. -5. Hormone .und Fermente z43. -Gonado-tropine, thyreotropes Hormon 243. -Erythropoietin 243. -Kalli-krein, Enterokinase, Takaamylase A 243.

V.. Enzymatischer Aufbau und Abbau von Aminozuckern. z44

I. Monosaccharide z44a.) Glucosa.min und Galaktosamin 244b) Mannosamin Z46

c) N-Acetyl-Ileuraminsaure z47d) N-Acetyl-muraminsaure 247

2. Polysaccharide , Z48a) Chitin. : 248b) Uronsaure- und schwefelsaure-haltige Polysaccharide. Z48

c) Zellwand-polysaccharide 249


J Structure and Stereochemistry of the Lycopodium Alkaloids. By KAREL

WIESNER, Department of Chemistry, The University of New Brunswick,Fredericton, N.B.. Ca.nada Z7I

1. Introduction Z7I

II. The Structure of Annotinine 272

The Relationship of Functional Groups. ,. ...z7zDerivation of the Complete Annotinine Structure. z75The Configuration of the Remaining Asymmetric Centers and Some

Rearrangements , z80

~

x Inhaltsverzeichnis. -Contents.- Ts\.bie des matieres.

~

III. The Structure of Lycopodine; 283

IV. The Structures of Some Related Alkaloids. 286Acrifoline , 286Annofoline 287Fawcettiine and Clavolonine 288

V. Stereochemistry and Interrelations of Alkaloids with the LycopodineSkeleton ( 288

VI. The pytidone and Pyridine Alkaloids of Lycopodium. 290

Selagine 290The Obscurines arld Lycodine 293

VII. The Biogenesis of the Lycopodium Alkaloids. 294

References. 2afi

J Newer Developments in the Field of Veratrum Alkaloids. By C. R.

NARAYANAN, NationC1l Chemical Laboratory, Poona. India. 298

I. Introduction 300

Classification 300. -Occurrence 300. -Extraction 3°I.

Part A. The Jerveratrum Alkaloids 301

II. Rubijervine and Isorubijervine 30I

I. Structure and Configuration 301

2. Some Abnormal Dehydrogenation Products. 302

III. Jervine and Veratramine 304

I. Dehydrogenation Products 304

2. Structure of J ervi~e. 305

3. Structure of Veratramine 306

4. Jervine. Further Transformations. 3°7

5. Veratramine. Further Transformations. 311

IV. On the Configuration of Jervine and Veratramine 31I

V. Glycosides of the Alkamines 312

VI. Alkaloids of Unknown Structure 312

I. Veratrobasine 312

2. Geralbine. 3I3

3. Amianthine 313

VII. PharI!1acological Activity 313..

Part B. The Ceveratrum Alkaloids. 313

VIII. Occurrence 313

IX. Cevine :..'... 315

I. Dehydrogenation,Products and Skeletal Structure. 315

2~ Oxidation Products 3I7a) Decevinic Acid 317. -b) Hexane- and Heptane-tetracarboxylicAcids 319.

3. Alkaline Isomerization Products. , ~20

~

XI'---'

tnhaltsverzeichnls. ~Oolltentg.- Table desmatieres.

~

t

i

~

!

~,

"&

"tj

4. Assignment of Structure 322

5. Configuration 324a) Rings A and B 324. -b) COnfiguration at C12o) 325. -

c) Configuration at C(12P C(14) and CI17). (Th~ Two IsoIf1eric Ortho-acetates) 325. -The Relative Strain on the Ring D-Ortho-acetate 327. -d) Configuration at C(13P C(18P C(20) and C(22).(The Labile CI18)-Ester) 328. -e) X-Ray Study of the Cevine

Configuration 333.6. Cevine Betaine 333

7. Natural Esters of Veracevine 334

X. Germine 335.

I. Introduction. Alkalolds of the Germine Family. 335

2. Skeletal Structureof Germine ; 335

3. Alkaline Isomerization 335

4. Other Reactions 337

5. Periodate Oxidation and Structure 337

6. Configuration. .., 342

7. Natural Esters of Germine 346

XI. Zygadenine. , 346

I. Structure and Configuration 346

2..Natural Esters of Zygadenine 347

XII. Protoverine 348

I. Structure. 348

2. Configuration , , 351

3. Natural Esters of Protoverine 353.' XIII. Some General Remarks 353

XIV. Alkaloids of UnknoWIl Structure 354

I. Neosabadine 354

2. Veragenine 354

3. Fritillaria Alkaloids. 355a) Imperialine 355. -b) Peimine. Peiminine and others 355. -

c) Raddeanine 355.

XV. Pharmacological Activity of Veratrum Alkaloids. 355

XVI. Synthetic Esters and their Pharmacological Effects. 356

XVII. Biogenesis of Veratrum Alkaloids. 358

References. 361I

,

1 i

,

,

1

J Equilibrium Sedimentation of Macromolecules and Viruses in a Density

Gradient. By JEROME VINOGRAD and JOHN E. HEARST, CaliforniaInstitute of Technology, P~sadena. California. 372

I. Intrt;>duction. 373

II. Experimental Procedures , 377

I. Experiments in the Analytical Ultracentrifuge. 380

382

383

383

3833843843B5

." 386

2- Experiments in the Preparative Ultracentrifuge. ,

3. The Time to Attain Equilibrium. .0 , -

4- Recording of Results a) Absorption Optics ,-,._-

b) Schlieren Optics ,-,--

c) Autoradiograms d) Preparative Experiments. III. Theoretical Considerations and Evaluation of Results. ..

I. The Buoyant Medium 0 2. The Distribution of the Macrospecies. ., ~ 3- Experimental 'Determination of Various Density Gradients. 393

a) Composition Density Gradient ,...393

b) Compression Density Gradient 394

c) Physical Density Gradient " , 394

d} The Buoyancy Density Gradient , 394

e) The Effective Density Gradient.." , 394

4. The Determination of Buoyant Density. , 395

5, The Determination of the Solvated and the Anhydrous Molecular

Weight. 396

6, Effects of Macrospecies Concentration. 397

7. Density Heterogeneity , , , 397

8. An Alternative Method for Evaluating Molecular Weights. 398

IV- Applications to Some Physical and Biological Problems. 398

I- The Net Solvation of DNA ' " 398

2. Tr~nsfer Experiments with Stable Isotopes. , too

a) ReplicationofDNAinE:.coli ,... 4o0c,,~ b) R l ' t . f DNA - H ' h F~, eplcalono In 1ger orms , 4O2

"" C) Conservation of Ribosomal RNA during Bacterial Growth. 402

d) Transfer of Genetic Information to Ribosomes by Template RN A 403

3. The Guanine-Cytosine (G-C) Content of D.NA in Various Organisms. .4o4

) M- b '1 DNAa lcro la. ...,. .., 4°4

b) DNA in HigherForms 4o6

4. Separation of DNA Duplex Molecules into Single Strands and their

Recombination into Double Strands, The Formation of Heterozygote

Moiecules 406

5, The Buoyant Behavior of Bovine Mercaptalbumin and other Proteins 409

6. The Buoyant"Behavior of Viruses 4I2

a) Plant Viruses. ~12

b) Animal Viruses , 4I2

c) Bacterial Viruses 4I3

7. Buoyant Density Titrations 4I4

8. Buoyant Behavior of Synthetic High Polymers in Organic Density

Gradients 416

V. Tables 417

I. Density versus Refractive Index Relations for Various Aqueous Salt

Solutions. : 4I7

XIIInhaltsverzeichni ble des matieres.Conten1

2. Variation of po X:

3. Densities of Cesiun.

References.

[0-9 with Solution Density. \ Sulfate and Cesium Chloride Solutions.

423

423

425

425

440

445

445

447

448

448

449

450

45°

40;0

Current Theories on the Origin of Life. By N. H. HOROWITZ, California

In;titute of Technology, Pasaden~, and STANLEY L. MI.LLER, Scripps

Institution for Oceanography, La Jolla. California. ~ I. Introduction. II. The Nature of Living Organisms "

Wh t . L . f ,..

I. a lS le. 2. Nature of the Genetic Material 3. The Structure and Replication of DNA 4. The Heterocatalytic Fu.nction of the Genetic Material. 5. The Evolution of Proteins : 6. Conc'usions III. The Origin of Life on the Earth I. The Geological Record 2. The Formation of the Earth 3. The Primitive Atmosphere 4. Energy Sources on the Primitive Earth. 5.,The Synthesis of Organic Compounds a. Electric Discharges , b. Ultraviolet Light. c. Radioactivityand Cosmic Rays d. Thermal Energy. e. Synthesis of Purines and Pyrimidines. f. General Comments 6. Some Other Problems Connected with the Origin of Life. a. The Origin of Optical Activity b. Porphyrin Synthesis c. Organic Phosphates. d. 9xygen IV. Space Research and.the Origin of Life References

454


Sachverzeichnis. Index of Subjects. Index des Matieres

460

480

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