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Organic Preparations and ProceduresInternational: The New Journal forOrganic SynthesisPublication details, including instructions for authors andsubscription information:http://www.tandfonline.com/loi/uopp20

α-HALONITROSO COMPOUNDS. A REVIEWGünter Kresze a , Bernhard Ascherl a , Heinz Braun a & Helena Felbera

a Organisch-chemisches Institut der Technischen UniversitätMünchen , Lichtenbergstr. 4, D-8046, Garching, FEDERAL REPUBLICOF GERMANYPublished online: 12 Feb 2009.

To cite this article: Günter Kresze , Bernhard Ascherl , Heinz Braun & Helena Felber (1987) α-HALONITROSO COMPOUNDS. A REVIEW, Organic Preparations and Procedures International: The NewJournal for Organic Synthesis, 19:4-5, 329-426, DOI: 10.1080/00304948709356201

To link to this article: http://dx.doi.org/10.1080/00304948709356201

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ORGANIC PREPARATIONS AND PROCEDURES INT . l g ( 4 . 5 ) . 329-426 ( 1 9 8 7 )

a-- a"E . A REVIEW Giinter Kresze* , Bernhard Ascherl, Heinz Bran

and

Helena Felber

Organisch-chenisches Institut der Technischen UniversitSt Mihchen Lichtenbergstr . 4. D-8046 Garching

FEDERAL REPUBLIC OF GEWdW

I . ION.................................. .................... 331

11 . a-HALONITROSOALKANES ......................................... 332

1 . AND -SCRY ................................. 332

2 . ELEClXNIC SPECTRA, PH(JIDcHEMISTRY AND DISSOCIATION ........... 334

3 . PREPARATION ................................................... 338

a) From mimes ................................................ 338

i) a-Halonitrosoalkanes .................................... 339

ii) a-Halonitroso "penes .................................. 342

iii) Steroidal a-Halonitroso OMnpOunds ....................... 343

iv) Carbohydrate-derived a-Halonitroso Compounds ............ 345

v) Bifunctional a-Halonitroso Compounds .................... 346

vi) EXceptions .............................................. 348

b) From Nitroalkanes .......................................... 349

c) From Diazodlkanes .......................................... 352

d) Chloronitrosation of Haloalkanes ........................... 353

e ) pfiotochanical Syntheses .................................... 355

f) other Methods .............................................. 355

g ) a-Fluoronitmso Cmpunds by Special Methods ............... 356

i) via Radical Reactions ................................... 356

ii) Decarboxylation of Perfluoroacyl nitrites ............... 356

.

01987 by Organic Pmparations and Procedures Inc . 329

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KRESZE. ASCHEIIL. BRAUN AND FELBER

iii) Addition of Nitrosyl Compounds (NOX) to Fluoroalkenes .... 357

iv) Other Methods ............................................ 360

4 . REACTIONS ................................................... 361

a) Cycloadditions and Pericycl ic Reactions .................. 362

i) Diels-Alder Reactions of a-olloronitroso Compunds .... 362

ii) Diels-Alder Reactions of a-Fluoronitroso Compounds .... 371

iii) Ene Reactions w i t h a-Halonitroso Compunds ............ 372

i v ) 2+3 Cycloadditions .................................... 375

v) Reactions w i t h Fluoroalkenes .......................... 376

b) Reactions with Nucleophiles .............................. 377

i) w i t h Nitrogen Compounds ............................... 377

ii) with Trivalent Phosphorus Compounds ................... 381

iii) with Carbanions and Organomtal l ic Compounds .......... 383

iv) Other (mssibly) Nucleophilic Reactions ............... 386

c) Rearrangements ........................................... 387

d) Reactions w i t h Radicals .................................. 389

e ) Oxidation-Reduction Processes ............................ 392

f) Reactions not i nwlv ing the N i t r o s o Group ................ 393

g) Miscellaneous Reactions .................................. 395

111 . a - ~ I ~ ~ ........................................ 396

1 . STRUCTURE AND F'HYSICQL PFU)pERTIES ........................ 397

2 . SYNTHESIS ................................................ 397

3 . REACTIONS ................................................ 398

REFERENCES ....................................................... 401

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a-HXLONITR.OS0 COE!TOYX=!S. A R E V T E K

Gifnter Kresze* , Bernhard Ascherl, Heinz Bran

and

Helena Felber

organisch-chemisches mstitut der Technischen miversiut Mtinchen Lichtenbergstr. 4 , D-8046 Garching m m REPUBLIC OF CzxUQm

Although several articles dealing with the chemistry of nitroso com-

pounds in general have appeared in n-onoqraphs, and in review

the behavior of a-halonitroso compounds has been covered only

cursorily i n these compilations. lb our knowledge, the recent report on the

synthesis and properties of aliphatic fluoronitroso conpunds6 constitutes

the sole exception to the above statement. This is certainly due to the

fact that cOmpOunds of type &and - B have been curiosities for a long time.

X X \ 0 or / c=c, \ 0 0 \ C

N=O N=O A -

( X = F, CI, B r )

B -

Wrk on the structure and the chemistry of such coqounds in the last three

decades has, e v e r , revealed some properties of general interest. The

pertinent results of this w r k are now sumMlrized in this review.

33 1

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KRESZE, ASCHERL, BRAUN AND FELBEP.

II. a-HALONITROSOALKANES

1. STRUCTLTRE AND S-STRY

Bond length and bond angles have been determined for several a-haloni- 7,8 a

troso compounds and are compiled in Table 1 .405 In a t least t w CaSeS,

characteristic feature of the structure is the coplanarity of the X-C-N=O

group. Such an eclipsed conformation has also been assumed to explain the

mlecular spectra ( I R and Raman) of CF'3N09'10 and several perhalonitroso-

methanes." ~n the case of cl2arm, tm stable (eclipsed) conformational

isomers (cis and c~auche) are observed by I R measurements. l 1 The spli t t ing

of the IR absorption v (NO), 1558-1580 an- ' , for chloronitroso steroids

has also been attributed to rotational isomerism of the nitroso group.

The barrier to internal rotation was calculated to be of the order of

3217 J ml-' for (T3N0.' Assignments of the fundamental frequencies of

12

13 CF3N0377 and C C l p have been made.

I n the case of a-chloronitroso terpenes and steroids, some infor-

mation about the stereoimrism has been obtained from the H- and 13C-NMR

spectra. Diastereceneric mmpunds show differences in the chemical shif t

values of methyl groups attached to the ring and, mtirnes, of the ring

B-methine hydrogen atoms. 12,14,15 Tfie position (equatorial or axial) of

the NO group my be deduced, in sorne cases, by such shif t differences due

to the mgnetic anisotropy of the NO group. 14,15 The 13c-m spectra of

such diastereorneric chloronitroso derivatives .show significant differences

for the shif t of the carbon atom a to the cl/NO miety , l6 the deshielding

for the isomers w i t h an axial No group being less than that of the equa-

torial NO isorners. 14N and 15N NMR spectra offer information about Wther

1

structural aspect of nitroso cOmpOunds. There is a general proprtionali ty

between the N chemical shif t and the wavelength of the low lying

n 4 TK" band. 17-20 men fluorine or perflwroalkyl groups replace a l e 1

332

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a-HALONITROSO COMPOVNDS . A REVIEW

Table 1 : Ekmd mgths (r) and Bond Angles (4 ) for a-Halonitroso Curpunds

canpound r (N=O) r (C-N) r (C-X) (C-N=O) Ref.

(R) (2) (2) [XI

1.198 1.512 1.324 cF3* [Fl

1.171 1.555 1.321

[Fl Yo ON ec' 1.139 1.505 1.784

I

CI [Cl l

1.121 1.542 1.804

112.4O 25

121 .oo 26

116.5O 8

128 .Oo 24

[ C l I

a) 1.16; 1.21 1.52; 1.44 1.81; 1.75 117O; 119' 27 No

a) The asymnetric crystal unit cmsists of t w o molecules

substituents on the a-carh, an increase in nitrogen shielding by ca.

140 ppn follows the stabilization of the N(N) HoElD relative to the n

UJKI with the increase in electronegativity of the group bonded to the 21 The dipole mcment of CF3No (0.31 D) is rather low.

Whereas aliphatic C-nitroso CcmpOundS and a-haloderivatives of the

structure RcHxNo22 a h s t invariably exist as d k s , a t least in the so-

l i d state, intramlecular dimerizatim of a-chlormitroso c-ds RR'(3xNo

cccurs only in a few cases: - cis-l,4-dichloro-l,4-dinitrosocyclahexene (1) has

dissociation of this "dimer" seems to be effected by warming the solutim

to exist as an azodioxide (la) - even in solutim.8'23 he

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KRESZE, ASCHERL, BRAUP; A-YP FELBER

NO

L - c' 1 - l a -

a s w e l l as by irradiation with W Other, bicyclic cis-azo N,N'- -

dioxides w i t h a-chloro substituents do not give nitroso mnomers in obser-

vable concentrations up to 250 C (cf. p. 3 4 7 ) . From the absence of color

in solution, dimerization has been deduced for 2-chloro-2-nitrosonorbor-

nane;28 the sam conclusion has been reached for the reaction products of

chlorine with al iphat ic a l d o x i m e ~ ~ ~ on the basis of

o 166

1 H-NMR spectra.

T r i f l u o r o n i t r o s o m e t e (CF3No) yields an orange-red d i m r when irra-

diated with W and vis ible l igh t . This di rer is not analogous to that of

other nitroso compounds but has the structure (CF3I2N*; 30,31 its f o m -

t ion is reversible and the dimer is subject to further p b t o t r a n s f o m -

33 ti on^^^ and t h e m l y s i s .

2. ELEcTFX)NIC SPECTRA, DISSOCIATICN AND PHOIWHIXtSTRY

The a-halonitroso ccmpounds possess the three electronic t ransi t ions

shown usually by all C-nitroso ccmpOundS:

n - n*(or: n*-n*) appr. 15,000 [un-ll (E-20) refs . 15,34,35

(with vibrational f ine structure)

n - n*(or: n-n" 30,000 - 35,000 (shoulder) re f . 15

and n+n* 40,000 - 45,000 ( € = 62 500) refs. 15,35 0

The %-niabsorption band i s shifted bathochromally by 500 cm-' going

3 3 4

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a-HALONITROSO COEPOUN2S. A REVIEW

from eq-NO derivatives to =-NO axpounds in the mthane series;15 it is

observed for CC13No at 16,750 ( a = 5.6 in Ccl4l1' and for W3No at

14,500 ( C = 23.8) .36 This carpxmd as well as other perfluor0 nitroso

alkanes and analogues have been investigated in detail with respect to

the geometry of the excited state 36r37 and to fluorescence excitation and

life times.38-46 For a critical evaluation of the electronic structure

of a-halogeno nitrosocampounds cf. lit. 81-83, p. 337.

ORD and CD spectra have been reported for some nitrosoterpenes, 14,15

for (-)-2-chloro-2-nitroso-canphane and the (+)-enantimr of its 10-

sulfonic acid derivative^,^^ as well as for some a-halogam nitroso ste- r o i d ~ . ~ ~ 2- And 3-substituted chloronitroso mthanes show a Cotton

effect of the %4rcxband which depds an the stereochemistry. 14,15 The

relation between the temperature dependence of the CD spectra and the hin-

drance of rotation of the nitroso group has been discussed. trans- and

cis-l,4-Dichloro-l,4-dinitrosocyclohexane are highly efficient O2 ( 1 4 ) g -

40 quenchers and sensitizers of triplet states.

The above data form the basis for m y studies in the pbtolysis of

nitroso coqmunds (for earlier mrk on fluomnitroso cmpunds see ref. 6 ) .

By excitation of the " ~ 3 n transition, hamlysis of the C-No bond of a- a

chloronitroso cOmpOunds occurs invariably as the first step 34 , 49-55

followed by the formation of a nitroxide A.

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K R E S Z E , A S C H E R L , BRAUP; ANG FELBER

The fa te of this intermediate - A depends on the structure of the nitro-

so compound and on the reaction conditions. In mst cases, in aprotic sol-

vents, the dichloro derivative R R CC12, the ketone R R CO and the oxime

R R C=NoH are the main products in variable yields, whereas in methanolic

solution methyl n i t r i t e and the acetal R R C(oMe)2 have been obser-

Ved.

1 2 1 2

1 2

1 2

34,49,50,52

The primary step seem to be reversible a t least in the case of ste-

reoisomeric a-chloronitroso terpenes, the recovered start ing material con-

sists of an epimeric mixture. s' r56r57 Quantum yields for the pb to lys i s of

geminal chloronitroso mnpunds depend on the structure of the substrate

and on the reaction conditions but are wavelength independent.

The kinetics of pb to lys i s of a-chloronitroso carpunds has been investi-

gated by several groups.

16,51,58

51,59

The photochemical homlysis of a-chloronitroso conpunds in the pre-

sence of excess branine leads to the formation of gem-branochloroalkanes.

This represents a useful method for the synthesis of such compounds. 60

In the case of

[52:48 - 66:341 are

7s - 92%

chloronitrosarenthanes, mixture of diastereamers

produced. 51

Plmtodissociation lifetimes for CC13N0, CF3N0 and similar mlecules

have been determined in connection with the fate of fluorocarbns in the

amsphere. 53n62 For CF3N0, the photodissociation caused by visible

1 ight 63-69 *06 or vacuum ultraviolet , 70-74 (data for C ~ C F ~ N O cf . ref . 75) has

been investigated in great detail, m s t l y t o get information about the

electronic and vibronic s ta tes of the fragments. The so-called "spntaneous"

formtion of radicals from CF3N0 has been sbwn t o be due t o inadvertent

336

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a-HALO!JITROSO C0MPOS':;BS. E, F E V I E K

photolysi~.~~ The action of radicals produced by the photolysis of nitroso

cmpunds has been used for sensitizing photodegradations of polymers. 77-79

Besides dissociation, photoionization has been observed during the

vacuum W photolysis of cxmpunds CFnC13-nN0.80 Photoelectron spectra of

perhalogenonitrosamethanes 81'82 and of several a-halogenonitroso canpounds

indicate generally that the electronic structure is characterized by un-

usually strong lone pair interactions on the NO group giving rise to

n-/n+ splitting up to 6 eV and increasing considerably with increasing

electronegativity of the a group. The upper antibonding orbital (n-) is

follcmxl by strongly -ding and closely adjacent n (ND) and n+ M.O.'s

their ionizations are preceded by halogen lone-pair ionizations. The NO

group in aliphatic C-nitroso compunds is thought to have an electron-

withdrawing character conprable with that of fluorine.

83

81

Mass spectrometric measurements supplement the above photochemical

results. F m appearence potential measurements of a-substituted C-nitroso

ampunds, the following C-N bond dissociation energies are obtained:

D(CF3-NO) 32 and D(CC13-NO) 32 k~al/ml~~; D(Me2CC1-NO) is estimated to

be 35 k~al/ml~~. These low values were thought to explain the possibility

of C-NO fission by photolysis in the red region of the spectrum as well as

the fact that the dissociative ionization dominates the ion chemistry of

CF~NO.'~ mre recent investigations, howe~er,

determined by appearence potential measurements are too low. As mre reli-

able values for CF3W have to be considered 39.6 - + 0.2 k~al/rnl~~ or 42

- + 2 kcal/m1401, for CF2ClN0 39 kcal/ml.

that the D(C-N) values

402

Themlysis of CC13N0 87'88 resulted in a rrailtitude of products. As 89,90 usual, the first step here and in the shock-wave therrrolysis of CH3N0

(cf.ref.91) consists in the CX3-N0 dissociation. y-Irradiation of CC13N0,

too, leads to CC13-radicals, the major electron capture radical being

probably

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K R E S Z E , ASCHEF.:, BRA7h’ AND FELBER

3. PREPARATION

The various methods for the synthesis of a-halonitroso compounds are

compiled in this and in the next section. In general, the older examples

for these methodsfcovering the literature up to ca. 1970, have been sunma-

rized in Hob-Weyl. The mre recent developwnts on the synthesis of a-

halonitroso cmpunds are described below with particular emphasis on the

synthetic applications.

Caution! a-Halonitroso compounds are thermally unstable. Great cau-

tion should be exercised especially in distilling them, because if the

pressure is allowed to rise, explosions m y occur !

a) From O x h s

119

The reaction of aldoximes and ketoximes with halogenating agents

constitutes the classical method for the synthesis of a-halonitroso COP

pounds. The halogenating reagents mst widely used are chlorine,

bromine,96f loof 108‘124-132 nitrosyl chloride130t133-143 and preferably

alkyl hphlorites. 1 4 ’ 144-150 N-bromsuccinimide, 15’-’ 55 N-bromcet-

and N-chlorourealOO have also been used. The formation of gem-

halonitroso compounds is thought to proceed = an addition-elimination

15,50,93-123

mechanism.

R ‘C=NOH + X - Hal -

R’

x 1

0 fl II d Hal = C l , Br 0

II X = NO,CI , Br , RO, R - 6 - N H , HZN-C-NH.

II 0

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a-HXLONITRCSO COMPUL?DS. A REVIE;

The reactim ccnditions used ammnly depend on the halogenating

agents .The reactions of oximes with elenrentdl chlorine or bromine are

usually carried out in aqueous acidic or basic solution. In alkaline me-

dium, further oxidation of the intermediate gem-halonitroso compund by

h p h l o r i t e or hypobranite to the corresponding a-halonitro cOmpOund has

been observed occasionally.156 Organic solvents (ether, di-, tri- and

te t rachlomthane, methanol, glacial acetic acid) have been employed

advantageously for the reactions of elemental halogens at lower tempera-

tures. gem-chloronitroso campounds may also be obtained by treatnent of

ethereal solutions or suspensions of oximes with scrnewhat mre than tw

equivalents of NOCl w i t h cooling. A mild procedure for the synthesis of

a-chloronitroso wnpunds from aldoximes or ketoximes involves the use of

a w l hypchlorites in trichlorofluormthane solution. Due to its ease

of preparation,157 r-butyl h p h l o r i t e is mst frequently used: the wrk-

up is convenient and the yields are If chiral alcohols (e.g., (-1-

isoborneol) are used for the preparations of alkyl h p h l o r i t e s , opti-

146 cally active a-chloronitroso CcBnpOunds are formed stereoselectively.

Typical examples for the application of these methods are given below.

i) a-Halcmitrosoalkanes

a43lorcmitromcycloalkanes have been synthesized fran oximes with

chlorine in hexane solution. I-Chloro-1-nitrosocyclodecarle is a blue,

crystaline material; the 5-, 6-, 7- and Binembered ring compounds are dark

blue liquids wfiich may be purified by disti l lat ion under reduced pressure.

n = 4, 5, 6, 7 , 9

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KRESZE, ASCHERL, BRAUN AND FELBER

The m method was used to prepare gem-chloronitrosoadamntane 2 from

the oxime as shown below. Even the severely hindered 2,2,6,6-tetramthyl-

ether I RT in the dark

+ CI* _7

94 '1' 2 -

cyclohexanone oxime has been successfully converted (C12, in CFcl3) to

the gem-chloronitroso compound (40%) . Q-~ly one of the diastereomeric chiral a-chlormitroso conpounds (2) with

the axial nitroso group was formed from the oxime of optically active 9-

cyano-trans-2-decalone and x - b u t y l h p h l o r i t e . 148 As in similar cases,

this probably is due to the steric approach control of the reaction.

158

Geminal chloronitroso campounds

have been prepared from Mannich

60 ' l e

3 - with an m n i u m group in the B-position

base oximes by the use of tert-butyl hypo- - chlorite. The compounds are blue crystall ine solids which are stable in

the dark. ' 47 W i t h N-bromsuccinimide' 51 ' 53 or N-bromcetamidel 53 as

,OH N NO

R ~ - C - C H - C H ~ - N H R ~ II 8 3 x 0 1 ) R 3 X R ' - C - C H - C H Z - N R : I 8 0 X 2) (CH3)jCOCI I I

k 2 C I R 2

340

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a - H X O I ; I T R O S O COMP3rJNCS. A F.EVIEW

brominating agents, dialkylketoximes or cycloalkylketoximes afford a-bro-

mitroso derivatives which are easily oxidized to a-bromxlitro derivati-

ves with n i t r ic acid or a mixture of 30% hydrogen paroxide/conc. n i t r ic

acid. Subsequent reduction with sodium borohydride provides a practical

synthesis of SeCQndary nitmalkanes (yields 1+48%) and nitrocycloalkanes,

respectively.

3a - n = 3 - 6

NaBHL CHJOH/H~O* (CH2)n CH-N02 u

33 - 80 */e

33 - 80 */e

Another convenient preparation of secondary nitmalkanes in &rate to

good yields also involves the intermdiacy of chloronitroso mxtpunds,

prepared by treatment of an oxime with chlorine; the correspnding chloro-

ni t ro derivative, obtained by oxidation of the chloronitroso cOmpOund

with o m e , gives the nitroalkane on catalytic hydrogenation in the pre-

Sence of sodium hydroxide. 114

NO 03/CH2C12 R, ,NO2 D C C CI2ICH2CI2 R' 0

R' ' CI R' ' CI C=NOH R, R'

H21 Pd - C m R>CH-N02

NaOH R

37 - 95%

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KP,ESZE , A S C H E E L , BRAUIJ AIZ3 FELBPR

Several classes of a-halonitroso compounds derived from natural pro-

ducts have been prepared from oximes and are described in section ii-iv.

ii) a-Halonitroso Terpenes

2-CNoro-2-nitrosocqhe 5 w i t h the NO group i n the ex0 position has - 14,46,56 been isolated as the sole product from c q h r oxime - 4 and chlorine.

160 However, chlorination of camphor ox- under similar conditions was la ter

reported to give a 3:2 mixture of the =- and E-conpunds I6O [in that

reference, possible by a result of a mix-up, the NMR data ascribed earlier

to the - ~ O - c o m p O ~ n d ~ ~ were incorrectly ass ign4 to the =-isomer]. Irra-

diation of - 5 with red l ight produces isomer - 6 , which has been shown t o

arise by interchange of the No and C1 group in position 2. 15’ The 2-chloro-

2-nitroso derivatives of pinane, carane and rrwthane, prepared analogously

from the oxires and chlorine, also sbwed p h t o i s o m e r i ~ a t i o n . ~ ~ Treatment

of 4 w i t h potassium hypbromite w i t b u t isolation of the in t emdia t e bro-

mnitroso compound gave diastereoselectively 2-~-brom-2-enen-nitrobr-

nane 1. 132 Surprisingly, t!-ie attack of bromine in this case takes place

exclusively from the mre hindered side.

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a-HALONITROSO COMPXTK3S. A REVIEW

Halogenation of (-) -mthone oxhe gave 3-halo-3-nitrosomthanes (8) - hhich could be i m r i z e d on silica gel to the corresponding d i a s t e r m s

- 9.” The m t h a n e skeleton remains unchanged during t h i s isomerization as

shown by the synthesis of both the diastereomeric a-chlomnitroso deriva-

t ives start ing with isomenthDne axhe. 15

siiica gel

A d:, A A

x 2 .

9 - 8 - X = C I , 69’/0 x = CI. 12%

X = Br, 21 ./. X = Br. 67%

Mixtures of diastereomeric a-chloronitroso terpenes have been obtained

from the reactions of E - b u t y l hypochlorite w i t h the oxim of 3-methyl-

cyclohexmone , canam=n*e, f m c b n e 14,56 and thujcme.160 me diastereo-

mer of 2-chloro-2-nitrosofencnchane was found to be quite unstable; it under-

went epimerization during mrk-up by colm chranatcgraphy even a t -30 . o 14

iii) Steroidal a-Halonitroso Compounds

Treatmnt of the 3,2O-dioxims of pregn-rl-ene-3,20-dione, Sa-pregnane-

lla-ol-3,20-dione and 5a-pregnane-3,11,2O-trione with chlorine gave the

corresponding 3,2O-dichlor0-3,2O-dinitroso derivatives. 154,161,162

y 3

C=NOH CI ’NO

CI

ON

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K P E S Z E , ASCHERL, BRAUFJ AND FELBER

3,7,l2-Trioxocholanic acid trioxime gave the 3,7,12-trichloro-3,7,12- tri-

nitroso CaTlpound. These blue crystalline carcpounds did not dirrrerize and

w.re stable at roan temperature for years. 62 chlorination of the .~a-cho-

lestan-6-0ne oxim in the dark yielded the 6a-chlor0-6B-nitroso derivati-

ve - 10. Sa-cholestane could be prepared. 17-Y.droxyimino-5a-andmsMe gave the

17-cN0ro-17-nitroso derivative. 54 The 3-chloro-3-nitroso-5lestane

154 Ardcgously, the 3-, 4- and 7 ~ h l o m i t r o s o derivatives of

#H:l,2 17

20"/10 min e t h e r

10 ON"=CI - II NOH

was later shown to be a mixture of the 3a-chlorc-3fi-nitroso (main prcduct)

and 3~-chlOro-3a-nitroso derivatives. 15

By treatrrrent of e p i a n d r o ~ e oxime w i t h E-butyl hypochlorite,

a mixture of the two diasterecmeric a-chlomitroso ccmpounds is forrred

fmn wh ich the enantimically pure 17a-chloro-17B-nitroso 1SCmer 11 could be separated by Hpu3. 49 The two-step procedure for the synthesis of

nitro caqmunds f m axirrres 15' t155 has keen applied to steroid oximes, for

example, 3a-ace~-lll3-~dmxy-l7~-nitro-5~-andms~e _- 12 and 3B-acetoxy-

17B-nitro-5-androstene 13 were prepared fran the correspnding steroid

344

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a-HALONITROSO COI-!POLTSS. A P-EVIEW

1. NBS/Dioxane-H.$

2. NaBHL AcO’

12 - H 29 *I*

5 5 *I* 154

gembrcarpnitroso and bromnitro compounds in l o w yield.

iv) Carbohydrate Derived a-Halonitroso Compounds

The intermediate forrnation of geminal chlomnitroso conpunds and

their dirners in the chlorination of aldehydo sugar oximes to hy~xirrrryl

chlorides 116‘163 could be denanstrated by NMR. 164 ~n some instances,

these intermediates could be isolated.116 Treatment of tri+acetyl-D-

CH=NOH

8 2 *I*

glucal w i t h an excess of nitrosyl chloride yielded the ggwchlomitroso

cOmpOund 14 via the dimeric nitroso cOBnpOund and the ~xime.’~’ D i a s t e r e o -

selective broynination of several aldDnolactone 0x-s (e.g. 15) gave the

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K R E S Z E , A S C H E R L , BRAUrI AND FELSEF.

C H 2 0 AC

OAc OAc NOH NO CI

II -2

corresponding bromnitroso compounds which were oxidized to the stable bro-

mnitro derivatives in overall yields ranging from 38 to 86%.165 The reac-

tion of -- 15 with -- tert-butyl hphlorite gave diastereoselectively the a-

chloro-a-nitrosoether 16 in nearly quantitative yield. 150

16 15 - - v) Bifunctional a-Halonitroso Ompunds

The chlorination of the cyclohexane-1,I-dione-dioxime 17 in concentra- ted HC1 gives a mixture of the trans- and cis-dichloro dinitroso mvunds

(18 I and 2) . C h standing in HCl/acetic acid at room temperature, 18 is con- verted the reverse reaction to the thenrodynamically mre stable cis-

CI

ON

18 -

- H C I / C H3COO H

HNoH c1* H O N ~ ,7 -

19a -

346

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a-HAL3NITROSO COMPOURDS . X REVIEW

isoaner 2 I2O (cf. p . 3 3 3 )

oxide 19a. In contrast to the above example, the colorless am dioxide 22 - prepared fran dioxime 20 via the blue dichloro dinitroso cOmpOund 21 - once

formed, is not equilibrated w i t h the "n~ncmer" 21 prior to decorpsition. 166

"dimerizes intranolec~larly" to the a&-

- --

--

For dichloro-dinitroso and trichloro-trinitroso derivatives of steroids

see p. 3 4 3 .

Chlorination of malondldehyde dioxime normdlly leads to plychlorina-

ted derivatives. under carefully controlled conditions, the 1,3-bis-chloro-

1,3-nitroso propane - 23 could be obtained in 30% yield together with the tri-

chlorinated cmpund 24. 115,165 Compound 23 is stable in ether, ethanol or

NOH It N=O

\0 N=O C I cI, 0

CH CH 'CH I CH2 + CI2

I

I + CHCl

I - 70°C/2 min I ether CH II NOH

CH N'

CI N=O

CH 0\

C I N=O

24 - 23 - benzene solutions even upon warming. By heating in 13Mso the isomeric bis-

hydroxamic acid dichloride - 25 could be obtained in 67% yield. 2,4-Di-

CH2 9OoCI45 min

DMSO 23

I NOH - @ -

t 'CI

25 -

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KRESZE, ASZHERL, BRAUN AP!D FELBER

chloro-lr4-dinitrosopentane - 26 has been synthesized from ptane-2,4-dione

dioxime and - tert-butyl hphlorite. The bifunctional chloronitroso compound

m y be useful in crosslinking polymers. 144

CI CI

I

(CH313COCL I I CH3-C-CH C-CH3 CH3- C-CH2- C-CH3

I NO NO

II 2- II NOH NOH

26 - vi) Exceptions and Side-reactions

The formation of a-halonitro carrpounds from oximes and elemental halo-

gen ’ 32r ’ 56 ‘ ’ 77 or N-bmsuccinimide ’ 3’ ‘ ’ 5’ ‘ ’ 53 by further oxidation of

the intermediate nitroso derivatives has been reported. With aldoximes,

tautanerizatim to the corresponding hydroximic acid chlorides and further

chlorination to give 1,l-dichloronitroso canpun& occurs. 178

CI CL I

I -HCI I CI CI NO

R-CH: y R - C z N O H R-C-NO

The chlorination of chloral mime gives tetrachloronitrosoethane

a blue liquid, which deposits colorless crystals of trichloroacethydroxi-

mic acid chloride 2 on standing. No pentachloronitrosoete was obtai-

ned. ’ ’

as

Dehydmhalogenation of hydroximic acid halides formed in side-

/,NOH - CI3CC\ CClL 2‘ 20-60’ \ NO CL

CL3CCH C13CCH=NOH + CI2

27 - 28 -

reactions in basic media m y yieid nitrile oxides, which m y dimerize to

furoxanes. 133,179-184

R HR

NO - 2 R C S N O - N\ 0 NOH

- 2 HX 0 2 R-C@ ‘X

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a-HALONITROSO COMPOLVIDS . A P.EVIEW

The addition of nitrosyl chlorides to oximes n o d l y leads to -0-

ronitroso cOmpOundS, but exceptions are also known for this meth0d;in special

cases the mimino group is oxidized and nitrimines are isolated. 142

R T + NOCl

The reaction of nitrosyl chloride w i t h a,B-dibrmmximes also gives

chloronitrimines. This process consists of tw separate reactions: replace-

ment of the activated bromine by chlorine and oxidation of the oximino

function to a nitrimine. 143

CH30 0 C H - C H - T - C H C H O O e C H - C H - C - C H 3 - NOCl

I I II sealed tube - 1 1 Br Br NOH CI 6r N - N 0 2

b) From N i t r o Ccanpounds

Chly a few examples for the preparation of nitroso ccmpunds by reduc-

tion of nitro cOmpOunds are described because of the difficulty i n stoping

the reaction a t the correct stage. 167 'Prichloronitrosarrethane has been pre- 168 pared by cathodic reduction of trichloronitmwthane in yields up to 70%.

Elect ro I y s i s CI3C-NO2 CCI3 NO

EtOH I HzSOr,

29 - Dimeric a-chloronitrosoethane is reported to be formed by treatment of the

sodium salt of nitroethane w i t h excess hydrogen chloride. 163

Z R-CH=N @0- Ole - HCl l ether [ R-!;NO] \ONa - NaOH

2 30 -

If R is an acceptor group (R = COOH, COOR, CN, Ph) only the corresponding

hydroximic acid chlorides can be isolated. 69 ' 70 Mmomeric chloronitroso

349

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KRESZE, ASCHERL, BRAT: A m FELBER

conpunds, howver, have been obtained in a similar way from a-disubstitu-

171 ted n i t r o cOmpOunds in good yield.

@ 51' HCl/ether R,C/ NO >C=N'- - R'ONa R

R' ' CI \ ONa -NaOH CH-NO2 - R'

R' -R'OH R

The reaction of polyfluoronitroalkanes containing an acidic hydrogen

atom with benzoyl chloride in the presence of triethylamine gives a-chloro- 172 nitrosoalkanes and, as a secondary product, the corresponding ketoxime.

- 1 5 O (CF312CHN02 + PhCOCl + NEt3 without

I,?

NEt3He 0

- PhCOZNEt3H CI ( C F ) C'

29 %

CF3,L m/E? C=N

Q-i-Ph 3 2 'NO cF3

When chlorofluoronitroacetic acid is heated w i t h 21% hydrochloric acid di-

c h l o r o f l u o r o n i t r o s t h a n e 2 is formed. The *-form of the n i t r o compound

is thought t o be an intermediate. 173 The same reaction occurs w i t h

MI (NO2) m2H. 407

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a-HALONITROSO C9MPOUNDS. A ?,CVIEW

a-Nitmcarbqlic acid chlorides, e.g. chlodtroacetyl chloride or di-

chlomitroacetyl chloride are converted to chlomnitroso ccmpOundS _32

and - 33 in t!! presence of A1C13 or A D 3 . 174

32 R = H (42 -La0 / . , as dichloroformoximel - 33 R = CI SO"/. -

From a-substituted nitroalkenes and hydrogen chloride, 1,2-dicNoronitroso

compounds have been prepared. It was suggested that the init ial step is a

1,4-addition of hydrogen chloride to the nitroolefin.

R2 I

I I CI CI R1 = R2 = CH3 ( 35'/0)

RICH-C-NO R1= H I R2 = CH3 (45'l.I

If an a-hydrogen is present (R2 = HI, the correqmnding a-chlorohydroxamic

acid chlorides are formed. 175 The conversion of nitroolefins into 1,2-di-

chloronitroso cOmpOundS may be achieved also by reaction with phosphorus

pentachloride. 176

y 3 PC15 /CCId CH3 I * CH CH-C-NO POC13

3-1 I CH3- C H=C- NO2

35 1

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KRESZE, A S C H E R L , BRAVTI A N D FELBER

c) From Diazoalkanes

a-Chloronitroso ccmpOundS should be the primary reaction products of

diazo compounds w i t h Nocl. Wwever, they have been isolated only in a few

cases; thus, the deanuna ’ tion of fi-octylamine w i t h nitrosyl chloride in

aprotic solvents gave two main products, l-chlorooctane and l-chloro-l-ni-

trosooctane 34, which rapidly rearranged t o octanoyl chloride ox& 35. Compound 34 was also shown to be one of the products from the reaction bet-

2 RCH2-NH2 + NOCl - RCHN2 + H20 + RCH2NH: CI’

NO ,/NOH

CI RC, R-CHN2 + NOCl - RCH, ’ -

- N2 CI

35 - 31 - R = n-C7H5

Wen diazooctane and nitrosyl chloride. 185 The formation of diazoalkanes

from primary amines and nitrosyl chloride in aprotic solvents is w e l l do-

c m t e d . 185’ 186 Nitrosyl chloride converts ethyl diazoacetate into ethyl

chloroacetate and a plwr believed t o have arisen from n i t r i l e oxide

36. 187 Nitrosvl chloride reacts with tho mles of perfluoroallql diamm- I

EtOZCCHN2 + NOCl - +

POLYMER

thanes in an analogous way to form hydroxirroyl chlorides and the dimers of

the nitriloxides, furoxanes, the former predominating. 188

+ ,/NOH

‘CI RFCHN2 + NOCl - R C

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a-HkLONITROSO COMPO'L.JDS. A REVIEW

d) chloronitrosation of Haloalkenes

In general, chloronitrosation with nitrosyl chloride witbout catalysts

and without irradiation takes place only with olefins highly reactive in

electmphilic additions. In the reaction of l-chlorocycloptene 21 with nitrosyl chloride, 1,2-dichloronitro~clopentane is formed as a mixture

of the mmmeric and dimeric The reaction of 2-chlor0-2-butene

C H2Cl2 NOCl - Q

dl c{ NO

50% 19 */* 37 - with Nocl in a sealed tube gives 2,3-dichlor0-2-nitrosobutane 2 and 2,2-

- 30 35% - 39 42%

dichloro-3-nitrobutane 9. The formation of the nitro derivative has been explained by a radical process. 189

Prolonged standing (3-15 days at 20°) of mixtures of nitrosyl chloride

and chloro- or fluoroethenes in sealed tubes did not give nitroso cOmpOundS.

Instead, nitro aqmmds along with other products were isolated. 190 Qily

in the case of l-chlom-2-fluoroethene did nitrosochlorination occur; the

hydroximic acid chloride was is01ated.l~~ In the dark and above looo,

R T ,,NOH F C H = C H C I + NOCl FCHCI-C, Cl sealed tube

353

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KRESZE, X S C H E R L , BRhUlI A N 2 FELSER

nitrosyl chloride behaves as a chlorinating agent; in sunlight a t room tem-

perature it reacts as a chlorinating, nitrosating, nitrating and oxidizing

reagent. 92 Tetrachloroethene yields hexachloroethane , pentachloronitroso-

C12C=CHCI + NOCl ---/ sun l i g h t CHC12CC13 + CCl3CHCINO + CC13CHCIN02

+ CHC12COOH + other products

ethane and tetrachloro-2-(pentachloroethyl)-1,2-oxazetidine. With U C l 3 as

a catalyst, chloronitrosation of chloro-, dichloro-, trichloro- and tetra-

fluoroethenes has been achieved: tetrachloroethene failed to react. 193

AIC13

- 20'1 - 30' R-CH=CHCI + NOCl b

AIC13

-20Ot0 -30' R-CH=CCI2 + NOCl *

// N O H R-CHCI-C,

CL

R- CHCI-CC12 NO

R = H , 72%

R = CL, 30%

The addition proceeds with anti-Wkovnikov orientation and is accompanied

by t e l m r formation. The nitrosochlorination of fluorochloroethenes may

be achieved also in the presence of F&13 a t 45O i n a flow reactor. 194

FeC13 CF2=CCI + NOCl - CF2CI-C(X) CI NO I 45'1 2Lh

x X = F, 80%

x = CI, 0291.

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a-EALONITROSO COMPOUNDS. A R.EVIEU

a-Halclnitroso derivatives have also been obtained by photocherm 'cal reacticns

of nitrosyl chloride w i t h haloethenes. 194

e) photocherm 'cal syntheses

The photochemical gas-phase reaction of an alkane w i t h nitr ic oxide

and chlorine or with nitrosyl chloride may lead to bis(nitrosodlkanes1 and

gem-chlorcmitroso cornpunds and oximes, depending on the reaction conditions

and the amcentration of starting mterids. lo2 95 , lo3 T r i ~ o m i t r o -

somethane fi has been prepared by irradiatian of an equirrplar mixture of

nitrosyl chloride and chlorofoxm. High-energy electron radiation-induced

reactions of nitric oxide with tetrachloromethane or bramotrichloromthane

gave - 41, hhile dichloronitrosomethme, dichlorofomldoxime and 41 were ob-

tained f r o m chloroform. 198,199

R - rays x c C l 3 NO CI3CNO X = C l , Br

41 - f ) OtherMethOds

Che of the syntheses of trihdlonitrosomthanes (41 or 42, resp.) in-

valves a tm-step reaction starting w i t h methyl trihaloacetate and hydro-

- _-

qlamine. Thermdl deccanposition of the primary products, trihaloacethydro-

x = CI, 85% 4 l , X = CI, 62%

X = F , 76% G t , X = F , 63'/.

200 xamic acids, gives fi (or -- 42) and paraformaldehyde as the main products.

Conpnmd - 41 was prepared f i r s t by the reaction of trichlorcmethylsulfinic

acid w i t h nitric acid a t relatively high temperatures.

law-temperature synthesis f r o m sodium trichloromethanesulfinate and nitro-

syl chloride has been reported.

201, 202 An improved

88, 203

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KRESZE, ASCHERL, BRAUK AND FELSEP,

C13C-S02Na + NOCl - 41 + SO2 + N a C l -

g) a-Fluoronitroso Compounds by Special Methods

6 As reported before, a comprehensive review of the synthesis and

perties of fluomnitroso CCmpOUnds, covering the l i terature up to 198

has been published. The intention here is to u-te t h i s review.

pro-

I

i) y& Radical %actions

Photochemical nitrosation of dichlorofluormethane and chlorodiflu-

oromethane with nitrosyl chloride afforded the corresponding flwronitroso

ccanpounds 43 or 44 respectively.

h V SOOW mercury arc

1 96

R - H + NOCl R-N=O + HCl

R = C C l 2 F ( S l I CCIFz(LLl - Analogues treatment of trifluorcaoethane and formy1 fluoride failed t o give

the corresponding nitroso compunds. CF3N0 has been prepared by the photo-

chemical reaction of CF31 with an excess of NO in the presence of Hg. 283 , 381

ii) Decarboxylation of Perfluoroacyl Nitrites

Compound 44 was prepared in a one-pot reaction from nitrosyl chloride

and sodium chlorodif luoroacetate. 204 Nitrite esters of perf luorosuccinic

1L8'12 h d i g l y m e

C IF2CCOONa + NOCl - C l F 2 C N 0 + N a C l + C 0 2

and perflwrogl.utaric acid are easily prepared from the corresponding di-

acid anhydrides and methyl n i t r i t e in nearly quantitative yields.

The same products were obtained in yields of 85-95% by the nitrosation of

the silver salts of the mnoalkyl perfluorodicarboxylates with nitrosyl

chloride. 208t382 Themlysis under reduced pressure (yields 38-45%), m-

205-207

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a-HALCNITROSO C@P:FO=I?:3S. k REVIEF'

A RON0 NOCl

d sealed tube

(CF2In 0 - R02ClCF21nC02N0 0 R02C(CF2)nCOOAg R T /1-2 h - 2 0 /2h

II 0 R =CH3 n = 2 , 3

lys i s or W irradiaticm (yields 20-47%) of these n i t r i t e esters gave the

co r re spd ing nitroso coqounds. 203t3a2 he nitroso esters m y be m v e r -

A o r h V R02C(CF21n-C02N0 - R 0 2 C(CF21n NO - coz

ted into the mrrespnding acids by hydrolysis in neutral

boiling acetic acid.

or in 208

"rifluoronitrosomethane -- 42 has been prepared in 77% yield by pyrolysis

of nitrosyl trifluoroacetate in a flow of nitrogen mmxide a t 190O using

refluxing perfluorobutylamine as a diluent.209 ~ L e r perfluoroallcy~itmso

ccdnpounds (C1-C,2) my be obtained analogously. 210

0 ii 190°/ NO

CF3-C-O-NO - C F 3 N O + C 0 2 (FgC413 N

77%

42 - iii) Addition of Nitrosyl Compounds (NOX) to Fluomalkenes

Trifluoramine oxide has been found to react rapidly with n i t r i c oxide

to give nitrosyl fluoride. This reaction has been used as an in s i tu

3 RF-CF=CF2 + 2 NO + NF30 K F ' 2 - 4 d 3 R F C ( F I C F 3 R T I C H 3 C N I

NO

357

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KP.ESZE, A S C H E R L , BRAVN AND F E L B E R

source of nitrosyl fluoride to synthesize a-fluoronitroso compounds f r o m

f lwroalkenes. 21 1

The preparation of perflwro-2-nitrosopropane 45 f r o m hexafluoropropene

and nitrosyl chloride via the indirect "silver salt route" proved to be

highly useful. 212

KFlCF3COOAg CF3-CF=CF2 (CF3 12 CFAg

CH3CNI R T I 1 h * sealed tube

NOCl

20 ' 1 2 h - (CF312CFN0 (80% over a l l )

The method w r k s also w e l l for the follcwing Perfluoroni-

y 3 cF3,C=CF2 CF3-C-NO CF3' I

cF3

trosoalkanes prepared by t h i s route from perfluoroalkenes are interesting

intermediates for the conversion of these alkenes into perfluoroketoximes

(e.g- - - 45 4 6 ) . 214 D i r e c t f luor ide in i t ia ted react im of hexaflwmpmpene

KH SO3 /20° CF3CF=CF2 - (CF3I2CFNO . (CF3 12 C = NOH

45 6 2 ' f a

46 - with nitrosyl chloride and cesium fluoride was found to give an approx. 6:l

mixture of heptafluoro- and l-chlomhexafluoro-2-nitrosoprope (45 and 4 7 ) .

212 When CsF was substituted by CsC1, 9 coul? be isolated in 91% yield.

358

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a-HALONITROSO C9MFOUKDS. X REVIEW

2OOILd cF3\ HF + CF3, C 0 F CF2C10 ' NO

/ \ CF$F=CF2 + NOCI + CSX - CF3 NO sulfolanc

- 47

X = F : 6 1

x = C I : - 91 */*

- 45 -

Hexafluorocyclobutene and octafluorocyclopentene reacted with an eccess

of nitrosyl chloride in the presence of excess KF to give an 80% yield of

heptafluoranitrosocyclobutane _- 48 and nonafluoronitrosocyclopentane 42, re- ~pectively.~'~ Unlike C F p , both cyclic nitrosofluomalkanes were found

n = 2 , 3

to be stable mnomers.

80% 9: n = 2

9 : n = 3

Hexafluoroacetone mime nitrite adds to 21nethylpropene and tetra-

methylethene at -15O to Oo to give nitrosoalkenes containing the hexaflu-

orodimethybthylenneaminoxy group.217 ~ o c l reacts with the en01 of penta-

R = H,CH3

fluoroacetone without solvent at -78O to give the corresponding nitroso

conpund 51 which is stable at -60° but deampses on warming to room tan-

peratwe. The corresponding ethyl enolether does not react with Nocl

either at -78O nor at 25°.216 Hydrolysis of 50 yielded the gem-diol 51. - - OH OH

NOCl I H20* CN-CF2-C-CF3 I CF2=F-CF3 - ON-CF C-CF3

OH CI - 780 2- I 00 I

OH

- 50 - 51 65 Y e

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KRESZE, ASCHERL, BRAUI! AFTD FELBED

Nitrosyl fluorosulfate does not react in inert solvents with tetra-

fluoroethene in the absence of strmg acid. €Imever, w h m an excess

HS03FI 60' F2C=CF2 ONS03F * ON-CF2CF20S02F 0 - N-CF2CF20S%F

I I CF2- C F2

56 *I* 20 .I.

of tetrafluoroethene is bubbled through a mixture of nitrosylfluomsulfate

and fluorosulfonic acid dissolved in tris(perflmrobutyl)amine, the blue,

liquid nitroso cOmpOund 52 is collected from the gaseous current in a

cooled trap. From the remaining solution, the 2+2 cycloaddition product

of tetrafluoroethene and -- 52 could be isolated.218 The addition of nitro-

sylfluorosulfate to trifluoroethene takes place analogously. 21 9

20 O CHF=CF2 + O N 0 3 S F - ON-CHF-CF2Q3SF

49 OI*

iv) Other Methods

"reaimxk of hexafluorodimethylketene with nitrogen mnoxide in liquid NO2

gave perfluoroacetone oxime nitrite 22, which reacted with tetrafluoro- ethene at 150° to yield the addition product - 54.220 With Rl3, -- 53 gave the

CFz'CF2 (CF3 )zC=NO NO - NO2 C=C=O + NO

cF3,

CF3' - 5/10° * l 5Oo - 53 70%

I CF3 l2 C = NOCF2CF2 N 0

5L 35% - ~hlormitroso cqmund 55 m g other products. 220 "rif luoronitroso-

methane is formed in the reaction of (a,) jsn ( W 2 ) with (a3) 2cd (diglyd

as the mly volatile product. 221

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a-HALONITROSO COMPOUNDS. A REVIEX

20° NO (CF3)2C=N-ONO + PCI3 - ( C F ) C’ 34 %

3 2 ‘CI 53 c

4. EWCTIONS

55 -

‘Ihe often cited analogy between nitroso and carbonyl compounds - nucle- ophilic additions as the most cmmm reaction type in both cases - holds only as a first approximation; in many cases, subsequent transfonmtions or

another course of the first step (e.g. electron transfer instead of polar

addition) change the results of a reaction entirely. For a-halogmated

nitroso compounds, this is especially true if a single chlorine (or bro-

mine) is the a-substituent whereas perfluoro derivatives behave somewfiat

more “normally”, although these derivatives s b w m y other types of reac-

tions unknown in the case of carbonyl cOmpOundS.

Generally, nitroso ccqounds and their a-halogam derivatives are mch mre

prone to pericyclic reactions than aldehydes or ketones; they are m g

the mst reactive diqhiles and some derivatives undergo

readily. Therefore, this review will discuss these reactions first. 2+2

Cycloadditions of perfluoronitroso capounds form a special topic; as

stated earlier, only nay developnents which have been disclosed since the

publication of the Russian review article will be covered.

reactions

6

Nucleophilic additions, reactions with radicals,/(prinrary) nitroxide

formation and oxidation-reduction reactions are discussed in other sec-

tions of this chapter which sumnarizes also same transfonmtions which

can be classified only arbitrarily.

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KRESZE, ASCHEP.L, BRAUN AND FELBEF.

a) Cycloadditions and Pericyclic Reactions

i) Diels-Alder Reactions of a-chloronitroso Cmpunds

Since a-chloronitroso cOmpOunds have been found to act as dienophiles

in Diels-Alder reactions by Wichterle,222 m y papers dealing with this

reaction have appeared. The subject has been investigated extensively by

the groups of Wichterle,

Kresze 149‘150’236-251 and the results have been reviewed several

times. 252-255 The first formed cycloadciucts ionize to give immnium salts.

222-228 Arburn, 229-232 233-235 and

- [ c’ - c? ‘IeR1] - R ~ O H

N‘ 0 e ‘C ‘R2

N, ,R1 C CI‘ ‘R2

R’, / OR^ C

N H * HCI R2’ ‘OR3

56 - In the presence of an alcohol in the medium, these salts are solvolysed to

the hydrochlorides of 3,6-dihydrmxazines unsubstituted on the N atom. The

reactivity of the No-compound depends on the electron acceptor properties

of the a-substituents. Electron-withdrawinq substituents increase the reac-

tivity. Thus, CCl3N0 and especially cF3N0 are known to be m n g the most

reactive a-halonitroso dienophiles.

ro-Diels-Alder reaction, including that of l-chloro-1-nitroso canpounds,

234 236 The regiochemistq of the hete-

has been surveyed several times.119,236,237,254,256 ~n general, the orien-

tation in the cycloadditian depends on steric as well as polar factors. Ihe

-1 group bonded to nitrogen will allm this atan to approach mre readily

the last bul@ end of the dime. ckl the other hand, the nitrogen atan binds

preferentially to the carh atan of the 1,3-diene with the maximal electron

density.

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a-HhLONITROSC COMPOUNDS. A REVIEW

The 3,6-dihydro-l,2-oxazines are widely used in the synthesis of M-

turd products or heterocycles. Mst of the reactions will begin with the

cleavage of the NO bond, thus providing amino alcohols, which are useful

starting mterials for the synthesis of aminosugars, inosamines or other

polyhydmxymino derivatives.

60 - 61 - I

HO lii, C H 3

62 -

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KRESZE, ASCHERL, BRAWN AND FELBER

The first route to some aminosugar derivatives was devised by Belleau

and Y m k i n A u - ~ a n g . ~ ~ ~ The reaction sequence involves a Diels-Alder conden-

sation between methyl sorbate and l-chloro-I-nitrosocyclohexane to give the

adduct - 57. Selective hydroxylation affords, stereospecifically, different

amino sugar derivatives. Thus, hydroxylation of the N-benzayladduct - 58 with

osmium tetrcmide followed by hydrolysis and catalytic hydmgenolysis gives

the amino acid -- 59 of the allose series, while epxidation to a 1:l mixture

of the epoxides 60 and 61, oxirane ring opening with formic acid, methanoly- sis and, finally, hydmgenolysis leads to the amino acid 62 of the N o s e

I

NHRS N H R 5

series. Kresze and caworkers have utilized the adducts of l-chloro-I-nitre

socyclohexane with various l13-cyclohexadienes as key intermediates in the 238-243,245-250 Reductive synthesis of inosamine and inosamine derivatives.

cleavage of the -bridge of these cycloadducts leads to the e-4-amino-

cyclohexenols - 63. Simple but highly specific reactions on the double bond

afford the plyhydroxyamines - 64 which m y serve, inter alia, as substrates

in the mtasynthesis with streptomyces griseus. For example, cis-hydroxyla-

tion and acetylation of compound 65 gives the 2t13t,4c-trisacetoxy-lr-amino

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a-HALOMITROSO COMPOUNCS. A REVIEW

6 OAc

65 -

derivative -- 66

6 5 -

1 ) KMnOb / H 2 0 AcO .. ACO’

2 ) A c ~ O

0 Ac

66 -

OAc

67 2\ W.-p 2 ) 11 Hfl Br2 . Aco$Ac -

3 ) AczO Br OAc ” ko4c/h04c A c O G c

AcO’*

OAc

68 - while reaction w i t h Br2 wi th neighboring group participation

and solvolysis under different conditions leads to the a l l - c i s -67 or the

2c, 3 t , 4c-cmpund 68, respectively. 238‘246 In an analogous way, konduramine

F1 - 69 and ChiroinoSamine-1-hexaacetate 70 have been synthesized from adduct

63 (R ,R = QAC). 1 2 239,240,243,247 -

N H A c AcO.. OAc

D O A C *‘OAc + cGo n, Q.1;: -4 AcO‘. 0 Ac OAc

OAc

70 - 69 -

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K R E S Z E , A S C H E R L , BRAE:: AND F E i B E F

Deacylated 69 is incorporated in saw S. griseus mtants, the resulting

aminoglycoside products show &tibiotic activity. 248’258 ‘Ihe Diels-Alder

reaction of - cis-1,3-cyclohe~adiene-5,6~~b~ylic acid esters as dimes

results in fomtim of 1-acetamido-4-ace~~y-2-cyclohexme-trans,trans-

5,6-dicarboxylates 71, which may be transformed into many iscm-eric tris-

hydmxyamincderivatives. 241 Another of the stereoselective syntheses of

-

-- -

o:.cooR + CL ON0 n p-1; f O O R

OAc

71 - hosdiamine derivatives proceeds via epoxidation on the double bond in the

intermediate cyclohexene derivatives 63. 238,241 ,243 ~n alternative synthesis

-

NHAc

OAc

7 2 R1 = O H , R2 = N3 - 74 R1 = OAC, R 2 = N H A c - 7 5 R1 = NHAc, R 2 = O A c - 7 3 R1 = O A c , R2 = NHAc -

of inosamines has been reported by Kresze, Weiss and Ditte1.243 Diels Alder

reaction of trans-6-azido-5-hydro~-l,3-cyclohexadiene 72 or transd-acet-

amido-5-acetoxy-l,3-cyclohexadiene 73 and reduction affords the isareric

- cis-1 ,4-amin0alcohols 74 or 25, respectively.

-

-

Asynetric induction occurs in Diels-Alder-reactions with optically

active a-chloronitroso compounds as start ing materials. The first example

reported by Nitsch and Kres~el~~ involves the reaction of 2-chloro-2-nitro-

so-9-cyanodecaline 76 with excess trans,trans-2,4-hexadiene to yield 3,6-

dihydro-3,6-dimethyl-l,2-oxazine - 77 in 83% chemical yield and 39% ee.

- --

366

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a -HALONITROSO COMPOU1:DS. A REVIEM

77 - 76 - Sabuni, Kresze and Bran isolated optically pure lR,3S-2-aza-3-0xa-[2.2.21-

bicyclo-A ‘6-octenehydrochloride - 79a from 17-~hlo~l7-nitroso-3-hydro-

xy-5a-ancbmstane - 78 and 1,3-cyclohexadiene. 149,251 similarly, addition of

;::O

HO

78 -

trans-5.6-dimetbxy-I .3-cyclohaadiene gives (+)-2-aza-3-oxa-[2.2.2lbicyc-

lo-trans-7, S-dimetbxy-b ‘6-octenhydrochloride 79b in 95% ee. 408

Another chiral a-chloronitroso dienophile, l-C-nitrOso-2,3:5,6-di+-

isopropylidenemannofuranosylchloride 80 has proved to be highly reactive in Diels-Alder synthesis. It adds to various dimes to yield optically pure

mno- and bicyclic oxazines 150’244, sane of hich have to be considered as

potential starting mterials for the synthesis of chiral aminosugar and

inosamine derivatives.

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KR-ESZE, ASCHERL , BRAL'N AND FELBEP.

q 0 0 x

80 -

0

ooMe "OMe

6

&' &OMe

OMe

The depdence of reactivity in Diels-Alder reactions on plar effects is

shcrwn also by so11lc3 simple a-chloronitxosoethers 81 which react rapiay under very mild conditions with various dimes, even with the usually

sluggishly reactive ethyl sorbate. 244 1 ,3-Cyclopentadiene adds to 1 -chloro-

I-nitrosocyclohexane to give 2-aza-3~~a-bicyclo[2.2.llheptane hydrochlo-

ride - 82 in 89% yield.259 This provides a novel route to diverse oxazabi-

cyclopentenes. pGGenQperoxide+FGE type cleavage (knawn in prostaglandin

R-CH~-C-OCH~CH~ I

CI

- 81 R =CI , H, CH3

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a-HALONITROSO COMPOUT3S. A REVIEW

chemistry) to - 83 is absenred in the reactim of the free m i n e w i t h excess

r

N-CPh - &: 0 n

benzayl chloride. Diimide reduction gives the parent oxazabicyclohe~e

system, which is directly related to FG-enen-~eroxide.~~~ Thebahe reacts

KOOC-N=N-COOK. [ &{] 0COCl &? N-*

II ij

with l-chloro-1-nitrosocyclohexane under oxidizing conditions to give 14-

(hydroxyamino) ccdeinone, (84) which has analgesic properties. 260 Further

C H30 PhCONHOH or R ~ C ( X I NO

*

0 85 OCH3 - reduction of 84, methylation and brarrPacetylation lead to the biological active 148- (2-brceroacetamido) mrphinone. 26 1

A new synthesis of tropane alkaloids was recently reported by Kibayashi

and -rkers.262 The aFproach atploys a Diels-Alder cycloaddition of cyc-

lohepta-l,3-dimylbenzcate 85 with l-chloro-1-nitrosocyclohme, followed

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KRESZE, X S C H E R L , BRAU!? A N 2 FELHER

OCO CgH5 I

H3N @OOH c1e

NR

by reduction and intrmlecular C-N bond formation, which leads to the tro-

p e skeleton. Final deprotection reactions provide pseudotropine and tropa-

cocaine. A total synthesis of the cell division stimulant cis-zeatin 87 has

been described by I e ~ n a r d . ~ ~ ~ This synthesis starts with the adduct 86

from isoprene and l-chloro-I-nitrosocyclohexane. Kesler has prepared 2-0xa-

3-aza-bicyclo [ 2.2.21 -A

2-chloro-2-nitrosopm~ane and lr3-cyclohexadiene.

6-octene hydrochloride by Diels-Alder reaction of 264

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a-HALONITROSO COMPOUNDS. A REVIEE;

ii) Diels-Alder Reactions of a-Fluomnitroso Oxpunds

!IYifluormitrosomethane is knawn to be m e of the mst reactive dieno-

philes in Diels-Alder reactions. An extensive ampilation of the material

may be found in the previously published review.6 A large part of the work

on this subject has been done by the groups of Haszeldine, Banks and co- 26 5

workers. 265-272 Wifluormitromthane reacts easily with htadiene,

cycl~pentadiene~~~ and its C6- and C7-hmlOgues, hexafluorobutadiene, 266

perfluorccycl~pentadiene~~~ and tetrafluorodllene dimer.268 The addition

of butadiene affords 3,6-dihyd10-2-trifluoranethyl-l,2~zine gg in nearly

quantitative yield.

As Forkin et al. have shown, tetrafluoro-I-nitro-2-nitrosoethane (89) and bu-

tadiene react in similar way to give an N-substituted oxazine, while chloro-

difluoronitrosomethane yields an unstable adduct 90, which can be solvolysed with water or methanol. 273'274t383 The same nitroso conpunds undergo cyclo-

-

addition with hexafluorobutadiene to form the corresponding N-substituted

oxazines in yields up to 40% wether with l:l-coplymer, probably struc-

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KRESZE, ASCHERL, BRAUN AND FELBER

275 ture [ -NwxF2CF=CF-~2- 1

The fomtion of coplyrners is probably a peculiar feature of the reactions

of fluorinated nitroso coqounds with fluorine mtaining dienes, as many

examples show . Recently Marden and Shreeve2I5 isolated the N-substituted

oxazines - 91 and - 92 in 35% yield from hexafluoro-l,3-butadiene and heptaflu-

oronitrosocyclobutane or nonafluoronitrosocycloptane, respectively.

6

4N It +

0

0 - N .. II 0

+ 0- F2 - 0 '3' F

iii) Reactions with a-Halonitroso Compounds

RPactions between arcmatic nitroso compounds and alkenes with allylic

CH bonds have been studied as early as 1910 by Ale~sandri.~~~ Later, it was

shown by Knight and ~ 0 m r k e . r ~ ~ ~ ~ that the products - labile N-aryl-N-alkenyl- hydroxylamines - resulted from an addition/hydrogen abstraction process ("E reaction"). In mst cases, further transfomtions of these products

occured. The mst frequently investigated a-halonitroso cOmpOund in this

respect is C F p . g reactions of this compund with m y alkenes have been

described.265r270'278'383 2-proPenyl derivatives CH2:CH.M X (X = C1, Br, 2

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a-HXSONITROSO COMPOUNDS. A R E V I E K

or CN) also give

than the unsubstituted alJcenes and yield mixtures of stereoisaoeric ad-

reactions with CF3No but they are mch less reactive

ducts 93.270

OH 93 -

&action of CF3No with isopmpenylacetate occurs fa i r ly readily and

results i n a mixture of the expected = product and the O-acetylhydrOXYl-

amine - 94, formed possibly by a [2n + 2n + 2u1 process.270 I ,I-Cy~lohexa-

0 ii

+ F O C O C H 3 N-OH

- F0 ,CH3 0-C-CH3

N-0-C 0

CF3 II

CF: 0

\” K L p

/

F3 94

dime gives the a d d u c t s , apparently resulting from a D i e l s - A l d e r addi-

tion of the nitroso cOmpOund to the ini t ia l ly formed a ad duct.^^' Acetyl-

acetone gave a product C F 3 N ( O H ) C H ( m 3 ) 2 f o n d l y derived by an =-reac-

tion of the en01 tau-r . 270

The double bond system of allenes often appears to be reactive in addi-

tion-hydrogen-abstraction reactions w i t h various type of enophiles. But,

m g these, reactions w i t h nitroso canpounds are rarely e n m t e r e d

(ArN0314). A m t h

ne and 2,4-dimethyl-2,3-pentadiene. Beside ‘T3No, only t m examples of

reaction is observed between trifluoronitrosametha-

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KRESZE, A S C H E R L , BRAUN AGD FELAEF

ene reactions of a-halonitroso compunds have been reported so far. Schenk

and DeBoer285 described the addition of several a-chloronitroso mmpunds

t o alkenes possessing a l ly l i c CH bonds. The products, nitrone hydrochlori-

des - 97, mst likely originate from an in i t i a l ly forrmd N-a-chlorcalkyl-N-

alkenylhydroxylamine; hydrolysis of - 97 a t room temperature afforded the

hydmxylamine hydrochlorides (98) -- and the ketone, e.9. adamantanone (2).

-

97 90 0L% - 99 96% - -

( i n case of 96 a s R1 + R2 = C H 3 , C H 3 ; C H 3 , C 2 H 5 ; C H 3 , CH2CCH5 starting material)

R’ + R 2 = -(CH2I5- (96)

Several chloronitroso compounds have been used, the mst suitable reagent

to undergo - ene reactions was the adarnantyl derivative 5. Its products were

m r e stable and could be isolated mre easily in p r e form than those of

other a-chloronitroso compounds. Nitrone hydrochlorides are also the reac-

tion products of the reaction of t e t rmthy la l l ene with a-chloronitro-

so compounds. 279

The chloronitroso compound 80 derived from m o s e undergoes reac-

tions with various alkenes even mre readily then 96; the resulting nitrone

hydrochlorides are rapidly hydrolyzed t o the hydroxylamines. These pro-

ducts, i f chiral , are optically active; for the I-methylcyclohexene deri-

vatives - 100, an optical yield e.e. > 80% was determined. 398

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a-HALONITROSO COMPOUNDS. A REVIEW

HO-N H

CH3 100 -

For reactions of CF3N0 with alkenes not possessing allylic CH bonds

Cf. p. 376.

iv) 2+3 Cycloadditions

There are only a few q l e x -1es for the participation of halo-

nitroso compunds in such processes; CF3m reacts with azomethineimines by

di-mlar cycloaddition and subsequent fragmentation. 280

A sequence of [2+3lcycloadditions and eliminations seems to occur also

during the interaction of C F p with bis [trifluoron~thyll diamthane. 28 1

CF3N-C-CF3

2 CF3NO + 3 (CF312C-NZ - I I CF3 N=C(CF3I2 0

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KRESZE, ASCHEP.L, BRAUN AND FELBER

Addition of (CF3l2Co increases the yield of the dioxazoline 101 to 53%. A

m w h a t similar sequence has been observed for the reaction of perflmro-

nitroso Ccsnpaunds with di~yldiazcanet.385 m e reaction of diphenyl-

diamthane with the perflmro-2-nitrosopropane takes another course, 282

while with (CF3) 3cNo the oxaziridine 102 is With CH2N2, CF3No -

102 - yields a coplymer [-N(CF3)+XH2-)n. 397 a-Chloronitroso derivatives with

diazo compounds afforded unstable a-chloronitrones. 386

CI C I R 3 R', e I

+ 'c' - C=N-C-R ON' 'R"

v) Reactions with Fluorodkenes

mereas interaction of cF3m with

nitrosyl or ene addition products (cf.

alkenes, especially CF2=CF2, gives 1:l

-

isobutene or other alkenes leads to

p. 3 7 2 ) , its reaction with fluoro-

copolymers as the main products

+ polymer [ref. 2151 N - 0

55 -60' + CF2=CF2 - 4 NO

+ copolymer [ref. 2861 - 2 8 v. cF3 - ? - 7 2 8 a t m

80'

CF3N0

+ CF2=CFCOF 1 week F2C-CFCOF

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a-HALONITROSO COMPOUNDS - A REV1 EW

6,283,284 are abser- ("nitroso r ~ b b e r s l * ~ ) . ~n scm cases , I ,2-axazetidines ved. ~n the gase #we, (CF3l3N0 yields mixtures of products w i t h

a2~:B8 and m 2 a 2 probably - via radicdl in the k t case;

35% of the axazetidine derivative was found, N,N-bis(trifluoranethyl)amino

dlkines (CF3)2NC=CX (X = H, Br, CF3, N(O?3)2: M3) give high yields of

the 1 :1 (90°C, 3-14 aayS), mostly of the structm (m3) 2-+JcE"Cl?, 287 which are supposedly formed* 2+2 cycloadducts.

b) FeacticHls w i t h Nucleophiles

(i) With Nitrogen Ccmpounds

T h e reacticn betwleen primary amires arad perfluomnitroso canpmds

(for a rev iew of earlier work, see ref. 6) may prcceed as a nucleophilic

addition to the NO group. 'Ihe group Alk may be also cyclOdLky1, bi- and

70 MeOH

CF3NO + AlkNH2 - CF3N=NAlk [refs. 289, 3101

103 - tricyclic derivatives such as admmtyl; &amino ampounds also react,

as -11 as fluorine substituted aniline derivatives. - per- 290, 302

CF3N0 + ArNH2 - CF3N=NAr

fluoro nitrosodLkanes react analogously. The reactivity of the amino can-

po~nd decreases with the decrease in basicity.399 his is also true for

the rea~tims of perfluoronitrosg(c1obutane and p e r f l ~ h t r 0 ~ 0 cy~lopen-

tane w i t h aniline derivatives (relatively low yield) .291 Haever, the last

mtioned nitroso campounds react w i t h rethylamcine by HF eliminatim after

the primary addition to give - 104 or its hanologw. 291,292

377

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KRESZE, A S C H E R L , BRAUN AND FELBER

Fa! ,CH3 CH3NH N=N

104 80' -

Elimination of HC1 also occurs to a certain extent in the interaction of

prinary amines w i t h a-chloronitroso perfluoroalkanes.

RFCFClNO + HZNR - RFCFCLN-NHR - [ AH 1 8

be [ref. 3991

- RFCHF-N=NR

[Trialkylsilyl]trifluoromethyl diazenes 105 w i t h bulky alkyl groups have

been prepared by condensation of lithiumbis (trialkylsilyl) amides with CF3N0

[-8OoC, 6-33%) ; 293f365 they may be used. under mild conditions [-loO°C, THF)

as CF3 group transfer reagents; CF3 anion transfer has been assumed. 293

O H CF3N0 + LiN(SiR312 - -

10 5 -

R1 = C6H5 , R2 = CF3 30% ; R1 + R2 = -(CH2I5- 34"/,

Photolysis of the alkyltrifluorolnethyldiazene, on the other hand, results

in cage combination of cF3- and R * radicals. 289

hv CF3 N=N-AI k CF3-Alk ( 7 - 69%)

- N2

378

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a-HALONITROSO COMPOLXCS . A R-E'JIEK

290, 291 The correspxding N-aryldiazenes do not extrude dinitmqen.

hother trifluorcmethylation rnethod amsists in the reaction of CF3N

with hydroxylamine follawled by treatmznt w i t h a base in the presence of

sulfonyl hdlides, carboxylic acid halides or similar reagents.

NH2OH CgH1js02CI , S02C6H 5

DMF/THF/ - 78O NO

CF3N0 - 7 8 0 [CF3N=NOH] + BuOK * CF3N,

Et20 [ refs294 - 296, 4091

Ar CF3 [refs. 295, 2971 /S02C6H5 h v . biacety l ArCN o r NO

\

+ A r H Me2C0 24 - 59%

I f mixtures of regioisomers are possible, they are formed with some selec-

t ivifq. Reaction with disulfides RSSR gives CF3sR.

of intermediate occurs i n the following reaction.

295, 297a The same type

298

c NH20H

> S o

02NCFzCF2NO - 02NCF2CF*N=NOH H20

0 2 N CF2C+ - H20 02 N CF2CO2 H [ re f . 2981 0

'F

For the reactions of cF3N0 with hydmxylamine, hydrazine and the i r de-

rivatives ref . 387 should be consulted. The reaction bet- CF3N and alkyl-

299, 399 hydroxylamines RMK)H yields azoxy ccmpounds CF3N(0) =NR (-70°C, l5'tCX-I) . Hmever, there are side-reactions as shcrwn in the following equation.

8 XCF2CF2N =N-CF3

be X CF2CF2N0 + CF3NHOH L CF3N0 4 XCF2-CF=NOH

379

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KRESZE, ASCHERL , BF.AUN A N D FELBER

Although CF3N0 does not react with electron-deficient amino cOmpOundS

such as formamide or urea,m many bases cause its condensation with sulfon-

amides in high yields: these products, too, m y serve as trifluormthyla-

ting agents. 303

Na2C03

1 ) liquid N2 temp. T H F

21 room temp.

CF3N0 ArS02NH2 c CF3 N=N S02A r

81 - 93 '/e

2 - 3 h [refs. 30.4, 3051

CH3

Whereas acyl and carban-oyl hydrazines shw normal condensations with CF3N0

to give triazenes, 306 sulfonyl hydrazines yield N-trif luormthyl-N-hydro-

C F 3 N 0 + RCONHNH2 RCONHN=NCF3

(R = Ph. Me, PhNH: 97, 50, 98%) xyarenesulfonamides probably due to the instability of the initially-formed -

,OH MeOH 2 \rc-

CF3N0 + ArS02NHNH2 - ArSO N [refs. 306,3071 r.t. 3

74 -9 9 '/o

308 adduct. The products m y be useful as herbicides.

Clear-cut nucleophilic additions to the nitroso group of a-halogenated

derivatives have been investigated dLrrPst exclusively in the case of per-

fluorinated compounds. In the case of other halo derivatives, only the reac-

tion of a,B-dichloronitroso compounds (sometimes prepared in situ) with

3 80

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a-HASONITROSO COMPOUNDS. A REVIEW

bifunctional thionamido derivatives has been reported and applied in hetero-

cyclic syntheses. N-Alkyl derivatives of the thionamides have been employed

similarly; by using N-amino dithiccarbamtes, 1,3,4-thiadiazines have been

prepared. 31 1

R1, ,CL C + H2N-C-Se N H ~ ~ -

II S R ~ C H ' ' NO

I

P e r f l m r ~ o r o n i t m s o cmpounds react, in sane cases extremely readi-

ly, with triethyl phosphite (in R20, between -80 and -50°C) . The same pro-

+ HOPIOEtI2 - HCI

ducts result by treatment of such a-chlomnitroso aqounds with diethyl-

hydmgwphosphite. 2-Chlom-2-nitrosopropane reacts analogously in the pre-

sence of N E ~ ~ . ~ ~ ~ he pr- product in these reactions is thought to

stem from a nucleophilic attack of the P atom on the nitrogen.312 Diethyl-

hydmgenphosphite cxmbines with CF3N0 to give CF3N(OH)P(0) (OEXl2 317 and

with C ~ F ~ + p ~ 1 ~ ~ ~ ~ to form - 106. various types of phosmlanes give an aria-

CF CF2 /2 - \

\ CF3N

38 1

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KRESZE, ASCHERL, BRAVN A X 3 FELBEF:

logous reaction. For

into 107 by reaction

*. 0, p/(

I Y

2 Y = F (R' = R = ~ e ) , the pr- product is converted

with Me2CClN0 (Et20, 5-10°C, 48%) .314 This transforma-

R1, ,CI - U 0, /x C

R2' 'NO P \ 9' O-N=C

'R2 X Y

o OR^ [ re fs . 313. 31301 (R'=F. R 2 = C l )

NMe OR3 tion corresponds to a mild form of oxidation of the phosphor0 fluoridite. Ring-

+-t MeN, ,O

F P

107

opening of the primry adduct may also occur. For the reaction of FCCl2N0

()// \

-

Y = C I , NEt2, O'Bu: R = F , Et ; R ' = C I , Me

C=N-0, ,OEt R, - R, ,CL C

NO Me' P R

'R' o+ '@-N=C'

C=N-O-P(OEt12 + R'' \

R, Me'

R , R ' = Me, Me: C I . F [ref. 3161

with phospholane derivatives, see refs. 389 and 390. Triphenylphosphane reacts

with I-chloro-I-nitrosocycloalkanes in the m e r of a BeclaMnn rearrange-

382

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a-HALONITROSO COMPOUNDS. A RE7IEW

m t . The reaction is exothermic in various solvents and proceeds generally

in good yields (57-96%). 188

iii) With Carbanions and Organcmtallic Conpounds

Nucleophilic attack, followed by one-electron oxidation, has been dxmn to be the course of reaction of CF3ND with CIi-acidic oompounds in CClq. 319

R'

OH RCOCH2COR' RCOCH=C<

e RCOCHCOR'

CF3N0 I COR

'COR' CF3 N- CH '

,COR

I 'COR' CF3 N - C H

OH I

1 CF3N0 0 COR

cF3y-c*c/R'

0 . 'OH

' ,COR

I COR' CF3N-CH,

0. R,R'= Mc,Me; CF3,CF3: Me, C 3

The first step may also be regarded as an oxa-ene reaction. In the presence

of triethylamine, carbanion addition leads to the imine 108 in the case of

a~etylacetone~~~ and to the hydroxylamine -- 109 with a-hydroperfluom iso-

butyronitrile .

~

32 I

NEt3

-1 oo CF3N0 + MeCOCH2COMe (MeC012 C=NCF3

C N CF3N0 (CF312CHCN (cF 1 C 0

;N-CF3 EtZO HO

383

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KRESZE, A S C H E R L , BRAUN AND FELBER

1 The analogous hydroxylamine - 110 (R = CR (CF3N(OH)CF3) 1 is also isolated

(70 and 41%) in the reaction (Et3N, -15O to -2OOC) of CF3N0 with the dhxa-

line 110, R = (CF ) CH; CF C H ( C 0 p ) . By reaction of a-chloronitroso cam- - 3 2 3

C = N I \

R,

R = (CF312CH ; CF3CH(C02Mel CF3 O X 0 CF3

&I

pounds, especially that of the adamantime derivative, with Grignard reagents

RMgX, three products are isolated in strongly varying yields: the corres-

ponding nitrone (6 - 8%), adamantanone oxime (4-60%) and its ether (trace -

R1, ,CI

R2’ \N. ,OMgX R M g X -

I SET + R1 CI 8

‘C’ R M g X / \

R 2 y-Oe

R -

- R CMgXCI

R1

R1

\c=N-OR R2’

R2’ ‘C =NOH

R1 ?- ‘C=Y-R

R2’ (combinat ion)

(disproport ionat ion)

28%). Different mechanisms have been suggested for their formation. Their

relative influence on the course of the reaction depends on the nature of

R: 1,2-Addition (for R = Ph, mainly nitrone) or single electron transfer

384

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a-HALONITROSO COMPCCrPI3S. A REVIEFi

(SET, for R = “Bur tsu, e3m2 and ma2, only minor m u n t s of ni-

tnme 322,323,96) can occur. Lithim organyls react in the same 392 manner.

The course of the reaction betwen a-chloronitroso capunds and tri-

alkylaluminim oomprxlnds depends also on the structure of the reagents and

on the reaction conditions. Ether q l e x e s of AlR3 afford the same types

of products as Grignaxd oomprxlnds radicals f i c h can abstract hydrogen

f m various solvents. In the presence of olefinic solvents, radical addi-

tion to the double bond also takes place. 350, 403 men the triwlalmi-

nium cOmpOundS are not cmplexed by ethers, they react w i t h a-chloronitm-

so ccanpounds predaninantly

(see p.

- B are &served.

160 heterolytic processes; rearrangemnts

388) or formation of well-defined complexes l ike 5 or salts like

Z N - O - A I Et CI

A - 0

These can react further by hydrolysis or rearrangemnt to a-chloroimines

or, in the case of sterically hindered chloranitroso oomprxlnds, undergo

carbon-carbon bond rupture. 404

355

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KRESZE, ASCHERL, B R A X AND FELBER

iv) Other (Possibly) Nucleophilic Reactions 410 A polar addition occurs in the reaction of CF3N0 with sulfinic acids

or with sodium or potassium hydrogen sulfite, the product in the last case

is oxidized without isolation to the N-oxyl. 303

r.t.,l h

The first process (without Pb02) is rapid and exothermal at ambient tempe-

rature but the intermediate anion disappears fairly quickly (2h) by hydro-

lysis (prcduct cF3NHoH). In the analogous reaction of some perfluoro horrp-

logs, hydrolysis was followed by HF elimination.213 Addition of HSO, and -

hydrolytic HF elimination to give the oximes is also observed for perfluoro-

nitrosocyclobutane and (CF3)2CF"0214 as well as for CF3(cF2C1)cFNo (yield

of oxime 41%) .212 Intermediate addition to the N-atom is assumed to explain

the complex mixture obtained by the interaction of C10S02F or S206F2 and

f luoronitroscalkanes. 324

0,NCF2CF2OSO2F *

+ FS03NO + C12 1) -60'. 3-5 h ClOSO2F + 02NCFZCF2NO

2) *2O0to L O O ) 2.5 h

+ %NCFzCF2NO2 + S205F2

Nucleophilic attack, of [RNClI', or involvement of nitrenes is tbught

to take place in the reaction of nitroso compounds (inter alia, of l-chloro-

I-nitroso cyclohexane and 1,4-dichl0~-1,4-dinitroso cyclohexane) with N,N-

dichloro-amines. mever , other mxhanistic pssibilities (SET) exist

--

386

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a-HALONITROSO COI.IPOUNI?s. k REVIEW

00 CU2CI* I

e R N C I ~ + R'N=O RN=NR'

(cf. p. 384 ) depending on the nature of the promtor. 325,326 his reaction

has been used to synthetize the a,B-unsatwated azaxy ccqounds 111. 327

00 00 I

B r 6 7 y C 0 2 I Et eN=NC02Et

Na I

6 h BrG MeCN r,t., Sh -0 Me2C0

" Cu Br2

+ Et02CNCL2 9 2 *I. 96% 111 The formation of an amxy derivative in the reaction shown helaw seems

R-CF=C02Et + F2N-NF2 - R-CFC02Et 70 -80' I

QN=NF I NO

R = CL, F, CF3 [ref. 3281 24 - 35 *to

scanewfiat

derivatives of cyclobutane or cyclopentane in the presence of finely divi-

ded Pyrex glass (5SoC, 16h, 50% or 25%, resp.). Without the glass, law

yields of y2 ccanpounds

perfluomnitroso derivatives (formation of fluoroazoxy campounds),see

refs. 329-331, 394.

me same reaction occurs w i t h the perfluomnitroso

For the interaction of N ~ F ~ w i t h

c) Reaxrangerents

Interconversions of diastereaners in a-halonitroso ampounds due to

i n t d i a t e horrplysis were described in Chapter 2. Another way to effect

racemization of chiral a-chlomnitroso ccqounds is by reaction w i t h HC1

in glacial acid. 1 20

387

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K R E S Z E , A S C H E R L , BRAUN AND F E L B E F

NO

CI + HCI R, / ‘C=NOH e

R C R” \ R”

This mechanism was established by isotopic exchange121 and kinetic experi-

A Beclmmn-like rearrangement occurs in the reaction of l-chloro- 2-nitrosofenchane 112 with ~ 1 ~ 1 ~ ( c H ~ c ~ ~ , OOC) . 160 -

Both endo- and - exo-forms of 2-chloro-2-nitroso camphane react with AlC13 or

(with higher yield) with M e P C 1 to give the chloronitrone 5, which may be hydrolyzed to the correspnding hydroxarnic acid. No rearrangenwt pro-

ducts were isolated from the reaction of l-chloro-1-nitrosocyclohexane with

A1c13. 2-cNoro-2-nitroso carane - 114, however, gives the hydroxamic acid 115 by treatment with AlC13 and hydrolysis.

160

388

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a-HALONITROSO COMPOUN3S. A REVIEW

d) Reactions w i t h Radicals

Spin trapping by nitroso caqnmds, cormrx~ to altmst all derivatives,

occurs also with a-halonitroso catpunds. Nitrmrides are formed by scavenging

of alkyl, alkoxy or acyl radicals by a-chloronitroso ccmpOundS. 323,332

X

I 0-

R X R‘‘ 0 R’‘ 0 + R * - C C

R2’ ‘NO R 2’ ‘N/

Hmever, these ccanpounds are unsuitable for practical application as spin

traps because of the lability of chlorine in the B-position of the nitro-

xides and because of the carplaity of the ESR spectra due +& Chlorine

hyperfine splitting. A review on the interaction of fluomnitroso cOmpOundS

w i t h radicals and carbenes is available. 6

cF3ND reacts with alkoxy radicals generated by nitrite photolysis to

yield N,N’-dialkoxy-N.N’-bis (trifluorarnethyl) hydrazines - 1 16333 perhaps in

the following mer. Nitratides generated by addition of proxy radicals

389

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KRESZE, A S C H E R L , BRAWN AND FELRER

CF3 NO OR CF3N=O ’ RO. - CF3N-OR CF3N<

I O-NCF3 0- I

- CF3N02 + [CF3&OR] - CF3N-NCF3 I 1 OR OR

116 - to either 2-chlor0-2-nitrosopropane~~~ or CF3N0335 could not be detected;

it is probable that their rapid decay leads to the alkoxynitroxides A - ob-

served. R’. / x C

0 \ rD1 V 1 V R2 NO RO - m

R’ X ‘C’ OR

R 2’ ‘N’

A - tert.-Butyloxy radicals generated in several ways gave a much mre persis-

tent spin adduct with CT3N0 than other alkoxy alkyl nitro~ides.~~~ The

conplex reaction sequence for the interaction of the radical NO with a-

halonitroso compounds has been discussed in detail mstly in connection

with investigations of the photolysis mchanisn [cf. Chapter 2, see also

refs. 158, 336, 3371. For the kinetics of the reaction CF3N0 + NO, see

ref. 338.

The result of reactions of a-halonitroso cOmpOunds with radicals

usually is equivalent to a reduction. Therefore, this section and the

following one are closely correlated.

e) Reduction+%idation Processes

Eleclxon-transfer in reactions of nitroso compounds has been investi-

390

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a-HALO!JITEOSO COI.IPCV:JDS. A REVIEW

gated thoroughly by Ginsburg and his group. Oxidations and reductions of

perfluoronitroso coqmnds are fllmrrarized in ref. 6. There, only some per-

tinent new results will be discussed.

The polaroqraphic half-wave potentials of some halogenonitroso deri- 345 vatives have been determined [(CH3)2CClN0 - 0.95 V in ethanol].

Me2CXN0 (X = C1, Br) and MeCCl2NO are reduced polarographically to the oxi-

mes M~C=NOH or MKC~=NOH, respectively.346 The character of the reductim

depends substantially on the nature of the solvent. Electrolytic redwtion

of CF3N0 (El,* -0.25 V in DMF, acetonitrile, or DMSO) produces a substance

whose ESR spectrum was assigned347 to the structure shcr~n belaw.

O8 I

CF3N-N-CF3 I 0.

Chemical reduction of l-chloro-1-nitrosocyclohexane by dibrane (25OC,

THF) yields N-cyclohexylhydrmyla~nine.~~~ This conpund as well as other

chloronitroso derivatives RR'CClNO may be reduced by LiAlH4 or NaBH4 to the

corresponding oximes RR'C=NOH (yields 41-72% or 9 7 8 % , resp.) . These products are also forred emthermally by hydrogenation with Pt02 as

the catalyst in ethyl acetate; W/A1203, w/BaS04 or Raney-Ni are ineffec-

tive."' mimes are also produced by the reaction with stannous chloride.

161

349

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KRESZE, ASCHERL, BRXUN AND FELBER

a-Chloronitroso ccmpunds react relatively slowly with Bu3SnH, but rapidly

with alkyl radicals produced by the interaction of this reagmt with -1-

halides, to give non-symnetrical di-sec-allqlnitmxides. For the reduc-

Bu3SnH R1, /H H, R3 m C C

" N ' 'RL + R3'CHCI

R', 0 CI

R2/ 'NO RhO R 2 C

1

tion of perfluoronitroso compounds with hydrogen sulfite see p. 386; alka-

line sodium dithionite reacts with solutions of a-halonitroso conpounds to

Rt X 2/ 'C' / SO2' Nae

R N I

give stable radicals which are destrayed by excess of reagent or strong

11 7 - R = 0 , CEH,~-, Me2C(CH2I3CMe2CN

acids.339 Trhthylaluminium functions as an electron-donor tcwards 1-

chloro-I -nitroso-2,2,6,6-tetran~thylcyclohemne 1 1 7 ; 350 an iminyl radical

has been shrrrwn to be an intenrediate.

-

Interaction of aliphatic nitroso ccmpounds with the pentacyano mbal-

tate(11) anion in aqueous soluticn affords cobalt-substituted nitmxides

- 118 of moderate ~tability.~~"~~~ The addition product of CF3N0 persisted

3 9 2

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a -HALOHITROSO C3MPOLTDS. A REVIEW

for several weeks under nitrogen, the adduct of bis(dimethylg1yoximato) 342 cobalt (11) behaves similarly.

Radicals as in- 'ates have been postulated and/or observed in reac-

tions of CFP w i t h t r i m e t h y l ~ i l a n e ~ ~ ~ and with 1 , 3 - d i e n e ~ . ~ ~ ~ Radical

anions FWO-

action of m3No and 02m2N0 w i t h nucleophilic solvents (ether, ethanol,

amines) .351 W i t h dlkenes CH2=CXR (R = Me, OEt, ph) and 2-pmpenyl ctxpunds

CH2=CHCHp (X = C1, Br , SiC13, -N=C=S) , CF3No yields radicals by one-elec-

tmn transfer reactions.

- or RN(O-)-N(O-)R are thought to be the products of the inter-

395

Aliphatic Ntroso canpounds, in general, are subject to cmidatim to

the corresponding nitro canpounds by a w i d e range of

Of perfluomnitroso carboxylic acid esters by N204 or CF3m3H yields (65%)

the corresponding nitro derivatives.352 he sequence of axiciatim of an a-

Oxidation

halogemnitroso cOmpOund followed by reductive displacement of the halogen

has often been used as a valuable synthesis of nitro conpunds, cf . p. 34 1.

f ) f(eactions N o t Inmlvinq the N i t r o s o G m u ~

Often the success of a synthesis depends on the "chermselectivity" of

one of the steps involved: this means the preferential or exclusive reac-

tion of one functionality in the molecule and the lack of reactivity of the

other possible reaction centers under the reaction conditions. I n the case

of a-halogenated nitroso cxnqmunds, only the perfluoro derivatives seem

to have been investigated in this respect. The results of such experiments

are mmar ized belaw. Thimyl chloride gives mixtures which may be separated 70% AcOH

ON-(CFZln-C02R ON-(CF21nC02H [refs. 205,2081 ref lux

( R = Me, E t l LO m i n

PhCOCL

80°C, 7 h ON-(CFZln CO2H ON-( CF212COCI [ref. 2081

34 - 48%

393

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KRESZE, ASCHERL, BRAUN AND FELBER

cnly w i t h difficulty; phosphorus chlorides react w i t h the nitroso grcnxp.

M2C03 b

€120, 2h

Na F 16h. r . t . sealed tube

b

NH3 e -78OC, Et20

1 AgCN 7O0C.sealed tube

b

ON-(CF2I2 C O F

78 'I8

[ref. 3531

ON-(CF2I2CO N H2 [ref. 3531

L 8 '1.

ON-(CF2 l2 COCN [ref. 3531

8 2 *I*

ON-KF2 l2 CONH2 PLOlO ON-(CFZ 12 C N d i s t i l l a t i o n a t

[ref. 353 ]

15O0C/1O0 m m Hg 46 *la

ON-(CF2 I2CO2H p4010 + (ON CF2CF2C0 I2O [ref. 3531 d i s t i l l a t i o n a t

200mm Hg

w -Nitrosoperfluompropionic and w -nitrosoprfluoro butyric acids form

adducts w i t h m y organic cc~npounds (e.g. ethyl acetate, ether, acetone,

dioxane, benzoyl chloride) which are reprted to deaxpse only when

heated w i t h concentrated sulfuric acid under vacuum. 247

394

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a-HALONITROSO COMPOL"2S. X REVIEW

g) Miscellaneous w l e x Reactions

Same of the reactions of a-halonitroso cOmpOunds defy systematization.

These reactians w i l l be r ep r t ed here without comtwt.

When C13W in dimthylfommmide was treated with NaF (4*8OoC), a 12%

yield of CF3W2 was isolated. The yield of this product was mch lower

wlaen AgF =S used instead of NaF. In this CF3W(0)CF3 w a s the chief

fluozxxarbn product. In the absence of EMF, ( C F 3 ) 2 ~ was found as the

main product. 354

a-Qiloranitroso ccqounds give a very complex reaction mixture with

azide ion in methanol. In the case of the adamantyl derivative, the azido

am ccmpund could be isolated. 355

356 The perfluoro nitroso ccmpound 119 is solwlyzed by water and ethanol.

Another path for solwlysis is followed by 2~hlom-2-nitrosobutane in me-

thanol which affords 2-butanone ox* and 2,3-butanedione mnoxime

A very old pblication claims the replacement of bromine by NO2 in

the reaction of Me2C13rN3 by AgN02.358 Q1 the other hand, a replacement of 359

the nitroso group is reported to take place in the following reaction.

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KRESZE, A S C H E R L , BRAUK AND FELBER

man the reaction of 1 ,1 dichloronitrosoethane and El3 or BBr

aUqlideniminoxyboranes 120 are obtained.

*ic 3' 360 -

X., 0 0--8;

'8-0' CH3CCI=N N=CCI C H 3

Metal carbonyls react with a-halonitroso cmpunds t- give differen pro-

ducts, depending on the reagent used. In the interaction of l-brom-2-

nitroso-propane w i t h c ~ H ~ ~ (CO) 3e, the ~e c (NO) miety acts as a three-

electron donor to give c ~ H ~ ~ ( c o ) ~ c ( N o ) M ~ ~ as the product.361 ( ~ 1 the other

hand, w i t h Na& (CO) [M = Cr, W l , yellow volatile dimethylketimine corn-

plexes [Me2C=NHl M(CO) are formed 361r362 and w i t h Na2Fe(CO)4, a mixture

of [Me2C=N] 2Fe2 (CO) and [Me2C=Nl 20F'e2 (a) has been isolated. 36 1

Fe (CO)

a mltitude of degradation products.

2

reacts vigorously w i t h CF3N0 (starting temperature -2OOC) to give

36 3

111. a-HATL3lITFOmALKmES

Detailed reviews for a l l types of nitroso alkenes have been provided

5 by Gilchrist and Viehes These compounds pssess a very large

synthetic potential. They behave as activated alkenes and as hetero-l,3-

dimes; on the other hand, the nitroso group reacts w i t h m y reagents. 1 r 3

A sinultaneous incorporation of nitrogen and oxygen takes place by Diels-

Alder reactions, - ene reactions and [2+21 cycloadditions.

The first 1-halo-1-nitrosoalkene isolated was trifluoronitrosoethe-

ne.366 Other such compounds have usually bulky a w l or halo substituents

a t the B - c a r b c o l atom. 364,367-373 he lifet-s of a-cuorinated nitroso

alkenes vary from m y weeks a t room temperature t o short periods a t l c w

tenpratures.

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a-HALONITROSO COMPOU!T2S. A REVIEI:

No X-ray or microwave structure determinations have been carried out

on a-chlormitroso allcenes. M3calculations, using the Hikkel-374 and the

cM3(F375 mew have been carried out for nitrosoethene; the transoid

structure 122a is calculated to be of slighly lower energy than the cisoid

form - 1 2 2 b . ~ ~ ~ The blue color of the a-chlomitrosodlkenes is due to the

n - b n absoxption band (675-795 nm) . Another band in the 250-350 nm region r'

N=O - -0 122a -

is also observed; th i s band may be due to an excitation involving conside-

rable charge transfer to the nitroso Infrared spectra normally

show tw bands in the region 1420-1660 an-', the 1-r one [v(No) 1 shows

the influence of conjugation (1500-1620-'). The higher frequency band

(1500-1660 an-' ) can be attributed to the v (C=C) . 364

2. SYNTHESIS

A general method for the prepration of nitrosoalkmes cansists in

the treatment of a-hdlooximes with WC03 or K2m3 in dichloromethane

N=O R2 0

'R3 Be

For the long lived species, t r i e t ~ y l a m i n e ~ ~ ~ and 1,5-diazabicyclo[4.3.01

nm-5-ene368 have been used as bases. ~ r o m a-nDnohdloaximes, no nitroso-

alkenes could be isolated. lheir instability my be acplained on the basis

of formation of an intrmlecular [2+2l-cycloadduct - 121 *ich deccenposes

readily to yield formaldehyde and the corresponding ni t r i le .

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KRESZE, ASCHERL, BRAUN AND FELBER

N i t r o s o d l k e n e s participate in cycloaddition reactions ei ther as 2n-

electron systems (mde A or B) or as a 4n-electron (heterodiene) system

4 N

0) R ) I c A

0 '3

W i t h dienes, products are usually formed y& mode B. The realization of

Itlode A remains uncertain; possible products of Itlode A my easily undergo

a [3,3]-sigmatropic rearranganent t o give one of the possible products

formed directly by Itlode C.

Reactions of the t i t l e cOmpOunds with e e n e s have been described

only recently. "richloronitrosethene ( 2 1 , generated from trichloroacet-

hydroxamic acid chloride (123) -- ,364 was Shawn to react w i t h a number of

electron-rich rtpno-alkenes - via [4n + 2x1 reaction to yield I ,2-oxazines

(2%) in good yield. 376

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a-HALONITROSO COKPOUNDS. A REVIEW

0 C I c13cc 11 NOH

CI 0 c=c, cI\

CI' NO

I n a l l cases only one regioisamsric product was isolated. compound 124 also reacts with t h i o c a r b y l cmpunds and with alkines to form [4+2lcyclo-

a d c ~ u c t s , ~ ~ ~ 126a or 126, respectively; the oxazine 126a is very sensitive

(72%) 1 2 6 a -

CHZOCH3

126 b - to misture.

With substituted butadienes, cycloaddition occurs according to mode B. 364

R1 Rz H H CH3 H H OCH3

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K R E S Z E , ASCHERL, BRALTN AND F E L B E F

a4iLoronitrosoal.s - 127 react with cycl-tadiene, 380 cyclahe~adiene~~~

and

rrerize at rum temperature to form epoxyaziridines.

to form [4n + 2nl adducts; these products are unstable and iso- 364 canpaund 124 gives

0- &? N, C ,C‘ -& N. C / CI ~ 1 ~ 2 C=C(CI) NO +

127 - E It

C R1 R2 R1’ ‘R2 R1/ ‘R2 H CI CI C I

‘gH5

129 - 128 -

only - m e stereoisaneric product, 130, with trans-5,6-diacetoxy-l,3-~yclo- hexadiene .

OA c

O A C d N, CCI=CC$

AchowledgmL-We thank Dr. J. Pfab, Herriot-Watt University, Edinburgh,

Prof. 7%. J. DeBoer, University of Amsterdam, and Prof. A. Vasella, Univer-

sitst Z i i r i c h , for helpful discussion. Our own mrk in the field covered by

the review was supported by the Deutsche Forschungsgemeinschaft and the

Fcolds der chemischen Industrie. We wish to thank these organizations for

their help.

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a-HALONITROSO COMPOUNDS. A REVIEW

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KRESZE, A S C H E R L , BRAUN AIJC FELBE,%

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a-ERLOMITROSO COMPOUNDS. A P.EVIEW

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KRESZE, A S C H E R L , BRAUI; AND FELBE?

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a-HALONITROSO COKPOUKDS . X R E V I E R

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KRESZE, ASCHERL, BRXUN AIJD FELRER

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a-HXLONITROSO COMPOUNDS. A REVIEW

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KRESZE, ASCHERL, BRXUN AND FELBER

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113. A.F. Childs, L.J. Goldsworthy, G.F. Iiardirg, S.G.P.

Plant and G.A. Weeks , J. Chen.. SOC., 2321 (i948).

114. M . W . Barnes and J.M. Pattersor,, J . Org. C h e ~ . , 41, 733 (1976).

115. S. Ailricchio, A . Ricca and O.V. DE Pava, Z. Hetero-

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117. A.D. Nik.c.laeva, V. S. Fer~kj A ' k o and I .J .G. D'yarhenko,

2 h . 01-s. K ~ L ~ T . , 2 , 1€24 ( 1 9 7 3 ) .

11s. I. Sakai, N. Kawabe ar.d M. Ohna, Bd11. C h s r , . Sac. Jpr. . ,

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119. H. Labazlewicz and F.G. Riddell, J. C t e m . SOC., Perkin

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12C. H. Diekz.ann and W. L5ttke, Clip?.. Ber., 105, 1SS2 (1972).

121. H. Ditkr.ai.Yi W. Luttke, ibid., m, 1899 (1972). 132. ti. Diekrann a22 W. Luttkz, ibid., 105, i911 (1972).

123. 3.L. Han:xik and ! - I . V . L i t e r , Z . Che-,. S O C . , 490 (1937).

121. 0. Graul and H. Hantzsch, Bcr., 31, 2 8 5 7 i i S ? E E l .

125. G. Endrfs and H. Bottranr,, ibid., 65, 6 8 (:F;3-7:.

126. L. Birckenbach and K. Se.;r.ewald, Ann., E, 15 (1931). 127. A . Langhans, J. Prakt. Chez:.. 2, 98, 207 ( 1 9 1 8 ) .

128. A. Langhans, 2 . Analyt. Chey., 57, 402 ( 1 9 1 E ) .

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a-HALONITROSO COMPOUNDS. h REVIEW

129. L. de Paolini, Gazz. Chin. Ital., 59, 818 (1929).

130. 0. Piloty, Ber., 31, 452 (1898).

131. S. Ranganathan, H. Raman and C.V. Srinivasan, Tetrahe-

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134. H. Rheinboldt and M. Dewald, ibid., 460, 305 (1928).

135. H. Rheinboldt and 0. Schriitz-I)amont, ibid., 444, 114

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13E. E. >:filler and H. Metzger, Chem. Ber., 87, 1287 (i954).

137. 14. K ~ g e l - a . , A.R. Mallarrs and H.F. Vernay, ?. Cl-:EF. SOC.,

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138. L.W. Kissinger and F.E. 'Jr.gr,ade, J. Org. C h s n , . , B, 1517 (1958).

139. E. Miiller and H. Metzger, C t - 2 % . Ber., 8E;, 396 (155.6).

14C. 3. Rksir-.Soldt, Ann., 451, 161 (1927).

14:. H. Rheinboldt an2 M. Dewald, ibid., 455, 300 (1927).

14-1. Ck.-Y. Shiue, K . F . Park and L.B. Clapp, J. Org. Chez.,

35, 2C63 (1970).

143. E.G. BoZzi, Ch.-Y. S h i i a a23 L.B. Clapp, ibid., 38, 5E

(i972i.

134. P . Davls, E . C . Vcgt and C.F. Deck, 7s . 3,95f,822 ;1F.7€) ;

P . L - . n . , c, 79082q (1976). 115. H. 9iekr:ar.z ard W. Liittke, Angew. Ckd.:.. Int. Ecgl. E C . ,

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1 4 6 . H. Diekmann and W. Luttke, ibid., 1, 387 (i962). 147. B. IJacef, M. Dacdon and H. Plnatel, Synth. C C - : ~ : ~ . , 1,

153 (1977).

409

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KRESZE, ASCHERL, BRAUN AND FELBEF:

1 4 8 .

1 4 9 .

153.

151.

1 5 2 .

153.

1 5 c .

i 5 5 .

1 5 6 .

1 5 7 .

1 5 8 .

159.

160.

H . I l i t s c h and G . K r e s z e , Angew. Chen:. I n t . E n g l . E d . ,

- 1 5 , 7 6 0 ( 1 9 7 6 ) .

M. S a b u n i , G. Kresze a n d H . B r a u n , T e t r a h e d r o c L t ? t t . ,

25, 5377 ( 1 9 8 4 ) .

H . F e l b e r , G. K r e s z e , H . B r a u n and A . V a s e l l a , i b i d . ,

25, 5381 ( 1 9 8 4 ) .

D . C . I f f l a n d an2 G . X . C r i r i s r , J. A n . Chrni. S O C . , 3,

4047 (1953).

D . C . I f f l a n d arid T . Fu-Yen, i b i d . , 76, 4G84 ( 1 9 5 4 ) .

D . C . I f f l a n d and T . Fu-Yen, i b i d . , 76, 4GE3 ( 1 9 5 4 ) .

J . R . B u l l , S i r Ewar t R . H . J o n e s and G . D . M e a k i n s ,

Z . C b t ~ . . SO:., 2 6 0 1 (19651.

A . X . F a t c h e t t , F . Hoffxai.:,, F . F . G i a r r : i s s o , E. Schwa3

a n d G . E . A r t h , Z . O r y . Ck,;.::,., 27, 3 S 2 2 ( 1 9 6 2 : .

G . P o c z i o , Gazz . C h l x . I t a l . : 36, 1 G l (1906).

L . F . F i e s e r and M . F i e s e r , R e a ~ ~ n t s f o r O r g a n i c S y n -

thesis, 1, 90 (1967).

A . E . M . Kayen , F:. D c Boer and T h . J . D s Boi-r , R e c l .

T r a v . Cf ' in. Pays-ass, 96, 1 ( 1 9 7 7 ) .

A.1.J. Hope and S . M i t c k s l l , J. ?'..--. - L A C . , ! . S O C . , 3483 ( 1 9 5 3 )

J. Lab a n d Th.J. D e B o e r , R e c l . T r a v . Chiir:. P a y s - E , : . . ~ ,

103, 3 2 8 (1984).

1 6 i . R . H u t t e n r a u c h , D . P . ( D D R ) 2 2 , 3 5 6 ( 1 9 6 1 ) ; C . A . , 59

9.252~ (1963).

16,2. R . H i i t t e n r a u c h , Arch . Pha r r . . (Weinhs i rn ) , 294, 33E. 19611.

1 6 3 . J.M.J. T r o n c h e t and J . F o n c e t , C a r b o t y d r . R e s . , e, 1 1 9

( 1 5 7 6 ) .

1 6 4 . J.M.J. T r o n c h s t a n d F . B a r b a l a t - R e y , P h a r ? . A c t a Etlv.,

4 10

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a-EXLONITROSO COMTOU1,IDS. A REViESi

- 5 0 , 404 ( 1 9 7 5 ) .

1 6 5 . B. Aebischer, A. Vasella and H.-P. Weber, H2lv. Chim.

Acta, 65, 6 2 1 ( 1 9 8 2 ) .

1 6 6 . J.P. Snyder, M.L. Heyman and E.N. Suciu, J. Org. Chem.,

40, 1 3 9 5 ( 1 9 7 5 ) .

1 6 7 . J . Kovacs, Acta Univ. Szeged. Phys. et Chin:., 2, 56

(19483 ; C.A., 44, 6364g ( 1 9 5 0 ) .

1 6 8 . H. Brintzinger, H.W. Ziegler azd E . Schneider, 2. Elek-

trocr;e.n.., 53, 110 ( 1 9 4 9 ) .

1 6 9 . W. Steinkopf and B. Jiirgens, J. Prakt. Che-.., 84, 686

( 1 9 1 1 ) .

170. W. Steinkopf and B. Jurgens, ibid., 83, 453 1 1 9 1 1 ) .

1 7 1 . I.L. Kxiunyants, k.V. Fokin and V.S. B l a g o v * s c t n s k i j ,

Dokl. Akad. Nadk SSSR, 146, 1088 ( 1 9 6 2 ) ; C.A., 58,

7840 ( 1 9 6 3 ) .

1 7 2 . X.M. Krzhizhevskii, N. Mirzabekyants, Su.A. Chebukov

and I.L. Knunyants, Izv. Akad. Nauk SSSR, Ser. Khim.,

2513 ( 1 9 7 4 ) .

1 7 3 . I.V. Martynov aEr? Y.L. Kruglyak, Zh. O k s h c t . Kkim., 35,

2 C E ( i . 9 6 5 ) .

1 7 4 . I.V. Martynov and A.N. Degtyarev, Izv. Akar?. T;aA S S S R ,

Ser. Khirr., 650 ( 1 9 9 3 ) .

1 7 5 . R.L. Heath arid J.D. Rose, J. Chen. SOC., 1 4 8 5 ( 1 9 4 7 ) .

1 7 6 . R.Z. Fakhrutdinov, L.E. Ryabova, T.A. Arkhipcva and R.G.

Musina, Zh. Obshch. Khin., 54, 474 ( 1 9 9 4 ) .

1 7 7 . M.O. Forster, J. Chem. SOC., 75, 1 1 4 1 (1859).

1 7 8 . 0. Piloty and H. Steinbock, Ber., 35, 3115 (19G2) .

1 7 9 . A. Werner and H. Buss, ibid., 3, 2199 ( 1 8 9 4 ) .

411

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KRESZE, ASCHERL, BRAUN AND FELBEF.

180. H. Wieland, i b i d . , 40, 1670 (1907).

181. H . R h e i n b o l d t , M . Dewald, F . J a n s s n and 0 . S c h r l t z -

Dumont, Ann., 451, 166 (1927). 182. E . M i l l e r and H . Metzger , Chen. B e r . , 87, 1286 (1954).

183. R . H . Wiley and B.J. Wakef ie ld , J. Org. Che;?., 25, 546

(1960).

184. I . V . R . Kaufmari ar,d J . P . P i c a r d , Chem. Rev. , 59, 439

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185. 2 . Bakke, Acta Chec.. S c a n d . , z, 1833 (19651. 186. E . I- izller and W . Rudei , Cher:. B e r . , 91, 466 (1958).

i F 7 . G.S. S k i n n e r , J . Az:. C k L = ~ , . SOC., c, 731 (1924). leS. L.W. K i s s l n g - ; r , W . E . HcQuist ion and I<. S c h w a r t z , T e t r a -

hsdror., S L ; ? ~ . 1, =, 137 (19t5.3). 169. E . X . Gglcbir , , T.11. Grigcrri;-a a n d A . h . F s t k k h i n , Zh. Grs.

Khim., 2, 13EO (1959).

19G. X.Ya. Yakubpvic t , V.A. St ,panski i and A . L . . Lc:?k.c, 211.

Obshch. Khi:., 24, 2257 (1954).

191. X.Ya. Yakubovizh, V . A . Shpariski i ar.d A . L . Leyke, Pcki.

Akad. Nauk SSSR, 96, 773 (i954).

192. Y. C a l v e z , J. T u a i l l c n and R . P s r r c t , H e i v . C h i p . Ac+a ,

- 57, 1433 (1574).

193. A . I . T i t o v , Dokl. Akad. Nauk S S S R , 149, 619 (1953).

194. J.D. P a r k , A . P . S t e f a n i and J . R . Lacher , J. 3 r g . Cherr.,

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195. E . Mul le r , H. Metzgsr and D . F r i e s , DE 1,001,9S3 (1957);

C . A . , 53, 17926d (1959).

196. B.W. T a t t e r s h a l l , J. Chrm. S C C . , Cherr,. Comm~n., 1522

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3-HALONITROSO COMPOUNDS. A REVIEW

197. B.W. Tattershall, J. Chem. SOC. A, 3261 (1970).

198. A. Henglein, Intern. J. Appl. Radiation and Isotope, 8 ,

149 (1960); C.A., 55, 23302b (1961).

199. A. Henglein, Angew. Che?n. 72, 603 (1960).

200. I.L. Knunyants and G.A. Sokol'skii, Dokl. Akad. Nauk

SSSR, 132, 602 (1960). 201. W. Prandtl and E. Sennewald, Ber., 62, 1754 (1929).

202. W. Prandtl and W. Dollfus, ibid., 65, 754 (1932).

203. H. Sutcliffe, J. Org. Chen., 30, 3221 (1965).

204. M . K . Fein and J.E. Paustian, U.S. 3,304,335 (1967);

C.A., G, 75663q (1967).

205. E.C. Star;>, W.H. Oliver and C . D . Padgett, J. Org. Chem.,

- 33, 2102 (1968).

205. W.H. Oliver, U.S. 3,554,885 (1971); C.A., 74, 885215

(197i!.

207. W.H. Oliver, C.D. Padgett ard E.C. Stump,

U.S. 2,726,885 (1973); C.A., 78, 1637204. (1973).

208. L.V. Sarikixa, I.N. Belyaeva, P.O. Gitel', L.I. Kostikir,

acd V.A. Ginsburg, Zh. O r g . Khia., g , 1357 (1972).

209. T. Umezoto and H. Tsutsurni, Bull. Chen. Soc. Jpn., 56,

631 (1983).

210. SaZani Chemical Research Center, JP 57,70,841 (1982);

C.A., 97, 1443.40~1 (1982).

211. S . A . F.ink?aC! and J.M. Shreeve, Ir.org. Chem., 23, 4174

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212. R.E. Banks, 11. Dickins3iL, A.P. Morrisssy and

k . Richards, J. Fluorine Che3., 26, 87 (19843.

213. R.E. Banks and N. Dickinson, J. Cke!x. SOC., P ~ r k i ~ .

413

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KRESZE, ASCHERL, BRAUN AND FELBER

214.

21 5

216.

217.

218.

219.

220.

2 2 1 .

222.

223.

224

225.

226.

227.

Trans. 1, 685 (1982).

R.E. Banks and N. Dickinson, J. Fluorine Chem., 19, 97

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H.M. Marsden and J.M. Shreeve, Inorg. Chem., 23, 3651

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R.A. Bekker, G.G. Melikyan, B.L. Dyatkin and I.L.

Knunyants, Zh. Org. K h l m . , 11, 1604 (1975). T.D. Truskanova, V.I. Panteleev and A.F. Koloiniets,

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A.V. Fokin, Yu.N. Studnev, A . I . Rapkin and V.G.

Chilikic, Izv. Akad. Nauk SSSR, Ser. Khim., 2838 (1982).

A.V. Fokin, Yu.N. Studnev, A.I. Rapkin and V.B.

Chilikic, ibid., 1196 (1984).

V.L. Isaev, R.K. Sterlin, V.M. Izmailov and

I.L. Kr.unyants, Zh. Vsis. K!-.ix'. Obshchest., 18, 713

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H. Lange and D. Naunan.?, J. Fluorine Che-i., 26, 93

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0. Wichterle, Coll. Czech. Chem. Commun., 12, 292 (1947 1 . 0. Wichterle, M. Kolinsky, Chem. Listy, 47, l7E7 (195-7);

C.A., 49, 201h (1955).

0. Wichterle and J. Novak, Coll. Czech. Cher.. Commun.,

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0. Wichterle and S. Svastal, ibid., 16, 33 (1951).

0. Wichterle and M. Kolinsky, ibid., 19, 493 (1954).

0. Wichterle, V. Gregor, A. Dubansky and V. Seidl,

Chern. Listy, 51, 605 (1957); C.A., 51, 1797713 (1957).

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a-HkLOrIITROSO COMPOUNDS. A REVIEW

228. 0. Wichterle, V. Gregor, A. Dubansky and V. Seidl,

Coll. Czech. Chem. Commun., 24, 1158 (1959).

224. Y . A . Arbuzov and A. Markovskaya, Izv. Akad. Nauk SSSR,

Ser. Khim., 363 (1952).

230. Y.A. Arbuzov and A.A. Onishchenko, Dokl. Akad. Nauk

SSSF., 146, 1075 (1962).

231. Y.A. Arbuzov, Doctoral Thesis, (1953).

232. A.J. Finkelshtein, Y.A. Arbuzov and P.P. Shorygin, Zk.

Fiz. Khir., 24, 802 (1950); C.A., 45, 2948g (1951).

233. D. Klamann, P. Weyerstahl and M. Fligge, Angew. Chec.,

- 75, 1120 (1963).

234. D. Klanann, P. Weyerstahl, M. Fligge and J. Kratzer,

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235. D. Klanam, P. Weyerstahl, M. Fligge and K. Ulm, Chem.

BET., 99, 561 (1966).

236. G. Kresze and 0. Korpiur,, Tetrahedron, 22, 2493 (1966).

237. 0. Korpiun, Ph. I). Thesis, TU Munchen, (1966).

238. G. Kresze and E. Kysela, Ann., 202 (1981).

239. G. Kresze and W. Dittel, ibid., 610 (19el).

240. G. Kresze, W. Dittel and H. Melzer, ibid., 224 (1981).

241. G. Kr*sze, E. Kysela and W. Dittel, ibid., 210 (1981).

242. G. Kresze, M.M. Weip and W. Dittel, ibid., 203 (1984).

243. G. Kresze and H. Melzer, ibid., 1874 (1984).

244. H. Felber, G. Kresze, R. Prewo and A. Vasella, Helv.

Chilr.. Acta, 69, 1137 (1986).

245. H. Braun, K. Klier, G. Kresze, S. Sabuni, 0. Werbitzky

and J. Winkler, Ann., 1360 (1986).

246. E. Kysela, Ph. D. Thesis, TU Munchen, (1972).

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KRESZE, ASCHERL, BRAUN AND FELBER

247. W. Dittel, Ph. D. T!:Esis, TU l-ll!lck-,sri, ( 1 9 7 7 ) .

2 4 8 . 0. Werbltzky, Ph. D. Thesis, TU I.lG?cher,, ( 1 9 E 6 ) .

249. N.1-I. WeiP, Ph. D. Thesis, TiJ Munchen, (3982).

250. K. Klier, Ph. D. Thesis, TU MCncten, ( 1 9 8 6 ) .

251. U. Dederer, Ph. D. Thesis, TU Munchsn, ( 1 9 8 4 ) .

2 5 2 . S.B. Needleman and M.C. ChaLgkuo, Cher. Rev., 63, 405

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253. Y.A. Arbuzov, Russ. Cl-izn. Rev., 33, 437 ( 1 9 6 4 ) .

254. G. Kr=sze and J. Firl, Fortschr. Cher. Forsch., 11, 245

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2 5 5 . S.W. Weinreb and R.R. Staib, Tetrahedron, 38, 3087

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255. H. Labaziewicz, F.G. Riddell and 3.G. Sayer, J. ChsT.

S O C . , Perkin Trans. 2 , 519 ( 1 9 7 7 ) .

257. B. Bellead and Y. Ax-Young, Z . Ar. Cher;. SOC., a, 6 4

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253. J. Distler, IC. Klier, W. Piendl, 0. Werbitzky, A. Bock,

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2 5 9 . D. Ranganathar, S . Rangarlathan, C.B. Raa and K. Raman,

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260. L. Schwab, J. Med. Cher., 23, 698 (1980).

261. S. Archer, A. Seyed-Mozaffari, P. Osey-Gyirah, J.M.

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262. H. Iida, Y. Watanabe and Ch. Kibayashi, Tetrahcdron

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263. N.J. Leonard, A.J. Playtis, F.S. Skoog and R.Y. SchTitz,

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a-HALONITROSO COMPOUNDS. A REVIEW

264. E. Kesler, J. Heterocycl. Chem., 17, 1113 (1980). 265. R.E. Banks, M.G. Barlow and R.N. Haszeldine, J. Chez.

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266. R.E. Banks, M.G. Barlow and R.N. Haszeldine, ibid., 6149

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267. R.E. Banks, R.N. Haszeldine and D.R. Taylor, ibid., 5602

(1965).

268. R.E. Banks, R . N . Haszeldine and D.R. Taylor, ibid., 978

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269. R.E. Banks, A.C. Harrison, R.N. Haszeldine and K.G.

Orrell, J. Chem. SOC., Chen. Commun., I, 41 (1965).

270. M.G. Barlow, R . N . Haszeldine and K.W. Murray, J. Cher,.

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271. R.E. Banks, A.C. Harrison, R.M. Haszeldine and K.G.

Orrell, J. Chem. SOC. C, 1608 (1967).

272. R.N. Haszeldine, R.E. Banks, M. Bridge, D.W. Roberts

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273. A.V. Fokin, A.T. Uzun and O.V. Dement'eva, Zh. Obshch.

Khix., 37, 781 (1967).

274. A.V. Fokin and A.T. Uzun, ibid., 38, 836 (1968).

275. A.V. Fokin, A.T. Uzun arid O.V. Dement'eva, ibid., 37,

834 (1967).

276. A. Angeli, L. Alessandri and R. Pegna, Atti Acad. Lincei,

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277. G.T. Knight and B. Pepper, Tetrahedron, 27, 6201 (1971).

278. V.A. Ginsburg, A.N. Medvedev, M.F. Lebedeva and

L.L. Martynova, Zh. Org. Khim., 10, 1416 (1974).

279. C. Schenk and Th.J. De Boer, Recl. Trav. Chir. Pays-Bas,

417

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KRESZE, ASCHERL, BRAUN AND FELBER

28C.

2 8 1 .

282 .

2 8 3 .

2 8 4 .

285 .

286 .

2 8 7 .

2 8 8 .

2 8 9 .

2 9 0 .

291 .

292 .

293 .

2 9 4 .

2 9 5 .

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K. Burger and 0. Dengler, Chem.-Ztg., 106, 408 ( 1 9 8 2 ) .

J. Varwig and R. Mews, Angew. Chem. Int. Engl. Ed., 16,

646 ( 1 9 7 7 ) .

R.E. Banks and A . Richards, J. Chem. SOC., CCcr. Comnm.,

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D.A. Barr and R.N. Haszeldine, J. Chem. SOT., 1 8 8 1 ( 1 9 5 5 ) .

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a-HALONITROSO COMPOUNDS. A REVIEW

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KRESZE, ASCHERL, BRAUN AND FELBER

C.A., 88, 121164g (1978).

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a-HALONITROSO COMPC'JNDS. A REVIEW

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KRESZE, ASCHERL, BRAUN AND FELBER

336. K.A. Ogloblin, V.A. Nikitin, T.L. Yufa arid A.A. Potekhin,

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345. V.X. Ginsburg, V.V. Smolyanitskaya, A.N. Medvedev, V.S.

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a-HALONITROSO COKPO'JNDS . A REVIEW

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KRESZE, ASCHERL,, BRAUN AN3 FELBER

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a-HALONITROSO COMPOUNDS. A REVIEW

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K R E S Z E , ASCHERL, BRAWN AND FELBER

397.

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N i k o f o i s c a , DcL.1. A k a d . Nauk SSSR, 141, 3 5 7 (19€1).

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(Received February 10, 1986; i n r e v i s e d form March 16, 1987)

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