Temhedron Vol. 24, pp. 1931 to 1944. Fergamon Run 1968. Printed is Cheat BnUin

NUCLEOPHILIC 1 ,ZADDITI(?NS TO THE CARBONYL GR~JJP : OF &~IN~NES I -

HYDROLYSIS AND ALCOHQLYSIS OI+l-?-iE PEF-i?AOXYPHOSPHORANES DERIVED FROM THE CO~DENSATIb’i f3F a-DIKETONES WITH

p-QUINONES BY MEANS OF TRIALKkL PHOSPHITES’

F. RMam,* H. J. KUGLW and C. P. SWTH Department of Chemistry of the State University of New York, Stony Brook, N.Y. 11790

(Received in USA 14 July 1967; accepted/or publication 18 August 1967)

Ahabmet-The tendency of certain nucleophiles to perform 1 ,Zadditions to the Co group of pquinones has been demonstrated. The nucleophile was 2,2,2-trimethoxy4,5dimethyl-2,2dihydro-l,3,2dioxa- phospholene, made from biacetyl and trimethyl phosphite. The products of the 1,2-additions top-bemo- quinone and to l+naphthoquinone were derivatives of the 2,2dihydro-1,3,2dioxaphospholane ring system with pentacovalent phosphorus. These pentaoxyphosphoranes were converted by one equivalent of water into biacetyl, methanol and the phosphate ester of the corresponding hydroquinone. Methanol induced a molecular rearrangement of the pentaoxyphosphoranes; the products were methyl acetate, trimethyl phosphate and the p-acetyl-phenols, i.e. acetophenone and I-hydroxy-4acetyl-naphthalene, respectively.

INTRODUCTION

THE ability of 2,2,2-trimethoxy-4,5-dialkyl-2,2dihydro-1,3,2-dioxaphospholenes, I, to act as nucleophiles was first reported’ in 1962.

Me Me Me Me Me Me Me Me

A& I I I I I A 9 ,A 5 + 1-A - a

MedPbMe A Me

1: aP31 = +489 ppm Ila : cis Me/Me; aP3’ = + 548 ppm

us. H,PO, IIb : tram Me/Me ; aP”t = + 52.6 ppm

This discovery was a corollary of the previous observation to the effect that one mole of trialkyl phosphite caused the condensation of two moles of the adiketone acenaphthenequinone. 3 The product of this condensation was a derivative of the 2,2-dihydro-1,3,2dioxaphospholane ring system (V). It was reasoned that the 2 : 1-adduct V was formed by reaction of the 1: :l-adduct, III or IV, with a second molecule of acenaphthenequinone It was not possible to establish if the 1: l-adduct in this case was an open dipolar structure III or a cyclic pentaoxyphosphorane IV.

l Th& investigation was supportal by Public Health Service Grant, CA*769 from the National Cancer Institute.

1931

1932 F. RAMWE, H. J. KUGLIS and C. P. SMITH

+ (MeO),P -

III

IV

III-IV + - y$-p<TJ

MedPbMe OMC

V: dP3’ = +48*ppm

The derivatives of the 2,2dihydro-1,3,2dioxaphospholene ring system (I) were made from the reaction of trialkyl phosphites with adiketones and with o-quinones.’ This reaction was reported independently by three different groups of investigators,c6 Recent work has shown the generality of the formation of phospholenes of type VI from the reaction of trialkyl phosphites with vicinal polycarbonyl compounds.’

I-! + (R’O) P

bl 8

3 _u

A b A/ R’tiPAOR’

AR’

VI

Our studies of the reactions of trialkyl phosphites with adiketones and with oquinones were suggested by the observation that the phosphorous of trialkyl phosphites attacked the CO oxygen of ~uinones8 This reaction was first described in 1957 and provided a new route to monoalkyl ethers of wuinol phosphates (VIII).s

VII I: LIPa1 = +37 ppm

Nucleophilic I ,2-additions to the carbonyl group of p-quinones 1933

The phenolic pquinol phosphates (IX) were made, at about the same time, by the reaction of dialkyl phosphites (dialkyl hydrogenphosphonates) with pquinones9

9 + gg-H -

OH

IX

The present paper relates several of these observations and is concerned with the condensation of adiketones with p-quinones by means of trialkyl phosphites. Other investigations from this laboratory” had shown that trialkyl phosphites could be used to condense adiketones with a variety of monocarbonyl and of polycarhonyl compounds.

+ uI’O),P - 1 t r R#,’

a 0 ‘P

b

R’O’ 1 ‘OR’ OR’

X

It seemed desirable to study the addition of phospholenes of type I to pquinones because no authentic products of nucleophilic 1,24dition to the CO carbon of pquinones had been reported. Bishop et al.” provided indirect evidence that bisullite ions and hydroxide ions were capable of performing reversible nucleophilic l&ulditions to the CO carbon of pquinones. However, the adducts could not be isolated and, therefore, their structures could not be established unequivocally.

RESULTS

Reaction of ~2-trimethoxy-4,5dinrethyl-2~dihydro-1,3,2-dioxaphosphole (I) with pquinones

The phospholene I added to p-benzoquinone at 20” in methylene chloride solution. The crystalline adduct which was isolated from this reaction in nearly quantitative yield was assigned the pentaoxyphosphorane structure XI.

Me Me

*; + o+ - #.o. ‘P’

bled 1 ‘OMe ‘P’

OMe MeO’ 1 ‘OMe

OMe

1 x1: aP31 = +*3ppm

1934 F. RAMIRE?, H. J. KUGLW and C. P. SMITH

The IR spectrum of adduct Xl is reproduced in Fig 1. The bands at 5.84, 5.98 and 6.13 u are entirely consistent with the presence of the a&y1 and the cyclo- hexadienone groupings. The UV spectrum had a max at 230 nq.t with a relatively high extinction coefficient, E = 9600.

‘40 ‘6 0 ‘70 ‘80 100 ]

i%G. 1.

(81 A. #

640 ID) Ii’ NMR IA) 9H' 3 H’

60 MClSEC (0) “A+ cc14

-0 c*\ 0 c--iD,

"%",P, o H H

CH30 F 0

-43

(Cl

k-l P3’ + 50.3 PPM

vs li3PO.$

“HP * 12 5 CPS

(Cl

3 Ii’

1 7e3r

--L 1 es57

r)rls

FIG. 2

The ‘H NMR spectrum of the adduct is shown in Fig. 2; it is in good agreement with the proposed structure. Note the singlets due to the AC and the Me groups attached to the phospholene ring, and the doublet due to the three magnetically equivalent or indistinguishable OMe groups attached to the phosphorus. The doublet is due to H-P coupling, and the apparent equivalence of the three OMe groups is analogous to the equivalent situation observed in a rather large number of pentaoxyphosphoranes.

The positive value of the 31P NMR shift is characteristic of structures having 5 oxygens covalently bound to the phosphorus X-ray analysis of a related penta- oxyphosphorane has shown that compounds of this type have the configuration of trigonal bipryramids, XII, in the crystalline state.12 The phosphorus was at the center of the bipyramid and the 1,3,2dioxaphospholene ring was situated in an

Nucleophilic 1 J-additions to the carbonyl group of p-quinones 1935

apical-equatorial plane. In solution, the three OMe groups apparently underwent relatively rapid positional exchange at 20”, and even at - 70”, as shown by the ‘H NMR spectrum.10*13*

OMe

XII

The phospholene I reacted very slowly with 1.4naphthoquinone at 0” in methylene chloride. The reaction was carried out also at 20”. It was found that the rate of formation of the adduct, XIII, was only slightly greater than the rate of its de- composition. Therefore, the reaction of the phospholene with the naphthoquinone was allowed to proceed only to 60% completion and the adduct XIII was isolated as described in the Experimental.

I +

XIII: dP3’ = +SOppm

The spectral data were consistent with the pentaoxyphosphorane structure. This compound was significantly less stable than the corresponding p-benzoquinone adduct, both in solutions and in the solid state.

Two diastereomers are possible for the oxyphosphorane structure, but only one could be characterized. Its configuration was not established with certainty; how- ever, the ‘H NMR spectrum suggested that the acetyl group was cis to the Ph ring as shown in XIII. Thus, the AC signal was at a significantly higher magnetic field, T 8.34, in XIII than in the pbenzoquinone analog XI, r 7.83. On the other hand, the Me groups attached to the phospholene ring gave comparable signals in both compounds, i.e. r 8.56 in XIII and r 865 in XI. The upfield shift of the AC signal is probably due to the shielding of the protons by the benzene ring.

Hydrolysis of the trimethyl biacetyfquinone-phosphite adducts When a 2M solution of the biacetyl-pbenzoquinone-phosphite adduct, XI, in

methylene chloride was treated with one mole equiwlent of water, methanol, biacetyl and dimethyl phydroxyphenyl phosphate (XIV) were produced.

l Apparently, cyclic tetraoxyakylphosphoran~ unlike cyclic pentaoxyphosphoranes, showed magnetic non-equivalency of the three OMe groups at -67”, but not at 20”.13

1936 F. RAMZREZ, H. .I. KUG and C. P. Swm

XIV: i?P = +4*1 pprn

stances were formed in eq ol ph~§~~t~ XI-V,

quincllne and dimethyl phosphite? 1 de ’ 5

Hydrolysis of the biacetyl-1,4_naphthoquinone_phosphite adduct with one mcrk equivalent of water in benzene solution gave methauo~ biacztyl, and dimethyl 4-hydroxy- 1 -naphthylphosphate (XV).

1N~O XIII - MGOH +

Me Me 1 I r--- +

xv

The addition of a k~ge excex~ of WU&T to the benzene solutions of the penta- oxyphosphoranleq XI and XII& gave differat products than those obtained in the ~ydr~ly~ with one mole ~uiv~~nt of water.

With excess of water the ponding pquinols, i.e. hyd

independently shown that t hydruquinone and 1,4&h

rc~lyses of the ~~~0~ equivalent of wat and when an excess of water were & Possible mechanisms are proposed in the Discussion.

1937

Me Me EXCESS

XIII -jy-g + HIJP04 + + 3MeOH i

XVII

XVIII

ment was siflcautly faster in mHha.nol than this solvent, no usably

reaction occurred up. to w The f~~t~~ of about 20% of t-butyl acetate was demonstrated, but ther crystalline products

XIX

This investi@tibn showed that nucleop add to the CO group of pquiuones to form relatively stible products of 1,2-ad&.ion~.~~~ I6 ‘The &&i&y&-a-

1938 F. RAMIW.Z, H. J. KUGLER and C. P. SKITH

1.3.2~dioxaphospholen system is particularly suitable for the demonstration of this phenomenon because the products of the l&carbonyl additions are stabilized in the form of the 2,2dihydro- 1,3,2dioxaphospholan system It may be that many nucleophiles, N, add reuersibly to the CO of pquinones but end up finally as the more stable products of the l+additions of the nucleophile to the carbon of the quinone, i.e. l+addition.

The results of the hydrolyses and of the methanolysis of the pentaoxyphosphorane were of considerable interest. The following mechanisms explain our results satis- factorily.”

The nucleophilic attack by one equivalent of water on the cyclic pentaoxyphos- phorane in solvents of low polarity should lead to a cyclic hydroxytetraalkoxy- phosphorane XX. The latter should collapse to the observed products, biacetyl and dimethyl phydroxyphenylphosphate (XIV) as shown. The intermediate, XXI, is a quinonoid cz,lMihydroxyketone and should decompose rapidly to the observed products, i.e. the diketone and the pquinol phosphate. The hydrolysis may be a concerted process not involving XXI as an intermediate at alL The alternate mode of cleavage of the phosphorane XX to quinone and dimethyl phosphoacetoin (XXII) is, evidently, a less favorable reaction.

pl~!&=J=o - :P.c Me0 1 OH

OMe

xx

H

NOT OBSERVED

NOT OBSERVED

XXIII

It is kmwn that the r ite with in tFrte preserve of water, t~ethy~ phusp~a~ and hydr~~ui~~n~ This is t

from the hydr~~ysjs ~~~~~e~~~a~ WI ~re~~usly shown. The latter on ad~it~u~ of water.

If the bydr~ly~ are should be rapidly d~~k~~ypb~sph~~ XXVI. The latter should col~ap~ to the observed phosphoric acid and hydr~u~~~e~

1940 F. RAMIIUZ, H. J. KUGLER and C. P. SMITH

The cyclic hydroxytetraalkoxyphosphorane, XX, can collapse with retention of the ring to yield the cyclic phosphotriester XXVIIL This has been observed in a number of related cyclic oxyphosphoranes, for example II.” However, it is knownl*~lg that the reactivity of 5-membered cyclic phosphate esters toward nucleophiles is extraordinarily high. Therefore, rapid methanolysis of XXVIII to the open phos- photriester XXI would be expected. This methanolysis probably involves an addition of methanol to the phosphoryl group with formation of the common intermediate XX having pentavelent phosphorus.20

MCO, ,o HP\

t 0 0 + XXVIII .

A solvent with a relatively large dielectric constant like methanol, capable also of hydrogen-bonding to the phosphorane, could induce the series of changes shown in formulas XXIX + XXXX + XXXL Methanolysis of the enol-acetate XXX1 should give the observed products, methyl acetate and phydroxyacetophenone (XVIII).

,&*p ‘-; + J ‘i’ Mco’ ‘0%

MC0

XXIX

;:o,r - 1 v- =c-

OP(OCH,&

XXX1

xxx

Me MeQH I

C-OMe + H

XVIII

The driving force for this rearrangement is the ejection of a molecuk of the stable trimethyl phosphate.

A structure very similar to XXX was suggested by Kuart2’ to explain the formation of an anhydride from the reaction of a peroxyanion with an adiketone.

Another mechanism for the formation of phydroxyacetophenone, trimethyl phosphate and methyl acetate from the methanolysis of the oxyphosphorane is shown in formula XXXII.

MeO-iLt%(=)O -M&-5’ + ;p MeONP'OMe d MC OP( OMe),

XVIIhl

xxx11

Nuckophilic 1,2-additions to the carbonyl group of p-quinona 1941

This involve addition of methanol to the keto group, followed by cleavage of a C-O bond. This mechanism would not involve the formation of an enolacetate intermediate. It was shown that the methanolysis of the pentaoxyphosphorane V made from acenaphthenequinone and trimethyl phosphite gave an en01 lactone.3 This rearrangement is strikingly similar to that observed in the quinonediketone adducts, XI and XIIL Therefore, the former mechanism, proceeding via the en01 acetate XXX1 is favored.

EXPERIMENTAL

AnaIyecs wem performed by Schwarzkopf Microanalytical Laboratory. Woodsidq N.Y. “P NMR shifEswcrcmeasuredat~SMc/s;thcyarcgivarinppmmH,PO,asna’HNMRwmmcasurtd at6OMc/s;theyaregi~inppmmTMS= lO(rvaluea).

~-TrimnhoxrsJ_diy~-~~~~~l,3~-d&~s~&~ (I) Freshly dktilkd biityl was added dropwise_ undo N2, to 1.1 mole-cquivta of anhyd trimethyl phosphite held at O-5”. The mixture was aIlowzd to nacb 20”, kept there Overnight and thcll distilled. The oolorkss phosphokne I 45 14385, b.p. 45” (@2 mm) was obtained in 95% yield It must be protected against moisture and oxygen.

Reaction of the phpholene I wizh p-benzoqubwne A soln d 304 g (@280 moles) pbenzoquinone in 150 ml CHICll was added ova a 10 min ptriod to a

&I Oz m g (0280 molea) d the phosphoknc in 150 ml CH,C& at 0”. The soln was stirred for 2 hr at 0”. The solvent was evaporated at 20” (20 mm) Tlx residue was a thick glass which cry&all&d what kept at -15”. RecrystaGation from hexanc afforded XI, mp 65q in 90% yield (Found: C 48%; H, 6-3; P, 9-5. C,aH,,O,P requirea: C 49-O; H, 6-O; P, 9.77’) -l%e ‘H NMR spedrum had the following signals: multipleta at T 3.3 and 3-8 (4H), doubkt at T 664, JH, = 12.5 c/s (9H), aingkt at T 7.83 (3H), sin@ at T 865 (3H). J:’ = +5@3 ppm (in CH,CI,) The IR spectrum had main bands at 5.84 (AC), 593 (dienone ~),613(~and935(POCH1)~(inCH1CI,).TbcW~hed~-2#)mHe=9600.

Reaction of the pbsphokme I with 1,4-naphthoquinone A soln of 16-6 g (0014 moles) 1,4-naphthcquinone in 100 ml CH,CI, was added all at once to a ~oln

of 22Qg (0104moles) of the phosphoknc in lOOmI Cl&C& at 2@’ with stirring The soln wed stirred ZLlhratU)“andwaskcptanadditionalZAhratO”.ThtsolvcntwasremovadimaniaebathatlOmm press and the residue was immediately treated with 80 ml MeOH, previously eookd to - 15”. The mixture was vigoroualy shaken for a few set and immediately filtered through a coarse synthered glans filter. The colorleracrystallinematcrialwasq~~washcdwithtwo30mlportiom~anddriadinadryN, atm (the rate of the reaction of the phospholane with MeOH is sufIiciently slow to pamit thin method of purilkatioo~ Compound XIII was obtained in 50% yield (19g) F phoepholanc underwent rapid decomposition at #p in the solid state and therefore, it was not submittal to analysis Howevex, the spectral data dieclosed its identity. The H’ NMR +xtrum had tbc following signals: multiple& at T 1.84 and 362(6H), doublet at T 6-25, IHT= 12ac/8 (9H), singkt at T 8.34(3H), and singb at T 856(3H).

J:' = + 50 ppm. The IR spectrum had main bands at 585 (AC), 5% (dienone G=Oh and 936 (POCH,), ~1 (in CHIC&).

Reaction of the t&ethyl biacetyl-pbenzoquinone~pbite dduu (Xl) with one mok-updde~ uf water Wata(l~ml)wasaddadanatonct,toaso~d34.7gdaddudin240mldbeMcatot200,with

&ring. The reaction was exothermk and the soln temp rose 45” within 15 min. Quantitative VPC of the soln showed the formation d cquimohr amounts d biaatyl and MeOH in tht amounb e+cted from the complete hydrolysis d XL The standard for tk VPC was made from authentic b&etyl and MeOH in bmzene at tlx concentrations expe&ed. The bulk d the nwtioo mixture was conccntratai at 20”(20mm)antltheresiduewasrecrystalli&at-15”from ~exalle compound XIV was obtained in nearly quantitatiw yield The aampk had mp. 71-72” aod ita spectral chuaacriatig were identical with those da sample ma& from p-benzoquinone and dimethyl phoaphite

Reaction of the trimethyl biacetyl l.~nap~ne~sphite adduct (XIII) wfth one v o$ water

1942 F. RAMIREZ, H. J. KUGLER and C. P. Swm

separate afta 15min The soln will submittal to VPC after 45min; the chromatogram showed the presence of 50-55 % of the theoretically expected amount of biacetyl. The soh was filtered and the 3.5 g (50% yield) of XV thus obtained was recrystallixed from bcxane-ethanoL (Found: C, 53.7; H, 4.8; P, 116. CtsHi,OQ requires: C 53.8; II, 49; P, %.)

Reaction qf tk trimethyl biacetyl-pbenzoquirtoneophosphite adduet (XI) with excess water A som of 14.1 g (0044 moles) of adduet in 50 ml CHsCI, was treated with 50 ml water at 203 The soln

&U stirred vigorously for 1 hr and was then refhrxed for 24 hr. The 2 layers were separated; the water layer was extracted twice with 30 ml CH#l,, ami added to the first CHsCls layer. The combined CH,Cls soln was subjeoted to VPC, IR, and H’ NMR analysis and was shown to contain 90% of the theoretically expected amounts of biacetyl and MeOH. This was done by comparison with CHsCl, solns containing biacetyl and MeOH in the expected amounts The water soin was extra&d 6 times with 60ml ether. The ether was evaporated at 20” (20 mmj The residue was a crystalline material which was identi6ed by H’ NMR spectrometry as hydroquinone The identify was eonfirmed by comparison with an authentic sample The hydroquinom was obtained in 78% d the expectad amounta Tk rcmaix@ watu soln was analyxed by means of P3’ NMR spectroscopy and was found to contain phosphoric acid.

Reaction of trimethyl biacetyl-1,4_naphthoquinonephosphite addud (XIII) with excess water A soln d 3 g (00102 moles) of XIII, in 10 ml CH,Cl, was treated with 20 mole-equivs water. After

10 mitt crystals had separated out of th stirred soIn. Mixed mp with authentic 1.4dihydtoxynaphthakne showed no depression.

Reaction of tk trimethyl biacetybpbenzoquinonephosphite addud (Xl) with methanol A suspension of 109 g (fHJ34 moles) d adduct in 50 ml MeOH was stirred at #)“. A vigorous exothcrmic

rcactionwaenotcdwithinlSmin;atthispointtheflasLwesimmcrsedinaniabathf~30min.Fi~y, the mixture was kept 15 min at 609 VPC d the McOH sohi showed the formation d MeOAc in nearly quantitative yield; this ester was also characterized by IR analysis Tk MeOH was removed at 20” (20mm) and the residue was seeded with crystals of phydroxyacetophcnone. Tk mixture was allowed to crystallize giving after filtration 1 g d p-hydroxyaeetophenonc Short path distihation afforded 32 g of trimethyl phosphate and a residue consisting danother 3.15 g dphydroxyaatophenonc These materials were identitied by comparison with authentic sample-s The yields d trimethyl phosphate and phydroxy- aeetophenone were 93 and 90 % respectively.

Reaction of rhe trimethyl biacetyl-gbenzoqubwneophosphite adduct (XI) with ethatwl A mixture d 19.3 g @062 moles) phospholane and 80 ml EtOH were stirred at 20”. In this ease, unlike

the situation that was observed with MeOH no exothermie step could be de&ted. The mixture was stirred for 36 hr. IR spectra and VPC disclosed the formation d biaeetyi and EtOAc in about 35% of the expected amounts respectively. The sotn was evaporated at 45” (20 mm) and the residue was submitted to short path distillation to remove trimethyl phosphate Tk residue was seeded with crystals dphydroxy- acetophenone The phydroxyacetophenont was isolated in 49% d tk theoretical amount (3 gj The trimethyl phosphate was isolated in 30% yield (3 gj

Reaction oftk trimethyl biclcetyl-l,eMphthoquinoncphosphae adduct, (XIII) with methad A suspension of 9.2g (OiJ28 moles) phosphola in 30ml MeOH was stirred at room temp An exo-

thermic reaction wSi noted after 5 min at which point the reaction flask was immersed in an ia bath for 3Omin WC d the MeOH soln showed the formation of MeOAc in 75% of the theoretically expected amount Tbe. solvent was evaporated at HP (20 mm) and the residuq a thick oil, erystallixed when kept at - 1” for a few hr. Filtration afforded 3.6g of I-hydroxy4acetylnaphthal~ in 78% yield TM structure of this material was established by corn- d tbc spectral properties and a mixed m.p determination with an authentic sample The trimethyl phosphate was obtained in 85 % yield (3.2 g).

Reaction elf pbenzoquinone with dimethyf phosphite (dimethyl hydrogenphosphonate) (a) A soln of 7.85 g pbenxoquinone in 60 ml benzene was added dropwise, over a 1 hr period, to a soln

d 8.6 g (1.1 mok equivs) dimethyl phosphite, (CH,O) P(O)H, in 20 ml benxene, containing 5 drops of Et,N, maintained at retlux temp TM light brown soln was kept an additional hr at reflux and was then evaporati at 20” and 25 mm (f&ly at @l mm). Tk spectral properties d the crude crystdlinc residue

Nucleophilic 1 ,Zadditions to the carbonyl group of pquinones 1943

(16gl were very similar to those of tk material obtained afta rarryatallizatioa from CHCls-kxane. Pure XJV had mp 72-73”. (Found: C, 44.2; H, 5.3. CsH, tOsP requirea: C, 449; H, 53 %.) Tk ‘H NMR spectruminCDCI,hadasinglctatsl.5(lHXamultipldatr3.2(4H)andadoubletatr~24J~= 11.SC/S (6H) bP” = +4-l ppm Tk IR spectrum had bands at: 2.80 (w), 3.10 (rnh 623 (VW), 662 (sh 690 (m), 7.8-8.1 (m), 8130 (ms), 9.50 (vs), 1@40 (vs), 11.60 (s) and 1190 (9).

(b) Quind phosphate, XIV, of hi& purity was obtained in hi& yield whut solid pbenxoquinone (5.5 g) was added in very small portions to dimethyl phosphite (5.5 g; 1 molt equiv) containing 5 drops EtIN, at 0”. About ok quarter of tk quinone was added within 1 hr; tk resulting solid mixture was diluted with 2Oml of CH,Cl, and the rest d tk quinok (dissolved in 25 ml d CH,Cls) was added dropwise at 0”. The mixture was kept 10 hr at 20”, and was then evaporated yielding 11 g d dimetbyl phydroxy- phenyl phosphate melting at 55-65”. Recrystallization gave 8 g of mp. 72-73” (CHCl,-cyc1ohexane)

(c) In the absena d Et,N, a mixture d pknxoquinone (24 g) and dimetbyl phosphite (7.4 g), kept 72 hr at 20”, contained a relatively large amount d unrtacted quinonc Quinone was still present even after3hrat 100”and20hrat#)“,intkabsenadtkamine.

REFERENCES

* a Organic compounds with pentavaknt phosphow part XXXVII ; b part XXXVI, F. Ramira, S R Bbatia, A. V. Patwardhan, E H Chm and C P. Smith, J. Ore. Chew. 32 (1967); c A preliminary communication describing part of this work has appeared, F. Ramircz, H. J. Kuglcr and C P. Smith. Terrahedroa Letters 261 (1965).

2 F. Ramirex N. Ramanathan and N. B. Desai, J. Am C/ten Soo M 1317 (1%2). 3 ’ F.RamirexandN.R amanathal& J. Org. Chem 26 3041 (1961);

b F. Ram&z. N. B. Desai and N. Ramanathan, Terrahedron Letters 323 (1963). l ’ F. Ramirex and N. B. Desai, J. Am Chen Sot 8l& 2652 (1960);

b F. Ramirex and N. B. D=sai, Ibid 85, 3252 (1963). ’ G. H. Birum and J. L Devcr, Abstracts, Division of Organic Chemistry, 135th Narional Meeting of the

Americmt Chemical Society; p 1OlP. Chicago+ EL, Sept (1958); b U.S. Patents, 2961,455 (1960x and 3,014,949 (1961).

6 . V. A. Kukht& Dokl. Akad. Nauk SSSR 121466 (1958); b V. A Kukhtin and K_ M. Chekhova, J. Gen C/ten USSR 30,1229 (1960); c V. A. Kukhtin, K. M. Kirillova and R. R. Shagidullin, ZA Obshch Khlm 32 649 (1962).

’ ’ F. Ramirex A V. Patwardhan and C P. Smith J. Org. Chem 30.2575 (1965); b F. Ramirer, A. V. Patwardhan and C P. Smith, J. Org. Chem 3l, 474 (1966).

s ’ F. Ramirex and S. Dershowitx, J. Org. Chem 22 856 (1957); b F. Ramirex and S Dershowig Ibid 23, 778 (1958); ’ F. Ramira and S Dershowitr, J. Am C/rem Sot gl, 581(1959); ’ F. Ramirex E H Chat and S. Dershowitx Ibid 81.4338 (1959).

9 F. Ramirex and S Dershowitx, J. Org. C/tern U, 1282 (1957). lo ’ F. Ramirex, Pure Appl. Chm 9. 337 (1964);

b F. Ramirex Bull. Sot. C&m Fr. 2443 (1966); c F. Ramirex A V. Patwardhan and C. P. Smith, J. Org. C/tern 313159 (1966); ’ F. Ramira, S. B. Bhatia, A_ V. Patwardhan and C P. Smith, Ibid 32 (1967); ’ F. Ramira. S. B. Bhatia and C P. Smith, J. Am C/tern Sot 89.3026 (1967); ’ F. Ramirex S B. Bhatia and C P. Smith. Ibid. 89,30X) (1967).

r’ ’ C. A Bishop, R. F. Porta and L K J. Tong Ibid 85,399l (1963); b C A. Bishop and L K J. Tong Tetruhedrcm Letters 3043 (1964).

” ’ W. C Hamilton. S J. LaPlaca and F. Ramirer, 1. Am Chem Sot 87,127 (1965); b W. C. Hamilton, S. J. LaPlaca, F. Ramircz and C P. Smith Ibid. 09.2268 (1%7); ’ R. D. Spratlcy, W. C Hamilton and J. Ladell, Ibid 89,2.272 (1967)

I3 D. G. Gorenstein and F. H. Westheimcr, Ibid 89, 2762 (1967) and F. Ramirex 0. P. Madan and S R. Hcllcr, Ibid. 87, 731 (1%5).

1944 F. RAMIREZ, H. J. Kuoum and C. P. Swni

I4 For otha reports of the readiom of dialkyi phosphitc~ with pquinone see: (a) B A Arbuzov, N. A Pokzhseva and V. S Vinogradon, Jzu. Aka& Navk SSSR, O&i Kti Na& 1219 (1960); Chem tisrr. !q 469 (1961); ’ D. I. Sanin, hf. G. Voronkov, E S Shepclcva amJ B. L Ionic DokL Akod Nmk SSSR 132,145 (1960); them. Abstr. n, 11119 (1962); ’ Y. Nisbizawa, BulL Chem Sot lapm, 34,688 (1961); ’ V. M. Clark, D. W. Hutchinso~ G W. Kirby and A Todd, 1. Chrm. Sot. 715 (1961); ‘AMustafa,M.USidlryandF.MSoliman.TctroMrmU,107(1%6).

I’ For a discussion of tautomcricnn io dialkyl hydrogmphosphonatar (dialkyl phosphitca) see : ’ W. J. Bailey and R B. Fox, J. Org. Ghan 2g, 531 (lW3); b D. Samud and R L Silver, Ibid 2J& 2089 (1963); c G. 0. Dank and L D. Friedmum, Chmr. Rcu 61,31 (1961); ’ K Mocdriaer, 1. Inorg. NucL Chtm. 22 19 (1961).

l6 For recent examples of otha tvpes of additions to tbc carbonyl of p-quinones, see: ’ B. Eistcrt, He Fink and A Muller, Chem Ber. 95.2403 (1%2); b D. Bryce-Smith and A Gilbert, Pruc Chem Sot. 87 (1964).

” The hydrolysis ol a pcntaoxyphosphoranc was fti reported by F. Ramircz N. R Dzaai and N. Ramanathan, J. Am Char See g!l, 1874 (1963) and F. Bamirc& N. Bamanatban and N. R De& Ibid. 85.3465 (1%3).

Ia ~‘Ix cxcluxivc formation of 5-membered cyclic phosphoditsta from tk addition done mole cquivalcnt cf water to a S-cyclic phosphotrkata iu aprotk solvmta was tint reported by F. Rm 0. P. Madan, N. R Deai, S Meyersan and E M. Baoaa, Ibid SC?+2681 (1963) For a recent d&u&an aftha problan, see: D. Swanlr, C N. Caughla~ F. Ramire& 0. P. Madan and C P. Smi& Ibid 89 (1967).

I’ l J. Kumamoto and F. I& Wcstheimer, Ibid 77.2515 (1955); b P. C. Haake and F. H. Wcstbcimcr, Ibid 83 1102 (1961); c D. A Usher, E A Dcxmia and F. H. Wcstbcimer, Ibfd 87.2320 (1965); ’ E A Dennis and F. Ii. Wcstheimcr, Ibfd es,3431 3432 (1966); ’ G. Akma and K. Bcrgcsen, Acra Chmr Scond 20.2508 (1966); ’ R L Collin, J. Am Cha Sot 88,3281(1966).

1o F. Ramirq 0. P. Madan and C P. Smith, Ibid 87,670 (1965). 11 H. Kwart and N. J. Wegeacr, Ibid. 83.2746 (1961).