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THE REACTION OF TRIPHENYLPHOSPRINEBX'RYLENESWITH LITHIUM ALUMINUM RYDRIDE

Martin Saunders nd Gracie urchman~Sterling hemistry aboratory, ale University, ew Haven, Corm.**

(Received 6 January1959)

ALTHOUGH triphenylphoaphineacylmethyleneaave been known for some time,'Wittig'e recent preparation f the simpler analoge has been of interestbecause of their eynthetio tility.2

We wish to report a new reaction hich these compounds ndergo ontreatment ith lithium luminum ydride, When the triphenylphosphine-methylenee, C6H5)3P-CHR:

(I) R=H, (II) R= COCH3, (III) R-COC6H5,(IV) R=COC(CH3)2COCH(CH3)2

l United States Public Health Predoctoral ellow of the NationalInstitute f Arthritis nd Metabolic iseases,1957 - 59.** Contribution o. 1518 from the Sterling Chemistry aboratory,Yale University, ew Haven, Connecticut.

A. Miohaelie nd E. Kohler, Ber. Dtrrah. hem. Ges, 22,1566 (1899).G. Wittig and U. Bchollkopf, er. Dteoh. Chem. Gee, :I, 1318(1954)1 . Wittig, Exwrientia 22, 41 (1956); G. Wittig,Azwer. Chem, pi, 505 (1956); . Ramire% and S. Dershowltz,J. Org. memm, 22, 41 (1957).Preparation nd structural nformation re desoribed inPh. D. Theeie of P. Saunders, arvard University(1956).

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Triphenylphosphlneue~lenos 9ware rtlrred ith exoess eagent n either-tetrahydrofuran,roduotr ereobtained n hydrolysis n whloh ydrogen ad been added o the methylonecarbon nd whioh ad loot ensene.

(I) gave a liquid hosphine hioh ielded imethyldiphenylphosphon-fun Iodide pon treatment eth ethyl odide 2meldf m.p. 249.5-2510,1it.4 241. ound: , 48.9f , 5.Of , 9.2. Cal% for C14E16PI c, 49.11B, 4.7f P, 9.d). Illu hosphiner eadily xldised n standing n air toorysblllne hosphine xides.

(II) aw (C6%,)2P(0)cH2CocB5ltieldf m.p. 127-1290 , 5.84(C-O), .4W (P +-O -). Found: , 70.28 , 6.31 P, 12.0. lfi502Preqdrea C, 69.88 , 5.91 , 12.0%).

(III) m (C6E5&P(0)CI$COC6H546 jieldf .~. 140-140.5.L5.96 (C-O), 8.47~ (P+-O-1. Found: , 74.98 , 5.61 , 10.0.C&70$ mamm C# 75.Of e 5.45 , 9.796).

(Iv) ve (c6E5)2p(0)~c~(~~)2~OE~(~)2 (54 kY5 - Y7.5O. x, 2.96 (OH), 5.87 (C - 01, 8.47 v @+Found:P, 8.6

C, 70.7, He 7.61 P, 8.9. C21&$3P$>. requlror , 70.6rafter eaotlon nhe 18olatlon f ketonio roduotr

rI*ldf ma.- o-1.E, 7.6

the preaenaoof excess iAlE4 is most readily plloable n tense f an enolate altuhiohle reslrtant o further ttaoh. uohan enolate ight be formed yeither ttaah f the LUllI on the phony1 roup roduoing ensona lreot3Jor addition o the phosphorourtom giving pentavalentntermediatehlohaan lose bnsbnb in a manner lmllar o thelorr ofbiphenylfrompenta-phenMwhorow5

4 A. Hiohaells ndA. Link, Llebinr Aan% gOJ, 1935 0. Wittlg nd 0. Coirsler, lebl&s nn, a, 44

(1891).(1953).