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ALTHOUGH triphenylphoaphineacylmethylenea have been known for some time,' Wittig'e recent preparationof the simpler analoge has been of interest because of their eynthetioutility.2 We wish to report a new reaction which these compoundsundergo on treatmentwith lithium aluminum hydride, When the triphenylphosphinemethylenee, (C6H5)3P-CHR: (I) R=H, (II) R= COCH3, (III) R-COC6H5, 3 (IV) R=COC(CH3)2COCH(CH3)2
United States Public Health PredoctoralFellow of the National Instituteof Arthritis and Metabolic Diseases, 1957 - 59. Yale University,New Haven, Connecticut. A. Miohaelie and E. Kohler, Ber. Dtrrah. Chem. Ges, 22,
1566 (1899). G. Wittig and U. Bchollkopf,Ber. Dteoh. Chem. Gee, :I, 1318
(1954)1G. Wittig, Exwrientia 22, 41 (1956); G. Wittig, Azwer. Chem, pi, 505 (1956); F. Ramire% and S. Dershowltz, J. Org. memm, 22, 41 (1957). Preparationand structuralinformationare desoribed in Ph. D. Theeie of P. Saunders,Harvard University (1956).
Triphenylphosphlneue~lenos
ware rtlrred with exoessreagentin either-tetrahydrofuran, produotr were obtained on hydrolysis in whlohhydrogen had been addedto the methylone carbonand whiohhad lootbensene. (I) gave a liquidphosphine uhiohfieldeddimethyldiphenylphosphonfun Iodideupon treatment Seth methyliodide(2meldf m.p. 249.5-2510,
orysblllnephosphine oxides. (II)6aw (C6%,)2P(0)cH2CocB5 (ltieldf m.p. 127-1290 A, (C-O), 8.4W (P +-O -). Found:C, 70.288, 6.31 P, 12.0.Clfi502P reqdrea C, 69.88H, 5.91P, 12.0%). (III)@m
L5.96 C&70$ (C-O), mamm
5.84
8.47~
(Iv)eve (c6E5)2p(0)~c~(~~)2~OE~(~)2
Y5 - Y7.5O. x, 2.96 (OH), 5.87 (C - 01,
ma.
o- 1.
C, 70.6rE, 7.6 Found:C, 70.7, He 7.61 P, 8.9. C21&$3P requlror P, 8.6 $>. The 18olatlon of ketonioproduotr afterreaotlon In the preaenao In tenseof an enolate salt of excessLiAlE is most readilylrplloable 4 uhiohle reslrtant to further attaoh.Suohan enolate might be formedby eitherattaahof the LUllI on the phony1groupproduoing bensona dlreot3J or addition to the phosphorour atom givinga pentavalent Intermediate whloh aan lose bbnsbnb phenMwhorow5
in
4 A. Hiohaells and A. Link, Llebinr Aan% gOJ, 193 (1891). 5 0. Wittlgand 0. Coirsler, Jlebl&sAnn, a, 44 (1953).