Experiment 21 The Wittig Reaction Introduction: Wittig Reaction, the reaction of an aldehyde or ketone with a triphenyl phosphonium ylide

e (the Wittig reagent) to produce an alkene and triphenylphosphine oxide, is of great use in forming carbon-carbon bond between reactants. The Wittig reaction was disco ered in !"#$ by %eorg Wittig, for which he was awarded the &obel 'ri(e in )hemistry in !"*". ! The de elopment of Wittig Reagents were examined in a recent general re iew by +isch, in which the author discussed %eorg Wittig,s disco ery of the reaction along with his other significant contributions in organic chemistry..n this experiment, methyl (triphenylphosphoranylidene) acetate (1) was used to react with --nitroben(aldehyde (2), with the application of heat from microwa e radiation, to produce both (/)-methyl 0-(--nitrophenyl) acrylate (3) and (+)-methyl 0(--nitrophenyl) acrylate (4), with (+)-methyl 0-(--nitrophenyl) acrylate as the ma1or product, and triphenylphosphine oxide (5) (2cheme !).

Scheme 1 Wittig Reaction of methyl (triphenylphosphoranylidene) acetate with --nitroben(aldehyde.

The mechanism of this reaction (2cheme -) in ol es the nucleophilic addition of the phorphorus ylide (1) to the carbonyl carbon in --nitroben(aldehyde (2), forming a new carbon-carbon bond and pro iding the intermediate (!). 3ddition from the electron rich oxygen to the positi ely charged phosphorus could then produce either the (+) oxaphosphetane (") or the (/) oxaphosphetane (#). 4pon breaking of the ring, triphenylphosphine oxide (5) and either the (/)-methyl 0-(--nitrophenyl) acrylate (3) or the (+)-methyl 0-(--nitrophenyl) acrylate (4) could be produced.

Scheme 2 5echanism of the Wittig Reaction.

Experimenta$ Section:

 (%)&meth'$ 3&(2&nitrophen'$) acr'$ate (3) (E)&meth'$ 3&(2&nitrophen'$) acr'$ate (4) Triphen'$pho(phine oxide (5) 2olid --nitroben(aldehyde (67 mg,7.#7 mmol), methyl (triphenylphosphoranylidene) acetate (!*# mg, 7.#- mmol), and silica gel (!7$ mg) were combined in a !-dram ial. The e enly distributed mixture was heated with microwa e radiation at power le el four for two minutes. The solid mass was mixed again and cooled to room temperature. 3 chromatography column was packed with !7 m8 of #79#7 ethyl acetate9 hexane solution and 7.:# g of silica gel. The reaction mixture was then added directly to the packed column. 2ubse;uently, column chromatography was used to separate the products. $ fractions of !.# m8 of solution was collected as well as a fifth fraction of the remaining solution. 2olutions of triphenylphosphine oxide and the fi e fractions were each spotted in a lane on T8) pates. The plates were de eloped in #79#7 hexane9 ethyl acetate and isuali(ed using 4< lamp. =ractions determined to contain only the alkene product were combined in a tared -#-m8 filter flask. >ellow particle-like crystals of the alkene product were collected by e aporating the sol ent with air and pulling a acuum on the system. 'roduct of 7.7""7g (7.$*6 mmol, "7.0?) impure (/)-methyl 0-(--nitrophenyl) acrylate (0) and (+)-methyl 0-(-nitrophenyl) acrylate ($) crystalline solid were obtained, with the (+) alkene isomer determined to be the ma1or product, mp #$.6 @ :$.- A) (lit0 *- @ *$A)). !B &5R ($77

5B(, )C)l0) D 0.6- (s, 0B), :.0: (d, J E !#.6 B(, !B), *.## (d of d, J E -.!: F J E !.#:, !B), *.:$ (d of d, J E #.*! F J E -.-0, !B), *.:: (d, J E :."$ B(, !B), 6.70 (d, J E 6.7 B(, !B), 6.! (d, J E !#." B(, !B). !0) &5R (!77.: 5B(, )C)l0) D !::.-, !$6.-, !$7.!, !00.#, !07.#, !07.0, !-".!, !-$.", !--.6, #-.7!. Re)erence(: !) %ericke, C. !"*" &obel 'ri(e in chemistry for the Wittig reaction as the source of multiple syntheses. %eorg Wittig the sixtieth %erman &obel 'ri(e recipient. Fortschritte der Medizin 1*"*+ "*($0), !"#6-!":$. -) G. G. +isch, Organometallics, -77-, 21, #$0"@#$:0. 0) Methyl (2E)-3-(2-nitrophenyl)acrylate http9HHwww.chemspider.comH)hemical-2tructure.$#!7$::.html (accessed =eb --, -7!-)