Reactions of Highly Nucleophilic Triphenylphosphines

高亲核三苯基膦的反应

• 批准号: 60550611
• 负责人: WADA Masanori
• 金额: $ 1.28万
• 依托单位: Tottori University (1986)Osaka University (1985)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1985
• 资助国家: 日本
• 起止时间: 1985 至 1986
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-60550611/
• 关键词: Nucleophile; Tertiary phosphine; Quarternary phosphonium salt; Alkyl chloride; Epoxide; Michael addition; ニトロアルカン

Triphenylphosphines bearing methoxy substituents at the 2,6-positions of the phenyl groups, (2,4,6) <_3P> and (2,6) <_3P> [abbr. (2,4,6)= 2,4,6- <MeO_3> <C_6> <H_2> and (2,6)= 2,6- <MeO_2> <C_6> <H_3> ], exhibit unusually high nucleophilicity. Thus, they reacted under mild conditions with a variety of alkyl halides including butyl chloride and 2-propyl chloride to give the corresponding quarternary phosphonium salts. Treatment of (2,6) <_3P> with epoxides <CH_2> <CR^1> <R^2> O in alcohol at room temperature readily gave the [(2,6) <_3P> - <CH_2> <CR^1> <R^2> OH] <^+> species. Thermolysis of these salts in the presence of the ethoxide anion gave the [(2,6) <_3P> -Me] <^+> salt and ketone <R^1> <R^2> CO [ <R^1> <R^2> = Me,Me; Me,Ph; Ph,Ph, <(CH_2CH_2)_2> CH <Bu^t> ], the [(2,6) <_3P> - <CH_2> CH <R^1> OEt] <^+> salt ( <R^1> <R^2> = Me,H; H,H), the [(2,6) <_3P> -CH=CH=CHMe] <^+> salt ( <R^1> <R^2> =Et,H), or the [(2,6) <_3P> -CH=CHPh] <^+> salt ( <R^1> <R^2> = Ph,H); however, no phosphorus-carbon bond cleavage product was obtained. (2,4,6) <_3P> was found to work as a convenient and excellent catalyst (initiator) for the Michael addition of <CH_2> =CHCN, <CH_2> CHCOOEt, and <CH_2> =CHC(O)Me with some nitroalkanes.

苯基2,6位上含有甲氧基取代基的三苯基膦(2,4,6)<_3P>和(2,6)<_3P> [abbr. (2,4,6)= 2,4,6- <MeO_3> <C_6> <H_2>和(2,6)= 2,6- <MeO_2> <C_6> <H_3>]，具有异常高的亲核性。因此，它们在温和的条件下与各种烷基卤化物（包括氯化丁酯和2-丙基氯）反应，得到相应的季铵盐。在室温下用环氧化物<CH_2> <CR^1> <R^2> O在醇中处理(2,6)<_3P> - <CH_2> <CR^1> <R^2> OH] <^+>。这些盐在乙氧阴离子存在下热裂解得到[(2,6)<_3P> -Me] <^+>盐和酮<R^1> <R^2> CO [<R^1> <R^2> = Me,Me；我,Ph值;Ph值、Ph值、< (CH_2CH_2) _2 > CH < Bu ^ t >],在[(2,6)< _3P > - < CH_2 > CH < R ^ 1 >诗人]< ^ + >盐(< R ^ 1 > < R ^ 2 > =我,H, H, H),在[(2,6)< _3P > CH = CH = CHMe] < ^ + >盐(< R ^ 1 > < R ^ 2 > =, H),或[(2,6)< _3P > CH = CHPh] < ^ + >盐(< R ^ 1 > < R ^ 2 > = Ph值、H);但没有得到磷碳键解理产物。（2,4,6） <_3P>是<CH_2> =CHCN, <CH_2> = CHCOOEt, <CH_2> =CHC(O)Me与某些硝基烷烃的Michael加成反应的一种简便、优良的催化剂（引发剂）。

项目成果

Masanori Wada: J.Chem.Soc.,Perkin Trans.I. (1987)

和田正德：J.Chem.Soc.，Perkin Trans.I.

Masanori Wada: "Michael Addition of Nitroalkanes Catalysed by Highly Nucloephilic Triarylphosphine, [2,4,6-( <CH_3> O) <_3> <C_6> <H_2> ] <_3P> " Journal of Japan Chemical Society (Nippon Kagaku Kaisi). 39. (1987)

Masanori Wada：“高亲核三芳基膦催化硝基烷烃的迈克尔加成，[2,4,6-( <CH_3> O) <_3> <C_6> <H_2> ] <_3P>” 日本化学学会会刊 (Nippon Kagaku Kaisi)

Masanori Wada: "Highly Nucleophilic Triphenylphosphines" Journal of Synthetic Organic Chemistry, Japan. 44. 957-960 (1986)

Masanori Wada：“高度亲核三苯基膦”合成有机化学杂志，日本。

和田正徳: 有機合成化学協会誌. 44. 957-960 (1986)

和田正德：合成有机化学学会杂志 44. 957-960 (1986)

和田正徳: 日本化学会誌. 39. (1987)

和田正德：日本化学会杂志 39。（1987）