申请人:Takasago Perfumery Co., Ltd.
公开号:EP0170470A2
公开(公告)日:1986-02-05
An allylamine derivative of the formula
where R1 = H or CH3, R2 = 4-methyl-pentyl or-OCH3, R3, R4 = 1-4C alkyl or 5-8C cycloalkyl and R3 can be H, and R3 + R4 can link to form a 5- or 6-numbered ring, is treated with rhodium-phosphine complex as catalyst, of the formula [Rh (Y)L]+ X - Where Y = ethylene, 1,3-butadiene, cycloxadiene, cycloactadiene or L; X= Cl O4, BF4 or PF6, and L is a binaphthyl derivative of formula
where R = H, -CH3 or tert-butyl, so as to isomerise the double bond (a) to the position (b) to form the corresponding enamine; if R3 = H, hydrotropy tautomerism occurs at the CH2-N-Y-group to form the imine.
The preparation of the catalyst is described.
The reaction is preferably carried out in a solvent such as an ether, ketone or halide at 80° to 120°C for 1-15 hours using 1:2,000 to 1:10,000 mole catalyst per mole of derivative (I), followed by distillation off of the solvent..
The products are obtained in high yield and of high optically active purity.
式中的烯丙胺衍生物
式中 R1=H 或 CH3,R2=4-甲基戊基或-OCH3,R3、R4=1-4C 烷基或 5-8C 环烷基,R3 可以是 H,R3+R4 可以连接成 5 或 6 数环,用铑膦络合物作催化剂处理,其式为 [Rh (Y)L]+ X - 式中 Y= 乙烯、1,3-丁二烯、环己二烯、环己二烯或 L;X= Cl O4、BF4 或 PF6,L 是式中的联萘衍生物
其中 R = H、-CH3 或叔丁基,从而将双键(a)异构到位置(b),形成相应的烯胺;如果 R3 = H,则在 CH2-N-Y 基团上发生氢致同分异构,形成亚胺。
催化剂的制备方法已作说明。
反应最好在诸如醚、酮或卤化物等溶剂中进行,温度为 80° 至 120°C,时间为 1-15 小时,每摩尔衍生物 (I) 使用 1:2,000 至 1:10,000 摩尔催化剂,然后蒸馏掉溶剂。
产品的收率高,光学纯度高。