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    • 1. 发明授权
    • Process for production of allyl carboxylate
    • 生产烯丙基羧酸酯的方法
    • US4567292A
    • 1986-01-28
    • US695024
    • 1985-01-25
    • Nobuyuki NagatoKenichiro MakiTomoe UematsuRyoji Ishioka
    • Nobuyuki NagatoKenichiro MakiTomoe UematsuRyoji Ishioka
    • C07C67/05
    • C07C67/055
    • A process for producing an allyl carboxylate comprising the step of reacting propylene, oxygen or oxygen-containing gas, and a lower saturated carboxylic acid in the presence of a catalyst at a temperature of 100.degree. C. to 300.degree. C. and a pressure of 0 to 30 atm (gauge) in a vapor phase. The catalyst is prepared by supporting, on a carrier, at least one alkali metal acetate and at least one bivalent palladium salt in the presence of: (A) at least one organic base selected from the group consisting of (i) aliphatic amines having the formula: ##STR1## wherein R.sup.1, R.sup.2, and R.sup.3 may be the same or different and represent hydrogen, or an alkyl group having 1 to 10 carbon atoms or benzyl group optionally substituted with --CN, --OR, --COOR, or a --N(R).sub.2 group wherein R is H or an alkyl group having 1 to 3 carbon atoms, or any two groups of R.sup.1, R.sup.2, and R.sup.3 may together form a ring provided that R.sup.1, R.sup.2, and R.sup.3 are not simultaneously hydrogen; (ii) aromatic amines having the formula: ##STR2## wherein X represent --R, --CN, --OR, --COOR, --NO.sub.2, or --N(R).sub.2 wherein R is the same as defined above, R.sup.2 and R.sup.3 are the same as defined above; and (iii) nitrogen-containing cyclic compounds having the formula: ##STR3## wherein X is the same as defined above; and/or (B) at least one carboxylic acid having the formula:Y--CH.sub.2).sub.n COOHwherein Y represents --OR, --CN, --COOR, --CH(R)NH.sub.2, --COR, --N(CH.sub.2 COOH).sub.2, --NHCH.sub.2 COOH, or --CH(R.sup.1)X group wherein R, R.sup.1, and X are the same as defined in (A) above, and n is an integer of 1 to 4.This catalyst has a high activity and a long durability and can produce the desired allyl carboxylate at a high selectivity.
    • 一种制备烯丙基羧酸酯的方法,包括在催化剂存在下,在100℃至300℃的温度下,使丙烯,氧或含氧气体和较低饱和羧酸反应的步骤, 0〜30atm(表压)气相。 所述催化剂是通过在载体上负载至少一种碱金属乙酸盐和至少一种二价钯盐来制备的:(A)至少一种有机碱,所述有机碱选自:(i)具有 式:其中R 1,R 2和R 3可以相同或不同,表示氢,或具有1-10个碳原子的烷基或任选被-CN,-OR,-COOR或 - N(R)2基团,其中R为H或具有1至3个碳原子的烷基,或任何两个R 1,R 2和R 3可以一起形成环,条件是R 1,R 2和R 3不同时为氢; (ii)具有下式的芳香胺:其中X表示-R,-CN,-OR,-COOR,-NO 2或-N(R)2,其中R与上述定义相同,R 2和R 3为 与上述相同; 和(iii)具有下式的含氮环状化合物:其中X与上述定义相同; 和/或(B)至少一种具有下式的羧酸:Y-CH 2)n COOH其中Y表示-OR,-CN,-COOR,-CH(R)NH 2,-COR,-N(CH 2 COOH) -NHCH 2 COOH或-CH(R 1)X基团,其中R,R 1和X与上述(A)中所定义相同,n为1至4的整数。该催化剂具有高活性和长的耐久性, 可以以高选择性产生所需的烯丙基羧酸酯。