Method of preparing amino-, imino- and nitrilocarbonxylic acids and silver-promoted copper catalyst for use in said method
申请人:Atanor S.A.
公开号:EP1067114A1
公开(公告)日:2001-01-10
A method is described for preparing amino-, imino-, and nitrilocarboxylic acids of formula
R1R2R3N , (I)
and alkaline salts of these, here R1, R2, and R3, which may be the same or different, represent: ydrogen, n alkyl group having 1-10 C atoms, carboxyalkyl group having 1-10 C atoms [in the alkyl moiety], n aminoalkyl group having 1-10 C atoms [in the alkyl moiety], carboxycycloalkyl group having 3-6 C atoms [in the cycloalkyl moiety], a cycloalkyl-alkyl group having 3-6 C atoms in the cycloalkyl moiety and 1-10 C atoms in the alkyl moiety and having a carboxy group substituent, or an alkyl-cycloalkyl group having 1-10 C atoms in the alkyl moiety and 3-6 C atoms in the cycloalkyl moiety and having a carboxy group substituent; wherewith said alkyl groups may be linear or branched; and wherewith at least one of the groups R does not represent hydrogen; the method comprising:
(a) subjecting alkanolamines of formula
R1'R2'R3' N, (II)
wherein the groups R' have the same significations as set forth above for the groups R, except that the aforesaid carboxy groups are hydroxyl groups,
to an oxidative dehydrogenation reaction in aqueous alkaline medium in the presence of a copper catalyst of the Raney type promoted with 50-5000 ppm silver;
(b) separating the resulting carboxylate salts from the reaction medium, and (optionally) purifying said salts or converting them to the corresponding amino acids by precipitation in acid medium;
(c) separating the catalyst from the reaction medium, washing said catalyst with demineralized water, and (optionally) recycling the catalyst to re-use in step (a) [(of the same or another production run)]; and
(d) recovering and collecting the hydrogen liberated in the reaction.
Also described is a catalyst for use in the described method. The catalyst is comprised of a Raney-type catalyst comprised of copper promoted with 50-5000 ppm silver supplied as follows:
-- incorporated in an alloy;
-- deposited on [the] surface from salts of silver; or
-- in a physical mixture comprising finely divided metallic silver.
The compounds of formula (I) have been found to be important synthesis intermediaries, e.g. in preparation of N-phosphonomethylglycine (the herbicidal agent known as glyphosate).
描述了一种制备式中氨基羧酸、亚氨基羧酸和亚硝基羧酸的方法
R1R2R3N , (I)
及其碱性盐的方法,其中 R1、R2 和 R3 可以相同或不同,分别代表氢、具有 1-10 个 C 原子的 n 个烷基、[在烷基中]具有 1-10 个 C 原子的 n 个羧基、[在烷基中]具有 1-10 个 C 原子的 n 个氨基、[在环烷基中]具有 3-6 个 C 原子的羧基环烷基、在环烷基中具有 3-6 个 C 原子、在烷基中具有 1-10 个 C 原子且具有羧基取代基的 环烷基-烷基,或在烷基中具有 1-10 个 C 原子、在环烷基中具有 3-6 个 C 原子 且具有羧基取代基的烷基-环烷基;其中至少一个基团 R 不代表氢; 方法包括
(a) 将式
R1'R2'R3' N,(ii)
其中基团 R'具有与上述基团 R 相同的意义,但上述羧基为羟基、
在水性碱性介质中,在用 50-5000ppm 银促进的雷尼型铜催化剂存在下,进行氧化脱氢反应;
(b) 从反应介质中分离出生成的羧酸盐,并(选择性地)纯化所述盐或通过在酸性介质 中沉淀将其转化为相应的氨基酸;
(c) 将催化剂从反应介质中分离出来,用去矿物质的水洗涤催化剂,并(选择性地)回收催化剂,以便在步骤 (a) [(同一次或另一次生产)]中再次使用;以及
(d) 回收并收集反应中释放出的氢气。
还描述了一种用于所述方法的催化剂。该催化剂由 Raney 型催化剂组成,该催化剂由用 50-5000ppm 银促进的铜组成,其供应方式如下:
-- 与合金结合;
-- 沉积在银盐表面;或
-- 在由细小的金属银组成的物理混合物中。
已发现式 (I) 化合物是重要的合成中间体,例如在制备 N-膦酰甲基甘氨酸(称为草甘膦的除草剂)时。