A carbonylation catalytic system comprises (A) a combination of (A1) a Group VIII metal source of Periodic Table of the Elements (e.g., palladium, palladium chloride) supported on a carrier, (A2) a ligand such as triphenylphosphine and (A3) an acid such as an alkyl-sulfonic acid, or (B) a combination of (B1) the Group VIII metal source except for palladium (e.g., a platinum compound), (B2) a ligand such as triphenylphosphine and (B3) an electron donative compound having an electron donability ΔνD of not less than 2 (for instance, an amine such as a heterocyclic tertiary amine). The catalytic system (B) may further comprise (B4) an acid such as methanesulfonic acid. In the presence of the catalytic system (A) or (B), an acetylenic or olefinic unsaturated compound is allowed to react with carbon monoxide and a nucleophilic compound having an active hydrogen such as water, an alcohol and a carboxylic acid in a liquid phase to give an unsaturated or saturated carboxylic acid or an ester thereof with high transformation rate and selectivity.
一种羰基化催化体系包括(A) (A1)支撑在载体上的元素周期表第八族
金属源(如
钯、
氯化钯)、(A2)
配体(如
三苯基膦)和(A3)酸(如烷基
磺酸)的组合,或(B) (B1)除
钯以外的第八族
金属源(如
铂化合物)、(B2)
配体(如
三苯基膦)和(B3)电子捐献化合物(电子捐献率ΔνD不小于2实例)的组合、
铂化合物)、(B2)
三苯基膦等
配体和 (B3) 电子捐赠性 ΔνD 不小于 2 的电子捐赠化合物(例如,杂环叔胺等胺)的组合。催化体系 (B) 可进一步包括 (B4) 酸,如
甲磺酸。在催化体系(A)或(B)的存在下,
乙炔基或烯烃基不饱和化合物可与
一氧化碳和具有活泼氢的亲核化合物(如
水、醇和
羧酸)在液相中发生反应,以高转化率和高选择性得到不饱和或饱和
羧酸或其酯。