Process for preparing esters from formates and olefinically unsaturated compounds
View Patent ↗The invention provides a process for preparing esters from formates and olefinically unsaturated compounds with catalysts based on palladium compounds. In addition, the invention discloses a polyphasic reaction mixture and nonyl methyl ester mixtures prepared by the process according to the invention.
1. A method of producing esters by carbonylation, wherein the method is carried out:
i) with at least one palladium-containing compound;
ii) at least one olefinically unsaturated compound selected from the group consisting of unsaturated olefins having between 2 and 20 carbon atoms, unsaturated alcohols, unsaturated ethers, unsaturated amines, unsaturated esters, unsaturated carboxylic acids, unsaturated amides, unsaturated urethanes, unsaturated halides, unsaturated aldehydes, unsaturated ketones, and unsaturated epoxides;
iii) at least one phosphorus-containing compound comprising a trivalent phosphorous;
iv) at least one formate;
v) at least one alcohol;
vi) at least one acid;
vii) in a temperature range of 80° C. to 120° C.; and
viii) at a reaction pressure of 0.1 to 0.6 MPa.
2. The method of claim 1 , wherein the phosphorus-containing compound has a bidentate structure.
3. The method of claim 2 , wherein the phosphorus-containing compound having a bidentate structure has formula 1:
4. The method of to claim 1 , wherein the formate is selected from methyl formate, ethyl formate, benzyl formate, phenyl formate.
5. The method of claim 4 , wherein the at least one alcohol corresponds to the particular formate used.
6. The method of claim 1 , wherein the acid is selected from the group of sulphonic acids.
7. The method of claim 6 , wherein the sulphonic acids are selected from methanesulphonic acid, p-toluenesulphonic acid.
8. The method of claim 1 , that wherein the at least one olefinically unsaturated compound is an olefin-containing mixture comprising unsaturated olefin compounds having 6 to 12 carbon atoms.
9. The method of to claim 8 , wherein the carbonylation is effected with isomerization to the n-terminal ester.
10. The method of claim 1 , wherein the olefinically unsaturated compounds comprise nitrogen and/or oxygen and is selected from the group consisting of unsaturated alcohols, unsaturated ethers, unsaturated amines, unsaturated esters, unsaturated carboxylic acids, unsaturated amides, unsaturated urethanes, unsaturated halides, unsaturated aldehydes, unsaturated ketones, and unsaturated epoxides.
11. The method of claim 1 , wherein the palladium-containing compound with palladium in the oxidation states 0 to +II is selected from the group consisting of:
palladium halides;
palladium acetylacetonate;
palladium acetate;
palladium dibenzylideneacetone; and
palladium triphenylphosphine.
12. The method of claim 1 , wherein the phosphorus-containing compound is selected from the group consisting of phosphorous-containing compounds of formula (1), (2), (3), (4), (5), and (6):