Method for producing aldehydes by means of hydroformylation of olefinically unsaturated compounds, said hydroformylation being catalyzed by unmodified metal complexes in the presence of cyclic carbonic acid esters
View Patent ↗The present invention relates to a process for preparing aldehydes by hydroformylation catalyzed by metals of groups 8 to 10 of the Periodic Table of the Elements in the presence of cyclic carbonic esters.
1. A process for the catalytic hydroformylation of an olefinically unsaturated compound having from 3 to 24 carbon atoms using an unmodified catalyst comprising rhodium, wherein the hydroformylation is carried out in the presence of a cyclic carbonic ester of the formula I
where
R 1 , R 2 , R 3 , R 4 are identical or different and are each H or a substituted or unsubstituted aliphatic, alicyclic, aromatic, aliphatic-alicyclic, aliphatic-aromatic or alicyclic-aromatic hydrocarbon radical having from 1 to 27 carbon atoms,
n is 0–5
X is a divalent substituted or unsubstituted, aliphatic, alicyclic, aromatic, aliphatic-alicyclic or aliphatic-aromatic hydrocarbon radical having from 1 to 27 carbon atoms,
with the proportion of the carbonic ester being at least 1% by weight of the reaction mixture.
2. The process as claimed in claim 1 , wherein R 1 , R 2 , R 3 , R 4 and X are substituted by identical or different substituents selected from the group consisting of O, N, NH, N-alkyl, N-dialkyl, fluorine, chlorine, bromine, iodine, —OH, —OR, —CN, —C(O)alkyl and —C(O)O-alkyl.
3. The process as claimed in claim 1 , wherein said hydroformylation is carried out in the presence of from 5 to 50% by weight, based on the reaction mixture, of a solvent which is nonpolar compared to the cyclic carbonic ester I and is immiscible with the cyclic carbonic ester I.
4. The process as claimed in claim 1 , wherein the reaction product from the hydroformylation is extracted with a nonpolar solvent which is immiscible with said cyclic carbonic ester.
5. The process as claimed in claim 3 , wherein substituted or unsubstituted hydrocarbons having from 10 to 50 carbon atoms or olefins having from 3 to 24 carbon atoms are used as nonpolar solvent.
6. The process as claimed in claim 1 , wherein said hydroformylation is carried out in the presence of HRh(CO) 3 as catalyst.
7. The process as claimed in claim 1 , wherein the reaction product mixture from the hydroformylation reaction is separated into a fraction comprising predominantly the catalyst and the cyclic carbonic ester and a fraction comprising predominantly the hydroformylation products.
8. The process as claimed in claim 1 , wherein a fraction comprising said catalyst is recirculated to the hydroformylation reaction.
9. The process as claimed in claim 1 , wherein the cyclic carbonic ester is ethylene carbonate, propylene carbonate, butylene carbonate or a mixture thereof.
10. The process as claimed in claim 1 , wherein the unreacted olefinically unsaturated compound is separated off from the reactor output or from the hydroformylation products and are returned to the same hydroformylation reaction or passed to a second hydroformylation reaction.
11. The process as claimed in claim 1 , wherein the olefinically unsaturated compound is a compound which has been obtained as unreacted olefinically unsaturated compound from the reactor output of a first hydroformylation reaction.
12. The process as claimed in claim 11 , wherein the olefinically unsaturated compound is a compound which has been obtained as unreacted olefinically unsaturated compound from the reactor output of a first hydroformylation reaction carried out in the presence of a ligand-modified catalyst.
13. The process as claimed in claim 4 , wherein substituted or unsubstituted hydrocarbons having from 10 to 50 carbon atoms or olefins having from 3 to 24 carbon atoms are used as nonpolar solvent.
14. The process as claimed in claim 1 , wherein said cyclic carbonic ester is present as a solvent in said reaction mixture.
15. The process as claimed in claim 1 , wherein said cyclic carbonic ester is present in said reaction mixture in an amount of from 1 to 98% by weight.
16. The process as claimed in claim 1 , wherein said cyclic carbonic ester is present in said reaction mixture in an amount of from 5 to 70% by weight.
17. The process as claimed in claim 1 , wherein said cyclic carbonic ester is present in said reaction mixture in an amount of from 5 to 50% by weight.
18. The process as claimed in claim 1 , wherein said cyclic carbonic ester is present in said reaction mixture in an amount of at least 5% by weight.
19. The process as claimed in claim 1 , wherein said cyclic carbonic ester is present in said reaction mixture in an amount of from 5 to 98% by weight.
20. A process for the catalytic hydroformylation of an olefinically unsaturated compound having from 3 to 24 carbon atoms using an unmodified catalyst comprising at least one metal of groups 8 to 10 of the Periodic Table of the Elements, except cobalt,
wherein the hydroformylation is carried out in the presence of a cyclic carbonic ester of the formula I
where
R 1 , R 2 , R 3 , R 4 are identical or different and are each H or a substituted or unsubstituted aliphatic, alicyclic, aromatic, aliphatic-alicyclic, aliphatic-aromatic or alicyclic-aromatic hydrocarbon radical having from 1 to 27 carbon atoms,
n is 0–5
X is a divalent substituted or unsubstituted, aliphatic, alicyclic, aromatic, aliphatic-alicyclic or aliphatic-aromatic hydrocarbon radical having from 1 to 27 carbon atoms,
with the proportion of the carbonic ester being at least 1% by weight of the reaction mixture.
21. The process as claimed in claim 1 , wherein said cyclic carbonic ester is present in said reaction mixture in an amount of from about 50 to 98% by weight.