Method for telomerizing non-cyclic olefins
View Patent ↗The invention provides a process for the telomerization of acyclic olefins having at least two conjugated double bonds (I) or mixtures comprising such olefins by means of nucleophiles (II) using a palladium-carbene complex as catalyst.
1. A process for the telomerization of acyclic olefins, comprising:
reacting acyclic olefins having at least two conjugated double bonds (I) or mixtures comprising said acyclic olefins with nucleophiles (II) in the presence of a palladium-carbene complex catalyst.
2. The process as claimed in claim 1 , wherein the nucleophiles are compounds selected from the group consisting of water, alcohols, phenols, polyols, carboxylic acids, ammonia and primary and secondary amines.
3. The process as claimed in claim 1 , wherein the nucleophiles (II) are compounds of formula (Ila) or (Ilb),
where R 1 , R 1′ are selected independently from the group consisting of hydrogen, linear, branched or cyclic C 1 –C 22 -alkyl groups, alkenyl groups, alkynyl groups, the carboxyl group and C 5 –C 18 -aryl groups, where these groups optionally bear substituents selected from the group consisting of —CN, —COOH, —COO-alkyl-(C 1 –C 8 ), —CO-alkyl-(C 1 –C 8 ), -aryl-(C 5 –C 10 ), —COO-aryl-(C 6 –C 10 ), —CO-aryl-(C 6 –C 10 ), —O-alkyl-(C 1 –C 8 ), —O—CO-alkyl-(C 1 –C 8 ), —N-alkyl 2 -(C 1 –C 8 ), —CHO, —SO 3 H, —NH 2 , —F, —Cl, —OH, —CF 3 , —NO 2 , and the radicals R 1 , R 1′ optionally are joined to one another via covalent bonds.
4. The process as claimed in claim 1 , wherein the palladiumcarbene complex comprises carbene ligands of the formula (III) or (IV),
where R 2 and R 3 are each, independently of one another, a linear, branched or cyclic C 1 –C 24 -alkyl or C 5 –C 18 -aryl group and the alkyl and aryl groups optionally, independently of one another, bear the substituents —CN, —COOH, COO-alkyl-(C 1 –C 8 ), —CO-alkyl-(C 1 –C 8 ), -aryl-(C 6 –C 18 ), -alkyl-(C 1 –C 24 ), —COO-aryl-(C 6 –C 10 ), —CO-aryl-(C 6 –C 10 ), —O-alkyl-(C 1 –C 8 ), —O—CO-alkyl-(C 1 –C 8 ), —N-alkyl 2 -(C 1 –C 8 ), —CHO, —SO 3 H, —NH 2 , —F, —Cl, —OH, —CF 3 , —NO 2 , ferrocenyl,
and R 4 R 7 are each, independently of one another, hydrogen, —CN, —COOH, —COO-alkyl-(C 1 –C 8 ), —CO-alkyl-(C 1 –C 8 ), —COO-aryl-(C 6 –C 10 ), —CO-aryl-(C 6 –C 10 ), —O-alkyl-(C 1 –C 8 ), —O—CO-alkyl-(C 1 –C 8 ), —N-alkyl 2 -(C 1 –C 8 ), —CHO, —SO 3 H, —NH 2 , —F, —Cl, —OH, —CF 3 , —NO 2 or a linear, branched or cyclic C 1 –C 24 -alkyl or C 6 –C18-aryl group and the alkyl and aryl groups, independently of one another, optionally bear the substituents —CN, —COOH, —COO-alkyl-(C 1 –C 8 ), —CO-alkyl-(C 1 –C 8 ), —-aryl-(C 6 –C 10 ), —COO-aryl-(C 6 –C 10 ), —CO-aryl-(C 6 –C 10 ), —O—alkyl(C 1 –C 6 ), —O—CO-alkyl-(C 1 –C 8 ), N-alkyl 2 -(C 1 –C 8 ), —CHO, —SO 3 H, —NH 2 , —F, —Cl, —OH, —CF 3 , —NO 2 , where the radicals R 4 and R 5 optionally are part of a bridging aliphatic or aromatic ring.
5. The process as claimed in claim 1 , wherein the acyclic olefin is 1,3-butadiene or isoprene.
6. The process as claimed in claim 1 , wherein 1,3-butadiene is combined in admixture with other C 4 -hydrocarbons or C 5 -hydrocarbons.
7. The process as claimed in claim 1 , wherein the nucleophile (II) or an inert organic solvent or a mixture thereof functions as a solvent.
8. The process as claimed in claim 1 , wherein the reaction is conducted at temperatures ranging from 10 to 180° C. and a pressure ranging from 1 to 300 bar.
9. The process as claimed in claim 1 , wherein the ratio of carbene ligand to Pd [mol/mol] ranges from 0.01:1 to 250:1.
10. The process as claimed in claim 1 , wherein the palladium-carbene complex is an isolated complex.
11. The process as claimed in claim 1 , wherein the palladium-carbene complex is generated in situ during the telomerization reaction.
12. The process as claimed in claim 1 , wherein catalytic amounts of a basic component having a pK b of <7 are added to the reaction.
13. The process as claimed in claim 12 , wherein the basic component is a compound selected from the group consisting of amines, alkali metal salts, alkaline earth metal salts and mixtures thereof.
14. The process as claimed in claim 13 , wherein the basic component is present in an amount ranging from 0.01 mol % to 10 mol %, based on the olefin compound.
15. The process as claimed in claim 1 , wherein the palladium concentration in the reaction mixture ranges from 0.01 to 1000 ppm.