Method for manufacturing ruthenium carbene complexes
View Patent ↗The invention is directed to aryl alkylidene ruthenium complexes and the use of these complexes as catalysts in metathesis reactions.
1. A Ru-carbene complex of the general formula (VI)
where L and L′ are identical or different and are selected independently from the group consisting of triisopropylphosphane, tricyclohexylphosphane and 9-cyclohexyl-9-phosphabicyclo[3.3.1]nonane, X is an anionic ligand, Ar is a naphthyl radical or a (C 3 -C 14 ) heteroaryl radical, wherein the (C 3 -C 14 ) heteroaryl radical is selected from the group consisting of 1-, 2-, 3-furyl, 1-, 2-, 3-pyrrolyl, 1-, 2-, 3-thienyl, 2-, 3-, 4-, pyridyl, 2-, 3-, 4-, 5-, 6-, 7-indolyl, 3-, 4-, 5-pyrazolyl, 2-, 4-,5-imidazolyl, acridinyl, quinolinyl, phenanthridinyl, 2-, 4-, 5-, 6-pyrimidinyl, where Ar may be substituted by halogen, (C 1 -C 8 )-alkyl, (C 1 -C 8 )-alkoxy, NH 2 , —NO, —NO 2 , NH(C 1 -C 8 )-alkyl, —N((C 1 -C 8 )-alkyl) 2 , —OH, —CF 3 , —C nF 2n+1 , NH(C 1 -C 8 )-acyl, N((C 1 -C 8 )-acyl) 2 , (C 1 -C 8 )-acyl, (C 1 -C 8 )-acyloxy, —S(O) 2 ((C 1 -C 8 )-alkoxy), —S(O)((C 1 -C 8 )-alkoxy), —P(O) ((C 1 -C 8 )-alkoxy) 2 or —OP(O)((C 1 -C 8 )-alkoxy) 2 .
2. A Ru-carbene complex of the general formula (VI)
where wherein L is a heterocyclic carbene and L′ is selected from the group consisting of triphenylphosphane, triisopropylphosphane, tricyclohexylphosphane and 9-cyclohexyl-9-phospha-bicyclo[3.3.1]nonane, X is an anionic ligand, Ar is a naphthyl radical or a (C 3 -C 14 ) heteroaryl radical, wherein the (C 3 -C 14 ) heteroaryl radical is selected from the group consisting of 1-, 2-, 3-furyl, 1-, 2-, 3-pyrrolyl, 1-, 2-, 3-thienyl, 2-, 3-, 4-, pyridyl, 2-, 3-, 4-, 5-, 6-, 7-indolyl, 3-, 4-, 5pyrazolyl, 2-, 4-,5-imidazolyl, acridinyl, quinolinyl, phenanthridinyl, 2-, 4-, 5-, 6pyrimidinyl, where Ar may be substituted by halogen, (C 1 -C 8 )-alkyl, (C 1 -C 8 )-alkoxy, NH 2 , —NO, —NO 2 , NH(C 1 -C 8 )-alkyl, —N((C 1 -C 8 )-alkyl) 2 , —OH, —CF 3 , —C n F 2n+1 , NH(C 1 -C 8 )-acyl, N((C 1 -C 8 )-acyl) 2 , (C 1 -C 8 )-acyl, (C 1 -C 8 )-acyloxy, —S(O) 2 ((C 1 -C 8 )-alkoxy), —S(O)((C 1 -C 8 )-alkoxy), —P(O) ((C 1 -C 8 )-alkoxy) 2 or —OP(O)((C 1 -C 8 )-alkoxy) 2 .
3. The Ru-carbene complex according to claim 1 , wherein Ar is a furyl or thienyl radical.
4. A metathesis reaction which comprises utilizing the Ru-carbene complex according to claim 1 as a catalyst in the metathesis reaction.
5. The Ru-carbene complex according to claim 1 , wherein X is halogen, carboxylate, sulphate or diketonate.
6. The Ru-carbene complex according to claim 1 , wherein X is bromine or chlorine.
7. The Ru-carbene complex according to claim 1 , wherein X is chlorine.
8. A Ru-carbene complex of the general formula (VI)
where L and L′ are identical or different and are selected independently from the group consisting of triphenylphosphane, triisopropylphosphane, tricyclohexylphosphane and 9-cyclohexyl-9-phosphabicyclo [3.3.1]nonane,
X is halogen, carboxylate, sulphate or diketonate,
Ar is a naphthyl radical or a (C 3 -C 14 ) heteroaryl radical, wherein the (C 3 -C 14 ) heteroaryl radical is selected from the group consisting of 1-, 2-, 3-furyl, 1-, 2-, 3-pyrrolyl, 1-, 2-, 3-thienyl, 2-, 3-, 4-, pyridyl, 2-, 3-, 4-, 5-, 6-, 7-indolyl, 3-, 4-, 5pyrazolyl, 2-, 4-,5-imidazolyl, acridinyl, quinolinyl, phenanthridinyl, 2-, 4-, 5-, 6-pyrimidinyl, where Ar may be substituted by halogen, (C 1 -C 8 )-alkyl, (C 1 -C 8 )-alkoxy, NH 2 , —NO, —NO 2 , NH(C 1 -C 8 )-alkyl, —N((C 1 -C 8 )-alkyl) 2 , —OH, —CF 3 , —C n F 2n+1 , NH(C 1 -C 8 )-acyl, N((C 1 -C 8 )-acyl) 2 , (C 1 -C 8 )-acyl, (C 1 -C 8 )-acyloxy, —S(O) 2 ((C 1 -C 8 )-alkoxy), —S(O)((C 1 -C 8 )-alkoxy), —P(O) ((C 1 -C 8 )-alkoxy) 2 or —OP(O)((C 1 -C 8 )-alkoxy) 2 .
9. The Ru-carbene complex according to claim 2 , wherein Ar is a furyl or thienyl radical.
10. A metathesis reaction which comprises utilizing the Ru-carbene complex according to claim 2 as a catalyst in the metathesis reaction.
11. The Ru-carbene complex according to claim 2 , wherein X is halogen, carboxylate, sulphate or diketonate.
12. The Ru-carbene complex according to claim 2 , wherein X is chlorine.
13. The Ru-carbene complex according to claim 8 , wherein Ar is a furyl or thienyl radical.
14. A metathesis reaction which comprises utilizing the Ru-carbene complex according to claim 8 as a catalyst in the metathesis reaction.
15. The Ru-carbene complex according to claim 8 , wherein X is bromine or chlorine.
16. The Ru-carbene complex according to claim 8 , wherein X is chlorine.
17. The Ru-carbene complex according to claim 11 , wherein Ar is a furyl or thienyl radical.
18. The Ru-carbene complex according to claim 15 , wherein Ar is a furyl or thienyl radical,
19. The Ru-carbene complex according to claim 2 , wherein L is a heterocyclic carbene of the formula (X) or (XI)
where
R and R′ is identical or different and can be selected from the group consisting of hydrogen, (C 1 -C 18 )-alkyl, (C 3 -C 8 )-cycloalkyl, (C 2 -C 7 )-heterocycloalkyl, (C 6 -C 14 )-aryl and (C 3 -C 14 )-heteroaryl,
X and Y are, independently of one another, a nitrogen or phosphorus atom and
A is part of a C 2 -C 4 bridge, saturated or unsaturated, substituted or unsubstituted, with bridge carbons being able to be substituted by heteroatoms.
20. The Ru-carbene complex according to claim 2 , wherein L′ is selected from the group consisting of triisopropylphosphane, tricyclohexylphosphane and 9-cyclohexyl-9-phospha-bicyclo [3.3.1]nonane.