Catalysts for metathesis reactions
View Patent ↗Catalysts for metathesis reactions, in particular for the metathesis of nitrile rubber, are provided.
1. A ruthenium- or osmium carbene complex catalyst having the general formulae (IIa),
where
M is ruthenium or osmium,
X 1 and X 2 are identical or different and are two ligands,
L 1 and L 2 are identical or different ligands, where L 2 can alternatively also be bridged by the radical R 8 ,
n is 0,
R 1 -R 8 are identical or different and are each hydrogen, halogen, hydroxyl, aldehyde, keto, thiol, CF 3 , nitro, nitroso, cyano, thiocyano, isocyanato, carbodiimide, carbamate, thiocarbamate, dithiocarbamate, amino, amido, imino, silyl, sulphonate (—SO 3 − ), —OSO 3 − , —PO 3 − or OPO 3 − or alkyl, cycloalkyl, alkenyl, alkynyl, aryl, carboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl, alkylsulphinyl, dialkylamino, alkylsilyl or alkoxysilyl, where these radicals may each optionally be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl radicals or alternatively two directly adjacent radicals from the group R 1 -R 8 together with the ring carbons to which they are bound form, by bridging, a cyclic group, preferably an aromatic system, or alternatively R 8 can be bridged to another ligand of the ruthenium- or osmium-carbene complex catalyst
m is 0 or 1, and
A is oxygen, sulphur, C(R 9 R 10 ), N—R 11 , —C(R 12 )═C(R 13 )—, —C(R 12 )(R 14 )—C(R 13 )(R 15 )—, where R 9 -R 15 are identical or different and each have one of the meanings of the radicals R 1 -R 8 .
2. The catalyst according to claim 1 , wherein
X 1 and X 2 are identical or different and are two anionic ligands,
L 1 and L 2 are identical or different uncharged electron donor ligands, where L 2 can alternatively also be bridged by the radical R 8 , and
n is 0.
3. The catalyst according to claim 1 , wherein X 1 and X 2 are identical or different and are each hydrogen, halogen, pseudohalogen, a straight-chain or branched C 1 -C 30 -alkyl, C 6 -C 24 -aryl, C 1 -C 20 -alkoxy, C 6 -C 24 -aryloxy, C 3 -C 20 -alkyldiketonate, C 6 -C 24 -aryldiketonate, C 1 -C 20 -carboxylate, C 1 -C 20 -alkylsulphonate, C 6 -C 24 -arylsulphonate, C 1 -C 20 -alkylthiol, C 6 -C 24 -arylthiol, C 1 -C 20 -alkylsulphonyl or C 1 -C 20 -alkylsulphinyl radical.
4. The catalyst according to claim 1 , wherein X 1 and X 2 are identical or different and are each halogen, benzoate, C 1 -C 5 -carboxylate, C 1 -C 5 -alkyl, phenoxy, C 1 -C 5 -alkoxy, C 1 -C 5 -alkylthiol, C 6 -C 24 -arylthiol, C 6 -C 24 -aryl or C 1 -C 5 -alkylsulphonate.
5. The catalyst according to claim 1 , wherein X 1 and X 2 are identical and are each chlorine, CF 3 COO, CH 3 COO, CFH 2 COO, (CH 3 ) 3 CO, (CF 3 ) 2 (CH 3 )CO, (CF 3 )(CH 3 ) 2 CO, PhO (phenoxy), MeO (methoxy), EtO (ethoxy), tosylate (p-CH 3 —C 6 H 4 —SO 3 ), mesylate (2,4,6-trimethylphenyl) or CF 3 SO 3 (trifluoromethanesulphonate).
6. The catalyst according to claim 1 , wherein the two ligands L 1 and L 2 are each, independently of one another, a phosphine, sulphonated phosphine, phosphate, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, sulphoxide, carboxyl, nitrosyl, pyridine, thioether or imidazolidine (“Im”) ligand.
7. The catalyst according to claim 6 , wherein one or both ligands L 1 and L 2 is/are a pyridine ligand, a picoline (α-, β- and γ-picoline), lutidine (2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-lutidine), collidine (2,4,6-trimethylpyridine), trifluoromethylpyridine, phenylpyridine, 4-(dimethylamino)pyridine, chloropyridine (2-, 3- and 4-chlorpyridine), bromopyridine (2-, 3- and 4-bromopyridine), nitropyridine (2-, 3- and 4-nitropyridine), quinoline, pyrimidine, pyrrole, imidazole and phenylimidazole.
8. The catalyst according to claim 6 , wherein one or both ligands L 1 and L 2 is/are an imidazolidine radical (Im) having a structure of the general formula (XIa) or (XIb),
where
R 16 , R 17 , R 18 , R 19 are identical or different and are hydrogen, straight-chain or branched C 1 -C 30 -alkyl, C 3 -C 20 -cycloalkyl, C 2 -C 20 -alkenyl, C 2 -C 20 -alkynyl, C 6 -C 24 -aryl, C 1 -C 20 -carboxylate, C 1 -C 20 -alkoxy, C 2 -C 20 -alkenyloxy, C 2 -C 20 -alkynyloxy, C 6 -C 20 -aryloxy, C 2 -C 20 -alkoxycarbonyl, C 1 -C 20 -alkylthio, C 6 -C 20 -arylthio, C 1 -C 20 -alkylsulphonyl, C 1 -C 20 -alkylsulphonate, C 6 -C 20 -arylsulphonate or C 1 -C 20 -alkylsulphinyl and the abovementioned radicals may optionally be monosubstituted or polysubstituted.
9. The catalyst according to claim 8 , wherein one or both ligands L 1 and L 2 is/are an imidazolidine radical (Im) having a structure of one of the general formulae (XIIa)-(XIIf), where Ph is a phenyl radical, Bu is a butyl radical and Mes is in each case 2,4,6-trimethylphenyl or alternatively in all cases 2,6-diisopropylphenyl
10. The catalyst according to claim 1 of the general formula (IIa) in which
M is ruthenium,
X 1 and X 2 are both halogen,
n is 0,
L 1 and L 2 have the meanings mentioned for the general formulae (IIa),
R 1 -R 8 have the meanings mentioned for the general formulae (IIa),
m is either 0 or 1,
and, when m=1,
A is oxygen, sulphur, C(C 1 -C 10 -alkyl) 2 , —C(C 1 -C 10 -alkyl) 2 -C(C 1 -C 10 -alkyl) 2 -, —C(C 1 -C 10 -alkyl)=C(C 1 -C 10 -alkyl)- or —N(C 1 -C 10 -alkyl).
11. The catalyst according to claim 1 of the general formula (IIa) in which
M is ruthenium,
X 1 and X 2 are both chlorine,
n is 0,
L 1 is an imidazolidine radical having one of the formulae (XIIa) to (XIIf),
L 2 is a sulphonated phosphine, phosphate, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, sulphoxide, carboxyl, nitrosyl, pyridine radical, an imidazolidine radical having one of the formulae (XIIa) to (XIIf) or a phosphine ligand,
R 1 -R 8 have the meanings mentioned for the general formulae (IIa),
m is either 0 or 1,
and, when m=1,
A is oxygen, sulphur, C(C 1 -C 10 -alkyl) 2 , —C(C 1 -C 10 -alkyl) 2 -C(C 1 -C 10 -alkyl) 2 -, —C(C 1 -C 10 -alkyl)=C(C 1 -C 10 -alkyl)- or —N(C 1 -C 10 -alkyl).
12. The catalyst according to claim 11 of the general formula (IIa) in which L 2 is PPh 3 , P(p-Tol) 3 , P(o-Tol) 3 , PPh(CH 3 ) 2 , P(CF 3 ) 3 , P(p-FC 6 H 4 ) 3 , P(p-CF 3 C 6 H 4 ) 3 , P(C 6 H 4 —SO 3 Na) 3 , P(CH 2 C 6 H 4 —SO 3 Na) 3 , P(isopropyl) 3 , P(CHCH 3 (CH 2 CH 3 )) 3 , P(cyclopentyl) 3 , P(cyclohexyl) 3 , P(neopentyl) 3 or P(neophenyl) 3 .
13. The catalyst according to claim 1 , wherein the radical R 8 is bridged to another ligand of the complex catalyst to form a structure of the general formula (XIIIa)
where
Y 1 is oxygen, sulphur, an N—R 21 radical or a P—R 21 radical, where R 21 is as defined below,
R 20 and R 21 are identical or different and are each an alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl or alkylsulphinyl radical which may all optionally be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl radicals,
p is 0 or 1 and
Y 2 is, when p=1, —(CH 2 ) r — where r=1, 2 or 3, —C(═O)—CH 2 —, —C(═O)—, —N═CH—, —N(H)—C(═O)— or alternatively the overall structural unit “—Y 1 (R 20 )—(Y 2 ) p —” is (—N(R 20 )═CH—CH 2 —), and
M, X 1 , X 2 , L 1 , R 1 -R 8 , A, m and n have the same meanings as in the general formulae (IIa).
14. A catalyst having the following structural formulae
where Mes is in each case 2,4,6-trimethylphenyl, Ph is a phenyl radical, Cy is a cyclohexyl radical, and
R 20 and R 21 are identical or different and are each an alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl or alkylsulphinyl radical which may all optionally be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl radicals.
15. A process for preparing catalysts of the general formulae (IIa) according to claim 1 , wherein a catalyst precursor compound of the general formula (XVII),
where
M, X 1 , X 2 , L 1 and L 2 have the same meanings as in the general formulae (IIa) and
AbL is a “leaving ligand” and has the same meanings as L 1 and L 2 in the general formula (IIa),
is reacted with a compound of the general formula (XVI)
where R 1 -R 8 , m and A have the meanings mentioned in claim 1 ,
at a temperature in the range from −20° C. to 100° C. and a molar ratio of the catalyst precursor compound of the general formula (XVII) to the compound of the general formula (XVI) of from 1:0.5 to 1:5.
16. A method of subjecting a chemical compound to a metathesis reaction by bringing such compound into contact with the catalyst according to claim 1 .
17. The method according to claim 16 , wherein the metathesis reaction is a ring-closing metatheses (RCM), a cross metatheses (CM), a ring-opening metatheses (ROM), a ring-opening metathesis polymerization (ROMP), a cyclic diene metathesis polymerization (ADMET), a self-metatheses, a reaction of alkenes with alkynes (enyne reactions), a polymerization of alkynes or an olefinization of carbonyls.
18. The method according to claim 16 , wherein the catalyst is brought into contact with a nitrile rubber, thereby decreasing the molecular weight of said nitrile rubber.
19. The method according to claim 18 , wherein the amount of catalyst based on the nitrile rubber used is from 1 to 1 000 ppm of noble metal.
20. The method according to claim 18 , wherein a copolymer or terpolymer containing repeating units of at least one conjugated diene, at least one α,β-unsaturated nitrile and, optionally, one or more further copolymerizable monomers is used as nitrile rubber.
21. The method according to claim 18 , wherein a copolymer or terpolymer containing repeating units of at least one conjugated diene, at least one α,β-unsaturated nitrile and, optionally, one or more further copolymerizable monomers selected from the group consisting of fumaric acid, maleic acid, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate and methoxyethyl (meth)acrylate, is used as nitrile rubber.
22. The method according to claim 18 , wherein a hydrogenation reaction is performed subsequent to the reduction in molecular weight of the nitrile rubberic followed by a hydrogenation.
23. The catalyst according to claim 1 where L 1 and L 2 are uncharged electron donors.
24. The process for preparing catalysts of the general formulae (IIa) according to claim 15 , where AbL is a phosphine ligand.
25. The catalyst of claim 8 where R 16 , R 17 , R 18 , R 19 substituents may be substituted by one or more radicals which are selected from the group consisting of halogen, C 1 -C 5 -alkyl, C 1 -C 5 -alkoxy and phenyl.
26. The catalyst of claim 25 where R 16 , R 17 , R 18 , R 19 substituents may be substituted by one or more radicals which are selected from the group consisting of chlorine and bromine.