IP Library › Granted Patent US 10,744,494

Granted Patent B2

US 10,744,494 · App. 16/062,852 · Granted Aug 18, 2020

Immobilized metal alkylidene catalysts and use thereof in olefin metathesis

Inventors: Christophe Coperet (Zurich, CH); Margherita Puccino (Zurich, CH); Victor Mougel (Zurich, CH); Michael Buchmeiser (Stuttgart, DE); Roman Schowner (Stuttgart, DE); Csaba Hegedus (Horw/Lucerne, CH); Florian Toth (Horw/Lucerne, CH)

Assignee: XiMo AG

B01J31/2278 B01J21/08 B01J31/2273 B01J31/2295 C07C1/213 C07C6/04 C07C67/333 C07C67/475 C07D307/28 C07F7/083 C07F11/00 C08G61/08 B01J2231/14 B01J2231/54 B01J2531/64 B01J2531/66 C07C2531/22 C08G2261/418 Y02P20/52

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Quick Facts

Patent No.: US 10,744,494
App. No.: 16/062,852
Granted: Aug 18, 2020
Kind: B2

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Abstract

The invention relates to immobilized metal alkylidene catalysts. The catalysts are useful in olefin metathesis.

Claims (173)

1. A compound of general Formula I or Formula II

wherein:

A 1 is NR 2 or PR 2 ;

A 2 is CR 2 R 2′ , NR 2 , PR 2 , O or S;

C is a carbene carbon atom;

ring B includes A 1 —C—A 2 and is a unsubstituted or mono- or multisubstituted 5 to 7-membered ring, which may contain besides A 1 and A 2 further heteroatoms selected from nitrogen, phosphorus, oxygen or sulfur, and the substituents of which have the meaning of R 2 ;

R 2 and R 2′ are independently from one another H, a linear, a partially cyclic or branched C 1 to C 18 -alkyl residue, a linear, a partially cyclic or branched C 1 to C 18 -alkenyl residue, a C 3 to C 12 -cycloalkyl residue, a linear, partially cyclic or branched C 6 to C 100 -polyoxaalkyl residue, a C 5 to C 14 -aryl or heteroaryl residue, a C 3 to C 14 -aryloxy residue, a linear, partially cyclic or branched C 1 to C 18 -perfluoroalkyl residue, a linear, partially cyclic or branched C 1 to C 18 -perchloroalkyl residue, a linear, partially cyclic or branched partially fluorinated C 1 to C 18 -alkyl residue, a partially chlorinated linear, partially cyclic or branched C 1 to C 18 -alkyl residue, a perfluorinated or partially fluorinated C 6 to C 14 -aryl residue, a perchlorinated or partially chlorinated C 6 to C 14 -aryl residue;

and, when A 1 and A 2 are NR 2 or PR 2 , respectively, R 2 may be the same or may be different, or

R 2 and R 2′ taken together form a linear or branched C 1 to C 18 -alkylene residue;

M is Cr, Mo or W;

X 1 is a residue of a solid oxide, wherein the solid oxide is linked to M via oxygen;

X 2 is selected from the group comprising or consisting of halogenide, C 1 to C 18 -carboxylates, C 1 to C 18 -alkoxides, fluorinated C 1 to C 18 -alkoxides, C 1 to C 18 -mono- or polyhalogenated carboxylates, unsubstituted, mono or multisubstituted C 6 to C 18 -monophenolate, -biphenolate or -terphenolate, wherein the substituents at the monophenolate, bisphenolate or terphenolate have the meaning of halogen or R 2 , C 1 to C 18 -thiolate, unsubstituted, mono or multisubstituted C 6 to C 18 -monothiophenolate, -thiobiphenolate or -thioterphenolate, wherein the substituents at the thiomonophenolate, thiobisphenolate or thioterphenolate have the meaning of halogen or R 2 , trifluoromethane sulfonate, pyrrol-1-yl, optionally substituted with one or more of R 2 , —NH—(CO)—R 2 , —N(R 2 ) 2 , wherein R 2 is selected independently from one another, or non-coordinating anions;

Y is oxygen, sulfur, N-adamantyl, N-tert-butyl, N—(C 6-14 )aryl, wherein aryl may be substituted with one or more of halogen, linear or branched C 1 to C 18 -alkyl, linear or branched C 1 to C 18 -alkyloxy or substituted or unsubstituted phenyl, the substituents of which have the meaning of R 2 ;

R 1 and R 1 ′ are independently from one another H, linear or branched C 1 to C 18 -alkyl or unsubstituted or substituted C 6 to C 14 -aryl, wherein the substituents have the meaning of R 2 ; or R1 and R 1 ′ are independently from one another ortho-alkoxyphenyl, wherein alkoxy is C 1 to C 6 -alkoxy; or wherein R 1 and R 1 ′ are independently from one another H and ortho-alkoxyphenyl, wherein alkoxy is C 1 to C 6 -alkoxy.

2. The compound according to claim 1 , wherein M is Mo or W.

3. The compound according to claim 1 , wherein Y is oxygen.

4. The compound according to claim 1 , wherein R 1 and R 1 ′ are independently from one another H and tert-butyl, or H and CMe 2 Ph; or wherein at least one of R 1 and R 1 ′ is ortho-alkoxyphenyl, wherein alkoxy is C 1 to C 6 -alkoxy; or wherein R 1 and R 1 ′ are independently from one another H and ortho-alkoxyphenyl, wherein alkoxy is C 1 to C 6 -alkoxy.

5. The compound according to claim 1 , wherein ring B is a heterocycle selected from the group comprising or consisting of: 1,3-disubstituted imidazol-2-ylidene, 1,3-disubstituted imidazolidin-2-ylidene, 1,3-disubstituted tetrahydropyrimidin-2-ylidene, 1,3-disubstituted diazepin-2-ylidene, 1,3-disubstituted dihydro-diazepin-2-ylidene, 1,3-disubstituted tetrahydrodiazepin-2-ylidene, N-substituted thiazol-2-ylidene, N-substituted thiazolin-2-ylidene, N-substituted triazol-2-ylidene, N-substituted dihydrotriazol-2-ylidene, mono- or multisubstituted triazolin-2-ylidene, N-substituted thiadiazol-2-ylidene, mono- or multisubstituted thiadiazolin-2-ylidene and mono- or multi-substituted tetrahydrotriazol-2-ylidene,

wherein the heterocycle may have one or more further substituents, wherein said substituents independently have the meaning of R 2 or halogen or NR 2 .

6. The compound according to claim 5 , wherein ring B is selected from 1,3-dimesitylimidazol-2-ylidene, 1,3-dimesitylimidazolidin-2-ylidene, 1,3-di-tert-butylimidazol-2-ylidene, 1,3-di-tent-butylimidazolidin-2-ylidene, 1,3-diisopropylimidazol-2-ylidene, 1,3-diisopropylimidazolidin-2-ylidene 1,3-dimethyl-benzimidazol-2-ylidene, 1,3-dicyclohexylimidazol-2-ylidene, 1,3-dicyclohexylimidazolidin-2-ylidene, 1-mesityl-3-[2-(pyridine-2-yl)-2-eth-2-yl]imidazole-2-ylidene, 1-mesityl-3-(2-phenyl-eth-2-yl)-imidazol-2-ylidene, 1-mesityl-3-(2-phenyl-eth-2-yl)-imidazolidin-2-ylidene, 4,5-dichloro-1,3-dimethyl-2-imidazol-2-ylidene, 1,3,5-triphenyl-triazol-2-ylidene, 3,5-tetramethyl-1-mesityl-pyrrolidin-2-ylidene.

7. The compound according to claim 1 , wherein when X 2 is a non-coordinating anion, said anion in Formula II is selected from tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tetrakis(pentafluorophenyl)borate, tetrakis(nonafluoro-t-butoxy)aluminate, tetrafluoroborate, hexafluorophosphate and hexafluoroantimonate.

8. The compound according to claim 1 , wherein the solid oxide is selected from the group comprising or consisting of: silica, titania, zirconia, cerium oxide, alumina, or a mixture of two or more thereof.

9. The compound according to claim 1 , wherein the solid oxide is silica and X 1 is O—Si(O—) 3 .

10. The compound according to claim 9 , wherein silica is comprised in a solid support.

11. The compound according to claim 1 , wherein

M is selected from Mo or W;

Y is selected from oxygen, sulfur, N-adamantyl, N-tert-butyl, N—(C 6-14 )aryl, wherein aryl may be substituted with one or more of halogen, linear or branched C 1 to C 18 -alkyl, linear or branched C 1 to C 18 -alkyloxy or substituted or unsubstituted phenyl, the substituents of which have the meaning of R 2 ;

ring B is selected from 1,3-dimesitylimidazol-2-ylidene, 1,3-dimesitylimidazolidin-2-ylidene, 1,3-di-tert-butylimidazol-2-ylidene, 1,3-di-tert-butylimidazolidin-2-ylidene, 1,3-diisopropylimidazol-2-ylidene, 1,3-diisopropylimidazolidin-2-ylidene 1,3-dimethyl-benzimidazol-2-ylidene, 1,3-dicyclohexylimidazol-2-ylidene, 1,3-dicyclohexylimidazolidin-2-ylidene, 1-mesityl-3-[2-(pyridine-2-yl)-2-eth-2-yl]imidazole-2-ylidene, 1-mesityl-3-(2-phenyl-eth-2-yl)-imidazol-2-ylidene, 1-mesityl-3-(2-phenyl-eth-2-yl)-imidazolidin-2-ylidene, 4,5-dichloro-1,3-dimethyl-2-imidazol-2-ylidene, 1,3,5-triphenyl-triazol-2-ylidene, 3,5-tetramethyl-1-mesityl-pyrrolidin-2-ylidene;

R 1 and R 1 ′ are independently from one another H and tert-butyl, or H and CMe 2 Ph; or wherein at least one of R 1 and R 1 ′ is ortho-alkoxyphenyl, wherein alkoxy is C 1 to C 6 -alkoxy; or wherein R 1 and R 1 ′ are independently from one another H and ortho-alkoxyphenyl, wherein alkoxy is C 1 to C 6 -alkoxy;

X 1 is (—O—) 3 Si—O—; and

X 2 is selected from the group comprising or consisting of halide, C 1 to C 18 -alkoxides, fluorinated C 1 to C 18 -alkoxides, trifluoromethane sulfonate, tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tetrakis(pentafluorophenyl)borate, tetrakis(nonafluoro-t-butoxy)aluminate, tetrafluoroborate, hexafluorophosphate and hexafluoroantimonate; or

wherein

M is selected from Mo or W;

Y is selected from oxygen, N-adamantyl, N-tert-butyl, N—(C 6-14 )aryl, wherein aryl may be substituted with one or more of halogen, linear or branched C 1 to C 18 -alkyl, linear or branched C 1 to C 18 -alkyloxy or substituted or unsubstituted phenyl, the substituents of which have the meaning of R 2 ;

X 1 is (—O—) 3 Si—O—; and

X 2 is selected from the group comprising or consisting of F and Cl, fluorinated C 1 to C 18 -alkoxides, trifluoromethane sulfonate, tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tetrakis(pentafluorophenyl)borate, tetrakis(nonafluoro-t-butoxy)aluminate, tetrafluoroborate, hexafluorophosphate and hexafluoroantimonate; or

wherein

M is selected from Mo or W;

X 1 is (—O—) 3 Si—O—; and

X 2 is selected from the group comprising or consisting of F and Cl, trifluoromethane sulfonate, tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tetrakis(pentafluorophenyl)borate, tetrakis(nonafluoro-t-butoxy)aluminate, tetrafluoroborate, hexafluorophosphate and hexafluoroantimonate.

12. The compound according to claim 1 , wherein

M is W;

Y is oxygen;

ring B is 1,3-dimesitylimidazol-2-ylidene;

R 1 and R 1 ′ are independently from one another H and CMe 2 Ph;

X 1 is (—O—) 3 Si—O—; and

X 2 is trifluoromethane sulfonate;

M is W;

Y is oxygen;

ring B is 1,3-dimesitylimidazol-2-ylidene;

R 1 and R 1 ′ are independently from one another H and CMe 2 Ph;

X 1 is (—O—) 3 Si—O—; and

X 2 is tetrakis(3,5-bis(trifluoromethyl)phenyl)borate;

M is W;

Y is N-tert-butyl;

ring B is 4,5-dichloro-1,3-dimethyl-imidazol-2-ylidene;

R 1 and R 1 ′ are independently from one another H and tert-butyl;

X 1 is (—O—) 3 Si—O—; and

X 2 is Cl;

M is W;

Y is N-tert-butyl;

ring B is 4,5-dichloro-1,3-dimethyl-imidazol-2-ylidene;

R 1 and R 1 ′ are independently from one another H and tert-butyl;

X 1 is (—O—) 3 Si—O—; and

X 2 is tetrakis(nonafluoro-t-butoxy)aluminate;

M is W;

Y is O;

ring B is 1,3,5-triphenyl-triazol-2-ylidene;

R 1 and R 1 ′ are independently from one another H and CMe 2 Ph;

X 1 is (—O—) 3 Si—O—; and

X 2 is tetrakis(3,5-bis(trifluoromethyl)phenyl)borate;

M is Mo;

Y is N-2,6-dichlorophenyl;

ring B is 1,3,5-triphenyl-triazol-2-ylidene;

R 1 and R 1 ′ are independently from one another H and CMe 2 Ph;

X 1 is (—O—) 3 Si—O—; and

X 2 is tetrakis(3,5-bis(trifluoromethyl)phenyl)borate;

M is Mo;

Y is N-2-trifluoromethylphenyl;

ring B is 1,3,5-triphenyl-triazol-2-ylidene;

R 1 and R 1 ′ are independently from one another H and CMe 2 Ph;

X 1 is (—O—) 3 Si—O—; and

X 2 is tetrakis(3,5-bis(trifluoromethyl)phenyl)borate;

M is Mo;

Y is N-3,5-dimethylphenyl;

ring B is 1,3,5-triphenyl-triazol-2-ylidene;

R 1 and R 1 ′ are independently from one another H and CMe 2 Ph;

X 1 is (—O—) 3 Si—O—; and

X 2 is tetrakis(3,5-bis(trifluoromethyl)phenyl)borate;

M is Mo;

Y is N-2,6-dimethylphenyl;

ring B is 1,3-dimesitylimidazol-2-ylidene;

R 1 and R 1 ′ are independently from one another H and CMe 2 Ph;

X 1 is (—O—) 3 Si—O—; and

X 2 is tetrakis(3,5-bis(trifluoromethyl)phenyl)borate;

M is Mo;

Y is N-2,6-dimethylphenyl;

ring B is 1,3-dimesitylimidazolidin-2-ylidene;

R 1 and R 1 ′ are independently from one another H and CMe 2 Ph;

X 1 is (—O—) 3 Si—O—; and

X 2 is tetrakis(3,5-bis(trifluoromethyl)phenyl)borate;

M is W;

Y is O;

ring B is 1,3-dimesitylimidazol-2-ylidene;

R 1 and R 1 ′ are independently from one another H and 2-methoxyphenyl;

X 1 is (—O—) 3 Si—O—; and

X 2 is tetrakis(3,5-bis(trifluoromethyl)phenyl)borate;

M is Mo;

Y is N-2,6-dimethylphenyl;

ring B is 1,3-dimesitylimidazolidin-2-ylidene;

R 1 and R 1 ′ are independently from one another H and 2-methoxyphenyl;

X 1 is (—O—) 3 Si—O—; and

X 2 is tetrakis(3,5-bis(trifluoromethyl)phenyl)borate;

M is Mo;

Y is N-2,6-dimethylphenyl;

ring B is 1,3-dimesitylimidazol-2-ylidene;

R 1 and R 1 ′ are independently from one another H and 2-methoxyphenyl;

X 1 is (—O—) 3 Si—O—; and

X 2 is tetrakis(3,5-bis(trifluoromethyl)phenyl)borate;

M is Mo;

Y is N-2-tert-butylphenyl;

ring B is 1,3-dimesitylimidazol-2-ylidene;

R 1 and R 1 ′ are independently from one another H and CMe 2 Ph;

X 1 is (—O—) 3 Si—O—; and

X 2 is tetrakis(3,5-bis(trifluoromethyl)phenyl)borate;

M is W;

Y is O;

ring B is 1,3-dimesitylimidazol-2-ylidene;

R 1 and R 1 ′ are independently from one another H and CMe 2 Ph;

X 1 is (—O—) 3 Si—O—; and

X 2 is tetrakis(pentafluorophenyl)borate.

13. A method of making a compound of the general Formula I or II as defined in claim 1 , comprising at least the following step (S):

(S): reacting a solid oxide with a compound of the general Formula III or IV

wherein:

A 1 is NR 2 or PR 2 ;

A 2 is CR 2 R 2′ , NR 2 , PR 2 , O or S;

C is a carbene carbon atom;

and, when A 1 and A 2 are NR 2 or PR 2 , respectively, R 2 may be the same or may be different, or

R 2 and R 2′ taken together form a linear or branched C 1 to C 18 -alkylene residue;

M is Cr, Mo or W;

R 1 and R 1 ′ are independently from one another H, linear or branched C 1 to C 18 -alkyl or unsubstitued or substituted C 6 to C 14 -aryl, wherein the substituents have the meaning of R 2 ; or R1 and R 1 ′ are independently from one another ortho-alkoxyphenyl, wherein alkoxy is C 1 to C 6 -alkoxy; or wherein R 1 and R 1 ′ are independently from one another H and ortho-alkoxyphenyl, wherein alkoxy is C 1 to C 6 -alkoxy; and

X 1 is C 0-8 sulfonate; halogenide; nitrate and phosphate and C 1-8 esters of phosphate; C 1-8 alcoholate.

14. The method according to claim 13 , further comprising step (R) prior to step (S):

(R): heating the solid oxide.

15. A method of forming an olefin from a first and a second olefin in a metathesis reaction, comprising step (T):

(T): reacting the first olefin with the second olefin in the presence of a compound of general Formula I or II as defined in claim 1 ;

wherein the first and the second olefin may be the same or may be different from one another.

16. A method of converting a compound of general Formula I or general Formula II as defined in claim 1 into a compound of general Formula VI or general Formula VII, comprising at least step (U):

(U): reacting said compound of general Formula I with a compound of general Formula V to yield said compound of general Formula VI, or reacting said compound of general Formula II with a compound of general Formula V to yield said compound of general Formula VII,

wherein at least one of R 1 ′ and R 1 in compound of Formula V is different from at least one of R 1 ′ and R 1 as defined in general Formula I or general Formula II, and wherein R 1 ′ and R 1 in general Formula VI and general Formula VII have the same meaning as in general Formula V.

Assignments (4)

CHANGE OF NAME Recorded Jan 26, 2024

From: VERBIO VEREINIGTE BIOENERGIE AG

To: VERBIO SE

Reel/Frame 066376/0063 →

CORRECTIVE ASSIGNMENT TO CORRECT THE US APPLICATION NO. 13/639,067 AND US APPLICATION NO. 14/001,811 WERE RECORDED IN ERROR PREVIOUSLY RECORDED ON REEL 050392 FRAME 719. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT. Recorded Sep 4, 2020

From: XIMO AG

To: VERBIO VEREINIGTE BIOENERGIE AG

Reel/Frame 053705/0924 →

ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Sep 16, 2019

From: XIMO AG

To: VERBIO VEREINIGTE BIOENERGIE AG

Reel/Frame 050392/0719 →

ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 15, 2018

From: COPERET, CHRISTOPHE; PUCCINO, MARGHERITA, DR.; MOUGEL, VICTOR; BUCHMEISER, MICHAEL, DR.; SCHOWNER, ROMAN; HEGEDUS, CSABA; TOTH, FLORIAN

To: XIMO AG

Reel/Frame 047516/0908 →

Priority Claims (1)

EP 15003700 · Dec 23, 2015 · regional

Continuity (1)

Related Publication 20190001315A1 · Jan 3, 2019