Metathesis catalysts and reactions using the catalysts
The invention relates to a method of forming an olefin from a first olefin and a second olefin in a metathesis reaction, comprising step (i): (i) reacting the first olefin with the second olefin in the presence of a compound that catalyzes said metathesis reaction such that the molar ratio of said compound to the first or the second olefin is from 1:500 or less, and the conversion of the first or the second olefin to said olefin is at least 50%, characterized in that as compound that catalyzes said metathesis reaction a compound of formula (A) is used: wherein M is Mo or W; R 1 is aryl, heteroaryl, alkyl, or heteroalkyl; optionally substituted; R 2 and R 3 can be the same or different and are hydrogen, alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, or heteroaryl; optionally substituted; R 5 is alkyl, alkoxy, heteroalkyl, aryl, heteroaryl, silylalkyl, silyloxy, optionally substituted; and R 4 is a residue R 6 —X—, wherein X═O and R 6 is aryl, optionally substituted; or X═S and R 6 is aryl, optionally substituted; or X═O and R 6 is (R 7 , R 8 , R 9 )Si; wherein R 7 , R 8 , R 9 are alkyl or phenyl, optionally substituted; or X═O and R 6 is (R 10 , R 11 , R 12 )C, wherein R 10 , R 11 , R 12 are independently selected from phenyl, alkyl; optionally substituted; and to the catalysts used in the method.
1. A composition, comprising:
a compound of Formula (A):
wherein
M=Mo or W;
R 1 is aryl, heteroaryl, alkyl, or heteroalkyl; optionally substituted;
R 2 and R 3 can be the same or different and are hydrogen, alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, or heteroaryl; optionally substituted;
R 5 is optionally substituted pyrrol-1-yl; and
R 4 is a residue R 6 —X—, wherein
X═O and R 6 is aryl, optionally substituted;
wherein R 6 is a phenyl ring which is at least substituted in 4-position with respect to O,
wherein R 6 is substituted in 2- and 4-position with respect to O; or
R 6 is substituted in 3- and 4-position; or
R 6 is substituted in 2-, 3- and 4-position; or
R 6 is substituted in 2-, 5- and 4-position; or
R 6 is substituted in 3-, 5- and 4-position; or
R 6 is substituted in 2-, 6- and 4-position; or
R 6 is substituted in 2-, 3-, 5- and 4-position; or
R 6 is substituted in 2-, 3-, 5-, 6- and 4-position;
and
a first and a second olefin or a first or a second olefin, which are comprised in a feedstock.
2. The composition of claim 1 , wherein in the compound of Formula (A)
R 1 is aryl or adamant-1-yl; optionally substituted;
R 2 is —C(CH 3 ) 2 C 6 H 5 or —C(CH 3 ) 3 ;
R 3 is H;
R 4 is a residue R 6 —X—, wherein
X═O and R 6 is phenyl substituted with up to five substituents independently selected from alkyl, preferably C 1 -C 4 alkyl, such as methyl, isopropyl or t-butyl, alkoxy, preferably C 1 -C 4 alkoxy, phenoxy, phenyl, halogen, optionally substituted.
3. The composition of claim 1 , wherein in the compound of Formula (A)
R 1 is selected from 1-(2,6-dimethylphenyl), 1-(2,6-diisopropylphenyl), 1-(2,6-di-t-butylphenyl), 1-(2,6-dichlorophenyl), adamant-1-yl;
R 2 is —C(CH 3 ) 2 C 6 H 5 or —C(CH 3 ) 3 ;
R 3 is H;
R 5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; and
R 4 is R 6 —X—, wherein
X═O and R 6 is phenyl substituted with up to five substituents independently selected from alkyl, preferably C 1 -C 4 alkyl such as methyl, isopropyl or t-butyl, alkoxy, preferably C 1 -C 4 alkoxy, phenoxy, phenyl, halogen, optionally substituted.
4. The composition of claim 1 , wherein in the compound of Formula (A)
R 1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, adamant-1-yl;
R 2 is —C(CH 3 ) 2 C 6 H 5 or —C(CH 3 ) 3 ;
R 3 is H;
R 5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; and
R 4 is R 6 —X—, wherein
X═O and R 6 is phenyl which bears at least three substituents, from which two substituents are in ortho position with respect to O and one substituent is in para position with respect to O.
5. The composition of claim 4 , wherein
R 4 is selected from 4-bromo-2,6-diphenylphenoxy, 4-fluoro-2,6-diphenylphenoxy, 4-methyl-2,6-diphenylphenoxy, 4-methoxy-2,6-diphenylphenoxy, 4-dimethylamino-2,6-diphenylphenoxy, 2,4,6-triphenylphenoxy, 4-fluoro-2,6-dimesitylphenoxy, 4-bromo-2,6-di-tert.-butylphenoxy, 4-methoxy-2,6-di-tert.-butylphenoxy, 4-methyl-2,6-di-tert.-butylphenoxy, 2,4,6-tri-tert.-butylphenoxy, 4-bromo-2,3,5,6-tetraphenylphenoxy; 4-bromo-2,6-di(4-bromophenyl)-3,5-diphenylphenoxy.
6. The composition of claim 1 , wherein the compound is selected from the following structures:
7. The composition of claim 1 , wherein in the compound of Formula (A)
R 1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-di-t-butylphenyl, 2,6-dichlorophenyl, adamant-1-yl;
R 2 is —C(CH 3 ) 2 C 6 H 5 or —C(CH 3 ) 3 ;
R 3 is H;
R 5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; and
R 4 is R 6 —X—, wherein
X═O and R 6 is phenyl which bears two substituents in ortho position with respect to O and a substituent in para position with respect to O.
8. The composition of claim 7 , wherein
R 1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, adamant-1-yl;
R 2 is —C(CH 3 ) 2 C 6 H 5 or —C(CH 3 ) 3 ;
R 3 is H;
R 4 is selected from 4-bromo-2,6-diphenylphenoxy, 4-fluoro-2,6-diphenylphenoxy, 4-methyl-2,6-diphenylphenoxy, 4-methoxy-2,6-diphenylphenoxy, 4-dimethylaminophenyl-2,6-diphenylphenoxy; 2,4,6-triphenylphenoxy, 4-fluoro-2,6-dimesitylphenoxy, 4-bromo-2,6-di-tert.-butylphenoxy, 4-methoxy-2,6-di-tert.-butylphenoxy, 4-methyl-2,6-di-tert.-butylphenoxy, 2,4,6-tri-tert.-butylphenoxy, 4-bromo-2,3,5,6-tetraphenylphenoxy; 4-bromo-2,6-di(4-bromophenyl)-3,5-diphenylphenoxy.
9. The composition of claim 1 , wherein the substituent of residue R 6 in 4-position is selected from the group consisting of: halogen, dialkylamino, cyano, optionally substituted alkyl, optionally substituted alkyloxy, optionally substituted aryl, optionally substituted aryloxy; or wherein the further substituents of residue R 6 may be the same or may be different from the substituent in 4-position and may be independently selected from the group consisting of: halogen, dialkylamino, cyano, optionally substituted alkyl, optionally substituted alkyloxy, optionally substituted aryl, optionally substituted aryloxy; or
wherein R 1 is phenyl or alkyl, optionally independently substituted with halogen, C 1-4 dialkylamino, C 1-4 alkyl, C 1-4 alkyloxy, phenyl, optionally substituted, phenyloxy, optionally substituted;
R 2 and R 3 can be the same or different and are hydrogen, C(CH 3 ) 3 , or C(CH 3 ) 2 C 6 H 5 ;
R 5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl;
the substituent of residue R 6 in 4-position is selected from the group consisting of: halogen, C 1-4 dialkylamino, C 1-4 alkyl, optionally substituted, C 1-4 alkyloxy, optionally substituted, phenyl, optionally substituted, phenyloxy, optionally substituted;
and the further substituents of residue R 6 may be the same or may be different from the substituent in 4-position and may be independently selected from the group consisting of halogen, C 1-4 dialkylamino, C 1-4 alkyl, optionally substituted, C 1-4 alkyloxy, optionally substituted, phenyl, optionally substituted, phenyloxy, optionally substituted; or
wherein R 6 is a phenyl ring which is substituted in 2- and 4-position independently with halogen and in 6-position with phenyl, which optionally may be substituted with halogen, alkyl, alkyloxy, phenyl, phenoxy; or phenyl or phenoxy optionally substituted with halogen, alkyl, alkyloxy, phenyl, phenoxy, respectively; or
wherein R 6 is a phenyl ring which is substituted in 2- and 6-position by substituents via carbon atoms, and in 4-position by a substituent via any atom; or
wherein R 6 is a phenyl ring which is substituted in 4-position with bromine and in 2-, 3-, 5- and 6-position with phenyl, respectively, wherein said phenyl residues may be independently substituted with fluoro, chloro, bromo, dimethylamino, diethylamino, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, methoxy, ethoxy, propyloxy, butyloxy, t-butyloxy, trifluoromethyl, phenyl optionally substituted with halogen, alkyl, alkyloxy, phenyl, phenoxy; phenoxy optionally substituted with halogen, alkyl, alkyloxy, phenyl, phenoxy.
10. A composition comprising a compound of Formula (A)
wherein
M=Mo or W;
R 1 is aryl, heteroaryl, alkyl, or heteroalkyl; optionally substituted;
R 2 and R 3 can be the same or different and are hydrogen, alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, or heteroaryl; optionally substituted;
R 5 is optionally substituted pyrrol-1-yl;
R 4 is [8-(naphthalene-1-yl)-naphthalene-1-yl]oxy, optionally substituted; or
R 4 is (8-phenylnaphthalene-1-yl)oxy, optionally substituted.
11. The composition of claim 10 , wherein in the compound of Formula (A)
R 1 is aryl or adamant-1-yl; optionally substituted;
R 2 is —C(CH 3 ) 2 C 6 H 5 or —C(CH 3 ) 3 ; and
R 3 is H.
12. The composition of claim 10 , wherein in the compound of Formula (A)
R 1 is selected from 1-(2,6-dimethylphenyl), 1-(2,6-diisopropylphenyl), 1-(2,6-di-t-butylphenyl), 1-(2,6-dichlorophenyl), adamant-1-yl;
R 2 is —C(CH 3 ) 2 C 6 H 5 or —C(CH 3 ) 3 ;
R 3 is H; and
R 5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl.
13. The composition of claim 10 , wherein in the compound is selected from the following structures:
14. A compound of Formula (A):
wherein
M=Mo or W;
R 1 is aryl, heteroaryl, alkyl, or heteroalkyl; optionally substituted;
R 2 and R 3 can be the same or different and are hydrogen, alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, or heteroaryl; optionally substituted;
R 5 is optionally substituted pyrrol-1-yl; and
R 4 is a residue R 6 —X—, wherein
X═O and R 6 is aryl, optionally substituted;
wherein R 6 is a phenyl ring which is at least substituted in 4-position with respect to O,
R 6 is substituted in 2- and 4-position with respect to O; or
R 6 is substituted in 3- and 4-position; or
R 6 is substituted in 2-, 3- and 4-position; or
R 6 is substituted in 2-, 5- and 4-position; or
R 6 is substituted in 3-, 5- and 4-position; or
R 6 is substituted in 2-, 6- and 4-position; or
R 6 is substituted in 2-, 3-, 5- and 4-position; or
R 6 is substituted in 2-, 3-, 5-, 6- and 4-position;
or wherein
M=Mo or W;
R 1 is aryl, heteroaryl, alkyl, or heteroalkyl; optionally substituted;
R 2 and R 3 can be the same or different and are hydrogen, alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, or heteroaryl; optionally substituted;
R 5 is optionally substituted pyrrol-1-yl;
R 4 is [8-(naphthalene-1-yl)-naphthalene-1-yl]oxy, optionally substituted; or
R 4 is (8-phenylnaphthalene-1-yl)oxy, optionally substituted.
15. The compound of claim 14 , wherein the compound is selected from the following structures: