Claims
- 1. A process for converting a less active or slower to initiate catalyst system to a higher activity catalyst system, the process comprising contacting a protected N-heterocyclic carbene with a metathesis initiator and an olefin in the presence of energy.
- 2. The process of claim 1 wherein the protected N-heterocyclic carbene is of the formula NHC—X2—Y; wherein NHC is any N-heterocyclic carbene ligand and X2—Y is any moiety that is released in the presence of energy.
- 3. The process of claim 2 wherein the protected N-heterocyclic carbene is of the formula:
- 4. The process of claim 3 wherein the at least one substituent is substituted with one or more substituted or unsubstituted moieties selected from the group consisting of C1-C10 alkyl, C1-C10 alkoxy, and aryl.
- 5. The process of claim 4 wherein at least one moiety is substituted with one or more groups selected from the group consisting of halogen, a C1-C5 alkyl, C1-C5 alkoxy, and phenyl.
- 6. The process of claim 3 wherein at least one of the R6, R7, R8, R9, R10 and R11 substituent groups includes one or more functional groups selected from the group consisting of hydroxyl, thiol, alcohol, sulfonic acid, phosphine, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, imide, imido, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodimide, carboalkoxy, carbamate, acetal, ketal, boronate, cyano, cyanohydrin, hydrazine, oxime, hydrazide, enamine, sulfone, sulfide, sulfenyl, and halogen.
- 7. The process of claim 3 wherein R7, R8, R9 and R10 are each independently selected from the group consisting of hydrogen, methyl, aralkyl, and aryl and R6 and R11 are each independently selected from the group consisting of substituted or unsubstituted C1-C10 alkyl, C1-C10 cycloalkyl, C2-C10 alkenyl, aralkyl, and aryl.
- 8. The process of claim 7 wherein R7, R8, R9 and R10 are each hydrogen and R6 and R11 substituents are each independently substituted or unsubstituted and are selected from the group consisting of phenyl, vinyl, methyl, isopropyl, tert-butyl, neopentyl, or benzyl.
- 9. The process of claim 8 wherein the substituent is substituted with one or more moieties selected from the group consisting of C1-C5 alkyl, C1-C5 alkoxy, phenyl, and a functional group.
- 10. The process of claim 8 wherein R6and R11 are each independently substituted or unsubstituted aryl.
- 11. The process of claim 3 wherein at least two of R6, R7, R8, R9, R10 and R11 is linked to form an substituted or unsubstituted, saturated or unsaturated ring structure.
- 12. The process of claim 2 wherein the NHC—X2—Y is selected from the group consisting of 1,3-dimesityl-2-methoxy-imidazolidine, 1,3-dimesityl-2-(trichloromethyl)imidazolidine, 1,3-dimesityl-2-ethoxy-imidazolidine, 1,3-dimesityl-2-tert-butoxy-imidazolidine, 1,3-dimesityl-2-benzyloxy-imidazolidine, 1,3-diphenyl-2-(trichloromethyl)imidazolidine, 1,3-bis(3-chlorophenyl)-2-(trichloromethyl)imidazolidine, 1,3-bis(4-methylphenyl)-2-(trichloromethyl)imidazolidine, 1,3-bis(4-fluorophenyl)-2-(trichloromethyl)imidazolidine, 1,3-bis(3-methylphenyl)-2-(trichloromethyl)imidazolidine, 1,3-bis(4-chlorophenyl)-2-(trichloromethyl)imidazolidine, 1,3-bis(4-bromophenyl)-2-(trichloromethyl)imidazolidine, 1,3-bis(4-iodophenyl)-2-(trichloromethyl)imidazolidine, 1,3-bis(4-methoxyphenyl)-2-(trichloromethyl)imidazolidine, 1,3-bis(4-ethoxyphenyl)-2-(trichloromethyl)imidazolidine, 1,3-bis(4-ethylphenyl)-2-(trichloromethyl)imiidazolidine, 1,3-bis(4-nitrophenyl)-2-(trichloromethyl)imidazolidine, 1,3-bis(3,4-dimethylphenyl)-2-(trichloromethyl)imidazolidine, 1,3-bis(3,5-dichlorophenyl)-2-(trichloromethyl) imidazolidine, 1,3-bis(3,5-dimethylphenyl)-2-(trichloromethyl imidazolidine, 1-(4-chlorophenyl)-3-phenyl-2-(trichloromethyl)imidazolidine, 1,3-bis(4-fluorophenyl)-2-(trichloromethyl)imidazolidine, 1-(4-methoxyphenyl)-3-phenyl-2-(trichloromethyl imidazolidine, 2-(trichloromethyl)-1,3-bis(2,6-dimethyl-4-tert-butylphenyl)imidazolidine, 2-(trichloromethyl)-1,3-bis(2,6-diisopropylphenyl)imidazolidine, 1,3-dimesityl-2-dimethylamino-imidazolidine, 1-(1,3-dimesityl-2-imidazolidinyl)-piperidine, and, 4-( 1,3-dimesityl-2-imidazolidinyl)-morpholine.
- 13. A process for preparing a protected N-heterocyclic carbene, the process comprising contacting N-heterocyclic carbene salt with a base to form an N-heterocyclic carbene; and reacting the N-heterocyclic carbene with chloroform.
- 14. The process of claim 13 wherein the base is selected from the group consisting of lithium tert-butoxide, potassium tert-butoxide, sodium tert-butoxide, sodium hydride, lithium hydride, potassium hydride, potassium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, lithium bis(trimethylsilyl)amide, sodium hydroxide, lithium hydroxide, and potassium hydroxide.
- 15. The process of claim 13, wherein the process occurs in the absence of a solvent.
- 16. A process for the ring-closing metathesis of one or more acylic olefins comprising contacting a protected N-heterocyclic carbene with a metathesis initiator and the one or more acylic olefins in the presence of energy.
- 17. The process of claim 16 wherein the protected N-heterocyclic carbene is of the formula NHC—X2—Y; wherein NHC is any N-heterocyclic carbene ligand and X2—Y is any moiety that is released in the presence of energy.
- 18. The process of claim 17 wherein the protected N-heterocyclic carbene is of
- 19. The process of claim 18 wherein the at least one substituent is substituted with one or more substituted or unsubstituted moieties selected from the group consisting of C1-C10 alkyl, C1-C10 alkoxy, and aryl.
- 20. The process of claim 18 wherein R7, R8, R9 and R10 are each independently selected from the group consisting of hydrogen, methyl, aralkyl, and aryl and R6 and R11 are each independently selected from the group consisting of substituted or unsubstituted C1-C10 alkyl, C1-C10 cycloalkyl, C2-C10 alkenyl, aralkyl, and aryl.
Parent Case Info
[0001] This application is a continuation-in-part of U.S. patent application No. 10/101,531, filed Mar. 25, 2002 and entitled “High Activity Ru Alkylidene & Vinylidene Derivatives Suitable for Olefin Metathesis Generated Using a Thermally Deprotectable N-Heterocyclic Carbene” (a) which claims priority from U.S. Provisional Patent Application No. 60/278,311, filed Mar. 23, 2001 and entitled “High Activity Ru Alkylidene & Vinylidene Derivatives Suitable for Olefin Metathesis Generated Using a Thermally Deprotectable N-Heterocyclic Carbene”, and (b) U.S. Provisional Patent Application No. 60/288,680, filed May 3, 2001 and entitled “High Activity Group 8 Alkylidene and Vinylidene Derivatives Suitable for Olefin Metathesis Generated Using a Thermally Activated N-Heterocyclic Carbene (NHC) Precursor”, and (c) U.S. Provisional Patent Application No. 60/360,775, filed Mar. 1, 2002 and entitled “Polymer Processing Methods and Techniques Using Pentacoordinated or Hexacoordinated Ruthenium or Osmium Metathesis Catalysts”. The contents of each of these prior filed applications is incorporated herein by reference.
Provisional Applications (3)
|
Number |
Date |
Country |
|
60278311 |
Mar 2001 |
US |
|
60288680 |
May 2001 |
US |
|
60360775 |
Mar 2002 |
US |
Continuation in Parts (1)
|
Number |
Date |
Country |
Parent |
10107531 |
Mar 2002 |
US |
Child |
10138188 |
May 2002 |
US |