US4291187A
Expired / Lapsed
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Olefin disproportionation process
Assignee: Phillips Petroleum Co
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Filing: 1980-09-05
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Granted: 1981-09-22
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Expires: 2000-09-05
Abstract
Abstract A disproportionation of olefins is disclosed which employs a novel catalyst system consisting essentially of (I) at least one neutral carbene complex and (II) at least one chlorinated or chlorobrominated saturated organic compound containing only carbon and chlorine or carbon, chlorine, and bromine.
Inventors
- 👤 Dennis S. Banasiak
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-31 21:49
CPC Classifications
C; C07; C07C; C07C6/00; C07C6/02; C07C6/04; C07C6/06; B; B01; B01J; B01J31/00; B01J31/16; B01J31/20; B01J31/22; B01J31/2265; B01J31/24; B01J31/2404; B01J2231/00; B01J2231/50; B01J2231/54; B01J2231/543; B01J2531/00; B01J2531/60; B01J2531/66; B01J2531/70; B01J2531/74
Claims Analysis
Total Claims: 23
Claim 1
Independent Claim
245 words
A process for the disproportionation of olefins comprising contacting at least two suitable non-conjugated olefinic reactants under suitable reaction conditions with a catalytic amount of a catalyst composition consisting essentially of (1) at least one neutral carbene complex having the general formula ##STR17## wherein R is an aryl or substituted aryl radical containing 6 to 30 carbon atoms per radical wherein the substituted aryl radical can have one or more substituents each of which can be the same or different and selected from the group consisting of halides, alkoxides and alkyl radicals containing 1 to 20 carbon atoms per radical; R I is selected from the group consisting of alkyl, cycloalkyl, aryl, substituted aryl, trialkylsilyl, and triarylsilyl radicals containing 1 to 30 carbon atoms per radical with the aryl substituents being the same as for the sustituted aryl of R; Y is 0, Se, S, N, or P; m is 1 when Y is 0, Se, or S and 2 when Y is N or P; M is tungsten or rhenium; each L is individually selected from CO, NO, PF 3 , PCl 3 , or pyridine; L I is cyclopentadienyl or allyl; p is 0 or 1; and n is 5 when p is 0 or 2 when p is 1, and (2) at least one activator selcted from chlorinated or chlorobrominated saturated organic compound having 1 to 20 carbon atoms per molecule and containing only carbon and chlorine or carbon, chlorine, and bromine.
Claim 2
Dependent Claim
245 words
A process for the disproportionation of olefins comprising contacting at least two suitable non-conjugated olefinic reactants under suitable reaction conditions with a catalytic amount of a catalyst composition consisting essentially of (1) at least one neutral carbene complex having the general formula ##STR17## wherein R is an aryl or substituted aryl radical containing 6 to 30 carbon atoms per radical wherein the substituted aryl radical can have one or more substituents each of which can be the same or different and selected from the group consisting of halides, alkoxides and alkyl radicals containing 1 to 20 carbon atoms per radical; R I is selected from the group consisting of alkyl, cycloalkyl, aryl, substituted aryl, trialkylsilyl, and triarylsilyl radicals containing 1 to 30 carbon atoms per radical with the aryl substituents being the same as for the sustituted aryl of R; Y is 0, Se, S, N, or P; m is 1 when Y is 0, Se, or S and 2 when Y is N or P; M is tungsten or rhenium; each L is individually selected from CO, NO, PF 3 , PCl 3 , or pyridine; L I is cyclopentadienyl or allyl; p is 0 or 1; and n is 5 when p is 0 or 2 when p is 1, and (2) at least one activator selcted from chlorinated or chlorobrominated saturated organic compound having 1 to 20 carbon atoms per molecule and containing only carbon and chlorine or carbon, chlorine, and bromine.
Claim 3
Dependent Claim
216 words
A process according to claim 1 wherein at least one of said non-conjugated olefinic reactants contain 3 to 30 carbon atoms per molecule and at least one of the olefinic reactants contains a maximum of two olefinic double bonds and is either (1) an acyclic olefin of the formula R.sup.II CH═CHR.sup.III wherein R II and R III are independently selected from hydrogen, alkyl radicals, alkenyl radicals, or alkyl or alkenyl radicals containing chloride, bromide, aryl, or alkyl-aryl substituents wherein the halides are at least two carbon atoms from the carbons of any olefinic bond and the aryl or alkyl-aryl substituents are at least one carbon from the carbons of any olefinic bond and wherein said radicals contain 1 to 18 carbon atoms or (2) a monocyclic olefin of the formula ##STR18## wherein R IV is an alkylene or alkenylene radical, or an alkylene or alkenylene radical containing chloride, bromide, aryl or alkyl-aryl substituents wherein the halides are at least two carbon atoms from the carbons of any olefinic bond and the aryl or alkyl-aryl substituents are at least one carbon atom from the carbons of any olefinic bond and the aryl or alkyl-aryl substituents are at least one carbon from the carbons of any olefinic bond and wherein R IV contains 5 to 16 carbon atoms.
Claim 4
Dependent Claim
31 words
A process according to claim 2 wherein the R II , R III , and R IV radicals contain only carbon and hydrogen and 1 to 10 carbon atoms per radical.
Claim 5
Dependent Claim
18 words
A process according to claim 3 wherein the olefinic reactants consist essentially of olefins of the formula ##STR19##
Claim 6
Dependent Claim
34 words
A process according to claim 4 wherein the olefinic reactants are selected from the group consisting of 1-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, 1-octene, 2-octene, 4-methyl-1-heptene, 2-decene, 6-dodecene, 1-tetradecene, 1-eicosene, 1,4-hexadiene, 4-chloro-1-butene, 4-phenyl-1-butene, and 4-phenyl-1-octene.
Claim 7
Dependent Claim
27 words
A process according to claim 5 wherein the molar ratio of said activator to said carbene complex is in the range of about 1/1 to about 1000/1.
Claim 8
Dependent Claim
23 words
A process according to claim 6 wherein R is a phenyl radical, Y is 0, and R I is a hydrocarbyl alkyl radical.
Claim 9
Dependent Claim
25 words
A process according to claim 7 wherein said activator is selected from the group consisting of carbon tetrachloride, bromotrichloromethane, hexachloroethane, dibromodichloromethane, chlorotribromomethane, tribromotrichloroethane, octachloropropane, octachlorocyclobutane.
Claim 10
Dependent Claim
17 words
A process according to claim 8 wherein said activator is selected from bromotrichloromethane, carbon tetrachloride, and hexachloroethane.
Claim 11
Dependent Claim
13 words
A process according to claim 9 wherein R I is a methyl radical.
Claim 12
Dependent Claim
33 words
A process according to claim 10 wherein said activator is carbon tetrachloride and the molar ratio of said activator to said carbene complex is in the range of about 20/1 to about 1000/1.
Claim 13
Dependent Claim
27 words
A process according to claim 10 wherein the molar ratio of said activator to said carbene complex is in the range of about 30/1 to about 500/1.
Claim 14
Dependent Claim
23 words
A process according to claim 12 wherein said olefinic reactants are the same and are of the formula R II CH═CHR III .
Claim 15
Dependent Claim
34 words
A process according to claim 13 wherein said disproportionation conditions include a temperature in the range of about 50° C. to about 100° C. and said process is conducted using hexane as a diluent.
Claim 16
Dependent Claim
26 words
A process according to claim 14 wherein the mole ratio of carbon tetrachloride to said carbene complex is about 30/1 and said olefin reactants are 1-pentene.
Claim 17
Dependent Claim
20 words
A process according to claim 14 wherein the mole ratio of carbon tetrachloride to said carbene complex is about 235/1.
Claim 18
Dependent Claim
36 words
A process according to claim 10 wherein said activator is selected from bromotrichloromethane and hexachloroethane and the molar ratio of said activator to said carbene complex is in the range of about 5/1 to about 100/1.
Claim 19
Dependent Claim
23 words
A process according to claim 17 wherein said olefinic reactants are the same and are of the formula R II CH═CHR III .
Claim 20
Dependent Claim
34 words
A process according to claim 18 wherein said disproportionation conditions include a temperature in he range of about 50° C. to about 100° C. and said process is conducted using hexane as a diluent.
Claim 21
Dependent Claim
26 words
A process according to claim 19 wherein the mole ratio of said activator to said carbene complex is about 13.6/1 and said olefin reactants are 1-pentene.
Claim 22
Dependent Claim
43 words
A process according to claim 17 wherein said olefinic reactants are cyclooctene, said activator is hexachloromethane, said disproportionation conditions include a temperature in the range of about 50° C. to about 100° C., and said process is conducted using hexane as a diluent.
Claim 23
Dependent Claim
20 words
A process according to claim 21 wherein the molar ratio of said hexachloroethane to said carbene complex is about 3/1.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
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| 3.5 Years (Year 4) | 1984-09-21 | 1985-03-23 | 1985-09-22 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1988-09-21 | 1989-03-23 | 1989-09-22 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1992-09-21 | 1993-03-23 | 1993-09-22 | $7700.00 | Window Closed / Lapsed |