US3974196A
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Method for disproportionating ethylenically unsaturated compounds having functional ester groups
Assignee: JSR Corp
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Filing: 1974-11-26
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Granted: 1976-08-10
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Expires: 1994-11-26
Abstract
Abstract A method for the conversion of an unsaturated compound having a functional group, characterized by contacting [1] at least one compound selected from the group consisting of carboxylic acid esters, nitriles, ketones, amides, and ethers and having a carbon-to-carbon double bond and no unsaturation at the position conjugate to said double bond, or a mixture of said compound [1] and [2] at least one compound selected from the group consisting of ethylenically unsaturated compounds having a carbon-to-carbon double bond and neither unsaturation at the position conjugate to said double bond nor a functional group, with a catalyst system consisting essentially of a combination of (A) at least one member selected from the group consisting of tungsten compounds, molybdenum compounds, and rhenium compounds, with (B) at least one organolaluminum compound having at least one carbon-to-aluminum bond.
Inventors
- 👤 Ryuichi Nakamura
- 👤 Seiji Fukuhara
- 👤 Shuichi Matsumoto
- 👤 Koei Komatsu
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-04 12:23
CPC Classifications
C; C07; C07C; C07C49/00; C07C49/20; C07C49/203; C07C1/00; C07C1/20; C07C1/207; C07C1/213; C07C255/00; C07C67/00; C07C67/30; C07C67/333; C07C67/343; C07C67/475; C07F; C07F7/00; C07F7/02; C07F7/08; C07F7/18; C07F7/1804; C07C2527/00; C07C2527/06; C07C2527/08; C07C2527/10; C07C2527/132; C07C2531/00; C07C2531/02; C07C2531/12; C07C2531/14; C07C2531/16; C07C2531/20
Claims Analysis
Total Claims: 13
Claim 1
Independent Claim
345 words
A method for disproportionating an ethylenically unsaturated compound or a mixture of ethylenically unsaturated compounds, which comprises: reacting at a temperature from -30°C to +300°C a compound (1) having the formula: R.sup.1 R.sup.2 C = CR.sup.3 X wherein R 1 is hydrogen, C 1-15 alkyl, alkenyl or X; R 2 and R 3 are independently hydrogen or C 1-3 alkyl, and X is a group having the formula: --CR.sup.4.sub.2).sub.a Y (a ≧ 1) wherein Y is --C(=0)OR 5 or --OCOR 6 in which R 5 and R 6 represent C 1-15 alkyl or aryl; and R 4 represents principally hydrogen of C 1-15 alkyl and all of the R 4 groups are not required to be the same, with the proviso that no sites of unsaturation exist at a position conjugate to the double bond, or a mixture of said compound and a compound selected from the group consisting of 1,4-polybutadiene; 1,2-polybutadiene; a compound having the formula, R.sup.7 R.sup.8 C = CR.sup.9 R.sup.10 wherein R 7 and R 9 are hydrogen or C 1-3 alkyl and R 8 and R 10 represent hydrogen, C 1-15 alkyl, aralkyl, aryl, or halohydrocarbon groups, with the proviso that no sites of unsaturation exist at a position conjugate to the double bond, or a cyclic compound having the formula, ##EQU2## wherein --Z-- represents --CH 2 ) b or --CH 2 ) c CH = CH --CH 2 ) d (b ≧ 1, c ≧ 1, d 24 1), with a catalyst consisting essentially of a combination of (A) at least one member selected from the group consisting of the halides, oxyhalides, carbonyl complexes, alkoxides, oxyalkoxides and alkoxyhalides of tungsten, molybdenum, or rhenium with (B) at least one compound having the formula, R p AlX 1 3 -p wherein R represents alkyl, X 1 represents halogen, hydrogen, or --OR and p is a number from 1 to 3, wherein the components (A) and (B) are used in such a ratio that the atomic ratio Me/Al, wherein Me is W, Mo or Re, falls within the range from 1/1 to 1/15.
Claim 2
Independent Claim
345 words
A method for disproportionating an ethylenically unsaturated compound or a mixture of ethylenically unsaturated compounds, which comprises: reacting at a temperature from -30°C to +300°C a compound (1) having the formula: R.sup.1 R.sup.2 C = CR.sup.3 X wherein R 1 is hydrogen, C 1-15 alkyl, alkenyl or X; R 2 and R 3 are independently hydrogen or C 1-3 alkyl, and X is a group having the formula: --CR.sup.4.sub.2).sub.a Y (a ≧ 1) wherein Y is --C(=0)OR 5 or --OCOR 6 in which R 5 and R 6 represent C 1-15 alkyl or aryl; and R 4 represents principally hydrogen of C 1-15 alkyl and all of the R 4 groups are not required to be the same, with the proviso that no sites of unsaturation exist at a position conjugate to the double bond, or a mixture of said compound and a compound selected from the group consisting of 1,4-polybutadiene; 1,2-polybutadiene; a compound having the formula, R.sup.7 R.sup.8 C = CR.sup.9 R.sup.10 wherein R 7 and R 9 are hydrogen or C 1-3 alkyl and R 8 and R 10 represent hydrogen, C 1-15 alkyl, aralkyl, aryl, or halohydrocarbon groups, with the proviso that no sites of unsaturation exist at a position conjugate to the double bond, or a cyclic compound having the formula, ##EQU2## wherein --Z-- represents --CH 2 ) b or --CH 2 ) c CH = CH --CH 2 ) d (b ≧ 1, c ≧ 1, d 24 1), with a catalyst consisting essentially of a combination of (A) at least one member selected from the group consisting of the halides, oxyhalides, carbonyl complexes, alkoxides, oxyalkoxides and alkoxyhalides of tungsten, molybdenum, or rhenium with (B) at least one compound having the formula, R p AlX 1 3 -p wherein R represents alkyl, X 1 represents halogen, hydrogen, or --OR and p is a number from 1 to 3, wherein the components (A) and (B) are used in such a ratio that the atomic ratio Me/Al, wherein Me is W, Mo or Re, falls within the range from 1/1 to 1/15.
Claim 3
Dependent Claim
76 words
The method according to claim 1, wherein the catalyst further contains as the third component a compound selected from the group consisting of n-butyl chloride, n-butyl bromide, dichloroethane, tetrachloroethylene, benzyl chloride, ethylene chlorohydrin, benzoyl chloride, acetic acid, trichloroacetic acid, trifluoroacetic acid, lactic acid, tetrahydrofuran, styrene oxide, ethyl ether, anisole, isobutyl vinyl ether, acetone, naphthoquinone, ethanol, n-decyl alcohol, phenol, p-chlorophenol, α-nitroso-β-naphthol, dinitrophenol, nitrobenzene, triethylamine, ethanolamine, morpholine, acetamide, azobenzene, benzaldehyde, acetal, water, oxygen, carbon dioxide, or carbon disulfide.
Claim 4
Dependent Claim
110 words
The method according to claim 1, wherein the compound is selected from the group consisting of ethyl vinylacetate, isobutyl vinylacetate, cyclohexyl vinylacetate, phenyl vinylacetate, ethyl 4-pentenoate, amyl 4-pentenoate, benzyl 4-pentenoate, propyl 3-decenoate, methyl 10-undecenoate, ethyl 10-undecenoate, methyl oleate, ethyl oleate, butyl oleate, methyl isooleate, ethyl 6-octadecenoate, butyl 6-octadecenoate, ethyl elaidate, butyl elaidate, methyl brassidate, methyl linolate, diethyl 2-allylmalonate, allyl acetate, oleyl acetate, 3-hexenyl acetate, oleyl oleate, 2-hexenyl 2-methylpropionate, 3-hexenyl valerate, 2-hexenyl acetate, allyl propionate, oleyl benzoate, 9-octadecenenitrile, 6-octadecenenitrile, 3-butenenitrile, 1,4-dicyano-2-butene, 4-pentenenitrile, octadecenedinitrile, 9,12-octadecadienenitrile, 9-decenenitrile, 10-undecenenitrile, 9-octadecenyl ethyl ether, 9-octadecenyl isopropyl ether, crotyl isopropyl ether, trimethylallyloxysilane, allylanisole, allyl phenyl ether, 8-heptadecenyl ethyl ketone, 5-heptadecenyl ethyl ketone, 5-hexen-2-one, 6-methyl-5-hepten-2-one, N,N-diethyloleamide, and N,N-diethylvinylacetamide.
Claim 5
Dependent Claim
39 words
The method according to claim 1, wherein the compound (2) is selected from the group consisting of ethylene, propylene, 1-butene, 2-butene, 1-pentene, 1-hexene, 3-hexene, 3-heptene, 1-octene, 2-octene, 4-octene, 1-decene, 5-decene, 1-pentadecene, allylbenzene, p-chlorostyrene, 1,7-octadiene, 1,9-decadiene, oleyl chloride, and 4-methyl-1-pentene.
Claim 6
Dependent Claim
27 words
The method according to claim 1, wherein the compound (2) is selected from the group consisting of cyclooctene, cycloheptene, cyclododecene, cyclododecatriene, cyclopentene, cyclobutene, 1,5-cyclooctadiene, nobornene and dicyclopentadiene.
Claim 7
Dependent Claim
52 words
The method according to claim 1, wherein the component (A) of the catalyst is selected from the group consisting of WCl 6 , MoCl 5 , MoCl 3 , ReCl 5 , W(C0) 6 , W(OC 6 H 5 ) 6 , and Mo(OC 2 H 5 ) 2 Cl 3 .
Claim 8
Dependent Claim
35 words
The method according to claim 1, wherein the component (A) of the catalyst is selected from the group consisting of WCl 6 , MoCl 5 and Mo(OC 2 H 5 ) 2 Cl 3 .
Claim 9
Dependent Claim
67 words
The method according to claim 1, wherein the component (B) of the catalyst is selected from the group consisting of (CH 3 ) 1 .5 AlCl 1 .5, (C 2 H 5 ) 3 Al, (C 2 H 5 ) 2 AlCl, (C 2 H 5 ) 1 .5 AlCl 1 .5, (iso-C 4 H 9 ) 3 Al and (n-C 8 H 17 ) 3 Al.
Claim 10
Dependent Claim
22 words
The method according to claim 1, wherein the component (B) of the catalyst is (CH 3 ) 1 .5 AlCl 1 .5.
Claim 11
Dependent Claim
31 words
The method according to claim 1, wherein the components (A) and (B) are used in such a ratio that the atomic ratio Me/Al falls within the range from 1/2 to 1/6.
Claim 12
Dependent Claim
25 words
The method according to claim 2, wherein the third component of the catalyst is a compound which has an aromatic ring bearing an electron-attracting substituent.
Claim 13
Dependent Claim
18 words
The method according to claim 1, wherein the reaction temperature is in the range from -10°C. to +200°C.
References Cited (Backward Citations)
US3725305A
Cited
US3783136A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1979-08-10 | 1980-02-09 | 1980-08-10 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1983-08-10 | 1984-02-09 | 1984-08-10 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1987-08-10 | 1988-02-09 | 1988-08-10 | $7700.00 | Window Closed / Lapsed |