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US4025570A
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Preparation of 1,4-dienes of high trans-isomer content
Assignee: EIDP Inc
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Filing: 1976-01-09
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Granted: 1977-05-24
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Expires: 1996-01-09
Abstract
Abstract 1,4-Dienes of high trans-isomer content are prepared by contacting ethylene with a 1,3-diene in the presence of a catalyst system comprising an organic solvent-soluble organonickel compound in which the nickel is zerovalent or divalent, a hydrocarbylaluminum chloride or bromide, and an aryl phosphinite. Optionally, the catalyst system may also contain a heteroorganoaluminum compound.
Inventors
- 👤 Richard David Cramer
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-27 19:02
CPC Classifications
C; C07; C07F; C07F15/00; C07F15/04; C07C; C07C2/00; C07C2/02; C07C2/04; C07C2531/00; C07C2531/02; C07C2531/12; C07C2531/14; C07C2531/16; C07C2531/22
Claims Analysis
Total Claims: 14
Claim 1
Independent Claim
183 words
Method of preparing 1,4-diene of high trans-isomer content which comprises contacting ethylene with 1,3-diene of the formula CH.sub.2 =C(R.sup.1)CH=CHR.sup.2 or CH.sub.2 =CHC(R.sup.1)=CHR.sup.2 where R 1 is hydrogen, methyl, ethyl or chlorine, and R 2 is hydrogen, C 1 -C 15 alkyl, C 6 -C 12 aryl, or C 7 -C 18 alkaryl, in the presence of a catalyst system which comprises (a) organic solvent-soluble organonickel compound in which the nickel is zerovalent or divalent, (b) hydrocarbylaluminum halide selected from the group consisting of hydrocarbylaluminum chlorides and hydrocarbylaluminum bromides, and (c) aryl phosphinite of the formula R.sup.3 R.sup.4 POR.sup.5 where R 3 and R 4 , alike or different, are phenyl, or substituted phenyl containing up to two substituents selected from the group consisting of C 1 -C 6 alkyl, chlorine, fluorine, bromine and iodine, and R 5 is C 6 -C 12 aryl or substituted C 6 -C 12 aryl containing up to two substituents selected from the group consisting of C 1 -C 6 alkyl, C 1 -C 6 alkoxy, chlorine, bromine, iodine, fluorine, trifluoromethyl and di(C 1 -C 6 alkyl) amino.
Claim 2
Dependent Claim
183 words
Method of preparing 1,4-diene of high trans-isomer content which comprises contacting ethylene with 1,3-diene of the formula CH.sub.2 =C(R.sup.1)CH=CHR.sup.2 or CH.sub.2 =CHC(R.sup.1)=CHR.sup.2 where R 1 is hydrogen, methyl, ethyl or chlorine, and R 2 is hydrogen, C 1 -C 15 alkyl, C 6 -C 12 aryl, or C 7 -C 18 alkaryl, in the presence of a catalyst system which comprises (a) organic solvent-soluble organonickel compound in which the nickel is zerovalent or divalent, (b) hydrocarbylaluminum halide selected from the group consisting of hydrocarbylaluminum chlorides and hydrocarbylaluminum bromides, and (c) aryl phosphinite of the formula R.sup.3 R.sup.4 POR.sup.5 where R 3 and R 4 , alike or different, are phenyl, or substituted phenyl containing up to two substituents selected from the group consisting of C 1 -C 6 alkyl, chlorine, fluorine, bromine and iodine, and R 5 is C 6 -C 12 aryl or substituted C 6 -C 12 aryl containing up to two substituents selected from the group consisting of C 1 -C 6 alkyl, C 1 -C 6 alkoxy, chlorine, bromine, iodine, fluorine, trifluoromethyl and di(C 1 -C 6 alkyl) amino.
Claim 3
Dependent Claim
135 words
The method of claim 1 in which the catalyst system also contains a heteroorganoaluminum compound of the formula (R.sup.6).sub.a AlZ.sub.b where R 6 is C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 7 -C 18 aralkyl, or C 6 -C 12 aryl, Z is OR 7 , --NR 8 (R 9 ), or =NR 10 where R 7 , r 8 , r 9 and R 10 , alike or different, are C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 7 -18 aralkyl, or C 6 -C 12 aryl, a is 1 or 2, b is 1 or 2, and a+ b is 3, except that when Z is =NR 10 , a is 1, b is 1, a+ b is 2, and R 6 can also be hydrogen.
Claim 4
Dependent Claim
171 words
Method of preparing 1,4-diene of high trans-isomer content which comprises contacting ethylene with 1,3-diene of the formula CH.sub.2 =C(R.sup.1)CH=CHR.sup.2 or CH.sub.2 =CHC(R.sup.1)=CHR.sup.2 where R 1 is hydrogen, methyl or ethyl, and R 2 is hydrogen or C 1 -C 15 alkyl, in the presence of a catalyst system which comprises (a) organic solvent-soluble organonickel compound in which the nickel is zerovalent or divalent, (b) hydrocarbylaluminum halide selected from the group consisting of hydrocarbylaluminum chlorides and hydrocarbylaluminum bromides, and (c) aryl phosphinite of the formula R.sup.3 R.sup.4 POR.sup.5 where R 3 and R 4 , alike or different, are phenyl, or substituted phenyl containing up to two substituents selected from the group consisting of C 1 -C 6 alkyl, chlorine, fluorine, bromine and iodine, and R 5 is C 6 -C 12 aryl, or substituted C 6 -C 12 aryl containing up to two substituents selected from the group consisting of C 1 -C 6 alkyl, C 1 -C 6 alkoxy, chlorine, bromine, iodine, fluorine, trifluoromethyl and di(C 1 -C 6 alkyl)amino.
Claim 5
Dependent Claim
171 words
Method of preparing 1,4-diene of high trans-isomer content which comprises contacting ethylene with 1,3-diene of the formula CH.sub.2 =C(R.sup.1)CH=CHR.sup.2 or CH.sub.2 =CHC(R.sup.1)=CHR.sup.2 where R 1 is hydrogen, methyl or ethyl, and R 2 is hydrogen or C 1 -C 15 alkyl, in the presence of a catalyst system which comprises (a) organic solvent-soluble organonickel compound in which the nickel is zerovalent or divalent, (b) hydrocarbylaluminum halide selected from the group consisting of hydrocarbylaluminum chlorides and hydrocarbylaluminum bromides, and (c) aryl phosphinite of the formula R.sup.3 R.sup.4 POR.sup.5 where R 3 and R 4 , alike or different, are phenyl, or substituted phenyl containing up to two substituents selected from the group consisting of C 1 -C 6 alkyl, chlorine, fluorine, bromine and iodine, and R 5 is C 6 -C 12 aryl, or substituted C 6 -C 12 aryl containing up to two substituents selected from the group consisting of C 1 -C 6 alkyl, C 1 -C 6 alkoxy, chlorine, bromine, iodine, fluorine, trifluoromethyl and di(C 1 -C 6 alkyl)amino.
Claim 6
Dependent Claim
11 words
The method of claim 3 in which the 1,3-diene is 1,3-butadiene.
Claim 7
Dependent Claim
13 words
The method of claim 4 in which the hydrocarbylaluminum halide is alkylaluminum dihalide.
Claim 8
Dependent Claim
15 words
The method of claim 5 in which the aryl phosphinite is a substituted phenyl diphenylphosphinite.
Claim 9
Dependent Claim
12 words
The method of claim 6 in which the organonickel compound is nickel(O)bis(cyclooctadiene).
Claim 10
Dependent Claim
135 words
The method of claim 3 in which the catalyst system also contains a heteroorganoaluminum compound of the formula (R.sup.6).sub.a AlZ.sub.b where R 6 is C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 7 -C 18 aralkyl, or C 6 -C 12 aryl, Z is OR 7 , --NR 8 (R 9 ), or =NR 10 where R 7 , r 8 , r 9 and R 10 , alike or different, are C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 7 -18 aralkyl, or C 6 -C 12 aryl, a is 1 or 2, b is 1 or 2, and a+ b is 3, except that when Z is =NR 10 , a is 1, b is 1, a+ b is 2, and R 6 can also be hydrogen.
Claim 11
Dependent Claim
11 words
The method of claim 8 in which the 1,3-diene is 1,3-butadiene.
Claim 12
Dependent Claim
13 words
The method of claim 9 in which the hydrocarbylaluminum halide is alkylaluminum dihalide.
Claim 13
Dependent Claim
15 words
The method of claim 10 in which the aryl phosphinite is a substituted phenyl diphenylphosphinite.
Claim 14
Dependent Claim
12 words
The method of claim 11 in which the organonickel compound is nickel(O)bis(cyclooctadiene).
References Cited (Backward Citations)
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| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
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| 3.5 Years (Year 4) | 1980-05-23 | 1980-11-22 | 1981-05-24 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1984-05-23 | 1984-11-22 | 1985-05-24 | $3760.00 | Window Closed / Lapsed |
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