Patent US3856868A successfully refreshed from Google Patents.
US3856868A
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Synthesis of 5-vinylcyclohexa-1,3-diene
Assignee: Phillips Petroleum Co
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Filing: 1974-01-11
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Granted: 1974-12-24
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Expires: 1994-01-11
Abstract
Abstract At least one alkyne compound is reacted with butadiene, piperylene and/or isoprene in the presence of the reaction product obtained by reducing a nickel(II) compound in the presence of at least one ligand material having the formula R3Z wherein Z is phosphorus or arsenic, and each R is an alkyl radical having from 1 to 12 carbon atoms with no branching nearer the Z than the second carbon atom. In a specific embodiment butadiene and acetylene are reacted in the presence of nickel(0) and tri-n-alkylphosphine to produce 5-vinylcyclohexa-1,3-diene and benzene.
Inventors
- 👤 D Fahey
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 20:29
CPC Classifications
B; B01; B01J; B01J31/00; B01J31/16; B01J31/18; B01J31/1895; B01J31/24; C; C07; C07C; C07C2/00; C07C2/02; C07C2/50; C07C2/52; B01J2231/00; B01J2231/30; B01J2231/32; B01J2231/324; B01J2231/326; B01J2531/00; B01J2531/80; B01J2531/84; B01J2531/847; C07C2531/00; C07C2531/16; C07C2531/22; C07C2531/24; C07C2601/00; C07C2601/12; C07C2601/16
Claims Analysis
Total Claims: 11
Claim 1
Independent Claim
174 words
A METHOD FOR PRODUCING 5-VINYCYCLOHEXA-1,3-DIENE WHICH COMPRISES REACTING UNDER SUITABLE REACTION CONDITIONS REACTANTS CONSISTING ESSENTIALLY OF BUTADIENE AND ACETYLENE IN CONTACT WITH A CATALYST SELECTED FROM THE GROUP CONSISTING OF: A. A REACTION PRODUCT OBTAINED BY THE REDUCTION OF A NICKEL(II) COMPOUND IN CONTACT WITH A LIGAND HAVING THE FORMULA R3Z WHEREIN Z IS SELECTED FROM THE GROUP CONSISTING OF PHOSPHORUS AND ARSENIC, AND EACH R IS INDIVIDUALLY SELECTED FROM GROUP CONSISTING OF ALKYL RADICALS HAVING FROM 1 TO 12 CARBON ATOMS AND NO BRANCHING NEARER THE Z THAN THE SECOND CARBON ATOM, SAID NICKEL(II) COMPOUND BEING SELECTED FROM THE GROUP CONSISTING OF NICKEL CHLORIDE, NICKEL BROMIDE, NICKEL ACETATE, NICKEL IODIDE, NICKEL PROPIONATE, NICKEL CYANIDE, NICKEL BENZOATE, NICKEL NAPHTHENATE, NICKEL OXALATE, NICKEL ACETYLACETONATE, NICKEL BENZOYLACETONATE, AND CONBINATIONS THEREOF, B. A MIXTURE OF BIS(1,5-CYCLOOCTADIENE)NICKEL(0) AND TRI-NBUTYL PHOSPHINE, AND C. A REACTION PRODUCT OBTAINED BY THE REDUCTION OF A NICKEL(II) COMPLEX SELECTED FROM THE GROUP CONSISTING OF TRANSBROMO(O-TOLYL)BIS(TRIETHYLPHOSPHINE)NICKEL(O) AND TRI-NDICHLOROBIS(TRIETHYLPHOSPHINE)NICKEL(II), TRANS-CHLORO(2,5DICHLOROPHENYL)BIS(TRIETHYLPHOSPHINE)NICKEL(II), TRANSDIBROMOBIS(TRIETHYLPHOSPHINE)NICKEL(II), TRANSDIIODOBIS(TRI-N-BUTYLARSINE(NICKEL(II), AND COMBINATIONS THEREOF; TO PRODUCE 5-VINYLCYCLOHEXA-1,3-DIENE AS A PRINCIPAL PRODUCT OF THE REACTION.
Claim 2
Independent Claim
174 words
A METHOD FOR PRODUCING 5-VINYCYCLOHEXA-1,3-DIENE WHICH COMPRISES REACTING UNDER SUITABLE REACTION CONDITIONS REACTANTS CONSISTING ESSENTIALLY OF BUTADIENE AND ACETYLENE IN CONTACT WITH A CATALYST SELECTED FROM THE GROUP CONSISTING OF: A. A REACTION PRODUCT OBTAINED BY THE REDUCTION OF A NICKEL(II) COMPOUND IN CONTACT WITH A LIGAND HAVING THE FORMULA R3Z WHEREIN Z IS SELECTED FROM THE GROUP CONSISTING OF PHOSPHORUS AND ARSENIC, AND EACH R IS INDIVIDUALLY SELECTED FROM GROUP CONSISTING OF ALKYL RADICALS HAVING FROM 1 TO 12 CARBON ATOMS AND NO BRANCHING NEARER THE Z THAN THE SECOND CARBON ATOM, SAID NICKEL(II) COMPOUND BEING SELECTED FROM THE GROUP CONSISTING OF NICKEL CHLORIDE, NICKEL BROMIDE, NICKEL ACETATE, NICKEL IODIDE, NICKEL PROPIONATE, NICKEL CYANIDE, NICKEL BENZOATE, NICKEL NAPHTHENATE, NICKEL OXALATE, NICKEL ACETYLACETONATE, NICKEL BENZOYLACETONATE, AND CONBINATIONS THEREOF, B. A MIXTURE OF BIS(1,5-CYCLOOCTADIENE)NICKEL(0) AND TRI-NBUTYL PHOSPHINE, AND C. A REACTION PRODUCT OBTAINED BY THE REDUCTION OF A NICKEL(II) COMPLEX SELECTED FROM THE GROUP CONSISTING OF TRANSBROMO(O-TOLYL)BIS(TRIETHYLPHOSPHINE)NICKEL(O) AND TRI-NDICHLOROBIS(TRIETHYLPHOSPHINE)NICKEL(II), TRANS-CHLORO(2,5DICHLOROPHENYL)BIS(TRIETHYLPHOSPHINE)NICKEL(II), TRANSDIBROMOBIS(TRIETHYLPHOSPHINE)NICKEL(II), TRANSDIIODOBIS(TRI-N-BUTYLARSINE(NICKEL(II), AND COMBINATIONS THEREOF; TO PRODUCE 5-VINYLCYCLOHEXA-1,3-DIENE AS A PRINCIPAL PRODUCT OF THE REACTION.
Claim 3
Dependent Claim
37 words
A method in accordance with claim 1 wherein said catalyst is the reaction product obtained by the reduction of nickel acetylacetonate in contact with a ligand selected from the group consisting of triethyl phosphine and tri-n-butyl phosphine.
Claim 4
Dependent Claim
20 words
A method in accordance with claim 2 wherein the reduction is accomplished by the addition of an organometallic reducing agent.
Claim 5
Dependent Claim
25 words
A method in accordance with claim 3 wherein said reaction conditions comprise a temperature in the range of about 0* C to about 30* C.
Claim 6
Dependent Claim
18 words
A method in accordance with claim 1 wherein said catalyst is a mixture of bis(1,5-cyclooctadiene)nickel(0) and tri-n-butyl phosphine.
Claim 7
Dependent Claim
25 words
A method in accordance with claim 5 wherein said reaction conditions comprise a temperature in the range of about 0* C to about 30* C.
Claim 8
Dependent Claim
20 words
A method in accordance with claim 1 wherein said catalyst is the reaction product obtained by the reduction of trans-bromo(o-tolyl)bis(triethylphosphine)nickel(II).
Claim 9
Dependent Claim
39 words
A method in accordance with claim 7 wherein the reduction is accomplished by heating the nickel complex in the presence of butadiene, acetylene, and methanol to a temperature in the range of about 50* C to about 120* C.
Claim 10
Dependent Claim
38 words
A method in accordance with claim 2 wherein the reduction is accomplished by heating the nickel compound in the presence of butadiene and acetylene to a temperature in the range of about 50* C to about 120* C.
Claim 11
Dependent Claim
51 words
A method in accordance with claim 1 wherein said catalyst is the reaction product obtained by the reduction of trans-dichlorobis(triethylphosphine)nickel(II), and thE reduction is accomplished by heating the nickel complex in the presence of butadiene and acetylene to a temperature in the range of about 50* C to about 120* C.
References Cited (Backward Citations)
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1977-12-23 | 1978-06-24 | 1978-12-24 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1981-12-23 | 1982-06-24 | 1982-12-24 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1985-12-23 | 1986-06-24 | 1986-12-24 | $7700.00 | Window Closed / Lapsed |