US3823199A - Production of 1,6-and 1,7-octadienes - Google Patents

Production of 1,6-and 1,7-octadienes Download PDF

Info

Publication number
US3823199A
US3823199A US00278343A US27834372A US3823199A US 3823199 A US3823199 A US 3823199A US 00278343 A US00278343 A US 00278343A US 27834372 A US27834372 A US 27834372A US 3823199 A US3823199 A US 3823199A
Authority
US
United States
Prior art keywords
phosphine
palladium
octadienes
butadiene
benzene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US00278343A
Inventor
D Wright
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Imperial Chemical Industries Ltd
Original Assignee
Imperial Chemical Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Imperial Chemical Industries Ltd filed Critical Imperial Chemical Industries Ltd
Application granted granted Critical
Publication of US3823199A publication Critical patent/US3823199A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/74—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition with simultaneous hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/42—Platinum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/46—Ruthenium, rhodium, osmium or iridium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06—Halogens; Compounds thereof
    • C07C2527/128—Compounds comprising a halogen and an iron group metal or a platinum group metal
    • C07C2527/13—Platinum group metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/22—Organic complexes

Definitions

  • 1,6- and/or 1,7-octadienes are produced by reacting a 1,3-butadiene such as butadiene itself with metallic platinum, palladium, rhodium, ruthenium or osmium or preferably with a compound of one or more of these metals in a non-polar solvent such as benzene in the presence of a reducing agent such as formic acid.
  • a 1,3-butadiene such as butadiene itself with metallic platinum, palladium, rhodium, ruthenium or osmium or preferably with a compound of one or more of these metals in a non-polar solvent such as benzene in the presence of a reducing agent such as formic acid.
  • the present invention relates to the production of olefines.
  • 1,6- and/ or 1,7-octadienes are produced by contacting one or more acyclic conjugated di-olefines with metallic platinum, palladium, rhodium, ruthenium or osmium or with a compound of one or more of these metals in a non-polar solvent in the presence of a reducing agent.
  • the acyclic conjugated diolefine contains the structure:
  • the residual valencies may be satisfied by organic or inorganic groups or by hydrogen.
  • the residual valencies are satisfied by alkyl groups, particularly lower alkyl groups containing up to four carbon atoms, or by hydrogen.
  • the most suitable acyclic conjugated diolefines for use in the process of the invention are those in which the residual valencies are satisfied by methyl groups and/or by hydrogen. Butadiene and isoprene are particularly preferred.
  • Halogen atoms such as chlorine are examples of suitable inorganic substituents in the acyclic conjugated diolefine. If desired two or more diolefines may be used in admixture.
  • the products of the process are substantially acyclic dimers of the acyclic conjugated diolefines and comprise an octadiene chain in which unsaturation is present in the 1,6- or 1,7-position.
  • platinum or a platinum compound and palladium or a palladium compound tend to produce a product comprising substantially the 1,6- isomer without any of the 1,7-isomer. If the palladium or platinum catalysed reaction is carried out in the presence of a phosphine, however, the 1,7-isomer is also formed, the relative proportions of the two isomers obtained being influenced by the nature of the phosphine.
  • phosphine used is a triaryl phosphine then formation of the 1,6-octadiene is favoured whereas in the presence of a trialkyl phosphine the 1,7-isomer tends to be produced.
  • Suitable triaryl phosphines include triphenyl phosphine; tri (alkyl phenyl) phosphines, particularly those in which each alkyl group contains up to 6 carbon atoms such as tri(p-tolyl phosphine); and tri(substituted phenyl) phosphines in which the substituent is non-hydrocarbon, e.g.
  • Trialkyl phosphines which may be used include alkyl phosphines in which each alkyl group contains up to 6 carbon atoms, e.g. triethyl and tributyl phosphine and trialkyl phosphines in which the alkyl group contains other substituents, e.g. a phenyl group as in tribenzyl phosphine. Tricycloalkyl phosphines may also be used, influencing the reaction in the same way as the trialkyl phosphines.
  • the concentration of the phosphine preferably lies in the range 10" to 10* molar.
  • the reaction may be carried out heterogeneously using the metal or a metal compound.
  • the metal or metal compound may be supported on an inert support such as silica, alumina, charcoal or pumice.
  • the reaction is carried out homogeneously in the liquid phase.
  • Suitable noble metal compounds which may be used in both the homogeneous and heterogeneous reactions include metal halides, particularly the chlorides, e.g.
  • platinous chloride rhodium trichloride and palladous chloride
  • metal carboxylates particularly metal alkanoates derived from alkanoic acids containing up to six carbon atoms such as platinous acetate and palladium acetate, and complexes of the metals such as platinum or palladium acetylacetonate, bis-benzonitrile palladium (II) and lithium palladous chloride.
  • concentration of the metal or metal compound is preferably catalytic, e.g. in the range 10 to 10- molar, preferably 10 to 10 molar.
  • the non-polar solvent may be a hydrocarbon such as a paraffin, cycloparafiin or an aromatic.
  • the solvent is a parifiin containing 5 to 16 carbon atoms, e.g. hexane, dodecane, or pentadecane, or is benzene, or an alkyl benzene, particularly an alkyl benzene containing up to 12 carbon atoms such as toluene or a xylene, or is a cycloparaflin, e.g. cyclohexane or methyl cyclohexane.
  • the reducing agent is preferably a liquid reducing agent.
  • examples of such agents include hydrazine and formaldehyde and solutions containing an alcohol, particularly a lower alkanol such as isopropanol.
  • a preferred reducing agent is formic acid.
  • the concentration of the reducing agent is preferably in the range 0.5 to 10 molar.
  • a gaseous reducing agent such as hydrogen may also be used.
  • the process may be carried out at a temperature in the range 20 to 200 C.
  • the reaction may take place in a sealed system under the autogeneous pressure of the reactants.
  • a copper salt e.g. copper sulphate, or a copper halide such as copper chloride or a copper alkanoate such as copper acetate
  • a phosphine such as a trialkyl, a mixed alkylaryl or a triaryl phosphine, e.g. triphenyl phosphine in the reaction mediuml tfo improve the activity of the catalyst and to prolong its 1 e.
  • the product of the process is either a 1,6 or 1,7 octadiene or a mixture of the two.
  • the terminal unsaturation in the 1,7-diolefine makes it particularly useful as a chemical intermediate while the 1,6-isomer finds use as a termonomer with ethylene and propylene in EP rubbers.
  • EXAMPLE 1 A mixture of formic acid (12 grams, 0.26 mole), benzene (20 mls.), palladous acetate (22 m. grams, 0.0001 mole) and butadiene (50 mls. 0.63 mole) was heated in an autoclave at 50 C. for 20 hours. At the end of this time the excess formic acid was removed by washing with water and the organic phase dried and distilled to give 3.0 grams of 1,6-octadiene boiling at 46 C./50 mm.
  • EXAMPLE 2 A mixture of formic acid (12 grams, 0.26 mole), benzene (20 mls.), platinum acetylacetonate (9.3 m. grams, 0.000024 mole) and butadiene (50 mls.) was heated in an autoclave at 80 C. for 10 hours. The excess formic acid was removed from the product by washing with water subsequent distillation of the organic phase yielding 8 grams of 1,6-octadiene boiling at 66 C./ 130 mm.
  • a process for the production of a member of the group consisting of 1,6- and 1,7-octadienes which comprises contacting at least one acyclic conjugated diolefine selected from the group consisting of butadiene and isoprene with a member of the group consisting of metallic platinum, palladium, rhodium, ruthenium, osmium and compounds of at least one of these metals in a non-polar solvent in the presence of formic acid.
  • a non-polar solvent selected from the group consisting of a paraflin containing 5 to 16 carbon atoms, benzene, toluene, xylene, cyclohexane and methylcyclohexane,

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

1,6- AND/OR 1,7-OCTADIENES ARE PRODUCED BY REACTING A 1,3-BUTADIENE SUCH AS BUTADIENE ITSELF WITH METALLIC PLATINUM, PALLADIUM, RHODIUM, RUTHENIUM OR OSMIUM OR PREFERABLY WITH A COMPOUND OF ONE OR MORE OF THESE METALS IN A NON-POLAR SOLVENT SUCH AS BENZENE IN THE PRESENCE OF A REDUCING AGENT SUCH AS FORMIC ACID.

Description

United States Patent Office Patented July 9, 1974 3,823,199 PRODUCTION OF 1,6- AND 1,7-OCTADIE NES Donald Wright, Stockton-on-Tees, England, asslgnor to Imperial Chemical Industries Limited, London, England No Drawing. Filed Aug. 7, 1972, Ser. No. 278,343 Claims priority, application Great Britain, Aug. 18, 1971, 38,734/71 Int. Cl. C07c 11/12 US. Cl. 260-680 B 7 Claims ABSTRACT OF THE DISCLOSURE 1,6- and/or 1,7-octadienes are produced by reacting a 1,3-butadiene such as butadiene itself with metallic platinum, palladium, rhodium, ruthenium or osmium or preferably with a compound of one or more of these metals in a non-polar solvent such as benzene in the presence of a reducing agent such as formic acid.
The present invention relates to the production of olefines.
In our co-pending Application No. 79,323, now US. Pat. 3,732,328, we have described and claimed a process for the production of 1,6- and/or 1,7-octadienes by contacting one or more acyclic conjugated di-olefines with metallic platinum, palladium, rhodium, ruthenium or osmium or with a compound of one or more of these metals in a polar solvent in the presence of a reducing agent.
We have now found that the process may also be carried out in a non-polar solvent such as benzene.
According to the present invention 1,6- and/ or 1,7-octadienes are produced by contacting one or more acyclic conjugated di-olefines with metallic platinum, palladium, rhodium, ruthenium or osmium or with a compound of one or more of these metals in a non-polar solvent in the presence of a reducing agent.
The acyclic conjugated diolefine contains the structure:
in which the residual valencies may be satisfied by organic or inorganic groups or by hydrogen. Preferably the residual valencies are satisfied by alkyl groups, particularly lower alkyl groups containing up to four carbon atoms, or by hydrogen. The most suitable acyclic conjugated diolefines for use in the process of the invention are those in which the residual valencies are satisfied by methyl groups and/or by hydrogen. Butadiene and isoprene are particularly preferred. Halogen atoms such as chlorine are examples of suitable inorganic substituents in the acyclic conjugated diolefine. If desired two or more diolefines may be used in admixture.
The products of the process are substantially acyclic dimers of the acyclic conjugated diolefines and comprise an octadiene chain in which unsaturation is present in the 1,6- or 1,7-position. Thus platinum or a platinum compound and palladium or a palladium compound tend to produce a product comprising substantially the 1,6- isomer without any of the 1,7-isomer. If the palladium or platinum catalysed reaction is carried out in the presence of a phosphine, however, the 1,7-isomer is also formed, the relative proportions of the two isomers obtained being influenced by the nature of the phosphine. If the phosphine used is a triaryl phosphine then formation of the 1,6-octadiene is favoured whereas in the presence of a trialkyl phosphine the 1,7-isomer tends to be produced. Suitable triaryl phosphines include triphenyl phosphine; tri (alkyl phenyl) phosphines, particularly those in which each alkyl group contains up to 6 carbon atoms such as tri(p-tolyl phosphine); and tri(substituted phenyl) phosphines in which the substituent is non-hydrocarbon, e.g.
tri(p-methoxy phenyl)-phosphine. Trialkyl phosphines which may be used include alkyl phosphines in which each alkyl group contains up to 6 carbon atoms, e.g. triethyl and tributyl phosphine and trialkyl phosphines in which the alkyl group contains other substituents, e.g. a phenyl group as in tribenzyl phosphine. Tricycloalkyl phosphines may also be used, influencing the reaction in the same way as the trialkyl phosphines. The concentration of the phosphine preferably lies in the range 10" to 10* molar.
The reaction may be carried out heterogeneously using the metal or a metal compound. In the heterogeneous reaction the metal or metal compound may be supported on an inert support such as silica, alumina, charcoal or pumice. Preferably, however, the reaction is carried out homogeneously in the liquid phase. Suitable noble metal compounds which may be used in both the homogeneous and heterogeneous reactions include metal halides, particularly the chlorides, e.g. platinous chloride, rhodium trichloride and palladous chloride; metal carboxylates, particularly metal alkanoates derived from alkanoic acids containing up to six carbon atoms such as platinous acetate and palladium acetate, and complexes of the metals such as platinum or palladium acetylacetonate, bis-benzonitrile palladium (II) and lithium palladous chloride. The concentration of the metal or metal compound is preferably catalytic, e.g. in the range 10 to 10- molar, preferably 10 to 10 molar.
The non-polar solvent may be a hydrocarbon such as a paraffin, cycloparafiin or an aromatic. Preferably the solvent is a parifiin containing 5 to 16 carbon atoms, e.g. hexane, dodecane, or pentadecane, or is benzene, or an alkyl benzene, particularly an alkyl benzene containing up to 12 carbon atoms such as toluene or a xylene, or is a cycloparaflin, e.g. cyclohexane or methyl cyclohexane.
The reducing agent is preferably a liquid reducing agent. Examples of such agents include hydrazine and formaldehyde and solutions containing an alcohol, particularly a lower alkanol such as isopropanol. A preferred reducing agent is formic acid. The concentration of the reducing agent is preferably in the range 0.5 to 10 molar. A gaseous reducing agent such as hydrogen may also be used.
The process may be carried out at a temperature in the range 20 to 200 C. When operating at the higher temperatures the reaction may take place in a sealed system under the autogeneous pressure of the reactants.
If the process is carried out in a steel reaction vessel then it is advantageous to provide a copper salt, e.g. copper sulphate, or a copper halide such as copper chloride or a copper alkanoate such as copper acetate, or a phosphine such as a trialkyl, a mixed alkylaryl or a triaryl phosphine, e.g. triphenyl phosphine in the reaction mediuml tfo improve the activity of the catalyst and to prolong its 1 e.
The product of the process is either a 1,6 or 1,7 octadiene or a mixture of the two. The terminal unsaturation in the 1,7-diolefine makes it particularly useful as a chemical intermediate while the 1,6-isomer finds use as a termonomer with ethylene and propylene in EP rubbers.
The invention will now be further described with reference to the following Examples.
EXAMPLE 1 A mixture of formic acid (12 grams, 0.26 mole), benzene (20 mls.), palladous acetate (22 m. grams, 0.0001 mole) and butadiene (50 mls. 0.63 mole) Was heated in an autoclave at 50 C. for 20 hours. At the end of this time the excess formic acid was removed by washing with water and the organic phase dried and distilled to give 3.0 grams of 1,6-octadiene boiling at 46 C./50 mm.
EXAMPLE 2 A mixture of formic acid (12 grams, 0.26 mole), benzene (20 mls.), platinum acetylacetonate (9.3 m. grams, 0.000024 mole) and butadiene (50 mls.) was heated in an autoclave at 80 C. for 10 hours. The excess formic acid was removed from the product by washing with water subsequent distillation of the organic phase yielding 8 grams of 1,6-octadiene boiling at 66 C./ 130 mm.
What I claim is:
1. A process for the production of a member of the group consisting of 1,6- and 1,7-octadienes which comprises contacting at least one acyclic conjugated diolefine selected from the group consisting of butadiene and isoprene with a member of the group consisting of metallic platinum, palladium, rhodium, ruthenium, osmium and compounds of at least one of these metals in a non-polar solvent in the presence of formic acid.
2. The process of Claim 1 in which the process is carried out homogeneously in the liquid phase.
3. The process of Claim 2 in which the metal compound is a halide or a carboxylate or is a complex of one of said metals.
4. The process of Claim 2 in which the solvent is a parafiin, a cycloparaffin or an aromatic hydrocarbon.
5. The process of Claim 2 when carried out in a steel reaction vessel in which a copper salt is present.
6. The process of Claim 2 in which a phosphine is present.
7. The process of Claim 2 in which isoprene or butadiene is contacted at a temperature of 20 to 200 C. with, (a) a 10* to 10' molar concentration of a metal compound selected from the group consisting of palladous chloride, platinous chloride, a palladous alkanoate containing up to 6 carbon atoms, a platinous alkanoate containing up to 6 carbon atoms, platinum acetylacetonate, palladium acetylacetonate, bis-benzonitrile palladium (II) and lithium palladous chloride,
(b) in a non-polar solvent selected from the group consisting of a paraflin containing 5 to 16 carbon atoms, benzene, toluene, xylene, cyclohexane and methylcyclohexane,
(c) in the presence of formic acid in a concentration of 0.5 to 10 molar.
References Cited UNITED STATES PATENTS 3,398,209 8/1968 Schneider et al. 260-680 B 3,478,123 11/1969 Brennan 260-677 R 3,510,536 5/ 1970 Brennan 260-680 B 3,732,328 5/1973 Wright 260-680 B 3,354,236 11/1967 Klein 260-683.15 B 3,534,088 10/1970 Bryant et al. 260-666 B PAUL M. COUGHLAN, JR., Primary Examiner
US00278343A 1971-08-18 1972-08-07 Production of 1,6-and 1,7-octadienes Expired - Lifetime US3823199A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB3873471 1971-08-18

Publications (1)

Publication Number Publication Date
US3823199A true US3823199A (en) 1974-07-09

Family

ID=10405366

Family Applications (1)

Application Number Title Priority Date Filing Date
US00278343A Expired - Lifetime US3823199A (en) 1971-08-18 1972-08-07 Production of 1,6-and 1,7-octadienes

Country Status (6)

Country Link
US (1) US3823199A (en)
JP (1) JPS4829703A (en)
DE (1) DE2240719A1 (en)
FR (1) FR2149539B1 (en)
GB (1) GB1344887A (en)
IT (1) IT964013B (en)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0004408A2 (en) * 1978-03-27 1979-10-03 Shell Internationale Researchmaatschappij B.V. A process for preparing 1,7-octadiene and for activating a catalyst suitable for use in the process
EP0004409A2 (en) * 1978-03-27 1979-10-03 Shell Internationale Researchmaatschappij B.V. A process for preparing 1,7-octadiene
EP0004410A2 (en) * 1978-03-27 1979-10-03 Shell Internationale Researchmaatschappij B.V. A process for preparing 1,7-octadiene
US4177220A (en) * 1978-11-06 1979-12-04 Shell Oil Company 1-Octen-7-yne production
EP0007666A1 (en) * 1978-07-24 1980-02-06 Shell Internationale Researchmaatschappij B.V. A process for preparing 1,7-octadiene
EP0008139A1 (en) * 1978-07-24 1980-02-20 Shell Internationale Researchmaatschappij B.V. A process for preparing 1,7-octadiene
EP0012475A1 (en) * 1978-12-13 1980-06-25 Shell Internationale Researchmaatschappij B.V. A process for preparing 1,7-octadiene
EP0012472A1 (en) * 1978-12-13 1980-06-25 Shell Internationale Researchmaatschappij B.V. A process for preparing 1,7-octadiene
US4243829A (en) * 1976-10-04 1981-01-06 Charles U. Pittman, Jr. Production of 1,7-octadiene from butadiene
FR2464933A1 (en) * 1979-09-10 1981-03-20 Kuraray Co PROCESS FOR MANUFACTURING ALKADIANS
US4377719A (en) * 1976-10-04 1983-03-22 Charles U. Pittman, Jr. 1,7-Octadiene synthesis
US4536604A (en) * 1984-03-15 1985-08-20 Texaco Inc. Butadiene reductive dimerization using a platinum catalyst and polymeric amine promoter
US4687876A (en) * 1978-03-27 1987-08-18 Shell Oil Company Production of 1,7-octadiene from butadiene
US4992609A (en) * 1987-06-24 1991-02-12 Kuraray Co., Ltd. Phosphonium salts and processes for production of and uses for the same
US5043504A (en) * 1990-09-05 1991-08-27 The Dow Chemical Company Inhibition of butadiene-polymerization during the conversion of butadiene to vinylcyclohexene

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2437390A1 (en) * 1978-09-29 1980-04-25 Elf Union Selective dimerisation of conjugated diene - using catalyst system comprising Gp=VIII metal cpd. and in situ formed hydrogen donor
JPS6198859U (en) * 1984-12-03 1986-06-24
US5113033A (en) * 1990-01-12 1992-05-12 Exxon Chemical Patents Inc. Ruthenium salt and aluminum halide catalyst system for codimerization of alpha monoolefins and conjugated diolefins

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4243829A (en) * 1976-10-04 1981-01-06 Charles U. Pittman, Jr. Production of 1,7-octadiene from butadiene
US4377719A (en) * 1976-10-04 1983-03-22 Charles U. Pittman, Jr. 1,7-Octadiene synthesis
EP0004409A2 (en) * 1978-03-27 1979-10-03 Shell Internationale Researchmaatschappij B.V. A process for preparing 1,7-octadiene
EP0004410A2 (en) * 1978-03-27 1979-10-03 Shell Internationale Researchmaatschappij B.V. A process for preparing 1,7-octadiene
EP0004409A3 (en) * 1978-03-27 1979-10-31 Shell Internationale Research Maatschappij B.V. A process for preparing 1,7-octadiene
EP0004410A3 (en) * 1978-03-27 1979-10-31 Shell Internationale Research Maatschappij B.V. A process for preparing 1,7-octadiene
EP0004408A3 (en) * 1978-03-27 1979-10-31 Shell Internationale Research Maatschappij B.V. A process for preparing 1,7-octadiene and for activating a catalyst suitable for use in the process
US4687876A (en) * 1978-03-27 1987-08-18 Shell Oil Company Production of 1,7-octadiene from butadiene
EP0004408A2 (en) * 1978-03-27 1979-10-03 Shell Internationale Researchmaatschappij B.V. A process for preparing 1,7-octadiene and for activating a catalyst suitable for use in the process
EP0007666A1 (en) * 1978-07-24 1980-02-06 Shell Internationale Researchmaatschappij B.V. A process for preparing 1,7-octadiene
EP0008139A1 (en) * 1978-07-24 1980-02-20 Shell Internationale Researchmaatschappij B.V. A process for preparing 1,7-octadiene
US4177220A (en) * 1978-11-06 1979-12-04 Shell Oil Company 1-Octen-7-yne production
EP0012472A1 (en) * 1978-12-13 1980-06-25 Shell Internationale Researchmaatschappij B.V. A process for preparing 1,7-octadiene
US4229605A (en) * 1978-12-13 1980-10-21 Shell Oil Company 1,7-Octadiene process
US4229606A (en) * 1978-12-13 1980-10-21 Shell Oil Company 1,7-Octadiene process
EP0012475A1 (en) * 1978-12-13 1980-06-25 Shell Internationale Researchmaatschappij B.V. A process for preparing 1,7-octadiene
FR2464933A1 (en) * 1979-09-10 1981-03-20 Kuraray Co PROCESS FOR MANUFACTURING ALKADIANS
US4334117A (en) * 1979-09-10 1982-06-08 Kuraray Co., Ltd. Process for producing alkadienes
US4536604A (en) * 1984-03-15 1985-08-20 Texaco Inc. Butadiene reductive dimerization using a platinum catalyst and polymeric amine promoter
US4992609A (en) * 1987-06-24 1991-02-12 Kuraray Co., Ltd. Phosphonium salts and processes for production of and uses for the same
US5100854A (en) * 1987-06-24 1992-03-31 Kuraray Co., Ltd. Phosphonium salts and processes for production of and uses for the same
US5043504A (en) * 1990-09-05 1991-08-27 The Dow Chemical Company Inhibition of butadiene-polymerization during the conversion of butadiene to vinylcyclohexene

Also Published As

Publication number Publication date
DE2240719A1 (en) 1973-03-01
FR2149539A1 (en) 1973-03-30
GB1344887A (en) 1974-01-23
JPS4829703A (en) 1973-04-19
FR2149539B1 (en) 1976-08-13
IT964013B (en) 1974-01-21

Similar Documents

Publication Publication Date Title
US3823199A (en) Production of 1,6-and 1,7-octadienes
CN108430627B (en) Catalytic composition comprising nickel, a phosphine-type ligand and a Lewis base and its use in a process for oligomerizing olefins
US3644564A (en) Ethylene oligomerization in the presence of complex nickel-fluorine-containing catalysts
US4533651A (en) Catalysts for olefin oligomerization and isomerization
US3732328A (en) Process for the production of octadienes
US3620981A (en) Heterogeneous catalyst compositions
US3592869A (en) Olefin oligomerization
US5196625A (en) Detergent grade to C10 to C28 olefins, (C10 to C28 alkyl) benzenes and (C10 to C28 alkyl) benzene sulfonates and process for preparing same using a phosphite containing catalyst
EP1807381B1 (en) Process for isomerization of alpha olefins to internal olefins
US5196624A (en) Detergent grade to C10 to C28 olefins, (C10 to C28 alkyl)benzenes and C10 to C28 alkyl) benzene sulfonates and process for preparing same using a phosphine containing catalyst
US3644563A (en) Ethylene oligomerization
US20030130551A1 (en) Catalytic composition and process for oligomerizing ethylene, in particular to1-hexene
US3792101A (en) Process for producing reaction product of 1,3-conjugated diene compound and compound having terminal vinyl group and catalyst used therefor
US3726938A (en) Olefin production
US3482001A (en) Dimerization of propylene to dimethylbutenes
JPH0342249B2 (en)
JP3521912B2 (en) Method for synthesizing trans non-conjugated diolefin
US3800000A (en) Process for recovering a nickel(0) oligomerization catalyst in the form of a nickel(ii) dimerization catalyst
US3803254A (en) Process for producing oligomers of unsaturated compounds
US3917730A (en) New catalyst for the dimerization of diolefins
US5260499A (en) Ethylene dimerization and catalyst therefor
US3592870A (en) Nickel complex olefin dimerization
US3471581A (en) Isomerization of cyclic olefinic hydrocarbons
US3524898A (en) Homogeneous dehydrogenation of paraffins
US9193814B1 (en) Heterogeneous supports for homogeneous catalysts