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

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

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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
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Prior art keywords
phosphine
palladium
octadienes
butadiene
benzene
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US00278343A
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English (en)
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D Wright
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Imperial Chemical Industries Ltd
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Imperial Chemical Industries Ltd
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    • 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,

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)
US00278343A 1971-08-18 1972-08-07 Production of 1,6-and 1,7-octadienes Expired - Lifetime US3823199A (en)

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GB3873471 1971-08-18

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Country Status (6)

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US (1) US3823199A (enrdf_load_stackoverflow)
JP (1) JPS4829703A (enrdf_load_stackoverflow)
DE (1) DE2240719A1 (enrdf_load_stackoverflow)
FR (1) FR2149539B1 (enrdf_load_stackoverflow)
GB (1) GB1344887A (enrdf_load_stackoverflow)
IT (1) IT964013B (enrdf_load_stackoverflow)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
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
EP0012472A1 (en) * 1978-12-13 1980-06-25 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
US4243829A (en) * 1976-10-04 1981-01-06 Charles U. Pittman, Jr. Production of 1,7-octadiene from butadiene
FR2464933A1 (fr) * 1979-09-10 1981-03-20 Kuraray Co Procede de fabrication d'alcadienes
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 (fr) * 1978-09-29 1980-04-25 Elf Union Nouvelle synthese selective d'octadienes a partir du butadiene catalysee par les metaux du groupe viii
JPS6198859U (enrdf_load_stackoverflow) * 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 (19)

* 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
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
US4687876A (en) * 1978-03-27 1987-08-18 Shell Oil Company Production of 1,7-octadiene from butadiene
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
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
US4229606A (en) * 1978-12-13 1980-10-21 Shell Oil Company 1,7-Octadiene process
US4229605A (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
EP0012472A1 (en) * 1978-12-13 1980-06-25 Shell Internationale Researchmaatschappij B.V. A process for preparing 1,7-octadiene
FR2464933A1 (fr) * 1979-09-10 1981-03-20 Kuraray Co Procede de fabrication d'alcadienes
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
JPS4829703A (enrdf_load_stackoverflow) 1973-04-19
DE2240719A1 (de) 1973-03-01
IT964013B (it) 1974-01-21
FR2149539A1 (enrdf_load_stackoverflow) 1973-03-30
GB1344887A (en) 1974-01-23
FR2149539B1 (enrdf_load_stackoverflow) 1976-08-13

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