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US3274271A - Process for the preparation of bicyclo-(3, 2, 1)-octene-(2) - Google Patents

Process for the preparation of bicyclo-(3, 2, 1)-octene-(2) Download PDF

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Publication number
US3274271A
US3274271A US257738A US25773863A US3274271A US 3274271 A US3274271 A US 3274271A US 257738 A US257738 A US 257738A US 25773863 A US25773863 A US 25773863A US 3274271 A US3274271 A US 3274271A
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US
United States
Prior art keywords
bicyclo
octene
aluminum
preparation
vinylcyclohexene
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
US257738A
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English (en)
Inventor
Muller Karl Heinz
Borner Peter
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.)
Bayer Pharma AG
Original Assignee
Schering AG
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Filing date
Publication date
Application filed by Schering AG filed Critical Schering AG
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Publication of US3274271A publication Critical patent/US3274271A/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
    • C07C1/325—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a metal atom
    • C07C1/327—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a metal atom the hetero-atom being an aluminium atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
    • C07C2602/44—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing eight carbon atoms

Definitions

  • the preparation of the aluminumtrialkyl compounds having at least one alkyl radical of the formula can be carried out according to methods known by themselves.
  • a favorable procedure is, for example, the re- United States Patent 0 "ice action of 4-vinylcyclohexene with suitable aluminumalkyl compounds, particularly aluminum-triisobutyl or aluminum-diiso'butylhydride.
  • 4-vinylcyclohexene can be easily obtained by thermal dimerization from 'butadiene, the process of this invention creates a possibility of obtaining bicyclo(3,2,l)-octene-(2), with utilization of the petrochemical butad-iene which is produced on a large scale.
  • a commercial scale preferably a continuous cyclic process can be used.
  • a starting amount of aluminum-alkyl compounds is reacted in a suitable reactor with 4-vinylcyclohexene.
  • the bicyclo-(3,2,l)-octene-2 formed is recovered from the reaction product.
  • the aluminum-alkyl compounds and a rest of 4-vinylcyclohexene which eventually has not reacted yet, are likewise separated and returned to the process and mixed there with fresh 4-vinylcyclohexene, i.e. conducted in a cycle.
  • the bicyclo-(3,2,1)-octene-(2) is of particular utility and importance in the preparation of intermediate products which are capable of polymerization and polycondensation.
  • Example 1 412 g. of 4-vinylcyclohexene are heated to 180 C. together with 226 g.
  • Example 2 300 g. of 4-vinylcyclohexene and 303 g. of
  • Example 4 and 250 g. i-b-utene were heated in a one liter shaking autoclave for 2 hours to 180 C. After cooling, the excess i-butene was discharged and the reaction mixture was transferred into a distillation apparatus provided with a short fractionating attachment. The residual i-butene was removed under vacuum at about 30 torr. Subsequently, under stirring heating was carried out up to 110 C. under 5-7 torr. Thereby, 96 g. of distillate passed to the cooled receiver. To the distillate which contained some aluminum alkyl, carefully some dilute hydrochloric acid was added; it was then shaken, washed with water and dried over potassium carbonate. 89 g. of a mixture of hydrocarbons containing 46% bicyclo- (3,2,1)-octen-(2) were obtained.
  • Example 5 are heated in a round-bottomed flask provided with a reflux cooler for 5 hours to 150-180 C. After cooling down of the reaction mass, the yellow, very viscous reaction product is caused to pass at 130-140 C. and 01-2 torr through a thin-layer evaporator. Thereby 8 g. of material distilled over and were recovered in a trap cooled with dry CO and acetone. It has been found by means of a gas chromatogram that the distillate consisted to about 80% of bicyclo(3,2,1)-octene-2.
  • Bicyclo-(3,2,l)-octene-2 is formed also in the presence of mixtures of ot-OlClfiIJS, such as propene and 4vinyl-cyclohexene and also butene-l and 4-vinylcyclohexene.
  • bicyclo-(3,2,l)-octene-2 can be converted over bicyclooctanol, and over the bicyclooctanon into the cyclopentane-(1)-cauboxylic acid-3- acetic acid.
  • This dicauboxylic acid can be condensed with dioles or diamines to polyesters or polyamides which can be used as thermoplastic materials.
  • the temperature of the reaction is carried out in the range or l30-350 C. and under a pressure in the range between 1 atmosphere up to the pressure which corresponds to the vapor tension of the reaction mixture at the reaction temperature used.
  • the lower limit for the proportions of olefin and aluminum compound is at 1:01.
  • the upper limit is stated with an aluminum compound without olefin-reactant.
  • CHr-CHCH5 comprising heating aluminum trialkyl compounds, in which at least one alkyl radical is and the rest of the alkyl radicals is selected from the group consisting of and lower alkyl radicals, to a temperature in the range of C. to 350 C. and separating the bicyclo-(3, 2,1)- octene (2) from the reaction mixture, the aluminum trialkyl compound being heated together with i butene.
  • a process for the preparation of bicyclo-(3,2,l)- octene-(Z) CHz(lJH(3H (1H2 CH CHzCH-CH2 comprising heating aluminum trialkyl compounds, in which at least one alkyl radical is and the rest of the alkyl radicals is selected from the group consisting of and lower alkyl radicals, to a temperature in the range of 130 C. to 350 C. and separating the bicyclo(3,2,l)- octene-(2) from the reaction mixture, the aluminum trialkyl compound being heated together with an alphaolefin.
  • CH2CH2 References Cited by the Examiner and the rest of the alkyl radicals is selected from the UNITED STATES PATENTS group consisting of 2,826,598 3/ 1958 Ziegler et a1 260666 CHZCH2O DELB'ERT E. GANTZ, Primary Examiner.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US257738A 1962-02-21 1963-02-11 Process for the preparation of bicyclo-(3, 2, 1)-octene-(2) Expired - Lifetime US3274271A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DESCH31020A DE1190459B (de) 1962-02-21 1962-02-21 Verfahren zur Herstellung von Bicyclo-[3, 2, 1]-okten-(2)

Publications (1)

Publication Number Publication Date
US3274271A true US3274271A (en) 1966-09-20

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US257738A Expired - Lifetime US3274271A (en) 1962-02-21 1963-02-11 Process for the preparation of bicyclo-(3, 2, 1)-octene-(2)

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US (1) US3274271A (de)
DE (1) DE1190459B (de)
GB (1) GB982264A (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3361837A (en) * 1965-10-18 1968-01-02 Phillips Petroleum Co Bicyclization

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4398978A (en) * 1982-04-26 1983-08-16 The United States Of America As Represented By The Secretary Of The Navy High density, low viscosity airbreather fuel (RJ-4-I)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2826598A (en) * 1951-06-21 1958-03-11 Ziegler Karl Production of organic compounds of aluminum and beryllium

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2826598A (en) * 1951-06-21 1958-03-11 Ziegler Karl Production of organic compounds of aluminum and beryllium

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3361837A (en) * 1965-10-18 1968-01-02 Phillips Petroleum Co Bicyclization

Also Published As

Publication number Publication date
DE1190459B (de) 1965-04-08
GB982264A (en) 1965-02-03

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