US3251894A - Process for the production of 1-methylcyclohexene-(1) - Google Patents

Process for the production of 1-methylcyclohexene-(1) Download PDF

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US3251894A
US3251894A US29692563A US3251894A US 3251894 A US3251894 A US 3251894A US 29692563 A US29692563 A US 29692563A US 3251894 A US3251894 A US 3251894A
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Prior art keywords
methylcyclohexene
alkaline earth
production
liquid ammonia
amide
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Amagasa Masataka
Yamaguchi Tadashi
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Amagasa Masataka
Yamaguchi Tadashi
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Application filed by Amagasa Masataka, Yamaguchi Tadashi filed Critical Amagasa Masataka
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/2729Changing the branching point of an open chain or the point of substitution on a ring
    • C07C5/2732Catalytic processes
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/23Rearrangement of carbon-to-carbon unsaturated bonds
    • C07C5/25Migration of carbon-to-carbon double bonds
    • C07C5/2506Catalytic processes
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/23Rearrangement of carbon-to-carbon unsaturated bonds
    • C07C5/25Migration of carbon-to-carbon double bonds
    • C07C5/2506Catalytic processes
    • C07C5/2556Catalytic processes with metals
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/2729Changing the branching point of an open chain or the point of substitution on a ring
    • C07C5/2732Catalytic processes
    • C07C5/2754Catalytic processes with metals

Description

United States Patent PROCESS FOR THE PRODUCTION OF I- METHYL- CYCLOHEXENE-(l). Masataka Amagasa, 1 Komegafukuro-Uwacho, and
Tadashi Yamaguchi, 66 Nakajima-cho, both of Sendai shi, Japan n. r No'Drawing. Filed July 23, 196$,Ser. No. 296,925 Claims priority, applicatiogsJzapan, July 28, 1962,
5' Claims. claw-666 The present invention relates to a process'for the production of l-methylcyclohexerie-(l), represented by the structural formula, viz.
Clia' from l-metliylcyclohexen-(3l represented by the structural formula, viz.
or l-methylcyclohirene-(Z) represented 'by the structural formula, viz.
in liquid ammonia by use of a substance selected from the group consisting of alkali metals, alkaline earth metals, alkali metal amides and alkaline earth metal amides.
The essential object of this invention is to provide a process for producing easily and completely l-methylcyclohexene-(l) from 1-methylcyclohexene-(2) or l-methylcyclohexene-(3) by an isomerization reaction wherein a peculiarity of liquid ammonia is utilized.
The present inventors have studied the organic chemistry field employing liquid ammonia and its application;
The present invention is based on a part of their studies As the result of said studies, the present inventors have found that l-methylcyclohexene-(Z) f EL-n J or 1-methylcyclohexene-(3) U1 is isomerized into 1-methylcyclohexene-(1) can which is considered to have the most stable structure, in liquid ammonia in the presence of a substance selected from the group consisting of alkali metals, alkaline earth metals, and the amides thereof.
Since the alkali metals, alkaline earth metals, or their 3,251,894 Patented May 17, 1966 amides employed in the above-mentioned case act as catalysts, their quantity so employed has no relation to the quantity of l-methylcyclohexene-(3) or I-methylcyclohexene-(Z) Example I 20 cc. of liquid ammonia, 2 g. of l-methylcyclohexcue-7(3) and 0.1 g. of metallic sodium were placed in a pressureresisting glass reaction tube having a capacity of 50 cc., and left standing at 20C. for 8'hours. Thereafter, ammonia was recovered and 20 cc. of water was gradually added to the residue. As the result of an analysis of the oil layer by gas chromatography, it was found that the said l-methylcyclohexene-(3) was isomerized into l-methylcyclohexene-(l) Example II 20 cc. of liquid ammonia, 2 g. of l-methylcyclohexene-(2) and 0.2 g. of potassiumamide were placed in a pressureresisting glass reaction tube having a capacity of 50 cc., and left standing at 40 C. for 3 hours. Then, the same procedure as that in Example (I) was carried out, whereby said l-methylcyclohexene-(Z) 3 was isomerized into l-methylcyclohexene-(l) As described above, according to the present invention since l-methylcyclohexene-(l can be easily and completely produced from. l-methylcyclohexene- (2) CHa or 1-methylcyclohexene-( 3) Accordingly, it will be observed that the present invention is very useful in the petroleum chemical industry.
What is claimed is:
1. A process for production of l-methylcyclohexene- (l)- consisting essentially of: contacting in liquid ammonia a compound selected from the group consisting of l-methylcyclohexene-(Z) and 1-methylcyc1ohexene-(3) with a substance selected from the group consisting of alkali metals, alkaline earth metals, alkali metal amides and alkaline earth metal amides, whereby an insomerization reaction takes place to produce l-methylcyclohexene- (1).
2. A process according to claim 1, wherein said alkali metal is selected from group consisting of lithium, sodium and potassium.
3. A process according to claim 1, wherein said alkaline earth metal is selected from group consisting of calcium, strontium and barium.
4. A process according to claim 1, wherein said alkali metal amide is selected from group consisting of lithium amide, sodium amide and potassium amide.
5. A process according to claim 1, wherein said a1- kaline earth metal amide is selected from group consisting of calcium amide, strontium amide and barium amide.
References Cited by the Examiner UNITED STATES PATENTS 2,182,242 12/1939 Wooster '260667 -2,432,843 12/1947 Whitman 260--666 OTHER REFERENCES A. P. Krapcho et al.: J. Am. Chem. Soc., 81, pp. 3658- 3666, July 20, 1959.
DELBERT E. GANTZ, Primary Examiner.
V. OKEEFE, Assistant Examiner.

Claims (1)

1. A PROCESS FOR PRODUCTION OF 1-METHYLCYCLOHEXENE(1) CONSISTING ESSENTIALLY OF: CONTACTING IN LIQUID AMMONIA A COMPOUND SELECTED FROM THE GROUP CONSISTING OF 1-METHYLCYCLOHEXENE-(2) AND 1-METHYLCYCLOHEXENE-(3) WITH A SUBSTANCE SELECTED FROM THE GROUP CONSISTING OF ALKALI METALS, ALKALINE EARTH METALS, ALKALI METAL AMIDES AND ALKALINE EARTH METAL AMIDES, WHEREBY AN INSOMERIZATION REACTION TAKES PLACE TO PRODUCE 1-METHYLCYCLOHEXENE(1).
US29692563 1962-07-28 1963-07-23 Process for the production of 1-methylcyclohexene-(1) Expired - Lifetime US3251894A (en)

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JP3193262 1962-07-28

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3347944A (en) * 1965-10-01 1967-10-17 Union Carbide Corp Production of alkylidenebicycloheptenes

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2182242A (en) * 1938-05-03 1939-12-05 Du Pont Process for hydrogenating aromatic hydrocarbons
US2432843A (en) * 1946-06-07 1947-12-16 Du Pont Process for hydrogenating mononuclear aromatic and cycloalkene hydrocarbons

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2182242A (en) * 1938-05-03 1939-12-05 Du Pont Process for hydrogenating aromatic hydrocarbons
US2432843A (en) * 1946-06-07 1947-12-16 Du Pont Process for hydrogenating mononuclear aromatic and cycloalkene hydrocarbons

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3347944A (en) * 1965-10-01 1967-10-17 Union Carbide Corp Production of alkylidenebicycloheptenes

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GB1025058A (en) 1966-04-06

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