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 PDFInfo
- 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
Links
- 238000000034 method Methods 0.000 title claims description 12
- 238000002360 preparation method Methods 0.000 title claims description 10
- 229910052782 aluminium Inorganic materials 0.000 description 15
- BBDKZWKEPDTENS-UHFFFAOYSA-N 4-Vinylcyclohexene Chemical compound C=CC1CCC=CC1 BBDKZWKEPDTENS-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- -1 cyclo-hexenyl-ethylaluminum compound Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004508 fractional distillation Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000013844 butane Nutrition 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
PROCESS FOR THE PREPARATION OF BICYCLO- (3,2,1)-CTENE-(2) Karl Heinz Miiller and Peter Borner, Kamen, Westphalia, Germany, assign ors to Schering Aktiengesellschaft, Berlin, Germany No Drawing. Filed Feb. 11, 1963, Ser. No. 257,738 Claims priority, application Germany, Feb. 21, 1962,
Sch 31,020 3 Claims. (Cl. 260-666) Ann-0H0 and that it is of advantage to carry out this reaction in the presence of olefins, preferably alpha-olefins. From the reaction mixture the bicyclo(3,2,tl)-0ctene-(2) is recovered in the manner described hereinafter.
According to a specific modification, instead of the before named aluminum trialkyl compounds a mixture of 4-vinyl-cyc'lohexene,
CH.=CH(J with other aluminum-alkyl compounds is used, which are capable of forming aluminum trialkyl compounds containing at least one alkyl radical of the formula As examples of being used in the process of this invention 4-vinylcyclohexene or i-butene are named by way of example.
It could not be expected that the Al-C bonds could be added to the double bond of the cyclohexyl ring with the formation of a bicyclic system, that this addition takes place in such uniform manner and that, for example, from a cyclo-hexenyl-ethylaluminum compound bicyclo(3,2,- 1)-octene-(2) can be obtained.
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. Furthermore, as 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.
In carrying out the present invention a commercial scale preferably a continuous cyclic process can be used. For example, 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) can be isolated by fractional distillation. It is of advantage in this connection to previously separate the C hydrocarbon by vacuum distillation from the higher molecular, eJg. dimerized, products and aluminum alkyl compounds. From concentrated mixtures the bicyclo-(3,2,l)-octene (2) can be recovered also by crystallization. After purification by recrystallization and sublimation the product of the invention is a white camphorli-ke mass which is very volatile and has a melting point, in a sealed tube, of 42.5-43.5 C. and a boiling point of B.P. =l35 C. Its index of refraction is n =1.4689.
The reactions with aluminum organic compounds must be carried out in conventional manner with the exclusion of oxygen and humidity.
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.
for 2 hours in a one liter shaking autoclave. The pressure did not exceed 5 atmospheres superatmospheric pressure. After permitting the autoclave to cool, the reaction mixture was transferred to a distillation device provided with a Claisen attachment. Upon stirring and heating up to C. under a pressure of 4 torr, 210 g. of distillate were collected in the well-cooled receiver. The distillate contained 80% of bicycle-(3,2,l)-octene-(2). The pure Ebicyclo-(3,2,l)-0ctene(2) was recovered by fractional distillation 'with an efiicient column.
Example 2 300 g. of 4-vinylcyclohexene and 303 g. of
were introduced into a glass flask provided with a reflux cooler and a stirring device. The mixture was heated under reflux until the temperature reached C. The
Example 3 2511 g. of 4-vinylcyclohexene and 544 g. Al(i-C -H H were heated in a liter shaking autoclave .for 3 hours to 180 C. The pressure reached thereby about 20 atmospheres of super-atmospheric pressure. The autoclave was permitted to cool and the reaction mixture was transferred to a distillation apparatus provided with a Claisen attachment. Upon stirring and heating to 110 C., under a pressure of tor-r, 99 8 g. distillate were collected in the well cooled receiver. Subsequently, the distillate was subjected to distillation with a short tractionating attachment under atmospheric pressure. Between 130 and 140 C. head temperature 924 g. of distillate were obtained, which contained 87% of -bicyclo-(3,2,1)- octene-(2) and from which the pure'product was isolated in the manner described in the above Example 1.
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.
The preparation of the compound i Qi from aluminum triisobutyl and 4-vinylcyclohexene is described in Metallorganische Verbindungen, XL, Synthesis of Alcohols from Organo-Aluminum Compounds, K. Ziegler, F. Krupp and K. Zosel, Liebigs Annalen der Chemie, 62 9, 241 1960).
The preparation or the compound Aummnmmwm-O-q from aluminum diethyl hydrid and 4-vinylcyclo'hexene is described in Metallorganische Verbindungen, XIX, Reaction or the Aluminum-Hydrogen Bond with Oleiins,
243 g. of
97 g. of
4 K. Ziegler, H. G. Gellert, H. Martin, K. Nagel and J. Schneider, Liebigs Annalen der Chemie, 58 9.
From the a-ole'fius primarily 4-v-inylcyclohexene and i-bu-tene are used. 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.
Purification of the bicyclo-(3, 2,l)-2-o'ctene was carried out (from highly concentrated, but still liquid (or remelted) crude product.
It has been known that 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. In the example 5, the upper limit is stated with an aluminum compound without olefin-reactant.
What is claimed is:
1. A process for the preparation of bicyclo-(3,2,1)- octene-(Z) CH: CH
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.
2. 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.
3. A process for the preparation of bicyclo-(3,2,1)- octene-(2) Gm-( JHAEH (3H1 CH CHPCH-(IJHZ comprising heating aluminum trialkyl compounds, in alkyl compound being heated together with 4-viny1cyclowhich at least one alkyl radical is hexene.
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.
and lower alkyl radicals, to a temperature in the range 10 LEONARD FORMAN Examiner of 130 C. to 350 C. and separating the bicyclo-(3,2,1)- V. OKEEFE, Assistant Examiner. octene-(2) from the reaction mixture, the aluminum tri-
Claims (1)
- 2. A PROCESS FOR THE PREPARATION OF BICYCLO-(3,2,1)OCTENE- (2)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DESCH31020A DE1190459B (en) | 1962-02-21 | 1962-02-21 | Process for the preparation of bicyclo- [3, 2, 1] octene- (2) |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3274271A true US3274271A (en) | 1966-09-20 |
Family
ID=7431948
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US257738A Expired - Lifetime US3274271A (en) | 1962-02-21 | 1963-02-11 | Process for the preparation of bicyclo-(3, 2, 1)-octene-(2) |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US3274271A (en) |
| DE (1) | DE1190459B (en) |
| GB (1) | GB982264A (en) |
Cited By (1)
| 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)
| 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)
| 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 |
-
1962
- 1962-02-21 DE DESCH31020A patent/DE1190459B/en active Pending
-
1963
- 1963-02-11 US US257738A patent/US3274271A/en not_active Expired - Lifetime
- 1963-02-13 GB GB5912/63A patent/GB982264A/en not_active Expired
Patent Citations (1)
| 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)
| 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 |
|---|---|
| GB982264A (en) | 1965-02-03 |
| DE1190459B (en) | 1965-04-08 |
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