DE1036847B - Process for the production of halogenated hydrocarbons from unsaturated cyclic hydrocarbons - Google Patents

Description

It is known that polyhalomethanes, e.g. B. carbon tetrachloride or chloroform, to olefinic Add hydrocarbons in the presence of acyl peroxides as catalysts or by exposure to UV light can.

In the technical implementation of such a process, however, the use of peroxides as catalysts undesirable because the same on the one hand cause difficulties in technical handling and there on the other hand, they have to be destroyed before the reaction product can be worked up. Carrying out the reaction under the action of UV light brings technical difficulties with it. Besides, it is with these procedures so far not successful, for example the addition of chloroform or carbon tetrachloride to medium-sized companies To achieve double bonds.

It has now surprisingly been found that is obtained in a simple manner, even without the use of catalysts, halocarbons of unsaturated cyclic hydrocarbons when heated polyhalomethanes with unsaturated hydrocarbons of the cyclo octane number at 120 to 25O ⁰ C and is advantageously carried out in the presence of solvents.

According to this process, it is possible to carry out the addition of polyhalomethanes either continuously or batchwise. An additional use of catalysts, e.g. B. the known chlorination catalysts of the Friedel-Crafts type or platinum halides, especially chlorides, is possible, but not necessary. Carried out at temperatures between 120 and 250 ⁰ C, particularly at 120 to 17O ⁰ C, preferably at 15O ⁰ C.

The reaction can be carried out in the presence of a solvent. It is advantageous to use what is to be implemented Polyhalomethane itself in a corresponding excess, so that it does the function of the solvent Fulfills. However, it is also possible to use other substances that do not react under the implementation conditions themselves, to be used as a solvent, e.g. B. hydrocarbons, such as petroleum ether, or halogenated hydrocarbons, benzene and toluene, cycloaliphatic compounds such as cyclohexane and cyclooctane, and ethers.

Since the boiling points of the polyhalomethanes are below the optimal reaction temperature, it is advisable to the. Implementation in a closed vessel. The conversion takes place under the steam pressure of the solvent at the reaction temperature. However, the application of pressure is not necessary Reaction condition. The polyhalomethane can be either partially or fully halogenated methane use, e.g. B. carbon tetrachloride, carbon tetrabromide, chloroform and bromoform. As cycloolefinic or cyclopolyolefinic hydrocarbons are suitable compounds which are derived from the basic structure cyclooctane Method of manufacture

of halogenated hydrocarbons

from unsaturated cyclic

Coals were burned to death

Applicant:

Aniline & Soda Factory in Baden

Aktiengesellschaft, Ludwigshafen / Rhein

Dr. Franz Reicheneder and Dr. Hubert Suter,

Ludwigshafen / Rhine,
have been named as inventors

derive, e.g. B. cyclooctene, cyclooctadiene, cyclooctatriene and cyclooctatetraene.

During the reaction, a weight ratio of cycloolefin to polyhalomethane is advantageously chosen within the limits 1: 2 to 1: 10.

The new compounds produced by the process are insecticides that have a good effect on certain Pest species, e.g. B. Blatta o.ientalis, show. Various halogenated ones made by this process But hydrocarbons are also valuable solvents.

The parts mentioned in the examples are parts by weight.

example 1

In e ^; A mixture of 122 parts is filled into the pressure vessel

Cyclooctane and Cyclootadien (90 ° / ₀ cyclooctane = 100- In a pressure vessel is filled, a mixture of 122 parts of cyclooctene and cyclooctadiene (90% cyclooctene

= HO "parts), dissolved in 954 parts of carbon tetrachloride.

It displaces the air with nitrogen, and the mixture is heated then to 15O ⁰ C. The pressure rises to 10 atm. After 4 hours, the mixture is allowed to cool. The crude product is fractionally distilled.

In addition to a preliminary run of excess, one obtains

Carbon tetrachloride and 45 parts of unreacted starting material in the 1st fraction: Kp _OjOO1 75 to 80 ⁰ C, n'S 1.5225, IS parts;. 2nd fraction: _o Kp, _oal 107 to 110 ⁰ C, n ° 1.5330%, 121 parts, and 20 parts of a residue..

The 1st fraction is a trichloromethylcyclooctene, that by splitting off hydrochloric acid from the carbon tetrachloride addition p-oduct with cyclooctene arises.

809 598/559

Claims (1)

The analysis gives: C ₉ H ₁₆ Cl ₃ (molecular weight 228). Cl: Calculated: 47.00%, found: 46.10%. The 2nd fraction is trichloromethyl-2-chlorocyclooctane. The analysis gives: C ₉ H ₁₄ Cl ₄ (molecular weight 264). Cl: Calculated: 53.70%, found: 53.30%. This substance is an effective insecticide, especially against Blatta orientalis. The yield of trichloromethyl-2-chlorocyclooctane corresponds to 74.3%, that of trichloromethylcyclooctene 12.8%, based on converted cyclooctene. Example 2 A solution of 106 parts of a mixture of cyclooctatriene and cyclooctatetraene (90% cyclooctatriene [mixture of 1,3,5- and 1,3,6-cyclooctatrienes] = 96 parts) in 954 parts of carbon tetrachloride is placed in a pressure vessel. The air is then displaced by nitrogen and the mixture is heated to 150 ^° C. The pressure rises to ~ 10 atm. After 4 hours, the mixture is allowed to cool and the crude product is worked up by distillation, hydrochloric acid being split off. In addition to a preliminary run of excess carbon tetrachloride and 50 parts of unreacted starting material, 62 parts of a compound _{with a b.p. 1> 5} = 135 to 145 ° C with a refractive index n * g = 1.5630, the structure of which has not yet been clarified. 24 parts of residue remain. The analysis gives: C ₉ H ₉ Cl ₃ (molecular weight: 224). Cl: Calculated: 47.80%, found: 47.80%. Example 3 A mixture of 110 parts of cyclooctene, 37 parts of cyclooctane and 920 parts of chloroform is placed in a pressure vessel. After displacing the air with nitrogen, the mixture is heated to 15O ⁰ C, wherein the pressure to 10 atmospheres gauge increases. After 4 hours, the mixture is allowed to cool. By fractional distillation unreacted cyclooctene, Cyclooctangemisch is obtained in addition to the flow of excess chloroform and 97 parts of 36.8 parts of a compound, which merges in the boiling range of Kp. _{0) 9} 70 to 9O ⁰ C and a refractive index of N'O = 1.5130, the structure of which has not yet been clarified. The analysis gives: C ₉ H ₁₄ Cl ₂ (molecular weight: 193). Cl: Calculated: 36.80%, found: 36.80%. In addition, 43 parts of a resinous mass remain as a residue. Example 4 A mixture of 104 parts of cyclooctatetraene and 954 parts of carbon tetrachloride is placed in a pressure vessel filled. The molar ratio is 1: 6.2. The vessel is first flushed with nitrogen and then heated 150 ° C, the pressure increasing to 10 atm. After 4 hours, the mixture is allowed to cool. Fractional distillation gives 42 parts of unreacted cyclooctatetraene in addition to a first run of excess carbon tetrachloride. Two different reaction products are obtained by distillation at 0.6 mm Hg: ^{21 parts in the boiling range from 80 to HO 0} C and 43.4 parts between 135 and 160 ° C. Analysis of the fraction from the boiling range 80 to 110 ° C. gives: C ₀ H ₇ Cl ₃ (molecular weight: 225). Cl: Calculated: 48.20%, found 47.50%. For the second fraction (135 to 16O ⁰ C) a chlorine content of 51.3 to 51.9% is found. There remain 52 parts of residue. P.V T EN TA Χ S P Il LCII. ■ Process for the production of halogenated hydrocarbons by reacting unsaturated ones cyclic hydrocarbons with polyhalomethanes, characterized in that unsaturated Hydrocarbons of the cyclooctane series and polyhalomethanes heated to 120 to 250 ° C and expediently works in the presence of solvents. Θ 809 598/559 p.