DE1046054B - Process for the production of organic peroxides - Google Patents

Description

GERMAN

It is known that organic hydroperoxides are bound to the C = C double bond under the action of alkalis of a, /? - unsaturated nitriles.

A, /? - unsaturated ketones and acids react in the same way and nitro compounds with organic hydroperoxides.

It is also known, monohalo-di-tertiary-alkylperoxyde produce by Monohälogentertiär-alkylhydroperoxyde with an excess of an equivalent mixture of tertiary butyl alcohol, and 65%> was added sulfuric acid and the mixture thus prepared a longer time, for example 72 hours at 15 to 3O ⁰ C leaves.

It has now been found, surprisingly, that organic hydroperoxides also have such C =C double bonds which are not attached by a polar substituent adjacent to the double bond are activated.

An organic hydroperoxide of the general formula ROOH with an olefin is used for addition general formula

Method of manufacture
of organic peroxides

Applicant:

Farbwerke Hoechst Aktiengesellschaft formerly Master Lucius Sd Brüning,

Frankfurt / M., Brüningstr. 45

Dr. Klaus Weissermel and Dr. Michael Lederer,

Frankfurt / M.-Unterliederbach,
have been named as inventors

In the general formula

implemented in the presence of an organic hypohalite.

The reaction proceeds according to the following reaction equation

R ₁ ,

/ R3

ROOH + X = C + BOX

R ₂ R ₄

: c-c

ROO X

+ BOH

For the compound of the general formula ROOH it is a monosubstitution product of hydrogen peroxide, in which R is an alkyl, cycloalkyl or can be aralkyl.

Suitable hydroperoxides are, for. B. tertiary butyl hydroperoxide, tertiary amyl hydroperoxide or cumene hydroperoxide.

R ₁ ,

: c = c:

at least one of ReStCR ₁ to R ₄ denotes an alkyl, cycloalkyl, aralkyl or aryl radical, while the remaining radicals can represent hydrogen or also alkyl, cycloalkyl, aralkyl or aryl groups. Furthermore, according to the invention, cyclic olefins can also be used for the reaction. Suitable olefins are e.g. B. alkenes and cycloalkenes, provided that they are present as a liquid under the chosen reaction conditions, e.g. B. butene, pentene, cyclohexene and methylcyclohexene.

The compounds of the general formula BOX are organic hypohalites in which X is a halogen with an atomic weight of at least 35, but preferably chlorine or bromine, and B is a primary, secondary or preferably tertiary alkyl radical, an aromatic, cycloaliphatic, means heterocyclic radical or a combination of the listed organic radicals with one another.

Suitable hypohalites are e.g. B. tertiary butyl hypochlorite, tertiary butyl hypobromite, tertiary amyl hypochlorite, tertiary amyl hypobromite and other hypochlorites or hypobromites, in which the hypohalite group with a tertiary carbon atom

809 698/562

connected is. The tertiary alkyl hypohalites are Preferably used as a donor of positive halogen, as they are easily accessible and quite stable are.

The addition of hydroperoxides with olefins in the presence of hypohalite proceeds very rapidly under strongly exothermic and is advantageously carried out at temperatures between -30 and + 5O ⁰ C. It is advantageous to proceed in such a way that the olefin component is placed in a reaction vessel together with the calculated amount of organic monohydroperoxide in the presence or absence of a solvent which is not involved in the reaction and the hypohalite is added dropwise with stirring. Suitable solvents are e.g. B. liquid hydrocarbons, ether or carbon tetrachloride. Under the chosen reaction conditions there is neither polymerization of the olefin component nor decomposition of the hydroperoxide. The reaction products are worked up and recovered according to customary organic procedures.

The reaction of hydroperoxides with olefins in the presence of organic hypohalites results in a one-step process to new halogen-containing organic peroxides based on another synthetic Paths are difficult to access. The manufacturable by this new method, in the With the exception of monochloro and monobromo-di-tertiary butyl peroxide, literature has not been described so far Organic peroxides are used as polymerization catalysts.

example 1

In a vessel equipped with a stirrer and dropping funnel reaction vessel, 56 g of n-pentene-2 and 51 g of tertiary-butyl hydroperoxide under exclusion of moisture to -15 to - 20 ⁰ C cooled. 61 g of tert-butyl hypochlorite are added dropwise over the course of 8 hours with stirring. After warming to room temperature, the reaction mixture is fractionally distilled. The addition product passes between 33 and 37 ° C at 0.09 mm. The refractive index « ² S is 1.4277. The yield is 30 g.

C ₉ H ₁₀ O ₂ Cl: molecular weight 194.7

Calculated. C55.6, H9.8, Cl 18.2, O-active 16.4; found ... C55.0, H9.9, CI 18.5, O-active 16.4.

C ₁₀ H ₁₀ O ₂ Cl

Calculated ... C58.1, H9.2, Cl 17.2, O-active 15.5; found .... C57.8, H8.9, Cl 17.2, O-active 16.1. separate the volatile constituents, 47 g of residue remain, which still contains a little cumene hydroperoxide. 10 g of the residue are taken up in pentane and extracted three times with 10% potassium hydroxide solution. After washing with water, drying and vacuum distillation, 5.9 g of a non-distillable compound remain, which has the following analytical values:

Ci5 H ₂ IO ₂ Cl

Calculated ... C67.5, H7.9, Cl 13.2, O-active 5.95; found .... C67.0, H8.0, Cl 11.3, O-active 5.3.

Example 4

30 g of 2-methylpentene and 26 g of tertiary amyl hydroperoxide are reacted with 27 g of tertiary butyl hypochlorite at -5 to 0 ° C. in the presence of 10 g of sodium bicarbonate. It is diluted with 50 cc pentene, washed with water, ⁿ / io-sodium thiosulfate solution, water and dried over sodium sulfate. The volatile components are then separated off in vacuo, and a crude yield of 28 g is obtained. The addition product distills over at 1 mm and 36 ° C and has the following analytical values:

C ₁₁ H ₂₃ O ₂ Cl

Calculated C 59.3, H 10.4, Cl 15.9;

found C 58.4, H 10.1, Cl 16.1.

The refractive index n ² g is 1.4378.

Example 5

15 g of cumene hydroperoxide and 20 g of 2-methylpentene are added in the presence of 3 g of sodium bicarbonate - 20 ° C reacted with 11 g of tertiary butyl hypochlorite. Then it is diluted with 100 ecm pentene, the solution is washed with 20% sodium hydroxide solution, then three times with water and dry over sodium sulfate. The volatile components are in a vacuum severed. 16 g of a non-distillable residual ice are obtained, which has the following analytical values:

C ₁₅ H ₂₃ O ₂ Cl

Calculated ... C66.5, H8.6, C113.1, O-active 5.9; found .... C68.0, H9, l, Cl 10.8, O-active 5.75.

45

Example 2

70 g of cyclohexene and 40 g of tertiary butyl hydroperoxide are, as indicated in Example 1, with 37 g tertiary butyl hypochlorite at -17 to -20 ° C 10 to Implemented for 12 hours. The pale yellow solution is fractionally distilled in vacuo. That Addition product passes over between 39 and 41 ° C at 0.01 mm.

The refractive index n ² g is 1.4618. The yield is 15 g.

Example 3

As in Example 1, 34 g of cumene hydroperoxide and 35 g of cyclohexane are reacted with 24 g of tertiary butyl hypochlorite at -10 ° C. Then it is diluted with 50 cc of ether and the solution is washed successively with water, ⁿ / io-sodium thiosulfate solution, water and dried over sodium sulfate. After leaving

Claims (1)

Claim: Process for the preparation of organic peroxides of the general formula R ₄ ROO X 60 in which at least one of the radicals R ₁ , R ₂ , R ₃ or R _{4 is} identical or different alkyl, cycloalkyl, aralkyl or aryl radicals and the remaining hydrogen, R is an alkyl, cycloalkyl or aralkyl radical and X is a halogen are an atomic weight of at least 35, characterized in that olefins of the general formula R ₁ R, in the presence of organic hypohalites 5 6 of the general formula BOX with hydroperoxy cycloaliphatic ^ heterocyclic or aromatic converts that of the formula ROOH, in which R, is a radical. R ₁ , R ₂ , R ₃ and R ₄ and X have the above have meaning and B is a primary, secondary publications considered: or preferably a tertiary alkyl radical or a 5 United States Patent Nos. 2,446,797, 2,403,758. © 809 698/562 12.58