CS239491B1 - Process for the preparation of chlorinated derivatives of nitrodiphenyl ethers - Google Patents

Abstract

The aim of the solution is a method for preparing chlorinated derivatives of nitrodiphenyl ethers by reacting mixtures of salts of chlorinated phenols with benzene derivatives containing one or two -NO groups and one or more chlorine atoms, one of which is in the ortho or para position to the N group of the derivative. The aim was achieved by using a mixture of chlorinated phenols, which has a composition of 4 to 12 wt. % 2-chlorophenol, 1 to 10 wt. % 4-chlorophenol, 75 to 95 wt. % 2,4 dichlorophenol, 0.5 to 3 wt. % of higher chlorinated phenols.

Description

(54) A process for the preparation of chlorinated derivatives of nitrodiphenyl ethers

The object of the present invention is to provide a process for the preparation of chlorinated nitrodiphenyl ethers by reacting a mixture of chlorinated phenol salts with benzene derivatives q containing one or two -NO "and one or more chlorine atoms, one of which is ortho or para to the N group

This was achieved by using a mixture of chlorinated phenols having a composition of 4 to 12% by weight. % Of 2-chlorophenol, 1 to 10 wt. % Of 4-chlorophenol, 75 to 95 wt. 2.4 dichlorophenol, 0.5 to 3 wt. above chlorinated phenols.

O ₂ , in the melt of the reactants and at a temperature of 80 to 160 ° C.

The invention relates to a process for preparing chlorinated derivatives of formula XX nitrodiphenyl _w x <O O- (O

XXY wherein X is a chlorine or hydrogen atom, each of which at least one of them is a chlorine atom, and Y is a nitro group or a chlorine atom or a hydrogen atom, wherein one or two of these substituents are nitro groups which are generally prepared by reaction of the respective chlorinated phenol , respectively. its salts (preferably sodium and / or potassium salts) with benzene derivatives containing one or two nitro groups and one or more chlorine atoms, one of which is ortho or steam to the nitro group, thereby being activated by this group due to its pronounced electronceptor nature to the extent that its nucleophilic substitution by anionic halogenated phenol may occur.

This reaction is carried out in a variety of ways using various reaction media, respectively. in the melt and using various catalysts. According to German Pat. No. 2,626,791 also uses phase transfer catalysts.

The chlorinated nitrodiphenylether derivatives described above serve as semi-finished products for the manufacture of e.g. dyes or insecticides.

In the production of insecticides in particular, chlorination to the diphenylether group is carried out during the synthesis, so that in principle it is not necessary to start from pure phenol halide derivatives for the preparation of such products, but cheaper mixtures of chlorinated phenols or phenol itself can be used.

However, the use of phenol is not possible for the following reasons:

1) The preparation of the respective nitrodiphenyl ethers by the melt process produces dark brown to black products in the form of viscous liquids, not usable for further processing.

2) Using phenol, a good nitrodiphenyl ether can be obtained by reaction in a solvent; however, these reactions proceed considerably slower than melt processes, and there is a need for disadvantageous solvent recovery.

The literature describing the synthesis of chlorinated derivatives of nitrodiphenyl ethers is always based on pure chlorinated phenol derivative. The process, based on a mixture of chlorinated phenol derivatives, is nowhere published or patented, since the mixture of chlorinated nitrodiphenyl ethers thus prepared constitutes eutectics of the nature of viscous liquids, which makes their further processing impossible.

It has now surprisingly been found in the preparation of the halogen derivatives of the nitrodiphenyl ethers of the above formula by melt reaction that it is an object of the present invention to start with a mixture of chlorinated phenols used in the reaction as their salts, preferably Na * and / or K * provided that the mixture contains 4 to 12 wt. % Of 2-chlorophenol, 1 to 10 wt. % Of 4-chlorophenol, 75 to 95 wt. % Of 2,4-dichlorophenols and 0.5 to 3 wt. % of chlorinated phenols, preferably 8 to 9% of 2 chlorophenols, 2 to 6% of 4-chlorophenol, 62 to 90%

% Of 2,4-dichlorophenols and 1 to 2% of the above-chlorinated phenols; a boiling mixture of chlorinated derivatives of nitrodiphenyl ethers which is solid at normal temperature and its melt readily crystallizes or is easily granular.

The aforementioned mixture of chlorinated phenols can be prepared in a conventional manner, preferably directly in a reaction vessel in which it is reacted with an aromatic nitro compound; Phase transfer catalysts can also be advantageously used for the synthesis of the halogenated derivatives described above.

He did

318 g of a 7.1 wt.% Mixture of chlorinated phenols were charged to the vessel. % 2-chlorophenol, 88.2 wt. % 2,4-dichlorophenol, 2.2 wt. % 4-chlorophenol, 1.2 wt. % of chlorinated phenols and 1.3 wt. The mixture is heated to 85 ° C and 145 g of potassium hydroxide 83.8% are slowly added with stirring so that the temperature does not exceed 95 ° C. Thereafter, the reaction mass is heated to 100 ° C and 336 g of 2,5-dichloronitrobenzene are slowly added such that the temperature does not exceed 110 ° C. The reaction mass is then maintained with stirring at a temperature range of 110 to 20 ° C for 4 hours.

Thereafter, the melt of the reacted mass is poured with stirring into hot water and washed several times with hot water to lose a positive reaction to chlorodi in the wash water. By cooling with stirring, the product is granulated and filtered. 443 g of a product having the following composition is obtained:

4,2, 4-trichloro-2-nitrophenyl ether 83.9 wt. 4,2-dichloro-2-nitrophenyl ter 7.6 wt. 4,4-dichloro-2-nitrophenyl ether 2.4 wt. above chlorinated 2-nitrodiphenyl ether 1.1 wt. water 5.0 wt.

Example 2

319.2 g of a 6.1 wt.% Mixture of chlorinated phenols were charged to the vessel. % Of 2-chlorophenol, 89.1 wt. % 2,4-dichlorophenol, 2.0 wt. % 4-chlorophenol, 1.5 wt. % of chlorinated phenols and 1.3 wt. The mixture is heated to 85 ° C and 131.6 g of 85.1% potassium hydroxide are slowly added with stirring so that the temperature does not exceed 100 ° C. Then, 13.5 g of a 50% solution of dodecylbenzyldimethylmonium chloride (Orthosan MB) are added and 384 g of 2,5-dichloronitrobenzene are slowly metered in such a way that the temperature does not exceed 110 ° C.

The reaction mass is then kept under stirring at 20 ° C for 14 hours. The reaction mass is further processed as in Example 1. 521 g of a product having the following composition are obtained:

4,2,4-trichloro-2-nitrodiphenyl ether 87.5 % wt. 4,2-dichloro-2-nitrophenyl ether 6.8 % wt. 4,4-dichloro-2-nitrodiphenyl ter 2.2 % wt. above chlorinated 2-nitrodiphenyl ether >, 4 % wt. water 2.1 % wt.

Example 3

940 g of phenol are charged to the vessel and, at 80 [deg.] C., gaseous sulfur is introduced with stirring for 0 hours so that the weight gain of the reaction mixture is 641 g. 1581 g of a mixture of chlorinated phenols are obtained. 39 g was collected for analysis. The composition of the chlorophane phenol mixture thus obtained is as follows:

8.6 wt. % Of 2-chlorophenol, 83.4 wt. % 2,4-dichlorophenol, 5.2 wt. 4-chlorophenol,

1.5 wt. % of chlorinated phenols and 1.3 wt. below the boiling substances.

The mixture thus obtained was reacted in the same reaction vessel by the same procedure as in Example 2, adding 654.7 g of potassium hydroxide 83.4%, 65.8 g of 50% Orthosan MB and 1872.6 g of 2.5 g. -dichlornitrobenzene. 2 992 g of product are obtained with the following composition:

4,2-4-trichloro-2-nitrodiphenyl ether 4,2-dichloro-2-nitrodiphenyl ether

79.9 wt. 9.3 wt.

239491 4 '´ 4,4-dichloro-2-nitrodiphenylether above chlorinated 2-nitrodiphenylether water

5.6 wt. 1.3 wt. 3.9 wt.

Claims (2)

SUBJECT OF THE INVENTION A process for the preparation of chlorinated nitrodiphenyl ethers of the general formula X XXY wherein X is a chlorine or hydrogen atom, wherein at least one of these atoms is a chlorine atom and Y is an nitro or chlorine atom or a hydrogen atom, wherein one or two of these substituents are nitro groups, by reacting a mixture of salts of chlorinated phenols, preferably sodium and / or potassium, with benzene derivatives containing one or two nitro groups and at least one chlorine atom, one of which is in the ortho or para position to the nitro group, in the melt of the reactants in the product at a temperature of 80 to 160 ° C, optionally % of a phase transfer catalyst, characterized in that a mixture of chlorinated phenols and / or salts thereof of 4 to 12 wt. % 2-chlorophenol, 1 to 0 wt. % 4-chlorophenol, 75 to 95 wt. % Of 2,4-dichlorophenol, 0.5 to 3 wt. % of chlorinated phenols, preferably from 6 to 9 wt. % Of 2-chlorophenol, 2 to 6 wt. % Of 4-chlorophenol, 82 to 90 wt. % Of 2,4-dichlorophenol and 1 to 2 wt. % of chlorinated phenols, optionally containing up to 2 wt. low-boiling substances.