SU406827A1 - METHOD FOR PRODUCING HALOGEN PRODUCTS OF ACENAFTENHIPONES - Google Patents

Description

one

This invention relates to a process for the preparation of halogen-producing acenaphthenhinoins, e.g., 3-bromocenaphthenquinone, 5,6-dichlorocenated phenoquine, 5-chlorocenated phenequinone, which are used in the synthesis of dyes.

A known method for the preparation of halogen-producing acenaphthenchinoins, for example, 3-bromocephaphenequinone, is that the corresponding halo-derived acephaphthene is oxidized with sodium bichromate in glacial acetic acid. The yield of the desired products is 20-52%.

In order to increase the yield of halogen-producing acenaphthenhiones, a new method has been proposed: the corresponding halogen derivatives of acenaftepap or acenaphthylene are subsequently brominated, dehydrobrominated, brominated, chlorinated, and hydrolyzed with sulfuric acid, followed by separation of the target products by known methods.

The proposed method allows to obtain halogen derivatives of acenaphthenquinones with a yield of 60-85%.

The proposed method can be carried out in a tubular flow-type apparatus, in the first part of which the halogeno-derivative of acenaphthylepa is subjected to vapor-phase oxidation with air on manganese dioxide, in the second part - bromination with an excess of bromine into the cycle. Then the crude reaction product is dehydrobrominated, brominated, chlorinated and hydrolyzed.

Example 1. Preparation of 3-bromoacetaftenhocin.

A. Preparation of 1,2,3, -bromocenaphthleep.

To a 2.31 g (0.01 mol) of 3-bromoacetylene, dissolved in 10 ml of benzene, a solution of 1.6 g (0.01 mol) of bromine in 15 ml of benzene is poured slowly while cooling and moving. The mixture is kept for 15 minutes, and then a hot solution of 0.6 g of potassium hydroxide in 25 ml of ethyl alcohol is added and the mixture is refluxed for 30 minutes.

50 ml of water are poured into the reaction product, shaken vigorously, and after separation, the benzene layer is separated. The benzene layer is washed with water and calcium chloride. The dried benzene solution is filtered off from calcium chloride and the latter is washed with 15 ml of benzene. 2.34 g (50% excess) of bromine in 5 ml of benzene was added to the filtrate and kept for 1 hour. Then the solvent is distilled off, with which all (0.75 g) excess bromine is distilled off. 3.8 g of technical 1,2,3-tribromo-ctenaphthylene are obtained, which, without purification, is used to obtain 1,1,2,2-tetrachloro-3-bromo-phenaphene, m.p. 208-208.5 ° С (from benzene).

Found,%: 37.10, 37.25; H 1.54, 1.31; Br 61.53, 61.71.

CisHsBrs.

Calculated,%: C 37.06; H 1.29; Br 61.64.

B. The resulting 1,1,2,2-tetrachloro-3-bromo-cafaphene.

3.8 g of 1,2,3-tribromoaphthylene is dissolved in 50 ml of carbon tetrachloride and, when cooled to 0 ° C, is chlorinated with dry chlorine to a gain of 1.7 g. After 24 hours, the solvent is removed. 4.8 g of 1,1,2,2-tetrachloro-3-bromo-caenaphthene remain, m.p. 159-159,5 ° С (from benzene). The product without purification can be used for the next step.

Found,%: C 38.78, 38.87; H 1.28, 1.34; the sum of Cl + Br is 59.53, 59.78.

Ci2H5Cl4Br.

Calculated,%: C 38.86; H 1.36; the sum of Cl + Br is 59.77.

B. Hydrolysis of 1,1,2,2-tetrachloro-3-bromo-cafaphene.

PO 4 ml of 90% sulfuric acid is added to 4.3 g of 1,1,2,2-tetrachloro-3-bromo-tsenaphthene and heated vigorously under a boiling water bath for 2 hours, poured into 500 ml of water and taking out the precipitate. after cooling, it is filtered and washed with water. 25 ml of a 40% sodium bisulfite solution, 150 ml of water are added to the precipitate and heated in a water bath to dissolve and then filtered. 25 ml of concentrated sulfuric acid are poured into the filtrate and boiled until the odor of sulfur dioxide is removed. The precipitated 3-bromoacetafteichinone is filtered off and dried. 1.86 g of 3-bromocenaphtenquinone without admixture of 2-bromonaphthalic acid is obtained, which is 70% of the yield from the theory, based on the initial 3-bromoacenefaphthylene.

Found,%: Br 30.47, 30.72.

CiaHsBrOs.

Calculated,%: Br 30.60.

Example 2. Obtaining 5,6-dichloracenaphenequinone

A. Preparation of 1,2-dibromo-5,6-dichloracenaphthylene

To a boiling solution of 2.23 g (0.01 mol) of 5.6 dichlorocenaphthene I in 50 ml of benzene, when illuminated with three incandescent lamps of 200 W each, located symmetrically around the reaction flask at a distance of 80-100 mm from its walls, and A solution of 6.4 g of bromine (0.04 mol) in 10 ml of benzene is added dropwise in vigorous dislocation in 15 minutes. Heat another 15 minutes and cool. The product is not isolated, and the reaction mass is used to obtain 1,1,2,2,5,6-hexachloro-manthaphene. Pure 1,2-dibromo-5,6-dichloracenaphthylene II - orange crystals, t. Nl. 232 234 ° C (from benzene).

Found,%: C 38.15, 37.98; H 0.99, 1.04; (C1 + Br) 60.90, 61.12.

C, 2H., C12VG2.

Calculated,%: C 38.00; H 1.05; (C1 + Br) 60.95.

B. Preparation of 1,1,2,2,5,6-hexachloracenaphthene.

After broaming from the previous operation, 200 ml of benzene was added to the reaction mass to prevent 1,2-dibromo-5,6-dichloracenatethylene from falling out and, at 10-15 ° C, it was chlorinated with dry chlorine to a weight gain of 2.1 g, sealed tightly and left for 48 hours

0 After removal of the solvent, 3.7 g of a colorless crystalline product are obtained, m.p. 123-124 ° C (from alcohol). The product is hydrolyzed without any purification.

Found,%: C 39.70, 39.91; H 1.02, 1.03, 5 Cl 58.94, 59.14.

C, 2H4C1b.

Calculated,%: C 39.89; H 1.11; C1 59.00. B. Hydrolysis of 1,1,2,2,5,6-hexachloroacetate. 50 ml of 90% sulfuric acid are added to 3.7 g of 1,1,2,2,5,6-hexachloroacetylene, and heated for 2 hours with vigorous stirring on a boiling water bath. Poured into 300 ml of water and the precipitated technical 5,6-dichloracenedaphtequinone is filtered off. In order to remove contaminants, it is dissolved in 200 ml of acetic acid, filtered, and the solvent is distilled off. 2.12 g (84.4%) of pure 5,6-dhnloracenaphenenequinone are obtained.

Notice 3. Combined vapor-phase oxide of 5-chloro-centaftene with vapor-phase bromination of the resulting 5-chloro-acetylene.

Catalyst. In a solution of 30 g of manganese nitrate crystallohydrate in 100 ml of water

5, 200 ml of pumice (bulk volume, particles of 2-3 mm) are added and evaporated, with frequent setting dry. Then, hot air is blown through the pumice heated to 250 ° C until complete elimination of the dioxide

0 nitrogen (2 hours).

Installation for combined vapor phase oxidation and bromination. The main unit of the installation is a tubular glass reactor, diameter 14 mm, length 350 mm. Reactor

5 is filled with a catalyst to two thirds of the heated zone, and one third of the heated zone is left as the reaction volume for the reaction of vapor-phase bromination of 5-chloroacetylene, which forms in the first part of the heated zone.

An example of a combined vapor phase oxidation of 5-chloroacene-naphthene with vapor-phase bromination of the resulting 5-chloroacetylenethylene. The temperature of the reactor is 450 ° C, the catalyst volume is 30 ml, the air flow rate: oxidation at 0.63 l / min, the supply of bromine is 0.21 l / min, the reaction time is 9 min. Under these conditions, out of 7.7 g of 5-chloroenazaphthene, 13 g of a dark orange solid reaction product, containing 54.6% of the total halogen, is obtained.

Dehydrobromide. A solution of 1.5 g of potassium hydroxide in 60 ml of alcohol is added to a solution of 5.5 g of the reaction product in 60 ml of benzene and refluxed for 30 minutes,

5, the reaction mass is diluted with water, the benzene layer is separated, dried with calcium chloride and the solvent is removed in air. 4.05 g of solid dehydrobrominated product are obtained.

Bromination A solution of 2.34 g of bromine in 5 ml of benzene is added dropwise to a solution of 2.83 g of the product obtained above in 30 ml of benzene, allowed to stand for 1 hour and the solvent is removed in air. 3.27 g of a solid bromination product — 1,2-dibromo-5-chloroacetylene a.

Chlorination. Dry chlorine to a weight gain of 2.5 g is passed through a solution of 3.25 g of the product obtained after bromination in 40 ml of carbon tetrachloride, and cooling with ice water until it is tightly closed with a stopper and left to stand for 24 hours. The reaction mass is then poured into a cup and the solvent is allowed to evaporate in air. 3.11 g of 1,1,2,2,5-nentachlorocenaphthene are obtained.

Gndroliz. To 2.9 g of the product obtained after chlorination, 66 ml of 90% sulfuric acid are added and heated in a water bath with vigorous stirring for 2 hours. The contents of the reaction flask are poured into 350 ml of cold water, mixed thoroughly and the precipitated precipitate is filtered off. 25 ml of a 40% sodium bisulfite solution are added to it, heated on a water bath for 15-20 minutes, 100 ml of water are added and heated again for 15 minutes. The warm solution is filtered, the filtrate is acidified with sulfuric acid and boiled until the odor of sulfur dioxide is removed. The precipitated 5-chloroacetylene is filtered off, washed with water and dried. 1.36 g of 5-chloroacetaphephequinone is obtained, which is more than 60% of the theory, taken as 5-chlorocenaphthene.

Subject invention

The method of producing halogen-ferrous acenaphthene quinones based on halon derivatives of acenaphthene or acenaphthylene and isolation of the target products by known methods, characterized in that, in order to increase the yield of the target products, the corresponding halopdronasetransferenum or acenaphtilek are sequentially brominated, dehydro-synths, and, in the same way, the patterns and the halogen-boron acenaphthene or acenaphtilek are successively brominated, dehydro-synthane, and the originating groups of the acetaphtenone adenaphene quinone;