SU209460A1 - Method of producing hydroperoxides of mono- or diisopropylbenzene - Google Patents

Description

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The mono, - or diisopropyl benzenes tidroperexides are intermittent, with the production of phenol, resrrdine, and hydroquinone.

A known method for the preparation of the indicated hydroperoxides in liquid phase oxidation of mono- and diisopropylbenzenes with atmospheric oxygen. At the same time, alkylaromatic -compounds containing one or two carbiol groups, for example dimethylphenylcar: binol, oxyhydroperisp, dicarbinol, are in oxidate as the primary products.

C Zelk) to increase the output of hydroperoxides and to improve their quality, it is proposed hydroxy. dates directly or mixtures obtained: when isolating hydroperoxides from oxidation products I, process in an inert environment; solvent, at a temperature of 10-60 ° C, grow. thieves containing 10-25 wt. o / o jerkeys; si hydrogen, and 10-40 weight. o / ,, mineral; acid.

The oxidation reaction of carbinolv and α-oxygide; roperperoxides to avoid acid races. pada: hydroperoxides should be carried out at: temperature not more than 60 ° C. The optimum temperature of the oxidation reaction, darbinol per: sour hydrogen, depends on the composition of the aqueous phase and, in particular, on the content of the Misseral acid in it -. with an increase in the concentration of mineral acid, it must be reduced. and vice versa.

For carrying out the oxidation reaction with hydrogen peroxide of carbinols and oxyhydroperoxides, a neutral organic solvent is used in which water, sulfuric acid and hydrogen peroxide are practically insoluble and which, under the conditions of the oxidation reaction, do not react with hydrogen peroxide.

As such solvents can be

0 used aromatic hydrocarbons

(for example, benzene, toluene, etc.), chlorinated hydrocarbons (for example, dichloroethane,

carbon tetrachloride, chlorobenzenes

/ and so forth.), as well as various mixtures of the indicated 5 h1d p. of solvents. The products of the oxidation reaction of carbinols. Hydrogen peroxide into the corresponding hydroperoxides, which are in the indicated solvents, can be isolated using aqueous alkali, crystallization or directly in the form of solutions, and

then aim at acid decomposition with

the purpose of obtaining resorcinol or hydroquinone.

Example 1. In a reactor placed in a thermostatic bath and equipped with fur 1) In the case of hydrogenation of oxdate hydrogen peroxide, obtained by oxidation of isopropylbenzene, after the reaction is completed, the hydrocarbon layer is separated from the water, neutralized, freed from hydrogen peroxide and then directed to concentration or directly to acid decomposition.

a stirrer, a thermometer, a reflux condenser, is charged with a solution of dichloroethane containing hydroperoxides L-diisopropyl benzene, wt. / o: monohydroperoxide 0.34, oxyhydrogen dioxide 5.26, dihydroperoxide 6.29.

After the temperature in the reactor was set at 20 ° C, an aqueous solution containing 37.4 wt. about / about sulfuric acid and 19.6 weight. 9 / d of hydrogen peroxide, in such an amount that 3 mol of hydrogen peroxide per 1 mole of oxyhydroperoxide. The reaction is carried out for 5 hours.

Every hour, an emulsion is sampled from the reactor and, after separation from the aqueous layer, the organic solution in the separating funnel is washed with an aqueous solution of sodium bicarbonate from sulfuric acid and hydrogen peroxide and dried with prokalein magnesium sulfate. At the end of the reaction, the contents of the reactor are discharged into a separating funnel and, after separation from the aqueous layer, the organic solution is washed from sulfuric acid and hydrogen peroxide, as described above.

The reaction practically ends in .2 hours. About 94.50 / 0 oxyhydroperoxide, which was in the initial solution of dichloroethane, was converted with hydrogen peroxide to dihydroperoxide. The consumption of hydrogen peroxide was 1.5 mol per 1 jol of oxyhydroperoxide.

Example 2. The original solution of dichloroethane contained hydropokil. L-diisopropylbenzene (in wt. O / o): monohydroperoxide of 0.62, hydroxyperoxide of 5.43, dihydroperexia 6,29. The specified dichloroethane solution is placed in a reactor (see example 1), where it is treated at 25 ° C with an aqueous solution containing (in wt. O / o) sulfuric acid -38.10, hydrogen peroxide 18.83. The aqueous solution is taken in such an amount that 3 mol of hydrogen peroxide was used per 1 mole of oxyhydropere- sion. The reaction time is 2 hours. At the end of the reaction, about 92J / 0 of hydroxy-peroxide, which had been in the initial solution of dichloroethane, was converted into hydrochroperoxide using hydrogen peroxide. The consumption of hydrogen peroxide was 1.37 mol per 1 mol of hydroxypropane.

Example 3. The initial solution of dichloroethane contained g-diisopropylbenzene hydroperoxide (in weight. O /); monohydroperoxide 0.37, oxyhydroperoxide 5.20, dihydroperoxide 6.44.

The dichloroethane solution is placed in a reactor and treated at 40 ° C for 4 hours with an aqueous solution containing (in wt. O / o): sulfuric acid 16.45, hydrogen peroxide 19.92. The aqueous solution is taken in such an amount that about 1 mole of hydrogen peroxide is used per 1 mole of oxyhydroperoxide.

At the end of the reaction 84, oxyhydroperoxide, which was in the initial solution of dichloroethane, was converted by

hydrogen peroxide to dihydroperoxide. The consumption of hydrogen peroxide was 1.02 mol per 1 mol of hydroxyhydroperoxide.

Example 4. The original solution of toluene contained hydroperoxide / and-diisopropylbenzene (in wt.%): Monohydroperoxide 0.07, oxyhydroperoxide 5.20, dihydroperoxide 18.97. The toluene solution is placed in a reactor and treated at 50 ° C for 3.5 hours with a water solution containing (in wt. E / c): sulfuric acid 12.30 and hydrogen peroxide 20.30. The aqueous solution contained hydrogen peroxide at the rate of 2.67 mol per 1 mol of oxyhydroireoxide. At the end of the reaction, 80.5 o / o of oxyhydroperoxide, which was in the initial toluene solution, was converted to dihydroperoxide with hydrogen peroxide. The consumption of hydrogen peroxide was 1.5 mol per 1 mol of hydroxyhydroperoxide.

PRI me R 5. The initial solution of p-diisopropylbenzene contained p-diisopropylbenzene hydroperoxide (in wt. O / p): monohydroperoxide 53.53, oxyhydroperoxide 7.55, dihydroperoxide 0.76. The solution was placed in a reactor and treated at 40 ° C for 3.5 hours with an aqueous solution containing (w / v): sulfuric acid 15.20 and hydrogen peroxide 20.90. The aqueous solution contained hydrogen peroxide in an amount of 3.1 lyl per 1 mol oxyhydroperoxide. At the end of the reaction, the hydrocarbon layer is separated from the aqueous, washed with an aqueous solution of sodium bicarbonate and dried. According to the analysis, the final hydrocarbon solution contained (in wt. O / c): monohydroperoxide 54.89, oxyhydroperoxide 1.82, dihydroperoxide 7.81.

Based on these data, it was determined that 76o / 0 oxyhydroperoxide was converted from

using hydrogen peroxide in dihydroperoxide.

The concentration of monohydroperoxide increased due to the conversion of monocarbinol, which was in the starting mixture, to monohydroperoxide.

Example 6. The product of oxidation of isopropylbenzene with atmospheric oxygen is loaded into the reactor (see Example I). According to chromatographic analysis,

the oxidate had the following composition (in weight. o / c);

isopropyl benzene 68, isopropyl benzene hydroperoxide 29, dimethylphenylcarbinol 2.56,

acetophenone 0.44.

After a constant temperature of 50 ° C was established, the stirrer was started and an aqueous solution containing 16.2 wt. o / sulfuric acid and 19.6 wt. o / o P2O2 in such an amount that the total content of hydrogen peroxide in it

3 times the amount required for the oxidation of dimethylphenylcarbinol to hydroperoxide. The reaction is carried out for 3 hours. At the end of the reaction, the hydrocarbon layer is separated from the aqueous layer and washed with a small amount of sulfuric acid and hydrogen peroxide, dried and analyzed.

The oxidate obtained after treatment with hydrogen peroxide had the following composition (in weight. O / o): isopropylbenzene 67.79, isopropylbenzene hydroperoxide 31.6, acetophenone 0.52, dimethylphenylcarbinol 0.09. Almost all of the dimethylphenylcarbinol {96.6 o / o) contained in it was converted to isopropyl benzene hydroperoxide. The consumption of hydrogen peroxide was 1.2 mol per 1 mol of dimethylphenylcarbinol.

After processing the Original oxidate with an aqueous solution containing hydrogen peroxide, the purified oxidate is concentrated by heating the flask with the oxidate in a nitrogen atmosphere under vacuum, first with a residual pressure of 20 mm Hg. Art., and at the end with a residual pressure of 4 mm Hg. Art. Concentration is performed by slowly raising the temperature of the water bath from 60 to 100 ° C.

A concentrated hyperise was obtained with a content of 98.1o / o of isopropylbenzene hydroperoxide, 0, dimethylphenylcarbinol and 1.00 / 9 acetophenone. With a similar concentration of the starting oxidate, not treated with hydrogen peroxide, a concentrated hyperise was obtained with the content of isopropyl benzene hydroperoxide 89.450 / 0, dimethylphenylcarbinol 9.250 / 0 and acetophenone

1.3 "/ o.

Example 7. The original oxidate contained (in weight. O / o): isopropylbenzene 69,32, hydroperoxide isopropylbenzene 27.7, dimethylphenylcarbinol 2.54, acetophenone 0.44. The oxide is re-baked in the reactor for 4 hours at 40 ° C with an aqueous solution containing 9.83 wt. about / about sulfuric acid and 19,45 weight. about / about hydrogen peroxide. The aqueous solution is taken in such an amount that the total content of hydrogen peroxide in it is 3.3 times higher than the theoretically necessary for the oxidation of dimethylphenylcarbinol to isopropylbenzene hydroperoxide. Upon completion of the reaction, the oxidate is washed with an aqueous solution of sodium bicarbonate and dried.

Purified ox dates have the following composition (in wt. O / o): isopropyl benzene 68.6, hydroperoxide isopropyl benzene 30.25, dimethylphenylcarbinol 0.70, acetophene 0.45.

Thus, after treating the starting oxidate with an aqueous solution containing hydrogen peroxide, 72.5o / o dimethylphenylcarbinol, contained in the starting oxidate, was converted to isopropylbenzene hydroperoxide. The consumption of hydrogen peroxide in this example was 1.05 mol per 1 mol of dimethylphenylcarbinol. The purified oxidate was concentrated under the same conditions as in Example 6. A concentrated hyperis was obtained containing hydroperoxide isopronylbenzene, dimethylphenylcarbinol 2.6E / B and acetophenone 1.4o / o.

In all the following experiments, a water peroxide solution of hydrogen peroxide was taken in such quantities that the total content of hydrogen peroxide in it was 3 times higher than the theoretically necessary for the oxidation of dimethylphenylcarbinol to isopropylbenzene hydroperoxide.

In all experiments at the end of the treatment, the oxidate was washed with an aqueous solution of sodium bicarbonate and dried, after which it was subjected to chromatographic analysis.

Example 8. According to chromatographic analysis, the initial oxidate had the following composition (in wt.%): 1 iso. Pro: p, and l benzene

68.47, isopropylbenzene hydroperoxide 28.72, dimethylphenylcarbinol 2.34, acetophenone 0.47. The oxidate is stirred in the reactor for 11 hours at 10 ° C with an aqueous solution containing 39.6 wt. v / o sulfuric acid and 9.7

weight. 0/0 hydrogen peroxide.

The purified oxidate had the following composition (w / v): isopropyl benzene 68.53, isopropyl benzene hydroperoxide 30.60 dimethylphenylcarbinol 0.40, acetophenone 0.47.

830/0 dimethylphenylcarbinol, which was in the starting oxidate, was converted to isopropylbenzene hydroperoxide. The consumption of hydrogen peroxide, in this example was 1.22 mol per 1 mol of the starting dimethylphenylcarbinol.

Example 9 The starting oxidate was taken up in the same composition as in Example 8. The reactor was stirred for 6 hours at 20 ° C with an aqueous solution containing sulfuric acid and hydrogen peroxide of the same composition as in Example 8.

The purified oxidate had the following composition (w / v): isopropyl benzene 68.60, isopropyl benzene hydroperoxide 30.90, dimethylphenylcarbinol 0.14, acetophenone 0.36, 94o / o dimethylphenylcarbinol, which was present in the starting oxidate, was converted into hydroperoxide from isopropylpropyl, it was converted into hydroperoxide from isopropylcarbinol, converted into hydroperoxide of isopropylcarbinol. . The consumption of hydrogen peroxide was 1.5 mol per 1 mol of the starting dimethylphenylcarbinol.

Example 10. The starting oxidate was taken up as in Example 8 and 9. The oxide was stirred in the reactor for 5 hours at 40 ° C with an aqueous solution containing 9.8

weight. about / c of sulfuric acid and 25.3 wt. o / hydrogen peroxide. The purified oxidate had the following composition (in weight. O / c); isopropyl benzene 68.54, isopropyl benzene hydroperoxide 30.90, dimethylphenylcarbinol 0.21, acetophenone 0.35.

910 / Q of dimethylphenylcarbinol, which was in the starting oxidate, was converted to isopropylbenzene hydroperoxide. The consumption of hydrogen peroxide was 0.9 mol per 1 mol of the starting dimethylphenylcarbinol.

The subject of the image 7. air boron, characterized in that, for the purpose of output and quality of hydroperoxides, oxidation products and directly or mixtures obtained in the isolation of hydroperoxides from oxidation products, co-5 containing alkylaromatic compounds with 8 one or two carbinol groups, are treated in an inert solvent with solutions containing 10-25 weight. about / about hydrogen peroxide and 10-40 weight. o / o mineral acid, for example sulfuric, at temperaura 10-60 ° C.