SU696015A1 - Method of preparing alkyl or cycloalkylaromatic hydrocarbon hydroperoxides - Google Patents

Description

The invention relates to a method for producing hydroperoxides of alkyl or cycloalkyl aromatic hydrocarbons, which can be used for the joint production of phenols and ketones, in the chalcone process for the synthesis of oC-oxides of olefins, as initiators of radical polymerization. Known methods for producing hydroperoxides by the oxidation of aromatic hydrocarbons with oxygen and oxygen-containing gases in the presence of catalysts at 70-140 ° C. As catalysts, variable-valence metal compounds are used, such as a complex of cobalt with alkyls substituted with ammonia derivatives 1, complexes of polytrephthaloyloxalbisamidrazone and polyfumaroyl bisamidaraone with copper, nickel, cerium, cobalt, lead or calcium 2. These catalysts can be used to be abraded (duration of oxidation up to 0.5 h). A disadvantage of the known methods is that the catalyst used decomposes the hydroperoxide formed, which leads to a decrease in the selectivity of the process for the desired product at the production stage and the subsequent recovery of hydroperoxide. Thus, the selectivity of the process for the target product According to these methods does not exceed 85 wt.%. The proposed method is the closest to obtaining hydroaroxides of alkylaromatic hydrocarbons, in particular isopropylbenol, by oxidation of alkylaromatic hydrocarbons, such as isopropylbenzene, with oxygen or air 3. The catalyst is used as an catalyst with an LR of the formula Cjo Hgo (9 f) The process is carried out for 3-10 hours at 80-140 ° C. At this, the hydroperoxide process selectivity reaches 90%. The disadvantages of this method are the relatively low oxidation rate (average rate for the first 3 hours at oxidation of the ligand of the complex catalyst itself, which leads to the need to introduce new portions of the catalyst, and, as a consequence, to the high costs of it. Moreover, the method does not provide a sufficiently high selectivity of the process. is an increase in the selectivity, process, reduction in catalyst consumption and reduction; duration1 of the process. The goal is achieved by the fact that according to this method of producing alkyl or cycloalkylaromatic hydroperoxides in levorods by liquid phase oxidation and corresponding -hydrocarbons with oxygen or oxygen-containing gas — at 80–140 ° C, 1,10 phenanthroline complexes, cc, d, -dipyridyl or 5-NITRO-1,10-phenanthroline complexes, or 1,7-dimethyl-1, are used as catalysts. , 10-phenanthroline, or ct, obc-tripiridyl with salts of alkali or alkaline earth metal carboxylic acids, or beryllium, or magnesium, The catalyst is preferably used in an amount of 10 mol per 1 liter of hydrocarbon. A distinctive feature of the proposed method is the use of the above catalyst in the process. Such a method of producing hydroperoxide allows, in comparison with the known methods, to increase the oxidation rate by 40-50%, which contributes to the intensification of the production of hydroperoxides, and also to increase the selectivity of the process on the target product to 99.6%. The use of a small amount of catalyst and the possibility of its repeated use make the process highly profitable. Example 1. In a selective bubble type reactor, 100 g of cumene is oxidized with air at a flow rate of 0.1 l / min in the presence of naphthene and barium (concentration of 1-10 mol / l and about, o.-dipyridyl {3 10 mol / l ) - and 82.5 s. The initiator is the crossing; - benzoyl (110 mol / l), reaction time 5 hours. Hydroperoxide is separated from the reaction mass distillate K, "Dft-B vacuum, or converted to 30-40% sodium hydroxide solution in the sodium salt, which precipitates. The latter is separated by filtration, washed with pentane, dissolved in water and carbon dioxide is passed through the solution. The liberated free hydroperoxide is extracted with pentane and dried with anhydrous sodium sulfate. After distilling off pentane, a product with a content of cumene hydroperoxide of 98-99% is obtained. The yield of hydroperoxide is 17 wt.%, The selectivity of the process of hydroperoxide is 99.6%. Example 2 The cumene is acidified at 12 OC for 2 hours. The remaining conditions are the same as in Example 1. The yield of hydroperoxide is 35 wt.%, The selectivity is 97.2%. Example 3. In the reactor of Example 1, 100 g of cumene is oxidized. air at a flow rate of 0.1 l / min in the presence of calcium naphthenate (2 10 mol / l) and 1,10-phenanthroline (4 -10 mol / l) at 100 ° C. The initiator is isopropylbenzene hydroperoxide (1 - 10 mol / l). The reaction time is 3 h. The yield of hydroperoxide is 20 wt.%, The selectivity is 98.1%. Examples 4-9. In the reactor box of example 1, 25 g of p-cymol is oxidized with air at a flow rate of 0.0 l / min in the presence of a complex catalyst. The initiator is p-cymol hydroperoxide (510 mol / l). The conditions and the results of the oxidation are given in t abl. Table

-3

100

ten

Magnesium naphthenate

-four

100

ten

Barley naphthenate

-3

100

ten

Also

- b 120

ten

-3 120

Naphthenate 2-10 mg

-four

120

Sodium naphthenate 10

-3

99.2

ten

3-10

-43-10

98

-3

2-10

20.5

96

2 SW

26.5 93 10-3 24.0 94

-four

22.5 94, S

10 Example 10. In the reactor of example 1, 20 g of m-diisopropylbeneol is oxidized by air at a flow rate of 0.14 l / min in the presence of magnesium naphthenate (8-10 mol / l) and 1,10-phenanthroline (1.6-10 mol / l) at. The initiator is dicumyl peroxide (0.04 mol / l). The duration of oxidation 4h. The output of hydroperoxide m-diisopr pilbenzene (in terms of mologidro peroxide) 79 wt.%, The selectivity of 92% Examples 11-21. In the reactor of example 1, 94.4 g of phenyl 0, 5 naphthenate 4-10 1,10-Fe-1-10 are oxidized.

140 calcium nantroNaftenat 1 10 1,10-Fe-I-IO

130 1 strontium nantro-naphthenate 410 To.zhe bari Example 22. In the reactor of example 1, 25 g of p-cymol are oxidized with air at a flow rate of 0.2 l / min in the presence of barium naphthenate (I-IO mol / l) and 1.10 phenanthroline (310 mol / l) at. The oxidation time is 3 hours. The yield of hydroperoxide is 7 wt.%. .0 Selectivity of 99.3%. Example 23, the same as in example 22. Temperature, the yield of hydroperoxide 16.3 wt.%, Selective-. ness 96.5%. 65

Table

96.2

7.3

ling

98.2

6.9

 LINE 2 cyclohexane with air at a flow rate of 0.14 l / min in the presence of a catalyst. The initiator is hydroperoxide of phenylcyclohexane (10 mol / l). Hydroperoxide is separated from the oxidate by transferring its 30-40% sodium hydroxide solution to the sodium salt, from which hydroperoxide is regenerated by carbon dioxide. The output of hydroperoxide 713 wt.%, The selectivity of 96-99%. The results are presented in t abl. 2 6.4-10 Example 24. Same as Example 22. Catalyst sodium benzoate (5 mol / L) and 1,10-phenanthroline (10 mol / L). The output of hydroperoxide 6.7 wt.%. 96% selectivity. - Example 25. m-diisopropyl benzene is acidified in the presence of barium naphthenate (mol / l) and 1,10-phenanthroline (4-10 mol / l) at 90 ° C for -. 8 hours. Hydroperoxide yield 69.2 wt.%. Selectivity of 94.1%. iTurimer 26. The m-diiso propyl benzene is acidified in the presence of calcium naphthenate (1 10 mol / l) and o (., o-di pyridyl (2.10 mol / l) at 100 ° C. Oxidation time 5 The yield of gyroperoxide is 48.4% by weight. Selectivity is 98.3%. Example 27. M-diiso propyl benzene is acidified in the presence of calcium stearate (210 mol / l) and 1,10-phenanethylroline (4-10 mol / l) at .. Initiator - dicumyl peroxide (2 10 mol / l). The oxidation time is 4 h. The yield of m-diisopropyl benzene hydroperoxide (in terms of monohydroperoxide) is 62.4% by weight. Selectivity is 96.8%. Examples 28 -29. In the reactor of example 1, 93.4 g of phenylc are oxidized with clododecane with air at a flow rate of 0.2 l / min at 130 ° C in the presence of a catalyst — beryllium naphthenate (1 10 mol / l) and a heterocycle (2 Yu mol / l). In Example 28 with an oxidation time of 1.8 h and using 5-nitro-1,10-phenanthroline as the heterocycle, the yield of hydroperoxide is 9.4 wt.%, the selectivity is 86.1%, in Example 29 with an oxidation time of 1 hour and using 4,7-dimethyl as the heterocycle The 1,10-phenanthroline hydroperoxide yield was 5.2, the selectivity was 89.4%. Examples 30-31. In the reactor of Example 1, 87.5 g of phenylcyclopentane is oxidized at a flow rate of 0.2 l / min at 130 s in the presence of a catalyst. Table 3