RU2039038C1 - Process for preparing dintroso compound - Google Patents

Abstract

FIELD: organic chemistry. SUBSTANCE: preparation is carried out by oxidation of the corresponding p-quinonedioxines with hydrogen peroxide in the presence of sodium tungstate in a hydrochloric acid solution. N-dinitroso toluene and p- dinitrosocimmal are prepared with a yield of 39.3 and 99.0 respectively. EFFECT: more efficient preparation process. 6 tbl

Description

где R H; CH(CH₃)₂ которые могут быть использованы как низкотемпературные вулканизующие агенты для непредельных углеводородных каучуков.The invention relates to the synthesis of organic compounds of the formula

where RH; CH (CH ₃ ) ₂ which can be used as low temperature vulcanizing agents for unsaturated hydrocarbon rubbers.

 A known method of producing n-dinitrosotoluene (p-DNT) and n-dinitrosocimol (p-DNC) by oxidizing the corresponding p-quinondioxime with potassium ferricyanide in an alkaline solution (1).

 The main disadvantages of this method include the fact that ferricyanide and potassium are used as the oxidizing agent, the latter being taken in a 5-fold excess with respect to quinondioxime. The use of potassium ferricyanide makes the industrial production of p-DNT and p-DNTs impossible, since a large amount of cyanides is contained in wastewater.

 In addition, it is difficult to obtain dinitroso compounds of sufficient purity by a known method, since filtration and washing of the product is impossible due to the formation of a fine precipitate.

 The aim of the invention is the creation of a more technological and environmentally friendly method for producing p-DNT and p-DNTs, allowing to teach these products more clean and with high yield.

 This goal is achieved by the fact that p-DNT and p-DNC can be obtained by oxidation of the corresponding p-quinondioximes with a mixture of technical hydrogen peroxide and hydrochloric acid in the presence of a catalyst of sodium tungstate dihydrate.

 PRI me R 1. The resulting p-dinitrosotoluene.

30.4 g (0.2 m) of toluquinondioxime were suspended in 150 ml of water, 0.66 (0.002 m) of sodium tungstate dihydrate, 3 ml of n-butanol and 50 ml (0.6 m) of concentrated hydrochloric acid were added. Then dropwise over 1.5 h. At 40-60 ^{° C} was added 45 mL of 30-35% hydrogen peroxide. After holding at 40-50 ^{° C} for 6 hours, the reaction mixture was filtered, washed with water to neutral pH, and dried in air for 72 hours.

The yield of n-dinitrosotoluene 30.1 (99.5), so pl. 133 ^about C, mp lit. 133 ^about S.

 We give the influence of qualitative indicators to achieve the goal in the oxidation of p-toluquinondioxime with hydrogen peroxide in the presence of sodium tungstate dihydrate in a hydrochloric acid solution.

 Thus, the influence of all factors on the yield of p-dinitrosotoluene is shown.

 Butanol-1 is used as an anti-foaming additive, therefore, the authors believe that it is impractical to study the effect of the amount of butanol-1 on the yield of the target product.

As can be seen from table 1, 2, 3, the optimal conditions for the synthesis of p-dinitrosotoluene from 0.2 mol of p-toluquinondioxime are:
Water 150 ml
Tungsten Dihydrate
sodium mat 0.66 (g / 1 mol.)
Hydrochloric acid
concentrated 50 ml (0.60 M)
Hydrogen peroxide
30-35th solution of 45 ml (0.41 m)
The reaction time is 6 hours

PRI me R 37. Obtaining dinitrosocimol
41.2 g (0.2 m) of thymochonondioxime (0.2 m) were suspended in 200 ml of water, 0.66 g (0.002 m) of 3 ml of n-butanol (to prevent foaming of the reaction mass) and 50 ml (0, 60 m) of concentrated hydrochloric acid. Then dropwise over 1.5 h ave and 40-50 ^{° C} was added 45 mL of 30-35% hydrogen peroxide. After 30 soaking for 4 h at 40-50 ^C. The reaction mixture was filtered, washed with water to neutral pH, and dried in air for 72 hours. Dinitrozotsimola Yield 40.6 g (99%) m.p. 130 ^C. (dec.) M.p. lit. 130 ^C. (dec.).

 We give the effect of quantitative indicators to achieve the goal in the oxidation of thymoquinondioxime by hydrogen peroxide in the presence of sodium tungstate in a hydrochloric acid solution.

 Thus, the influence of all factors on the yield of dinitrosocimol is shown.

As can be seen from. Tables 4, 5, 6, the optimal conditions for the synthesis of dinitrosocimol from 0.2 moles of tikhmohondondioxime are:
water 200
dihydrate vol
sodium fram 0.66 g (1 mol.)
hydrochloric acid
concentrated 50 ml (0.60 M)
hydrogen peroxide
30-35 p. 45 ml (0.41 M)
reaction time 4 hours.

Claims (1)

METHOD FOR PRODUCING N-DINITROSOLLENES of the general formula

where RH, (CH (CH ₃ ) ₂ ,
oxidation of the corresponding n-quinondioximes, characterized in that the oxidation is carried out with a mixture of hydrogen peroxide and hydrochloric acid, taken in a molar ratio of 1.51 in the presence of 1 mol. sodium tungstate dihydrate and at 40 50 ^o C.

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