SU691446A1 - Method of preparing organic peroxides - Google Patents

Description

one

This invention relates to the field of organic chemistry, specifically to an improved method for producing organic peroxides which are used in the chemical industry.

A known method for producing organic peroxides by a nucleophilic substitution reaction at the carbon center under the action of a peroxide reagent according to the scheme:

R oor

2.2

where X is OH, OVOGON,, H, OR alkyl 1.

This method requires the use of alcohols or their sulfates or alkyl sulfonates as reagents.

The closest in technical essence and the achieved result to the invention is a method of obtaining organic peroxides by the interaction of alkyl bt (bicarbonate and tertiary) or iodide (primary) and peroxide. hydrogen or alkyl hydroperoxide with triofluoroacetate seoeber in an organic solvent medium with ice cooling. 2

The disadvantage of the method is the use of the inaccessible silver trifluoroacetate as a reagent, as well as the preparation of only peroxide compounds of the aliphatic series. The peroxide yields are 38-60%.

The purpose of the invention is to simplify the process of obtaining peroxide compounds, increase the yield of target pro + HX compounds and expand the versatility of the method. .

The goal is achieved by the described method of obtaining organic peroxides of the general formula

20.

(I)

,

where RJ is isopropyl, -butyl or

triphenylmethyl; 25 Rg hydrogen, tert-butyl, dimethyl Cyclohexylmethyl or s.-cumyl,

By the reaction, an organic halide of the general formula 30R- "X (II)

where R has the above meaning;

K is chlorine, bromine or iodine, and peroxides of the general formula

(Iii)

RgOOH,

where R-is as defined above, with a salt of an aliphatic carboxylic acid in an organic sodium benthenium medium, the distinguishing feature of which is that monovalent mercury acetate is used as the salt of an aliphatic carboxylic acid. The reaction proceeds according to the scheme:

2R.X + 2R, jOOH + Nd, (OOSNz) 2 - + 2CHjCOOH +,

where R. is С (СНз) з, СН (СНз) 2 / С (), R is Н, С (СНз)}, С (СН,) 2,.

С (СНз) 2 SbN;

X .- CI, VG / J.

The individual peroxide compounds obtained and their PMR spectra are listed in the table.

Example 1. Synthesis of tertiary butyl peroxide. ,,

In a reactor equipped with a mechanical stirrer and a thermometer, 50 ml of Pentane, 0.1 g-mole {9.0 g) hydroperoxide, -butyl and 0.1 g are placed.

mole (13.7 g) trem-butyl bromistog. The mixture is cooled until it is added with 0.05 g mole (25.9 g) of mono-mercury acetate and mixed for 3-4 hours at room temperature.

. The monovalent bromide precipitate formed. The mercury is filtered off and the acetic acid is neutralized in the filtrate

acid solution of sodium carbonate 1B organic salt is separated and dried

over anhydrous magnesium sulphate. After removal of the solvent, the residue is dispersed with a Y in vacuum (30 mm Hg) and the desired product peroxide, g / 5g-butyl, is isolated at 30 ° C in an amount of 14.7 g, 1.3881, yield 90%.

Example 2. Synthesis of tert-butyl hexahydro-L-cumyl peroxide.

The target product is obtained according to example I from 0.05 g. Mol (8.0 g)

. Hydroperoxides hexahydro-cc cumyl, 0.05 g mol (6.8 g) of methyl bromide / Jer butyl and 0.025 g MOL (13.0 g) of mercury monovalent acetate. Vacuum distillation out 1 are 7.51 g of the desired product, t. Kip. 62-64s (2 mm Hg, 75% yield, 1.4610.

Example 3. Synthesis of tert-butyl-cumyl peroxide. .

The desired product is obtained according to Example 1 from 0.05 (7.6 g) of A-Kumyl hydroperoxide, 0.05 g mol (6.8 g) of methyl bromide / tetbutyl, and 0.025 g. mol (13.0 g) of monovalent mercury acetum. Acetic

the acid is washed with water until it is completely absent. The chain product was vacuum distilled, i.k. 58-60 ° C (2 mm Hg), yield 64%, n d ° 1.4825

PRI me R 4. Synthesis of isopropyl-t / E-butyl peroxide.

The desired product is obtained according to example 1 from 0.15 g mol mol fl3.5 g) hydroperoxide r Jer-butyl, 0.15 g "mol (25.5 g) of isopropyl iodide and 0.75 g mol (39.0 g) of monovalent acetate mercury To shorten the reaction time, 0.2 ml of trifluoroacetic acid was added to the reaction mixture. 10.92 of the desired product were isolated, i.e. bale. 5lc (123 mm Hg), yield 55%.

Example 5. Synthesis of hydroperoxide GuOeg-butyl.

In a reactor equipped with a mechanical stirrer and a thermometer, 50 ml of “absolute ether, 0.05 g-mol (6.8 g) Tfier-butyl bromide, 0.05 g-mol (6 ml) of ethereal hydrogen peroxide solution (with concentration 0.29 g B.1 ml). The mixture is cooled to 7-10 ° C and 0.025 g of mol (13.0 g) of monovalent mercury acetate is added in portions. The stirring is then continued at room temperature. The precipitated bromide monovalent mercury is purified by distillation. In the filtrate, acetic acid is neutralized with sodium bicarbonate solution, the mixture is transferred to a separatory funnel, the organic layer is separated and dried over anhydrous magnesium sulphate. After removal of the solvent, the residue is dispersed under vacuum and the desired product, hydrophoreKHcbT / Jeg-butyl, is isolated at 20 mm Hg, yield 70%.

Example 6. Synthesis of hydroperoxide triphenylmethyl ..

According to Example 5, the desired product is obtained in absolute ether at 20–25 ° C. 0.02 g "hmol (5.56 g) of triphenyl chloromethane, 0.02 g. MOL (2.5 ml) of ethereal plant are taken into the reaction. a thief, (with a concentration of 0.29 GV, 1 ml of solution) and 0.01 g mol (5.2 g) of monovalent mercury acetate. Crystallization from a mixture of ether and pentane isolated 3.96 g of the desired product, triphenylmethyl hydroperoxide, yield 70%, m.p. 82C. :

Claims (2)

From the examples and data in the table it can be seen that the target products are obtained with good yields and a high degree of purity. The use of monovalent mercury acetate as a reagent greatly simplifies the process of obtaining the target products and makes it possible to obtain peroxide compounds with aliphatic, cycloaliphatic and araliphatic radicals. 7 69 Claim of the invention. A method of obtaining organic peroxides of the general formula. 12 . (where R is isopropyl, g is β-butyl or triphenylmethyl; R is hydrogen, tert-butyl, dimethylcyclohexylmethyl or α-ku by reacting an organic halide of the general formula: (where R has the above values, - X. chlorine, bromine or iodine ; and peroxides of the general formula R2OOH, (Ill) 1446 g g e R2. has the above values; with an aliphatic carboxylic acid salt in an organic solvent, characterized in that, in order to simplify the process, increase the yield of the target products and increase the versatility of the method, as an aliphatic salt more .. j, use acetate of single-mercury mercury., f4 Sources of information taken in examination C. Hakkins EJ Organic Peroxides, M., 1964, pp. 19-249. 2. Cobkson P. G., Davies A. G., t, .Roberts B. P, A convenient and 15general preparation of alkyl hydroperoxides and dialkyi peroxides. . j, hem Soc., Chem Cortmun., 1976, p. 24, 1022-3 (prototype).