SU721431A1 - Method of preparing 3,4-bis-(halomethyl)furoxanes - Google Patents

Description

(54) METHOD FOR OBTAINING 3,4BIS (GALOIDMETHYL) FUROXLONS

one

The invention relates to a process for the preparation of 3,4-bis (talondmethyl) furoxanes which can be used as starting compounds for the synthesis of other functional derivatives of furoxanes and for the preparation of polymers with heterocycles in a chain.

A known method for producing di (c-halo-methylmethyl) furoxanes by oxidizing bis ((X-halomethyl) glyoximes with nitrogen oxides in a medium of dry diethyl ether at a temperature of about-5 h3 Sch.

A disadvantage of the known method is the use of a combustible solvent - diethyl ether, which has the most widely used of the most widely used solvents, explosive concentrations in mixture with air. In addition, the use of nitrogen tetroxide in a mixture with ether, as well as in a mixture with other flammable solvents, makes the method even more explosive, which complicates its use under production conditions.

The disadvantages of the method should be OT-V also bear the need for labor-intensive operations to remove excess nitrogen tetroxide.

The chain of the invention is to simplify the process technology by reducing explosion and fire hazards.

This goal is achieved by the described method of obtaining 3,4-bis (halomethyl) furoxans by oxidizing the corresponding bis (halomethyl) glyoximes with bromine or chlorine in the presence of an alkali metal acetate in acetic acid.

The difference of the proposed method is that the oxidation is carried out with bromine or chlorine in the presence of an alkali metal acetate in an acetic acid medium.

Claims (1)

A feature of the use of acetic acid is the freezing in it of the process of replacing the halogen by the acetate group, which occurs in the case of using other organic solvents, such as alcohol. The developed method is non-explosive, easy to use and provides a quantitative yield for mail. Isolation of the product is achieved by simple dilution with water and evacuation of the oil selected therewith. Example 1. 3,4-Bis (bromomethyl) furoxan. , To a solution of 1.80 wt.h sodium acetate in 10 wt. including acetic acid at 20.25 C and stirring powdered 2.74 wt.h. bis (bromomethyl) glyoxime and 1.80 p.w. bromine. Next, the temperature is raised to 35–30 ° C and the reaction mass is maintained for 2–30 minutes. The precipitate is filtered with BaibT, the liquor is diluted with 20 parts by weight. water and separate the heavy liquid. After evacuation, a yellow oil is obtained. Output 2.50 weight.h. (93%), df 1.9192; P 1.5711. Found,%: N 1O, 72 and 1O, 64; Вг 59.04 and- 59.1О. , 02 Bh. Calculated,%: N 10.31; BP 58.8O. IR spectrum, cm-: 1860, 1030j 1110 (-C-Cl: 1350 (-N-0) -, 1615 M-0-N-0 C (CN-); 13 1430, 1485 (-ON-Yu Similar by transferring chlorine to a solution of 1.80 parts by weight of acetate per three to 10 parts by weight of acetic acid and 2.74 parts by weight of bis (bromomethyl) glyoxime, 2.58 parts (95%) of light are obtained. IR liquid spectrometry is identical to that of 3,4-bis- (bromomethyl) furoxan. EXAMPLE 2 3,4-Bis (chloromethyl) furoxan. To a solution of 1.80 parts by weight of sodium acetate in 10 parts by volume of acetic acid, at 2.50 ° C, 1.85 parts by weight of bis (hlrmethyl) glyoxime were added with stirring and 1.80 parts by weight of bromine were added, and then the temperature was raised to 30 -35. and maintain the reaction mass for 2O-30 minutes, the precipitate is filtered, the mother liquor is diluted with 20 parts by weight of water and the liquid is separated, which is evacuated. The yield is 1.73 parts by weight (95%). (1.453 O; 1 , 5322. Found,%: N 14.72; 14.69; Ce 38.51, 38.47 sn, computed%: N 15.29; ce 38.77. IR spectrum, cm : 86О, 1035, -С-С110О II 1618 С (-С -N -1 .. 1435, 1485 (-6-: i- -o, 133S () Similarly, when chlorine is passed into a solution of 1.8 O of weight.h sodium acetate in 1O weight.h. acetic acid and 1.85 weight. including bis (chloromethyl) glyoxime was allocated 1.7 O parts.h. (93.5%) of a yellow oil, the IR spectrum of which is identical to that of 3,4-bis (chloromethyl) furoxan. The invention of the method for producing 3,4-bis (halomethyl) uroxans by the oxidation of bis (halomethyl) glyoximes. It is distinguished by the fact that bromine or chlorine is used as an oxidizing agent in order to simplify the process and acetic acid medium. Sources of information taken into account in the examination 1. Copyright svcetsepstvo USSR № 422736, C O71) 2G1 / O4, published. 1974 (prototype).