SU1225842A1 - Method of producing 21,25-dinitro-2,3,11,12-dibenz-1,4,7,10,13,16-hexaoxacyclooctadecadien-2,11 - Google Patents

Description

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This invention relates to an improved process for the preparation of 21,25-dinitro-2,3,11,12-dibenz-1,4, 7,10,13,16-hexa-oxacycloooctadedecadien-2,11, (21,25-dinitrodibenz-18 - crown-6), which can be used in the chemical industry as a semi-product in the plastics industry, as well as a catalyst,

The purpose of the invention is to increase the yield of 21,25-.DIN-nitro-2,3,11,12-di6enz 1,4,7,10,13,16-hexa-oxacycloooctadecadiene-2,11,

Example 1. In a 1 L reactor equipped with a stirrer, an addition funnel and a reflux condenser, 18.02 g (0.05 M) of dibenz-18-crown-6 was placed, dissolved in 300 ml of chloroform, then 200 ml of ice was added. acetic acid and 0.66 g (0.0025 M) DHEPEF. While stirring, 8.2 ml (M) of nitric acid (52) are added dropwise to the mixture, kept at room temperature and stirring for 0.5 h, then heated to boiling the mixture and after 4 hours soaking up in these conditions.

Changing these ratios leads to a decrease in the yield of the target product or does not give effect.

17.66 g (78.4 wt.%) of 21.25-dinitrodibenz-18-crown-6 emerge.

After 48 hours, 4.03 g (17.9 wt.%) Of 20.25-dinitrodibenz-18-crown-6 was removed from the filtrate after 48 hours.

The total yield of 96.3 wt.%.

M.p. 21,25-dinitrodibenz-18-kpayn-6 248-254 ° С, and 20,25-dinitro dibenz-18-crown-6 228-232 ° С.

Elemental analysis.

Found,%: C 53.31; H 5.00; N 6.18.

SgoNgg Ao

Calculated,%: C 53.33; H 4.92; N 6.22.

Mol weight 450.40.

IR spectrum: 1140 ("sim-CH,); 1275 (asim Ph-0-CH., -); 1530 weight N-0).

The IR spectra of both isomers are identical in the fingerprint area.

Analogously to Example 1, a series of syntheses was carried out with varying reagent ratios and temperature conditions.

The results of the nitration of dibenz-1B-crown-6 (Kp) are given in Table. one.

Table 1

Example 2, the experimental procedure is similar to that shown in example 1. Unlike the latter, nitration of dibenz-18-crown-6- is carried out in the absence of DHPEP - 3,9-dichloro-2,4,8,10-tetraox-3, 9-diphosphapiro (5.5) undecane.

The yield of 21.25-dinitrodibenz-18-crown-6 is 11.73 g (52.1 wt.), And 20.25-β-dinitrobenz-18-crown-6 is 8.89 g (39.5 wt.% ).

The total yield of 91.6 wt.%.

The structure of the nitration products is confirmed by the data of IR spectroscopy, as well as the data of elemental

analysis and melting point, identical to those shown in example 1

The proposed method allows for the reuse of a mixture of solvents, residual nitric acid and a catalyst.

Example 9. To the filtrate of Example 1, 18.02 g (0.05 M) of dibenz-18-crown-6 was added and then 8.0 ml (0.193 M) of nitric acid (, 52) were added with stirring. Further, the procedure synthesis is similar to example 1.

The yield of 21,25-dinitrodibenz-18-crown-6 is 17.79 g (79.0 wt.%).

The total yield of 97.2 wt.%.

Example 10. The experimental procedure is similar to example 1. In contrast to the latter, the mixture containing the filtrate of. for example 1 and 18.02 (0.05 M) dibenz-18-crown-6, 6 ml (0.145 M) of nitric acid (, 52) are added.

The yield of 21,25-dinitrodibenz-18-crown-6 is 18.03 g (80.1 wt.%). . The total yield of 97.7 wt.%.

Example 11. The experimental procedure is similar to Example 1. Unlike the latter, a mixture containing the filtrate of Example 1 and 18.02 g (0.05 M) of dibenz-18-crown-6 was added 4.0 ml (0.096 M). nitric acid (, 52).

Yield 21,25-dinitrodibenz-18-crown-6 18.20 g (80.8 wt.%).

The total yield of the cx and throne isomer is 98.4 wt.%.

Compiled by

Editor N. Gunko Tehred L, 0 Lane

Order 2101/18 Circulation 379Subscription

VNIIPI USSR State Committee

for inventions and discoveries 113035, Moscow, Zh-35, Raushsk nab., 4/5

Production and printing company, Uzhgorod, st. Project, 4

,

2258424

The physicochemical constants of the target products obtained in Examples 9-11 without further purification are almost identical. At the same time to the last use of the filtrate consumption of nitric acid is reduced by half.

The decrease in the concentration of nitric acid below 80 wt.% Leads to a significant decrease in the yield of the target isomer.

The effect of acid concentration on the yield of isomers is shown in Table. 1 (experimental conditions — molar ratio of reagents, loading sequence, temperature, isolation of isomers, etc., are identical to Example 1, except for the concentration of added nitric acid).

table 2

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15

20

25

thirty

35

40

A decrease in the acid concentration (less than 70%) leads to the appearance of significant amounts of mononitro compounds. Thus, a positive 45 effect is achieved with the use of nitric acid with a density of 1.41 (70 wt.%), Reaching its maximum when using an acid with a density of 1.52 (100 wt.%).

. Kashina

Proof-reader I. Erdeyi

Claims (1)

METHOD FOR PRODUCING 21.25-DINITRO-2,3,11,12-DIBENZ-1,4,7,10,13, 16-HEXAOXACYCLOUCTADECADIENE-2,11 of the formula ο ₂ ν · by the interaction of dibenz-18-crown-6 jc concentrated nitric acid in a medium of chloroform and acetic acid at the boiling point of the reaction mixture, characterized in that, in order to increase the yield of the target product, an acid with a density of 1.41-1.52 is used and the process is carried out in the presence of a catalyst 3,9-dichloro-2 , 4,8,10-tetraoxa-Z, 9diphosphaspiro (5.5 *) undecane with a molar ratio of dibenz-18-crown-6, nitric acid and catalyst equal to 1: (3.5-4.5) (0, 03-0, 1) respectively.