RU2021273C1 - Method of synthesis of 2,6-disubstituted 2,4,6,8-tetraazabicyclo[3,3,0]octane-3,7-diones - Google Patents

Abstract

FIELD: organic chemistry. SUBSTANCE: product of the formula where 1a - R-tert. -butyl, m. p. is 347-349 C or 1b - R - phenyl, m. p. is 375-380 C. Structure is confirmed by data of IR-, NMR- and mass-spectrum. Reagent 1: corresponding mono-N-substituted urea. Reagent 2: glyoxal. Reaction conditions: at 85-90 C in the presence of sulfuric acid in the medium of aqueous isopropanol at the definite ratio of reagents. EFFECT: improved method of synthesis. 2 tbl

Description

где R - третбутил или фенилрадикал, относящихся к классу бициклических бисмочевин (ББМ), которые могут найти применение в качестве промежуточных продуктов в синтезе взрывчатых, дезинфицирующих и биологически активных веществ.The invention relates to methods for producing new 2,6-disubstituted 2,4,6,8-tetraazabicyclo 3.3.0 octane-3,7-dione of general formula 1

where R is tert-butyl or phenyl radical, belonging to the class of bicyclic bismoureas (BBM), which can be used as intermediate products in the synthesis of explosive, disinfectant and biologically active substances.

 A known method of producing 2,6-diphenyl-2,4,6,8-tetraazabicyclo [3.3.0] octane-3,7-dione, selected as a prototype, which consists in the fact that the solution contains 0.1 mol of phenylurea, 0.05 mol of 80% crystalline glyoxal and 15 ml of concentrated hydrochloric acid in ethanol are heated with stirring for 2.5 hours until the reaction mass solidifies, the precipitate is filtered off, the filtrate is boiled for another 4 hours until solidification. Both precipitates are combined, recrystallized from cyclohexanone and get the target product with a yield of 22% [1].

 The disadvantages of the described production method include the very low yield of the target product, the presence of two stages in the process of obtaining the target product, the use of a hard-to-reach high boiling solvent of cyclohexanone for purification of the target product.

 The aim of the invention is to increase the yield and expansion of the assortment of the target product and reduce the process time.

Described object is achieved by a process characterized in that glyoxal is reacted with a corresponding mono N-substituted urea in a mixture of water and isopropyl alcohol in a ratio of 10: (3-5) in the presence of sulfuric acid at 85-90 ^{° C} and at a ratio of glyoxal : mono-N-substituted urea: sulfuric acid 0.1: (0.25-0.3) :( 0.1-0.15), then after 2 hours water is added to the hardened reaction mass and the mixture is further incubated for 1 hour at indicated temperature.

 In the described invention, the first obtained 2,6-di- (tert-butyl) -2,4,6,8-tetraazabicyclo [3.3.0] octane-3,7-dione. The structures of the obtained BBMs are proved using the data of elemental analysis, IR, PMR spectra.

PRI me R 1. In a one-necked flask equipped with a reflux condenser, load 37.7 g (0.27 mol) of phenylurea, pour 100 ml of water, 30 ml of isopropyl alcohol and, with shaking, 5.3 ml (0.1 mol, 9.8 g, d = 1.84) sulfuric acid. The flask is heated in a water bath to 85 ^° C and held for 2 hours until the contents of the flask have solidified. Then another 100 ml of water is added, shaken and heated for 1 hour. The hot reaction mass is filtered, the residue is poured with isopropyl alcohol (100 ml) and boiled for 1 hour. The precipitate is filtered off, dried and 25.3 g of 2,6-diphenyl-2,4 are obtained. , 6.8-tetraazabicyclo [3.3.0] octane-3,7-dione (85%).

М = 294,33; Т_пл = 375-380^оС; ИК-спектр, см^-1: 1670 (ν С=0); 3250 (ν NH).

M = 294.33; _Mp = 375-380 ^{° C;} IR spectrum, cm ^-1 : 1670 (ν С = 0); 3250 (ν NH).

 PMR spectrum, ppm: 9.28 C (2H, NH); 7.87-7.47 m (1 OH, Ph); 5.85 s (2H, CH).

 PRI me R 2. As a substituted urea take tert-butylurea 29.1 g (0.35 mol), the synthesis is carried out analogously to example 1 and get 2,6-di- (tert-butyl) -2,4, 6.8-tetraazabicyclo [3.3.0] octane-2,7-dione (80%).

М = 254, Т_пл = 347-349^оС, ИК-спектр, см^-1 ν: 1690 (С=0); 3250 (NH).

M = 254, _mp = 347-349 ^C. IR spectrum cm ^-1 ν: 1690 (C = 0); 3250 (NH).

1 H-NMR spectrum, ppm: 7.28 s (2H, H), 4.75 s (2H, CH), 1.09 s (18H, CH ₃ ).

 Thus, the method for producing 2,6-disubstituted 2,4,6,8-tetraazabicyclo- [3,3,0] octane-3,7-dione in comparison with the prototype contains a number of technical and economic advantages, which are expressed in which increases the yield of target products from 22 to 80-85%, reduces the process time from 6.5 to 3 hours, reduces the staging process. The combination of newly introduced features allows the most economical and efficient synthesis of target BBM.

Claims (1)

METHOD FOR PRODUCING 2,6-DISPLACED 2,4,6,8-TETRAAZABICYCLO [3,3,0] OCTAN-3,7-DIONES of the general formula 1

where R is tert-butyl or phenyl radical,
by the interaction of glyoxal with the corresponding mono-N-substituted urea when heated in the presence of mineral acid, characterized in that, in order to increase the yield and expand the range of the target product and reduce the process time, the interaction is carried out in a mixture of water and isopropyl alcohol in a ratio of 10: (3 - 5) in the presence of sulfuric acid at a temperature of 85 - 90 ^o C and with a ratio of glyoxal: mono - N-substituted urea: sulfuric acid 0.1: (0.25 - 0.3): (0.1 - 0 , 15), then after 2 hours into the hardened reaction mass add add water and additionally incubated for 1 h at the above temperature.

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