RU2342370C1 - "method of obtaining n-[1',3',5'-dithiazinan-5'-yl-carbonyl]-1,3,5-dithiazinan-5-carboxamide" - Google Patents

Abstract

FIELD: chemistry, pharmacology.

SUBSTANCE: claimed invention relates to method of obtaining N-[1',3',5'- DITHIZIANAN -5'-YL-CARBONYL]-1,3,5-DITHIAZINAN-5-CARBOXAMIDE, which can find application as selective sorbent and extragent of noble and precious metals. Essence of method lies in interaction of saturated with hydrogen sulfate water solution of formaldehyde with water or alcohol solution of carbamyl urea in molar ratio carbamyl urea: formaldehyde: hydrogen sulfate, equal 1:6:4, at temperature 40-80°C and mixing during 6 hours.

EFFECT: obtaining N-[1',3',5'- DITHIAZAN-5'-YL-CARBONYL]-1,3,5-DITHIAZINAN-5-CARBOXAMIDE with output 56-82%.

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Description

The present invention relates to the field of organic chemistry, and in particular to a method for the synthesis of N- [1 ′, 3 ′, 5′-dithiazinan-5′-yl-carbonyl] -1,3,5-dithiazinan-5-carboxamide of the formula (I) :

The presented compound can be used as a modified selective sorbent of noble and precious metals [Murinov Yu.I., Maistrenko VN, Afzaletdinova NG, Extraction of metals S, N-organic compounds, M., Science, 1993, p 192].

The synthesis of N- [1 ′, 3 ′, 5′-dithiazinan-5′-yl-carbonyl] -1,3,5-dithiazinan-5-carboxamide is not described in the literature.

It is known that heterocyclization based on 1-aroyl-2-phenylacetylenes (II, III) and 1,5-diphenyl-2,4-dithiobiuret proceeds with the formation of 1,3,5-dithiazine (V).

In ice-cold AcOH in the presence of an equimolar amount of BF ₃ · Et ₂ O at 20 ° C, 1-benzoyl- and 1- (2-tenoyl) -2-phenylacetylenes (II, III) interact with 1,5-diphenyl-2,4 -dithiobiuret (III) with the formation of trifluoroborates 2-aroylmethyl-2-phenyl-4,6-bis (phenylimino) -5H-1,3,5-dithiazinium (V) with good yields [Glotova T.E., Protsuk N. I., Albanov A.I. et al., Synthesis of New Derivatives of 1,3,5-dithiazinan, OX, 2003, T.73, Issue 5, pp. 834-838].

The literature describes the thiomethylation reaction of bifunctional ethylenediamine (VI) with the selective formation of predominantly 5- (1,3,5-dithiazin-5-yl) ethyl-1,3,5-dithiazine (VII), the content of which in the reaction mixture at 80 ° C is ~ 90%, along with thiazetidine (VIII) when diamine is mixed with formaldehyde and then the reaction mixture is sparged with hydrogen sulfide [S.R. Khafizova, V.R. Akhmetova, T.V. Tyumkina et al., Izvestiya AN, ser. . Chem., 2005, No. 2, pp. 423-427].

From literature data it is known that aliphatic amides (IX, X) enter into a thiomethylation reaction in the presence of a solution of sodium butylate in butanol with the formation of N-acyl-1,3,5-dithiazinans (XI, XII) [V.R. Akhmetova, PP Khayrullina, S.R. Khafizova et al., RF Patent 2291150 (01.20.2007), B.I. No. 1].

By the above methods, N- [1 ′, 3 ′, 5′-dithiazinan-5′-yl-carbonyl] -1,3,5-dithiazinan-5-carboxamide cannot be obtained.

The objective of the invention is to obtain N- [1 ′, 3 ′, 5′-dithiazinan-5′-yl-carbonyl] -1,3,5-dithiazinan-5-carboxamide by one-reactor condensation of carbamylurea (biuret) with formaldehyde and hydrogen sulfide.

The synthesis is carried out by the interaction of an aqueous or alcoholic solution of carbamylurea with a mixture of hydrogen sulfide-formalin (37%) at a molar ratio of carbamylurea: formaldehyde: hydrogen sulfide = 1: 6: 4, a temperature of 40-80 ° C and constant stirring for 6 hours. Formed N- [1 ′, 3 ′, 5′-dithiazinan-5′-yl-carbonyl] -1,3,5-dithiazinan-5-carboxamide (I), which is a crystalline product with so pl. 85-87 ° C. The yield of heterocycle (I) is 56-82%. The reaction proceeds regioselectively according to the following scheme:

The advantages of the proposed method:

Based on the proposed method, it is possible to selectively obtain N- [1 ′, 3 ′, 5′-dithiazinan-5′-yl-carbonyl] -1,3,5-dithiazinan-5-carboxamide, the synthesis of which has not been previously described in the literature. The proposed method is technologically simple, aliphatic alcohols are used as a solvent, the process does not require energy and toxic waste is not generated. In addition, the implementation of this synthesis paves the way for both solving the environmental problem of using highly toxic hydrogen sulfide and creating new practically useful products.

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EXAMPLE 1. In a glass reactor equipped with a magnetic stirrer, reflux condenser, gas tube and dropping funnel, at a temperature of 40 ° C, 6 moles of formaldehyde are placed (4.31 ml of a 37% aqueous solution), the solution of formaldehyde is saturated with hydrogen sulfide for 30 minutes . At the same time, carbamylurea (1 mol (1 g)) is dissolved in n-butyl alcohol with a ratio of biuret: n-butyl alcohol of 1:10, pinned in a reactor with formalin saturated with hydrogen sulfide and stirred for 6 hours, maintaining the temperature at 40 ° C. The resulting product precipitates in the form of a white powder. After filtration, crystalline N- [1 ′, 3 ′, 5′-dithiazinan-5′-yl-carbonyl] -1,3,5-dithiazinan-5-carboxamide is isolated in 82% yield.

EXAMPLE 2. Analogously to example 1, but ethyl alcohol, a temperature of 40 ° C, is used as a solvent. Crystalline N- [1 ′, 3 ′, 5′-dithiazinan-5′-yl-carbonyl] -1,3,5-dithiazinan-5-carboxamide was isolated in 62% yield.

EXAMPLE 3. Analogously to example 1, but as a solvent using water, a temperature of 80 ° C. Crystalline N- [1 ′, 3 ′, 5′-dithiazinan-5′-yl-carbonyl] -1,3,5-dithiazinan-5-carboxamide was isolated in 56% yield.

Spectral characteristics of N- [1 ′, 3 ′, 5′-dithiazinan-5′-yl-carbonyl] -1,3,5-dithiazinan-5-carboxamide

Yield 82%, mp. 85-87 ° C. IR spectrum, ν / cm ^-1 : 690-750, 995, 1160, 1350-1440, 1580, 1690, 2900, 3300. ¹ H NMR spectrum (δ, ppm, DMSO-d ₆ ): 3.92 s ( 4H, H ^{2.2 '} ); 4.71 s (8H, H ^{4.4 ', 6.6'} ); 6.82 br.s (1H, H ⁸ ). ¹³ C NMR spectrum (δ, ppm, DMSO-d ₆ ): 31.52 t (C ^{2.2 '} ); 63.46 t (C ^{4.4 ', 6.6'} ); 155.74 s (C ^{7.7 '} ). Calculated (%): C, 30.87; H, 4.18; N, 13.50; S, 41.15. C ₈ H ₁₃ N ₃ O ₂ S ₄ . Found (%): C, 31.15; H, 4.39; N, 14.10; S, 41.94.

¹ H NMR spectra were recorded on a Tesla BS-487 spectrometer (100 MHz), ¹³ C NMR spectra were recorded on a Jeol FX 90Q spectrometer (89.55 and 22.50 MHz), internal TMS standard, DMSO-d ₆ solvent. IR spectra were recorded on a Specord 75 IR spectrometer in suspension in liquid paraffin. Elemental analysis of the samples was determined on an Karlo Erba elemental analyzer, model No. 1106. The maximum error of determination is 2.0% rel. For the obtained compound, the melting temperature determined on the RNMK 80/2617 device is shown.

Claims (1)

The method of obtaining N- [1 ′, 3 ′, 5′-dithiazinan-5′-yl-carbonyl] -1,3,5-dithiazinan-5-carboxamide of the formula

consisting in the fact that an aqueous solution of formaldehyde saturated with hydrogen sulfide is subjected to interaction with an aqueous or alcoholic solution of carbamylurea in a molar ratio of carbamylurea: formaldehyde: hydrogen sulfide equal to 1: 6: 4 at a temperature of 40-80 ° C and constant stirring for 6 hours