Chemistry of bicyclic ureas. 5. Synthesis of 2,4,6,8-tetraazabicyclo[3.3.0]-3-octanone-7-thiones

Eres'ko, V. A.; Epishina, L. V.; Lebedev, O. V.; Povstyanoi, M. V.; Khmel'nitskii, L. I.; Новиков, С. С.

doi:10.1007/bf00949170

Cited by 10 publications

(13 citation statements)

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“…We also specified the structural factors and found the reaction conditions that favor the formation of 5,7 dialkyl 3 thioxoperhydroimid azo[4,5 e] [1,2,4]triazin 6 ones, 4,5 bis[3 thiosemi carbazido(guanidinoamino)]imidazolidin 2 ones, or 1,3 dialkyl 4 (guanidinoimino)imidazolidin 2 ones. 4,5 Bis(guanidinoamino) 1,3 dimethylimidazolidin 2 one dihydrochloride dihydrate was found to crystallize as a conglomerate.…”

Section: R = H (A) Me (B) Et (C)mentioning

confidence: 99%

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Optimum conditions for the targeted synthesis of 5,7 dialkyl 3 thioxoperhydroimid azo[4,5 e] [1,2,4]triazin 6 ones, 4,5 bis(3 thiosemicarbazido(guanidinoamino))imidazolidin 2 ones, and 1,3 dialkyl 4 (guanidinoimino)imidazolidin 2 ones by α ureidoalkylation of thiosemicarbazide or aminoguanidine were found. A novel conglomerate in the series of imidazolidin 2 one derivatives was detected: 4,5 bis(guanidinoamino) 1,3 dimethylimid azolidin 2 one dihydrochloride dihydrate.

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confidence: 98%

“…Then thiosemicarbazide (0.02 mol) was slowly added in portions for 0.5 h. The reaction mixture was stirred at 70-75 °C for 1 h and kept at 4 °C for 16 h. Crystalline precipi tates of compounds 5b,c that formed were filtered off and re crystallized from MeOH. The yields of 5,7 dimethyl 3 thioxo perhydroimidazo[4,5 e][1,2,4]triazin 6 one (5b) and 5,7 di ethyl 3 thioxoperhydroimidazo[4,5 e][1,2,4]triazin 6 one (5c) were 96 and 90%, respectively.…”

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confidence: 99%

“…The 1 H NMR spectra of products of the second type show signals attributable to bicyclic structures, viz., 5,7 dialkyl 3 thioxoperhydroimidazo[4,5 e] [1,2,4]tri azin 6 ones 5b,c. This assumption is supported by the presence of signals for the protons at the bridgehead methine C atoms (δ 4.61-4.79, AB system) and double signals for the alkyl substituents at the N atoms of the imidazolidine ring.…”

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α-Ureidoalkylation of thiosemicarbazide and aminoguanidine

et al. 2006

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Section: R = H (A) Me (B) Et (C)mentioning

confidence: 99%

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confidence: 98%

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α-Ureidoalkylation of thiosemicarbazide and aminoguanidine

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“…5 Only few examples of the synthesis of glycoluril heteroanalogs by condensation of ureas with 4,5 dihydroxy imidazolidine 2 thiones (DHIT) have been published. 6,7 The present work is devoted to α thioureidoalkylation of urea heteroanalogs (thiosemicarbazide, aminoguani dine, sulfamide, and sulfonamides) with DHIT 8a-c and development of the synthetic methods towards novel imidazolidine 2 thione derivatives.…”

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α-Thioureidoalkylation of urea heteroanalogs

et al. 2009

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α Thioureidoalkylation of urea heteroanalogs such as thiosemicarbazide, amino guanidine, sulfamide, and sulfonamides with 4,5 dihydroxyimidazolidine 2 thiones has been studied. Previously unknown 4,5 bis[thiosemicarbazido(guanidinoamino)]imidazolidine 2 thiones, 5,7 dialkylperhydroimidazo[4,5 e] [1,2,4]triazine 3,6 dithiones, 4,6 diethyl 5(3H) thioxotetrahydro 1H imidazo[4,5 c][1,2,5]thiadiazole 2,2 dioxide, and 1,3 dialkyl 4 [guanidinoimino(arylsulfonylimino)]imidazolidine 2 thiones have been synthesized. Key words: α thioureidoalkylation, thiosemicarbazide, aminoguanidine, sulfamide, 4,5 dihydroxyimidazolidine 2 thiones, 4,5 bis[thiosemicarbazido(guanidinoamino)]imidazol idine 2 thiones, 5,7 dialkylperhydroimidazo[4,5 e][1,2,4]triazine 3,6 dithiones, 4,6 diethyl 5(3H) thioxotetrahydro 1H imidazo[4,5 c][1,2,5]thiadiazole 2,2 dioxide, 1,3 dialkyl 4 [guanidinoimino(arylsulfonylimino)]imidazolidine 2 thiones.α Ureidoalkylation of ureas and their analogs with 4,5 dihydroxyimidazolidin 2 ones have been carefully studied in our laboratories. 1-5 α Ureidoalkylation of thiosemicarbazide, aminoguanidine, and sulfamides yielded 5,7 dialkyl 3 thioxoperhydroimidazo[4,5 e][1,2,4]tri azin 6 ones (1), 2 4,5 bis(thiosemicarbazido) and 4,5 bis (guanidinoamino)imidazolidin 2 ones (2, 3), 2 4 (guani dinoamino) and 4 (sulfonylimino)imidazolidin 2 ones (4-6), 2-4 and 5(3H) thioxotetrahydro 1H imidazo[4,5 c] [1,2,5]thiadiazole 2,2 dioxides (7). 5 Only few examples of the synthesis of glycoluril heteroanalogs by condensation of ureas with 4,5 dihydroxy imidazolidine 2 thiones (DHIT) have been published. 6,7The present work is devoted to α thioureidoalkylation of urea heteroanalogs (thiosemicarbazide, aminoguani dine, sulfamide, and sulfonamides) with DHIT 8a-c and development of the synthetic methods towards novel imidazolidine 2 thione derivatives.Thioureidoalkylation of thiosemicarbazide with DHIT 8a-c under conditions described previously 2 for the syn thesis of compounds 2 (water, pH 2, 80 °C, DHIT : thio semicarbazide = 1 : 2) resulted in 4,5 bis(thiosemi carbazido)imidazolidine 2 thiones 9a-c in 70-75% yields and perhydroimidazo[4,5 e][1,2,4]triazine 3,6 di thiones 10a-c (Scheme 1). Imidazotriazines 10b,c were isolated in 5-15% yields. Together with signals of the main product 9a, the signals that were attributed to com X = S (2), NH 2 + Cl -(3)pound 10a (4.94 and 5.25 (both d, each 1 H, CH-CH, J = 8.5 Hz); 5.69 (br.s, 1 H, NH); 7.29 (br.s, 2 H, 2 NH);

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The Synthetic Challenge of Thioglycolurils

et al. 2014

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The very high stability of cucurbiturils under harsh acidic conditions and their reported prolific chemistry over more than three decades pose a question: why has no thiocucurbituril been reported to date? Furthermore, although glycoluril is a highly stable, easily accessible precursor of all cucurbiturils, its sulfur analog represents a yet unmet synthetic challenge. The reaction between glyoxal and thiourea was found to stop at the level of dihydroxyimidazolidine‐2‐thione, which is quite unstable under various acidic conditions. In an attempt to answer these questions, several stable analogs of thioglycoluril, that is, monothioglycoluril, ditolylthioglycoluril, and its diether derivative were prepared and characterized in the hope that they could be employed as building blocks for the synthesis of thiocucurbiturils. Several side products were also obtained that highlight the complex reactivity of thiourea in these reactions. The crystal structures of the above‐mentioned thioglycolurils are dominated by networks of hydrogen‐bonding interactions. Attempts to co‐oligomerize these compounds with formaldehyde clearly suggest that it is impossible to synthesize thiocucurbiturils by the methods commonly used for the preparation of cucurbiturils. Given that thiocucurbiturils are expected to be stable molecules, alternative synthetic strategies that are different from the thermodynamically controlled approaches must be designed.

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Chemistry of bicyclic ureas. 5. Synthesis of 2,4,6,8-tetraazabicyclo[3.3.0]-3-octanone-7-thiones

Cited by 10 publications

References 6 publications

α-Ureidoalkylation of thiosemicarbazide and aminoguanidine

α-Ureidoalkylation of thiosemicarbazide and aminoguanidine

α-Thioureidoalkylation of urea heteroanalogs

The Synthetic Challenge of Thioglycolurils

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