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D’yachkova, S. G.; Гусарова, Н. К.; Никитина, Е. А.; Ларина, Л. И.; Sinegovskaya, L. M.; Abramov, A. V.; Трофимов, Б. А.

doi:10.1023/a:1013930105593

Cited by 6 publications

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“…The proposed scheme is qualitatively consistent with the results of quantum-chemical calculations of electron density distribution in the molecules of alkylsulfanylchloroacetylenes [7] and 1,1-dimethylhydrazine [12], according to which the sp-hybridized carbon atom linked to chlorine in acetylenes I possesses a positive charge and should undergo nucleophilic attack first. The alkylation of 1,1-dimethylhydrazine should involve the tertiary nitrogen atom which contributes most to the highest occupied molecular orbital.…”

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confidence: 81%

“…Depending on the nucleophile nature and conditions, these reactions could produce not only normal nucleophilic substitution products but also sulfanyl-substituted heterocyclic compounds [1][2][3][4][5][6][7]. Reactions of compounds I with 1,1-dimethylhydrazine (which is a large-scale product of chemical industry) have not been studied so far.…”

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confidence: 99%

“…Compounds IIa and IIb are colorless crystalline substances which are soluble in water, DMSO, and alcohols. The 13 C NMR spectra of tetrazines IIa and IIb contain signals from carbon atoms in the alkylsulfanyl, CH 3 N + , and exocyclic methylene groups (SCH 2 ), and a signal at C 128 ppm which should be assigned to the two magnetically equivalent carbon atoms in the tetrazine ring [7,10,11]. In the 1 H NMR spectra of IIa and IIb we observed signals from protons in the alkylsulfanyl group and two singlets at ~2.7 and 3.6 ppm, which correspond to the SCH 2 and CH 3 N groups, respectively.…”

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Reaction of Alkylsulfanylchloroacetylenes with 1,1-Dimethylhydrazine

et al. 2005

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Alkylsulfanylchloroacetylenes react with 1,1-dimethylhydrazine in diethyl ether at 20-22°C to give, depending on the reactant ratio, 3,6-bis(alkylsulfanylmethyl)-1,1,4,4-tetramethyl-1,4-dihydro-1,2,4,5-tetrazine-1,4-diium dichlorides (yield 67-80%) or 1-[2-(alkylsulfanyl)-1-(2,2-dimethylhydrazono)ethyl]-1,1-dimethylhydrazinium chlorides. The latter readily undergo dequaternization to the corresponding 2-alkylsulfanyl-N 1 ,N 2 ,N 4 -trimethylethanohydrazide hydrazones (yield up to 53%).We previously showed that organylsulfanylchloroacetylenes I react with mono-and polyfunctional nucleophiles according to different pathways. Depending on the nucleophile nature and conditions, these reactions could produce not only normal nucleophilic substitution products but also sulfanyl-substituted heterocyclic compounds [1][2][3][4][5][6][7]. Reactions of compounds I with 1,1-dimethylhydrazine (which is a large-scale product of chemical industry) have not been studied so far. Taking into account the presence of two nucleophilic centers in the molecule of 1,1-dimethylhydrazine and of three electrophilic centers in the molecule of acetylene I (chlorine and two sp-carbon atoms), it was difficult to predict a priori the result of reaction between these compounds.In the present work we were the first to examine reactions of ethylsulfanyl-and isopropylsulfanylchloroacetylenes Ia and Ib with 1,1-dimethylhydrazine with the goal of extending the scope of synthetic applications of organylsulfanylchloroacetylenes, obtaining new data on nucleophilic substitution of halogen at an sp-hybridized carbon atom, and synthesizing new polyfunctional compounds. Prior to our studies, the available information on reactions of haloacetylenes with hydrazine and its derivatives was limited to a brief report on the reactions of perfluoroalkyl-(bromo)acetylenes with hydrazine, which afforded the corresponding 1,2,4,5-tetrazine derivatives [8]. Later, Elokhina et al. [9] showed that the reaction of aryl bromoethynyl ketones with 1,1-dimethylhydrazine gives no nitrogen-containing heterocycles but only products resulting from polymerization and hydrobromination of intermediate ethynylhydrazines.We have found that alkylsulfanylchloroacetylenes Ia and Ib readily react with an equimolar amount of 1,1-dimethylhydrazine in diethyl ether at 20-22°C to RS Cl + 2 Me 2 NNH 2 N N N N Me Me Me Me RS SR IIa, IIb Ia, Ib 2 Cl -2 Scheme 1.

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Reaction of Alkylsulfanylchloroacetylenes with 1,1-Dimethylhydrazine

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“…The reaction course, however, dramatically changed without a base being present. Thus, when the reaction of phenylethynyl‐ λ 3 ‐iodane 1 a (X=OMs) with thiourea (1 equiv) was carried out in dichloromethane at −78→10 °C under nitrogen in the absence of triethylamine, no formation of 2 (R=Ph, R′=NH 2 ) was observed; instead, a hitherto unknown S ‐(phenylethynyl)isothiouronium mesylate 9 ‐MsOH (R=Ph, R′=NH 2 ) was isolated in 82 % yield after repeated decantation with hexane 11. The IR spectrum of this salt showed the characteristic peak of the triple bond at 2180 cm −1 , as well as the strong absorption of the iminium group at 1683 and 1662 cm −1 , whereas the 13 C NMR spectra revealed two peaks of acetylenic carbon atoms at δ =65.8 and 106.6 ppm.…”

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confidence: 99%

Thiazole Synthesis by Cyclocondensation of 1‐Alkynyl(phenyl)‐λ³‐iodanes with Thioureas and Thioamides

2005

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The isolation and intramolecular cyclization of (S)‐(1‐alkynyl)isothiouronium and (S)‐(1‐alkynyl)thiobenzimidonium salts suggest the mechanism for the one‐pot synthesis of 2,4‐disubstituted thiazoles (see scheme; Ms=methanesulfonyl): Michael addition of sulfur nucleophiles to hypervalent iodanes followed by the 1,2‐rearrangement of sulfenyl groups in the resulting alkylidene carbenes.

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“…They represent promising syntones for a targeted synthesis of various S - [1][2][3]; S,Se -; S,P - [4,5], and N,S -containing acyclic and heterocyclic compounds [6][7][8][9][10]. Esters and alkanammonium salts of organylsulfanylacetic acids, which may be easily obtained on the basis of organylthiochloracetylenes, have already manifested themselves as biologically active compounds with antiagregational, cancerostatic, protective, and adaptive properties [11,12].…”

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2-(Alkylthiomethylene)-3,3-dialkyl-1,3-oxazolidinium chlorides: a new class of cancerostatic and antibacterial drugs

et al. 2005

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Organylthiochloracetylenes RSC ≡ CCl (I) exhibit a high reactivity and a great synthetic potential. They represent promising syntones for a targeted synthesis of various S -[1-3]; S,Se -; S,P - [4,5], and N,S -containing acyclic and heterocyclic compounds [6][7][8][9][10]. Esters and alkanammonium salts of organylsulfanylacetic acids, which may be easily obtained on the basis of organylthiochloracetylenes, have already manifested themselves as biologically active compounds with antiagregational, cancerostatic, protective, and adaptive properties [11,12]. New convenient approaches to the synthesis of stable N -(organylthioethynyl)trialkylammonium chlorides have been developed. It was shown that all of them exhibit a broad spectrum of antibacterial activity and a strong antitumor effect both in vitro and in vivo (growth of tumors was suppressed by 82-100%) [13].Developing this new direction in chemistry of polyfunctional derivatives of acetylenes, we studied the reactivity of organylthiochloracetylenes with respect to anionic N -, O -, S -, and Se -nucleophiles; unchanged N -, P -, and S -nucleophiles; and bifunctional N,N -, N,O -, N,S -, and O,S -nucleophiles. In the course of these studies, we developed a convenient method of synthesis of 2-(alkylthiomethylene)-3,3-dialkyl-1,3-oxazolidinium chlorides with an yield of 90-96% and studied their structure [14]. Organylthiochloracetylenes readily react with N -(2-hydroxyethyl)-N,N -(dialkyl)amines in a diethyl ether medium at 20-22 ° C to form 2-(alkylthiomethylene)-3,3-dialkyl-1,3-oxazolidinium chlorides (II). The reaction apparently involves intermediate formation of quaternary in ammonium salts, which were recorded by IR spectroscopy:HO R = C 2 H 5 , R 1 = R 2 = CH 3 (IIa); R = Ì -C 4 H 9 , R 1 = R 2 = CH 3 (IIb); R = Ì -C 4 H 9 , R 1 = R 2 = C 2 H 5 (IIc); R = Ì -C 3 H 7 , R 1 = R 2 = CH 3 (IId); R = C 6 H 5 , R 1 = R 2 = CH 3 (IIe); R = C 2 H 5 , R 1 = CH 3 , R 2 = ë 2 ç 4 éç (IIf); R = Ì -C 3 H 7 , R 1 = CH 3 , R 2 = ë 2 ç 4 éç (IIg); R = R 1 = R 2 = C 2 H 5 (IIh); R = iso -C 4 H 9 , R 1 = R 2 = C 2 H 5 (IIi); R = C 2 H 5 , R 1 = C 4 H 9 , R 2 = ë 2 ç 4 éç (IIj).The 2-(alkylthiomethylene)-3,3-dialkyl-1,3-oxazolidinium chlorides (II) synthesized represented white crystalline hygroscopic compounds, stable when stored in the absence of moist and soluble in water and alcohols. The simplicity of synthesis and high yields (90-98%) allow this reaction to be proposed as a convenient preparative way of obtaining these compounds.Compounds (II) contain pharmacophore groups (the quaternary nitrogen atom, sulfur atom, and the oxazolidinium cycle) and are of interest as potential biologically active compounds. We studied the toxicity, cancerostatic, and antibacterial activity of 2-(alkylthiomethylene)-3,3-dialkyl-1,3-oxazolidinium chlorides (II). The existence of cancerostatic and antibacterial activity of chlorides (II) was not obvious, because data on similar compounds exhibiting antitumor or antimicrobial activity are absent in the literature.Fighting against infectious a...

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Cited by 6 publications

References 6 publications

Reaction of Alkylsulfanylchloroacetylenes with 1,1-Dimethylhydrazine

Reaction of Alkylsulfanylchloroacetylenes with 1,1-Dimethylhydrazine

Thiazole Synthesis by Cyclocondensation of 1‐Alkynyl(phenyl)‐λ³‐iodanes with Thioureas and Thioamides

2-(Alkylthiomethylene)-3,3-dialkyl-1,3-oxazolidinium chlorides: a new class of cancerostatic and antibacterial drugs

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Untitled

Cited by 6 publications

References 6 publications

Reaction of Alkylsulfanylchloroacetylenes with 1,1-Dimethylhydrazine

Reaction of Alkylsulfanylchloroacetylenes with 1,1-Dimethylhydrazine

Thiazole Synthesis by Cyclocondensation of 1‐Alkynyl(phenyl)‐λ3‐iodanes with Thioureas and Thioamides

2-(Alkylthiomethylene)-3,3-dialkyl-1,3-oxazolidinium chlorides: a new class of cancerostatic and antibacterial drugs

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Thiazole Synthesis by Cyclocondensation of 1‐Alkynyl(phenyl)‐λ³‐iodanes with Thioureas and Thioamides