Tautomerism of 1-methyl-5-amino-2,3-dihydro-1,2,4-triazolium-1-alkylidene(or arylidene)-2-methylaminoguanidinium iodide

¹H and ¹³C NMR spectroscopy has been used to examine the structures of the products of the condensation of aldehydes and ketones with 1-methyl-1-aminoguanidinium iodide, which in some instances in solution are involved in a ring-chain tautomeric equilibrium between 1-methyl-5-amino-2,3-dihydro-1,2,4-triazolium iodide and 1-alkylidene(or arylidene)-2-methylaminoguanidinium iodide.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1071–1074, August, 1987.     

Synthesis and Some Reactions of 1-α-Cyanoalkyl(aralkyl)-2-pyrazolines

1-α-Cyanoalkyl(aralkyl)-2-pyrazolines were obtained by the reaction of 1-alkylidene(arylidene)-2-pyrazolinium tetrafluoroborates with metal cyanides. Reduction of the products led to substituted β-aminoalkyl-2-pyrazolines. Hydrolysis of the nitrile groups gave the corresponding substituted acetamides. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, 10, 1558–1565, October 2005.     

Synthesis and ring-chain tautomerism of salts of alkylidene(arylidene) derivatives of amidrazones

A number of salts of alkylidene (arylidene) derivatives of amidrazones was obtained by the reaction of S-methylthioamidium iodides with hydrazones of monocarbonyl compounds. According to the ¹H and ¹³C NMR data, these compounds in solutions are capable of ring-chain tautomerism of the 1-alkylideneamidrazone-1,2,4-triazoline type. The position of the equilibrium is determined chiefly by steric interactions of the substituents attached to the C-N₂ bond.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1264–1267, September, 1982.     

Conversion of 4-amino-4H-1,2,4-triazole to 1,3-bis(1H-azol-l-yl)-2-aryl-2-propanols and 1-phenacyl-4-[(benzoyl or 4-toluenesulfonyl)-imino]-(1H-1,2,4-triazolium) Ylides

A series of 1,3-bis(1H-azol-1-yl)-2-aryl-2-propanols 17 were synthesized in an one-pot procedure by reacting l-aryl-2-(1H-1,2,4-triazol-l-yl)- or l-aryl-2-(1H-imidazol-l-yl)ethanones with dimethylsulfoxonium methide in the presence of either 1,2,4-triazole or imidazole. The aromatic groups in 17 were either 4-bromo-, 4-chloro-, 2,4-dichloro- or 2,4-difluorophenyl. 4-Amino-4H-1,2,4-triazole was acylated with either benzoyl or 4-toluene-sulfonyl chloride to afford [4-(benzoyl or 4-toluenesulfonyl)amino]4H-1,2,4-triazole. Subsequent alkylations with 4-bromo- or 4-chlorophenacyl bromide produced 1-(4-bromo- or 4-chlorophenacyl)-4-[(benzoyl- or 4-toluenesulfonyl)amino]-1H-1,2,4-triazolium bromides. Neutralizations of these salts provided the corresponding ylides.     

Novel synthesis of highly functionalized pyrazolone systems via rearrangement of 5-phenyl-1-oxa-5,6-diazaspiro[2.4]heptane-4,7-diones

Epoxidation of 4-alkylidene(arylidene)-1-phenyl-3,5-pyrazolidinediones using alkaline hydrogen peroxide gave the corresponding 5-phenyl-1-oxa-5,6-diazaspiro[2.4]heptane-4,7-dione derivatives. Their reaction with nucleophilic reagents was investigated. The resulting products depend on the type of the diazaspiro compound and/or the nucleophile used.     

Regioselective synthesis of 5-alkylidene and 5-(iodoalkylidene)-pyrrol-2(5H)-ones by halolactamisation of (2Z,4E)-dienamides and (Z)-alk-2-en-4-ynamides

Stereo- and regioselective synthesis of 5-alkylidene (arylidene) and 5-(iodoalkylidene)-pyrrol-2(5H)-ones was achieved from (2Z,4E)-dienamides and (Z)-alk-2-en-4-ynamides by halocyclisation reaction. Selectivity was found to be highly dependent on the nature of the substituents and on the temperature.     

Synthesis of New 1,4-Benzodioxanуl-1,2,4-triazole Derivatives

The reaction of 5-(1,4-benzodioxan-2-yl)-4H-1,2,4-triazole-3-thiol with N-substituted chloroacetic acid amides obtained by condensation of chloroacetyl chloride with various primary amines furnished a series of S-amidomethyl derivatives. The corresponding thiazolotriazolone prepared from 2-[5-(1,4-benzodioxan-2-yl)-4H-1,2,4-triazol-3-ylthio]acetic acid reacted with aromatic aldehydes to form arylidene derivatives.

     

Reactions of 4-alkylidene (arylidene)-1-phenylpyrazolidine-3,5-dione

Reactions of 4-alkylidene(arylidene)-1-phenylpyrazolidine-3,5-dione with oxidizing (chromium trioxide/acetic acid) as well as with reducing (sodium borohydride/methanol) agents were carried out. Phenylhydrazine reacted with 4-arylidene-1-phenylpyrazolidine-3,5-diones via fission of exo C=C bond to give 1-phenylpyrazolidine-3,5-dione and the corresponding aryl hydrazones. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1335–1341, September, 2007.     

Synthesis and properties of 5-furyl(aryl)-Δ2-1,2,4-triazolines and -Δ2-1,3,4-thiadiazolines. Molecular and crystal structure of 2-acetylamino-5-phenyl-Δ2-1,3,4-thiadiazoline

We show that upon acylation of arylidene amidrazones of 5-nitro-2-furancarboxylic acid, 3-(5-nitro-2-furyl)-²-1,2,4-triazolines or 5-(5-nitro-2-furyl)-1,2,4-triazole are formed (depending on the structure of the arylidene moiety). ²-1,3,4-thiadiazolines are obtained by reaction of thiosemicarbazones of aromatic and furaldehydes and furan ketones. We discuss schemes for closure of the triazolidine, triazole, and thiadiazoline rings. We describe the molecular structure of 2-acetylamino-4-acetyl-5-phenyl-²-1,3,4-thiadiazoline.Kuban State Technological University, Krasnodar 350072. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1337–1344, October, 1994. Original article submitted October 11, 1994.     

2-Methylthio-4,5,6,7-tetrahydro-1,2,4-triazolo[1,5-<Emphasis Type="Italic">a</Emphasis>]pyrimidin-5- and -7-Ones

The cyclocondensation of methylcinnamates and arylidene derivatives of Meldrums acid with 3-amino-5-methylthio-1,2,4-triazole in DMF gives 2-methylthio-4,5,6,7-tetrahydro-1,2,4-triazolo[1,5-a]-pyrimidin-5-ones. The reaction involving arylidene derivatives of Meldrums acid or its synthetic equivalents in ethyl acetate with a catalytic amount of pyridine gives a mixture of 2-methylthio-4,5,6,7-tetrahydro-1,2,4-triazolo[1,5-a]pyrimidin-5- and -7-ones.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 246–251, February, 2005.     

Energetic bicyclic azolium salts

Bicyclic azoles, 2-methyl-5-(imidazol-1-yl)-2H-tetrazole (1), 2-methyl-5-(1,2,4-triazol-1-yl)-2H-tetrazole (4), 1-methyl-5-(imidazol-1-yl)-1H-tetrazole (7), 1-methyl-5-(1,2,4-triazol-1-yl)-1H-tetrazole (10), 1-methyl-4-nitro-2-(imidazol-1-yl)-1H-imidazole (13), and 1-methyl-4-nitro-2-(1,2,4-triazol-1-yl)-1H-imidazole (16) were prepared. Their thermally stable azolium salts, 3, 6, 9, 12, 15, and 18-21, with densities ranging between 1.519-1.674 g cm-3, were synthesized by quaternization with nitric or perchloric acid or with iodomethane followed by metathesis reactions with silver nitrate and silver perchlorate. The structures of 12 b and 21 b were confirmed by single-crystal X-ray analysis. The standard enthalpies of formation for some of the new salts were calculated by using the computationally feasible DFT(B3LYP) and MP2 methods in conjunction with an empirical approach based on densities of salts. The calculated values range from DeltaHdegreef=209.9 (21 a) to 412.3 (12 b) kJ mol-1 in which the experimental densities are >1.515 g cm-3.     

Phase-transfer catalyzed alkylation of pyrazoles and 1,2,4-triazole with cis- and trans-1,4-dichloro-2-butenes

The phase-transfer catalyzed (PTC) alkylation of pyrazoles and 1,2,4-triazole with cis- and trans-1,4-dichloro-2-butenes (DCB) has been examined. The monoalkylation products of pyrazoles with cis-DCB are bicyclic salts formed by intramolecular cyclization of the intermediate cis-1-(4-chloro-2-butenyl)pyrazoles. The corresponding trans-compounds are incapable of cyclization, but on prolonged standing they undergo intermolecular polyquaternization. Both cis- and trans-DCB undergo phase-transfer catalyzed reaction with 1,2,4-triazole to give polymeric quaternary salts. Conditions have been worked out for the dehydrochlorination of 1-(4-chloro-2-butenyl)azoles to 1-(butadien-2-yl)azoles.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 497–503, April, 1989.     

On triazoles XLIX. Synthesis of 5,6‐dihydrothiazolo[3,2‐b]‐[1,2,4]triazol‐2‐yl‐, 6,7‐dihydro‐5H‐[1,2,4]triazolo[5,1‐b][1,3]thiazin‐2‐yl‐, and 5,6,7,8‐tetrahydro[1,2,4]triazolo[5,1‐b] [1,3]thiazepin‐2‐yl‐isoquinolinium salts

5′‐Mercapto‐1′H‐1,2,4‐triazol‐3′‐yl‐isoquinolinium salts (6) were synthesised by the reaction of ortho‐acyl phenylacetones (2) or the corresponding pyrylium salts (3) and 5‐amino‐2,3‐dihydro‐1H‐1,2,4‐triazole‐3‐thione (5) . Treatment of thioles 6 withα,ω‐dibromoalkanes led to type 15, 16 and 17 isoquinolinium salts condensed with thiazole, thiazine and thiazepine rings. When 6 are reacted with dibromomethane (10) 11 type dimeric structures are obtained.     

Reaction of arylidene derivatives of Meldrum's acid with 3-amino-1,2,4-triazole

The condensation of arylidene derivatives of Meldrum's acid with 3-amino-1,2,4-triazole in nitrobenzene leads to 4,5,6,7-tetrahydro-1,2,4-triazolo [1,5-a]pyrimidin-5-ones. In DMF the reaction proceeds with the formation of arylsubstituted N-(2H-1,2,4-triazol-3-yl)-3-(2H-1,2,4-triazol-3-ylamino)propionamides. Ukrainian Research Institute for the Pharmacotherapy of Endocrine Diseases, Kharkov 310002. Kharkov State University, Kharkov 310077, Ukraine     

刚性配体1，3，5-三(1-咪唑基)苯与1，2，4-苯三甲酸构筑的金属配合物：水热合成及晶体结构

由水热法合成了2个配合物[Co(1,2,4-HBTC)(tib)](1)和[Ni4(1,2,4-BTC)2(tib)4(H2O)2]·(1,2,4-HBTC).9H2O(2)(1,2,4-H3BTC=1,2,4-苯三甲酸,tib=1,3,5-三(1-咪唑基)苯),并用元素分析、红外光谱、X-射线单晶衍射及热重分析等对其进行了表征。晶体结构分析结果表明:配合物1是由Co(Ⅱ)和tib连接形成的二维层状结构,1,2,4-HBTC2-作为端基配体与Co(Ⅱ)配位,而配合物2是通过1,2,4-BTC3-连接[Ni(tib)]2+二维网形成最终的二维多层结构,这2个化合物最终均被氢键连接形成三维超分子结构。     

Nonlinear optical and ferroelectric properties of a 3-D Cd(II) triazolate complex with a novel (6(3))2(6(10) x 8(5)) topology

A novel 3-D (3,6)-connected topological architecture, obtained by reacting Cd(ClO4)2 x 6H2O with Htrtr (Htrtr = 3-(1,2,4-triazole-4-yl)-1H-1,2,4-triazole) under solvothermal conditions, presents a non-centrosymmetric polar packing arrangement, resulting in a strong second harmonic generation (SHG) response and ferroelectric property.     

New Derivatives of 3,4-Polymethylene-1,2,4-benzothiadiazine S,S-Dioxides

A new method is proposed for obtaining 3,4-polymethylene-1,2,4-benzothiadiazine 1,1-dioxides by reacting o-halobenzenesulfonamides with lactim ethers. Attempts were undertaken to synthesize quaternary salts of the heterocycles obtained.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 225–229, February, 2005.     

The 1,2,4-triazolyl cation: thermolytic and photolytic studies

The generation of the 1,2,4-triazolyl cation (1) has been attempted by the thermolysis and photolysis of 1-(1,2,4-triazol-4-yl)-2,4,6-trimethylpyridinium tetrafluoroborate (2) and the thermolysis of 1- and 4-diazonium-1,2,4-triazoles, using mainly mesitylene as the trapping agent. Thermolysis of 2 gave mostly 1,2,4-triazole, together with 3-(1,2,4-triazol-4-yl)-2,4,6-trimethylpyridine, 4-(1,2,4-triazol-4-ylmethyl)-2,6-dimethylpyridine, and 4-(2,4,6-trimethylbenzyl)-2,6-dimethylpyridine. Thermolysis of each of the diazonium salts in the presence of mesitylene again gave mainly triazole together with very low yields of 1-(1,2,4-triazol-1-yl)-2,4,6-trimethylbenzene and the corresponding -4-yl isomer in about the same ratio. On the other hand, photolysis of 2 in mesitylene gave mainly 1-(1,2,4-triazol-1-yl)-2,4,6-trimethylbenzene. A photoinduced electron transfer from mesitylene to 2 has been observed and preliminary laser flash photolyses of 2 and the corresponding 2,4,6-triphenylpyridinium salt have been carried out. The observed transients are explained as arising from the first excited states of the pyridinium salts rather than from 1. Ab initio MO calculations are reported and indicate that the predicted electronic ground-state of the triazolyl cation is a triplet state of B1 symmetry with five pi electrons, which corresponds to a diradical cation (1c). Possible mechanisms for the formation of the various products are proposed.     

Investigations in the imidazole series LXXII. Synthesis of naphth[1,2-d]imidazo[3,2-b]-3-thiazolidone and its derivatives

Naphth[1,2-d]imidazo[3,2-b]-3-thiazolidone and its methyl homolog were synthesized by the reaction of 2-mercaptonaphth[1,2-d]imidazole with chloroacetic and -chloropropionic acids with subsequent cyclization of the naphth[1,2-d]imidazole-2-mercaptoacetic acids. The reactions of the first of them at the methylene group with aldehydes, nitroso compounds, and benzenediazonium salts were studied; the corresponding arylidene and azomethine derivatives of naphthimidazo-3-thiazolidone and the arylhydrazones of naphth[1,2-d]imidazo[3,2-b]thiazoline-2,3-dione were obtained. The arylidene derivatives of naphthimidazo-3-thiazolidone were also obtained by the reaction of naphthimidazole-2-mercaptoacetic acid or its methyl ester with aldehydes or (in one step) by the reaction of 2-mercaptonaphth[1,2-d]imidazole with chloroacetic acid and carbonyl compounds.See [1] for communication LXXI.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 399–402, March, 1972.     

Synthesis and reactions of 3-aminothiazolidine-2-thion-4-one derivatives. 2. 3-[R-(Alkylthio)methylene]aminothiazolidine-2-thion-4-ones

3-[R-(Alkylthio)methylene]aminothiazolidine-2-thion-4-ones were obtained by the reaction of 3-aminorhodanine with thioimino ester hydriodides.See [1] for Communication 1.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 199–201, February, 1981.