Synthesis and Crystal Structure of 5-Nitro-4-salicylideneamino-3-methyl-1,2,4-triazol-5-thione

The crystal structure of 5-nitro-4-salicylideneamino-3-methyl-1,2,4-triazole-5-thione ([C10H9N5O3S]·HCON(CH3)2, Mr=352.38)(CCDC No. 216094) was determined by the single crystal X-ray diffraction method. The crystal belongs to a triclinic system, the space group is P1 with unit cell constants a=0.6113(2) nm, b=1.0836(4) nm, c=1.3132(5) nm, α=74.523(7)°, β=117.68(3)°, γ= 79.769(7)°, V=0.8245(5) nm3, Z=2, Dc=1.419 g/cm3, μ=0.228 mm-1, F(000)=368, R and wR are 0.0579 and 0.1040, respectively, beasd on 3348 unique reflections of which 1925 reflections were observed[I>2σ(I)]. The results indicate that the title compound can be assigned to the thione tautomeric form rather than the thiol tautomeric form. It contains a five membered triazole ring and a phenyl ring with a dihedral angle of 4.35°. The intermolecular hydrogen bond N3-H3…S1, O1-H1…O4 can be observed.     

Synthesis and Crystal Structure of 4-Salicyli deneamino-3-methyl-1,2,4-triazol-5-thione

1 INTRODUCTION 3-Substituted-4-amino-1,2,4-triazol-5-thione is the key synthon in the formation of heterocyclic compound. As a bifunctional agent, it can react with various electrophilic reagents and its derivatives have been reported to show various biological activities to be employed as fungicide[1], micro- biocide[2, 3], bactericide[4], herbicides[5] and anti in- flammatory agents[6]. Furthermore, 3-substituted-4- amino-1,2,4-triazol-5-thione has potential electron donors. Though ma…     

Synthesis and Crystal Structure of 4-Phenyl-5-(1''''t-butyl-5''''-methyl-4''''-pyrazolyl)-1,2,4-triazol-3-thione

COOEtCOCH3(CH3)2NNHNH2NNCH3OOEtNH2NH2NNCH3ONHNH2PhNCSNNCH3ONHNHCNHSOH-NNCH3NNHNPhS12345 1 INTRODUCTION A large number of 1,2,4-triazole derivatives have been synthesized in recent years[1～4]. Many of them are reported to exhibit broad spectrum biologi-…     

Synthesis and crystal structure analysis of 2-(4-methyl-2′-biphenyl)-4-amino-1,2,4-triazole-3-thiol

The bioactive compound 2-(4-methyl-2′-bip-henyl)-4-amino-1,2,4-triazole-3-thiol, F.W. 282.09 was synthesized, characterized by spectroscopic techniques and confirmed by X-ray crystal structure analysis. The title compound crystallizes in monoclinic class under the space group P2₁/c with cell parameters, a=11.273(3) Å, b=17.245(1) Å, c=7.413(1) Å, β=97.742(5)° and Z=4. The structure exhibits inter-molecular hydrogen bonding of the type N–H···S.     

Synthesis of 4-amino-5-(4,6-diphenyl-2-pyrimidinyl)-3,4-dihydro-2H-1,2,4-triazole-3-thione and its reactions with C-electrophiles

4-Amino-5-(4,6-diphenyl-2-pyrimidinyl)-3,4-dihydro-2H-1,2,4-trazole-3-thione is formed from the reaction of 4,6-diphenylpyrimidinecarboxylic acid or its ethyl ester with thiocarbonyl hydrazide. Alkylation of the product leads to S-alkyl derivaties or 6-substituted 3-(4,6-diphenyl-2-pyriimidinyl)-7H-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazine. Acetylation of 4-amino-5-(4,6-diphenyl-2-pyrimidinyl)-3,4-dihydro-2H-1,2,4-triazole-3-thione gave under different conditions monoacetyl-, diacetyl, and triacetyl derivatives at the amino group and the N₍₂₎ atom, whereas benzoylation gave a benzoyl group at the amino group and 3-(4,6-diphenyl-2-pyrimidinyl)-6-phenyl-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazole. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, 1088–1094, July, 2007.     

Regioselectivity of the monohalogenation of 4-allyl-3-allylamino-1,2,4-triazole-5-thione

The monohalogenation of 4-allyl-3-allylamino-1,2,4-triazole-5-thione has been studied. It was established that the action of bromine and iodine on 4-allyl-3-allylamino-1,2,4-triazole-5-thione at low temperatures leads to selective closure of a thiazoline ring. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 922–926, June, 2007.     

Synthesis of 3‐(Pyridin‐4‐Ylmethyl)‐4‐Substituted‐1,2,4‐Triazoline‐5‐Thione

The reaction of the hydrazide of pyridine‐4‐acetic acid with isothiocyanate gave thiosemicarbazide derivatives respectively. Further cyclization with 2% NaOH led to the formation of 4‐substituted 3‐(pyridin‐4‐ylmethyl)‐1,2,4‐triazoline‐5‐thione and 3‐(pyridin‐4‐ylmethyl)‐1,2,4‐triazoline‐5‐thione. The structures of all new products were confirmed by analytical and spectroscopic methods.     

1-苯基-5-芳基-1,2-二氢-1,2,4-三唑-3-硫酮的合成

将取代苯甲酰氯1a～1f与硫氰酸钾反应, 得到的中间体不需纯化直接与苯肼反应, 成功地合成了1-苯基-5-芳 基-1,2-二氢-1,2,4-三唑-3-硫酮(2a～2f). 化合物2的结构通过红外光谱、核磁共振光谱和高分辨质谱进行了表征.     

Synthesis and Crystal Structure of 5-（p-Toly1）-4- [2-（2,4-dichlorophenoxy）acetamido]-l,2,4- triazole-3-thione Ethyl Acetate Solvate

A novel compound 5-（p-tolyl）-4-[2-（2,4-dichlorophenoxy）acetamido]-1,2,4-tria zole- 3-thione 2a has been synthesized by the reaction of 5-（p-tolyl）-4-amino-1,2,4-triazole-3-thione 1 with 2-（2,4-dich/orophenoxy）acetyl ch/oride. Interestingly, the title compound 2 was obtained when 2a crystallizes from a mixed solution of petroleum ether and ethyl acetate, and it has been characterized by elemental analysis, IR, ^1H NMR spectra and single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space group P1 with a = 9.780（5）, b = 10.876（6）, c = 11.615（6） /A, a = 104.822（7）, β= 94.105（6）, ）, = 94.305（6）°, V= 1185.7（11）/A3, Z = 2,μ = 0.397 mm^-1, Mr= 497.39, Dx= 1.393 g/cm^3, F（000） = 516, S = 1.097, the final R = 0.0730 and wR = 0.2133 for 4111 unique reflections （Rint = 0.0525） with 3212 observed ones. The dihedral angles made by the triazole ring with the methyl- and chloro-substituted benzene rings are 43.5（7） and 50.2（9）°, respectively. Some intra- and intermolecular hydrogen bonds together with C-H…π interactions existing in the lattice stabilize the crystal structure.     

Δ3- and Δ4-1,2,4-oxadiazolin-5- and 3-ones

Preparations for 2,3-diphenyl- and 2-benzyI-3-phenyl-Δ³-1,2,4-oxadiazolin-5-ones (3) and (4) and for 2,5-diphenyl-Δ⁴-1,2,4-oxadiazolin-3-one ( 7 ) are reported.     

5-甲基-1,2,4-三唑-3-硫酮类糖苷化合物的合成及抗菌活性

在KOH/丙酮体系中, 以5-甲基-4-N-取代苯基亚胺/胺基-1,2,4-三唑-3-硫酮为原料, 与溴-α-D-四乙酰葡萄糖进行Kenigs-Knorr反应合成了10个新颖的化合物—5-甲基-4-N-取代苯基亚胺基/胺基-3-S-(2',3',4',6'-四-O-乙酰基-β-D-吡喃葡萄糖基)-1,2,4-三唑(2a~2e, 5a~5e); 并在二氯甲烷/甲醇/甲醇钠混合体系中水解脱除乙酰基, 得到10个新颖的化合物—5-甲基-4-N-取代苯基亚胺基-3-S-(β-D-吡喃葡萄糖基)-1,2,4-三唑(3a~3e)及5-甲基-4-N-取代苯基胺基-3-S-(β-D-吡喃葡萄糖基)-1,2,4-三唑(6a~6e). 化合物的结构均经核磁共振波谱(NMR)、 红外光谱(IR)和高分辨质谱(HRMS)分析确证. 生物活性测试结果表明, 目标化合物对大肠杆菌、 金黄色葡萄球菌、 枯草芽孢杆菌和白色念珠球菌普遍具有较好的抗菌活性. 化合物3d和3e对4种菌株的最小抑菌浓度相对较低, 表现出较强的广谱抗菌活性.     

Synthesis and Crystal Structure of △~6－4－Amino－5，6－diphenyl－5－hydroxy－1，2，4－triaza－cyclohexene－3－thione－monohydrate

ＳｙｎｔｈｅｓｉｓａｎｄＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｏｆ△~６－４－Ａｍｉｎｏ－５，６－ｄｉｐｈｅｎｙｌ－５－ｈｙｄｒｏｘｙ－１，２，４－ｔｒｉａｚａ－ｃｙｃｌｏｈｅｘｅｎｅ－３－ｔｈｉｏｎｅ－ｍｏｎｏｈｙｄｒａｔｅ￥ＬｉｎＺｈｅｎ－Ｇｕａｎｇ；?..     

Synthesis,Characterization and Crystal Structure of the Dimeric Silver(I) Complex containing 4‐Amino‐5‐methyl‐2H‐1,2,4‐triazole‐3(4H)‐thione

The reaction of 4‐amino‐5‐methyl‐2H‐1,2,4‐triazole‐3(4H)‐thione (AMTT, 1 ) with AgNO₃ and triphenylphosphane in a molar ratio 1:1:2 in ethanol led to the dimeric complex {[Ag(AMTT)(PPh₃)₂]NO₃}₂·4EtOH ( 2 ). 2 was characterized by elemental analyses, IR, ³¹P NMR spectroscopy as well as single crystal X‐ray diffraction. Crystal data for 2 at ?80 °C: space group with a = 1265.5(2), b = 1300.9(2), c = 1509.5(2) pm, α = 83.77(2)°, β = 79.22(2)°, γ = 62.89(2)°, Z = 2, R₁ = 0.0330.     

Preparation of 3-Aryl-4-(5-ARYL-Δ2-1,2,4-Oxadiazolin-3-YL)Sydnones and their Conversion into 3-ARYL-4-(5-ARYL-1,2,4-Oxadiazol-3-YL)Sydnones

3-Aryl-4-(5-aryl-Δ²-1,2,4-oxadiazolin-3-yl)sydnones (5) were synthesized in high yields by the reaction of 3-arylsydnone-4-carboxamide oximes (prepared from the corresponding 3-arylsydnone-4-carbonitriles) with aromatic aldehydes in the presence of acid catalysts. No reaction occurred when aliphatic aldehydes were used. The oxadiazolin-3-ylsydnones (5) were easily converted into the corresponding 3-aryl-4-(5-aryl-1,2,4-oxadiazol-3-yl)sydnones by N-bromosuccinimide oxidation. The 3-arylsydnone-4-carbonitrile oxides were synthesized in good yields by N-bromosuccinimide oxidation of the corresponding 3-arylsydnone-4-carboxaldehyde oximes.     

Crystal Structure and DFT Studies of a Triazole Derivative： 4- （ 2-Hydrobenzylideneamino ） -3- （ 1,2,4-triazol-4-ylmethyl） 1H-1, 2,4-triazole-5 （4H） -thione

A novel triazole derivative 4-(2-hydrobenzylideneamino)-3-(1,2,4-triazol-4-ylmethyl)-1H-1,2,4-triazole-5(4H)-thione(1) was synthesized and characterized using elemental analysis, FTIR, and 1H NMR, and its crystal structure was determined via X-ray single crystal diffraction analysis. Crystal data: monoclinic, P2(1)/c, a=0.83335(9) nm, b=1.49777(16) nm, c=1.14724(12) nm, β =107.990(2)°, D=1.470 Mg/m3, and Z=4. The geometries and the vibrational frequencies were determined using the density functional theory(DFT) method at the B3LYP/ 6-31G level. To demonstrate the accuracy of the reaction route of compound 1, one of the important intermediates was also tested using the same method. The structural parameters of the two compounds calculated using the DFT study are close to those of the crystals, and the harmonic vibrations of the two compounds computed via the DFT method are in good agreement with those in the observed IR spectral data. The thermodynamic properties of the title compound were calculated, and the compound shows a good structural stability at normal temperature. The test results of biological activities show that it has a certain bactericidal ability.     

Synthesis and Molecular Structure of New S‐Nucleosides of 5‐(4‐Pyridyl)‐4‐Aryl‐4H‐1,2,4‐Triazole‐3‐Thiols

The synthesis of some new S‐nucleosides of 5‐(4‐pyridyl)‐4‐aryl‐4H‐1,2,4‐triazole‐3‐thiols ( 4a‐n ) is described. Direct glycosylation of ( 4a‐n ) with tetra‐O‐acetyl‐α‐D‐glucopyranosyl bromide in the presence of potassium hydroxide followed by deacetylation using dry ammonia in methanol gave the corresponding 3‐S‐(ñ‐D‐glucopyranosyl)‐5‐(4‐pyridyl)‐4‐aryl‐4H‐1,2,4‐triazoles ( 6a‐n ) in good yields. All the compounds were fully characterized by means of ¹HNMR, ¹³C NMR spectra and elemental analyses. To assist in the interpretation of the spectroscopic data, the crystal structure of 3‐S‐(2′,3′,4′,6′‐tetra‐O‐acetyl‐β‐D‐glucopyranosyl)‐5‐(4‐pyridyl)‐4‐phenyl‐4H‐1,2,4‐triazole ( 5a ) was determined by X‐ray diffraction.     

3-(N-取代苯基-2-乙酰胺基)硫基-4-N-取代邻羟苯基亚胺基-5-甲基-1,2,4-三唑类化合物的合成及生物活性研究

以对称二氨基硫脲为原料,与冰醋酸反应生成5-甲基-4-氨基-1,2,4-三唑-3-硫酮(1);在弱酸性条件下,1与取代水杨醛反应生成席夫碱中间体5-甲基-4-(N-取代邻羟苯基)亚胺基-1,2,4-三唑-3-硫酮(2a～2c);最后在碱性条件下分别与N-取代苯基-2-氯乙酰胺发生烷基化反应生成15种未见报道的目标化合物3-(N-取代苯基-2-乙酰胺基)硫基-4-(N-取代邻羟苯基)亚胺基-5-甲基-1,2,4-三唑(3a～3o),其结构经IR,1H NMR,13C NMR确证.初步生物测试表明,质量分数为0.01%时,3a～3o对白色念珠菌的抑菌率均达90%以上,具有很强的抑菌活性;对金黄色葡萄球菌、大肠杆菌的抑菌率达80%以上,具有较强的抑菌活性.     

PM3 semiempirical study and its comparison with X-ray crystal structure of 2-methyl-4-(4-methoxyphenylazo)phenol

The crystal and molecular structure of 2-methyl-4-(4-methoxyphenylazo)phenol have been determined by X-ray single crystal diffraction technique. The compound crystallizes in the monoclinic space group P2₁/c with a=9.7763(8) Å, b=11.3966(8) Å, c=11.9531(8) Å and β=108.752(6)°. In addition to the molecular geometry from X-ray experiment, its optimized molecular structure has been obtained with the aid of PM3 semiempirical quantum mechanical method, and then the corresponding geometric parameters were compared with those of X-ray crystallography. To determine conformational flexibility and crystal packing effects on the molecules, molecular energy profile of the title compound was obtained with respect to two selected degrees of torsional freedom, which were varied from ?180° to +180° in steps of 10°. Crystal structure of the title compound is a fibroid structure constructed by C–H···O and O–H···N type intermolecular hydrogen bonds. The most favorable conformer of the title compound has been determined by the crystal packing effects and there is no steric hindrance during rotation around the selected torsion angles.     

Study of the Products of Iodocyclization of 4-Allyl-5-phenyl-1,2,4-triazole-3-thione

The interaction of 4-allyl-5-phenyl-1,2,4-triazole-3-thione with iodine proceeds with the formation of a mixture of 6-iodomethyl-3-phenyl-5,6-dihydrothiazolo[2,3-c]-1,2,4-triazole and 6-iodo-3-phenyl-6,7-dihydro-5H-1,2,4-triazolo[3,4-b]-1,3-thiazine. The structures of the cyclization products obtained were established on the basis of the ¹H NMR spectra of their dehydroiodinated derivatives. 6-Methyl-3-phenylthiazolo[2,3-c]-1,2,4-triazole, 3-phenyl-5H-1,2,4-triazolo[3,4-b]-1,3-thiazine, and 3-phenyl-7H-1,2,4-triazolo[3,4-b]-1,3-thiazine are formed on eliminating HI from the cyclization products.