Synthesis and biological activity of some novel derivatives of 4-amino-3-(D-galactopentitol-1-yl)-5-mercapto-1,2,4-triazole

To discover new 1,2,4-triazole derivatives which may possess significant biological activities, we synthesized a series of novel 6-aryl-3-(D-galactopentitol-1-yl)-7H-1,2,4-triazolo[3,4-b][1,3,4]thiadiazines and 4-(arylmethylidene)amino-5-(D-galactopentitol-1-yl)-3-mercapto-4H-1,2,4-triazoles from 4-amino-3-(D-galactopentitol-1-yl)-5-mercapto-1,2,4-triazole. All the title compounds were characterized by elemental analysis, IR, 1H- and 13C-NMR. Plant growth-regulating activity tests showed that these compounds have remarkable effects on the growth of radish and wheat.     

Condensed systems based on 4-amino-3-mercapto-1,2,4-triazole

1,2,4-Triazolo[3,4-b]-1,3,4-thiadiazines, hydrazones, and -thio adducts were obtained by reactions of 4-amino-3-mercapto-1,2,4-triazole with -bromoacetophenones, aldehydes, and ,-unsaturated ketones. Conditions that promote the cyclocondensation of the -thio adducts to the previously undescribed 1,2,4-triazolo[3,4-b]-1,3,4-thiadiazepines were found. The chemical and spectral properties of the compounds obtained are discussed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 267–272, February, 1992.     

3-(2-吡啶基)-1,2,4-三唑衍生物的合成

1,2,4-三唑是五员含氮杂环化合物,其五员环上的三个N原子均可以同金属配位,因此它与金属离子的结合力很强,配位方式也很丰富,所构筑出来的配合物在生物、医药、磁性材料、手性催化剂、电致发光材料等方面都存在着诱人的应用前景,因而成为化学界和生物界的研究热点[1-4].     

Synthesis of 3-Azido-5-amino-1,2,4-triazole

3-Azido-5-amino-1,2,4-triazole was obtained from 3,5-diamino-1,2,4-triazole in two ways: by partial diazotization-substitution directly in the substrate or at its primarily nitrosation, and also with the use of direct or indirect protection of an amino group with subsequent conversion into azido compound followed by deprotection.     

Improved syntheses of 5-substituted-4-amino-3-mercapto-(4H)-1,2,4-triazoles

Two improved methods have been developed for the synthesis of 5-substiluted-4-amino-3-mercapto-(4H)-1,2,4-triazoles. One of these involves the direct hydrazinolysis of potassium 3-aroyldithiocarbazates and the other involves ring-opening and reclosure of 5-substituted-2-mereapto-1,3,4-oxadiazoles to the aminomercaptotriazoles. Both of these methods offer advantages over the classic Hoggarth synthesis.     

Synthesis and properties of 2-amino-5-(5-nitro-2-furyl) thiazole derivatives

The hydrochlorides of the corresponding 2-aminothiazoles, which were converted to the free bases, were obtained by hydrolysis of 2-acylamino-5-(5-nitro-2-furyl) thiazoles. Reactions that take place at the amino group of 2-amino-5-(5-nitro-2-furyl)thiazoles are described.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1038–1041, August, 1985.     

Iodocyclization of S-allyl derivatives of 3-mercapto-4-methyl-1,2,4-triazole

It has been established that iodocyclization of 3-(2-methyl-2-propenyl)thio-4-methyl-1,2,4-triazole occurs regioselectively with annelation of the thiazole ring, 3-(3-methyl-2-butenyl)thio-4-methyl-1,2,4-thiazole with annelation of the thiazine ring, and 3-allylthio-4-methyl-1,2,4-triazole with annelation of both rings to form derivatives of [1,3]thiazolo[3,2-b][1,2,4]triazolium and [1,2,4]triazole[5,1-b][1,3]thiazinium iodides.     

Complexes derived from 4-amino-3-methyl-5-thione-1,2,4-triazole and monoorganomercury moieties. Crystal structure of (4-amino-5-mercapto-3-methyl-1,2,4-triazolato)methylmercury(II)

The compounds [HgR(L)] (R = Me or Ph; L = 4-amino-5-mercapto-3-methyl-1,2,4-triazolate) have been prepared and the crystal structure of the methylmercury(II) compound determined. This compound crystallizes in the monoclinic space group P21/n with a = 5.087(1), b = 10.102(1), c = 16.167(2) Å, β = 98.56(1)°, Z = 4 (R = 0.027; R_w = 0.030). It is formed of molecules in which the triazolate anion is bound to mercury strongly via the S atom and weakly via the amine N; there is also a weak intermolecular interaction between the endocyclic N and the Hg atom of a neighbouring unit.     

Synthesis of 1,2,4-triazolo[3,4-b]-1,3,4-thiadiazepines and 4-amino-3-acylvinylthio-1,2,4-triazoles by reaction o acylacetylenes with 4-amino-3-mercapto-1,2,4-triazole

1,2,4-Triazolo[3,4-b]-1,3,4-thiadiazepines have been prepared by treating -acetylenic ketones with 4-amino-3-mercapto-1,2,4-triazole in glacial acetic acid. Terminal acetylenic ketones react with the triazole to form 4-amino-3-acylvinylthio-1,2,4-triazoles. Heating the latter with hydrazine hydrate in alcohol yields substituted pyrazoles.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 990–994, July, 1991.     

Synthesis and Crystal Structure of 1-[(1''-Phenyl-5''-methyl-4''-pyrazolcarbonyl)- 3-methylthio-5-amino-1H-yl-1,2,4-triazole

The crystal structure of 1-[(1'-phenyl-5'-methyl-4'-pyrazolcarbonyl)]-3-methyl thio-5-amino-1H-yl-1,2,4-triazole (C14H14N6OS, Mr = 314.37) has been determined by single-crystal X-ray diffraction analysis. The crystal belongs to triclinic, space group P with a = 8.026(3), b = 8.651(4), c = 11.369(5) (A), α = 89.917(7), β= 89.084(7), γ = 68.470(6)°, V = 734.2(5) (A)3, Z = 2, Dc = 1.422 g/cm3, ( = 0.232 mm-1, F(000) = 328, R = 0.0376 and wR = 0.0890 for 2950 unique reflections. The crystal structure shows the presence of a dimmer with intermolecular N(4)-H(4)…N(3A) hydrogen bonds.     

Complexometric titration of thallium(III), by use of 4-amino-5-mercapto-3-propyl-1,2,4-triazole as replacing reagent

A simple and selective EDTA method using a masking and demasking technique is proposed for the determination of thallium(III). The thallium is complexed with excess of EDTA, the surplus being back-titrated (pH 5-6, hexamine buffer) with zinc sulphate solution (Xylenol Orange as indicator). 4-Amino-5-mercapto-3-propyl-1,2,4-triazole is then added and the mixture heated on a water-bath for 5-10 min to displace EDTA from its thallium complex. The EDTA liberated is titrated with zinc sulphate solution. Reproducible and accurate results are obtained in the range 5-75 mg of thallium with both the relative error and coefficient of variation not exceeding 0.4%.     

Acyl derivatives of 3-amino-1,2,4-triazole

Only 3-acylamino-1,2,4-triazoles were isolated in the acylation of 3-amino-1,2,4-triazole with acid chlorides that contain strong electron acceptor substituents. Acylation takes place in the 2 position when aliphatic and aromatic acid chlorides are used as the acylating agents. The action of methoxy- and ethoxyformyl chlorides leads to the formation of 1- and 2-alkoxycarbonyl-3-amino-1,2,4-triazoles. When N-acyl-3-amino-1,2,4-triazoles are heated, they undergo intermolecular trans-aminoacylation to 3-acylamino-1,2,4-triazoles, which exist in the solid phase in the form of amido and imido tautomers. Under the conditions of massspectroscopic analysis the percentage of the imido form increases as the electronacceptor capacity of the substituent increases.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1414–1419, October, 1980.     

A survey of the lone pair effect on the ring geometry of 1,2,4-triazoles and analogous 1,2,3-triazoles and imidazoles : The structures of 1-methyl-5-amino-3-methylthio-1,2,4-triazole, 1-phenyl-5-amino-3-methylthio-1,2,4-triazole and 1-(4-methylbenzyl)-3-amino-5-methylthio-1,2,4-triazole

The structures of the title compounds have been established by X-ray crystallography from diffractometer data. Crystals of the first (I), C₄H₈N₄S, are monoclinic, space group P2₁/c, with a = 8.166(2), b = 10.481(1), c = 8.585(1) Å, β = 109.33(2)°, Z = 4, D_c = 1.381 g cm⁻³. Crystals of the second (II), C₉H₁₀N₄S, are monoclinic, space group P2₁/c, with a = 11.850(4), b = 7.898(1), c = 23.981 (6) Å, β = 117.23(2)°, Z = 8, D_c = 1.373 g cm⁻³. Crystals of the third (III), C₁₁H₁₄N₄S₁ are also monoclinic, space group P2₁/c with a = 12.829(3), b = 8.348(1), c = 11.088(4) Å, β = 94.40(4)°, Z = 4, D_c = 1.314 g cm⁻³. The structures, determined by direct methods (I, III) and Patterson synthesis (II) were refined to R = 0.039 for 1070 reflections of I, R = 0.040 for 2792 reflections of II and R = 0.041 for 1900 reflections of III. The characteristic features of the planar five-membered rings are studied in comparison with the analogous 1,2,3-triazoles and imidazoles. It is shown that these planar rings exhibit only two patterns of the endocyclic bond angles induced dominantly by the number and relative position of the N-lone pairs. A similar effect of the double bonds (attached to C atoms) is also discussed.     

3,5-二(2-吡嗪基)-4-氨基-1,2,4-三唑的水热合成及晶体结构

1,2,4-三唑及其衍生物作为配体与中过渡金属离子能形成多种配合物,这些配合物可表现出良好的生物活性或特殊的电磁性能.因此,过渡金属的三唑配合物的结构和物理特性引起了人们的广泛关注[1-6].     

3-（2-呋喃基）-4-芳基-1，2，4-三唑啉-5-硫酮的合成及生物活性

1-（2-呋喃甲酰基）-4-芳基氨基硫脲经过环化反应，制备了一系列新的化合 物3-（2-呋喃基）-4-芳基-1，2，4-三唑啉-5-硫酮类化合物，并通过元素分析和 IR，^1H NMR等波谱数据确证了上述化合物的结构。初步的生物活性实验表明其中 有些化合物的具有非常好的植物生长调节活性。     

Synthesis and study of 3-(pyrimidin-2-yl)amino-1(2)H-1,2,4-triazole derivatives

The previously unknown 3-[4(3H)-pyrimidinon-2-yl]amino-1H-1,2,4-triazoles, which were converted to 3-[4-chloro-, 3-(4-ethoxy)-, 3-(4-hydrazinopyrimidin-2-yl)]-amino-2(4)H-1,2,4-triazoles, were obtained by the reaction of 2-nitroamino-4(3H)-pyrimidinones with 3-amino-5-hexyl-1H-1,2,4-triazole. The condensation of the initial products with -diketones gave 3-[4-(1H-pyrazol-1-yl)pyrimidin-2-yl]-amino-2(4)H-1,2,4-triazoles. The IR, UV, and PMR spectra of the synthesized compounds were studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1678–1681, December, 1980.     

Crystal Structure and Spectra Characters of 2-Benzoly-3-(4-(1,2,4-triazole)-5-anilino-thiophene and 2-(4-Methyl-benzoly)-3-(4- chlrolphenyl)-3-(1,2,4-triazole)-5-anilino-thiophene

Triazole derivatives are widely studied, because they represent the largest group of modern fungicides and are widely used both in human and veterinary therapy and in agriculture. We synthesized the title compound in which the thiophene ring was substituted by a 1,2,4-triazole group, a phenacyl group, a phenylaminol group and a benzene ring.