Synthesis of Derivatives of Pyrazolin-1H-3-ones from 2′-N-Substituted Monohydrazides of Cyclohexenedicarboxylic Acids

2-(6-Aryl-4-methylcyclohex-3-enecarbonyl)-4-ethoxycarbonylpyrazolin-1H-3-ones have been synthesized from 2′-N-(2,2-diethoxycarbonylvinyl)monohydrazides of 6-aryl-4-methylcyclohex-3-ene-1,1-dicarboxylic acids by boiling in DMF, pyridine, or toluene in the presence of potassium carbonate. Under analogous conditions, but without potassium carbonate, 2′-N-substituted hydrazides of cyclohexenecarboxylic acids are obtained. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 1007–1011, July, 2005.     

Unusual amino acids. 5. Synthesis of 3,5-dioxopyrazolidine derivatives

Monohydrazides of 2-R-4-methyl-4-cyclohexene-1,1-dicarboxylic acids react with trifluoroacetic acid anhydride to give 4-substituted 3,5-dioxopyrazolidines, with phosphorus trichloride to give 4-(2-R-5-chloro-4-methylcyclohexane)-3,5-dioxopyrazolidines, and with acetic anhydride to give 4-(2-R-4-methyl-4-cyclohexene)-3,5-diacetoxypryazoles.For Communication 4, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 903–907, July, 2000.     

Synthesis of 1-Acyl-5-amino-4-ethoxycarbonylpyrazoles from Monohydrazides of Cyclohexenedicarboxylic Acids and Ethyl Ethoxymethylenecyanoacetate

Heating monohydrazides of cyclohexenedicarboxylic acids with ethyl ethoxymethylenecyanoacetate at reflux gives the corresponding N-substituted hydrazides. This reaction carried out in pyridine gives 1-acyl-5-amino-4-ethoxycarbonylpyrazoles. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1332–1335, September, 2005.     

1,4-二氢-2,6-二甲基-3,5-吡啶二甲酸二乙酯的合成

用季铵盐作相转移催化剂,在较温和的条件下使乙酰乙酸乙酯与甲醛和氨缩合,合成了1,4－二氢－2,6－二甲基－3,5－吡啶二甲酸二乙酯（DHP）,研究了多种反应因素对产物的影响,提出了合成DHP的最佳工艺条件,投料摩尔比mol乙酰乙酸乙酯：mol六次甲基四胺＝2：1.5,20％（wt％）乙醇水溶液作溶剂,反应温度55℃,反应时间45min,产品收率达88％。     

3,5-吡啶二羧酸镍配位聚合物的合成与晶体结构

采用水热法合成了3个新的3,5-吡啶二羧酸镍配位聚合物[Ni(3,5-Pydc)(H₂O)₄·H₂O]_n(1), [Ni₂(3,5-Pydc)₂(H₂O)₈·(H₂O)₂]_n(2)和[Ni(3,5-Pydc)(H₂O)₂]_n(3), 并通过X射线单晶衍射、FTIR及热重分析对其结构和组成进行了表征. 单晶衍射结果表明, 化合物1和2是一维折线型链状结构, 而化合物3是二维层状结构. 化合物1是由3,5-Pydc配体将中心镍离子连接起来形成的折线型一维链. 在化合物2中存在着两条各自独立的折线型一维链, 但它们的配位方式却完全相同, 每一条链都是由3,5-Pydc配体将镍离子连接而成. 而化合物3则是由3个镍离子和3个3,5-Pydc配体形成的二十元环构成的二维网格. 3个化合物分别通过链间或层间氢键作用(O-H…O)形成三维超分子结构, 化合物1和2中的客体水分子被氢键限域在超分子结构之中.     

Acyl and Sulfonyl Derivatives of 3,5-Diamino-1-R-1,2,4-triazoles

3-Acylamino-5-amino-1-R-1,2,4-triazoles are formed regioselectively on acylating 3,5-diamino-1-R-1,2,4-triazoles with an equimolar amount of anhydrides, carboxylic acid chlorides, and sulfonyl chlorides. With an excess of anhydride and carboxylic acid chloride 3,5-diacylamino-1-R-1,2,4-triazoles are formed. 3-Acylamino-5-amino-1-R-1,2,4-triazoles do not interact with sulfonyl chlorides. The higher reactivity of the 3-amino group towards acylating agents is determined by electronic and not steric factors. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1342–1350, September, 2005.     

Synthesis and Crystal Structure of Glycin·3,5-Dihydroxybenzoic Acid

The title compound glycin·3,5-dihydroxybenzoic acid (GDB) has been synthesized and characterized by single-crystal X-ray analysis. It crystallizes in orthorhombic, space group Pca21 with a = 25.513(10), b = 4.668(2), c = 9.150(4)(A), Z = 4, V = 1089.8(8)(A)3, C9H13NO7, Mr = 247.20, Dc = 1.507 g/m3, μ(MoKα) = 0.132 mm-1, F(000) = 520, R1 = 0.0322 and wR2 = 0.0611 for 885 observed reflections (I > 2σ(I)). The title compound is a 1:1 molecular complex of glycin and 3,5-dihydroxybenzoic acid, which is linked by O-H…O and N-H…O hydrogen bonds to form a three-dimensional framework. Test of SHG (second harmonic generation) indicates that NLO generation of the crystal is higher than that of KDP.     

Synthesis of New Substituted 4-Amino-3,5-dinitropyridine Derivatives

Facile synthetic routes for the preparation of some new 4-amino-3,5-dinitropyridine derivatives have been revealed. Nitration of 2-chloropyridin-4-amine （1） as a starting material, in an unexpected one-step reaction, to give dinitrated derivatives, followed by nucleophilic substitution reactions with sodium azide, potassium fluoride, ammonia, methylamine, and 4-nitroimidazol, respectively, gave substituted 4-amino-3,5-dinitropyridine derivatives. Meanwhile, its azide derivative underwent a ring closure conversion into 7-amino-6-nitro-[1,2,5]oxadiazolo[3,4-b]- pyridine-1-oxide. It is of significance that all of the nucleophilic substitution reactions were carried out under mild conditions.     

The quasi-symmetric OHN and ODN bridges in the adducts of 3,5-dimethylpyridine with 3,5-dinitrobenzoic acid

The crystal structure of the adduct of 3,5-dimethylpyridine and 3,5-dinitrobenzoic acid (DMP-DNB) has been determined at room temperature and 80 K for both undeuterated and deuterated compounds. The monoclinic crystals are isomorphous, space group P2₁/c and Z = 4. Very strong OHN hydrogen bonds are almost linear with fully disordered (1:1) bridge hydrogen atoms between oxygen and nitrogen atoms. This is well reflected in the difference in electron density maps the contours of which depend both on cooling and deuteration. The intramolecular hydrogen bond lengths are 2.550(2) Å for the (OHN) and 2.563(2) Å for (ODN) at room temperature and 2.529(2) Å for (OHN) and 2.531(2) Å for (ODN) at 80 K. Therefore, there is a small but meaningful isotope effect upon the O…N hydrogen bridge length at room temperature and no Ubbelohde isotope effect is observed at 80 K. The infra-red spectra show very broad stretching protonic bands in the 200–1600 cm⁻¹ range. The isotopic ratio v(H)/v(D) at room temperature is about 1.1.     

Convenient Solid-phase Synthesis of Benzothiazole Derivatives

Resin-bound cyclic malonic ester 1 reacted with aryl isothiocynate, then was treated with bromine, followed by cleavage from the resin under perchloric acid to give benzothiazoles 4.     

Synthesis and properties of lanthanide(III) complexes with 4-hydroxy-3,5-dimethoxybenzoic acid

Complexes of yttrium(III) and lanthanides(III) with 4-hydroxy-3,5-dimethoxybenzoic (syringic) acid were obtained as solids with metal to ligand mole ratio of 1: 3. The compounds were characterized by elemental analysis, IR spectroscopy, X-ray diffraction patterns, solubility, and thermal studies. The complexes are sparingly soluble in water and stable at room temperature. Compounds of light lanthanides (from La to Nd) are hydrated and they crystallize in a triclinic system. When heated, they lose water molecules in one step and in the next step they decompose to oxides. Complexes of yttrium and other lanthanides are anhydrous and crystallize in a monoclinic system. They are stable up to 300°C and then decompose to oxides. As the coordination number of lanthanide ions is usually equal to 9 or 8, one can suppose that hydroxy or methoxy groups take part in the coordination of these metal ions.     

Synthesis of N′-cyclohexenecarbonyl-substituted hydrazides of 2-aminobenzoic acids and preparation of 3-cyclohexenyl-amido-1,2-dihydroquinazolin-4-ones based on them

N′-Cyclohexenecarbonyl-substituted hydrazides of 2-aminobenzoic acids were obtained from the reaction of isatoic anhydride with monohydrazides of cyclohexenedicarboxylic acid. Reaction of the 2-aminobenzoic acid hydrazides with substituted benzaldehydes gave 3-cyclohexenylamido-1,2-dihydroquinazolin-4-ones. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, 894–898, June, 2007.     

Synthesis of 3,5-Diaryl-4-benzylideneamino-1,2,4-triazoles and 4-Amino-3,5-diaryl-1,2,4-triazoles

A one-pot reaction leading to 3,5-diaryl-4-benzylideneamino-1,2,4-triazoles is described, the key step of which is the reaction of arenecarbohydrazonoyl chloride with benzylidenehydrazide. Compounds obtained in this way were hydrolyzed to 4-amino-3,5-diaryl-1,2,4-triazoles.     

Synthesis and Crystal Structure of One New Adduct of Isonicotinamide and 3,5-Dinitrosalicylic Acid

One new organic adduct,isonicotinamide·3,5-dinitrosalicylic acid with isonico-tin-amide(ina) and 3,5-dinitrosalicylic acid(3,5-dnsa) in 1:1 molar ratio,has been synthesized.Its struc-ture(C13H10N4O8,Mr = 350.25) was characterized by elemental analysis,IR and single-crystal X-ray diffraction analysis.The crystal belongs to the triclinic system,space group P1,with a = 8.812(4),b = 9.487(5),c = 9.604(6) ,α = 116.54(2),β = 97.29(5),γ = 98.35(4)°,V = 693.8(7) 3,Z = 2,Dc = 1.677 g/cm3,λ(MoKα) = 0.71073 ,μ = 0.142 mm-1,F(000) = 360,the final R = 0.0539 and wR = 0.1402 for 2417 unique reflections(Rint = 0.0288) with 1819 observed ones(Ⅰ 2σ(Ⅰ)).Proton transfer reaction occurs between 3,5-dnsa and ina molecules,and the hydrogen bonds(N-H…O and C-H…O) with other interactions(π…π stacking and weak interactions of O…O and C…O) cooperatively construct a three-dimensional(3D) supramolecular structure.     

Facile Synthesis of 2-Aroyl-3,5-diarylthiophene

Abstract

2-Aroyl-3,5-diarylthiophenes were prepared in very good yields by reaction of 2,4,6-triarylpyrylium salts or 2,4,6-triarylthiopyrylium salts with an aqeous solution of sodium sulfide and iodine at room temperature.     

Synthesis, Mass Spectrometric Studies, and Biological Evaluation of 3,5-Dimethoxyhomophthalic Acid and Related Compounds

3,5-Dimethoxyhomophthalic acid was synthesized in four steps from 3,5-dimethoxycinnamic acid via a series of reactions including cyclization of 3-(3',5'-dimethoxyphenyl)propionic acid to 5,7-dimethoxy-1-indanone and oxidative decomposition of methyl-2-hydroxy-2-[5,7-dimethyoxy-1-oxo-1H-inden-2(3H)-ylidene]acetate to 3,5-dimethoxyhomophthalic acid.The synthesized compounds were characterized by elemental analysis,IR,1H NMR,and MS.The biological evaluation experiments of 3,5-dimthoxyhomophthalic acid and the related synthesized compounds were also carried out.Naturally occurring biologically active isocoumarins were prepared in a single step by the condensation of the homophthalic acid with appropriate acid chlorides.     

3,5-二烷氧基甲苯的溴化反应研究

3,5-二甲氧基甲苯在偶氮二异丁腈的存在下与N-溴代丁二酰亚胺(NBS)反应,产物不是3,5-二甲氧基苄溴,而是2-溴-3,5-二甲氧基甲苯和2,6-二溴-3,5-二甲氧基甲苯.同样条件下,3,5-二乙酰氧基甲苯与NBS反应则生成3,5-二乙酰氧基苄溴.GAUSSIAN 03计算的结果表明,3,5-二甲氧基甲苯中苯环碳原子上的电荷密度高于侧链上碳原子上的电荷密度,因此溴自由基更容易取代苯环上的氢,而3,5-二乙酰氧基甲苯的情况恰好相反,故产物是3,5-二乙酰氧基苄溴.     

Synthesis and Crystal Structure of Picrates of 3,5-Diamino-1,2,4-triazole

The title compound C2N5H6+C6N3O7H2-was synthesized by the reaction of 3,5-diamino-1,2,4-triazole and picric acid in the mixture of ethanol and water solution.Single crystals suitable for X-ray measurement were obtained at room temperature.The structure was characterized by elemental analysis and IR and determined by X-ray diffraction analysis.Crystallographic data:C8N8H8O7,Mr = 328.22,monoclinic,space group C2/c with a = 22.815(2),b = 4.8086(5),c = 22.564(2),β = 93.976(2)°,V = 2469.6(4)3,Dc = 1.766 g/cm3,Z = 8,μ = 0.156 mm-1,F(000) = 1344,the final R= 0.0309,wR= 0.0864.