在Lewis酸催化下N-苯乙基甘氨酸衍生物的分子内环化反应研究及苯并-3-氮杂环庚酮-1衍生物的合成

本文报导了不同N-苯乙基甘氨酸衍生物在Lewis酸催化下的分子内环化反应的若干规律,以及苯并-3-氮杂环庚酮-1衍生物的合成.     

A CONVENIENT SYNTHESIS OF NEW PYRIDOTHIENOPYRIMIDIN-4 (3H) ONES AND PYRIDOTHIENOPYRIMIDIN-2, 4(1H, 3H) DIONES

New derivatives of 2-substituted pyrido[3′,2′:4,5]thieno[3,2-d]pyri-midin-4(3H) ones and 3-substituted pyrido[3′,2′:4,5]thieno[3,2-d]pyri-midin-2,4(1H,3H) diones have been prepared by base catalyzed cyclocondensation of ethyl-3-aminothieno[3,2-b]pyridine-2-carboxylate with aryl nitriles and aryl- or alkyl isocyanates respectively.     

1—羟基—2（1H）—吡啶硫酮及其甲基衍生物与Cr（Ⅲ）配合物的合成和性质

Edrissi认为Cr(Ⅲ)与1-羟基-2(1H)-吡啶硫酮(HPT)的甲基衍生物不能给出任何反应,并且将与HPT的配合物注明为绿色溶液。本文在过去工作的基础上合成了S-(1-氧化-2-吡啶基)硫代苯甲酸酯(PTB)和3-CH_3-PTB;并合成了3个铬配合物。通过元素分析,紫外-可见,红外光谱,摩尔电导和TG-DTA-DTG作了表征。探讨了形成机理并研究了抑菌活性。     

THE CHEMISTRY OF (ECN)2 (E = S,Se) AND RELATED COMPOUNDS

The psuedohalogens (ECN)₂ (E = S, Se) have been prepared by reaction of AgNCS with bromine and AgNCSe with iodine respectively. (SCN)₂ spontaneously polymerises to give polythiocyanogen a polymer of unknown structure with empirical formula (SCN)_x. A series of late transition metal complexes bearing the ambidentate psuedohalide ligands (ECN) (E = S, Se) have been synthesised. In addition we have prepared a series of late transition metal complexes of the cyanodithioimidocarbonate ion [C₂N₂S₂]^2? and the first transition metal complexes of the cyanodiselenocarbonate ion [C₂N₂Se₂]^2?.     

含氮杂环三烃基锡衍生物的合成及其生物活性

本文合成了14个含氮杂环三烃基锡衍生物,红外光谱,核磁共振谱和质谱的研究表明三烃基锡-1,2,4-三氮唑为以氮原子作桥联的五配位聚合结构化合物,化合物的生物活性和生物选择性主要取决于锡原子上的三烃基。     

基于2,6-二甲基萘的杂环聚芳醚酮的合成

由1,5-二(4'-氟苯甲酰基)-2,6-二甲基萘(1)和类双酚单体(2a～2d)通过N—C偶联聚合反应合成了一系列基于2,6-二甲基萘的新型杂环聚芳醚酮(3a～3d).采用FTIR、1H-NMR、DSC、TGA、GPC等手段对聚合物进行结构表征和性能测试,并研究了其溶解性及特性黏数.结果表明,聚合物在室温下易溶于氯仿、DMAc、NMP、吡啶和间甲酚等非质子极性有机溶剂,其氯仿溶液能形成无色透明、韧性较好的膜,特性黏数(ηinh)在0.76～1.40 dL/g范围内.聚合物3b～3d的数均分子量(Mn)和分散指数(PDI)分别在78000～104000和1.66～2.21范围内.该类聚合物的玻璃化转变温度(Tg)均大于280℃,在氮气氛围和800℃时的残余量在53%～69%范围内.该类聚合物在氮气中5%和10%的热失重温度分别在423～440℃和434～467℃范围内.     

SYNTHESIS OF 7-THIA-1-AZABICYCLO (4,3,0) NONANE DERIVATIVES VIA FREE RADICAL REACTION

Abstract

Several β-aminothiols were prepared by condensation of 3-piperideine and different thiiranes.     

STUDY ON THE SYNTHESIS OF A NEW TYPE OF PHOSPHORUS HETEROCYCLIC COMPOUNDS-PYRAZOLO[3, 4-d]-1, 3, 2-DIAZAPHOSPHORIN-6-ONE

1-substituted-5-benzoylamino-4-pyrazolecarboxamides(2)were prepared by the reaction of 1-substituted pyrazolo[3, 4-d]-oxazinone(1)with amines in benzene.The compound 2 was refluxed with excess LiAlH₄ in a mixture of THF and ether, one of the two carbamoyl groups in the molecule 2 was reduced selectively.As the results, 1-substituted-5-benzylamino-4-pyrazolecarboxamides (3) were obtained.Compounds 3reacted with Cl₂PPh-X, or P(NET₂)3, producing the title compounds(4).The conditions of the reactions were studied.     

SYNTHESIS AND STRUCTURE OF A NOVEL MONONUCLEAR TUNGSTEN (VI) CITRATO COMPLEX, (NH4)3[Li(H2O)3WO3(C6 H4O7)]

Abstract

The first mononuclear tungsten-citrato complex, (NH₄)₃[Li (H₂O)₃WO₃(C₆H₄O₇)] (1), has been prepared by the reaction of ammonium tetrathio tungstate and lithium citrate in CH₃OH-H₂O solution at pH 8.2. There are two crystallographically independent anions in the asymmetric crystallographic unit. The crystal structure of the title compound (triclinic, space group P1, a = 6.901(1), b = 15.136(3), c = 16.107(3) Å, α = 75.85(3), β = 89.89(3), γ = 89.97(3), V = 1631.4(6) ų, R = 0.068, R _W = 0.1674 for 3878 reflections with I > 2σ(I)), reveals that in the compound a tungsten atom is coordinated to a fully deprotonated citrate as a tridentate ligand and three terminal oxygen atoms to form a distorted coordination octahedron.     

SYNTHESIS OF FUSED AND SPIRO HETEROCYCLIC COMPOUNDS DERIVED FROM 3,5-PYRAZOLIDINEDIONE DERIVATIVES

Abstract

The reaction of compound 1 with triethyl orthoformate afforded 2, which in turn reacted with CS₂ and active methlyene compounds or malononitrile to give dithiolane and 4-malononitrile methylene derivatives 3,4, respectively. Treatment of compound 4 with active methylene compounds afforded spiro cyclopentene derivatives 5_a-c. Compound 1 was reacted with bromomalononitrile or CS₂ and halocompounds to afford furo-. thieno- and dithiolano-pyrazole derivatives 6–11, respectively. The reaction of compound 12 with phenacyl bromide or benzylidenemalononitrile furnished oxathiol-2-ylidene and pyridinethione derivatives 13,14, respectively. The dibromo derivative 16 was reacted with CS₂ and active methylenes or malononitrile to obtain spiro dithietanes 17a-e and 4-dicyano-methlyene derivative 22, respectively. Compounds 17 underwent a cycloaddition reaction with thioglycolic acid, N-phenylbenzohydrazindoyl bromide, 2,5-dimethylfuran and 1-phenyl-3,5-pyrazolidinedi one to give cycloadducts 18–21, respectively. Treatment of > o-aminothiophenol or o-phenylenediamine with the dicyano compound 22 leads to the formation of spiro thiazepine or spiro diazine derivatives 23_a,b . The arylidene derivatives 24 was reacted with S,S-acetals, N,S-acetals or ammonium dithiocarbamate to afford dithiane, oxazine or pyrazolodithiocarbamate derivatives 25–29, respectively. Chemoselective cyclization of compound 29 with H₂SO₄, NaOH or MeI gave compounds 30–32, respectively. Benzopyrano derivatives 34,36 were obtained through the reaction of compound 1 with a mixture of thiourea, triethyl orthoformate and ethyl cyanoacetate or with cyanoketene S,S diacetals, respectively.     

SYNTHESIS AND FUNGICIDAL ACTIVITIES OF 2-BENZOTHIAZOLYLTHIO-SUBSTITUTED 4H-IMIDAZOL-4-ONES AND 4(3H)-QUINAZOLINONES

4H-Imidazol-4-ones 4 or 4(3H)-quinazolinones 8 were synthesized by base catalytic reactions of 2-mercaptobenzothiazole with carbodiimides 2 or 6, respectively, which were obtained via aza-Wittig reaction of iminophosphorane 1 or 5 with aromatic isocyanates. 4 and 8 exhibited fungicidal activity.     

AN UNUSUAL ADDITION AND RING-CLOSURE REACTION OF 1-(2-BROMOETHYL)-2,3-DIHYDRO- 3-PROPYL-1,3,2-BENZO-DIAZAPHOSPHORIN-4(1H)-ONE 2-OXIDE WITH CARBON DISULFIDE FOR A NEW AND CONVENIENT SYNTHESIS OF THE FUSED PHOSPHORUS HETEROCYCLIC COMPOUND

ABSTRACT

The reaction of 1-(2-bromoethyl)-2,3-dihydro-3-propyl-1,3,2-benzodiazaphosphorin-4(1H)-one 2-oxide with carbon disulfide takes an alternative pathway in the use of different bases. The sodium hydride mediated reaction leads to the formation of the tricyclic fused 1,2,3,4,4a,4b,5,6-octahydro-6-oxo-5-propyl-4-thia-3,4b,4a-thiazphosphaphenanthridine 4a-oxide via addition of H-P bond across the double bond of carbon disulfide followed by intramolecular cyclization. In the presence of triethylamine, refluxing a mixture of 1-(2-bromoethyl)-2,3-dihydro-3-propyl-1,3,2-benzodiazaphosphorin-4(1H)-one 2-oxide with carbon disulfide in benzene takes an unusual course with formation in excellent yield of the first example of fused phosphorus heterocyclic 4-[1′-(β-bromoethyl)-4′-oxo- 3′-propyl-1′,2′,3′,4′-tetrahydro-1,3,2-benzodiazaphosphorin-2′- sulfide]-1,2,3,4,4a,4b,5,6-octahydro-6-oxo-5-propyl-3,4b, 4a-thiazphosphaphenanthridine 4a,2′-dioxide, which was confirmed by spectroscopic methods, microanalyses and single crystal X-ray structure determination.     

SYNTHESIS AND REACTIONS OF SOME NEW HETEROCYCLIC COMPOUNDS CONTAINING THE THIENYLTHIENO[2,3-B]PYRIDINE MOIETY

(4-Aryl-3-cyano-6-(2-thienyl)pyridin-2-ylthio)acethydrazides (5a–c), 3-amino-4-aryl-6-(2-thienyl)thieno[2,3-b]pyridine-2-carbohydrazides (6a–c) and 3-amino-4-phenyl-6-(2-thienyl)thieno[2,3-b]pyridine-2-carboxylic acid (30) were prepared and employed as key intermediates in the synthesis of the title compounds.     

THE REACTIONS OF N3P3CL6 AND RELATED COMPOUNDS WITH DIFUNCTIONAL REAGENTS. COMPARISONS AND CONTRASTS

Abstract

The reactions of N₃P₃Cl₆ with a variety of difunctional reagents are discussed. NMR spectroscopic and X-ray crystallographic investigations are presented.     

STUDY ON THE SYNTHESIS OF BRASSINOLIDE AND RELATED COMPOUNDS 15.FORMAL SYNTHESIS OF BRASSINOLIDE VIA STEREOSELECTIVE SULFENATE-SULFOXIDE TRANSFORMATION

A formal synthesis of the natural growth promoting steroidbrassinolide is described,which involves construction of side chainby 1,3-sulfoxide-hydroxyl transposition with methylation from(24S)-22-E-24-sulfoxide 6 and(24R)-22-E-24-sulfoxide 9,respectively to(22S)-23-E-24-methyl compound 4.