3-芳基-6-(6-/8-取代-4-氯喹啉-3-基)1,2,4-三唑-[3,4-b]-1,3,4-噻二唑类化合物的合成

研究了3－芳基－4－氨基－5－巯基－1，2，4－三唑与6－／8－取代－4－羟基喹啉－3－酸在三氯氧磷催化下的反应，制得16个的3-芳基－6－（6－／8－取代－4－氯喹啉－3－基）1，2－4，－三唑[3,4-b)-1,3,4-噻二唑，新化合物的结构通过元素分析，IR,^1H NMR和MS确定，讨论了其波谱性质。     

1,4-二氢-2,6-二甲基-4-(3-硝基苯基)-3,5-吡啶二羧酸二(2-甲氧基乙基)酯的合成

对1，4－二氢吡啶类钙拮抗剂西尼地平进行了结构修饰。以双乙烯酮和乙二醇单甲醚为原料，经酯化、缩合、氨化和Hantzsch环化等反应合成了1，4－二氢－2，6二甲基－4－（3－硝基苯基）－3，5－吡啶二羟酸二（2－甲氧基乙基）酯，总收率71％。目标产物结构经^1H NMR和MS确证。     

三环己基锡-2-(1,2-亚乙二硫)亚甲基-3-羰基-5-芳基-4-戊烯酸酯的结构研究

合成了3个三环己基锡－2－（1,2－亚乙二硫）亚甲基－3－羰基－5－芳基－4－戊烯酸酯化合物。用IR,^1H NMR,^13C NMR^119Sn NMR光谱及X射线衍射对所合成的化合物进行了表征,结果表明标明化合物为四配位、具有畸变四面体结构的锡酯类化合物。     

α-[(1H-1,2,4-三唑-1-基)甲基]-β-芳基-β-芳硫基取代苯丙醇的合成及生物活性研究

利用1，3－二芳基－2－[（1H－1，2，4－三唑－1－基）甲基]－2－丙烯－1－酮7与取代硫酚进行1，4－亲核加成，经重排得到化合物4，将化合物4用NaBH4还原，得到目标化合物5，其结构经元素分析、^1H NMR和红外光谱所确证，并测试化合物5对小麦锈病的活性，结果发现大部分化合物的杀菌活性均较低。     

N-芳基-5-氨基-1,2,4-三唑-3-磺酰胺的合成

以5－氨基－3－巯基－1，2，4－三唑为原料，经氯气氧氯化后分别用邻氯苯胺和2，6－二氯苯胺胺解，合成了两个N－芳基－5－氨基－1，2，4－三唑－3－磺酰胺，产品结构经IR和1H NMR确认。     

5-[5-(4-硝基苄基)-2H-四唑亚甲基]-2-芳酰氨基-1,3,4-噻二唑的合成

1-[5-(4-硝基苄基)-2H-四唑乙酰基]4-芳酰氨基硫脲(自制)在冰醋酸的存在下,经脱水、环化制备了5-[5-(4-硝基苄基)-2H-四唑亚甲基]-2-芳酰氨基-1,3,4-噻二唑。其结构经元素分析,IR,^1H NMR和MS确认。     

N-[芳氧乙酰基]α-氨基膦酸二苯酯的合成

通过取代芳氧乙酸与α－氨基膦酸二苯酯的缩合反应合成了12个未见报道的目标化合物，用元素分析，IR，^1H NMR确定了化合物的结构。     

含三氟甲基均三唑衍生物的合成及结构表征

以3－三氟甲基－4－氨基－5－巯基－1,2,4－三唑为原料,在不同反应条件下与取代苯甲酸或芳醛缩合,得到15个含三氟甲基均三唑衍生物,利用元素分析,IR,^1H NMR和MS确定了这些化合物的组成与结构。     

1-取代苯基-1,4-二氢-6-甲基-4-哒嗪酮-3-酰氨基硫脲的合成及其抗烟草花叶病毒活性

用1－芳基－1，4－二氢－6－甲基－4－氧哒嗪－3－酰肼与取代苯基异硫氰酸酯反应合成了系列新型取代－1，4－二氢－6－甲基－4－哒嗪酮－3－酰氨基硫脲化合物，其结构经IR，1H NMR及元素分析确认，生物活性测定表明，该类化合物对烟草花叶病毒具有很高的抑制活性。     

2-溴甲基-3-(二溴甲基)喹喔啉的合成研究

以2，3－二（溴甲基）喹喔啉为原料，以N－溴琥珀酰亚胺为溴化试剂合成了2－溴甲基－3－（二溴甲基）喹喔啉（1），1是Diels-Alder环加成反应中形成含杂原子环的C60衍生物的一种重要中间体。通过IR，^1H NMR,^13C NMR,DEPT谱和MS对其进行了结构表征。     

S<Subscript>(2)</Subscript>- or N<Subscript>(3)</Subscript>-Substituted 2-Mercapto-5-(4-pyridyl)-1,3,4-oxadiazoles

New S₍₂₎- or N₍₃₎-substituted 2-mercapto-5-(4-pyridyl)-1,3,4-oxadiazoles have been obtained and characterized. The direction of substitution depends on the structure of the initial reactants and the reaction conditions. The synthesis of several thiosemicarbazides has been effected from isonicotinic acid hydrazide.     

Reactions of 4-Chloro-3-formylcoumarin with Arylhydrazines

The interaction of 3-formyl-4-coumarin with arylhydrazine hydrochlorides in the presence of sodium acetate gave the corresponding 3-arylhydrazonomethyl-4-chlorocoumarin, and with phenylhydrazine, 4-bromo- and 4-chlorophenylhydrazine hydrochlorides in the presence of two equivalents of triethylamine gave either 1-aryl- or 2-aryl[1]benzopyrano[4,3-c]pyrazol-4-ones depending on the reaction conditions. In reactions of 4-chloro-3-formylcoumarin with 2,4-dichloro-, 2,4-difluoro-, 2-hydroycarbonyl-, 4-nitro- and 3,5-di(trifluoromethyl)phenylhydrazine, 2-pyridyl- and 2-quinoxalylhydrazine in the presence of excess of triethylamine the 2-aryl[1]benzopyrano[4,3-c]pyrazol-4(2H)-ones were obtained exclusively. The structures of 1-phenyl- and 2-(2-pyridyl)[1]benzopyrano[4,3-c]pyrazolo-4(1H)ones were confirmed by X-ray crystallography. A simple method is proposed to distinguish between 1- and 2-substituted [1]benzopyrano[4,3-c]pyrazolo-4-ones on the basis of the ¹H NMR chemical shifts of the C(3)-H proton in two solvents - DMSO-d₆ and CDCl₃.     

Studies on Amidothiosemicarbazides and Related Hcterocyclic Derivatives ( XIII) --Synthetic Studies on 2-(3-Pyridyl)-5-Arylamino- 1,3, 4-Thiadiazoles and Oxadiazoles

By ring-closure of 1-nicotinyl-4-arylthiosemicarbazides under the catalysis of concentrated sulfuric acid or mercuric acetate, a series of 2-(3-pyridyl)-5-arylarnino-1,3,4-thiadiazoles and 2-(3-pyridyl)-5-ary-lamino-1,3,4-oxadiazoles were synthesized, respectively. All the products were subjected to testing of biological activity. Furthermore, the IR, 1H NMR and MS spectral properties of these new compounds were studied in details and some significant conclusions were drawn.     

3-(4-吡啶基)-4-(6-取代色酮-3-基-亚甲氨基)-5-芳氨基-1,2,4-三唑的合成

N-芳基-N'-[(4-吡啶基)羰基]氨基硫脲用85%的水合肼环化, 得到3-(4-吡啶基)-4-氨基-5-芳氨基-1,2,4-三唑(2a～2c). 然后再与3-甲酰基色酮(3a～3d)反应, 制备得到了一系列新化合物: 3-(4-吡啶基)-4-(6-取代色酮-3-基亚甲氨基)-5-芳氨基-1,2,4-三唑(4a～4c, 5a～5c, 6a～6c, 7a～7c). 化合物的结构经元素分析, IR, ¹H NMR和MS确证.     

Synthesis of N-Aryl-2- （1＇, 6＇-dihydro-6＇-pyridazinone-3＇-carbonyl） Thiosemicarbazides and Their Related Heterocyclic Compounds

1,6-Dihydro-3-hydrozinocarbonyl-6-pyridazinone (compound 2) were prepared from α-ketoglutaric acid and hydrazine hydrate. A series of N-aryl-2-(1‘,6‘-dihydro-6‘-pyridazinone-3‘-carbonyl) thiosemicarbazides 3a-3f were synthesized from the reaction of aryl isothiocyanates with compound 2. The terminal compounds 1,3, 4-thiadiazole, 1,3,4-oxadiazole and 1,2, 4-triazol-5-thione derivatives were cyclized from compounds 3a-3f. Their structures were confirmed by IR,^1H NMR, MS and elemental analyses.     

Pyridine-substituted hydroxythiophenes. I. Preparation of o-(2-, 3- and 4-pyridyl)-3-hydroxythiophenes.

2-(2-, 3- and 4-pyridyl)-3-hydroxythiophenes and 4-(2-, 3- and 4-pyridyl)- 3-hydroxythiophenes have been prepared by hydrogen peroxide oxidation of the corresponding boronic esters. In the former case the boronic esters were obtained in three steps from 2,3-dibromothiophene via the corresponding 3-bromo-2-pyridylthiophenes synthesized by Pd(0)-catalyzed coupling between 3-bromo-2-trimethylstannylthiophene and the corresponding bromopyridines. In the latter case the known isomeric pyridylthiophenes were converted into the corresponding boronic esters in three steps via tribromo- and 3-bromo-4-pyridylthiophenes successively. 4-(3- and 4-pyridyl) thiophen-2(5H)-ones were also obtained in the syntheses of 4-(3- and 4-pyridyl)-3-hydroxythiophene. They are suggested to arise from rearrangement during the halogen-metal exchange. Spectroscopic investigations by 1H NMR and IR show that these hydroxythiophene systems exist exclusively as enol forms.     

Synthesis of N-Aryl-2- (1'' , 6'' -dihydro-6'' -pyridazinone-3''-carbonyl) Thiosemicarbazides and Their Related Heterocyclic Compounds

1,6-Dihydro-3-hydrozinocarbonyl-6-pyridazinone(compound 2) were prepared from α-ketoglutaric acid and hydrazine hydrate. A series of N-aryl-2-(1' ,6'-dihydro-6'-pyridazinone-3'-earbonyl) thiosemicarbazides 3a-3f were synthesized from the reaction of aryl isothiocyanates with compound 2. The terminal compounds 1,3, 4-thiadiazole, 1,3,4-oxadiazole and 1,2, 4-triazol-5-thione derivatives were cyclized from compounds 3a-3f. Their structures were confirmed by IR, 1H NMR, MS and elemental analyses.     

Synthesis and structure of aryl(hetaryl)spiropyrrolidones

Hydrogenation of the diastereouniform 3-[1-aryl(hetaryl)-2-nitroethyl]-3-methoxycarb-onyl-4-phenyl(3-pyridyl)-2-pyrrolidones is accompanied by intramolecular acylation of the formed amino group to afford the diastereomerically pure 4,4′-aryl(hetaryl)-3,3′-spirobi-[2-pyrrolidones]. The structures of these diastereomers were characterized by IR, ¹H and ¹³C NMR spectroscopy using heteronuclear correlation experiments, and X-ray diffraction study.     

Synthesis and structure of nitroethylpyrrolidone carboxylates

3-Methoxycarbonyl-4-phenyl- and 4-(3-pyridyl)-2-pyrrolidones react with 2-aryl(heteryl)-1-nitroethenes to form C³-adducts as one or two diastereomers. Their structure was characterized by the IR, ¹H, and ¹³C NMR spectroscopy, using the two-dimensional correlation spectroscopy.     

4-Functionally Substituted 3-Heterylpyrazoles: IV. 1-Phenyl-3-aryl(heteryl)-5-(4-pyrazolyl)-2-pyrazolines

3-Aryl(heteryl)-4-formylpyrazoles in condensation with methyl aryl(heteryl) ketones afforded 1-aryl(heteryl)-3-[3-aryl(heteryl)-4-pyrazolyl]propenones. The latter reacted with phenylhydrazine yielding 1-phenyl-3-aryl(heteryl)-5-(4-pyrazolyl)-2-pyrazolines.