含1,3,4-噻二唑α-氨基膦酸酯的合成及其表征

以硫代氨基脲为前体原料, 合成了两种2位为不同烷硫基的5-氨基-1,3,4噻二唑, 采用“一锅煮”的方法, 与不同的醛及亚磷酸酯合成了一系列含1,3,4-噻二唑的α-氨基磷酸酯, 所得产物均经IR, MS, 1H NMR, 31P NMR和元素分析确证结构.     

2-氨基-5-硫代-噻二唑啉-β-D-核呋喃糖苷的合成

2-氨基-5-硫代-1,3,4-噻二唑啉和1-O-乙酰-2,3,5-三-O-苯甲酰核呋喃糖通过熔融缩合和Vorbruggen缩合, 所得两个产物经^1H, ^1^3C NMR, 质谱以及X射线结晶学分析, 鉴定为位置异构体2-亚氨基-5-硫代-1,2,4-噻二唑啉-3-β-D-核呋喃糖苷和2-氨基-5-硫代-1,3,4-噻二唑啉-4-β-D-核呋喃糖苷。     

2-（1,3,4-噻二唑胺甲基）苯酚的合成及其杀菌活性

以2-氨基-5-烃基-1,3,4-噻二唑和水杨醛为原料,分别用"分步法"和"一锅法"经还原中间产物Schiff碱的CN双键合成了一系列2-((1,3,4-噻二唑基)胺甲基)苯酚类新化合物,"一锅法"的产率较高,为56%～80%。产物的结构用IR、1H NMR、13C NMR和MS进行了表征。初步测试了目标化合物的杀菌活性,证明化合物对赤星病菌具有较好的抑菌活性,当浓度为25 mg/L时,化合物3i的抑制率为76%,化合物3f、3h、3k和3l的为70%。     

2—芳酰氨基—5—苄基—1,3,4—噻二唑的合成及其与苯甲醛反应的研究

1-酰基-4-芳基氨基硫脲类在酸催化下环化为具有广泛生物活性的2-芳氨基-5-芳基-1,3,4-噻二唑类的反应报道甚多,但1,4-二酰基氨基硫脲在相同条件下环化为类似结构衍生物的反应报道很少。为探索其规律,本文研究了1-苯乙酰基-4-芳酰氨基硫脲1_(a-m)在冰醋酸存在下的环化反应,制得2-芳酰氨基-5-苄基-1,3,4-噻二唑2_(a-m)。参考文献还探索了2_(a-m)在EtONa/EtOH体系中与苯甲醛的反应。得到预期产物2-芳酰氨基-5-(1′-苯基-2′-羟基苯乙基)-1,3,4-噻二唑3_(a-m),经元素分析、IR、~1H NMR及MS确认了产物结构。     

2-氨基-5-烷基-1,3,4-噻二唑修饰环糊精的制备与表征

在N2气保护下, 用单-(6-对甲苯磺酰基)-CD(β-CD-6-OTs)和过量的2-氨基-5-烷基-1,3,4-噻二唑在80 ℃反应2 d, 合成了5种新的2-氨基-5-烷基-1,3,4-噻二唑修饰β-环糊精. 化合物的结构用IR, 1H NMR, 13C NMR, UV, MS和元素分析等方法进行了表征. 由于环糊精的屏蔽效应, 在2-氨基-1,3,4-噻二唑修饰β-环糊精的 1H NMR中, 修饰产物中的噻二唑质子发生了高场位移. 其它的谱图数据同理论值相吻合, 这证明合成与分离方法是可行的. 研究了产物的生物活性, 结果显示部分化合物(2d, 2e)的抗菌活性明显增强.     

2-氨基-5-取代-1,3,4-噻二唑与2-氯代-1-(2,4-二氯苯基)乙酮的反应研究

2-氨基-5-烷基/芳基1,3,4-噻二唑与2-氯代-1-(2′,4′-二氯苯基)乙酮在热乙醇中反应生成一系列2-烷基/芳基-6-(4,4-二氯)苯基咪唑并[2-1-b]-1,3,4-噻二唑.产物通过元素分析, IR, 1H NMR, 13C NMR及MS分析,化合物5g的X衍射晶体结构分析表明,产物的芳基是在咪唑并[2-2-b]-1,3,4-噻二唑的6-位而不在5-位.     

1,3,4-噻二唑衍生物合成及其生物活性研究进展

1,3,4-噻二唑是含有N、S杂原子的五元杂环化合物,具有多种生物活性。目前,1,3,4-噻二唑及其衍生物广泛用于生物、医药等领域,尤其在抗菌、抗肿瘤、抗癌等方面的研究已取得重大突破。由于1,3,4-噻二唑结构的特殊性以及优越的生物活性,对其进行研究有重要意义。本文主要概述了近年来1,3,4-噻二唑衍生物的几种合成方法以及其在抗菌、抗肿瘤、抗癌方面的研究进展。     

2,5-二芳基-噻二唑的合成及其缓蚀性能研究

合成了四种噻二唑衍生物:2,5-二苯基-1,3,4-噻二唑(DPTD),2,5-二(2-羟基苯)-1,3,4-噻二唑(2-DHPTD),2,5-二(3-羟基苯)-1,3,4-噻二唑(3-DHPTD)和2,5-二(4-羟基苯)-1,3,4-噻二唑(4-DHPTD)。采用Tafel极化测试、电化学阻抗谱(EIS)和扫描电子显微镜(SEM)研究了噻二唑衍生物在50 mg·L-1硫-乙醇体系中对银的缓蚀作用。实验结果表明:添加缓蚀剂后,银片腐蚀得到抑制,且缓蚀效率大小顺序为:[DPDT][2-DHPDT][3-DHPDT][4-DHPDT]。通过量子化学计算和分子动力学模拟进一步研究了四种噻二唑衍生物的缓蚀机理,理论计算结果与实验结果一致。     

一些2-氨基-1,3,4-噻二唑类化合物的合成及其对水稻白叶枯病菌活性的研究

为了筛选防治水稻白叶枯病的新药剂,合成了16个2-氨基-5-烷基-1,3,4-噻二唑(Ⅰ)(其中7个是新化合物),11个O,O-二苯基-N-(5-烷基-1,3,4-噻二唑-2-基)磷酰胺(Ⅱ)及4个O,O-二烷基-S-(N-1,3,4-噻二唑)胺基甲基二硫代磷酸酯(Ⅲ)。对水稻白叶枯病原菌和桃冠瘿病原菌进行了离体药效试验,结果表明Ⅰ、Ⅱ类化合物均有活性,且活性的大小与5-位正烷基的碳原子数有关。     

具有植物激素活性的Schiff碱化合物的研究(Ⅲ)--噻二唑类Schiff碱的合成及其生物活性

含杂环的Schiff碱类化合物具有很高的植物生长激素的活性[1],近十几年来受到化学家的重视.前文[2]已报道了三唑类Schiff碱的合成及其生物活性.已发现含噻二唑环的化合物具有高的生物活性,1,3,4-噻二唑的衍生物可以作为杀菌剂、除草剂和植物生长调节剂[3～6],连有巯基(-SH)的噻二唑的席夫碱目前还未见报道.我们将2-氨基-5-巯基-1,3,4-噻二唑与芳醛或杂环醛作用,合成了12个新的Schiff碱化合物,发现其中一些化合物具有明显的植物激素活性,合成的反应式为:     

噻二唑衍生物的合成及摩擦学性能研究

以 2 ,5-二巯基 -1 ,3,4 -噻二唑为原料合成了两种 2 ,5-二烷氧甲硫基 -1 ,3,4 -噻二唑衍生物 ,运用红外光谱′H核磁共振谱和元素分析测定了这些化合物的分子结构。在四球摩擦磨损试验机上考察了这两种化合物的极压、减摩和抗磨性能以及结构与性能的关系 ,并与ZDDP(T2 0 2 )进行了比较。结果表明 ,这些衍生物具有良好的极压和抗磨损性能 ,在低于 30 0N负荷条件下具有和T2 0 2 相似的抗磨损性能 ,而在高于 30 0N负荷和质量分数低于 1 %的条件下具有比T2 0 2 更好的抗磨损性能。     

Synthesis and transformations of furan derivatives

Condensation of thiosemicarbazones of furfural, 3-(2-furyl)acrolein, as well as their 5-nitro derivatives with chloroacetone by boiling in alcohol or acetic acid gives the corresponding 4-methylthiazolyl-(2)hydrazones. 4-Methylthiazolyl-(2)-hydrazones of 5-nitro-2-acetylfuran and 5-nitro-2-furfurilydeneacetone can be prepared by condensing the corresponding thiosemicarbazones with chloroacetone by heating with glacial acetic acid containing fused sodium acetate.For Part IV see [1].     

一锅煮法合成苯基苄基酮缩氨基硫脲

以天然产物异黄酮与氨基硫脲为原料, 在碱性条件下乙醇为溶剂, 合成了10种苯基苄基酮缩氨基硫脲化合物. 此方法操作简便、条件温和、且产率较高, 是合成苯基苄基缩氨基硫脲的一种简便实用的方法. 采用IR, ¹H NMR, ¹³C NMR和元素分析对这10种化合物结构进行了表征.     

Synthesis of some 4-thiazolidone derivatives from 4-(cyclo-3-alkenyl)thiosemicarbazones

The reaction of 4-(cyclo-3-pentenyl)- and 4-(cyclo-3-hexenyl) thiosemicarbazones with chloroacetic acid gave 2-hydrazono derivatives of 3-cyclo-pentenyl (cyclohexenyl) thioazolid-4-one, the condensation of which with aromatic aldehydes gave 5-benzylidene derivatives. Representatives of 4-thiazolidone with a carboxy group in the 5 position were synthesized by condensation of the same thiosemicarbazones with maleic anhydride. Some of the substances obtained have bactericidal activity.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 627–628, May, 1981.     

Antitrypanasomal activity of novel benzaldehyde-thiosemicarbazone derivatives from kaurenoic acid

A series of new thiosemicarbazones derived from natural diterpene kaurenoic acid were synthesized and tested against the epimastigote forms of Trypanosoma cruzi to evaluate their antitrypanosomal potential. Seven of the synthesized thiosemicarbazones were more active than kaurenoic acid with IC?? values between 2-24.0 mM. The o-nitro-benzaldehyde-thiosemicarbazone derivative was the most active compound with IC?? of 2.0 mM. The results show that the structural modifications accomplished enhanced the antitrypanosomal activity of these compounds. Besides, the thiocyanate, thiosemicarbazide and the p- methyl, p-methoxy, p-dimethylamine, m-nitro and o-chlorobenzaldehyde-thiosemicarbazone derivatives displayed lower toxicity for LLMCK? cells than kaurenoic acid, exhibing an IC?? of 59.5 mM.     

Studies on the synthesis and reactivity of novel benzofuran-2-yl-[3-methyl-3-phenylcyclobutyl] methanones and their antimicrobial activity

Preparation in excellent yields of cyclobutyl benzofuran-2-yl- and naphthofuran- 2-yl-ketones, the corresponding ketoximes and thiosemicarbazones, ether derivatives of the ketoximes and thiazoles derived from the thiosemicarbazones are described. Two of the synthesized compounds have been tested against eight different microorganisms and found to be active against some of the species studied.     

Synthesis, spectral characterization and eukaryotic DNA degradation of thiosemicarbazones and their platinum(IV) complexes

The condensation products of acetophenone (or its derivatives), salicylaldehyde and o-hydroxy-p-methoxybenzophenone with thiosemicarbazide and ethyl- or phenyl-thiosemicarbazide are the investigated thiosemicarbazones. Their reactions with H(2)PtCl(6) produced Pt(IV) complexes characterized by elemental, thermal, mass, IR and electronic spectral studies. The coordination modes were found mononegative bidentate in the acetophenone derivatives and binegative tridentate in the salicylaldehyde derivatives. The complexes were analyzed thermogravimetrically and found highly stable. Some ligands and their complexes were screened against Sarcina sp. and E. coli using the cup-diffusion technique. [Pt(oHAT)(OH)Cl] shows higher activity against E. coli than the other compounds. The degradation power of the tested compounds on the calf thymus DNA supports their selectivity against bacteria and not against the human or related eukaryotic organisms.     

Synthesis of physiologically active compounds of the thiosemicarbazone series and derivatives

With a view to discovering new plant growth regulators, a series of thiosemicarbazones and derivatives of thiazolidine-2-4-dione were synthesized. Reaction of epichlorohydrin with derivatives of thiazolidine-2,4-dione without a substituent at positions gives 3-(β-hydroxy-γ-chloropropyl) derivatives of thiazolidine-2, 4-dione-2-hydrazone.     

Dérivés de la dihydro-2,4 triazole-1,2,4 thione-3 et de l'amino-2 thiadiazole-1,3,4 à partir de nouvelles thiosemicarbazones d'esters

A new general synthesis of 4,5-disubstituted 2,4-dihydro-1,2,4-triazole-3-thiones is proposed. These heterocycles are obtained by the action of primary amines, arylhydrazines or aroylhydrazines on the thiosemicarbazones of eaters. These last compounds are prepared by action of chlorhydrates of iminoethers on thiosemicarbazide in dimethylformamide. These thiosemicarbazones react also with strong acids, acid anhydrides and chlorides; by thermolysis and they give 2-amino-1,3,4-thiadiazole derivatives. Also, two derivatives of 1,2,4-triazolo[3,4-b]-1,3,4-thiadiazole have been prepared.