新型3-(1,3,4-噻二唑基)-1,3-苯并噁嗪类化合物的合成和杀菌活性

以2-[(1,3,4-噻二唑基-2-氨基)甲基]苯酚和CH2Cl2为原料,首次采用相转移催化法合成了一系列新型3-(1,3,4-噻二唑基)-1,3-苯并噁嗪类化合物,产率为47%～62%.研究了相转移催化剂的用量、反应物用量、反应温度等对反应产率的影响.产物结构用IR,1H NMR,13C NMR和元素分析进行了表征.初步研究了目标化合物的杀菌活性,大部分化合物具有一定的杀菌活性.     

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.     

取代-1H-吡唑-5-甲酸与取代噻二唑-2-氨的酰胺化合物的合成及生长素活性

采用"一锅法"合成3-(4-甲氧基苯基)-1H-5-吡唑甲酸乙酯,分别将吡唑环上1-位甲基化、4-位氯代后水解,得到2种吡唑羧酸;以取代羧酸和氨基硫脲为原料,三氯氧磷为脱水剂,合成6种5-取代-2-氨基-1,3,4-噻二唑化合物;再将吡唑结构单元及1,3,4-噻二唑结构单元以酰胺键结合在一起,合成了12种新的酰胺化合物,目标产物最终收率可达50%以上。用元素分析、IR和1HNMR测试技术确定了其结构。用小麦芽鞘法测试其生长素活性均不高,有的对小麦芽鞘生长显示抑制作用。     

微波辐射条件下N-芳基-N′-(5-苯并呋喃基-1,3,4-噻二唑-2-基)脲的合成

在微波辐射条件下,以2-氨基-5-苯并呋喃基-1,3,4-噻二唑和N-取代三氯乙酰苯胺为原料,在固体氢氧化钠作用下,"一锅法"高产率合成了10种N-(5-苯并呋喃基-1,3,4-噻二唑-2-基)-N'-芳基脲,并通过IR1、H NMR和元素分析表征了目标产物的结构.     

含吡啶环的N-(1,3,4-噻二唑-2-基)苯甲酰胺类化合物的合成及其抑菌活性

以3-吡啶乙酸盐酸盐与氨基硫脲为原料经环化反应制备中间体2-氨基-5-(3-吡啶亚甲基)-1,3,4-噻二唑,后者与取代苯甲酰氯反应合成了一系列含吡啶环的N-(1,3,4-噻二唑-2-基)取代苯甲酰胺(3a~3k),其结构通过IR、~1H NMR、~(13)C NMR、MS和元素分析确证。用菌丝生长速率法测定了目标化合物对灰霉菌的离体抑菌活性,结果表明,部分化合物对病原菌有一定的抑制活性。     

微波辐射条件下N-芳基-N''''-(5-苯并呋喃基-1,3,4-噻二唑-2-基)脲的合成

在微波辐射条件下,以2-氨基-5-苯并呋喃基-1,3,4-噻二唑和N-取代三氯乙酰苯胺为原料,在固体氢氧化钠作用下,"一锅法"高产率合成了10种N-(5-苯并呋喃基-1,3,4-噻二唑-2-基)-N'-芳基脲,并通过IR、1H NMR和元素分析表征了目标产物的结构.     

5-(2-羟基苯基)-1,3,4-噻二唑-2-硫基乙酰腙化合物的合成及抑菌活性

以2-巯基-5-(2-羟基苯基)-1,3,4-噻二唑为原料,经硫醚化、肼解、腙化反应合成了9个5-(2-羟基苯基)-1,3,4-噻二唑-2-硫基乙酰腙化合物,其结构由1H NMR,13C NMR,IR,MS表征和元素分析,并初步研究了目标化合物的抑菌活性.结果表明它们大多数具有优良的抑菌活性,芳香醛-5-(2-羟基苯基)-1,3,4-噻二唑-2-硫基乙酰腙(4a～4h)比2-丁烯醛-5-(2-羟基苯基)-1,3,4-噻二唑-2-硫基乙酰腙(4i)有更好的抑菌活性.     

N-[5-(Е)-1,3,4-噻二唑-2-基]-N'-芳基脲的合成、晶体结构及生物活性

为了寻找高活性的脲类细胞分裂素,通过2-氨基-5-(Е)-苯乙烯基-1,3,4-噻二唑与芳酰基叠氮化物反应,合成了11种新的含1,3,4-噻二唑环芳基脲类衍生物,其中芳酰基叠氮化物直接由芳酸、三氯氧磷与叠氮钠采用"一锅法"制得,再经加热发生Curtius重排转化为异氰酸酯.目标化合物的结构用红外光谱、核磁共振氢谱、质谱和元素分析进行了表征,并用X射线单晶衍射实验测定了化合物3g的结构.初步的生物活性测试表明,部分目标化合物在10 mg/L浓度下表现出良好的细胞分裂素活性,其中3c的活性超过50%.     

2-取代硫醚-5-(3,4,5-三甲氧基苯基)-1,3,4-噻二唑类化合物的合成、结构与体外抗癌活性

以天然产物没食子酸为原料经醚化、酯化、酰肼化、成盐、闭环、硫醚化六步反应合成了6个2-取代硫醚-5-(3,4,5-三甲氧基苯基)-1,3,4-噻二唑类衍生物, 釆用铟催化下水相合成目标化合物8, 具有反应条件温和, 合成收率高的特点; 用IR, ¹H NMR, ¹³C NMR和元素分析对各化合物进行了表征及结构确证, 并用X射线单晶衍射法测定了化合物8a [2-(2-氯-5-吡啶甲基)硫醚-5-(3,4,5-三甲氧基苯基)-1,3,4-噻二唑]的晶体结构, 采用MTT法进行了新化合物抑制PC3和BGC-823癌细胞体外试验, 结果表明在5μmol•L^－1浓度下化合物8e对PC3的抑制活性为55.71%. 化合物8b对BGC-823细胞抑制活性为66.21%.     

新型1,3,4-噻二唑衍生物的合成及抗肿瘤活性

以取代的苯乙酸为起始原料,通过成环、偶联、脱保护基并引入苯磺酰胺等反应得到了系列2,5-二取代-1,3,4-噻二唑类化合物,并利用1H NMR,13C NMR和HRMS对目标化合物进行了结构表征.用四甲基偶氮唑盐(MTT)法测试了目标化合物体外抑制前列腺癌细胞(PC-3)、乳腺癌细胞株(MDA-MB-231)和白血病细胞(K562)等肿瘤细胞的增殖活性.结果显示,部分目标化合物具有较好的抗肿瘤细胞增殖活性,其中(S)-N-(5-([1,1'-联苯]-4-基甲基)-1,3,4-噻二唑-2-基)-2-氨基-3-(4-溴苯基)丙酰胺(6a)和(S)-N-(5-([1,1'-联苯]-4-基甲基)-1,3,4-噻二唑-2-基)-2-氨基-3-苯基丙酰胺(6b)对K562细胞的活性与阳性对照药棉酚相当.     

一锅法合成4-(5-芳基-1,3,4-噻二唑-2-氨甲基)苯酚衍生物

以2-氨基-5-芳基噻二唑衍生物和对羟基苯甲醛为原料,经亲核加成/脱水、还原两步一锅法合成了一系列新的4-(5-芳基-1,3,4-噻二唑-2-氨甲基)苯酚衍生物,反应具有时间短、后处理简单等优点.采用元素分析,NMR,IR以及质谱等多种谱学技术对产物进行了详细表征.     

One-Pot Synthesis of 1,3,4-Thiadiazin-5-yl-chromen-2-one Derivatives via Three-Component Reaction

An expeditious, one-pot reaction has been described for the preparation of 1,3,4-thiadiazin-5-yl-chromen-2-one derivatives. These compounds were synthesized by the reaction of 3-(2-bromoacetyl)coumarin with thiocarbohydrazide and various carbonyl compounds. The newly synthesized compounds were characterized by infrared, ¹H NMR, and mass spectra.     

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.     

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.     

A Novel Approach to the Synthesis of 1,3,4-Thiadiazole-2-amine Derivatives

The main purpose of the study was the development of a new method for synthesis of 1,3,4-thiadiazol-2-amine derivatives in a one-pot manner using the reaction between a thiosemicarbazide and carboxylic acid without toxic additives such as POCl₃ or SOCl₂. The reaction was investigated in the presence of polyphosphate ester (PPE). It was found that, in the presence of PPE, the reaction between the thiosemicarbazide and carboxylic acid proceeds in one-pot through three steps with the formation of corresponding 2-amino-1,3,4-thiadiazole. Using the developed approach five, 2-amino-1,3,4-thiadiazoles were synthesized. The structures of all compounds were proven by mass spectrometry, IR, and NMR spectroscopies.     

Synthesis and evaluation of in vitro antibacterial activity of novel 2,5-disubstituted-1,3,4-thiadiazoles from fatty acids

A series of new 1-(alkenoyl/hydroxyalkenoyl)-4-benzoyl-thiosemicarbazides 2a-d and 2-benzamide-5-alkenyl/hydroxyalk-enyl-1,3,4-thiadiazoles 3a-d were synthesized from fatty acid hydrazides. Structure of all these compounds was confirmed by IR, 1H NMR, 13C NMR, mass spectra and elemental analysis. The bioassay results indicate that some compounds 2,c, 2d, 3c and 3d have good antibacterial activity.     

[5-(芳亚甲基氨基)-1,3,4-噻二唑-2-基]硫乙酰芳胺的合成及 生物活性研究

在K2CO3存在下利用聚乙二醇-400 (PEG-400)作相转移催化剂, 于固-液相转移催化条件下, 通过5-芳亚甲基氨 基-2-巯基-1,3,4-噻二唑与氯乙酰芳胺的硫烷基化反应, 合成了16个未见文献报道的[5-(芳亚甲基氨基)-1,3,4-噻二唑-2-基]硫乙酰芳胺衍生物. 经元素分析, FT-IR,1H NMR和13C NMR确证了其结构. 生物活性实验结果表明, 部分化合物对小麦幼苗的生长具有明显的植物生长调节活性, 并对枯草杆菌具有一定的抑制活性.     

Synthesis,Characterization, and Antimicrobial Properties of New 1,3,4‐Thiadiazoles Derived from Azo Dyes

Some new 1,3,4‐thiadiazoles derived from azo dyes were synthesized. Two different synthesis methods were used for these compounds: Esters pertaining to the azo dyes were converted into 1,3,4‐thiadiazoles, or benzothiazole ester derivatives were converted to 1,3,4‐thiadiazoles followed by the synthesis of azo dye derivatives. The desired products were successfully obtained using the latter method. The molecular structures of these compounds were characterized using spectroscopic methods such as FTIR, ¹H NMR, ¹³C NMR, and elemental analysis. Furthermore, antimicrobial activity was studied for the synthesized compounds. Compound 3e exhibited antimicrobial activity against three different microorganisms. Compounds 3a , 3b , and 3d had activity against two different microorganisms, while compound 3c showed activity against only one microorganism.