硫代氨基甲酸酯合成方法进展

硫代氨基甲酸酯是一类分子内含有多种官能团的化合物,大多数具有生物活性,在医学、生物、农药等方面有广泛的应用.本文总结了合成硫代氨基甲酸酯的几种主要方法,如水解醇解法、重排反应、光气衍生物法、羰基化法等,并分析了各种方法的利弊.指出利用一氧化碳进行硒催化的硫醇与硝基化合物或苯胺的羰基化反应来合成硫代氨基甲酸酯是一种比较有应用前景的方法.该方法具有环境友好、原子经济性高、步骤简短等优点,并对其做了比较详细的介绍.     

可见光照射下水介质中三组分合成S-烷基二硫代氨基甲酸酯

<正>S-烷基二硫代氨基甲酸酯具有抗肿瘤、抗真菌等多种生物活性,也被用作DNA拓扑异构酶II型抑制剂,是药物分子研发中的一种重要的骨架结构(图1)[1].此外,S-烷基二硫代氨基甲酸酯也被用作除草剂、驱虫剂和杀菌剂等[2].因此,发展新型高效地合成S-烷基二硫代氨基甲酸酯的方法引起较大关注,一些有效的合成策略也相继被报道[3].S-烷基二硫代氨基甲酸酯的传统合成方法是以二硫化碳、胺、与卤代烷烃、     

三苯基锗二硫代氨基甲酸酯的合成及表征

近年来 ,人们相继合成了有机锗倍半硫化物、有机锗硫杂环戊酮、含硫的螺环有机锗等化合Scheme1　 Synthetic route of compound物[1,2 ] .但烃基锗二硫代氨基甲酸酯类化合物尚未见报道 .我们 [3,4 ] 发现 ,有机锡二硫代氨基甲酸酯类化合物有很强的生物活性 .鉴于有机锗化合物比有机锡化合物毒性低得多 ,且副作用小 ,我们以三苯基氯化锗和二硫代氨基甲酸盐为原料 ,合成了一系列新型的有机锗含硫衍生物 (反应式如Scheme1所示 ) ,并对其结构进行了表征 ,初步生物活性测试结果表明 ,部分化合物显示出较强的抗癌活性 .1　实　　验1 .1　仪器与…     

二苄基一氯化锡二硫代氨基甲酸酯的合成

二烃基氯化锡及其衍生物具有较强的抗癌活性，日益受到人们的重视。关于含有Ｓｎ—Ｏ键的二烃基锡衍生物的合成研究已有大量报道［１］。但含Ｓｎ—Ｓ键二烃基锡衍生物的合成研究则较少［２］，而二烃基一氯化锡二硫代氨基甲酸酯的合成研究尚未见报道。为了寻找具有抗癌活...     

三苄基锡二硫代氨基甲酸酯的合成

三苄基锡二硫代氨基甲酸酯的合成尹汉东马春林＊张如芬（聊城师范学院化学系聊城２５２０５９）关键词三苄基氯化锡，二硫代氨基甲酸盐，合成１９９７－０７－１０收稿，１９９７－０９－０９修回山东省自然科学基金资助项目三烃基锡衍生物是一类具有较强生物活性的有机锡...     

高效液相色谱-二极管阵列检测法测定小麦粉及面粉改良剂中福美双

福美双是重要的二硫代氨基甲酸酯(DTC)杀菌剂,在小麦中使用限量以1 mg/kg二硫化碳(CS2)计.目前我国相关检测方法是针对二硫代氨基甲酸酯一类的化合物,二硫代氨基甲酸酯通过与酸反应生成CS2,采用光谱法或色谱法测定CS2,间接实现二硫代氨基甲酸酯测定.该方法无法特异性实现对福美双的检测,因此开展小麦粉中福美双检测...     

硒作用下苯胺和硫醇羰基化合成硫代氨基甲酸酯

报道了一种新颖且简易的合成硫代氨基甲酸酯的方法. 在硒作用下, 苯胺和硫醇的羰基化反应在室温常压条件下顺利进行, 大多数目标产物硫代氨基甲酸酯的收率从中等到较高. 硒在反应结束后可方便地回收并能循环使用.     

铜促进硫代色酮类化合物的合成研究

基于底物设计的概念,建立了一种以β-羰基二硫代羧酸酯和取代邻溴代苯乙酮为合成子,在碘化亚铜/邻菲罗啉促进下高化学选择性地合成硫代色酮类衍生物的新方法.该方法高效、简便且收率高.     

3-羟基邻苯二甲酰亚胺全水溶性次氯酸荧光探针及其应用

利用二甲基硫代氨基甲酸酯对次氯酸(HOCl)的特异性和吡啶盐的水溶性,以4-羟基异苯并呋喃-1,3-二酮作为原料,设计合成了一种检测HOCl的全水溶性激发态分子内质子转移(ESIPT)荧光探针.由于二甲氨基硫代甲酸酯对羟基的保护,探针分子内的ESIPT作用被阻碍,自身无荧光;当加入HOCl时,HOCl氧化二甲氨基硫代甲...     

超声辐射下2-硫代羰基-2H-噻喃和2-氨基-6-硫代羰基二氢吡啶衍生物的高效合成

探索了一种超声辐射下氢氧化钠催化的芳亚乙基丙二腈与二硫化碳或异硫氰酸酯的反应,方便、快速地合成了2-硫代羰基-2H-噻喃和2-氨基-6-硫代羰基二氢吡啶衍生物.本方法具有操作简单、反应时间短、产率高、环境友好等优点.产物的结构经过核磁共振氢谱和碳谱、红外及质谱进行确定.本报道的方法为合成2-硫代羰基-2H-噻喃和2-氨基-6-硫代羰基二氢吡啶衍生物提供了一条有效途径.     

Straightforward and highly efficient catalyst-free one-pot synthesis of dithiocarbamates under solvent-free conditions

[Structure: see text] A highly efficient and simple synthesis of dithiocarbamates is possible based on the one-pot reaction of amines, CS2, and alkyl halides without using a catalyst under solvent-free conditions. The mild reaction conditions, high yields, and broad scope of the reaction illustrate the good synthetic utility of this method. The reaction is a highly atom-economic process for production of S-alkyl thiocarbamates and successfully can be used in high quantities in the pharmaceutical or agrochemical industries.     

Highly efficient and catalyst-free synthesis of unsymmetrical thioureas under solvent-free conditions

A highly efficient and simple synthesis of unsymmetrical thioureas is reported based on the reaction of readily synthesized dithiocarbamates with amines, without using any catalyst under solvent-free conditions. The short reaction time, high yields, and solvent-free conditions are advantages of this method. We did not observe the formation of any symmetric disubstituted thiourea, under these reaction conditions.     

A novel isocyanide-based three-component reaction: a facile synthesis of substituted 2H-pyran-3,4-dicarboxylates

An efficient method for synthesis of 2H-pyran-3,4-dicarboxylates using the three-component reaction of dithiocarbamates, dialkyl acetylenedicarboxylates, and isocyanides in solvent-free conditions is described. In these reactions, synthesis of dithiocarbamates is possibly based on the one-pot reaction of secondary amines, CS₂, and alkyl halides in solvent-free conditions without using a catalyst. The mild reaction conditions and high yields of the reaction exhibit the good synthetic advantage of these methods.     

Synthesis of novel dithiocarbamates and xanthates using dialkyl azodicarboxylates: SN bond formation

A one?pot three?component route for the synthesis of a novel category of dithiocarbamates or xanthates is developed by a reaction of in-situ generated dithiocarbamic acids or xanthates with dialkyl azodicarboxylates under mild and catalyst-free conditions. The reaction is characterized by a wide scope, high efficiency and straightforward isolation protocol. The synthetic utility of the dithiocarbamates and xanthates was demonstrated on the preparation of symmetrical and unsymmetrical thioureas, isothiocyanates, and thiocarbamates.     

OH−/Silica-Mediated One-Pot Synthesis of Dithiocarbamates Under Solvent-Free Conditions

Abstract

An efficient, versatile, and environmentally benign method for the synthesis of dithiocarbamates under solvent-free conditions is reported. The Michael addition of electron-deficient alkenes with alkyl or aryl amines and CS₂ in the presence of OH^?/silica in a one-pot three-component reaction protocol gave the corresponding dithiocarbamates in good to excellent yields. This method is suitable for a wide range of amines and a variety of Michael acceptors in solvent-free conditions. The results of the present work show the desired products in excellent yields.     

Versatile and Large-Scale Synthesis of Functional Dithiocarbamates in Water

Structural diversity is possible in direct access to functional dithiocarbamates based on a highly efficient and simple one-pot reaction of CS₂, amines, and alkyl halides in nearly quantitative yields in water.     

An electron donor–acceptor photoactivation strategy for the synthesis of S-aryl dithiocarbamates using thianthrenium salts under mild aqueous micellar conditions

An eco-friendly and convenient method is developed herein for the synthesis of S-aryl dithiocarbamates via visible-light-induced SET process of an EDA complex between thianthrenium salt functionalized arenes and dithiocarbamate anions under mild aqueous micellar conditions. This strategy indirectly realizes the method for constructing S-aryl dithiocarbamates through site-selective C−H functionalization of arenes. Most importantly, the reaction proceeded smoothly without addition of any photocatalyst, and the by-product thianthrene is recycled in quantity, ultimately minimizing the production of chemical waste. This protocol provides a promising synthesis candidate for the construction of valuable S-aryl dithiocarbamates, which also opens up a new avenue for micellar photocatalysis.     

An easy access to functionalized allyl dithiocarbamates from Baylis-Hillman adducts in water

A facile and direct highly stereoselective synthesis of [E]- and [Z]-allyl dithiocarbamates has been accomplished from acetates of Baylis-Hillman (BH) adducts in catalyst-free one-pot three-component coupling reactions of carbon disulfide and amine in water under a mild and green procedure with high yields. The reaction pathway involves the nucleophilic displacement (SN2′) of BH acetates by dithiocarbamate anions. The utility of these allyl dithiocarbamates has also been demonstrated in heterocyclic chemistry. © 2009 Elsevier Science. All rights reserved     

Stannous Chloride–Promoted Synthesis of S-Allyl-N-aryl Dithiocarbamates under Solvent-Free Conditions

Abstract

A highly efficient method of synthesis of S-allyl-N-aryl dithiocarbamates using SnCl₂ as a catalyst under solvent-free conditions is described. The mild reaction conditions, high yields, and shorter reaction period illustrate the good synthetic utility of this method.     

Photochemical and thermal transformations of carboxylic dithiocarbamic anhydrides and acyl xanthates

The reaction of diphenylchloroacetyl chloride with different dithiocarbamates gave the corresponding dithiocarbamic anhydrides. Under analogous conditions, dithiocarbamyl phenylacetic acids and dithiocarbamyl acetic acids were formed from the reaction of dithiocarbamates with phenylchloroacetyl chloride and chloroacetyl chloride, respectively. O-Ethyl S-acyl xanthates were formed from the reaction of potassium O-ethyl xanthate with diphenylacetyl chloride, diphenylchloroacetyl chloride, cyclopentylphenylacetyl chloride and triphenylacetyl chloride. Photolysis of dithiocarbamic anhydrides gave a mixture of products consisting of 1,2-dichlorotetraphenylethane, carbon monoxide and the corresponding thiocarbamoyl sulfides. Acyl xanthates, on the other hand, gave carbon monoxide and the corresponding substituted ethane derivatives. When dithiocarbamic anhydrides were refluxed in hydroxylic solvents such as methanol, ethanol and n-propanol, the corresponding dithiocarbamyl acetates were formed. Thermal decomposition of acyl xanthates gave carbon disulfide and the corresponding esters.