新双硫代甲酸盐衍生物的合成

双硫代甲酸盐可用作抗菌剂,橡胶硫氏剂,也是过渡金属的良好配位体。但是大多数研究都只限于脂肪族一元胺衍生物,本文报道芳香族及脂肪族多元胺的双硫代甲酸盐的合成。产物的红外光谱,核磁共振谱和元素分析结果列于附表。     

Acylation of dithiocarbamates derived from l-ephedrine and d-pseudoephedrine

The acylation of dithiocarbamates derived from l-ephedrine and d-pseudoephedrine gives, depending on the structure of the acylating agent, acyl derivatives of the dithiocarbamates or their cyclic decomposition products, viz. oxazolidinethiones.     

Jodimetric estimation of water-soluble dithiocarbamates

Summary Iodimetric estimation of dialkyl dithiocarbamate in alcoholic solution is not accurate. The method has not met with success for the water-soluble dithiocarbamates before. A simple and accurate iodimetric method has been developed for the estimation of water-soluble dithiocarbamates. The success of the method is due to the removal of the oxidation product which interferes during the titration with iodine.     

三丁基锡二硫代氨基甲酸酯的合成及表征

通过三丁基氯化锡与二硫代氨基甲酸盐反应,合成了１０个 三丁基锡二硫代氨基甲酸酯,利用元素分析,ＩＲ、ＨＮＭＲ、ＵＶ和ＴＧ－ＤＴＡ表征了这些化合物结构,测定了部分化合物的生物活性。     

A new method for the synthesis of dithiocarbamates by CuI-catalyzed coupling reaction

The Ullmann-type coupling reaction of sodium dithiocarbamates with aryl iodides and vinyl bromides catalyzed by CuI/N,N-dimethylglycine proceeds smoothly in DMF at 110 °C to give corresponding dithiocarbamates in good yields.     

Analytical applications of copper(II) and copper(I) in acetonitrile: potentiometric and spectrophotometric determination of dithiocarbamates

The use of copper(II) perchlorate and tetra-acetonitrilocopper(I) perchlorate (in acetonitrile) for the potentiometric and spectrophotometric determination of dithiocarbamates in acetonitrile medium is described. The proposed methods are simple, accurate and reliable and show promise of wide applicability. They are recommended for routine determination of dithiocarbamates. Their advantages over the carbon disulphide evolution method, commonly employed for the determination of these compounds, are discussed.     

Monitoring and confirming primary alkylamines via a simple derivatisation procedure

Carbon disulphide reacts readily with primary alkylamines to yield dithiocarbamates. When injected into the heated injection port of a gas chromatograph, the dithiocarbamates yield the corresponding isothiocyanates. This reaction provides a simple and elegant derivatisation for quantifying, and also confirming the identify of, the primary alkylamines.     

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.     

Triton-B Catalyzed Efficient One-Pot Synthesis of Dithiocarbamate Esters

A novel process for the one-step chemoselective conversion of alkyl halides into dithiocarbamates as protected amines was developed using benzyltrimethylammonium hydroxide (Triton-B) in presence of carbon disulfide. Thus, dithiocarbamates of different amines were prepared in very good to excellent yields. This protocol is mild, chemoselective, and efficient compared to other methods.     

无溶剂无催化剂条件下二硫代氨基甲酸酯衍生物的合成研究

主要研究了二硫代氨基甲酸酯衍生物的合成,将脂肪胺、CS2与α,β-不饱和羰基化合物或卤代烃在无溶剂无催化剂室温条件下,"一锅法"进行了Michael-type的加成反应,合成了二硫代氨基甲酸酯衍生物.该方法产率高,操作简单,是一种原子经济的合成方法,并可大规模地用于制药及农药方面.     

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.     

Dithiocarbamates as universal reversible addition‐fragmentation chain transfer agents

Control of the radical polymerization of acrylates, styrene and vinyl acetate has been achieved by using novel dithiocarbamates as reversible addition‐fragmentation chain transfer agents. The key parameter for the control with N,N‐disubstituted (A) or cyclic (B) dithiocarbamates was found to be the conjugation of the lone pair of electrons of the nitrogen atom with carbonyl or aromatic groups.     

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.     

Spectrophotometric determination of some dithiocarbamates

A procedure has been developed for the determination of six dithiocarbamates [sodium dimethyldithiocarbamate (dibam), sodium diethyldithiocarbamate (NaDDC), tetramethylthiuram disulphide (thiram), zinc dimethyldithiocarbamate (ziram), sodium N-methylpiperazinecarbodithioate and potassium morpholine-4-carbodithioate] in microgram quantities by converting them into selenium dithiocarbamate complexes, which are then extracted into chloroform and measured at 430 nm against a reagent blank. The method is sensitive and can be used for the determination of dithiocarbamates in commercial samples and synthetic mixtures.     

Determination of N,N-Dialkyl Dithiocarbamates in Wastewater by Thin-Layer Densitometry

Abstract

The quantitative determination of N,N-dialkyl dithiocarbamates tetramethylthiuram disulfide and tetramethyl-thiuram monosulfide in industrial wastewater was studied by thin-layer densitometry of their copper complexes. It has been demonstrated that a densitometer provides a simple and rapid means to quantitate these compounds. N,N-dialkyl dithiocarbamates have been analyzed in microgram quantities using this method. Coefficients of variation of 2–6 per cent were obtained.     

氯代二苯基锗氨荒酸酯的合成及表征

以二苯基二氯化锗和氨荒酸钠为原料,合成了十三种氯代二苯基锗氨荒酸酯Ph2GeCl(S2CNRR'),利用元素分析、IR、1^HNMR、UV和MS表征了这些化合物的结构,确定了氨荒酸基是非均性的双齿形式与锗原子配位。生物活性测试表明,该类化合物对KB和BeL癌细胞具有较好的抑制活性。     

A High Yielding, One-Pot, Triton-B Catalyzed Synthesis of Dithiocarbamates Using Alcoholic Tosylates

Summary. A novel process for the one-step chemoselective conversion of alcoholic tosylates into dithiocarbamates as protected amines was developed using benzyltrimethylammoniumhydroxide (Triton-B) in presence of carbon disulfide. Thus, dithiocarbamates of different amines were prepared in very good to excellent yields. This protocol is mild, chemoselective, and efficient compared to other reported methods. Present address: Institute of Organic and Biomolecular Chemistry, Georg-August University, D-37077, G?ttingen, Germany     

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     

Triton-B Catalyzed Efficient One-Pot Synthesis of Dithiocarbamate Esters

Summary. A novel process for the one-step chemoselective conversion of alkyl halides into dithiocarbamates as protected amines was developed using benzyltrimethylammonium hydroxide (Triton-B) in presence of carbon disulfide. Thus, dithiocarbamates of different amines were prepared in very good to excellent yields. This protocol is mild, chemoselective, and efficient compared to other methods. Present address: Institute of Organic and Biomolecular Chemistry, Georg–August University, D-37077 G?ttingen, Germany     

Non-aqueous cerimetric determination of dithiocarbamates and its application to the determination of amines

A non-aqueous titrimetric method for determination of dithiocarbamates with cerium(IV), is described. The compounds are titrated at room temperature, with visual and potentiometric end-point detection. In visual titrations, the reagent serves as self-indicator and turns the solution yellow at the end-point. Methyl Red can also be used as the indicator. The method has been applied to the determination of amines after their quantitative conversion into dithiocarbamates by reaction with carbon disulphide. The proposed method is accurate to +/- 0.8% with a relative standard deviation of +/- 0.7%.