Dithioate esters

Carbon disulfide (1) reacts with compounds that possess acidic methylene a-hydrogens, like 1,3-dithian (24), sulfoxides and sulfones, in the presence of a strong base. Thus, 1,3-dithian (24) may be converted into either the dithioate ester (25) or the dithioacetal (26) via the intermediate (27) or (28), depending on the amount of base used (Scheme 12). Sulfoxides (RSOCH2R ) and sulfones (RS02CH2R ) react similarly with carbon disulfide, butyllithium and an alkyl halide (R"X) to yield either (29) or (30) (Scheme 13). 

When the reaction of an aminophenol with A -ethoxycarbonylthioamide or a dithioate ester is applied to an aminothiophenol, a high yield of benzothiazole is obtained [2860, 2899]. The same substrate is converted into a benzothiazole efficiently at ambient temperature with hydroxamoyl chloride (the chloride of a hydroxamic acid) [3468]. Similar compounds in which the 2-phenyl group is varied are of interest as dye intermediates and are synthesized from quinonoid aminothiols [3477] the chemistry of quinonoid heterocyclcs has been reviewed [2947, 3650]. 

Dithioate esters react with a diamine at room temperature in methanolic alkali at pH 8 to give high yields of 2-aIkyl- or 2-aryl-sub tituted benzimidazoles [2860]. It is diflicult to convert benzimidazoIe-2-carboxylic acid into its amides by conventional methods as it condenses with itself to form a pentacyclic product, but when o-phenylenediamine is heated with an oxamic ester, the... 

Section 15.4 contains anion radicals from nitro compounds. No subdivision has been made into compounds containg one, two or more nitro groups. In the case of a dianion that follows die monoanion directly. Section 15.5 contains tables of magnetic data obtained from anion radicals wifli carbonyl functionality and their sulphur analogs. The data have been divided into subsections consisting of esters and thioesters aldehydes, ketones and their thio analogs semidiones and acid anhydrides. These subsections have been furdier subdivided, for example the subsection Esters and thioesters has been subdivided into arylesters, fliioe-sters and oxocarbothioate and dithioate esters. 

Association of phosphoro and phosphono dithioate esters into dimeric units may also occur under suitable conditions. 

Phosmet phosphoro organic, phosphoro dithioate Phosphamidon phosphoro organic, phosphate ester, amide... 

SYNS CDEC CHLORALLYLDIETHYLDITHIO-CARBAMATE 2-CHLOROALLYL DIETHYLDITHIO-CARBAMATE 2-CHLOROALLYL-NA -DIETHYLDITHIOCARBAMATE 2-CHLORO-2-PROPENE-1-THIOL DIETHYLDITHIOCARBAMATE 2-CHLORO-2-PROPENYL DIETHYLCARBAMO-DITHIOATE CP 4572 DIETHYLCARBAMO-DITHIOIC ACID 2-CHLORO-2-PROPENYL ESTER DIETHYLDITHIOCARBAMIC ACID-2-CHLOROALLYL ESTER NCI-C00453 SULFALLATE THIOALLATE VEGADEX VEGADEX SUPER... 

SYNS S-(6-CHLORO-3,4-DIHYDRO-2H-l-BENZO-THIOPYRAN-4-YL) o,o-DIMETHYL PHOSPHORO-DITHIOATE PHOSPHORODITHIOIC ACID, S-(6-CHLORO-3,4-DIHYDRO-2H-l-BENZOTHIOPYRAN-4-YL) 0,0-DIMETHYL ESTER... 

S-(((p-CHLOROPHENYL)THIO)METHYL) 0,0-DI-METHYL PHOSPHORODITHIOATE S-(((4-CHLORO-PHENYL)THIO)METHYL) 0,0-DIMETHYLPH0SPH0R0-DITHIOATE DIMETHYL-p-CHLOROPHENYLTHIO-METHYL DITHIOPHOSPHATE 0,0-DIMETHYL-S-(p-CHLOROPHENTXTHIOMETHYL)PHOSPHORODITHIOA TE 0,0-DIMETHYLTHI0PH0SPH0RIC ACID, p-CHLOROPHENYL ESTER ENT 25,599 G-29288 GEIGY G-29288 METHYLCARBOPHENOTHION R-1492 STAUFFER R-1492 TRI-ME... 

They experimented with four other proteins as carriers rabbit serum albumin, bovine serum albumin, bovine fibrinogen fraction I, and bovine )8-globulin fraction III. The structurally related derivatives of DDT and malathion, DDA, and 0,0-dimethyl S-carboxy-carboxyethyl phosphoro-dithioate (malathion half ester), respectively, were used as the specific haptens attached to these carrier proteins. These compounds contain free carboxyl groups, which when they reacted with thionylchloride, provide a means of coupling of the hapten to the amino groups of the protein carrier. 

These are named as dithioic acids for example, Me(CFI2)4CS2FI is hexanedithioic acid. The corresponding salts and esters are termed dithioates ... 

A Diels-Alder cycloaddition of methyl pentamethylcylopentadiene-5-carbo-dithioate (83 X=S) with AT-phenylmaleimide takes place with complete anti-n-facial selectivity to give antz-84, while that of the corresponding ester 83 (X=0) shows syn-7i-facial selectivity to give syn-S4 predominantly, as shown in Eq. 23... 

A variety of (dithioperoxo)thioic acid esters 220 were synthesized in moderate to good yields by reacting dithioate magnesium halides 221 with S-alkyl p-toluenethiosulfonates 222 or S-methyl methanethiosulfonates (223) (Scheme 43) [136,137]. Oxidation of 220 with m-CPBA gave the sulfines 224 as an E-Zgeometrical mixture [136]. These sulfines isomerized to acyl trisulfides (R C(O)-S3R ) after 10 days at room temperature. 

With electron-deficient acetylenes, the dithioate anions can be involved in the reactions of both 1,3-anionic cyclo- and nucleophilic additions [550], The reactions of 1,3-anionic cycloaddition are typical provided that the central atom of [S-C-S] has aromatic substituents ensuring the anion stabilization [551,552], For instance, potassium pyrrole-l-carbodithioate selectively reacts (acetonitrile, -30°C, CH3COOH) with dimethyl ester of acetylenedicarboxylic acid to form rapidly polymerizing 2-(pyrrol-l-yl)-4,5-dimethoxycarbonyl-l,3-dithiol (Scheme 2.80) [552,553]. 

Kuz mina, N.Ya., M.L. Petrov, and A.A. Petrov. 1984. The effects of substituents in dithioate-anions on the course of the reaction with acetylenedicarboxylic acid dimethyl ester. Zh Org Khim 20 (12) 2511-2517. 

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