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The reaction of bis(acyl) tellurides with primary or secondary amines or potassium ethanolate yielded the corresponding tellurocarboxylic acid salts, which are readily oxidized with iodine or benzenesulfonyl chloride to afford novel bis(acyl) ditellurides.

A number of unsymmetrical acyl thioacyl sulfides [RC(S)S(O)CR'] have been prepared and characterized by the reaction of piperidinium or sodium dithiocarboxylates with acyl chlorides or by desulfurization reaction of acyl thioacyl disulfides with triphenylphosphine. They are deep blue oils or light green crystals and very unstable thermally and for moisture. The n →π transitions of the thiocarbonyl group of 1 appear in higher wave length region than those of the corresponding symmetrical bis(thioacyl) sulfides [RC(S)S(S)CR']. Some reactions with nucleophiles are discussed. It was found that the symmetricallization reaction of these unsymmetrical acyl thioacyl sulfides occurs in the presence of base such as lithium ethanethiolate to give the symmetrical bis(thioacyl) disulfides in fair yield.

Un fragment du catalyseur Co(CO) 4 − servirait comme equivalent d'un agent d'oxymethylation

The reaction of sodium or caesium dithiocarboxylates with diphenylthiophosphinic and diphenylselenophosphinic chlorides gives purple thioacyl diphenylthiophosphinoyl 5 and dark green thioacyl diphenylselenophosphinoyl sulfides 6, which are useful thioacylating reagents under mild reaction conditions. Thioacyl diphenylphosphino sulfides 22, which can be obtained by the similar method using diphenylphosphinous chlorides, react with methanol to yield the corresponding methyl dithiocarboxylates 15, while the reactions of 22 with N-chlorosuccinimide leads to hitherto unknown N-(thioacylthio)succinimides 28. Darstellung und einige Reaktionen von Thioacyl(diphenylthiophosphinoyl)- und Thioacyl(diphenylphosphino)sulfiden Durch Umsetzung von Natrium- oder Casium-dithiocarboxylaten mit Diphenylthiophosphinsaure- oder Diphenylselenophosphinsaurechloriden werden die rot-violetten Thioacyl(diphenylthiophosphinoyl)- 5 und tiefgrunen Thioacyl(diphenylselenophosphinoyl)sulfide 6, die nutzliche und unter milden Reaktionsbedingungen einsetzbare Thioacylierungsmittel sind, dargestellt. Die Thioacyl-(diphenylphosphino)sulfide 22, die sich nach der gleichen Methode aus Chlor(diphenyl)-phosphan darstellen lassen, reagieren mit Methanol zu den entsprechenden Methyl-dithiocarboxylaten 15. Die Reaktionen von 22 mit N-Chlorsuccinimid liefern bisher nicht bekannte N-(Thioacylthio)succinimide 28.

Synthese d'anhydrides d'acides dithiobenzoique, dithiotoluique, dithioanisique et dithionaphtoique-1 par reaction d'arenedithioates de piperidinium avec l'iodure de (chloro-2 methyl-1) pyridinium dans le methanol

5-Phenylthio-1,3-cyclopentadiene reacted with maleic anhydride to give a 4 : 6 mixture of syn- and anti-attack adducts. In contrast, the selenium isologue, 5-phenylseleno-1,3-cyclopentadiene reacted with dienophiles with remarkable anti-π-facial selectivity to give the corresponding anti-attack adducts, exclusively.

A number of selenium- 2 and tellurium bis(dithiocarboxylates) 3 have been prepared by the reaction of piperidinium or sodium dithiocarboxylates 1 with sodium seleno- and telluropentathionates. The orange or red products are stable towards heat and moisture. It was found that 2 and 3 react with halogens and N-chloro- and N-bromosuccinimide to give the corresponding haloselenium- 4, 5 and halotellurium dithiocarboxylates 6–8 in good yields. The n π* transitions of the thiocarbonyl groups in 2–8 are observed in a region of shorter wavelengths (hypsochromic shift) than those of the corresponding bis(thioacyl) trisulfides and dithio- and thioneselenol esters. Darstellung und einige Reaktionen von Selen- und Tellur-bis(dithiocarboxylaten) Durch Umsetzung von Piperidinium- oder Natrium-dithiocarboxylaten 1 mit Natrium-seleno-oder -telluropentathionaten wurden die Selen- 2 und Tellur-bis(dithiocarboxylate) 3 dargestellt. Die orangefarbenen oder roten Kristalle sind thermisch stabil und nicht feuchtigkeitsempfindlich. Durch Umsetzung von 2 oder 3 mit Halogenen oder N-Chlor- oder N-Bromsuccinimid wurden Haloselen- 4, 5 und Halotellur-dithiocarboxylate 6–8 mit guten Ausbeuten erhalten. Die n πast;-Ubergange der Thiocarbonylgruppen in 2–8 treten bei kleineren Wellenlangen auf (hypsochrome Verschiebung) als die der entsprechenden Bis(thioacyl)-trisulfide sowie Dithio- und Thionselenolester.

Selenium (1) and tellurium bis(trithiocarbonates) (2) were found to react with bromine and iodine to give the corresponding haloselenium (11) and halotellurium trithiocarbonates (7, 8). Reaction of 2 with excess of bromine give tribromotellurium trithiocarbonates (9).

2-(Hydroxyimino)-2-phenylethyl arenedithiocarboxylates were cyclized to isothiazoles by the treatment with tosyl isocyanate.

A series of Se-aryl carboselenothioates 3 (RCSSeAr, R=alkyl, aryl) were synthesized and characterized from the reaction of bis(thioacyl) sulfides 1 with sodium areneselenolates. The thionselenolesters 3 are stable (liquid or crystals) both thermally and to moisture. Reactions of 3 with aliphatic primary and secondary amines gave the corresponding ammonium carbodithioates 8 together with diphenyl diselenide 7. In contrast, treatment with aromatic amines or sodium alcoholates afforded the corresponding thioamides or O-alkyl or O-aryl thionesters in good yields. The oxidation of 3 with m-chloroperbenzoic acid gave the corresponding sulfides 12 [RCS(O)SeAr] and acyl arylseleno sulfides 13 [RCOSSeAr] which are formed by a rearrangement of the ArSe group to the thiocarbonyl sulfur atom.

Reaction of dithioic acids with dicyclohexylcarbodiimide has been found to give the corresponding bis(thioacyl) sulfides 1 in good yield, which are very useful thioacylating reagents under mild reaction conditions. Most of the aromatic thioanhydrides (1, R = aromatic) are fairly stable green crystals at room temperature, but the aliphatic ones (1, R = aliphatic) are unstable purple oils which dimerize at room temperature to give the dithietanes 5. The reactions with nucleophiles are discussed. Darstellung und einige Reaktionen von Bis(thioacyl)sulfiden Durch Umsetzung von Dithiocarbonsauren mit Dicyclohexylcarbodiimid wurden die Bis-(thioacyl)sulfide 1, die nutzliche und unter milden Reaktionsbedingungen einsetzbare Thioacylierungsmittel sind, dargestellt. Die aliphatischen Thioanhydride (1, R = Aliphaten) sind thermisch labile und feuchtigkeitsempfindliche purpurne ole, die bei Raumtemperatur zu den Dithietanen 5 dimerisieren, wahrend die meisten aromatischen Derivate (1, R = Aromaten) tiefgrune, einigermasen stabile Kristalle bilden. Einige Reaktionen mit Nucleophilen werden diskutiert.

The reaction of diphenyltin bis(dithiophosphates) with N-bromo- and N-iodosuccinimides afforded corresponding thiophosphorosulfenyl bromides and iodides, which reacted with a variety of nucleophiles such as thiol, dithiocarboxylic acid, amine and olefin to give novel unsymmetrical disulfides, sulfenamides and dithiophosphoric acid esters.

Preparation par reaction des acides thiocarboxyliques avec les hydrures metalliques (LiH, NaH, KH) et les acetates de Rb et Cs. Proprietes physiques

Halogenation of thiocarboxylic acid O-silyl esters gave acylsulfenyl halides in high yields, involving a thiophilic attack of halogen ion on the sulfur atom of thiocarbonyl group. Aliphatic acylsulfenyl bromide was isolated for the first time.

It has been found that a series of anhydrous alkali metal dithiocarboxylates are readily obtained in good yields by the reaction of dithio acid with metal hydride (LiH, NaH, KH), n-butyl lithium, or rubidium or cesium acetates, respectively. Their spectral data were compared.

Some trimethylmetal(IVb) esters of dithio acids have been prepared by treatment of the secondary or tertiary amine salts of dithio acids with chlorotrimethylsilane, -germane, or -tin, and their IR, UV and NMR spectra recorded.

Cobalt carbonyl catalysed reaction of tetrahydrofurans with HSiEt 2 Me and CO (1 atm) took a new reaction pathway leading to enol silyl ethers when acetonitrile was employed as the solvent.

Halogenation of thiocarboxylic acid O-silyl esters gave acylsulfenyl halides in high yields, involving a thiophilic attack of halogen ion on the sulfur atom of thiocarbonyl group. Aliphatic acylsulfenyl bromide was isolated for the first time.

2-(Hydroxyimino)-2-phenylethyl arenedithiocarboxylates were cyclized to isothiazoles by the treatment with tosyl isocyanate.

It has been found that anhydrous sodium dithiocarboxylates are readily obtained by the reaction of dithiocarboxylic acid with sodium metal or sodium hydride.

Synthese des chlorures de thiobenzoyle substitues par reaction des complexes benzoylthio du diphenyl etain avec le N-chloro succinimide