Quantenchemische Ab‐initio‐Berechnungen an schwefelorganischen Verbindungen: Experimentelle und theoretische Untersuchungen an Thioformaldehyd und Dithioglyoxal

In Reaktionsgemischen von Acetylenen RC  CR (1) mit R  H, CH3, C2H5, C3H7, C4H9, C(CH3)3, C6H5 mit ClSSCl/AlCl3/H2CCl2 oder mit S8/SbCl5/H2CCl2 lassen sich bei 250 K zunächst 1,2‐Dithiet‐Radikalkationen R2C2S2⊕ (2a – g) und nach Erwärmen auf 300 K zusätzlich 1,4‐Dithiin‐Radikalkationen R4C4S2⊕ (3) ESR‐spektroskopisch nachweisen. Ihre Erzeugung gelingt auch durch Umsetzung von 1,2‐Dichlorethen‐ oder 1,1,2,2‐Tetrabrom‐ethan‐Derivaten mit Na2S2/AlCl3/H2CCl2, die sich zur 33S‐Isotopenmarkierung eignet. Nach geometrie‐optimierten closed und open shell MNDO‐Berechnungen ist sowohl für H2C2S2 wie für H2C2S 2˙⊕ die Vierring‐Struktur bevorzugt; hohe Spindichte in der Disulfid‐Gruppierung erklärt die beobachteten großen g‐Faktoren und 33S‐Koppungskonstanten.

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Radikalionen, 71. Oxidative Schwefelung von Acetylenen zu 1,2‐Dithiet‐ und 1,4‐Dithiin‐Radikalkationen

Bock

Rittmeyer

Stein

1986

Chem. Ber.

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MO‐LCAO‐Berechnungen an schwefelhaltigen π‐Elektronensystemen. XLIX. Tetramethinverbrückte Oxalsäurederivate – neue farbige Pigmente von indigoider Struktur

Beckert

Fabian

1986

J. Prakt. Chem.

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MO‐LCAO Calculations on Sulfur‐containing π‐Electron Systems. XLIX. Tetramethine Bridged Derivatives of the Oxalic Acid – Novel Coloured Pigments of Indigoid Structure Whereas thioamides react with the oxalylchloride to Δ2‐thiazoline‐4,5‐diones 1, which are precursors of the versatile thioacylisocyanate 2 synthons, the analogous reaction between thioamides and oxalyl‐bis(arylimidchlorides) completely fails. In the case of aliphatic thioamides the intermediate 2‐methyl‐Δ2‐thiazoline‐4,5‐diimides 3 undergo oxydative dimerization. The poorly soluble products are tetramethine bridged heteroanalogous oxalates 4 or isomers. The u.v./vis spectra of the blue compounds are in favour with structure 4 rather than with structure 6. This conclusion has been drawn from the results of Pariser‐Parr‐Pople(PPP) type calculations. According to the calculated position of the colour band of the pigments and of different molecular subunits, and the correspondence of their electronic states involved in the excitation, the dye molecules can be thought as consisting of two symmetrically crossed polymethine chains. This structural feature is inherent to the H indigo chromophore.

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Reaction of 3H, 6H‐1, 2‐Dithiolo[4,3‐c]1,2‐dithiole‐3, 6‐dithione with primary aliphatic amines

et al. 1991

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The reaction of 3H,6H‐1,2‐dithiolo[4,3‐c]1,2‐dithiole‐3, 6‐dithione (1) with primary aliphatic amines (8a,b) gives 3H,6H‐3,6‐bisalkylimino‐1,2‐dithiolo[4,3‐c]1,2‐ dithiole (9a,b), 3H,3‐N‐alkylamino‐5‐N‐alkylthiocarbamido‐1, 2‐dithiolium‐4‐thiolate (10a,b) and 3H,3‐N‐alkylimino‐4‐alkylamino‐5‐N‐alkylthiocarbamido‐1,2‐dithiole (11a,b). The compounds 9‐11 can be formed from one another. The compounds 10a,b react with nickel chloride to the stable complexes 14a,b. In basic medium 10 gives the salt of 3H,3N‐alkylthiocarbamido‐1,2‐dithiole‐4‐thiolate 15, which reacts with methyl iodide to 3H,3N‐alkylimino‐5‐N‐alkylthiocarbamido‐4‐methylthio‐1,2‐dithiole 16.

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Quantenchemische Ab‐initio‐Berechnungen an schwefelorganischen Verbindungen: Experimentelle und theoretische Untersuchungen an Thioformaldehyd und Dithioglyoxal

Cited by 18 publications

References 145 publications

Radikalionen, 71. Oxidative Schwefelung von Acetylenen zu 1,2‐Dithiet‐ und 1,4‐Dithiin‐Radikalkationen

Radikalionen, 71. Oxidative Schwefelung von Acetylenen zu 1,2‐Dithiet‐ und 1,4‐Dithiin‐Radikalkationen

MO‐LCAO‐Berechnungen an schwefelhaltigen π‐Elektronensystemen. XLIX. Tetramethinverbrückte Oxalsäurederivate – neue farbige Pigmente von indigoider Struktur

Reaction of 3H, 6H‐1, 2‐Dithiolo[4,3‐c]1,2‐dithiole‐3, 6‐dithione with primary aliphatic amines

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