E. Fanghänel

Donatorsubstituierte Polyacetylene und Analoga II. Notiz über die Synthese einfacher Derivate des neuen heterobicyclischen Grundkörpers 3H,6H-1,2-dithiolo[4,3-c](1,2)-dithiol

Abstract Sulfuration of 2,3-di-tert-butylthio-fumarates with phosphorus-pentasulfide leads to 3H,6H-1,2-dithiolo[4,3-c] (1,2)-dithiol-3,6-dithione. Desulfuration gives the mono-thione and di-one, respectively.

Organylselenoacetylene und selenocyanate; 77Se- und 13C-NMR-chemische verschiebungen und 77Se- 13C-spin-kopplungskonstanten

Abstract 77Se and 13C NMR chemical shifts and 77Se-13C spinspin coupling constants of mono- and bis(organylseleno)acetylenes and organyl selenocyanates are shown. The changes of 77Se chemical shifts caused by variation of the organyl groups are well reflected by known increments. The δ(77Se) and 1J(77Se13C) values of the investigated compounds are discussed in relation to the corresponding alkyl- and vinyl-selenides. The 1J(77Se13C) values of the selenoacetylenes and selenocyanates as well as alkyl- and vinyl-selenides are linearly dependednt (i) on 1J(13C1H) values of the corresponding hydrocarbons, hydrogen cyanide respectively and (ii) on the product of the s-characters of the coupled Se and C atoms. These linear correlations prove the predominance of the Fermi contact term for changes of the one-bond 77Se13C coupling in dependence on hybridization.

Addition compounds of nucleophiles and 3-ethylthio-6-oxo-6H-1,2-dithiolo[4,3-c]1,2-dithiolium tetrafluoroborate. Synthesis of 3H,6H-1,2-dithiolo[4,3-c]1,2-dithiole-3-one-6-thione

SummaryA smooth method of synthesizing 3H, 6H-1,2-dithiolo[4,3-c]1,2-dithiole-3,6-dithione (3), and also its partial desulfuration to yield 3H, 6H-1,2-dithiolo[4,3-c]1,2-dithiole-3-one-6-thione (4) is presented. The ethylation product5 of the monothione4 reacts with various nucleophilic reagents to form remarkably stable adducts. The adducts of5 with methanol,tert-butyl mercaptan, and with aniline could be isolated and characterized by their1H-NMR spectra.ZusammenfassungEine glatte Synthese für 3H,6H-1,2-Dithiolo[4,3-c]1,2-dithiol-3,6-dithion (3) und für dessen partielle Entschwefelung zu 3H,6H-1,2-Dithiolo[4,3-c]1,2-dithiol-3-on-6-thion (4) wird angegeben. Das Ethylierungsprodukt5 des Monothions4 reagiert mit unterschiedlichen Nukleophilen zu bemerkenswert stabilen Addukten. Die Addukte mit Methanol,tert.-Butylmercaptan und mit Anilin wurden isoliert und durch ihr1H-NMR-Spektrum charakterisiert.