No abstract

Since Wilmshurst’s method for calculation of group electronegativity has some defects, the revised method was proposed for counting the number of valence electrons (n*) on the central atom A in radical −AB, and group electronegativities of more than 150 substituents were reasonably calculated.

A phospha-indane derivative was obtained via intramolecular C–H insertion of the phosphinidene generated as an intermediate by the photolysis of E-1,2-bis(2,4,6-tri-t-butylphenyl)diphosphene whereas the photolysis through a Pyrex filter at −40 °C gave an equilibrium mixture of E and Z.

No abstract

Highly sterically demanding 2,4,6‐tri‐t‐butylphenyllithium (1) reacts with carbon disulfide to give 1,2‐dibutylthio‐1,2‐bis(2,4,6‐tri‐t‐butylphenylthio) ethene (3), l‐butylthio‐1‐(2,4,6‐tri‐t‐butylphenylthio)pent‐l‐ene (4), and 2‐butylthio‐3‐(2,4,6‐tri‐t‐butylphenylthio)‐1,3‐dithiole‐2‐thione (5) when 1 is prepared by the reaction of 1‐bromo‐2,4,6‐tri‐t‐butylbenzene with n‐butyllithium. When the reaction is carried out using 1 prepared from 2 and t‐butyllithium and then quenched with l‐iodoethane, 2‐ethylthio‐3‐(2,4,6‐tri‐butylphenylthio)‐1,3‐dithiole‐2‐thione and 1,2‐diethylthio‐1,2‐bis(2,4,6–tri‐t‐butylphenylthio) ethene are produced. The formation of all these products can be explained in terms of initial thiophilic attack of 1 on the sulfur of carbon disulfide and an intermediate with a dual property of carbanion and carbene (i.e., ArSC(Li)(S) ⇌ ArSC̈SLi) is suggested. The reaction of 1 with thiophosgene affords 1,2‐dichloro‐1,2‐bis(2,4,6‐tri‐t‐butylphenylthio) ethene, bis(2,4,6‐tri‐t‐butylphenylthio)acetylene, and 1‐chloro 2,4,6‐tri‐t‐butylbenzene, the first two of which are explained to be formed by thiophilic attack of 1 with thiophosgene.