Aromatic reactivity. Part XXXVIII. Protodesilylation of 1,2-dihydrobenzocyclobutene, indan, and tetralin

Journal of the Chemical Society B: Physical Organic Pub Date: DOI: 10.1039/J29690000012

Abstract

Rates of cleavage (protodesilylation) of some trimethylsilyl derivatives of reduced benzocycloalkenes and o-xylene by a mixture of 10·6M-aqueous perchloric acid and methanol (2 : 5 v/v) have been measured spectrophotometrically. Values (min.–1) of the first-order rate constants (×103) at 50·0° are as follows: 3-trimethylsilyl-o-xylene, 193; 4-trimethysilyl-o-xylene, 153; 1,2-dihydro-3-trimethylsilylbenzocyclobutene, 16·1; 1,2-dihydro-4-trimethylsilylbenzocyclobutene, 154; 4-trimethylsilylindan, 77; 5-trimethylsilylindan, 210; 5-trimethylsilyltetralin, 235; 6-trimethylsilyltetralin, 181. (Ring-opening, which complicates most studies of the behaviour of 1,2-dihydrobenzocyclobutene and its derivatives towards electrophilic reagents, does not occur under the cleavage conditions.)

The main features of the results are the low reactivity of the 3-(aryl α-) and the normal reactivity of the 4-(aryl β-) position of 1,2-dihydrobenzocyclobutene in comparison with the corresponding positions of o-xylene. The aryl α-position of indan shows a somewhat lower reactivity, but the aryl β-position shows a slightly enhanced reactivity, as do both the aryl α- and β-positions of tetralin. It is suggested that strain and carbon-hydridization effects of the small rings operate jointly to determine the reactivities.

Use of desilylation is suggested as a possible route to 3-substituted 1,2-dihydrobenzocyclobutenes.

Recommended Literature