The Dissociation Rates of 1,1,1,2-Tetraphenyl-2-Arylethanes Containing Tetralyl, Naphthyl, Fluoryl, and Tetrahydrophenanthryl Groups

Abstract

The present paper is a continuation of the study of the rates of dissociation of pentaarylethanes (1, 2, 3). Six new pentaarylethanes of the type (CgH6)3C-CH (CgH6) R have been synthesized in which R is 5,6,7,8-tetrahydro-1-naphthyl (I), 1,2,3,4-tetrahydro-9-phenanthryl (II), 4-methyl-l-naphthyl (III), 4-fluoryl (IV), 5,6,7,8-tetrahydro-2-naphthyl (V), and 1-fluoryl (VI).The rate constants (k) and half-life periods (ti) of these 1,1,1,2-tetraphenyl-2arylethanes in the reaction with iodine (2) at 80°have been determined; the values for these constants are shown beneath the formulas for the groups

Different Behavior of Nitrenes and Carbenes on Photolysis and Thermolysis: Formation of Azirine, Ylidic Cumulene, and Cyclic Ketenimine and the Rearrangement of 6-Phenanthridylcarbene to 9-Phenanthrylnitrene

“…At 1000 °C the following results were obtained: fluorene, 1.2%; 9-cyanofluorene, 95.9%; 1-cyanofluorene, 2.9% (uncorrected GC integration). 1-Cyanofluorene was isolated by sublimation (85 °C, 10 -3 mbar) and recrystallization from petroleum ether (bp 60−80 °C) and had a mp of 92−94 °C (literature value, 94−94.5 °C), and its IR and UV spectra were identical with those reported . The 2-, 3- and 4-cyanofluorenes were not detectable in this experiment.…”

“…The extract was dried over MgSO 4 , filtered, and evaporated to yield a crude solid (66 mg). This was purified by flash silica gel chromatography (eluent CH 2 Cl 2 ) to afford a white solid (30 mg, 73%; or 95% based on recovered fluorene-4-carboxylic acid (10 mg, 22%)); mp 77 °C (literature value, 77−78 °C); GC/MS R t 11.18 min; m / z 191, 163, 95, 81; 1 H NMR (200 MHz, CDCl 3 ) 3.89 (s, 2H), 7.30−7.46 (m, 3H), 7.58 (d, 1H, J = 7.8 Hz), 7.62 (d, 1H, J = 7.8 Hz), 7.72 (d, 1H, J = 7.6 Hz), 8.42 (d, 1H, J = 7.6 Hz).…”

“…Fluorene-1-carbonitrile 16. This was prepared analogously to 13 from 210 mg (1 mmol) of fluorene-1-carboxylic acid with chlorosulfonyl isocyanate to yield 121 mg (63%); mp 92 °C (literature value, 94−94.5 °C); GC/MS R t 10.97 min; m / z 191.…”