Propyl chloride, from decomposition

At various temperatures ranging from 200 to 300 °C, fso-propyldichloro-silane was obtained in the highest yield at 220 °C, but decreased as the reaction temperature increased due to the decomposition of iso-propyl chloride. Under these reaction conditions, the yield of fso-propyldichloro-silane was higher compared to those obtained from the direct reaction without hydrogen chloride addition, indicating that the decomposition of iso-propyl chloride was suppressed as expected. The yields generally increased with increased ratios of hydrogen chloride to /so-propyl chloride. 

Preparative photolysis of AETSAPPE (0.25 M aqueous solution) at 254 nm (Rayonet reactor) resulted in the formation of the disulfide product 2-amino(2-hydroxy-3-(phenyl ether) propyl) ether disulfide (AHPEPED) as the primary photoproduct Photolysis of AETSAPPE at 254 nm (isolated line of medium pressure mercury lamp) resulted in rapid initial loss of starting material accompanied by formation (analyzed by HPLC) of AHPEPED (Figure 12a and 12b) (Scheme IV). Similar results were obtained for photolysis- at 280 nm. Quantum yields for disappearance of AETSAPPE and formation of AHPEPED at 254 nm and 280 nm are given in Table I. The photolytic decomposition of AETSAPPE in water was also accomplished by sensitization ( x =366 nm) with (4-benzoylbenzyl) trimethylammonium chloride (BTC), a water soluble benzophenone type triplet sensitizer. The quantum yield for the sensitized disappearance (Table I) is comparable to the results for direct photolysis (unfortunately, due to experimental complications we did not measure the quantum yield for AHPEPED formation). These results indicate that direct photolysis of AETSAPPE probably proceeds from a triplet state. 

Cyclopropanoxyl radicals were generated by thermal and photochemical decomposition of cyclopropyl nitrites.The nitrites were prepared from cyclopropanols and nitrosyl chloride in pyridine, and they decomposed at low temperatures often below room temperature. A mixture of -bromo and jS-nitroso ketones was formed from the photolysis of pentamethylcyclo-propyl nitrite (19) in bromotrichloromethane. " ... 

Labeling in the carbonyl position can be also accomplished by the use of [ C] propyl ketene (Imahori et al. 1989, 1991) obtained by pyrolytic decomposition of [ C]butyric acid. [ C]methylisocyanate (Bonnot-Lours et al. 1993 Brown et al. 1994 Crouzel et al. 1995) prepared either from [ C]acetyl chloride or [ C]phosgene, and ["C]methylchloroformate (Ravert et al. 1995) synthesized from [ C]methanol and phosgene are other examples of useful reactive precursors (O Fig. 41.15). 

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