The Liquid-Phase Photochemical Chlorination of 2-Chloro-2-methylpropane and Some Related Compounds¹

Abstract

Photochlorination of 2-Chloro-2-methylpropanb 1027 for the length of time given in Column 4, Table II, before earbonation. It was usually necessary to warm the mixture at the start in order to initiate the reaction. Conditions and yields are summarized in Table II. ConclusionsWhen diamyl mercury was treated with sodium and the product of the reaction carbonated, yields as high as 40-50% of butylmalonic acid were obtained. Diethyl mercury by the same Oak Park, Illinois

Photochemical Gaseous Phase Chlorination of Isobutane

“…The crystalline nature of this product and its boiling range, b.p.60 = approximately 82°to 84°C ., indicate that a very small amount of l,l,l,2-tetrachloro-2-methylpropane is formed in the gaseous phase photochemical chlorination of isobutane. Rogers and Nelson (17) reported the following constants for this substance: b.p.j® => 174°( sublimes), b.p.mi = 192°C ., m.p. = 178.6°to 179.6°C.…”

“…so = 81.0°to 81.3°C ., b.p.737 = 162.2°to 162.6°C ., df = 1.3012, ref = 1.4736 with those reported in the literature for 1,2,3-triehloroisobutane identified this fraction, which analysis does indicate to be a trichloride (molecular weight by freezing point depression of benzene is 161, by theory is 161.5). Rogers and Nelson (17) give the following constants for this trichloride: b.p.veo = 162.0°to 163.1°C ., df = 1.3020, ref = 1.4765. 1,2,3-Trichloro-2-methylpropane is the trichloride obtained by Mouneyiat (11) and Porgorshelski (16) by the chlorination of 2-methylpropene, although Mouneyrat, on the basis of an empirical rule, erroneously reported it to be 1,1,2-trichloro-2-methylpropane.…”