Factors Determining the Course and Mechanism of Grignard Reactions. VII. Analysis of Gases Formed During the Reaction of Phenylmagnesium Bromide with Organic Halides in the Presence of Cobaltous Halides

Abstract

Gases in the Reaction of Phenylmagnesium Bromide with Halides 493 copper were found to be ineffective as catalysts anethole hydrobromide and Grignard reagents, in the synthesis of hexestrol dimethyl ether from Chicago, Illinois

Reactions of Atoms and Free Radicals in Solution. Xxvii. The Decomposition of Diacetyl Peroxide in Alcohols

“…Diacetyl peroxide has been decomposed in two primary alcohols, n-butyl and isobutyl; two secondary alcohols, isopropyl and sec-butyl; and one tertiary alcohol, tert-butyl. Quantitative results of these experiments are summarized in Tables I, 11, and 111.…”

“…The yield of gaseous product was calculated from the volume (corrected) of gas collected. The molecular weight of the gas and the percentage of unsaturated compounds was determined according t o the method of Kharasch, Lewis, and Reynolds (11). If the molecular weight of the gas corresponded t o that of methane no further analysis was made.…”

Reactions of Atoms and Free Radicals in Solution. Xxxv. Migration of a Methyl Group in the Rearrangement of the Free Di-Tert-Butylcarbinyl Radical. The Reaction of Di-Tert-Butylcarbinyl Chloride With a Grignard Reagent in the Presence of Cobaltous Bromide

“…wt., 244. The gas obtained from the reaction was analyzed by the method of Kharasch, Lewis, and Reynolds (5). It was found to contain 60% of propane and 40% of propylene.…”

“…soc. chim.,[5] 18, 41(1951) states that compound F is one of the products of the mixture of chlorinated products formed upon chlorination of 2,2,4,4-tetramethyIpentane. The authors were unable to separate the individual compounds by conventional means.…”

Factors Determining the Course and Mechanism of Grignard Reactions. Xviii. The Effect of Metallic Halides on the Reactions of Grignard Reagents With 1-Phenyl-3-Chloropropane, Cinnamyl Chloride, and Phenylethynyl Bromide

“…S.C.; 1.69 moles; 89% yield) was passed through a trap held at -80°and then collected over water. This gas [analyzed by the method of Kharasch, Lewis, and Reynolds (10)] had an average molecular weight of 17.4; it contained 5.4% of unsaturated hydrocarbons. These figures indicate that the gas contained methane (89%), ethane (5.5%), and ethylene (5.5%).…”