Edward L. McCaffery, S. Shalaby
Apr 1, 1967
Citations
0
Influential Citations
9
Citations
Journal
Journal of Organometallic Chemistry
Abstract
Abstract The reactions of 2-ethyl- and 2-n-propyl-2-(chloromethyl)-1,3-dichloropropanes with magnesium in tetrahydrofuran were investigated. Hydrolysis of these Grignard reagents produced 2-ethyl-1-butene and 2-ethyl-1-pentene as the major product in the respective cases; carboxylation of the same organomagnesium compounds gave 4-ethyl- and 4- n -propyl-4-pentenoic acid, respectively. These products were consistent with the postulate that the reaction proceeds through formation and rearrangement of an alkyl chloromethyl cyclopropane as previously reported 1 for the methyl homolog. The identity of the proposed compounds was established both by conventional analysis and by alternate synthesis. A quantitative analysis of the hydrolysis products of the reaction of 2-methyl-2-(chloromethyl)-1,3-dichloropropane with magnesium was carried out using vapor phase chromatography and nuclear magnetic resonance. The analysis revealed that in addition to the expected product, 2-methyl-1-butene, some 1,1-dimethylcyclopropane and methylcyclobutane was also formed. Strong support for the contention that 1-methyl-1-(chloromethyl)cyclopropane was an intermediate in this reaction was realized when it was demonstrated that hydrolysis of the Grignard reagent of this compound resulted in the formation of exactly the same products as were formed from hydrolysis of the parent compound.