Alkylation of alkyl, cycloalkyl and aralkyl halides

#Heretofore the prior art has shown that hydrogen bromide will add to an olefin compound in the presence of an organic peroxide to form an alkyl halide contrary to Markownikoff's rule. Likewise, the prior art as exemplified by U.S. Pat. Nos. 2,418,832 and 2,440,801 has shown a telomerization reaction in which recurring alkylaromatic or alkyl radicals may be prepared according to the equations set forth hereinafter.

#ROOR .fwdarw. 2RO.sup..

#ro.sup.. + hcl .fwdarw. ROH + Cl.sup..

#In this example 73 grams (0.79 mole) of n-butyl chloride along with 6 grams of di-t-butyl peroxide and 24 grams of concentrated hydrochloric acid were placed in the glass liner of a rotating autoclave. The glass liner was sealed into the autoclave and ethylene charged to the reactor until an initial operating pressure of 20 atmospheres was reached. In addition, nitrogen was also pressed in until the operating pressure reached 40 atmospheres, said 40 atmospheres consisting of 20 atmospheres of nitrogen and 20 atmospheres of ethylene. The reactor was then heated to a temperature of 130.degree. C. and maintained in a range of from 130.degree. to 140.degree. C. for a period of 4 hours, the maximum pressure during this period reached 56 atmospheres. At the end of this 4-hour period, heating was discontinued and the autoclave was allowed to return to room temperature, the final pressure at room temperature being 32 atmospheres. The excess pressure was discharged, the autoclave was allowed to return to room temperature, the final pressure at room temperature being 32 atmospheres. The excess pressure was discharged, the autoclave was opened and 106 grams of reaction product was recovered. The product was subjected to conventional means of separation of the upper organic layer from the lower aqueous layer followed by washing with water, drying and fractional distillation whereby 18 grams of product boiling chiefly in a range of from 110.degree. to 150.degree. C. was submitted to preparative gas chromatography followed by instrumental analyses. Six eluted peaks were observed in the following relative areas (weight percent): (1) 20; (2) 40; (3) 5; (4) 5; (5) 8; and (6) 22.

#In peak 1 the infrared spectrum of the peak was that of an alkyl chloride. A secondary chloride was indicated by the fact that the CCl was at 660 cm.sup.-1 and 610 cm.sup.-1. The CCl bands matched those reported for 3-chlorohexane. The mass spectroscopy spectrum had isotopic peaks at m/e 35, 36, 37 and 38 indicating the presence of chlorine. The most abundant ion in the mass spectrum was at m/e 55 which corresponded to a C.sub.4 alkene fragment ion, An important ion was observed at m/e 85 corresponding to a hexyl ion formed by dechlorination of 3-chlorohexane; beta-scission of the ion yielded the C.sub.4 fragment ion. In addition, nuclear magnetic resonance confirmed that the chlorine atom in the alkyl chloride of peak 1 was present as a secondary chloride.

#The infrared spectrum of peak 2 was that of an alkyl chloride. Absorption at 660 cm.sup.-1 for CCl indicated that RCH.sub.2 CH.sub.2 Cl was probable. In addition a single band at 1380 cm.sup.-1 for CH.sub.3 indicated that no isopropyl-type CH.sub.3 's were present. In addition, mass spectroscopy again indicated the presence of chlorine and nuclear magnetic resonance showed that peak 2 was a primary alkyl chloride with a significant amount of methyl group. There were two hydrogen atoms attached to a primary carbon atom and 6 hydrogen atoms attached to primary methyl groups. In addition there were 5 hydrogen atoms involved in other --CH.sub.2 -- and .tbd.CH-- groups. The analytical data indicated that the structure was 1-chloro-3-methylpentane.