L-Chloro-3,3-dimethylpentane

The Grignard reagent prepared from l-chloro-3,3-dimethylpentane in ether undergoes rapid inversion of configuration at the magnesium-containing carbon (demonstrated by nmr this compound is not chiral).132 The mechanism of this inversion is not completely known. 

The complex nature of alkylation of alkenes is illustrated by the reaction of 1- and 2-chloropropane with ethylene,53 which does not yield the expected isopentyl chloride. Instead, l-chloro-3,3-dimethylpentane is formed by isomerization of the primary product to give fcrf-amyl chloride, which adds to ethylene more readily than do starting propyl halides (Scheme 5.4). The same product is also obtained54 when ethylene reacts with neopentyl chloride in the presence of AICI3. 

Insight into another mode of formation of these by-products is furnished by the observation that l-chloro-3,3-dimethylpentane and 1-chloro-3,3-dimethylbutane are by-products of the condensation of ethylene with <-butyl chloride and <-amyl chloride, respectively, in the presence of aluminum chloride (Schmerling, 16). Partial conversion of either <-alkyl chloride into the other presumably occurs under the reaction conditions. It is apparent, then, that the alkyl chloride formed as indicated in step 3 of the three step chain mechanism may be converted into a chloride of higher or lower molecular weight before undergoing the condensation of... 

The product formed in largest amount by the hydrochloric acid-promoted and peroxide-induced reaction of isopentyl chloride with ethylene was also that formed by alkylation at the tertiary carbon atom, namely 1-chloro-3,3-dimethylpentane (Ig.) (Expt. 25). The remaining constituents of the reaction product were all obtained in very minor amount and were all alkyl chlorides. Among these were 4-chloro-2-methylhexane (y), 1-chlorohexane (formed by telomerization) and some chlorononanes including 5-chloro-3,3-dimethyl-heptane (3 ) formed by ethylation of 12, 4-chloro-2-methyloctane (15) and l-chloro-3-methyloctane (IT). ... 

The condensation of saturated hydrocarbons with haloolefins in the presence of anhydrous aluminum chloride also results in the formation of alkyl halides, as in the preparation of l-chloro-3,4-dimethylpentane from isobutane and allyl chloride (40%). Under the same conditions, alkyl halides react with olefinic halides to give dihaloalkanes. unsym-Heptachloropropane is synthesized from tetrachloroethylene and chloroform (93%). ... 

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