Methyl chloromethyl ether, solvolysis

The apparent order in wateris found to be 2 for solvent 1-5% water/acetone11, 1.4 for 1-4% ethanol/carbon tetrachloride144 and 2.0 for 1-40% ethanol/ ether144. This, however, may be a result of specific solvation. As pointed out by Kivinen92, Minato partly based his mechanism on different rates of solvolysis of acid chlorides in diethyl ether/ethanol and carbon tetrachloride/ethanol mixtures. This cannot be used as a criterion for detailed mechanism since, for example, Salomaa150 has found that the apparent order with respect to ethanol of the rate of alcoholysis of methyl chloromethyl ether (an SN1 reaction) in... 

The effect of solvent on the solvolysis of chloromethyl methyl ether has been pursued in detail " . Solvent effects were correlated with the Winstein rela-... 

The kgjko isotope effect for the solvolysis of chloromethyl methyl ether in isopropyl alcohol at 0° is 1.24 + 0.08 per deuterium atom " . This is in the range of other unimolecular reactions. The values of and AS for the chloroether in isopropyl alcohol are 10.7 0.6 kcal.mole" and —28.8 + 1.6 eu, respectively. In contrast, the corresponding values for solvolysis of alkyl chlorides are in the range of about 20-25 kcal.mole and —4 to —12 eu. The lower values of A/f and AS for the solvolysis of chloromethyl methyl ether are tentatively attributed to the double bond character between oxygen and carbon at the transition state (see above) . 

Synthesis of Primary Amines. iV,iV-Bis(trimethylsilyl)-methoxymethylamine, formally a +CH2NH2 equivalent, is obtained in high yield by treating chloromethyl methyl ether with LHMDS. Treatment of the bis-silylamine with organometallic reagents followed by mild solvolysis gives primary amines in good to excellent yield (eq 12). ... 

The rate constants for the solvolysis of chloromethyl ethyl ether, chloromethyl octyl ether, and chloromethyl methyl sulfide have been determined in several pure and binary solvents. Application of the extended Grunwald-Winstein equation, logffe/fe, ) = /Nj + mY + c, gave appreciable T values (0.55-0.71) for the three substrates indicating that there is significant nucleophilic solvation of the developing carbenium ion in the transition states of these reactions. The kQ lkp = 1.2 x 10 found for the hydrolysis of chloromethyl methyl ether in water is virtually identical to that observed for the uni-molecular solvolyses of t-butyl chloride and trityl halides confirming the unimolecular mechanism for these reactions. 

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