The Reactions of 1,2-Epoxypropane With Alkylmagnesium Chlorides

Mechanisms Of Epoxide Reactions

“…A further complication sometimes arises from the attack of a halide ion on one of the epoxide carbon atoms, giving rise to a halohydrin. Thus the action of alkylmagnesium chlorides on propylene oxide has been shown to give the chlorohydrin as well as the products of attack of an alkyl anion a t the normal position (123) :…”

Ethylene Oxides

“…The reaction course depends also on the structure of the Grignard reagent, and obviously on experimental conditions used for the condensation.625~ 927 Propylene oxide reacts with a wide assortment of primary and secondary Grignard reagents (Eq. 824), the products being those 1016,1256 In a clarification of conflicting earlier results,~45~ 849 Gaylord and Caul626 recently demonstrated, on the other hand, that propylene oxide gives on treatment with tert-butylmagnesium chloride a mixture of 1-chloro-2-propanol and 2,2-dimethyl-3-propanol. The latter is the product to be expected if propylene oxide undergoes preliminary isomerization to propionaldehyde.…”

“…Their work, along with later systematic studies by chemists in America, notably Cottle,3589 3 5 9 , 6 5 6 , 1 6 2 2 Huston,5099 [844][845][846][847][848][849] and others, has been exhaustively reviewed by Kharasch and Reinmuth,Q27 as well as by Gaylord and Becker.625 These encyclopedic articles should be consulted for a more complete treatment than can be given here.…”

“…849). Although a mechanism has been advanced to explain this curious effect,Qlz no subsequent work has appeared on the subject.…”

The Reaction between Grignard Reagents and the Oxirane Ring.

“…Note added in proof: Recently, Huston and Tiefenthal(234) have reported that tertbutylmagnesium chloride also gives 4,4-dimethyl -2-pentanol, but the structure is still based on the same conflicting evidence reported above.…”