Grignard reagent with ethylene oxide

Hudrlik, P. F. Ahmed, M. E. Roberts, R. R. Hudrlik, A. M. Reactions of (triphenylsilyl) ethylene oxide with Grignard reagents (and with MgBr2). A reinvestigation./. Org. Chem. 1996, 61, 4395-4399. 

Reaction of ethylene oxide with Grignard reagents... 

With GrignardReagents. Ethylene oxide reacts with Grignard reagents (66), RMgX, to yield the corresponding two carbon homologue, RCH2CH2OH (67-69). 

The characteristic ease with which ethylene oxides undi ruu nucleophilic attack or isomerization in tbe presence of Lewie acids made them obvious substrates for tbe org nometallic reagents intro duoed by Grignard 07 around the turn of the century, and subsequently named in his hunor. The earliest disclosure of a reaction between an epoxide and a Grignard reagent, however, bears the name of Blaise,1 who noted the formation of ethylene bromohydrin on troii merit of ethylene oxide with raethylmagneeium bromide. In the years... 

Among secondary Grignard reagents that havo been added to ethylene oxide with substantially similar result isopropyl magnesium halides, MC-butybnagneBium halides, and several others. 44- 47- 4 ... 

Thus two halohydrirua and no less than six alcohols are in prmciple obtainable from condensation of an ethylene oxide with a Grignard reagent. Fortunately, in the majority of cases, only two or three products appear in readily detectable amount. The factors governing OH x... 

What alcohols would be formed from the reaction of ethylene oxide with the following Grignard reagents ... 

Many syntheses have introduced substituents onto the thiophene ring by reacting a 2-iodothiophene with an organocopper derivative. One such example 11) is shown here in Scheme 20. In the same paper synthesis of the above reaction product was also accomplished by reacting ethylene oxide with the Grignard reagent from 2-ethynylbithio-phene. 

Note that ethylene oxide reacts with the Grignard reagent to gi e a 2-substi tuted ethanol e.g. with methyl magnesium iodide ... 

Prepare a Grignard reagent from 24 -5 g. of magnesium turnings, 179 g. (157 ml.) of n-heptyl bromide (Section 111,37), and 300 ml. of di-n-butyl ether (1). Cool the solution to 0° and, with vigorous stirring, add an excess of ethylene oxide. Maintain the temperature at 0° for 1 hour after the ethylene oxide has been introduced, then allow the temperature to rise to 40° and maintain the mixture at this temperature for 1 hour. Finally heat the mixture on a water bath for 2 hours. Decompose the addition product and isolate the alcohol according to the procedure for n-hexyl alcohol (Section 111,18) the addition of benzene is unnecessary. Collect the n-nonyl alcohol at 95-100°/12 mm. The yield is 95 g. 

Grignard reagents react with ethylene oxide to yield primary alcohols containing two more carbon atoms than the alkyl halide from which the organometallic compound was prepared... 

Section 15 4 Grignard and organolithium reagents react with ethylene oxide to give primary alcohols... 

We saw an example of nucleophilic ring opening of epoxides in Section 15 4 where the reaction of Grignard reagents with ethylene oxide was described as a synthetic route to primary alcohols... 

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