The Reaction of Styrene Oxide with Methylmagnesium Iodide Calvin Golumbic and D.L. Cottle JACS, 61, 996 (1939)
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Fourneau and Tiffeneau [6] found that methyl- and ethylmagnesium bromides reacted with styrene oxide as if it were phenylacetaldehyde...
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Some rambling about the iodohydrin of styrene, made from styrene oxide and HI, I skipped the experimental on it too
Experimental
The Preparation of Styrene Oxide:
When prepared from styrene and benzoyl hydrogen peroxide, prepared according to the method of Brooks and Brooks [20], the oxide always contained aldehyde but treatment of 2-iodo-1-phenyl-1-ethanol with potassium hydroxide gave an oxide which gave no test for aldehyde with Tollens' reagent, formed no precipitate with sodium bisulfite and only slowly gave a coloration with Schiff's reagent.
Powdered iodine (1.2 moles) was added, during four to five hours, to a mechanically shaken mixture of 0.6 mole of yellow mercuric oxide and 1200 cc. of a water-saturated ether solution of 1.2 moles of styrene. The mixture was filtered, the filtrate washed with dilute sodium bisulfite and potassium iodide solutions and dried. Finely powdered potassium hydroxide (3 moles) was added, during one to two hours, to the ice-cooled and mechanically stirred ether solution; finally the ice-bath was removed and stirring was continued for one and one-half days. The ether solution was decanted, the residue washed with ether, the solvent distilled from the combined, dried solutions and the residue distilled. The yield of oxide was 51%, bp 87-88°C (23 mm).
The reaction of Styrene Oxide, Styrene Iodohydrins and 3-Bromo-2-butanol with Methylmagnesium Iodide.
Solutions of one mole of methylmagnesium iodide in 350 cc. of ether, analyzed by Gilman's titration method [25], were used in each of the experiments reported in Table I with the exception of expt. 8. The molar ratio of Grignard reagent to the oxide was 1:1 and to the halohydrin, 2:1. The moles of compound treated with methylmagnesium iodide varied from 0.18 to 0.37, with the exception of expt. 6, in which 0.05 mole of iodohydrin was used. In expts. 1-7, the oxide or halohydrin, without solvent, but diluted with ether in expts. 9 and 10, was added to the well-stirred and ice-cooled Grignard reagent.
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Soon after reaching RT, the reaction mixture boiled spontaneously in every experiment, except 6, 7 and 10. No external source of heat was used in expts 3, 4 and 6. In expts 1,2,5,7,9 and 10, most of the ether was distilled on a water bath; the mixtures reacted violently in expts 7 and 10.
The reaction mixtures, with the exception of expts. 6, 9 and 10, were hydrolized, extracted with ether and the ether extracts steam distilled from 30% potassium hydroxide solutions. This separated the alcohol from the resin that was formed in all experiments, with the exception of 6, and converted the halogen in the unchanged halohydrin to halide ion, which was determined and is reported as percentage of unchanged iodohydrin. The resin in expt 8, extracted from the alkaline mixture with chloroform, weighed 13.8g.
The alcohol from all experiments, with the exception of 6,9 and 10, was extracted from the steam distillate with ether, the ether extract dried over potassium carbonate, distilled and the alcohol fractionated through a 3- or 6-bulb Snyder column under reduced pressure. The products from expts 9 and 10 were not steam distilled.
The products were identified by their phenylurethan and by mixed melting point with a sample prepared in 56% yield from phenylacetaldehyde and methylmagnesiumiodide.
Table I:
Expt. compound w/MeMgI Et2O dist on bath? Products yield, %
1 styrene oxide Yes P2Pol 53
2 PhCHICH2OH Yes Phenylethanol + a s-alcohol 13
3 styrene oxide No P2Pol 51
4 PhCHICH2OH No P2Pol 9.8
5 CH3CHBrCHOHCH3 Yes Hexene 13
6 PhCHOHCH2I No recovery of the iodohydrin ...
7 PhCHOHCH2I Yes Phenylethanol + a s-alcohol 15
8 styrene oxide + MgI2 ... P2Pol 15
9 PhCHICH2OH Yes P2Pol 56
10 PhCHOHCH2I Yes P2Pol 42
References:
[6] Fourneau and Tiffeneau, Compt. rendu 146, 698 (1908)
[20] Brooks and brooks, JACS, 55, 4309 (1933)
[25] Gillman, Wilkinson, Fishel and Meyers, JACS, 45, 156 (1923)
