Reactions of 2-Methoxy-1, 3-dioxolane with Grignard Reagents

Abstract

The possibility that 2-alkoxy-1, 3-dioxolane might be attacked by nucleophilic reagent to form 2-substituted-1, 3-dioxolane prompted us to conduct this set of studies.
Thus, 2-methoxy-1, 3-dioxolane was treated with Grignard reagents and heated to form the corresponding 2-alkyl- or 2-aryl-1, 3-dioxolanes, as follows :
O-CH₂-CH₂-O-CH-OCH₃+RMgX→O-CH₂-CH₂-O-CH-R
R=C₆H₅ (24% yield), o-CH₃C₆H₄ (39%), m-CH₃C₆H₄ (16%), p-CH₃C₆H₄ (19%), p-ClC₆H₄ (9%), o-CH₃OC₆H₄ (15%), m-CH₃OC₆H₄ (15%), p-CH₃OC₆H₄ (9%), n-C₃H₇ (10%), n-C₄H₉ (13%), CH₂=CH-_??_- (6%)
Similarly, p-vinylphenylmagnesium chloride gave 2-(p-vinylphenyl)-1, 3-dioxolane (VPD). This was bulk polymerized by 2, 2'-azobisisobutyronitrile to give a polymer with intrinsic viscosity of 0.18 dl. g^-1 in dioxane at 30°C. Possible initial processes of the radical polymerization and the simultaneous crosslinking reactions of VPD were discussed based on the infrared spectra of the product polymers.