Preparation and polymerization of the two isomeric (chloromethyl)oxetanes

✍ Scribed by Douglas A. Wicks; David A. Tirrell

• Book ID: 105337453
• Publisher: John Wiley and Sons
• Year: 1990
• Tongue: English
• Weight: 722 KB
• Volume: 28
• Category: Article
• ISSN: 0887-624X
• DOI: 10.1002/pola.1990.080280309

✦ Synopsis

Abstract

2‐(Chloromethyl)oxetane was prepared in 8% overall yield from 2‐propen‐1‐ol by protection of the alcohol with dihydropyran, epoxidation, ring expansion with dimethylsulfoxonium methylide, acid deprotection, and chlorination with triphenylphosphine in CCl~4~. 3‐(Chloromethyl)oxetane was prepared in 22% overall yield by hydroboration‐oxidation of 3‐chloro‐2‐chloromethyl‐1‐propene followed by base‐catalyzed cyclization. Each of the oxetanes was converted to the corresponding elastomeric homopolymer by treatment with a triethylaluminum–acetylacetone–water mixture. Poly[2‐(chloromethyl)oxetane] was found to be similar to polyepichlorophydrin in reactivity toward benzoate ion, whereas poly[3‐(chloromethyl)oxetane] is more reactive by a factor of 2.