Synthesis of Polyfluorinated Tertiary Alcohols Using Ring Opening Reactions of 2,2-Bis(trifluoromethyl)oxirane

Abstract

This paper describes new reactions of 2,2-bis(trifluoromethyl)oxirane (1). Ring opening of 1 by oxygen, nitrogen, sulfur or carbon nucleophiles (Nu -) proceeds regioselectively, with exclusive formation of tertiary alcohols: NuCH 2 C(CF 3 ) 2 OH. The reaction of 1 with strong acids (HX) is also regioselective and proceeds under mild conditions leading to the formation of XCH 2 C(CF 3 ) 2 OH (X = FSO 2 O, CF 3 SO 2 O, Cl, I). The addition of acetic acid to 1, however, requires an elevated temperature and TaF 5 a catalyst. Highly selective reactions of 1 with nucleophilic or electrophilic reagents provide a simple and general route to materials containing CH 2 C(CF 3 ) 2 OH group.

Synthesis of β-amino-α-trifluoromethyl alcohols and their applications in organic synthesis

“…It was also reported that 31 and ammonium hydroxide at ambient temperature undergo a threefold reaction to give tris(3,3,3-trifluoro-2-hydroxypropyl)amine [34]. Under similar conditions, the reaction of 2,2-bis(trifluoromethyl)oxirane (34) and ammonia or ammonium hydroxide yield β-amino-α,α-bis(trifluoromethyl)ethanol as the major product [35]. As a minor product, the secondary amine with two 2-hydroxy- In situ generated 34 (two mol.-equiv.)…”

New partially fluorinated epoxides by oxidation of olefins with sodium hypohalites under phase transfer catalysis

“…Crude reaction product was transferred out of the reactor under vacuum at 20-30 8C (250-50 mmHg) in a cold trap (at À78 8C). The crude product was dried over MgSO 4 and distilled to give a 33 g (yield 75%) of 1a, bp 41-42 8C at 760 mmHg (reported), bp 41-42 8C [5,20] and 39 8C [18]. Reaction conditions, analytical, NMR and IR data for epoxides 1a, 2a, 3a, 5a are given in Tables 1 and 2. 4.1.4.2.…”

Design of very transparent fluoropolymer resists for semiconductor manufacture at 157 nm

“…The known [17] exo-acetate, prepared by addition of acetic acid to norbornadiene, is hydrolyzed to the exo-alcohol. The sodium salt of the alcohol then reacts readily with hexafluoroisobutylene oxide [18] to afford NB-F-OH which polymerizes with TFE to give polymer with acceptable conversion and molecular weight.…”