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Perfluorovinyl Morpholine and Perfluorovinyl Pyrrolidine with Nucleophiles and Electrophiles
Author(s) -
Vij Ashwani,
Connors Patrick J.,
Rice Bobbie L.,
Kirchmeier Robert L.,
Shreeve Jean'ne M.
Publication year - 1995
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.19956211108
Subject(s) - morpholine , pyrrolidine , chemistry , nucleophile , diethylamine , electrophile , dimethylamine , medicinal chemistry , ethanolamine , hydrolysis , bifunctional , organic chemistry , catalysis
In this study, both monofunctional and bifunctional nucleophiles, as well as the electrophile FNO, are reacted with perfluorovinyl amines. The perfluorovinyl amines CFCF 2 and CFCF 2 have been reacted with dimethylamine and diethylamine in the presence of small amounts of water to give CHFC(O)N(CH 3 ) 2 ( 1 ), CHFC(O)N(CH 3 ) 2 ( 2 ), and CHFC(O)N(C 2 H 5 ) 2 ( 3 ). With perfluorovinyl pyrrolidine and perfluorovinyl morpholine, ethanolamine gives the cyclized products CHF ( 4 ) and CHF ( 5 ), respectively. Reaction of the vinyl amines with (CH 3 ) 3 SiOCH 2 CF 3 in the presence of catalytic amounts of CsF results in the formation of cis‐ ( 6 ) and trans‐ ( 7 ) CFCF(OCH 2 CF 3 ) and cis‐ ( 8 ) and trans‐ ( 9 ) CFCF(OCH 2 CF 3 ). The electrophile FNO reacts slowly with perfluorovinyl pyrrolidine and perfluorovinyl morpholine, and more rapidly with (CF 3 ) 3 CCFCF 2 to give CF(NO)CF 3 ( 10 ), CF(NO)CF 3 ( 11 ) and (CF 3 ) 3 CF(NO)CF 3 ( 12 ), respectively. Single crystal X‐ray analysis is used to confirm the identity of the product obtained from the controlled hydrolysis of the sultone of perfluorovinyl pyrrolidine as the sulfonic acid anhydride C(O)CF 2 OS(O) 2 OCF 2 C(O) ( 13 ). The X‐ray crystal structure of perfluorosuccinic acid monohydrate ( 14 ), which is obtained when the perfluorovinyl pyrrolidine sultone is hydrolyzed in excess water, is also reported for the first time.