THE REACTIONS OF BIS(TRIFLUOROMETHYL)AMINO-OXYL AND PERFLUORO-(2,4-DIMETHYL-3-OXA-2,4-DIAZAPENTANE) WITH ALPHA-PINENE AND BETA-PINENE

The reaction of the oxyl (CF3)2NO. (7) with alpha-pinene (1) (2:1 molar ratio) on warming from -196-degrees-C to room temperature gives the hydroxylamine (CF3)2NOH (9) (37% based on oxyl), 3-[N,N-bis(trifluoromethyl)amino-oxy]pin-2(10)-ene (10) (66.5% based on alpha-pinene) as a mixture of the exo and endo isomers (ratio 50:50) and 2,3-bis[N,N-bis(trifluoromethyl)amino-oxy]pinane (11) (20.5% based on alpha-pinene) as a mixture of several diastereomers. A corresponding reaction with beta-pinene (2) on warming from -196-degrees-C to room temperature affords hydroxylamine 9 (21% based on oxyl), 10-[N,N-bis(trifluoromethyl)amino-oxy]pin-2-ene (12) (48% based on beta-pinene), 1-{[N,N-bis(trifluoromethyl)amino-oxy]methyl}-4-{2-[N,N-bis(trifluoromethyl)amino-oxy]isopropyl}cyclo-hex-1-ene (13) (10% based on beta-pinene) and 2,10-bis[N,N-bis(trifluoromethyl)amino-oxy]pinane (14) (40.5% based on beta-pinene) as a mixture of two diastereomers (ratio 59:41). A second reaction involving slow passage of the oxyl 7 in nitrogen through a solution of pinene 2 in CF2ClCFCl2 as a solvent gave compounds 12 (64%), 13 (7%) and 14 (29%). The room temperature reactions of the oxadiazapentane (CF3)2NON(CF3)2 (8) with pinenes 1 and 2 (1:1 molar ratio) afforded complex product mixtures. The reaction with pinene 1 yields hydroxylamine 9 (22% based on compound 8), the amine (CF3)2NH (15) (23% based on compound 8) and an inseparable higher-boiling mixture containing c. 14 components, while the reaction of pinene 2 gives compounds 9 and 15 and a higher-boiling mixture (c. 11 components) from which compound 12 (7% based on beta-pinene), 10-[N,N-bis(trifluoromethyl)amino]pin-2-ene (16) (15% based on beta-pinene) and the rearrangement products 1-{[N,N-bis(trifluoromethyl)amino]methyl}-4-{2-[N,N-bis(trifluoromethyl)amino-oxy]isopropyl}cyclohex-1-ene (17) (10% based on beta-pinene) and 1-{[N,N-bis(trifluoromethyl)amino]methyl}-4-isopropylcyclohex-1-ene (18) (20% based on beta-pinene) could be separated and identified.