Fluorimines

Reactions of quadricyclane with fluorinated nitrogen-containing compounds. Synthesis of 3-aza-4-perfluoroalkyl-tricyclo[4.2.1.02,5]non-3,7-dienes

“…Molar ratios of reagent are calculated based on pure 1 (Table 1). Compounds 2 [24], 4 [25] and 6 [16,17] were prepared according to the literature procedures. Table 1.…”

Novel β-hydroxy-β-bis(trifluoromethyl) imines

“…Only mono methylation of 2 could be achieved using diazomethane to give the mono ether 7 (96%) because of the strong intramolecular hydrogen bonding OH Á Á Á N¼ ¼; dimethylation was successful under more drastic conditions applying KOH and MeI in DMSO to render diether 8 (15%). Reacting HFA imine [8] gave in 68% yield the imino amine 9, a colorless liquid (bp 78 8C/25 Torr); a further addition was not observed under the conditions applied. Only HFA was able to insert into the CH bond of the remaining methyl group to yield compound 10 (85%, mp 34 8C) (Scheme 1).…”

“…1 4.6. 2,6-Bistrifluoromethyl-2,6-dimethoxy-4-isopropylimino-1,1,1,7,7,7-hexafluoro-heptane (8) In 10 ml DMSO 5.4 g (100 mmol) KOH were dissolved, 5.10 g (12 mmol) 2 in 10 ml DMSO added. The mixture was cooled to 0 8C, 7.0 g (48 mmol) methyl iodide added slowly and stirred for 1 h. The solution was treated three times with 20 ml dichloromethane, dried over MgSO 4 and distilled in vacuo, obtaining a yellow oil; mp 54 8C (10 À2 hPa), yield 0.80 g (15%).…”

2.03 Prins Reactions and Carbonyl, Imine, and Thiocarbonyl Ene Reactions

“…263 Hexafluorothioacetone, generated in situ by reaction of tetratrifluromethyl-1,3-dithietane with KF in DMF reacts with most classes of alkenes to give allylic sulfides analogous to 481, R 1 ¼ R 2 ¼ CF 3 in 43-90% yield. 264,265 Methyl cyanodithioformate (480a) reacts with most classes of alkenes in toluene at 100 1C to give allylic sulfides such as 481a from b-pinene (20). 266 Baldwin showed that thiobenzaldehyde (480b), generated in situ by pyrolysis of the anthracene adduct, reacts with b-pinene (20) to give sulfide 481b in 19% yield and thiol 482b in 38% yield.…”