Perfluorinated N-fluoroimines

N-Fluorination of aziridinecarboxylates via fluorolysis of their N-aminomethyl derivatives

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A new and convenient method for the synthesis of 1-fluoroaziridinecarboxylates through the fluorolysis of N-aminomethylaziridinecarboxylates is revealed.1-Fluoroaziridines show an extraordinarily high configurational stability of the nitrogen atom (∆G inv = 35 kcal mol -1 ) 1 but only a few of these scarcely available compounds have been reported. [1][2][3] They are obtained by addition of CH 2 N 2 to the N-fluoroimine of hexafluoroacetone followed by acidolysis of the resulting ∆ 2 -1,2,3-triazoline (yield 38%). 2,3 Later, 1-fluoro-2,2-bis(trifluoromethyl)aziridine was obtained by direct fluorination of 2,2-bis(trifluoromethyl)aziridine (F 2 /NaF) in 50% yield and its NMR parameters were refined.

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“…2c: [a] 15 D +7.23° (c 9, CHCl 3 ). 1 H NMR (CDCl 3 ) d: 1.05 (t, 6H, 2CH 3 CH 2 , 3 J = 7.3 Hz), 1.26 and 1.29 [m, 12H, 2(CH 3 ) 2 CH, 3 J = = 6.4 Hz], 2.71 (m, 4H, 2MeCH 2 , ABX 3 spectrum, ∆n = 12 Hz, 2 J AB = = -12.6 Hz, 3 J AX = 3 J BX = 7.3 Hz), 2.29 and 2.82 (d, 2H, 2H-ring, 3 J = 6.1 Hz), 3.76 (q, 2H, NCH 2 N, AB spectrum, ∆n = 24 Hz, 2 J AB = = -12.6 Hz), 5.04 (hept, 2H, 2CHMe 2 , 3 J = 6.4 Hz).…”

“…2d: 1 H NMR (CDCl 3 ) d: 1.06 (t, 6H, 2CH 3 CH 2 , 3 J = 7.3 Hz), 2.43 (dq, 1H, H a , 2 J ab = -1.5 Hz, 4 J aCCCF3 = 1.5 Hz), 2.45 (d, 1H, H b , 2 J ab = = -1.5 Hz), 2.68 (m, 4H, 2CH 2 Me, ABX 3 spectrum, ∆n = 24 Hz, 2 J AB = = -12.8 Hz, 3 J AX = 3 J BX = 7.3 Hz), 3.57 (dd, 2H, NCH 2 N, AB spectrum, ∆n = 52 Hz, 2 J AB = -11.6 Hz), 3.84 (s, 3H, MeO). 3a: yield 91%, bp 61-63 °C (1 torr).…”

“…3a: yield 91%, bp 61-63 °C (1 torr). 1 H NMR (CDCl 3 ) d: 2.81 (dd, 1H, H a , 2 J ab = -5.5 Hz, 3 J aF = 29.3 Hz), 3.32 (dd, 1H, H b , 2 J ab = -5.5 Hz, 3 J bF = 40.9 Hz), 3.80 (s, 3H, A-MeO), 3.87 (s, 3H, B-MeO), cf. ref.…”

“…4. 3b: yield 90%, bp 71-72 °C (1 torr). 1 H NMR (CDCl 3 ) d: 1.30 and 1.34 [m, 12H, 2(CH 3 ) 2 CH, 3 J = 6.4 Hz], 2.74 (dd, 1H, H a , 2 J ab = = -5.5 Hz, 3 J AF = 29.3 Hz), 3.27 (dd, 1H, H b , 2 J ab = -5.5 Hz, 3 J bF = = 40.9 Hz), 5.11 (hept, 1H, A-CHMe 2 , 3 J = 6.4 Hz), 5.13 (hept, 1H, B-CHMe 2 , 3 J = 6.4 Hz). 19 F NMR (CDCl 3 ) d: 16.32 (dd, FN, 3 J aF = = 29.3 Hz, 3 J bF = 40.9 Hz).…”