982
L.V. Saloutina et al. / Journal of Fluorine Chemistry 126 (2005) 976–983
hexane–benzene (3:1) to give 4.1 g (67%) of colorless
crystals of benzoxazinol (10a), mp 126–127 8C (new
compound). H NMR [(CD3)2CO]: d 7.19–7.21 (1H, m,
356 (6.1), 346 (6.7), 267 (7.5), 266 (100, [M À C2F5]+), 246
(24.7,[M À C2F5-HF]+),238(21.8),218(43.0),190(9.1),169
(6.5), 168 (51.3), 119 (18.6, [C2F5]+), 102 (40.6, [C6H4NC]),
93(5.5,[C6H5O]+), 91(10.6,[C6H4NH]+), 76(12.2, [C6H4]+),
75 (5.4), 69 (13.6, [CF3]+), 65 (14.2), 64 (8.7), 63 (11.8), 52
(5.5),51(9.4),50(7.9).Anal.CalcdforC12H5F10NO2:C,37.4;
H, 1.3; F, 49.4; N, 3.6. Found: C, 37.8; H, 1.7; F, 49.6; N, 3.9.
1
CH), 7.26–7.30 (1H, m, CH), 7.53–7.57 (1H, m, CH), 7.64–
7.66 (1H, m, CH), 8.73 (1H, br.s, OH). 19F NMR
5
[(CD3)2CO]: d: À80.7 (3F, q, JFF = 8.5 Hz, CF3CO),
5
À65.5 (3F, q, JFF = 8.5 Hz, CF3CN). 13C NMR
[(CD3)2CO]: d 91.2 (q, 2JCF = 36.2 Hz, C-2), 117.3 (s, C-8),
1
120.1 (q, JCF = 276.2 Hz, CF3-2), 122.1 (q, 1JCF = 288 Hz,
CF3-3), 124.9(s, C-5), 129.4(s, C-4a), 134.4(s, C-7), 130.5(s,
4.5.2. Procedure 2
In a similar manner, oxirane (2) (5.5 g, 17 mmol) was
treated with 2-aminophenol (3.5 g, 32 mmol) in 20 ml of
DMAA for 1 h. Volatiles were removed (HC2F5 and
HC3F7) and the reaction mixture (Table 1, run 9) was
worked up as described above (Section 4.1.1). The
resulting precipitate consisting of compounds (12) and
(11b) and (11c) (ꢀ26: 57: 17, from 19F NMR and GCMS)
was collected by filtration and dried at room temperature.
Recrystallization from hexane–benzene (1:1) afforded
1.4 g (31.8%) of amide (11b), mp 115–116 8C (lit. mp
117–118 8C [5]) and 0.8 g of mixture of amides (11b and
c) (ꢀ7:3, from 19F NMR). The filtrate was concentrated
under reduced pressure, and the residue was twice
recrystallized from hexane to give 0.2 g (3%) of
benzoxazolidine (12) as colorless crystals, mp 97–98 8C
(new compound). 1H NMR (CDCl3): d 4.61 (1H br.s, NH),
6.83–6.85 (1H, m, CH), 6.92–6.96 (1H, m, CH), 7.06–7.13
(2H, m, 2CH). 19F NMR (CDCl3): d À119.6 (2F, dm,
CFAFBCN, 2JFF ꢁ 288, CFAFBCO, 2JFF ꢁ 288 Hz),
2
C-6), 143.8 (q, JCF = 35.9 Hz, C-3), 144.2 (s, C-8a). IR: n
1585, 1600, 1635 (C C, C N), 2770, 3120 broad (OH).
GCMS, m/z (rel. int.):285(39.2, M+), 268(12.5, [M À OH]+),
256 (19.6), 246 (27.5), 218 (7.5), 217 (8.1), 216 (94.8,
[M À CF3]+), 196 (90.0, [M À CF3-HF]+), 188 (78.5), 168
(100, [M À CF3-CO-HF]+), 140 (24.5, [M À CF3-C6H4]+),
132 (10.0), 103 (7.5), 102 (93.5, [C6H4NC]+), 90 (20.0,
[C6H4N]+), 76 (26.5, [C6H4]+), 69 (50.2, [CF3]+), 65 (31.5),
64 (21.2), 63 (32.0), 50 (20.8). Anal. Calcd for C10H5F6NO2:
C, 42.1; H, 1.8; F, 40.0; N, 4.9. Found: C, 42.3; H, 1.8; F, 39.9;
N, 4.9.
4.4.2. Procedure 2
In a similar manner, oxirane (1) (4.6 g, 21 mmol) was
treated with 2-aminophenol (4.7 g, 43 mmol) in 20 ml of
DMAA for 1 h. After the volatiles were removed 19F NMR
spectrum of the reaction mixture was recorded (Table 1, run
7) and the contents were worked up as described above in
Section 4.1.1. The resultant precipitate was dried (ꢀ50–
60 8C) and recrystallized from hexane–benzene (3:1). Yield
of compound (10a) 0.7 g (12%).
2
À114.2 (2F, dm, CFAFBCN, JFF ꢁ 288, CFAFBCO,
3
2JFF ꢁ 288 Hz), À70.09 (3F, t, JFF = 2.1 Hz, CF3),
3
À79.08 (3F, t, JFF = 2.1 Hz, CF3). IR: n 1504, 1605,
1632 (C C), 1763 (C O), 3315 (NH). EIMS, m/z (rel.
int.): 385 (27.8, M+), 267 (11.3), 266 (100, [M À C2F5]+),
238 (12.4, [M À C2F5CO]+), 218 (9.9), 169 (6.1,
[M À C2F5CO-CF3]+), 168 (13.5), 119 (5.8, [C2F5]+),
102 (14.2, [C6H4NC]+), 93 (7.2, [C6H5O]+), 69 (7.0,
[CF3]+), 65 (17.5), 52 (6.0). Anal. Calcd for C12H5F10NO2:
C, 37.4; H, 1.3; F, 49.4; N, 3.6. Found: C, 37.3; H, 1.4; F,
49.6; N, 3.4.
4.4.2.1. Amide (11a). 19F NMR[(CD3)2SO]:d À74.1 (s, CF3).
4.5. The reaction of oxirane 2 with 2-aminophenol
4.5.1. Procedure 1
In a similar manner, oxirane (2) (3.0 g, 9 mmol) was
treated with 2-aminophenol (2.0 g, 18 mmol) in 40 ml of
dioxane for 4 h. The reaction mixture (Table 1, run 8) was
worked up as described above (Section 4.1.1) and extracted
with CHCl3. The extract was dried over MgSO4, CHCl3 was
distilled off and the residue was subjected to vacuum
distillation to afford 1.5 g (42%) of benzoxazinole (10b) as
oil, bp 76–80 8C (10 Torr) (new compound). 1H NMR
(CDCl3): d 4.50 (1H, br.s, OH), 7.01–7.03 (1H, m, CH),
7.15–7.19 (1H, m, CH), 7.38–7.40 (1H, m, CH), 7.56–7.59
(1H, m, CH). 19F NMR (CDCl3): d: À125.0 (1F, ddd,
4.5.2.1. Amide (11b). 1H NMR [(CD3)2SO]: d 6.14 (1H,
br.s, OH), 6.91–7.00 (1H, m, CH), 7.10–7.14 (1H, m, CH),
7.12 (1H, m, CH), 7.98–8.00 (1H, m, CH), 8.58 (1H, br.s,
NH). 19F NMR [(CD3)2SO]: d À121.6 (2F, q, 3JFF = 1.6 Hz,
3
CF2), À82.4 (3F, t, JFF = 1.6 Hz, CF3). IR: n 1509, 1552,
1598, 1618 (C C), 1695 (C O), 3325, 3383 (OH, NH).
EIMS, m/z (rel. int.): 255 (39.5, M+), 168 (10.0), 137 (6.8),
136 (100, [M À C2F5]+), 119 (11.8, [C2F5]+), 108 (35.1,
[M À C2F5CO]+), 90 (6.3, [C6H4N]+), 80 (48.1), 79 (7.4), 69
(10.4). Calcd for C9H6F5NO2: C, 42.35; H, 2.35; F, 37.25; N,
5.49. Found: C, 42.23; H, 2.39; F, 37.55; N, 5.54.
5
2JFF = 282.8, JFF = 29.4, 19.8 Hz, CF3CFAFBCO), À124.2
(1F, ddd, 2JFF = 282.8, 5JFF = 15.2, 10.2 Hz, CF3CFAFBCO),
2
5
À114.3 (1F, ddd, JFF = 300.5, JFF = 29.4, 15.2 Hz,
2
5
CF3CFAFBCN), À111.8 (1F, ddd, JFF = 300.5, JFF = 19.8,
10.2 Hz, CF3CFAFBCN), À81.8 (3F, s, CF3CFAFBCO),
À80.0 (3F, d, J = 1.8 Hz, CF3CFAFBCN). IR: n 1589, 1598,
1625 (C C, C N), 3182 broad, 3445, 3595, 3687 (OH).
GCMS, m/z (rel. int.): 385 (9.9, M+), 368 (6.9, [M À OH]+),
4.5.2.2. Amide (11c). 19F NMR [(CD3)2SO]: d À126.7 (2F,
s, CF2CF2CF3), À119.3 (2F, q, 4JFF = 8.5 Hz, CF2CF2CF3,),
4
À80.3 (3F, t, JFF = 8.5 Hz, CF3,).