2668
V. K. Brel
PAPER
1H NMR (200 MHz, CDCl3): d = 7.70 (m, 2 H, Ar), 7.45 (m, 3 H,
Ar), 4.80 (m, 1 H, OCH), 4.60 (m, 1 H, ClCH), 4.01 (m, 2 H,
CH2SF5), 3.49 (dd, JH,H = 10.4 Hz, 16.6 Hz, 1 H, CH2), 3.06 (dd,
JH,H = 7.6 Hz, 16.6 Hz, 1 H, CH2), 2.11–1.85 (m, 4 H, 2CH2) (a mix-
ture of diastereomers).
Anal. Calcd for C13H14ClF6NOS: C, 40.90; H, 3.70; F, 29.86; N,
3.67. Found: C, 40.79; H, 3.75; F, 28.80; N, 3.70.
3-Acetyl-5-[3-(pentafluoro-l6-sulfanyl)allyl]-4,5-dihydroisox-
azole (14)
Method A. A mixture of diene 2 (0.194 g, 0.001 mol) and CAN
(0.558 g, 0.001 mol) in acetone (5 mL) was stirred under reflux for
5 h. The mixture was extracted with Et2O (3 × 10 mL) and washed
with aq NaHCO3 soln (2 × 5 mL), followed by sat. aq NaCl (2 × 5
mL). The ethereal solution was dried over Na2SO4 and concentrated
under vacuum. The resulting oil was chromatographed (silica gel,
CHCl3).
13C NMR (50.3 MHz, CDCl3): d = 156.53 (s, C=N), 130.20 (s, CH,
Ar), 129.43 (s, C, Ar), 128.78 (s, CH, Ar), 126.64 (s, CH, Ar),
80.46, 79.68 (s, OCH), 76.71, 76.50 (d pent, JC,F = 13.4 Hz, 0.8 Hz,
F5SCH2), 55.77, 53.34 (pent, JC,F = 4.0 Hz, CHCl), 40.26, 40.08 (s,
CH2), 33.94, 33.23 (pent, JC,F = 1.3 Hz, CH2-CHCl), 32.25, 31.72
(s, CH2).
19F NMR (188.3 MHz, CDCl3): d = 162.55–159.44 (9 lines,
JF–F = 146.4, 148.5 Hz, 1 F), 144.13 (dm, JF–F = 146.4 Hz, 4 F) (a
mixture of diastereomers).
Pale-yellow oil; yield: 0.223 g (80%); Rf = 0.35 (CHCl3).
Method B. In a procedure analogous to that used for the synthesis
of 6 (Method B), 16 (3.16 g, 0.02 mol) was allowed to react with
K2CO3 (20 g).
Anal. Calcd for C13H15ClF5NOS: C, 42.92; H, 4.16; F, 26.11; N,
3.85. Found: C, 42.80; H, 4.20; F, 26.23; N, 3.77.
Yield: 4.85 g (87%).
5-[2-Chloro-3-(pentafluoro-l6-sulfanyl)propyl]-3-(4-fluoro-
phenyl)-4,5-dihydroisoxazole (12)
In a procedure analogous to that used for the synthesis of 6 (Method
A), 4 (0.23 g, 0.001 mol) was allowed to react with 4-
FC6H4CCl=NOH (0.26 g, 0.0015 mol).
1H NMR (200 MHz, CDCl3): d = 6.64–6.39 (m, 2 H, CH=CH),
5.04–4.89 (m, 1 H, OCH), 3.31 (dd, JH,H = 11.0 Hz, 17.6 Hz, 1 H,
CH2), 2.85 (dd, JH,H = 7.4 Hz, 17.6 Hz, 1 H, CH2), 2.58–2.52 (m, 2
H, CH2), 2.50 (s, 3 H, CH3).
13C NMR (50.3 MHz, CDCl3): d = 193.10 (s, C=O), 158.30 (s,
C=N), 143.80 (d pent, JC,F = 20.2 Hz, 1.6 Hz, =CHSF5), 133.22
(pent, JC,F = 7.6 Hz, CH=CHSF5), 81.96 (s, OCH), 36.94 (s, CH2),
36.13 (s, CH2), 26.96 (s, CH3).
Colorless oil; yield: 0.35 g (95%); Rf = 0.39 (CHCl3–hexane, 10:4).
1H NMR (200 MHz, CDCl3): d = 7.70 (m, 2 H, Ar), 7.15 (m, 2 H,
Ar), 5.19–5.09 (m, 1 H, OCH), 4.78–4.58 (m, 1 H, ClCH), 4.25–
4.01 (m, 2 H, CH2SF5), 3.66–3.51 (dd, JH,H = 10.2 Hz, 16.6 Hz, 1 H,
CH2), 3.13–2.99 (dd, JH,H = 8.0 Hz, 16.6 Hz, 1 H, CH2), 2.32 (m, 2
H, CH2) (a mixture of diastereomers).
13C NMR (50.3 MHz, CDCl3): d = 163.88 (d, JC,F = 251.0 Hz, CF,
Ar), 155.75, 155.66 (d, JC,F = 1.0 Hz, C=N), 128.76, 128.60 (d,
JC,F = 8.0 Hz, CH, Ar), 125.46, 125.44 (d, JC,F = 3.5 Hz, C, Ar),
116.15, 115.73 (d, JC,F = 22.1 Hz, CH, Ar), 77.57, 77.34 (s, OCH),
76.61, 76.55 (pent, JC,F = 13.9 Hz, F5SCH2), 52.81, 52.55 (pent,
JC,F = 4.5 Hz, ClCH), 43.24, 42.06 (s, CH2), 40.52, 40.23 (s, CH2)
(a mixture of diastereomers).
19F NMR (188.3 MHz, CDCl3): d = 162.23–159.04 (9 lines,
JF–F = 148.52 Hz, 1 F), 140.11 (dm, JF–F = 148.52 Hz, 4 F).
Anal. Calcd for C8H10F5NO2S: C, 34.41; H, 3.61; F, 34.02; N, 5.02.
Found: C, 34.51; H, 3.67; F, 34.10; N, 5.14.
3-Acetyl-5-[4-(pentafluoro-l6-sulfanyl)but-3-enyl]-4,5-di-
hydroisoxazole (15)
In a procedure analogous to that used for the synthesis of 14 (Meth-
od A), 3 (0.208 g, 0.001 mol) was allowed to react with CAN (0.558
g, 0.001 mol).
19F NMR (188.3 MHz, CDCl3): d = 161.82–159.94 (18 lines,
JF–F = 144.0, 146.0 Hz, 1 F), 144.69, 143.96 (dm, JF–F = 144.0,
146.0 Hz, 4 F), –32.84 (m, 1 F) (a mixture of diastereomers).
Colorless oil; yield: 0.205 g (70%); Rf = 0.27 (CHCl3).
1H NMR (200 MHz, CDCl3): d = 6.51 (m, 2 H, CH=CH), 4.89–4.73
(m, 1 H, OCH), 3.22 (dd, JH,H = 10.8 Hz, 17.4 Hz, 1 H, CH2), 2.81
(dd, JH,H = 8.2 Hz, 17.4 Hz, 1 H, CH2), 2.51 (s, 3 H, CH3), 2.42–2.29
(m, 2 H, CH2), 1.95–1.77 (m, 2 H, CH2).
Anal. Calcd for C12H12ClF6NOS: C, 39.19; H, 3.29; F, 31.00; N,
3.81. Found: C, 39.10; H, 3.22; F, 31.12; N, 3.88.
13C NMR (50.3 MHz, CDCl3): d = 193.37 (s, C=O), 158.53 (s,
C=N), 141.71 (d pent, JC,F = 29.6 Hz, JC,F = 2.0 Hz, =CHSF5),
137.82 (pent, JC,F = 7.5 Hz, CH=CHSF5), 83.42 (s, OCH), 37.35 (s,
CH2), 33.37 (s, CH2), 26.95 (s, CH2), 26.83 (s, CH3).
19F NMR (188.3 MHz, CDCl3): d = 163.15–159.96 (9 lines,
JF–F = 148.50 Hz, 1 F), 140.48 (dm, JF–F = 148.50 Hz, 4 F).
5-[3-Chloro-4-(pentafluoro-l6-sulfanyl)butyl]-3-(4-fluoro-
phenyl)-4,5-dihydroisoxazole (13)
In a procedure analogous to that used for the synthesis of 6 (Method
A), 5 (0.244 g, 0.001 mol) was allowed to react with 4-
FC6H4CCl=NOH (0.26 g, 0.0015 mol).
Colorless oil; yield: 0.33 g (93%); Rf = 0.27 (CHCl3–hexane, 10:4).
1H NMR (200 MHz, CDCl3): d = 7.67 (m, 2 H, Ar), 7.11 (m, 2 H,
Ar), 4.79 (m, 1 H, OCH), 4.45 (m, 1 H, ClCH), 4.06 (m, 2 H,
CH2SF5), 3.46 (dd, JH,H = 10.4 Hz, 16.6 Hz, 1 H, CH2), 3.02 (dd,
JH,H = 8.0 Hz, 16.6 Hz, 1 H, CH2), 2.10–1.83 (m, 4 H, 2CH2) (a mix-
ture of diastereomers).
13C NMR (50.3 MHz, CDCl3): d = 163.52 (d, JC,F = 251.0 Hz, CF,
Ar), 155.37, 155.35 (d, JC,F = 1.0 Hz, C=N), 128.36 (d, JC,F = 8.1
Hz, CH, Ar), 125.55 (d, JC,F = 3.5 Hz, C, Ar), 115.60 (d, JC,F = 22.1
Hz, CH, Ar), 77.57, 77.34 (s, OCH), 76.61, 76.55 (pent, JC,F = 13.9
Hz, F5SCH2), 52.81, 52.55 (pent, JC,F = 4.5 Hz, ClCH), 43.24, 42.06
(s, CH2), 40.52, 40.23 (s, CH2).
Anal. Calcd for C9H12F5NO2S: C, 36.86; H, 4.12; F, 32.39; N, 4.78.
Found: C, 36.96; H, 4.62; F, 32.52; N, 4.88.
3-Acetyl-5-[2-chloro-3-(pentafluoro-l6-sulfanyl)propyl]-4,5-di-
hydroisoxazole (16)
In a procedure analogous to that used for the synthesis of 14 (Meth-
od A), 4 (0.23 g, 0.001 mol) was allowed to react with CAN (0.558
g, 0.001 mol).
Colorless oil; yield: 0.19 g (60%); Rf = 0.37 (CHCl3).
1H NMR (200 MHz, CDCl3): d = 5.29–5.08 (m, 1 H, OCH), 4.78–
4.46 (m, 1 H, ClCH), 4.22–3.89 (m, 2 H, CH2SF5), 3.35 (dd,
JH,H = 10.2 Hz, 17.0 Hz, 1 H, CH2), 2.82 (dd, JH,H = 7.6 Hz, 17.0 Hz,
1 H, CH2), 2.52 (s, 3 H, CH3), 2.40–1.84 (m, 2 H, CH2) (a mixture
of diastereomers).
13C NMR (50.3 MHz, CDCl3): d = 193.31, 193.23 (s, C=O), 158.61,
158.42 (s, C=N), 80.99, 80.61 (s, OCH), 76.84, 76.77 (pent,
19F NMR (188.3 MHz, CDCl3): d = 161.43–159.57 (18 lines,
JF–F = 144.7, 146.0 Hz, 1 F), 144.65, 143.56 (dm, JF–F = 144.7,
146.0 Hz, 4 F), –31.44 (m, 1 F) (a mixture of diastereomers).
Synthesis 2006, No. 16, 2665–2670 © Thieme Stuttgart · New York