9
4.3.5.
1,2-Dibromo-2-fluoro-1-phenylcyclopropane (2e)
Obtained by the general procedure (the reaction time — 18 hours) after column
chromatography (n-hexane/benzene, 10/1) as a colorless oil (209.0 mg, 71% yield, syn-/anti- =
43/57).
1H NMR (300.1 MHz, CDCl3) : 1.94 (dd, 1H, syn-2e, J = 9.5, 9.4 Hz), 2.17–2.30 (m, 2H,
19
anti-2e), 2.38 (dd, 1H, syn-2e, J = 18.5, 9.5 Hz), 7.27–7.53 (m, 5H, arom.). F NMR (282.4
MHz, CDCl3) : –125.4 (dd, anti-2e, J = 13.7, 9.5 Hz), –129.6 (dd, syn-2e, J = 18.5, 9.4 Hz).
13C NMR (75.5 MHz, CDCl3) : 31.9 (d, CH2-cycloprop., J = 10.9 Hz), 32.7 (d, CH2-
cycloprop., J = 11.0 Hz), 38.3 (d, C-cycloprop., J = 11.0 Hz), 39.3 (d, C-cycloprop., J = 11.8
Hz), 81.3 (d, CFBr, J = 205.7 Hz), 85.4 (d, CFBr, J = 201.4 Hz), 128.8 (s, CH-arom.), 128.9
(s, CH-arom.), 129.2 (s, CH-arom.), 129.3 (s, CH-arom.), 136.6 (s, C-arom.), 139.1 (s, C-
arom.). MS (EI, 70 eV) m/z 292/294/296 ([M+], 0.1/0.2/0.1), 213/215 ([M–Br]+, 18/18),
193/195 (2/2), 134 (38), 133 (100), 107 (8), 89 (6), 77 (7), 67 (12), 63 (9), 57 (5), 51 (6).
Anal.: calcd. for C9H7Br2F: C, 36.77%; H, 2.40%. Found: C, 36.86%; H, 2.56%.
4.3.6.
2-Bromo-2-fluoro-1-(1-naphthylmethyl)cyclopropane (2f)
Obtained by the general procedure (the reaction time — 18 hours) after column
chromatography (n-hexane/benzene, 10/1) as a colorless oil (229.3 mg, 82% yield, syn-/anti- =
46/54).
1H NMR (300.1 MHz, CDCl3) : 1.05–1.15 (m, 1H, syn-2f), 1.24–1.39 (m, 1H, anti-2f),
1.42–1.53 (m, 1H, anti-2f), 1.64–1.78 (m, 1H, syn-2f), 1.82–2.03 (m, 1H, both isomers), 3.06
(ddd, 1H, CH2-naphth., syn-2f, J = 15.7, 7.2, 2.8 Hz), 3.19 (ddd, 1H, CH2-naphth., anti-2f, J =
15.7, 7.1, 1.5 Hz), 7.37–7.55 (m, 4H, naphth.), 7.66–7.82 (m, 1H, naphth.), 7.82–7.89 (m, 1H,
naphth.), 7.96–8.03 (m, 1H, naphth.). 19F NMR (282.4 MHz, CDCl3) : –127.0 (dddd, syn-2f,
13
J = 19.8, 17.1, 7.1, 2.7 Hz), –148.4 (dd, J = 17.6, 7.8 Hz). C NMR (75.5 MHz, CDCl3) :
22.7 (d, CH2-cycloprop., syn-2f, J = 10.2 Hz), 23.1 (d, CH2-cycloprop., anti-2f, J = 10.8 Hz),
25.6 (d, CH-cycloprop., syn-2f, J = 9.6 Hz), 28.8 (d, CH-cycloprop., anti-2f, J = 10.6 Hz),
29.9 (d, CH2, anti-2f, J = 5.7 Hz), 34.2 (d, CH2, syn-2f, J = 1.1 Hz), 82.2 (d, CFBr-cycloprop.,
anti-2f, J = 301.5 Hz), 87.4 (d, CFBr-cycloprop., syn-2f, J = 298.9 Hz), 123.4 (s, CH-arom.),
123.4 (s, CH-arom.), 125.7–125.8 (m, nCH-arom.), 126.2 (s, CH-arom.), 127.3 (s, CH-arom.),
127.4 (s, CH-arom.), 129.0 (s, CH-arom.), 129.0 (s, CH-arom.), 131.9 (s, C-arom.), 133.9 (s,
C-arom.), 133.9 (s, C-arom.), 135.1 (s, C-arom.), 135.2 (s, C-arom.), 135.6 (s, C-arom.). MS
(EI, 70 eV) m/z 278/280 ([M+], 13/13), 199 (63), 183 (21), 179 (100), 165 (26), 153 (91), 141