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P.V. Ramachandran, A. Chatterjee / Journal of Fluorine Chemistry 130 (2009) 144–150
4.4.1. 4-(Benzyloxy)-3,3-difluoro-2-phenylpent-4-en-2-ol (11a)
(t, J = 252.7 Hz), 88.7, 76.7 (t, J = 25.2 Hz), 70.7, 24.2 HRMS Found:
349.1127. HRMS Calc. for C18H17F2NO4: 349.1126.
4.4.5. 4-(Benzyloxy)-1,1,1,3,3-pentafluoro-2-phenylpent-4-en-2-ol
(11e)
Liquid: 1H NMR (CDCl3, 300 MHz):
d 7.59–7.56 (m, 2H), 7.27–
7.45 (m, 8H), 4.79 (d, J = 11.4 Hz, 1H), 4.71 (d, J = 11.4 Hz, 1H), 4.64
(d, J = 3.3 Hz 1H), 4.40 (m, 1H), 3.37 (bs, 1H). 19F NMR (CDCl3,
282 MHz):
d
ꢀ111.34 (d, J = 260.4 Hz, 1F), ꢀ112.32 (d, J = 260.4 Hz,
154.7 (t, J = 27.4 Hz), 141.3, 135.3,
1F). 13C NMR (CDCl3, 75 Hz):
d
128.7, 128.4, 127.9, 127.7, 127.6, 126.2, 117.3 (t, J = 257.7 Hz), 88.3,
76.7 (t, J = 26.3 Hz), 70.6, 24.0. HRMS Found: 304.1280. HRMS Calc.
for C18H18F2O2: 304.1275.
Liquid: 1H NMR (CDCl3, 300 MHz):
7.43 (m, 6H), 7.38–7.32 (m, 2H), 4.90 (d, J = 4.2 Hz, 1H), 4.86 (d,
J = 10.8 Hz, 1H), 4.76 (d, J = 10.8 Hz, 1H), 4.61–4.57 (m, 1H), 4.47 (s,
d 7.81–7.77 (m, 2H), 7.52–
1H). 19F NMR (CDCl3, 282 MHz):
d
ꢀ73.89 (t, J = 9.9 Hz, 3F),
ꢀ109.03 (qd, J = 9.9 Hz and 268.3 Hz, 1F), ꢀ110.46 (dq, J = 9.9 Hz
and 268.3 Hz, 1F). 13C NMR (CDCl3, 75 Hz):
153.8 (t, J = 26.9 Hz),
4.4.2. 4-(Benzyloxy)-3,3-difluoro-2-(4-methoxyphenyl)pent-4-en-2-
ol (11b)
d
134.7, 131.9, 129.5, 128.9, 128.8, 128.1, 128.0, 127.4, 117.5 (t,
J = 254.7 Hz), 89.2, 71.4, 65.9. HRMS Found: 358.0997. HRMS Calc.
for C18H15F5O2: 358.0992.
4.4.6. 1-(2-(Benzyloxy)-1,1-difluoroallyl)cyclohexanol (11f)
Liquid: 1H NMR (CDCl3, 300 MHz):
d 7.51–7.41 (m, 5H), 7.29–
7.31 (m, 2H), 6.90–6.93 (m, 2H), 4.79 (d, J = 11.1 Hz, 1H), 4.73 (d,
J = 11.1 Hz, 1H), 4.66 (s, 1H), 4.43 (s, 1H), 3.87 (s, 3H), 3.35 (bs, 1H),
1.75 (s, 3H). 19F NMR (CDCl3, 282 MHz):
d
ꢀ111.46 (d, J = 256.6 Hz,
1F), ꢀ112.44 (d, J = 256.6 Hz, 1F). 13C NMR (CDCl3, 75 Hz):
d 159.1,
Liquid: 1H NMR (CDCl3, 300 MHz):
d 7.46–7.38 (m, 5H), 4.90 (s,
154.8 (t, J = 29.5 Hz), 135.4, 133.4, 128.7, 128.4, 127.7, 127.5,
117.5 (t, J = 252.6 Hz), 113.2, 88.3, 76.7 (t, J = 33.4 Hz), 70.6, 55.2,
2 H), 4.78 (m, 1H), 4.56 (m, 1H), 2.24 (bs, 1H), 1.82–1.58 (m, 10H).
19F NMR (CDCl3, 282 MHz):
d
ꢀ116.9 (s) 13C NMR (CDCl3, 75 MHz):
24.1. HRMS Found: 334.1380. HRMS Calc. for
334.1381.
C19H20F2O3:
d
154.9 (t, J = 29.5 Hz), 135.7, 128.7, 128.3, 127.5, 118.4 (t,
J = 250.6 Hz), 88.0 (t, J = 6.3 Hz), 74.1 (t, J = 25.3 Hz), 70.4, 30.6,
25.5, 20.8. HRMS Found: 282.1435. HRMS Calc. for C16H20F2O2:
282.1431.
4.4.3. 4-(Benzyloxy)-3,3-difluoro-2-(4-
(trifluoromethyl)phenyl)pent-4-en-2-ol (11c)
4.4.7. 5-(Benzyloxy)-4,4-difluoro-2,3-dimethylhex-5-en-3-ol (11g)
Liquid: 1H NMR (CDCl3, 300 MHz):
d 7.71 (d, J = 8.1 Hz, 2H), 7.64
Liquid: 1H NMR (CDCl3, 300 MHz):
d 7.60–7.39 (m, 5H), 4.92 (s,
2H), 4.85 (d, J = 2.7 Hz, 1H), 4.58 (m, 1H), 2.46 (bs, 1H), 1.98
(septet, J = 6.8 Hz, 1H), 1.28 (s, 3H), 1.06 (d, J = 6.8 Hz, 3H), 1.01
(d, J = 8.1 Hz, 2H), 7.44–7.38 (m, 3H), 7.27–7.22 (m, 2H), 4.79–4.69
(m, 3H), 4.48–4.45 (m, 1H), 3.39 (s, 1H), 1.77 (s, 3H). 19F NMR
(CDCl3, 282 MHz):
(CDCl3, 75 Hz):
d
ꢀ111.71 (s, 2F), ꢀ62.44 (s, 3F). 13C NMR
(dd, J = 2.1 Hz and 6.8 Hz, 3H). 19F NMR (CDCl3, 282 MHz):
d
d
154.3 (t, J = 29.5 Hz), 145.3, 135.0, 130.1, 129.7,
ꢀ108.4 (d, J = 259.2 Hz, 1F), ꢀ110.2 (d, J = 259.2 Hz, 1F). 13C NMR
128.8, 128.6, 127.6, 126.8, 126.0, 124.8, 117.1 (t, J = 252.8 Hz), 88.7,
70.7, 24.2. HRMS Found: 372.1147. HRMS Calc. for C19H17F5O2:
372.1149.
(CDCl3, 75 MHz):
d 155.5 (t, J = 29.5 Hz), 135.5, 128.8, 128.4,
127.6, 118.9 (t, J = 252.7 Hz), 87.8 (t, J = 6.3 Hz), 70.6, 33.7, 18.3,
17.3, 15.9. HRMS Found: 270.1439. HRMS Calc. for C15H20F2O2:
270.1431.
4.4.4. 4-(Benzyloxy)-3,3-difluoro-2-(4-nitrophenyl)pent-4-en-2-ol
(11d)
4.4.8. 5-(Benzyloxy)-4,4-difluoro-2,2,3-trimethylhex-5-en-3-ol
(11h)
Liquid: 1H NMR (CDCl3, 300 MHz):
d 8.17 (d, J = 8.7 Hz, 2H), 7.74
(d, J = 8.7 Hz, 2H), 7.44–7.36 (m, 3H), 7.26–7.20 (m, 2H), 4.77–4.71
(m, 3H), 4.50–4.47 (m, 1H), 3.34 (bs, 1H), 1.78 (s, 3H). 19F NMR
Liquid: 1H NMR (CDCl3, 300 MHz):
2H), 4.86 (d, J = 3.6 Hz, 1H), 4.54 (m, 1H), 2.8 (bs, 1H), 1.37 (t,
J = 2 Hz, 3H), 1.12 (s, 9H). 19F NMR (CDCl3, 282 MHz):
ꢀ105.9 (s).
13C NMR (75 MHz, CDCl3):
156.7 (t, J = 29.5 Hz), 135.4, 128.8,
128.5, 127.7, 119.1 (t, J = 252.7 Hz), 87.2 (t, J = 6.2 Hz), 79.1 (t,
d 7.45–7.40 (m, 5H), 4.89 (s,
(CDCl3, 282 MHz):
J = 257.2 Hz, 1F). 13C NMR (CDCl3, 75 Hz):
148.4, 147.4, 134.9, 128.7, 128.6, 127.7, 127.4, 122.9, 116.9
d
ꢀ110.07 (d, J = 257.2 Hz, 1F), ꢀ112.52 (d,
d
d
153.9 (t, J = 29.5 Hz),
d