The Journal of Organic Chemistry
Page 6 of 9
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2-(Difluoromethyl)-6-methoxynaphthalene (3m)
(69.6 mg, 69% yield). H NMR (300 MHz, CDCl3) 8.37 (t,
1H, J = 9.3 Hz), 8.25-8.17 (m, 5H), 8.14-8.11 (m, 1H), 8.08-
8.03 (m, 2H), 7.46 (t, 1H, JH-F = 55.4 Hz); 13C {1H} NMR (75
MHz, CDCl3) δ 133.2 (t, JC-F = 1.7 Hz), 131.2, 131.0, 130.5,
129.1, 129.0, 128.6 (t, JC-F = 3.8 Hz), 127.3, 126.5, 126.2, 126.1,
124.5, 123.7 (t, JC-F = 7.8 Hz), 122.4, 115.5 (t, JC-F = 236.8 Hz);
19F NMR (282 MHz, CDCl3) -108.8 (d, 2F, JF-H = 55.6 Hz).
HRMS (APCI-TOF) [M+H3O]+ calcd for C17H13F2O: 271.0935;
found: 271.0939.
1
2
3
4
5
6
7
8
White solid. NMR yield (93%) was determined by using BTF
as an internal standard. The residue was purified by silica-gel
column chromatography (3% Et2O in hexane) to afford the
compound (68.3 mg, 82% yield). The product is known
compound and the following data are identical to those given in
corresponding literature.12a 1H NMR (300 MHz, CDCl3) 7.89
(s, 1H), 7.80 (dd, 2H, J = 10.8 Hz, 8.0 Hz), 7.57 (d, 1H, J = 8.4
Hz), 7.24-7.21 (m, 1H), 7.20-7.16 (m, 1H), 6.78 (t, 1H, JH-F
=
56.5 Hz), 3.94 (s, 3H); 13C {1H} NMR (75 MHz, CDCl3) δ 158.9,
135.9 (t, JC-F = 1.2 Hz), 130.1, 129.5 (t, JC-F = 22.2 Hz), 128.1,
127.7, 125.8 (t, JC-F = 7.4 Hz), 122.7 (t, JC-F = 4.7 Hz), 119.8,
115.4 (t, JC-F = 236.6 Hz), 105.9, 55.5; 19F NMR (282 MHz,
CDCl3) -108.9 (d, 2F, JF-H = 55.6 Hz).
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1-(Difluoromethyl)-4-methoxybenzene (3i)
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Colorless liquid. NMR yield (83%) was determined by using
BTF as an internal standard. The residue was purified by silica-
gel column chromatography (2% Et2O in pentane) to afford the
compound (32.9 mg, 52% yield). The product is known
compound and the following data are identical to those given in
corresponding literature.7c 1H NMR (300 MHz, CDCl3) 7.44
(d, 2H, J = 8.4 Hz), 6.96 (d, 2H, 8.6 Hz), 6.60 (t, 1H, JH-F = 56.7
Hz), 3.84 (s, 3H); C {1H} NMR (75 MHz, CDCl3) δ 161.5,
127.3 (t, JC-F = 5.9 Hz), 126.9 (t, JC-F = 22.6 Hz), 115.0 (t, JC-F
235.8 Hz), 114.1, 55.5; 19F NMR (282 MHz, CDCl3) -108.2
(d, 2F, JF-H = 56.1 Hz).
1-(Difluoromethyl)-4-(trifluoromethyl)benzene (3n)
Colorless liquid. NMR yield (57%) was determined by using
trifluoromethoxybenzene (Ph-OCF3) as an internal standard.
The residue was purified by silica-gel column chromatography
(pentane only) to afford the compound (12.6 mg, 16% yield).
The product is known compound and the following data are
identical to those given in corresponding literature.27 1H NMR
(300 MHz, CDCl3) 7.74 (d, 2H, J = 8.2 Hz), 7.65 (d, 2H, 8.0
13
=
13
Hz), 6.71 (t, 1H, JH-F = 56.0 Hz); C {1H} NMR (75 MHz,
1-(Difluoromethyl)-4-phenoxybenzene (3j)
CDCl3) δ 137.8 (t, JC-F = 22.4 Hz), 132.8 (q, JC-F = 32.6 Hz),
Colorless liquid. NMR yield (91%) was determined by using
BTF as an internal standard. The residue was purified by silica-
gel column chromatography (3% EtOAc in haxane) to afford
the compound (74.9 mg, 85% yield). The product is known
compound and the following data are identical to those given in
corresponding literature.9a 1H NMR (300 MHz, CDCl3) 7.48
(d, 2H, J = 8.5 Hz), 7.42-7.37 (m, 2H), 7.18 (t, 1H, 7.4 Hz), 7.08,
7.05 (m, 4H), 6.64 (t, 1H, JH-F = 56.6 Hz); 13C {1H} NMR (75
126.1 (t, JC-F = 6.0 Hz), 125.8 (q, JC-F = 3.8 Hz), 123.6 (q, JC-F
=
270.8 Hz), 113.7 (t, JC-F = 238.5 Hz); 19F NMR (282 MHz,
CDCl3) -63.1 (s, 3F), -112.4 (d, 2F, JF-H = 55.4 Hz).
4-(Difluoromethyl)benzonitrile (3o)
Orange liquid. NMR yield (45%) was determined by using BTF
as an internal standard. The residue was purified by silica-gel
column chromatography (3% EtOAc in hexane) to afford the
compound (22.3 mg, 36% yield). The product is known
compound and the following data are identical to those given in
corresponding literature.7c 1H NMR (300 MHz, CDCl3) 7.79
MHz, CDCl3) δ 159.7 (t, JC-F = 2.1 Hz), 156.3, 130.1, 129.0 (t,
JC-F = 22.5 Hz), 127.5 (t, JC-F = 5.9 Hz), 124.2, 119.8, 118.4,
114.7 (t, JC-F = 236.5 Hz ); 19F NMR (282 MHz, CDCl3) -
109.0 (d, 2F JF-H = 55.4 Hz).
(d, 2H, J = 8.1 Hz), 7.66 (d, 2H, J = 8.6 Hz), 6.71 (t, 1H, JH-F
=
=
13
55.8 Hz); C {1H} NMR (75 MHz, CDCl3) δ 138.6 (t, JC-F
[4-(Difluoromethyl)phenyl](methyl)sulfane (3k)
22.8 Hz), 132.6, 126.4 (t, JC-F = 6.0 Hz), 117.9, 114.8, 113.3 (t,
JC-F = 239.4 Hz); 19F NMR (282 MHz, CDCl3) -113.1 (d, 2F,
JF-H = 55.6 Hz).
Yellow liquid. NMR yield (63%) was determined by using
BTF as an internal standard. The residue was purified by silica-
gel column chromatography (2% EtOAc in hexane only) to
afford the compound (40.4 mg, 58% yield). The product is
known compound and the following data are identical to those
given in corresponding literature.26 1H NMR (300 MHz, CDCl3)
7.41 (d, 2H, J = 8.3 Hz), 7.29 (d, 2H, 8.4 Hz), 6.61 (t, 1H, JH-F
Ethyl 4-(Difluoromethyl)benzoate (3p)
Colorless liquid. NMR yield (62%) was determined by using
BTF as an internal standard. The residue was purified by silica-
gel column chromatography (3% EtOAc in hexane) to afford
the compound (44.0 mg, 55% yield). The product is known
compound and the following data are identical to those given in
corresponding literature.7c 1H NMR (300 MHz, CDCl3) 8.13
13
= 56.5 Hz), 2.50 (s, 3H); C {1H} NMR (75 MHz, CDCl3) δ
142.3 (t, JC-F = 2.1 Hz), 130.9 (t, JC-F = 22.4 Hz), 126.1 (t, JC-F
=
5.3 Hz), 114.7 (t, JC-F = 236.7 Hz), 15.3; 19F NMR (282 MHz,
CDCl3) -109.9 (d, 2F, JF-H = 55.2 Hz).
(d, 2H, J = 8.0 Hz), 7.58 (d, 2H, J = 8.2 Hz), 6.69 (t, 1H, JH-F
=
56.1 Hz), 4.40 (q, 2H, J = 7.1 Hz), 1.41 (t, 3H, J = 7.1 Hz); 13C
{1H} NMR (75 MHz, CDCl3) δ 165.9, 138.5 (t, JC-F = 22.9 Hz),
132.8 (t, JC-F = 2.0 Hz), 130.0, 125.7 (t, JC-F = 6.0 Hz), 114.2 (t,
JC-F = 238.2 Hz), 61.5, 14.4; 19F NMR (282 MHz, CDCl3) -
112.2 (d, 2F, JF-H = 56.7 Hz).
1-(tert-Butyl)-4-(Difluoromethyl)benzene (3l)
Colorless liquid. NMR yield (78%) was determined by using
BTF as an internal standard. The residue was purified by silica-
gel column chromatography (pentane only) to afford the
compound (48.6 mg, 66% yield). The product is known
compound and the following data are identical to those given in
corresponding literature.7c 1H NMR (300 MHz, CDCl3) 7.51
(m, 4H, J = 8.8 Hz), 6.63 (t, 1H, JH-F = 56.7 Hz), 1.34 (s, 9H);
13C {1H} NMR (75 MHz, CDCl3) δ 154.1 (t, JC-F = 2.1 Hz),
131.7 (t, JC-F = 22.4 Hz), 125.5 (t, JC-F = 5.9 Hz), 125.4 115.0 (t,
JC-F = 236.6 Hz), 35.0, 31.4; 19F NMR (282 MHz, CDCl3) -
109.9 (d, 2F, JF-H = 55.7 Hz).
1-(Difluoromethyl)-4-fluoronaphthalene (3q)
White solid. NMR yield (61%) was determined by using BTF
as an internal standard. The residue was purified by silica-gel
column chromatography (3% Et2O in hexane) to afford the
compound (43.9 mg, 56% yield). 1H NMR (300 MHz, CDCl3)
δ 8.21 (d, 2H, J = 7.7. Hz), 7.70-7.62 (m, 4H), 7.18 (t, 1H, J =
8.6 Hz), 7.10 (t, 1H, JH-F = 55.1 Hz); 13C {1H} NMR (75 MHz,
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