The Journal of Organic Chemistry
Article
1.55 (m, 2H), 1.27 (d, J = 6.0 Hz, 3H), 0.96 (t, J = 7.5 Hz, 3H). 13C
NMR (100 MHz, CDCl3): δ (ppm) 154.4 (d, JC−F = 2.1 Hz), 152.5 (d,
1-Bromo-3-isopropoxybenzene (3ae). Prepared according to
the general procedure above on a 0.50 mmol-scale and a 0.50 mmol-
scale and obtained in 81% (0.087 g) and 86% (0.093 g) isolated yields,
respectively, as a colorless oil (83% average of two runs).
Spectroscopic data were consistent with those previously reported.60
1H NMR (400 MHz, CDCl3): δ (ppm) 7.10 (t, J = 8.3 Hz, 1H), 7.05−
7.02 (m, 2H) 6.81−6.78 (m, 1H) 4.54−4.45 (septet, J = 6.23 Hz, 1H)
1.31 (d, J = 6.24 Hz, 6H). 13C NMR (100 MHz, CDCl3): δ (ppm)
158.7, 130.5, 123.5, 122.7, 119.0, 114.7, 70.2, 21.9. Rf: 0.48 in 100%
hexane.
1-Bromo-3-(2,2,2-trifluoroethoxy)benzene (3af). Prepared
according to the general procedure above on a 0.50 mmol-scale and
a 0.50 mmol-scale and obtained in 65% (0.083 g) and 65% (0.083 g)
isolated yields (65% average of two runs). 1H NMR (400 MHz,
CDCl3): δ (ppm) 7.21−7.18 (m, 2H), 7.12−7.11 (m, 1H) 6.91−6.86
(m, 1H), 4.36−4.30 (m, 2H). 13C NMR (100 MHz, CDCl3): 158.0,
130.9, 125.8, 123.7, 123.0 (q, J = 277.8 Hz), 118.4, 113.8, 65.9 (q, J =
35.6 Hz). 19F NMR (377 MHz, CDCl3): δ (ppm) −73.94. FTIR:
2962, 1591, 1476, 1288, 1166 cm−1. HRMS (EI) m/z: [M]+ calculated
for C8H6BrF3O+ 253.9554; found 253.9563. Rf: 0.34 in 100% hexane.
1-Nitro-3-(tert-pentyloxy)benzene (3dg). Prepared according
to the general procedure above on a 0.50 mmol-scale and a 0.50
mmol-scale and obtained in 44% (0.046 g) and 45% (0.047 g) isolated
yields, respectively, as a light yellow oil (44% average of two runs). 1H
NMR (400 MHz, CDCl3) δ 7.92 (dd, J = 8.2, 2.2 Hz, 1H), 7.82 (t, J =
2.2 Hz, 1H), 7.41 (t, J = 8.2 Hz, 1H), 7.33−7.27 (m, 1H), 1.79−1.65
(m, 2H), 1.33 (s, 6H), 1.02 (t, J = 7.5 Hz, 3H). 13C NMR (101 MHz,
CDCl3): δ 156.5, 148.7, 129.7, 129.4, 118.0, 117.7, 82.6, 34.5, 26.0,
8.5. FTIR: 2970, 2934, 1710, 1243, 1026 m−1. HRMS (EI) m/z: [M]+
calculated for C11H15NO3+ 209.1051; found 209.1048. Rf: 0.32 in 10%
diethyl ether/hexane.
JC−F = 241.1 Hz), 121.0 (d, JC−F = 20.4 Hz), 117.7, 116.7 (d, JC−F
=
22.1 Hz), 115.6 (d, JC−F = 6.7 Hz), 76.3, 29.0, 19.0, 9.7. 19F NMR (377
MHz, CDCl3): δ (ppm) −111.31. FTIR: 2974, 2935, 1589, 1496,
1215, 1201 cm−1. HRMS (EI) m/z: [M]+ calculated for C10H12ClFO+
202.0561; found 202.0564. Rf: 0.26 in 100% hexane.
4-(sec-Butoxy)-1-methyl-2-nitrobenzene (3ja). Prepared ac-
cording to the general procedure above on a 0.51 mmol-scale and a
0.50 mmol-scale and obtained in 79% (0.084 g) and 84% (0.087 g)
isolated yields, respectively, as a light yellow oil (81% average of two
1
runs). H NMR (400 MHz, CDCl3): δ (ppm) 7.45 (d, J = 2.8 Hz,
1H), 7.35 (d, J = 8.4 Hz, 1H), 7.20−7.18 (dd, J = 7.4 Hz, 2.3 Hz, 1H),
4.48−4.10 (m, 1H), 2.39 (s, 3H), 1.70−1.51 (m, 2H),1.21 (d, J = 6.3
Hz, 3H), 0.90 (t, J = 7.5 Hz, 3H). 13C NMR (100 MHz, CDCl3): δ
(ppm) 156.7, 149.4, 133.4, 125.1, 121.4, 111.1, 75.8, 29.0, 19.7, 19.0,
9.6. FTIR: 2970, 2934, 1710, 1626, 1527, 1243, 1024 cm−1. HRMS
(EI) m/z: [M]+ calculated for C11H15NO3+ 209.1051; found 209.1053.
Rf: 0.29 in 2.5% diethyl ether/hexane.
4-(sec-Butoxy)-2-chloro-1-methylbenzene (3ka). Prepared
according to the general procedure above on a 0.50 mmol-scale and
a 1.02 mmol-scale and obtained in 70% (0.070 g) and 67% (0.137 g)
1
isolated yield, respectively, as a colorless oil. H NMR (400 MHz,
CDCl3): δ (ppm) 7.09 (d, J = 8.6 Hz, 1H), 6.91 (d, J = 2.6 Hz, 1H),
6.72−6.69 (dd, J = 5.6 Hz, 2.0 Hz, 1H), 4.25−4.21 (m, 1H), 2.29 (s,
3H), 1.76−1.56 (m, 2H), 1.26 (d, J = 6.0 Hz, 3H), 0.97 (t, J = 7.5 Hz,
3H). 13C NMR (100 MHz, CDCl3): δ (ppm) 156.9, 134.5, 131.1,
127.6, 116.5, 114.6, 75.5, 29.1, 19.1, 19.0, 9.74. FTIR: 2975, 2935,
1609, 1493, 1240 1040 cm−1. HRMS (EI) m/z: [M]+ calculated for
C11H15ClO+ 198.0811; found 198.0810. Rf: 0.31 in 100% hexane.
4-(sec-Butoxy)-2-chloro-1-methoxybenzene (3la). Prepared
according to the general procedure above on a 0.36 mmol-scale and
1-(Cyclopentyloxy)-3-fluorobenzene (3mh). Prepared accord-
ing to the general procedure above on a 0.51 mmol-scale and a 0.50
obtained in 69% (0.063 g) and 74% (0.067 g) isolated yields,
1
obtained in 67% (0.051 g) isolated yield as a colorless oil. H NMR
(400 MHz, CDCl3): δ (ppm) 7.02 (d, J = 9.1 Hz 1H), 6.99 (d, J = 3.0
Hz, 1H), 6.87−6.84 (dd, J = 6.0 Hz, 2.1 Hz, 1H), 4.30−4.23 (m, 1H),
3.77 (s, 3H), 1.65−1.46 (m, 2H), 1.17 (d, J = 6.0 Hz, 3H), 0.89 (t, J =
7.8 Hz, 3H). 13C NMR (100 MHz, DMSO): δ (ppm) 156.6, 135.5,
131.5, 126.7, 115.9, 114.6, 74.5, 28.4, 18.3, 18.5, 9.3. FTIR: 2973,
2936, 2838, 1497, 1272, 1211, 1059 cm−1. HRMS (EI) m/z: [M]+
calculated for C11H15ClO2+ 214.0760; found 214.0762. Rf: 0.45 in 10%
diethyl ether/hexane.
3-Bromoanisole (3ab). Prepared according to the general
procedure above on a 0.51 mmol-scale and a 0.50 mmol-scale and
obtained in 77% (0.073 g) and 71% (0.067 g) isolated yields,
respectively, as a colorless oil (74% average of two runs).
Spectroscopic data were consistent with those previously reported.58
1H NMR (400 MHz, CDCl3): δ (ppm) 7.13 (t, J = 5.2 Hz, 1H), 7.08−
7.04 (m, 2H) 6.83−6.80 (m, 1H) 3.70 (s, 3H). 13C NMR (100 MHz,
CDCl3): δ (ppm) 160.3, 130.5, 123.7, 122.8, 117.1, 113.0, 55.4. Rf:
0.24 in 100% hexane.
3-Bromophenetole (3ac). Prepared according to the general
procedure above on a 0.50 mmol-scale and a 0.50 mmol-scale and
obtained in 84% (0.084 g) and 77% (0.077 g) isolated yields,
respectively, as a colorless oil (80% average of two runs).
Spectroscopic data were consistent with those previously reported.59
1H NMR (400 MHz, CDCl3): δ (ppm) 7.11 (t, J = 16.1 Hz, 1H),
7.06−7.03 (m, 2H), 6.82−6.79 (m, 1H) 4.01−3.96 (q, J = 7.0 Hz, 2H)
1.39 (t, J = 7.0 Hz, 3H). 13C NMR (100 MHz, CDCl3): δ (ppm)
159.7, 130.4, 123.5, 122.7, 117.6, 113.5, 63.6, 14.7. Rf: 0.38 in 100%
hexane.
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respectively, as a colorless oil (72% average of two runs). H NMR
(400 MHz, CDCl3): δ (ppm) 7.20−7.14 (m, 1H), 6.64−6.55 (m, 3H),
4.73−4.68 (m, 1H), 1.93−1.73 (m, 6H) 1.66−1.55 (m, 2H). 13C
NMR (100 MHz, CDCl3): δ (ppm) 163.6 (d, JC−F = 245.2 Hz), 159.5
(d, JC−F= 10.8 Hz), 130.0 (d, JC−F = 10.3 Hz), 111.3 (d, JC−F = 2.8
Hz), 106.9 (d, JC−F = 21.9), 103.0 (d, JC−F = 24.2 Hz), 79.7, 32.7, 24.0.
19F NMR (377 MHz, CDCl3): δ (ppm) −111.98. FTIR: 3014, 2961,
1590, 1221, 1134 cm−1. HRMS (EI) m/z: [M]+ calculated for
C11H13FO+ 180.0950; found 180.0953. Rf: 0.32 in 100% hexane.
1-Fluoro-3-(3-(trifluoromethyl)phenethoxy)benzene (3 mi).
Prepared according to the general procedure above on a 0.510 mmol-
scale and a 0.505 mmol-scale and obtained in 78% (0.114 g) and 86%
(0.123 g) isolated yields, respectively, as a colorless oil (82% average of
1
two runs). H NMR (400 MHz, CDCl3): δ (ppm) 7.57−7.42 (m,
4H), 7.25−7.19 (m, 1H), 6.70−6.60 (m, 3H) 4.18 (t, J = 6.8 Hz, 2H)
13.16 (t, J = 6.7 Hz, 2H). 13C NMR (100 MHz, CDCl3): δ (ppm)
163.6 (d, JC−F = 245.6 Hz), 159.5 (d, JC−F = 10.3 Hz), 139.1, 132.4 (d,
JC−F = 1.4 Hz), 130.8 (q, J = 31.8 Hz), 130.2 (d, JC−F = 9.5 Hz), 128.9,
125.7 (q, JC−F = 3.7 Hz), 124.3 (q, JC−F = 274.3 H), 123.4 (q, JC−F
=
3.6 Hz), 110.3 (d, JC−F = 3.1 Hz), 107.6 (d, JC−F = 21.2 Hz), 102.3 (d,
JC−F = 24.7 Hz), 68.3, 35.4. 19F NMR (377 MHz, CDCl3): δ (ppm)
−111.59, −62.60. FTIR: 3086, 2961, 2936, 2867, 1607, 1488, 1124,
1066 cm−1. HRMS (EI) m/z: [M]+ calculated for C15H12F4O+
284.0824; found 284.0822. Rf: 0.28 in 100% hexane.
2-(2-(3-Fluorophenoxy)ethyl)thiophene (3mj). Prepared ac-
cording to the general procedure above on a 0.51 mmol-scale and a
0.51 mmol-scale and obtained in 76% (0.086 g) and 78% (0.090 g)
isolated yields, respectively, as a colorless oil (77% average of two
1-Bromo-3-propoxybenzene (3ad). Prepared according to the
general procedure above on a 0.51 mmol-scale and a 0.50 mmol-scale
and obtained in 77% (0.084 g) and 81% (0.088 g) isolated yields,
1
1
runs). H NMR (400 MHz, CDCl3): δ (ppm) 7.22−7.14 (m, 2H),
respectively, as a colorless oil (79% average of two runs). H NMR
6.95−6.89 (m, 2H), 6.69−6.59 (m, 3H), 4.15 (t, J = 6.6 Hz, 2H), 3.29
(400 MHz, CDCl3): δ (ppm) 7.10 (t, J = 8.3 Hz, 1H), 7.05−7.03 (m,
2H), 6.82−6.80 (m, 1H) 3.87 (t, J = 6.6 Hz, 2H) 1.89−1.73 (m, 2H)
1.01 (t, J = 7.4 Hz, 3H). 13C NMR (100 MHz, CDCl3): δ (ppm)
159.9, 130.4, 123.5, 122.7, 117.7, 113.5, 69.7, 22.4, 10.4. FTIR: 2964,
2936, 1591, 1469, 1244, 1228 cm−1. HRMS (EI) m/z: [M]+ calculated
for C9H11BrO+ 213.9993; found 213.9998. Rf: 0.39 in 100% hexane.
(t, J = 6.7 Hz, 2H). 13C NMR (100 MHz, CDCl3): 163.7 (d, JC−F
=
252.8 Hz), 159.9 (d, JC−F = 11.4 Hz), 140.0, 130.2 (d, JC−F =10.3 Hz),
126.8, 125.5, 124.0, 110.3 (d, JC−F = 2.4 Hz), 107.6 (d, JC−F = 21.5
Hz), 102.3 (d, JC−F = 25.0 Hz), 68.6, 29.8. 19F NMR (377 MHz,
CDCl3): δ (ppm) −111.63. FTIR: 3072, 2928, 1614, 1491, 1277, 1136
I
J. Org. Chem. XXXX, XXX, XXX−XXX