170
H. Jiang et al. / Journal of Fluorine Chemistry 133 (2012) 167–170
concentrated by rotary evaporation at reduced pressure. The
residue was then purified by column chromatography (2:1
petroleum ether:ethyl acetate) on basic aluminum oxide to obtain
the product 3.
1.0 Hz, 1H, ArH), 7.30–7.28 (m, 1H, ArH); 13C NMR (125 MHz,
CDCl3):
158.9 (t, 2JC-F = 37.5 Hz), 152.2, 147.6, 146.5, 143.9, 135.0,
d
129.4, 127.1, 127.0, 124.8, 124.1, 122.0, 118.3 (t, 1JC-F = 263.75 Hz);
19F NMR (470 MHz, CDCl3):
d
À63.28 (s, 2F); IR (cmÀ1):
v 3064,
2360, 1522, 1297, 1158, 1074, 1000, 763, 704; HRMS calcd for (M+)
4.3.1. 2-Difluorophenoxymethyl-benzothiazole (3bd)
C13H8F2N2OS: 278.0325, found 278.0329.
3bd was obtained as a white solid in 65% yield by flash column
chromatography; mp 39.5–41.1 8C; 1H NMR (500 MHz, CDCl3):
d
4.3.6. 2-Difluorophenylsulfanylmethyl-benzothiazole (3bi)
8.19 (d, J = 8.5 Hz, 1H, ArH), 7.91 (dd, J = 10.0, 2.5 Hz, 1H, ArH), 7.54
(td, J = 7.0, 1.0 Hz, 1H, ArH), 7.49–7.45 (m, 1H, ArH), 7.38–7.33 (m,
4H, ArH), 7.24 (tt, J = 6.5, 2.0 Hz, 1H, ArH); 13C NMR (125 MHz,
3bi was obtained as a white solid in 62% yield by flash column
chromatography; mp 93.5–94.0 8C; 1H NMR (500 MHz, CDCl3):
d
8.20 (d, J = 8.0 Hz, 1H, ArH), 7.93 (d, J = 8.0 Hz, 1H, ArH), 7.71 (d,
J = 7.0 Hz, 2H, ArH), 7.57 (t, J = 8.0 Hz, 1H, ArH), 7.51–7.44 (m, 2H,
CDCl3):
d
160.2 (t, 2JC-F = 40.0 Hz), 152.5, 149.8, 135.3, 129.7, 127.1,
1
127.0, 126.5, 124.9, 122.2, 122.1, 118.3 (t, JC-F = 261.3 Hz); 19F
ArH), 7.39 (t, J = 7.5 Hz, 2H, ArH); 13C NMR (125 MHz, CDCl3):
162.6 (t, JC-F = 33.8 Hz), 152.4, 137.0, 135.4, 130.6, 129.3, 127.1,
126.9, 125.6 (t, 1JC-F = 125.0 Hz), 124.8, 122.0; 19F NMR (470 MHz,
d
2
NMR (470 MHz, CDCl3):
1490, 1295, 1193, 1066, 999, 760, 689; HRMS calcd for (M+)
d
À63.03 (s, 2F); IR (cmÀ1):
v
3067, 1592,
C
14H9F2NOS: 277.0373, found 277.0372.
CDCl3):
d
À66.73 (s, 2F); IR (cmÀ1):
v 3059, 1510, 1244, 1057, 1019,
885, 689; HRMS calcd for (M+) C14H9F2NS2: 293.0144, found
293.0141.
4.3.2. 2-Difluoro-(4-nitro)-phenoxymethyl-benzothiazole (3be)
3be was obtained as a white solid in 73% yield by flash column
chromatography; mp 158.4–160.2 8C; 1H NMR (500 MHz, CDCl3):
d
Acknowledgements
8.28 (dt, J = 9.0, 3.0 Hz, 2H, ArH), 8.20 (d, J = 8.0 Hz, 1H, ArH), 7.99
(d, J = 7.5 Hz, 1H, ArH), 7.61 (td, J = 7.5, 1.0 Hz, 1H, ArH), 7.55 (td,
J = 8.0, 1.0 Hz, 1H, ArH), 7.49 (d, J = 9.0 Hz, 2H, ArH); 13C NMR
This work was financially supported by the National Natural
Science Foundation of China (Nos. 21072127 and 21032006) and
the Science Foundation of Shanghai Municipal Commission of
Sciences and Technology (10JC1405600).
2
(125 MHz, CDCl3):
d
158.7 (t, JC-F = 37.5 Hz), 154.6, 152.4, 145.6,
1
135.2, 127.5, 127.4, 125.7, 125.0, 122.2, 122.0, 118.5 (t, JC-
F = 263.8 Hz); 19F NMR (470 MHz, CDCl3):
À63.57 (s, 2F); IR
d
(cmÀ1):
v 3084, 1615, 1594, 1517, 1343, 1272, 1154, 997, 764;
Appendix A. Supplementary data
HRMS calcd for (M+) C14H8F2N2O3S: 322.0224, found 322.0220.
Supplementary data associated with this article can be found, in
4.3.3. 2-Difluoro-(4-methoxy)-phenoxymethyl-benzothiazole (3bf)
3bf was obtained as a white solid in 64% yield by flash column
chromatography; mp 79.1–81.3 8C; 1H NMR (500 MHz, CDCl3):
d
8.20 (d, J = 8.5 Hz, 1H, ArH), 7.92 (d, J = 8.0 Hz, 1H, ArH), 7.55 (dd,
J = 7.0, 7.0 Hz, 1H, ArH), 7.48 (dd, J = 7.5, 7.5 Hz, 1H, ArH), 7.26 (d,
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J = 9.0 Hz, 2H, ArH), 6.87 (dd, J = 7.5, 2.0 Hz, 2H, ArH), 3.76 (s, 3H, -
2
OCH3); 13C NMR (125 MHz, CDCl3):
d
160.2 (t, JC-F = 38.8 Hz),
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1
(t, JC-F = 261.3 Hz), 114.6, 55.6; 19F NMR (470 MHz, CDCl3):
d
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À63.42 (s, 2F); IR (cmÀ1):
v 3074, 2970, 1503, 1298, 1176, 1058,
998, 762; HRMS calcd for (M+) C15H11F2NO2S: 307.0479, found
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4.3.4. 2-Difluoro-(2-naphthyl)-oxymethyl-benzothiazole (3bg)
3bg was obtained as a white solid in 78% yield by flash column
chromatography; mp 89.7–91.3 8C; 1H NMR (500 MHz, CDCl3):
d
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8.24 (d, J = 8.0 Hz, 1H, ArH), 7.97 (d, J = 7.5 Hz, 1H, ArH), 7.86 (dd,
J = 16.0, 14.5 Hz, 4H, ArH), 7.60 (td, J = 7.0, 1.0 Hz, 1H, ArH), 7.54–
2
7.48 (m, 4H, ArH); 13C NMR (125 MHz, CDCl3):
d
160.1 (t, JC-
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F = 40.0 Hz), 152.5, 147.4, 135.3, 133.8, 131.7, 129.8, 127.9, 127.8,
127.1, 127.0, 126.9, 126.2, 125.0, 122.1, 121.5, 119.3, 118.5 (t, 1JC-
F = 261.3 Hz); 19F NMR (470 MHz, CDCl3):
d
À62.97 (s, 2F); IR
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v 3061, 1598, 1511, 1295, 1180, 1050, 997, 760, 732; HRMS
calcd for (M+) C18H11F2NOS: 327.0529, found 327.0525.
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4.3.5. 2-Difluoro-(3-pyridyl)-oxymethyl-benzothiazole (3bh)
3bh was obtained as a pale-yellow solid in 75% yield by flash
column chromatography; mp 43.7–44.6 8C; 1H NMR (500 MHz,
CDCl3):
d 8.63 (d, J = 2.5 Hz, 1H, ArH), 8.48 (dd, J = 5.0, 1.0 Hz, 1H,
ArH), 8.14 (d, J = 8.0 Hz, 1H, ArH), 7.91 (d, J = 7.5 Hz, 1H, ArH), 7.65–
7.63 (m, 1H, ArH), 7.53 (td, J = 7.0, 1.0 Hz, 1H, ArH), 7.46 (td, J = 8.0,