7
(38), 84 (48%); HRMS (ESI): MH+, found 282.9605.
146.8; HRMS (ESI): MH+, found 205.0501. C11H10ClN2
requires 205.0527.
ACCEPTED MANUSCRIPT
C11H979BrClN2 requires 282.9632.
4.2.14. 2-Amino-3-(4 -chlorophenyl)-5,6-dimethylpyridine (3af).
′
4.2.17. 3-Amino-2-(4
′
-fluorophenyl)pyridine (3bg), 3-Amino-4-
(3bg ), and 3-Amino-2-(4
, and 3bg′′
Compound 3af was prepared from 1a (179 mg, 1.0 mmol) and 2-
amino-5,6-dimethylpyridine 2f (2.44 g, 20.0 mmol) according to
the general procedure. Purification with column chromatography
(inner diameter: 2 cm and length: 30 cm) gave 3af (78 mg, 0.34
mmol, 34%). Recrystallized from hexane/AcOEt=1:1, 3af was
given as a pale orange needle; Rf (hexane/AcOEt=1:1) 0.2; mp
109.5-110.5 °C; νmax (neat) 3483, 3438, 3288, 3156, 1450, 1391,
1092 cm-1; δΗ (400 MHz, CDCl3) 2.18 (s, 3H, -CH3), 2.37 (s, 3H,
-CH3), 4.35 (bs, 2H, N-H), 7.09 (s, 1H, C-H), 7.37 (d, J 8.8 Hz,
2H, C-H), 7.40 (d, J 8.8 Hz, 2H, C-H); δC (100 MHz, CDCl3)
17.9, 21.9, 117.9, 121.5, 129.1, 130.1, 133.3, 136.8, 139.5, 153.0,
154.6; HRMS (ESI): MH+, found 233.0813. C13H14ClN2 requires
233.0840.
(4 -fluorophenyl)pyridine
′
′
′-
fluorophenyl)pyridine (3bg′′). Compounds 3bg, 3bg
′
were synthesized from 1b (163 mg, 1.0 mmol) and 2g (1.88 g,
20.0 mmol) according to the general procedure. Purification with
column chromatography (inner diameter: 3 cm and length: 30
cm) gave 3bg (71 mg, 0.38 mmol, 38%), and 3bg
mmol, 11%), and 3bg′′ (12 mg, 0.06 mmol, 6%). 3-Amino-2-(4
fluorophenyl)pyridine (3bg): Recrystallized from
′ (21 mg, 0.11
′
-
hexane/AcOEt=9:1, 3bg was given as a pale yellow needle; Rf
(hexane/AcOEt=1:3) 0.52; mp 74.4-75.4 °C; νmax (neat) 3393,
3295, 3208, 3055, 1624, 1584, 1509, 1217 cm-1; δΗ (400 MHz,
CDCl3) 3.79 (bs, 2H, N-H), 7.05 (dd, J 1.8 Hz, J 7.8 Hz, 1H, C-
H), 7.08 (dd, J 3.8 Hz, J 7.8 Hz, 1H, C-H), 7.16 (dd, JHF 8.8 Hz, J
8.8 Hz, 2H, C-H), 7.67 (dd, JHF 5.6 Hz, J 8.8 Hz, 2H, C-H), 8.12
(dd, J 1.8 Hz, J 3.8 Hz, 1H, C-H); δC (100 MHz, CDCl3) 115.7
(d, JCF 21.0 Hz), 122.8, 123.1, 130.3 (d, JCF 7.7 Hz), 134.7, 139.9,
140.1, 144.1, 162.9 (d, JCF 246.0 Hz); HRMS (ESI): MH+, found
189.0796. C11H10FN2 requires 189.0823. 3-Amino-4-(4′-
fluorophenyl)pyridine
hexane/AcOEt=9:1, 3bg
(hexane/AcOEt=1:3) 0.12; mp 108.5-109.5 °C; δΗ (400 MHz,
CDCl3) 3.81 (bs, 2H, N-H), 6.99 (d, J 5.2 Hz, 1H, C-H), 7.17 (dd,
JHF 8.8 Hz, J 8.8 Hz, 2H, C-H), 7.44 (dd, JHF 5.2 Hz, J 8.8 Hz,
2H, C-H), 8.05 (d, J 5.2 Hz, 1H, C-H), 8.15 (s, 1H, C-H); δC (100
MHz, CDCl3) 116.1 (d, JCF 21.0 Hz), 124.1, 130.2 (d, JCF 8.6 Hz),
132.6, 132.8, 138.2, 139.7, 140.2, 162.5 (d, JCF 247.0 Hz);
HRMS (ESI): MH+, found 189.0808. C11H10FN2 requires
4.2.15. 2-Amino-3-(4′-fluorophenyl)-5,6-dimethylpyridine (3bf).
Compound 3bf was prepared from 1b (163 mg, 1.0 mmol) and 2f
(2.44 g, 20.0 mmol) according to the general procedure.
Purification with column chromatography (inner diameter: 3 cm
and length: 30 cm) gave 3bf (64 mg, 0.30 mmol, 30%).
Recrystallized from hexane/AcOEt=9:1, 3bf was given as a pale
orange plate crystal; Rf (hexane/AcOEt=1:2) 0.28; mp 109.0-
110.0 °C; νmax (neat) 3480, 3292, 3169, 1454, 1216 cm-1; δΗ (400
MHz, CDCl3) 2.18 (s, 3H, -CH3), 2.38 (s, 3H, -CH3), 4.33 (bs,
2H, N-H), 7.09 (s, 1H, C-H), 7.12 (dd, JHF 8.8 Hz, J 8.8 Hz, 2H,
C-H), 7.40 (dd, JHF 5.4 Hz, J 8.8 Hz, 2H, C-H); δC (100 MHz,
CDCl3) 17.9, 21.9, 115.9 (d, JCF 21.0 Hz), 118.2, 121.4, 130.4 (d,
JCF 7.6 Hz), 134.3, 139.7, 153.1, 154.3, 162.1 (d, JCF 245.1 Hz);
HRMS (ESI): MH+, found 217.1127. C13H14FN2 requires
217.1136.
(3bg
′
):
Recrystallized
from
′ was given as a pale yellow needle; Rf
189.0823.
3-Amino-6-(4
′
-fluorophenyl)pyridine
(3bg′′):
Recrystallized from hexane/AcOEt=9:1, 3bg′′ was given as a
pale orange crystal; Rf (hexane/AcOEt=1:3) 0.40; mp 98.0-
99.5 °C; δΗ (400 MHz, CDCl3) 3.74 (bs, 2H, N-H), 7.04 (dd, J
2.8 Hz, J 8.4 Hz, 1H,C-H), 7.10 (dd, JHF 8.8 Hz, J 8.8 Hz, 2H, C-
H), 7.48 (d, J 8.4 Hz, 1H), 7.86 (dd, JHF 5.6 Hz, J 8.8 Hz, 2H, C-
H), 8.16 (d, J 2.8 Hz, 1H, C-H); δC (100 MHz, CDCl3) 115.4 (d,
JCF 21.0 Hz), 120.4, 122.4, 127.6 (d, JCF 7.7 Hz), 135.7, 137.1,
141.3, 147.2, 162.7 (d, JCF 245.0 Hz); HRMS (ESI): MH+, found
189.0801. C11H10FN2 requires 189.0823.
4.2.16. 3-Amino-2-(4
(4 -chlorophenyl)pyridine
chlorophenyl)pyridine (3ag′′). Compounds 3ag, 3ag
′
-chlorophenyl)pyridine (3ag), 3-Amino-4-
(3ag ), and 3-Amino-6-(4
, and 3ag′′
′
′
′-
′
were synthesized from 1a (179 mg, 1.0 mmol) and 3-
aminopyridine 2g (1.88 g, 20.0 mmol) according to the general
procedure. Purification with column chromatography (inner
diameter: 2 cm and length: 30 cm) gave 3ag (107 mg, 0.52 mmol,
52%), and 3ag
0.08 mmol, 8%). 3-Amino-2-(4
′
(31 mg, 0.15 mmol, 15%), and 3ag′′ (17 mg,
′
-chlorophenyl)pyridine (3ag):
4.2.18. 3-Amino-2-(4
′
-bromophenyl)pyridine (3cg), 3-Amino-4-
(3cg ),and 3-Amino-6-(4
, and 3cg′′
Recrystallized from hexane/AcOEt=1:1, 3ag was given as a pale
yellow needle; Rf (hexane/AcOEt=1:3) 0.64; mp 86.6-87.5 °C;
νmax (neat) 3458, 3309, 3184, 1631, 1579, 1444, 1088 cm-1; δΗ
(400 MHz, CDCl3) 3.80 (bs, 2H, N-H), 7.05 (dd, J 1.8 Hz, J 8.0
Hz, 1H, C-H), 7.08 (dd, J 4.8 Hz, J 8.0 Hz, 1H, C-H), 7.45 (d, J
8.8 Hz, 2H, C-H), 7.64 (d, J 8.8 Hz, 2H, C-H), 8.12 (dd, J 1.8 Hz,
J 4.8 Hz, 1H, C-H); δC (100 MHz, CDCl3) 122.9, 123.3, 129.0,
129.9, 134.1, 137.0, 139.9, 140.1, 143.7; m/z (EI) 203 (100, M+),
168 (45), 84 (22), 41 (47%); HRMS (ESI): MH+, found 205.0504.
(4 -bromophenyl)pyridine
′
′
′-
bromophenyl)pyridine (3cg′′). Compounds 3cg, 3cg
′
were synthesized from 1c (224 mg, 1.0 mmol) and 2g (1.88 g,
20.0 mmol) according to the general procedure. Purification with
column chromatography (inner diameter: 3 cm and length: 30
cm) gave 3cg (117 mg, 0.47 mmol, 47%), and 3cg
mmol, 11%), and 3cg′′ (13 mg, 0.05 mmol, 5%). 3-Amino-2-
(4 -bromophenyl)pyridine (3cg): Recrystallized from
′ (27 mg, 0.11
′
hexane/AcOEt=9:1, 3cg was given as a pale yellow solid; Rf
(hexane/AcOEt=1:3) 0.60; mp 98.0-99.0 °C (Lit.15 99-101 °C);
νmax (neat) 3467, 3313, 3183, 1633, 1579, 1445, 1075 cm-1. δΗ
(400 MHz, CDCl3); 3.80 (bs, 2H, N-H), 7.05 (dd, J 2.0 Hz, J 8.0
Hz, 1H, C-H), 7.08 (dd, J 4.0 Hz, J 8.0 Hz, 1H, C-H), 7.58 (d, J
8.8 Hz, 2H, C-H), 7.61 (d, J 8.8 Hz, 2H, C-H), 8.13 (dd, J 2.0 Hz,
J 4.0 Hz, 1H, C-H); δC (100 MHz, CDCl3) 122.4, 122.9, 123.3,
130.2, 131.9, 137.5, 139.9, 140.2, 143.7; HRMS (ESI): MH+,
found 249.0016. C11H1079BrN2 requires 249.0022. 3-Amino-4-
C11H10ClN2 requires 205.0527. 3-Amino-4-(4
′-chlorophenyl)-
pyridine (3ag ): Recrystallized from hexane/AcOEt=9:1, 3ag
′
′
was given as a brown needle; Rf (hexane/AcOEt=1:3) 0.16; mp
146.5-147.5 °C; δΗ (400 MHz, CDCl3); 3.77 (bs, 2H, N-H), 7.00
(d, J 5.0 Hz, 1H, C-H), 7.41 (d, J 8.6 Hz, 2H, C-H), 7.46 (d, J 8.6
Hz, 2H, C-H), 8.07 (d, J 5.0 Hz, 1H, C-H), 8.16 (s,1H, C-H); δC
(100 MHz, CDCl3) 123.9, 129.3, 129.8, 132.3, 134.3, 135.3,
138.3, 139.6, 140.3; HRMS (ESI): MH+, found 205.0509.
C11H10ClN2 requires 205.0527. 3-Amino-6-(4′-chlorophenyl)-
(4
′
-bromophenyl)pyridine
(3cg
′
):
Recrystallized
from
pyridine (3ag′′): Recrystallized from hexane/AcOEt=9:1, 3ag′′
was given as a brown solid; mp 96.5-98.2 °C; δΗ (400 MHz,
CDCl3) 3.77 (bs, 2H, N-H), 7.05 (dd, J 3.1 Hz, J 8.3 Hz, 1H, C-
H), 7.39 (d, J 8.6 Hz, 2H, C-H), 7.51 (d, J 8.3 Hz, 1H, C-H), 7.83
(d, J 8.6 Hz, 2H, C-H), 8.17 (d, J 3.1 Hz, 1H, C-H); δC (100 MHz,
CDCl3) 120.6, 122.2, 127.2, 128.7, 133.6, 137.2, 137.9, 141.5,
hexane/AcOEt=9:1, 3cg
′
was given as a pale orange solid; Rf
(hexane/AcOEt=1:3) 0.14; mp 159.0-160.5 °C; δΗ (400 MHz,
CDCl3); 3.80 (bs, 2H, N-H), 6.99 (d, J 4.8 Hz, 1H, C-H), 7.35 (d,
J 8.6 Hz, 2H, C-H), 7.61 (d, J 8.6 Hz, 2H, C-H), 8.06 (d, J 4.8 Hz,
1H, C-H), 8.15 (s, 1H, C-H); δC (100 MHz, CDCl3) 122.4, 123.8,
130.1, 132.3, 135.7, 138.3, 139.5, 140.2; HRMS (ESI): MH+,