The Journal of Organic Chemistry
Note
(4-Ethylphenyl)methanamine Hydrochloride (Table 2, 2).17
Colorless solid (84.6 mg, 99%); H NMR (600 MHz, DMSO-d6) δ
(FAB-TOF): Calculated for C8H9NF3 [M-Cl]+: 176.0687, Found:
176.0689.
1
8.66 (s, 3H), 7.42 (d, J = 7.7 Hz, 2H), 7.19 (d, J = 7.7 Hz, 2H), 3.92
(s, 2H), 2.56 (q, J = 7.6 Hz, 2H), 1.13 (t, J = 7.6 Hz, 3H); 13C NMR
(150 MHz, DMSO-d6) δ 144.4, 131.8, 129.5 (2C), 128.2 (2C), 42.3,
28.3, 16.1; HRMS (FAB-TOF): Calculated for C9H14N [M-Cl]+:
136.1126, Found: 136.1128.
(2-Chlorophenyl)methanamine Hydrochloride (Table 2, 12).
Colorless solid (78 mg, 88%); mp 222−224 °C; 1H NMR (400 MHz,
DMSO-d6) δ 8.81 (s, 3H), 7.81−7.63 (m, 1H), 7.58−7.47 (m, 1H),
7.46−7.30 (m, 2H), 4.10 (d, J = 8.3 Hz, 2H); 13C NMR (100 MHz,
DMSO-d6) δ 133.3, 132.1, 131.1, 130.7, 129.8, 127.9, 40.0; IR (cm−1):
2892, 1598, 1535, 1438, 1381, 1205, 1050, 890, 746; HRMS (FAB-
TOF): Calculated for C7H9ClN [M-Cl]+: 142.0424, Found: 142.0425.
(3-Chlorophenyl)methanamine Hydrochloride (Table 2, 13).
[1,1′-Biphenyl]-4-ylmethanamine Hydrochloride (Table 2,
3).13a Colorless solid (108.4 mg, 99%); 1H NMR (600 MHz, DMSO-
d6) δ 8.75 (s, 3H), 7.75−7.55 (m, 6H), 7.44 (t, J = 7.6 Hz, 2H), 7.35
(t, J = 7.4 Hz, 1H), 4.03 (s, 2H); 13C NMR (150 MHz, DMSO-d6) δ
140.5, 139.9, 133.7, 130.1 (2C), 129.4 (2C), 128.1, 127.1 (2C), 127.1
(2C), 42.2; HRMS (FAB-TOF): Calculated for C13H14N [M-Cl]+:
184.1126, Found: 184.1125.
1
Colorless solid (86.7 mg, 98%); mp 307−309 °C; H NMR (600
MHz, DMSO-d6) δ 8.72 (s, 3H), 7.65 (s, 1H), 7.59−7.25 (m, 3H),
4.00 (s, 2H); 13C NMR (150 MHz, DMSO-d6) δ 136.9, 133.4, 130.7,
129.4, 128.6, 128.2, 41.9; IR (cm−1): 2960, 2903, 1598, 1576, 1458,
1216, 1111, 1083, 969, 788; HRMS (FAB-TOF): Calculated for
C7H9ClN [M-Cl]+: 142.0424, Found: 142.0422.
o-Tolylmethanamine Hydrochloride (Table 2, 4).18 Colorless
solid (69.1 mg, 88%); 1H NMR (400 MHz, DMSO-d6) δ 8.58 (s, 3H),
7.43 (d, J = 7.2 Hz, 1H), 7.30−7.16 (m, 3H), 3.98 (s, 2H), 2.35 (s,
3H); 13C NMR (100 MHz, DMSO-d6) δ 137.1, 132.8, 130.7, 129.7,
128.9, 126.5, 39.9, 19.3; HRMS (FAB-TOF): Calculated for C8H12N
[M-Cl]+: 122.0970, Found: 122.0970.
Naphthalen-2-ylmethanamine Hydrochloride (Table 2,
14).4d Colorless solid (88.8 mg, 92%); 1H NMR (400 MHz,
DMSO-d6) δ 8.73 (s, 3H), 8.10−7.81 (m, 4H), 7.77−7.63 (m, 1H),
7.62−7.43 (m, 2H), 4.18 (s, 2H); 13C NMR (100 MHz, DMSO-d6) δ
133.0, 132.2, 128.6, 128.4, 128.2, 128.1, 127.1 (2C), 127.0, 127.0
(2C); HRMS (FAB-TOF): Calculated for C11H12N [M-Cl]+:
158.0970, Found: 158.0969.
(4-Methoxyphenyl)methanamine Hydrochloride (Table 2,
5).13a Colorless solid (78.7 mg, 91%); H NMR (600 MHz, DMSO-
1
d6) δ 8.59 (s, 3H), 7.43 (d, J = 8.2 Hz, 2H), 6.91 (d, J = 8.3 Hz, 2H),
3.88 (d, J = 5.8 Hz, 2H), 3.71 (s, 3H); 13C NMR (150 MHz, DMSO-
d6) δ 159.7, 131.0 (2C), 126.4, 114.3 (2C), 55.6, 42.0; HRMS (FAB-
TOF): Calculated for C8H12NO [M-Cl]+: 138.0919, Found: 138.0917.
(4-Phenoxyphenyl)methanamine Hydrochloride (Table 2,
(2,4-Dimethylphenyl)methanamine Hydrochloride (Table 2,
15).20 Colorless solid (83.8 mg, 98%); mp 215−216 °C; H NMR
1
(600 MHz, DMSO-d6) δ 8.57 (s, 3H), 7.30 (d, J = 7.8 Hz, 1H), 7.01
(s, 1H), 7.00 (d, J = 8.5 Hz, 1H), 3.90 (s, 2H), 2.30 (s, 3H), 2.24 (s,
3H); 13C NMR (150 MHz, DMSO-d6) δ 138.1, 136.9, 131.3, 129.8,
129.7, 126.9, 39.6, 21.1, 19.2.
1
6). Colorless solid (96.3 mg, 82%); mp 251−253 °C; H NMR (400
MHz, DMSO-d6) δ 8.59 (s, 3H), 7.54 (d, J = 8.6 Hz, 2H), 7.47−7.31
(m, 2H), 7.23−7.09 (m, 1H), 7.08−6.87 (m, 4H), 4.09−3.88 (m, 2H);
13C NMR (100 MHz, DMSO-d6) δ 157.3, 156.8, 131.5 (2C), 130.6
(2C), 129.6, 124.2, 119.2 (2C), 118.9 (2C), 42.0; IR (cm−1): 2950,
2875, 1588, 1507, 1487, 1250, 1171, 964, 872, 689; HRMS (FAB-
TOF): Calculated for C13H14NO [M-Cl]+: 200.1075, Found:
200.1074.
1,3-Phenylenedimethanamine Dihydrochloride (Table 2,
16).21 Colorless solid (102 mg, 98%); 1H NMR (600 MHz,
DMSO-d6) δ 8.73 (s, 6H), 7.66−7.46 (m, 3H), 7.41 (s, 1H), 3.95
(s, 4H); 13C NMR (150 MHz, DMSO-d6) δ 134.7 (2C), 130.2, 129.2,
129.1 (2C), 42.4 (2C).
(1,5-Dimethyl-1H-pyrrol-2-yl)methanamine Hydrochloride
1
(Table 2, 17). Brown solid; mp 203−205 °C; H NMR (400 MHz,
[4-(Triisopropylsilyloxy)phenyl]methanamine (Table 2, 7).
The general procedure was applied and the product was isolated by
flash column chromatography on silica gel (ethyl acetate/n-hexane,
3:7): colorless liquid (126.4 mg, 94%); 1H NMR (600 MHz, CDCl3) δ
7.13 (d, J = 9.0 Hz, 2H), 6.83 (d, J = 6.5 Hz, 2H), 3.76 (s, 2H), 2.02−
1.70 (m, 2H), 1.29−1.20 (m, 3H), 1.09 (d, J = 7.6 Hz, 18H); 13C
NMR (150 MHz, CDCl3) δ 154.9, 135.6, 128.1 (2C), 119.8 (2C),
45.9, 17.9 (6C), 12.6 (3C); 29Si NMR (120 MHz, CDCl3) δ 14.9; IR
(cm−1): 3331, 3228, 2943, 2865, 1669, 1607, 1508, 1460, 1261, 1167,
1071, 911, 672; HRMS (ESI-TOF): Calculated for C16H29NOSiNa
[M + Na]+: 302.1916, Found: 302.1890.
DMSO-d6) δ 8.41 (s, 3H), 6.18−5.90 (d, J = 2.8 Hz, 1H), 5.75 (d, J =
3.5 Hz, 1H), 3.95 (d, J = 5.6 Hz, 2H), 3.48 (s, 3H), 2.16 (s, 3H); 13C
NMR (100 MHz, DMSO-d6) δ 130.2, 124.3, 109.4, 105.9, 34.4, 30.8,
12.7; IR (cm−1): 2972, 1603, 1466, 1412, 1385, 1315, 1109, 1079, 990,
754.
N-[(1,5-Dimethyl-1H-pyrrol-2-yl)methyl]-4-methylbenzene-
sulfonamide (Table 2, 17a). To a flame-dried 50 mL round-bottom
flask were added B(C6F5)3 (77 mg, 0.3 mmol, 3 mol %), diethylsilane
(1.62 mL, 12.5 mmol, 2.5 equiv), and chloroform (5 mL) under argon
atmosphere. Benzonitrile (0.60 g, 5 mmol) was then added and the
reaction mixture was stirred at room temperature for 6 h. After
removing volatiles by rotary evaporator, 1 M HCl solution in ether (30
mL) was added and the reaction mixture stirred for 1 h at room
temperature to form the desired product 17 (HCl salt) as brown solid.
To a flame-dried round-bottom flask were added 17/HCl (5 mmol)
and dichloromethane (25 mL). After the dropwise addition of
triethylamine (2.1 mL, 15 mmol) at 0 °C, it was stirred for 15 min at 0
°C. p-Toluenesulfonyl chloride (1.14 g, 6 mmol) was added and the
reaction mixture was stirred at room temperature for 12 h. Water was
added and the reaction mixture was extracted with dichloromethane
(15 mL × 3). The combined organic layers were dried over Na2SO4,
evaporated under reduced pressure, and purified by flash column
chromatography on silica gel (ethyl acetate/n-hexane, 3:7) to afford
the corresponding product 17a (1.08 g, 78% over two steps): Brown
(4-Bromophenyl)methanamine Hydrochloride (Table 2,
8).13a Colorless solid (1.08 g/5 mmol, 98%); H NMR (600 MHz,
1
DMSO-d6) δ 8.70 (s, 3H), 7.57 (d, J = 8.1 Hz, 2H), 7.48 (d, J = 8.1
Hz, 2H), 3.96 (s, 2H); 13C NMR (150 MHz, DMSO-d6) δ 133.9,
131.8 (2C), 131.7 (2C), 122.1, 41.8; HRMS (FAB-TOF): Calculated
for C7H9BrN [M-Cl]+: 185.9918, Found: 185.9921.
(4-Iodophenyl)methanamine Hydrochloride (Table 2, 9).19
1
Colorless solid (126.4 mg, 94%); H NMR (400 MHz, DMSO-d6) δ
8.69 (s, 3H), 7.76 (d, J = 8.3 Hz, 2H), 7.34 (d, J = 8.3 Hz, 2H), 3.96
(s, 2H); 13C NMR (100 MHz, DMSO-d6) δ 137.7 (2C), 134.3, 131.8
(2C), 95.3, 42.0.
(4-Nitrophenyl)methanamine Hydrochloride (Table 2, 10).4c
Brown solid (77.1 mg, 82%); 1H NMR (400 MHz, DMSO-d6) δ 8.81
(s, 3H), 8.27 (d, J = 8.5 Hz, 2H), 7.81 (d, J = 8.5 Hz, 2H), 4.17 (d, J =
5.7 Hz, 2H); 13C NMR (100 MHz, DMSO-d6) δ 147.8, 142.2, 130.7
(2C), 123.9 (2C), 41.8; HRMS (FAB-TOF): Calculated for
C7H9N2O2 [M-Cl]+: 153.0664, Found: 153.0660.
1
solid (1.08 g/5 mmol, 78%); mp 107−108 °C; H NMR (600 MHz,
CDCl3) δ 7.74 (d, J = 8.2 Hz, 2H), 7.33 (d, J = 8.0 Hz, 2H), 5.83 (d, J
= 3.4 Hz, 1H), 5.73 (d, J = 3.3 Hz 1H), 4.45 (t, J = 5.8 Hz, 1H), 4.03
(d, J = 5.8 Hz, 2H), 3.42 (s, 3H), 2.45 (s, 3H), 2.16 (s, 3H); 13C NMR
(150 MHz, CDCl3) δ 143.5, 136.5, 130.8 (2C), 129.7, 127.1 (2C),
125.1, 108.2, 105.3, 39.9, 30.3, 21.5, 12.3; IR (cm−1): 3270, 2924,
1685, 1584, 1511, 1433, 1324, 1305, 1157, 1091, 1034, 832, 667;
HRMS (ESI-TOF): Calculated for C14H18N2NaO2S [M + Na]+:
301.0987, Found: 301.0983.
[4-(Trifluoromethyl)phenyl]methanamine Hydrochloride
(Table 2, 11).13a Colorless solid (84.4 mg, 80%); H NMR (400
1
MHz, DMSO-d6) δ 8.68 (s, 3H), 7.80 (d, J = 8.2 Hz, 2H), 7.75 (d, J =
8.2 Hz, 2H), 4.12 (s, 2H); 13C NMR (100 MHz, DMSO-d6) δ 139.3,
130.3 (2C), 129.3 (q, J = 32 Hz), 125.7 (q, J = 3.8 Hz, 2C), 124.6 (q, J
= 272.7 Hz), 42.0; 19F NMR (376 MHz, DMSO-d6) δ −61.5; HRMS
D
J. Org. Chem. XXXX, XXX, XXX−XXX