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and 1-hexyne (0.082 g, 1.0 mmol) following Method A except reacted
at room temperature and reduced using Method III. A combined yield
of 62% (0.115 g) was obtained for the mixture of regioisomers (1.6:1,
AM:M) as an oil, which were inseparable by chromatography. The 1H
27.3, 36.7, 53.8, 112.8, 116.4, 129.2, 148.2; MS (EI) m/z 178 ([M +
H)+). Anal. Calcd for C12H19N: C, 81.30; H, 10.80; N, 7.90. Found: C,
81.36; H, 10.80; N, 7.90.
N-(1,2-Diphenylethyl)benzeneamine60,132 (7c). This compound
was prepared from aniline (0.112 g, 1.2 mmol) and diphenylacetylene
(0.107 g, 1.0 mmol) following Method B and reduced using a literature
procedure.57 To a round-bottom flask, Pd/C (53 mg, 10 mol % of Pd,
0.05 mmol of Pd, 5 mol %) and dry THF was added and stirred under
an H2 atmosphere for 30 min. The volatile components of the crude
hydroamination reaction mixture was removed in vacuo, dissolved in dry
THF, and added to the Pd/C suspension. The resulting mixture was
stirred under 1 atm of H2 for 72 h. Filtration over Celite, removal of
solvent in vacuo and purification by column chromatography afforded
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for the mixture have been provided: H NMR (CDCl3, 400 MHz) δ
1.00 (6H, t, J = 7.2 Hz, AM and M), 1.26 (2H, d, J = 6.4 Hz, M),
1.36−1.54 (11H, m, AM and M), 1.62−1.72 (4H, m, AM and M),
3.17 (2H, t, J = 7.1 Hz, AM), 3.50−3.57 (1H, m, M), 3.62 (1H, br s,
M), 6.64−6.72 (4H, m, AM and M), 6.77−6.79 (2H, m, AM and M),
7.22−7.27 (4H, m, AM and M).
(4-Methoxy-phenyl)-(1-methyl-pentyl)-amine and Hexyl-(4-methoxy-
phenyl)-amine (6h). These compounds were prepared from para-
methoxyaniline (0.148 g, 1.2 mmol) and 1-hexyne (0.082 g, 1.0 mmol)
following Method A except reacted at room temperature and reduced
using Method III. A combined yield of 77% (0.160 g) was obtained for
the mixture of regioisomers (2.3:1, AM:M) as an oil, which were
inseparable by chromatography. The 1H and 13C NMR spectra as well
as the elemental analysis for the mixture have been provided: 1H NMR
(CDCl3, 400 MHz) δ 0.91 (6H, t, J = 7.2 Hz, AM and M), 1.17 (2H,
d, J = 6.4 Hz, M), 1.30−1.40 (11H, m, AM and M), 1.60−1.61 (4H,
m, AM and M), 3.07 (2H, t, J = 7.1 Hz, AM), 3.22 (1H, br s, M),
3.30−3.50 (1H, m, M), 3.76 (6H, s, AM and M), 6.57 (4H, d, J = 9
Hz, AM and M), 6.79 (4H, d, J = 9 Hz, AM and M); 13C{1H} NMR
(CDCl3, 101 MHz) δ 15.0, 15.1, 21.8, 23.7, 23.8, 27.9, 29.4, 30.7, 32.7,
38.0, 46.1, 50.5, 56.8, 115.0, 115.7, 116.0, 116.0, 143.1, 144.0, 152.8,
153.0; HRMS Calcd for C13H21NO [M+] 207.1623, found 207.16242.
Anal. Calcd for C13H21NO: C, 75.32; H, 10.21; N, 6.76. Found: C,
75.44; H, 10.09; N, 6.61.
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the pure product. Isolated as a colorless oil (0.269 g, 98%): H NMR
(CDCl3, 400 MHz) δ 3.02 (1H, dd, J = 8.4, 14.0 Hz), 3.15 (1H, dd,
J = 5.8, 14.0 Hz), 4.13 (1H, br s), 4.58−4.62 (1H, m), 6.47 (2H, d,
J = 7.8 Hz), 6.62−6.65 (1H, m), 7.04−7.08 (2H, m), 7.13 (2H, d, J =
6.7 Hz), 7.23−7.35 (8H, m).
4-Methoxy-N-(1-phenylpropan-2-yl)-aniline131 (7d). This com-
pound was prepared from para-methoxyaniline (0.074 g, 0.6 mmol)
and 1-phenyl-1-propyne (0.058 g, 0.5 mmol) following Method B and
reduced with Method III. Isolated as a colorless oil (0.123 g, >98%):
1H NMR (CDCl3, 400 MHz) δ 1.17 (3H, d, J = 6.0 Hz), 2.71 (1H, dd,
J = 7.2, 13.2 Hz), 2.97 (1H, dd, J = 4.8, 13.2 Hz), 3.30 (1H, br s),
3.71−3.75 (1H, m), 3.79 (3H, s), 6.63−6.67 (2H, m), 6.82−6.87
(2H, m), 7.21−7.36 (5H, m).
(1-Ethyl-butyl)-(4-methoxy-phenyl)-amine (7e). This compound
was prepared from para-methoxyaniline (0.074 g, 0.6 mmol) and
3-hexyne (0.041 g, 0.5 mmol) following Method C except at 110 °C in
toluene-d8 and reduced using Method III. Isolated as a colorless oil
N-(2,6-Dimethylphenyl)-benzeneethanamine114 (6i). This com-
pound was prepared from 2,6-dimethylaniline (0.133 g, 1.1 mmol) and
phenylacetylene (0.102 g, 1.0 mmol) following Method A and reduced
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(0.107 g, >98%): H NMR (CDCl3, 400 MHz) δ 0.94 (6H, t, J = 7.2
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using Method I. Isolated as a colorless oil (0.140 g, 62%): H NMR
Hz), 1.40−1.62 (6H, m), 3.15 (1H, br s), 3.19−3.24 (1H, m), 3.76
(3H, s), 6.56 (2H, d, J = 9.0 Hz), 6.77 (2H, d, J = 9.0 Hz) ; 13C{1H}
NMR (CDCl3, 101 MHz) δ 11.0, 15.3, 20.2, 28.2, 37.7, 55.9, 56.9,
115.3, 116.0, 143.6, 152.6; MS (EI) m/z 207 (M+). Anal. Calcd
for C13H21NO: C, 75.32 ; H, 10.21; N, 6.76. Found: C, 75.26; H,
10.10; N, 7.16.
(CDCl3, 400 MHz) δ 2.23 (6H, s), 2.97 (2H, t, J = 6.9 Hz), 3.13 (1H,
br s), 3.36 (2H, t, J = 6.9 Hz), 6.87−7.42 (8H, m).
[2-(tert-Butyl-dimethyl-silanyloxy)-1-methylethyl]-(2,6-dimethyl-
phenyl)-amine (6j). This compound was prepared from 2,6-
dimethylaniline (0.074 mL, 0.6 mmol) and (tert-butyldimethyl-
silyloxy)-1-propyne (0.084 g, 0.5 mmol) following Method C and
reduced using Method II. Isolated as a yellow oil (0.042 g, 23%). An
analytically pure sample was obtained by a bulb-to-bulb distillation
(1,2-Diphenyl-ethyl)-(4-methoxy-phenyl)-amine (7f). This com-
pound was prepared from para-methoxyaniline (0.074 g, 0.6 mmol)
and (phenylethynyl)benzene (0.089 g, 0.5 mmol) following Method C
except at 110 °C in toluene-d8 and reduced using Method III. Isolated
as a colorless oil (0.151 g, >98%): 1H NMR (CDCl3, 400 MHz) δ 3.06
(1H, dd, J = 8.2, 13.9 Hz), 3.18 (1H, dd, J = 5.6, 13.8 Hz), 3.72 (3H, s),
3.90 (1H, br s), 4.56−4.60 (1H, m), 6.50 (2H, d, J = 9 Hz), 6.71 (2H, d,
J = 9 Hz), 7.17−7.39 (10H, m) ; 13C{1H} NMR (CDCl3, 101 MHz) δ
45.4, 55.9, 60.3, 114.9, 115.1, 126.7, 126.9, 127.2, 128.7, 128.7, 129.4,
138.0, 141.7, 143.9, 152.3; MS (EI) m/z 303 (M+). Anal. Calcd for
C21H21NO: C, 83.13; H, 6.98; N, 4.62. Found: C, 83.12; H, 6.93; N, 4.72.
(4-Methoxy-phenyl)-(4-methylpentanyl)-amine (7g). This com-
pound was prepared from para-methoxyaniline (0.074 g, 0.6 mmol)
and 4-methylpent-2-yne (0.042 g, 0.5 mmol) following Method B and
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after column chromatography: H NMR (CDCl3, 400 MHz) δ 0.08
(6H, s), 0.95 (9H, s), 1.14 (3H, t, J = 6.4 Hz), 2.29 (6H, s), 3.33 (1H,
m), 3.56 (2H, br m), 3.65 (1H, m), 6.80 (1H, t, J = 7.3 Hz,), 6.98 (2H,
d, J = 7.0 Hz); 13C{1H} NMR (CDCl3, 101 MHz) δ −5.2, −5.1, 18.4,
18.7, 19.1, 26.2, 53.8, 66.7, 121.5, 129.0, 129.6, 145.4; MS (ESI) m/z
294 ([M + H]+). Anal. Calcd for C17H31NOSi: C, 69.56; H, 10.65; N,
4.77. Found: C, 69.41; H, 10.55; N, 4.90.
N-(Hexan-2-yl)-2,6-dimethylaniline5 (6k). This compound was
prepared from 2,6-dimethylaniline (0.133 g, 1.1 mmol) and 1-hexyne
(0.082 g, 1.0 mmol) following Method A and reduced using Method I.
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Isolated as a colorless oil (0.147 g, 72%): H NMR (CDCl3, 400
1
MHz) δ 0.99 (3H, t, J = 7.1 Hz), 1.13 (3H, d, J = 6.3 Hz), 1.13−1.47
(5H, m), 1.64 (1H, m), 2.34 (6H, s), 2.88 (1H, br s), 3.32−3.37 (1H,
m), 6.84−7.06 (3H, m).
reduced using Method III. Isolated as a yellow oil (0.081 g, 76%): H
NMR (CDCl3, 400 MHz) δ 0.93 (3H, d, J = 6.6 Hz), 0.96 (3H, d, J =
6.6 Hz), 1.15 (3H, d, J = 6.2 Hz), 1.44−1.54 (1H, m), 1.71−1.85 (1H,
m), 3.03 (1H, br s), 3.41−3.52 (1H, m), 3.76 (3H, s), 6.57 (2H, d, J =
9.0 Hz), 6.79 (2H, d, J = 12.8 Hz); 13C{1H} NMR (CDCl3, 101 MHz)
δ 21.2, 22.7, 23.2, 25.3, 47.1, 47.7, 56.0, 114.7, 115.1, 142.1, 155.2; MS
(EI) m/z 207 (M+). Anal. Calcd for C13H21NO: C, 75.32; H, 10.21; N,
6.76. Found: C, 75.38; H, 10.18; N, 6.51.
(1,2-Diphenyl-ethyl)-(4-methoxy-phenyl)-amine (7h). This com-
pound was prepared from pentafluoroaniline (0.110 g, 0.6 mmol) and
1-phenyl-1-propyne (0.058 g, 0.5 mmol) following Method B and
reduced using Method I. Isolated as a colorless oil (0.137 g, 91%): 1H
NMR (CDCl3, 400 MHz) δ 1.18 (3H, d, J = 6.7 Hz), 2.70 (1H, dd, J =
7.0, 13.4 Hz), 2.89 (1H, dd, J = 5.7, 13.7 Hz), 3.34−3.37 (1H, m),
3.95−4.03 (1H, m), 7.16−7.32 (5H, m); 13C{1H} NMR (CDCl3, 101
MHz) δ 21.2, 44.1, 52.3, 126.6, 128.4, 129 (13C NMR signals for the
fluorinated arene was not observed); 19F NMR (CFCl3, 282 MHz) δ
−171.9, −164.8, −159.1; MS (ESI) m/z 300 ([M − H]−); HRMS (ESI-
TOF) m/z Calcd for C15H11NF5 ([M − H]−), 300.0806, found 300.0812.
N-(1-Phenylpropan-2-yl)-aniline131 (7a). This compound was
prepared from aniline (0.058 g, 0.6 mmol) and 1-phenyl-1-propyne
(0.056 g, 0.5 mmol) following Method B and reduced using Method
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III. Isolated as a colorless oil (0.107g, >98%): H NMR (CDCl3, 400
MHz) δ 1.23 (3H, d, J = 6.4 Hz), 2.77 (1H, dd, J = 7.2, 13.2 Hz), 3.02
(1H, dd, J = 4.8, 13.2 Hz), 3.60 (1H, s), 3.83−3.88 (1H, m), 6.70−
6.80 (3H, m), 7.25−7.40 (7H, m).
N-(Hexan-3-yl)aniline (7b). This compound was prepared from
aniline (0.055 mL, 0.6 mmol) and 3-hexyne (0.057 mL, 0.5 mmol)
following Method C except at 110 °C in toluene-d8 and reduced using
Method II. Isolated as a colorless oil (0.086 g, >98%). An analytically
pure sample was obtained by a bulb-to-bulb distillation after column
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chromatography: H NMR (CDCl3, 400 MHz) δ 0.99 (6H, t, J = 7.5
Hz), 1.40−1.68 (6H, m), 3.36 (1H, quintet, J = 5.8 Hz), 3.45 (1H, br
s), 6.63 (2H, dd, J = 1.0, 8.5 Hz), 6.70 (1H, tt, J = 1.0, 7.2 Hz), 7.18−
7.18 (2H, m) ; 13C{1H} NMR (CDCl3, 101 MHz) δ 10.0, 14.2, 19.1,
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dx.doi.org/10.1021/jo402668q | J. Org. Chem. 2014, 79, 2015−2028