CID of protonated benzylamines
1197
reaction mixture was stirred for 1 h at 60 °C, diluted with
a white solid from the major band (R
D 0.85) (0.003 g, 25%).
f
1
water, and extracted with diethyl ether. The organic layer
was separated, concentrated and applied to a preparative
thin-layer chromatography plate. The plate was eluted with
hexanes–ethyl acetate (10 : 1). The product was isolated as a
H NMR: (400 MHz, CDCl
3
) υ 7.40 (6H, td, J D 8.4, 1.2 Hz),
7.31 (6H, tt, J D 7.6, 1.6 Hz), 7.22 (3H, tt, J D 7.2, 1.6 Hz);
1
3
C NMR: (400 MHz, CDCl
3
) υ 139.54, 128.76, 128.20, 126.84,
Cž
57.92; EI-MS: m/z (%), 293 (M , 20), 216 (25), 200 (20), 93
C
white solid from the major band (R
f
D 0.85) (0.003 g, 25%).
(100), 67 (10), 40 (5); Accurate mass ESI-MS [M C H] for
1
2
H NMR: (400 MHz, CDCl
3
) υ 7.41 (6H, d, J D 7.2 Hz), 7.31
C
21
H
16
H
6
N calc. 294.2129, found 294.2133.
(
6H, t, J D 7.6 Hz), 7.24 (3H, t, J D 6.8 Hz), 3.56 (6H, s);
1
3
2
C NMR: (400 MHz, CDCl
3
) υ 139.64, 128.73, 128.20, 126.83,
[2,3,4,5,6- H ]Benzyl alcohol
5
Cž
2
5
57.91; EI-MS: m/z (%), 287 (M , 20), 210 (20), 196 (20), 91
[2,3,4,5,6- H ]Benzoic acid (0.150 g, 1.18 mmol) in THF
C
(
C
100), 65 (20), 39 (10); Accurate mass ESI-MS [M C H] for
(0.5 ml) was reduced with LiAlD4 (0.072 g, 1.71 mmol) in
diethyl ether (0.5 ml) by a procedure similar to that described
for benzyl alcohol to give a colorless oil (0.097 g, 72%). H
21
H
22N calc. 288.1752, found 288.1757.
1
0
0 2
13
[
1 ,1 - H ]Benzyl alcohol
NMR: (300 MHz, CDCl
3
) υ 4.62 (2H, s), 1.92 (1H, s); C NMR:
2
Benzoic acid (0.150 g, 1.21 mmol) in THF (0.5 ml) was
reduced by LiAlD (0.072 g, 1.71 mmol) in diethyl ether
0.5 ml) by a procedure similar to that described for benzyl
(300 MHz, CDCl
MS: m/z (%), 113 (M , 100), 112 (40), 96 (20), 83 (90), 81 (40),
68 (10), 54 (40), 42 (15).
3
) υ 140.83, 128.41, 127.47, 126.86, 64.97; EI-
Cž
4
(
alcohol. The product was obtained as a colorless oil (0.097 g,
1
2
7
2%). H NMR: (300 MHz, CDCl
3
) υ 7.34 (5H, m), 1.93 (1H, s);
[2,3,4,5,6- H ]Benzyl bromide
5
1
3
2
5
C NMR: (300 MHz, CDCl
3
) υ 140.82, 128.39, 127.44, 126.85,
[2,3,4,5,6- H ]Benzyl alcohol (0.097 g, 0.86 mmol) in ace-
Cž
65.01; EI-MS: m/z (%), 110 (M , 80), 109 (60), 92 (20), 81 (80),
tonitrile (5 ml) was brominated with triphenylphosphine
(0.378 g, 1.45 mmol) and bromine (0.24 g 1.5 mmol) by a pro-
cedure similar to that described for benzyl bromide to give
the desired product (0.12 g, 80% yield). H NMR: (300 MHz,
) υ 4.49 (2H, s); C NMR: (300 MHz, CDCl
128.98, 128.78, 128.40, 46.45; EI-MS: m/z (%), 175/177 (M
7
9 (60), 67 (10), 52 (20), 40 (10).
0
0
0 2
2
1
[
[
(
1
1 ,1 - H ]Benzyl bromide
2
0
13
1 ,1 - H
5 ml) was brominated with triphenylphosphine (0.378 g,
.45 mmol) and bromine (0.24 g, 1.5 mmol) by a procedure
2
]Benzyl alcohol (0.097 g, 0.88 mmol) in acetonitrile
CDCl
3
3
) υ 144.01,
Cž
,
10/10), 96 (100), 69 (15), 42 (10).
0
0
similar to that described for benzyl bromide to give [1 ,1 -
H
CDCl
29.00, 128.77, 128.42, 46.44; EI-MS: m/z (%), 172/174 (M
0/10), 93 (100), 66 (15), 40 (10).
2
1
2
2
]benzyl bromide (0.12 g, 80% yield). H NMR: (300 MHz,
N,N-Bis[2,3,4,5,6- H ]benzylamine (3)
[2,3,4,5,6- H ]Benzyl bromide (0.010 g, 0.057 mmol) was
added to a stirred solution of acetonitrile (1 ml) and tetrahy-
drofuran (0.5 ml) and 30% aqueous ammonia (0.125 ml,
5
1
3
2
3
) υ 7.37 (5H, m); C NMR: (300 MHz, CDCl
3
) υ 144.09,
5
Cž
1
1
,
2
.20 mmol). The reaction mixture was stirred for 1 h at 60 °C,
diluted with water, extracted with diethyl ether, and the
product was isolated by preparative thin-layer chromatog-
0
0 2
N,N-Bis[1 ,1 - H ]benzylamine (2)
[
2
0
0
2
1 ,1 - H
to a stirred solution of acetonitrile (1 ml) and tetrahydrofuran
0.5 ml) and 30% aqueous ammonia (0.125 ml, 2.20 mmol).
2
]Benzyl bromide (0.010 g, 0.058 mmol) was added
raphy (hexanes-ethyl acetate, 4 : 1) as a colorless oil was from
1
(
the second major band at R
(400 MHz, CDCl
(400 MHz, CDCl
f
D 0.45 (0.003 g, 25%). H NMR:
1
3
The reaction mixture was stirred for 1 h at 60 °C, diluted with
3
) υ 3.82 (4H, s), 1.69 (1H, s); C NMR:
water and extracted with diethyl ether. The organic layer
was separated, concentrated and applied to a preparative
thin-layer chromatography plate. The plate was eluted with
hexanes–ethyl acetate (4 : 1). The product was isolated as a
3
) υ 140.29, 128.38, 128.15, 126.94, 53.14; EI-
MS: m/z (%), 207 (M , 10), 206 (15), 125 (10), 111 (50), 96
(100), 68 (15), 42 (5); Accurate mass ESI-MS [M C H] for
Cž
C
2
C
14
H
6
H10N calc. 208.1910, found 208.1914.
colorless oil from the second major band (R
f
D 0.45)(0.003 g,
1
2
2
5%). H NMR: (400 MHz, CDCl
3
) υ 7.34 (8H, m), 7.27 (2H,
N,N,N-Tris[2,3,4,5,6- H ]benzylamine (6)
5
1
3
2
5
m), 1.70 (1H, s); C NMR: (200 MHz, CDCl
1
3
) υ 140.28, 128.40,
); EI-MS: m/z
[2,3,4,5,6- H ]Benzyl bromide (0.010 g, 0.057 mmol) was
1
28.18, 126.98, 53.14; H NMR: (400 MHz, CDCl
3
added to a stirred solution of acetonitrile (1 ml) and tetrahy-
drofuran (0.5 ml) and 30% aqueous ammonia (0.025 ml,
0.44 mmol). By a procedure similar to that used for N,N,N-
Cž
(
4
%), 201 (M , 10), 200 (5), 124 (10), 108 (40), 93 (100), 67 (10),
0 (10); Accurate mass ESI-MS [M C H]C for C14
H
12
2
H
4
N
0
0
2
calc. 202.1534, found 202.1534.
tris[1 ,1 - H ]benzylamine (5), a white solid was obtained
2
1
from the major TLC band (R
NMR: (400 MHz, CDCl
f
D 0.85) (0.003 g, 25%).
H
0
0 2
13
N,N,N-Tris[1 ,1 - H ]benzylamine (5)
3
) υ 3.58 (6H, s); C NMR: (400 MHz,
2
0
0
2
[
1 ,1 - H
to a stirred solution of acetonitrile (1 ml) and tetrahydrofuran
0.5 ml) and 30% aqueous ammonia (0.025 ml, 0.44 mmol).
2
]Benzyl bromide (0.010 g, 0.058 mmol) was added
CDCl
3
) υ 139.66, 128.74, 128.20, 126.84, 57.90; EI-MS: m/z (%),
302 (M , 20), 220 (20), 107 (10), 96 (100), 68 (15), 42 (5); Accu-
rate mass ESI-MS [M C H] for C21
Cž
C
2
(
7
H H15N calc. 303.2694,
The reaction mixture was stirred for 1 h at 60 °C, diluted with
found 303.2700.
water and extracted with diethyl ether. The organic layer
was separated, concentrated and applied to a preparative
thin-layer chromatography plate. The plate was eluted with
hexanes–ethyl acetate (10 : 1). The product was obtained as
2
[2,6- H ]Toluene
2
2,6-Dibromotoluene (0.040 g, 0.16 mmol) and LiAlD
(0.030 g) were mixed with diethyl ether (0.30 ml) and heated
4
Copyright 2006 John Wiley & Sons, Ltd.
J. Mass Spectrom. 2006; 41: 1195–1204
DOI: 10.1002/jms