Stefan Michlik et al.
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KO-t-Bu (248 mg, 2.2 mmol), 48 h at 1108C. Purification by
column chromatography (pentane:EtOAc=2:3). Yield:
112 mg (0.82 mmol, 82%). 1H NMR (300 MHz, C6D6): d=
6.96 (dd, J=5.7, 3.4 Hz, 2H), 6.60 (dd, J=5.6, 3.5 Hz, 2H),
2.76 (s br, 2H), 2.42 (s, 6H); 13C NMR (75 MHz, C6D6): d=
139.1, 119.8, 111.1, 31.2; MS (70 eV, EI): m/z (%)=136
(100, M+), 121 (48), 94 (100).
6.73 (d, J=8.4 Hz, 1H), 6.48 (s br, 4H), 4.13 (s br, 4H), 4.09
(s br, 2H), 3.66 (s, 3H); 13C NMR (75 MHz, CDCl3): d=
159.4, 141.4, 141.2, 140.9, 132.8, 129.3, 129.0, 128.1, 127.5,
115.1, 114.4, 49.8, 49.2; MS (70 eV, EI): m/z (%)=318 (10,
M+), 314 (64), 225 (52), 207 (100), 120 (26), 91 (33), 77 (47);
elemental analysis calcd. (%) for C21H22N2O: C 79.21, H
6.96, N 8.80; found: C 79.12, H 6.87, N 8.93.
N,N’-Bis(furan-2-ylmethyl)-benzene-1,3-diamine
(2p):
N-Benzyl-N’-(4-methoxybenzyl)-benzene-1,3-diamine
(3e): From B (6.0 mg, 0.01 mmol), N-benzylbenzene-1,3-di-
AHCTUNGTREGaNNNU mine 3b (198 mg, 1.0 mmol), (4-methoxyphenyl)-methanol
From B (24.0 mg, 0.04 mmol), benzene-1,3-diamine (108 mg,
1.0 mmol), furan-2-ylmethanol (190 mL, 4.4 mmol), 400 mL
diglyme, KO-t-Bu (248 mg, 2.2 mmol), 48 h at 708C. Purifi-
cation by column chromatography (pentane:Et2O 4:1).
Yield: 193 mg (0.72 mmol, 72%). 1H NMR (300 MHz,
CD2Cl2): d=7.38 (dd, J=1.8, 0.8 Hz, 2H), 6.96 (t, J=
7.9 Hz, 1H), 6.34 (dd, J=3.2, 1.8 Hz, 2H), 6.23 (dd, J=3.2,
0.8 Hz, 2H), 6.07 (dd, J=8.0, 2.2 Hz, 2H), 5.98 (t, J=
2.2 Hz, 1H), 4.27 (s, 4H), 4.01 (s br, 2H); 13C NMR
(75 MHz, CD2Cl2): d=153.8, 149.4, 142.4, 130.4, 110.8,
107.3, 104.0, 98.2, 41.8; MS (70 eV, EI): m/z (%)=268 (69,
M+), 239 (4), 225 (6), 187 (10), 159 86), 81 (100); elemental
analysis calcd. (%) for C16H16N2O2: C 71.62, H 6.01, N
10.44.80; found: C 71.28 , H 6.18 , N 10.57.
(137 mL, 1.1 mmol), 400 mL diglyme, KO-t-Bu (124 mg,
1.1 mmol), 24 h at 708C. Purification by column chromatog-
raphy (pentane:EtOAc=4:1). Yield: 312 mg (0.98 mmol,
1
98%). H NMR (400 MHz, CDCl3): d=7.39–7.31 (m, 5H),
7.26 (d, J=8.1 Hz, 4H), 7.00 (t, J=8.1 Hz, 1H), 6.88 (d, J=
8.4 Hz, 2H), 6.10 (dd, J=8.01, 1.5 Hz, 2H), 5.97 (s, 1H),
4.30 (s, 2H), 4.22 (s, 2H), 3.81 (s, 3H); 13C NMR (100 MHz,
CDCl3): d=158.8, 131.2, 130.0, 128.9, 128.6, 127.6, 127.1,
113.9, 103.5, 97.7, 95.2, 94.7, 55.3, 48.4, 48.1; MS (70 eV, EI):
m/z (%)=318 (18, M+), 121 (100), 91 (34), 77 (10); elemen-
tal analysis calcd. (%) for C21H22N2O: C 79.21, H 6.96, N
8.80; found: C 79.56, H 6.96, N 8.93.
N-Benzylbenzene-1,4-diamine (3a): From
B
(71.0 mg,
N-Benzyl-N’-(4-methoxybenzyl)-benzene-1,2-diamine
(3f): From B (12.0 mg, 0.02 mmol), N-benzylbenzene-1,2-di-
amine 3c (198 mg, 1.0 mmol), (4-methoxyphenyl)-methanol
(137 mL, 1.1 mmol), 400 mL diglyme, KO-t-Bu (124 mg,
1.1 mmol), 24 h at 1108C. Purification by column chroma-
tography (pentane:Et2O=8:1). Yield: 239 mg (0.75 mmol,
0.12 mmol), benzene-1,4-diamine (6.48 g, 60.0 mmol), benzyl
alcohol (3.12 mL, 30 mmol), 12 mL diglyme, KO-t-Bu
(3.73 g, 33.0 mmol), 24 h at 708C. Purification by column
chromatography (pure Et2O). Yield: 4.5 g (22.8 mmol,
1
76%). H NMR (400 MHz, CD2Cl2): d=7.40–7.30 (m, 4H),
1
7.29–7.23 (m, 1H), 6.63–6.45 (m, 4H), 4.26 (s, 2H), 3.39 (s
br, 3H); 13C NMR (100 MHz, CD2Cl2): d=141.7, 140.8,
138.8, 129.0, 128.0, 127.5, 116.9, 114.9, 49.7; MS (70 eV, EI):
m/z (%)=198 (39, M+), 119 (3), 107 (100), 91 (15), 80 (13),
65 (10).
75%). H NMR (300 MHz, CD2Cl2): d=7.47–7.25 (m, 7H),
6.89 (d, J=8.8 Hz, 2H), 6.80–6.65 (m, 4H), 4.33 (s, 2H),
4.26 (s, 2H), 3.79 (s, 3H), 3.73 (s br, 1H), 3.67 (s br, 1H);
13C NMR (75 MHz, CD2Cl2): d=159.5, 140.3, 137.8, 132.2,
129.5, 129.1, 128.3, 127.7, 119.7, 114.4, 112.4, 55.8, 49.2, 48.7;
MS (70 eV, EI); m/z (%)=318 (10, M+), 227 (14), 197 (65),
180 (5), 121 (100), 91 (79); elemental analysis calcd. (%) for
C21H22N2O: C 79.21, H 6.96, N 8.80; found: C 79.16, H 7.12,
N 8.71.
N-Benzylbenzene-1,3-diamine (3b): From
B (35.0 mg,
0.06 mmol), benzene-1,3-diamine (6.48 g, 60.0 mmol), benzyl
alcohol (3.12 mL, 30 mmol), 10 mL diglyme, KO-t-Bu
(3.73 g, 33.0 mmol), 24 h at 708C. Purification by column
chromatography
(pentane:Et2O=1:1).
Yield:
4.85 g
N-Benzyl-N’-pentylbenzene-1,4-diamine (3g): From B
(24.5 mmol, 82%). 1H NMR (400 MHz, CD2Cl2): d=7.45–
7.36 (m, 4H), 7.33–7.30 (m, 1H), 6.96 (t, J=7.92, Hz, 1H),
6.08 (dt, J=7.0, 1.1 Hz, 2H), 5.96 (s, 1H), 4.32 (s, 2H), 4.11
(s br, 1H), 3.62 (s br, 2H); 13C NMR (100 MHz, CD2Cl2):
d=150.0, 148.4, 140.5, 130.4, 129.0, 127.9, 127.5, 105.2, 104,1.
99.7, 48.5; MS (70 eV, EI): m/z (%)=198 (78, M+), 195 (5),
180 (5), 121 (20), 91 (100), 80 (10), 65 (28).
(320 mL, 0.004 mmol, 0.125M in diglyme), N-benzylbenzene-
1,4-diamine 3a (198 mg, 1.0 mmol), 1-pentanol (120 mL,
1.1 mmol), 200 mL diglyme, KO-t-Bu (124 mg, 1.1 mmol),
24 h at 708C. Purification by column chromatography (pen-
1
tane:Et2O=4:1). Yield: 188 mg (0.70 mmol, 70%). H NMR
(400 MHz, CD2Cl2): d=7.40–7.29 (m, 4H), 7.25 (m, 1H),
6.52 (d, J=5.1 Hz, 4H), 4.25 (s, 2H), 3.59 (s br, 2H), 3.01 (t,
J=7.3 Hz, 2H), 1.59–1.54 (m, 2H), 1.38–1.34 (m, 4H), 0.91
(t, J=7.0, Hz, 3H); 13C NMR (100 MHz, CD2Cl2): d=140.7,
128.5, 127.6, 127.0, 114.9, 114.7, 49.6, 49.5, 45.5, 45.4, 29.4,
22.5, 14.0; MS (70 eV, EI): m/z (%)=268 (92, M+), 211 (24),
177 (100), 119 (11), 107 (30), 91 (42), 65 (8); elemental anal-
ysis calcd. (%) for C18H24N2: C 80.55, H 9.01, N 10.44;
found: C 80.50, H 9.34, N 10.49.
N-Benzylbenzene-1,2-diamine (3c): From
B (480 mL,
0.006 mmol, 0.125M in diglyme), benzene-1,2-diamine
(432 mg, 4.0 mmol), benzyl alcohol (108 mL, 1.0 mmol),
400 mL diglyme, KO-t-Bu (124 mg, 1.1 mmol), 24 h at 708C.
Purification by column chromatography (pure Et2O). Yield:
1
180 mg (0.91 mmol, 91%). H NMR (300 MHz, CD2Cl2): d=
7.46–7.24 (m, 4H), 7.32–7.25 (m, 1H), 6.79–6.70 (m, 2H),
6.69–6.60 (m, 2H), 4.33 (s, 2H), 3.77 (s br, 1H), 3.39 (s br,
2H); 13C NMR (75 MHz, CD2Cl2): d=140.3, 138.2, 135.0,
129.1, 128.2, 127.7, 120.9, 119.2, 116.8, 112.4, 49.0.
N-Benzyl-N’-(4-methoxybenzyl)-benzene-1,4-diamine
(3d): From B (6.0 mg, 0.01 mmol), N-benzylbenzene-1,4-di-
N-Benzyl-N’-pentylbenzene-1,3-diamine (3h): From
B
(6.0 mg, 0.01 mmol), N-benzylbenzene-1,3-diamine 3b
(198 mg, 1.0 mmol), 1-pentanol (120 mL, 1.1 mmol), 400 mL
diglyme, KO-t-Bu (124 mg, 1.1 mmol), 24 h at 708C. Purifi-
cation by column chromatography (pentane:Et2O=10:1).
Yield: 255 mg (0.95 mmol, 95%). 1H NMR (400 MHz,
CDCl3): d=7.43–7.33 (m, 4H), 7.30–7.27 (m, 1H), 7.01 (td,
J=8.1, 1.5 Hz, 1H), 7.05–6.98 (m, 2H), 5.99 (d, J=1.5 Hz,
1H), 4.20 (s br, 2H), 3.08 (td, J=7.1, 1.5 Hz, 2H), 1.67–1.57
(m, 2H), 1.42–1.31 (m, 4H), 0.93 (m, 3H); 13C NMR
ACHTUNGTRENNUNGamine 3a (198 mg, 1.0 mmol), (4-methoxyphenyl)-methanol
(137 mL, 1.1 mmol), 400 mL diglyme, KO-t-Bu (124 mg,
1.1 mmol), 24 h at 708C. Purification by column chromatog-
raphy (pentane:EtOAc=10:1). Yield: 317 mg (0.85 mmol,
1
85%). H NMR (300 MHz, CDCl3): d=7.30–7.11 (m, 8H),
858
ꢃ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2012, 354, 847 – 862