Benoꢀt Blank et al.
FULL PAPERS
added. Last, NaO-t-Bu (2.2 mmol, 1.1 equiv.) was dissolved
in the reaction mixture, the reaction vessel tightly closed
and stirred at 1108C for 24 h. The reaction mixture was
cooled to room temperature and quenched with water
(2 mL) and CH2Cl2 (7–8 mL). Then, 15 mL brine were
added and the aqueous layer was extracted with CH2Cl2 (6ꢅ
15 mL). The combined organic layers were dried over
Na2SO4, filtered and the solvent removed under vacuum. Fi-
nally, the residue was purified by column chromatography
(first: diethyl ether/methanol, 1:1, then: diethyl ether/metha-
nol/triethyl amine, 5:5:1) and dried under vacuum.
2H), 0.91–0.85 (m, 6H); 13C NMR (100 MHz, CDCl3): d=
159.0, 148.0, 137.2, 112.7, 107.2, 48.7, 48.7, 45.3, 24.7, 23.3,
22.1; MS (70 eV, EI): m/z (%)=193 (1, M+), 136 (2), 108
(100), 80 (24), 44 (8); elemental analysis (%) calcd. for
C10H16N3: C 68.35, H 9.91, N 21.74; found: C 68.38, H 10.34,
N 21.39.
1-Phenyl-N2-pyridin-2-yl-ethane-1,2-diamine (2f): Yield:
93%; 1H NMR (400 MHz, CDCl3): d=8.07 (dd, J=4.9,
0.9 Hz, 1H), 7.40–7.32 (m, 5H), 7.27 (dt, J=5.3, 2.4 Hz,
1H), 6.55 (dd, J=6.8, 5.3 Hz, 1H), 6.39 (d, J=8.4 Hz, 1H),
4.82 (s br, 1H), 4.19 (dd, J=7.9, 5.3 Hz, 1H) 3.57–3.51 (m,
1H) 3.45–3.38 (m, 1H), 1.64 (s br, 2H); 13C NMR
(100 MHz, CDCl3): d=158.7, 148.1, 143.9, 137.3, 128.6,
127.4, 126.4, 113.0, 107.2, 55.2, 49.8; MS (70 eV, EI): m/z
(%)=213 (3, M+), 106 (100), 79 (45), 51 (9), 28 (12); ele-
mental analysis (%) calcd. for C13H15N3: C 73.21, H 7.09, N
19.70; found: C 72.71, H 7.147, N 19.63.
N1-Pyridin-2-yl-propane-1,2-diamine (2a): Yield: 81%; bp
978C at 1.3ꢅ10À1 mbar. 1H NMR (400 MHz, CDCl3): d=
8.04 (ddd, J=5.1, 1.8, 0.7 Hz, 1H), 7.35 (ddd, J=8.6, 7.0,
2.0 Hz, 1H), 6.51 (ddd, J=7.1, 5.0, 0.7 Hz, 1H), 6.37 (d, J=
8.4 Hz, 1H), 4.83 (s br, 1H), 3.29 (ddd, J=12.6, 6.0, 4.4 Hz,
1H), 3.16–3.07 (m, 1H), 3.06–2.95 (m, 1H), 1.24 (s br, 2H),
1.11 (d, J=6.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): d=
158.9, 148.1, 137.3, 112.7, 107.1, 50.1, 46.4, 22.0; MS (70 eV,
EI): m/z (%)=151 (2, M+), 119 (2), 108 (100), 95 (18), 79
(38), 51 (6), 44 (4). elemental analysis (%) calcd. for
C8H13N3: C 63.54, H 8.67, N 27.79; found: C 63.29, H 8.770,
N 27.75.
3-Phenyl-N1-pyridin-2-yl-propane-1,2-diamine (2g): Yield:
1
77%; H NMR (400 MHz, CDCl3): d=8.05 (ddd, J=5.1, 1.8,
0.7 Hz, 1H), 7.36 (ddd, J=8.5, 7.1, 2.0 Hz, 1H), 7.31–7.25
(m, 2H), 7.22–7.16 (m, 3H), 6.53 (ddd, J=7.1, 5.1, 0.9 Hz,
1H), 6.36 (d, J=8.4 Hz, 1H), 4.89 (s br,1H), 3.45–3.40 (m,
1H) 3.28–3.20 (m, 1H) 3.16–3.09 (m, 1H), 2.87 (dd, J=13.2,
4.8 Hz, 1H), 2.53 (dd, J=13.4, 8.6 Hz, 1H), 1.22 (s br, 2H);
13C NMR (100 MHz, CDCl3): d=158.9, 148.1, 138.8, 137.3,
129.2, 128.6, 126.4, 112.8, 107.2, 52.4, 48.1, 42.6; MS (70 eV,
EI): m/z (%)=227 (0.5M+), 136 (16), 120 (35), 108 (100), 91
(10), 80 (20); elemental analysis (%) calcd. for C11H19N3: C
73.98, H 7.54, N 18.49; found: C 74.14, H 7.506, N 18.20.
N1-Pyridin-2-yl-propane-1,3-diamine (3a): Yield: 91%; bp
2-Methyl-N1-pyridin-2-yl-propane-1,2-diamine (2b): Yield:
84%; bp 858C at 1.0ꢅ10À1 mbar; 1H NMR (400 MHz,
CDCl3): d=8.03 (ddd, J=5.1, 1.8, 0.7 Hz, 1H), 7.34 (ddd,
J=8.6, 7.0, 2.0 Hz, 1H), 6.50 (ddd, J=7.1, 5.0, 0.7 Hz, 1H),
6.39 (d, J=8.4 Hz, 1H), 4.84 (s, 1H), 3.17 (d, J=6.2 Hz,
2H), 1.14 (s br, 8H); 13C NMR (100 MHz, CDCl3): d=
159.3, 148.0 137.2, 112.6, 107.3, 53.4, 50.2, 28.9; MS (70 eV,
EI): m/z (%)=165 (4, M+), 133 (4), 108 (56), 79 (20), 58
(100), 42 (6). elemental analysis (%) calcd. for C9H15N3: C
65.42, H 9.15, N 25.43; found: C 65.81, H 9.561, N 25.61.
N1-Pyridin-2-yl-butane-1,2-diamine (2c): Yield: 70%; bp
838C at 7.2ꢅ10À2 mbar; 1H NMR (400 MHz, CDCl3): d=
8.04 (ddd, J=5.1, 1.8, 0.7 Hz, 1H), 7.35 (ddd, J=8.8, 7.0,
1.8 Hz, 1H), 6.51 (ddd, J=7.1, 5.0 1.1 Hz, 1H), 6.37 (d, J=
8.4 Hz, 1H), 4.87 (s br 1H), 3.41–3.30 (m, 1H), 3.03–2.95
1
1038C at 1.3ꢅ10À1 mbar; H NMR (400 MHz, CDCl3): d=
8.04 (dd, J=5.1, 0.7 Hz, 1H), 7.39–7.32 (m, 1H), 6.53–6.50
(m, 1H), 6.34 (d, J=8.4 Hz, 1H), 4.80 (s br, 1H), 3.36–3.30
(m, 2H), 2.81 (t, J=6.6 Hz, 2H), 1.79–1.69 (m, 2H), 1.27
(s br, 2H); 13C NMR (100 MHz, CDCl3): d=158.9, 148.2,
137.3, 112.6, 106.7, 40.2, 40.1, 33.0; MS (70 eV, EI): m/z
(%)=151 (38, M+), 121 (100), 108 (98), 94 (26), 78 (68), 67
(16), 30 (22); elemental analysis (%) calcd. for C8H13N3: C
63.54, H 8.67, N 27.79; found: C 63.55, H 9.166, N 27.45.
(m, 1H), 2.89–2.80 (m, 1H) 1.58–1.47ACTHNUTRGNEUNG(m, 1H), 1.37–1.15 (m,
3H), 0.94 (t, J=7.3 Hz, 3H); 13C NMR (100 MHz, CDCl3):
d=159.0, 148.1, 137.2, 112.7, 107.2, 52.4, 48.1, 29.0, 10.5; MS
(70 eV, EI): m/z (%)=165 (2, M+), 108 (100), 95 (15), 80
(30), 58 (32); elemental analysis (%) calcd. for C9H15N3: C
65.42, H 9.15, N 25.43; found: C 65.42, H 9.508, N 24.87.
3-Methyl-N1-pyridin-2-yl-butane-1,2-diamine (2d): Yield:
93%; bp 848C at 1.1ꢅ10À1 mbar; 1H NMR (400 MHz,
CDCl3): d=8.04 (ddd, J=5.1, 2.0, 0.9 Hz, 1H), 7.35 (ddd,
J=8.6, 7.0, 2.0 Hz, 1H), 6.50 (ddd, J=7.1, 5.0, 1.1 Hz, 1H),
6.37 (dt, J=8.4, 0.9 Hz, 1H), 4.94 (s br, 1H), 3.44–3.35 (m,
1H), 3.04–2.94 (m, 1H), 2.72–2.67 (m, 1H), 1.69–1.61 (m,
1H), 1.34 (s br, 2H), 0.94–0.90 (m, 6H); 13C NMR
(100 MHz, CDCl3): d=159.0, 148.1, 137.2, 112.6, 107.3, 56.3,
46.1, 32.4, 19.4, 17.7; MS (70 eV, EI): m/z (%)=179 (1, M+),
136 (5), 119 (8), 108 (100), 95 (11), 80 (25), 72 (29), 55 (14);
elemental analysis (%) calcd. for C10H17N3: C 67.00, H 9.56,
N 23.44; found: C 66.57, H 9.841, N 23.37.
N1-Pyridin-3-yl-propane-1,3-diamine (3b): [IrCl
(320 mL, 0.02 mmol, 0.0625M in THF), Py2NPACHTUNGTRENNUNG
ACHTUNGTRENNUNG
(320 mL, 0.04 mmol, 0.125M in THF); yield: 75%; bp 1358C
1
at 7.4ꢅ10À2 mbar; H NMR (400 MHz, CDCl3): d=7.98 (dd,
J=2.9, 0.7 Hz, 1H), 7.90 (dd, J=4.6, 1.3 Hz, 1H), 7.03 (ddd,
J=8.4, 4.8, 0.7 Hz, 1H), 6.82 (ddd, J=8.1, 2.9, 1.5 Hz, 1H),
4.23 (s br, 1H), 3.18 (t, J=6.6 Hz, 2H), 2.84 (t, J=6.6 Hz,
2H) 1.79–1.69 (m, 2H), 1.26 (s br, 2H); 13C NMR
(100 MHz, CDCl3): d=144.4, 138.5, 136.0, 123.6, 118.2, 42.0,
40.3, 32.4; MS (70 eV, EI): m/z (%)=151 (48, M+), 133 (72),
119 (15), 107 (100), 95 (42), 78 (31), 56 (17), 30 (21); ele-
mental analysis (%) calcd. for C8H13N3: C 63.54, H 8.67, N
27.79; found: C 63.91, H 8.931, N 27.40.
N1-Pyridin-4-yl-propane-1,3-diamine (3c): [IrCl
(27 mg, 0.04 mmol), Py2NP(i-Pr)2 (23 mg, 0.08 mmol). Purifi-
ACHTUNGTRENNUNG(cod)]2
AHCTUNGTRENNUNG
cation by column chromatography (first: diethyl ether/meth-
anol, 1:5, then: diethyl ether/methanol/triethyl amine,
4-Methyl-N1-pyridin-2-yl-pentane-1,2-diamine (2e): Yield:
89%; bp 1028C at 8.7ꢅ10À2 mbar; 1H NMR (400 MHz,
CDCl3): d=8.02 (ddd, J=5.1, 1.8, 0.7 Hz, 1H), 7.34 (ddd,
J=8.8, 7.0, 1.8 Hz, 1H), 6.50 (ddd, J=7.1, 5.1, 0.9 Hz, 1H),
6.37 (dt, J=8.4, 0.9 Hz, 1H), 4.97 (s br, 1H), 3.39–3.31 (m,
1H), 3.04–2.94 (m, 2H), 1.75–1.66 (m, 3H) 1.31–1.18 (m,
2:10:1); yield: 68%; bp 1108C at 2.4ꢅ10À2 mbar; H NMR
1
(400 MHz, CDCl3): d=8.14 (d, J=5.5 Hz, 2H), 6.38 (d, J=
6.2 Hz, 2H), 4.90 (s br, 1H), 3.24–3.17 (m, 2H), 2.84 (t, J=
6.4 Hz, 2H), 1.76–1.69 (m, 2H), 1.18 (s br, 2H); 13C NMR
(100 MHz, CDCl3): d=153.4, 150.0, 107.4, 41.3, 40.4, 31.9;
MS (70 eV, EI): m/z=(%): 151 (30, M+), 133 (100), 107
2908
ꢃ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2009, 351, 2903 – 2911