5854
K. Kondo et al. / Tetrahedron 56 (2000) 5843±5856
(nujol): n3258, 1635 cm21. 1H NMR (CDCl3): d1.83 (s,
3H£2), 6.39 (br s, 1H), 7.22±7.51 (m, 8H), 7.73±7.78 (m,
2H). 13C NMR (CDCl3): d29.26, 56.35, 124.59, 126.64,
126.67, 128.36, 128.39, 131.15, 135.29, 146.62, 166.16.
FAB-MS: m/z240 (MH1).
N-Allyloxycarbonyl-N0-benzylethylenediamine. A pale
.
yellow oil. IR (neat): n3331, 1714 cm21 1H NMR
(CDCl3): d1.51 (s, 1H), 2.77 (t, J5.9 Hz, 2H), 3.29 (dt,
J5.9, 5.9 Hz, 2H), 3.78 (s, 2H), 4.56 (br d, J5.4 Hz, 2H),
5.16±5.27 (br, 1H), 5.20 (ddt, J10.5, 1.2, 1.2 Hz, 1H), 5.92
(ddt, J17.3, 1.2, 1.2 Hz, 1H), 5.92 (ddt, J17.3, 10.5,
5.4 Hz, 1H), 7.22±7.36 (m, 5H). 13C NMR (CDCl3):
d40.78, 48.42, 53.58, 65.50, 117.44, 126.90, 127.90,
128.29, 132.81, 139.90, 156.17. EI-MS: m/z235 (MH1),
234 (M1), 204, 164, 143, 120, 106, 91 (bp), 65. Anal. Calcd
for C13H18N2O2: C, 66.64; H, 7.74; N, 11.96. Found: C,
66.51; H, 7.81; N, 11.72.
Typical procedure for chemoselective acylation of
diamine with the N-Z-sulfonamide 4a corresponding to
entry 1 in Table 10
To a stirred solution of N-benzylethylenediamine (68 mL,
0.450 mmol) in THF (1.5 mL) was added the N-Z-sulfon-
amide 4a (178 mg, 0.450 mmol) at 08C. The reaction mixture
was stirred for 24 h at the same temperature, quenched by
the addition of piperidine (0.05 mL) and directly concen-
trated using a rotary evaporator. The residue was puri®ed by
silica gel column (EtOAc) to give N-benzyl-N0-benzyloxy-
carbonylethylenediamine (102 mg, 80%) as a colorless oil
together with the sulfonamide 3 (108 mg, 92%).
N-Acetyl-N0-benzylethylenediamine. A colorless solid of
1
mp 55±578C. IR (nujol): n3301, 3281, 1633 cm21. H
NMR (CDCl3): d1.59 (br s, 1H), 1.97 (s, 3H), 2.77 (t,
J5.9 Hz, 2H), 3.33 (dt, J11.5, 5.9 Hz, 2H), 3.78 (s,
2H), 6.10 (br s, 1H), 7.23±7.37 (m, 5H). 13C NMR
(CDCl3): d23.37, 39.23, 48.03, 53.54, 126.94, 127.89,
128.30, 139.85, 169.93. EI-MS: m/z193 (MH1), 192
(M1), 133, 132, 120, 91 (bp). Anal. Calcd for C11H16N2O:
C, 68.72; H, 8.39; N, 14.57. Found: C, 68.43; H, 8.55; N,
14.43.
N-Benzyl-N0-benzyloxycarbonylethylenediamine. The
physical data shown below were comparable to those repor-
1
ted.2w A colorless oil. IR (neat): n3332, 1714 cm21. H
NMR (CDCl3): d1.76 (br s, 1H), 2.76 (t, J5.9 Hz, 2H),
3.30 (dt, J5.9, 5.9 Hz, 2H), 3.77 (s, 2H), 5.10 (s, 2H), 5.26
(br s, 1H), 7.21±7.39 (m, 10H). 13C NMR (CDCl3):
d40.82, 48.40, 53.57, 66.64, 126.88, 127.89, 127.93,
128.28, 128.33, 136.46, 139.91, 156.29. EI-MS: m/z285
(MH1), 284 (M1), 194, 149, 133, 132, 118 (bp), 107, 105,
91, 89.
N-Benzyl-N0-benzoylethylenediamine. Colorless plates
(benzene±hexane) of mp 60±618C. IR (nujol): n3352,
1
3309, 1631 cm21. H NMR (CDCl3): d1.97 (s, 1H), 2.81
(dd, J5.9, 5.9 Hz, 2H), 3.47 (dd, J5.9, 5.9 Hz, 2H), 3.74
(s, 2H), 6.80 (br s, 1H), 7.15±7.45 (m, 8H), 7.65±7.74 (m,
2H). 13C NMR (CDCl3): d39.56, 47.88, 53.52, 126.77,
126.98, 127.95, 128.34, 131.16, 134.49, 139.93, 167.25.
EI-MS: m/z255 (MH1), 254 (M1), 132 (bp), 106, 77.
Anal. Calcd for C16H18N2O: C, 75.56; H, 7.13; N, 11.01.
Found: C, 75.78; H, 7.25; N, 10.99.
The physical data of the other acylated diamines are shown
below.
N-Benzyloxycarbonyl-N0-propylethylenediamine. A pale
yellow oil. IR (neat): n3325, 1714 cm21
.
1H NMR
N-Benzoyl-N0-propylethylenediamine. The physical data
shown below were identical with those reported.3b A pale
(CDCl3): d0.90 (t, J7.3 Hz, 3H), 1.47 (tq, J7.3,
7.3 Hz, 2H), 1.56 (br s, 1H), 2.55 (t, J7.3 Hz, 2H), 2.74
(t, J5.6 Hz, 2H), 3.29 (dt, J5.6, 5.6 Hz, 2H), 5.10 (s, 2H),
5.31 (br s, 1H), 7.28±7.39 (m, 5H). 13C NMR (CDCl3):
d11.80, 23.21, 40.79, 48.83, 51.37, 66.54, 127.83,
127.87, 128.10, 128.27, 136.44, 156.29. EI-MS: m/z237
(MH1), 236 (M1), 207, 149, 91, 72 (bp). Anal. Calcd for
C13H20N2O2: C, 66.07; H, 8.53; N, 11.85. Found: C, 66.35;
H, 8.76; N, 11.60.
yellow oil. IR (neat): n3300, 1644 cm21
.
1H NMR
(CDCl3) d0.90 (t, J7.3 Hz, 3H), 1.48 (tq, J7.3,
7.3 Hz, 2H), 1.57 (br s, 1H), 2.58 (t, J7.3 Hz, 2H), 2.83
(t, J5.9 Hz, 2H), 3.49 (d, J5.9 Hz, 1H), 3.52 (d,
J5.9 Hz, 1H), 6.98 (br s, 1H), 7.36±7.49 (m, 3H), 7.76±
7.80 (m, 2H). FAB-MS: m/z207 (MH1).
N-Benzoyl-N0-propyl-1,3-propanediamine. The physical
data shown below were identical with those reported.3b
A
pale yellow oil. IR (nujol): n3457, 3291, 1644 cm21. H
NMR (CDCl3): d0.93 (t, J7.3 Hz, 3H), 1.55 (tq, J7.3,
7.3 Hz, 2H), 1.57 (br s, 1H), 1.77 (tt, J5.9, 5.9 Hz, 2H),
2.60 (t, J7.3 Hz, 2H), 2.83 (t, J5.9 Hz, 2H), 3.57 (br d,
J5.9 Hz, 1H), 3.59 (br d, J5.9 Hz, 1H), 7.38±7.50 (m,
3H), 7.78±7.83 (m, 2H), 8.31 (br s, 1H). FAB-MS: m/z221
(MH1).
1
N-Benzyloxycarbonyl-N0-propyl-1,3-propanediamine. A
1
pale yellow oil. IR (neat): n3334, 1713, 1701 cm21. H
NMR (CDCl3, 508C): d0.91 (t, J7.1 Hz, 3H), 1.31 (br s,
1H), 1.48 (tq, J7.1, 7.1 Hz, 2H), 1.66 (tt, J6.6, 6.6 Hz,
2H), 2.54 (t, J7.1 Hz, 2H), 2.68 (t, J6.6 Hz, 2H), 3.25±
3.32 (br, 2H), 5.09 (s, 2H), 5.70 (br s, 1H), 7.26±7.40 (m,
5H). EI-MS: m/z250 (M1), 222, 149 (bp), 134, 120, 91.
Anal. Calcd for C14H22N2O2: C, 67.16; H, 8.85; N, 11.19.
Found: C, 67.34; H, 8.91; N, 10.79.
1-Benzoyl-3-methylpiperazine. The physical data shown
below were identical with those reported.3b A pale yellow
1
oil. IR (nujol): n3308, 1623 cm21. H NMR (DMSO-d6,
1-Benzyloxycarbonyl-3-methylpiperazine.
A colorless
oil. IR (neat): n3322, 1697 cm21. H NMR (DMSO-d6,
908C): d0.95 (d, J6.2 Hz, 3H), 2.39±2.63 (m, 4H),
2.75±2.83 (m, 2H), 3.77±3.83 (m, 2H), 5.08 (s, 2H),
7.28±7.38 (m, 5H). EI-MS: m/z234 (M1), 233, 134, 91
(bp), 78. Anal. Calcd for C13H17N2O2: C, 66.93; H, 7.34; N,
12.01. Found: C, 67.11; H, 7.76; N, 11.97.
1
1008C):d0.93 (d, J6.2 Hz, 3H), 2.09 (br s, 1H), 2.49±
2.70 (m, 4H), 2.80±3.00 (m, 3H), 7.29±7.43 (m, 5H). FAB-
MS: m/z205 (MH1).
N-Benzyl-N0-pivaloylethylenediamine. A pale yellow oil.
IR (neat): n3342, 1643 cm21. 1H NMR (CDCl3): d1.19