Helvetica Chimica Acta ± Vol. 83 .2000)
3031
{[9benzyloxy)carbonyl]amino}propyl)amino]butyl}carbamate .9) [21][22] .905 mg, 1.5 mmol) in CH2Cl2
.25 ml), 1.12 g .95%) of 11 were obtained. Slightly yellowish oil. IR .CHCl3): 3650w, 3440w, 2930m, 1705s,
1625m, 1510s, 1475m, 1415m, 1365m, 1215m, 1130m, 1075m, 1015m, 905w, 8 55w, 8 20w, 595w. 1H-NMR .CDCl3):
7.44 ± 7.25 .m, 35 arom. H); 7.11 .s, HÀC.4), HÀC.6)); 5.08, 5.05, 5.00 .3s, 6 PhCH2); 4.80 .s, PhCH2); 3.34 ±
3.22 .m, 2 CH2.1''), 2 CH2.5')); 3.11 .m, 2 CH2.3''), 2 CH2.12')); 3.09 ± 3.02 .m, 2 CH2.8'), 2 CH2.10')); 3.00
.br., 2 CH2.1')); 2.54 .br., 2 CH2.2')); 1.70 ± 1.48. m, 2 CH2.2''), 2 CH2.11')); 1.39 ± 1.34 .m, 2 CH2.6'),
2 CH2.7')); 1.27 .s, Me3C). 13C-NMR .CDCl3): 172.7 .s, 2 C.3')); 156.4 .s, 6 CO); 153.1 .s, C.2)); 147.4
.s, C.5)); 137.2, 136.7 .2s, 6 arom. C); 133.6 .s, C.1), C.3)); 128.5, 128.3, 128.1, 127.9, 127.8 .5d, 35 arom. C);
125.5 .d, C.4), C.6)); 75.5 .t, PhCH2); 67.1, 66.3 .2t, 6 PhCH2); 47.0 .t, 2 C.1'')); 46.3 .t, 2 C.5')); 45.1 .t, 2 C.8'));
44.0 .t, 2 C.10')); 42.0 .t, 2 C.12')); 38.3 .t, 2 C.3'')); 34.2 .s, Me3C); 33.8. t, 2 C.2')); 31.4 .q, Me3C); 28.8
.t, 2 C.1')); 27.6 .t, 2 C.2'')); 26.8. t, 2 C.11')); 25.7 .t, 2 C.7')); 25.1 .t, 2 C.6')). ESI-MS: 1580 .100, [M Na] ),
801 .75, [M 2 Na]2).
N,N'-Bis93-aminopropyl)-N,N'-bis[4-93-aminopropyl)butyl]-5-9tert-butyl)-2-hydroxybenzene-1,3-bis[pro-
panamide] .13). Analogous to the preparation of 12, reaction of 11 .780 mg, 0.5 mmol) and 10% Pd/C .350 mg)
in AcOH .glacial, 110 ml) in a Parr apparatus .3.5 bar H2 pressure) afforded 430 mg .98%) of 13. Colorless oil.
IR .KBr): 3415m, 2957vs, 1607s, 1484s, 1392m, 1294w, 1199m, 1153w, 1112w, 1061w, 1005w, 8 79w, 8 22w, 754w,
531w . 1H-NMR .CD3OD): 8.78, 8.09, 7.96 .br., 3s, 2 NH2, 4 NH3); 7.01 .s, HÀC.4), HÀC.6)); 3.49 ± 3.40
.m, 2 CH2.3''), 2 CH2.12')); 3.16 ± 3.10 .m, 2 CH2.1''), 2 CH2.5')); 3.00 ± 2.98. m, 2 CH2.8'), 2 CH2.10')); 2.90
.br., 2 CH2.1')); 2.74 .br., 2 CH2.2')); 2.16 ± 1.94 .m, 2 CH2.2''), 2 CH2.11')); 1.70 .br., 2 CH2.6'), 2 CH2.7'));
1.27 .s, Me3C). 13C-NMR .CD3OD): 170.5 .s, 2 C.3')); 151.5 .s, C.2)); 144.2 .s, C.5)); 129.0 .s, C.1), C.3));
126.6 .d, C.4), C.6)); 46.3 .t, 2 C.8')); 45.9 .t, 2 C.10')); 43.8. t, 2 C.1'')); 38.2 .t, 2 C.5')); 37.9 .t, 2 C.3'')); 35.3
.s, Me3C); 35.0 .t, 2 C.2')); 34.7 .t, 2 C.12')); 32.0 .q, Me3C); 27.8. t, 2 C.2'')); 26.8. t, 2 C.11')); 25.6 .t, 2 C.1'));
25.2 .t, 2 C.7')); 24.4 .t, 2 C.6')). ESI-MS: 664 .7, [M H] ), 332 .100, [M 2H]2), 222 .82, [M 3H]3).
2-9Benzyloxy)-N,N'-bis93-{[9tert-butoxy)carbonyl]94-{[9tert-butoxy)carbonyl]amino}butyl)amino}pro-
pyl)-5-9tert-butyl)benzene-1,3-bis[propanamide .18). Analogous to the preparation of 10, reaction of
7
.373.7 mg, 0.97 mmol), 1-methyl-2-chloropyridinium iodide .594 mg, 2.3 mmol), Et3N .471mg, 4.65 mmol),
and di9tert-butyl) N-93-aminopropyl)-N,N'-9butan-1,4-diyl)bis[carbamate] .17) .634 mg, 1.83 mmol) in CH2Cl2
.20 ml): 303 mg .30%) of 18 as colorless oil. IR .CHCl3): 3870w, 3450m, 3000vs, 2870m, 1660vs, 1585vs, 1540vs,
1515vs, 1480s, 1455s, 1420s, 1390m, 1365s, 1320m, 1245s, 1200s, 1170vs, 1050m, 1005m, 925w, 8 75m, 8 60w, 8 45w,
690w, 655w, 620w. 1H-NMR .CDCl3): 7.52 ± 7.34 .m, 5 arom. H); 7.08. s, HÀC.4), HÀC.6)); 6.60 .br. s,
NHBoc); 4.86 .s, PhCH2); 3.14 ± 3.12 .m, 2 CH2.5'), 2 CH2.7'), CH2.9'), 2 CH2.12')); 2.99 .t, J 7.4, 2 CH2.1'));
2.49 .t, J 7.4, 2 CH2.2')); 1.59 ± 1.47 .m, 2 CH2.10'), 2 CH2.11')); 1.42 .s, 4 Me3CO); 1.28± 1.22 . m, CH2.6'));
1.27 .s, Me3C). 13C-NMR .CDCl3): 172.2 .s, 2 C.3')); 156.0 .s, 4 CO); 152.8. s, C.2)); 149.4 .s, C.5)); 137.6
.s, arom. C); 133.4 .s, C.1), C.3)); 128.5, 127.9, 127.8 .3d, 5 arom. C); 125.4 .d, C.4), C.6)); 79.6, 79.1 .2s,
4 Me3CO); 75.6 .t, PhCH2); 46.7 .t, 2 C.12')); 43.4 .t, 2 C.7')); 40.1 .t, 2 C.9')); 37.7 .t, 2 C.5')); 35.8. s, Me3C);
35.8. t, 2 C.2')); 31.4 .q, Me3C); 29.6 .t, 2 C.1')); 27.4 .t, 2 C.6')); 28.4 .q, 4 Me3CO); 26.8. t, 2 C.11')); 25.7
.t, 2 C.10')). ESI-MS: 1061 .70, [M Na] ), 542 .100, [M 2 Na]2). Anal. calc. for C57H94N6O11 .1039.50):
C 65.86, H 9.11, N 8.08; found: C 65.64, H 8.87, N 8.51.
N,N'-Bis{3-[94-aminobutyl)amino]propyl}-5-9tert-butyl)-2-hydroxybenzene-1,3-bis[propanamide] .15). To
a soln. of 18 .120 mg, 0.11 mmol) in AcOH .glacial, 110 ml) was added 10% Pd/C .200 mg), and the mixture was
hydrogenated overnight in a Parr apparatus .3.5 bar H2 pressure). The mixture was filtered over Celite, and the
filtrate was evaporated. The crude product was dissolved in CF3COOH .5 ml) and stirred overnight at r.t.
Removal of the solvent in vacuo and purification of the residue by CC .SiO2; CHCl3/MeOH/25% aq. NH3 soln.
6 :3 :1) gave 25 mg .40%) of 15, which was converted to 15 ´ 4 HCl. IR .CHCl3): 3440w, 3240w, 2990m, 2960m,
2930m, 2860m, 1650m, 1600w, 1530m, 1490m, 1450w, 1410w, 1360w, 1300w, 1260m, 1200w, 1155w, 1115w, 1095w,
1050w, 1010w, 8 8w0, 8 60w, 8 15w, 710w, 665w. 1H-NMR .CD3OD): 8.13 ± 7.96 .br., NH2); 6.97 .s, HÀC.4),
HÀC.6)); 5.03 .s, OH); 3.19 .t, J 7.3, 2 CH2.5')); 2.87 .t, J 6.8, 2 CH2.1')); 2.65 .t, J 6.8, 2 CH2.12')); 2.54
.t, J 7.0, 2 CH2.2')); 2.49 ± 2.48. m, 2 CH2.7'), 2 CH2.9')); 1.64 .quint., J 7.1, 2 CH2.6')); 1.52 ± 1.51
.m, 2 CH2.10'), 2 CH2.11')); 1.26 .s, Me3C). 13C-NMR .CD3OD): 176.0 .s, 2 C.3'); 151.4 .s, C.2)); 143.6
.s, C.5)); 128.9 .s, C.1), C.3)); 126.2 .d, CH.4), CH.6)); 50.2 .t, 2 C.7')); 47.6 .t, 2 C.9')); 42.2 .t, 2 C.5')); 38.1
.t, 2 C.12')); 37.6 .t, 2 C.2')); 34.7 .s, Me3C); 32.0 .q, Me3C); 31.1 .t, 2 C.1')); 30.0 .t, 2 C.6')); 27.8. t, 2 C.11'));
27.7 .t, 2 C.10')). ESI-MS: 571 .6, [M Na] ), 549 .100, [M H] ), 478.5, [ M À .CH2)4NH2] ), 275 .88, [M
2 H]2). ESI-MS/MS .of m/z 549.3, À35 eV): 531 .< 5), 404 .11, [M À 146u 2 H] ), 387 .23), 333 .9), 316
.100, [M À 146u À 88u 2 H] ), 146 .12, [M of spermidine À H] ), 129 .11), 112 .5), 72 .11). ESI-MS/MS .of
m/z 549.3, À30 eV): 549 .12, [M H] ), 404 .63, [M À 146u 2 H] ), 387 .52), 333 .22), 316 .100, [M À 146u À
88u 2 H] ), 146 .30, [M of spermidine À H] ), 129 .115), 72 .11).