1
1698 s, 1601 s. H NMR(400 MHz, DMSO-d6) d 8.55 (br. s,
and dry toluene (5 ml), 1,1,1-tris(4-methylbenzoyloxymethyl)-
methylamine 11 (0.43 g, 0.9 mmol) and dichloromethane (10
ml) (0.47 g, 0.29 mmol, 97%); mp 111–112 1C. (ESMS+) 1634
(MLi+, 100%), 1650 (MNa+, 100%). Anal. calcd for
C93H90N6O21: C, 68.62; H, 5.57; N, 5.16. Found: C, 68.63;
H, 5.78; N, 5.02%. IR(KBr, pellet, cmꢁ1) 3392 m, 1718 s,
2H, NH), 7.65 (m (AA0), 12H, Ar–H), 7.23 (m (AA0), 4H,
core-Ar–H), 7.02 (m (XX0), 4H, core-Ar–H), 6.53 (m (XX0),
12H, Ar–H), 6.50 (br. s, 2H, NH), 5.99 (br. s, 12H, Ar–NH2),
4.60 (s, 12H, CH2), 3.75 (br. s, 2H, core-CH2). 13C NMR(100
MHz, DMSO-d6) d 165.45 (CO2R), 154.67 (NHCQONH),
153.71 (ArC–NH2), 137.74 (core-ArC–H), 134.54 (ArC–CO2),
131.28 (core-ArC–H), 128.83 (core-ArC–CH2), 117.96
(core-ArC–NHR), 115.21 (p-NH2–ArC–H), 112.59 (p-NH2–
ArC–H), 62.88 (CH2), 56.94 (Cq), 39.51 coincident with
residual solvent (core-CH2).
1
1268 s. H NMR (400 MHz, DMSO-d6) d 8.14 (s, 3H, NH),
7.91 (m (AA0), 18H, p-CH3–Ar–H), 7.28 (s, 3H, core-Ar–H),
7.25 (m (XX0), 18H, p-CH3–Ar–H), 6.30 (s, 3H, NH), 4.93 (s,
18H, CH2), 2.37 (s, 27H, CH3). 13C NMR (100 MHz, DMSO-
d6)
d
166.49 (CO2R), 155.58 (NHCQONH), 144.90
(ArC–CH3), 141.64 (ArC–NHR), 130.52 (p-CH3–ArC–H),
130.10 (p-CH3-ArC–H), 128.08 (ArC–CO2R), 102.57 (core-
ArC–H), 64.94 (CH2), 58.53 (Cq), 21.66 (CH3).
1,3,5-Tris((1,1,1-tris(4-nitrobenzoyloxymethyl)methylamino)
carbonylamino)benzene 21. 1,3,5-Benzenetricarbonyl triazide
19 (0.09 g, 0.3 mmol) was dissolved in dry toluene (5 ml)
and refluxed for one hour under an atmosphere of nitrogen.
The reaction was allowed to cool, the toluene was removed on
a rotary evaporator and 1,1,1-tris(4-nitrobenzoyloxymethyl)-
methylamine 8 (0.52 g, 0.9 mmol) dissolved in CH2Cl2 (10 ml)
was added under an atmosphere of nitrogen. The reaction
mixture was gently refluxed for 16 hours and cooled to room
temperature. The resulting precipitate was collected by filtra-
tion affording a yellow powder (0.53 g, 92% yield); mp
143–1451 C. (ESMS+) 1929 (MNa+, %). Anal. calcd for
C84H63N15O39: C, 52.92; H, 3.33; N, 11.02. Found: C, 52.79;
H, 3.41; N, 10.84%. IR(KBr, pellet, cmꢁ1) 3397 m, 1733 s. 1H
NMR (400 MHz, acetone-d6) 8.23 (m (AA0BB0), 36H, p-NO2-
Ar–H), 8.08 (br. s, 3H, NH), 7.22 (s, 3H, core-Ar–H), 6.43 (br.
s, 3H, NH), 5.07 (s, 18H, CH2). 13C NMR (100 MHz, acetone-
1,3,5-Tris((1,1,1-tris(4-maleimidobenzoyloxymethyl)methyl-
amino)carbonylamino)benzene 24. This compound was pre-
pared by a procedure analogous to that used for the prepara-
tion of 22 using 1,3,5-benzenetricarbonyl triazide 19 (0.04 g,
0.15 mmol) and dry toluene (3 ml), 1,1,1-tris(4-maleimidoben-
zoyloxymethyl)methylamine 12 (0.32 g, 0.45 mmol) and di-
chloromethane (10 ml) to yield a yellow solid (0.35 g, 0.15
mmol, 99%); mp 200 1C. IR(KBr, pellet, cmꢁ1). 1H NMR (400
MHz, DMSO-d6) d 8.80 (br. s, 3H, NH), 8.04 (m (AA0), 18H,
Ar–H), 7.44 (m (XX0), 18H, Ar–H), 7.22 (s, 3H, core-Ar–H),
7.19 (s, 18H, HCQCH), 6.53 (br. s, 3H, NH), 4.87 (s, 18H,
CH2). 3C NMR (100 MHz, DMSO-d6)
d
169.4
(CQONCQO), 164.69 (CO2R), 154.55 (NHCQONH),
140.43 (core-ArC–NHR), 135.96 (ArC–NR2), 134.83
d6)
d
165.03 (CO2R), 155.67 (NHCQONH), 151.70
(RHCQCHR),
129.93
(p-maleimide-ArC–H),
127.85
(ArC–NO2), 141.47 (ArC–NHR), 135.96 (ArC–CO2R),
131.83 (p-NO2–ArC–H), 124.51 (p-NO2–ArC–H), 103.43
(core-ArC–H), 65.73 (CH2), 58.50 (Cq).
(ArC–CO2R), 126.15 (p-maleimide-ArC–H), 100.57 (core-
ArC–H), 64.20 (CH2), 56.70 (Cq). Anal. calcd for
C120H81N15O39.H2O: C, 60.69; H, 3.52; N, 8.85. Found: C,
60.43; H, 3.71; N, 8.71%.
1,3,5-Tris((1,1,1-tris(4-methoxybenzoyloxymethyl)methylamino)
carbonylamino)benzene 22. This compound was prepared by a
procedure analogous to that used for the preparation of 21
using 1,3,5-benzenetricarbonyl triazide 19 (0.15 g, 0.52 mmol)
and dry toluene (7 ml), 1,1,1-tris(4-methoxybenzoyloxy-
methyl)methylamine 10 (0.82 g, 1.56 mmol) and dichloro-
methane (15 ml). The reaction mixture was gently refluxed
for 16 hours and cooled to room temperature. The solvent was
removed by rotary evaporation to yield a white solid (0.89 g,
0.50 mmol, 96%); mp 114–115 1C. (ESMS+) 1778 (MLi+,
100%), 1794 (MNa+, 100%). Anal. calcd for C93H90N6O30:
C, 63.05; H, 5.12; N, 4.74. Found: C, 63.09; H, 5.29; N, 4.74%.
IR(KBr, pellet, cmꢁ1) 3384 m, 2962 w, 1717 s, 1258 s.
1H NMR (400 MHz, acetone-d6) d 8.15 (s, 3H, NH), 7.97
(m (AA0), 18H, p-CH3O–Ar–H), 7.30 (s, 3H, core-Ar–H), 6.96
(m (XX0), 18H, p-CH3O–Ar–H), 6.28 (s, 3H, NH), 4.90 (s,
18H, CH2), 3.86 (s, 27H, CH3). 13C NMR (100 MHz, acetone-
1,3,5-Tris((1,1,1-tris(4-aminobenzoyloxymethyl)-methylamino)
-carbonylamino)benzene 25. 1,3,5-Tris((1,1,1-tris(4-nitroben-
zoyloxymethyl)methylamino) carbonyl-amino)benzene 21
(400 mg, 0.2 mmol) was dissolved in dry DMF (5 ml) and
0.04 g of 5% Pd/C was added. The reaction mixture was
pressurised with H2 gas (650 psi) and heated to 55 1C for
15 hours. The solution was filtered and evaporated under re-
duced pressure to give a brown oil that was solidified by the
addition of dichloromethane, collected by filtration and dried
under high vacuum to yield a yellow solid (0.21 g, 0.13 mmol,
65%); mp 258–260 1C. (HRMS) Found 1636.5692. C84H82
N15O21(+) requires 1636.5804. IR(KBr, pellet, cmꢁ1) 3368 m,
1700 s, 1602 s, 1268 s. 1H NMR (400 MHz, DMSO-d6) d 8.72
(br, s, 3H, NH), 7.65 (m (AA0), 18H, Ar–H), 7.15 (s, 3H, core-
Ar–H), 6.53 (m (XX0), 18H, Ar–H), 6.37 (br, s, 3H, NH), 5.98 (s,
18H, NH2), 4.60 (s, 18H, CH2). 13C NMR (100 MHz) d 165.44
(CO2R), 154.48 (NHCQONH), 153.70 (ArC–NH2), 140.51
(core-ArC–NHR), 131.29 (pNH2–ArC–H), 115.18 (pNH2–
ArC–H), 112.62 (core-ArC–H), 62.89 (CH2), 56.87 (Cq).
d6)
d
166.17 (CO2R), 164.73 (ArC–OCH3), 155.61
(NHCQONH), 141.70 (ArC–NHR), 132.55 (p-CH3O–ArC–H),
123.02 (ArC–CO2R), 114.73 (p-CH3O–ArC–H), 102.56 (core-
ArC–H), 64.87 (CH2), 58.57 (Cq), 56.01 (CH3).
1,3,5-Tris((1,1,1-tris(4-hydroxybenzoyloxymethyl)methylamino)
carbonylamino)benzene 26. A solution of aluminium bromide
(1.01 g, 3.8 mmol) and dodecanethiol (2 ml) in dry DCM
(7 ml) was cooled in an ice bath under an atmosphere of N2.
1,3,5-Tris((1,1,1-tris(4-
1,3,5-Tris((1,1,1-tris(4-methylbenzoyloxymethyl)methylamino)
carbonylamino)benzene 23. This compound was prepared by a
procedure analogous to that used for the preparation of 22
using 1,3,5-benzenetricarbonyl triazide 19 (0.09 g, 0.3 mmol)
ꢀc
This journal is the Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2007
New J. Chem., 2007, 31, 155–162 | 161