Tapes and Rosettes in Melamine-Cyanurate Assemblies
J. Am. Chem. Soc., Vol. 123, No. 31, 2001 7531
mmol) and DIPEA (0.5 mL) were added, and the resulting solution
was refluxed for 24 h. The solution was evaporated in vacuo and the
residue dissolved in CHCl3 (50 mL), washed with H2O (3 × 50 mL),
dried on MgSO4, and evaporated in vacuo to give a colorless oil.
dissolved in dibutylamine (10 mL) and refluxed overnight, whereafter
the excess of dibutylamine was evaporated under reduced pressure. The
remaining yellowish residue was dissolved in chloroform, washed with
H2O (3 × 50 mL), dried on Na2SO4, and evaporated to dryness to give
a yellow oil. Purification by preparative TLC (SiO2, chloroform/
Purification by column chromatography (SiO2; CHCl3/MeOH 9:1)
methanol 9:1) gave pure 3g (0.33 g, 83%). MS (FAB) m/z 351.4 (100%,
afforded 3d as a colorless oil (282 mg, 80%). MS (FAB) m/z 295.2
1
[M + H]+); H NMR δ 4.63 (br s, 2H, NH), 3.40 (t, 4H, J ) 7.6 Hz,
1
(M + H); H NMR (250 MHz, CDCl3) δ 0.89-0.95 (m, 9H), 1.23-
CH2), 3.27 (q, 4H, J ) 7.0 Hz, CH2), 1.6-1.4 (m, 8H, CH2), 1.4-1.2
(m, 8H, CH2), 0.85 (2t,12H, J ) 7.6 Hz, CH3). Anal. Calcd for
C19N6H38: C, 65.10; N, 24.00; H, 10.90. Found: C, 65.24; N, 24.05;
H, 10.83.
2-Benzylamino-4-(4′-tert-butylanilino)-2-dibutylamino-1,3,5-tri-
azine (3h). A solution of 3e (1.14 g, 2.92 mmol), DIPEA (2 mL), and
benzylamine (1 mL) in THF was refluxed for 23 h. The solvent was
evaporated under reduced pressure, and the residue was dissolved in
CH2Cl2 (100 mL), washed with HCl (1 M, 25 mL), H2O (50 mL), and
brine (25 mL), and dried MgSO4. Evaporation under reduced pressure
1.43 (m, 6H), 1.47-1.55 (m, 6H), 3.29-3.37 (m, 2H), 3.45 (t, J ) 7.0
Hz, 4H), 4.58 (br s, 2H), 4.70 (br s, 1H); 13C NMR (62.5 MHz, CDCl3)
δ 13.8 (CH3), 14.0 (CH3), 20.2 (CH2), 30.1 (CH2), 32.0 (CH2), 40.3
(CH2), 46.3 (CH2), 165.2 (C), 166.1 (C), 166.9 (C). Anal. Calcd for
C15H30N6: C, 61.18; H, 10.27; N, 28.55. Found: C, 61.51; H, 10.51;
N, 28.70.
4-Chloro-2-(4′-tert-butylanilino)-6-dibutylamino-1,3,5-triazine (3e).
A solution 4-tert-butylaniline (0.86 g, 5.76 mmol) in THF (5 mL) was
added dropwise to an ice-cooled solution of cyanuric chloride (1.06 g,
5.75 mmol) and DIPEA (2 mL) in THF (10 mL). The reaction was
stirred for 5 h and allowed to warm to room temperature, and a solution
of dibutylamine (0.78 g, 6.03 mmol) in THF (1 mL) was added
dropwise. Stirring was continued at room temperature for 20 h, and
the solvent was removed in vacuo. The residue was dissolved in CH2-
gave a colorless oil that was further purified by column chromatography
(SiO2; CHCl3/MeOH 95:5) to give 3h as a colorless gum (1.08 g, 80%).
MS (FAB) m/z 461.3 (M + H); 1H NMR (250 MHz, CDCl3) δ 0.90-
1.01 (m, 6H), 1.31 (s, 9H), 1.31-1.43 (m, 4H), 1.53-1.64 (m, 4H),
3.50 (m, 4H), 4.59 (d, J ) 5.8 Hz, 2H), 5.41 (br s, 1H), 7.06 (br s,
1H), 7.25-7.33 (m, 7H), 7.49-7.53 (m, 2H); 13C NMR (62.5 MHz,
CDCl3) δ 14.1 (CH3), 20.3 (CH2), 20.5 (CH3), 30.2 (CH2), 31.5 (CH2),
34.2 (C), 44.6 (CH2), 46.8 (CH2), 47.2 (CH2), 119.4 (CH), 125.4 (CH),
127.0 (CH), 127.5 (CH), 128.5 (CH), 137.2 (C), 139.8 (C), 144.8 (C),
164.2 (C), 165.1 (C), 166.0 (C). Anal. Calcd for C28H40N6‚0.5H2O: C,
71.60; H, 8.80; N, 17.90. Found: C, 71.93; H, 8.72; N, 17.91.
2,4-Bis(heptylamino)-6-chloro-1,3,5-triazine (3i). 1-Aminoheptane
(5 mL) was added dropwise to a solution of cyanuric chloride (2.21 g,
12 mmol) in THF (20 mL). The solution was stirred at room temperature
for 24 h, and then HCl (1 M, 50 mL) was added. The resulting
Cl2 (100 mL), washed with H2O (2 × 50 mL) and HCl (1 M, 50 mL),
dried on MgSO4, and evaporated in vacuo to give an orange oil which
was purified by column chromatography (hexane/ethyl acetate, 4:1) to
give 3e as a colorless oil (1.95 g, 87%). MS (FAB) m/z 390.3 (M +
1
H); H NMR (250 MHz, CDCl3) δ 0.92-0.99 (m, 6H), 1.31 (s, 9H),
1.31-1.42 (m, 4H), 1.55-1.63 (m, 4H), 3.47-3.58 (m, 4H), 6.98 (br
s, 1H), 7.30-7.34 (m, 2H), 7.46-7.50 (m, 2H).
2,4-Bis-(4′-tert-butylanilino)-6-dibutylamino-1,3,5-triazine (3f). A
solution of 2,4-bis-(4′-tert-butylanilino)-6-chloromelamine (540 mg,
1.31 mmol)55 and dibutylamine (1 mL) in THF (20 mL) was refluxed
for 21 h. H2O was then added, and the resulting amorphous solid was
filtered. Recrystallization from CHCl3/hexane gave 3f as fine white
precipitate was filtered, washed with HCl (1 M, 10 mL) and H2O (10
mL), and recrystallized from CHCl3 to give 3i as a white solid (2.1 g,
51%). Mp 164-165 °C; MS (FAB) m/z 342.4 (M + H); H NMR
(250 MHz, CDCl3) δ 0.85-0.91 (m, 6H), 1.28-1.30 (m, 16H), 1.54-
1.60 (m, 4H), 3.36-3.44 (m, 4H), 5.52 (br s, 2H).
2,4-Bis(N-heptylamino)-6-dibutylamino-1,3,5-triazine (3j). A solu-
tion of 3i (302 mg, 0.88 mmol) and dibutylamine (2 mL) in THF (5
mL) was refluxed for 27 h. The solvent was evaporated under reduced
pressure, and then the residue was dissolved in CHCl3 (50 mL), washed
with H2O (50 mL) and HCl (1 M, 50 mL), and dried on MgSO4.
Evaporation of the solvent under reduced pressure gave a pale yellow
gum, which was purified by column chromatography (SiO2; hexane/
1
needles (438 mg, 67%). Mp 188-189 °C; MS (FAB) m/z 503.4 (M +
1
H); H NMR (250 MHz, CDCl3) δ 0.99 (t, J ) 7.3 Hz, 6H), 1.33 (s,
18H), 1.33-1.48 (m, 4H), 1.61-1.73 (m, 4H), 3.56 (t, J ) 7.9 Hz,
4H), 7.16 (br s, 2H), 7.26-7.32 (m, 4H), 7.49-7.52 (m, 4H); 13C NMR
(62.5 MHz, CDCl3) δ 14.1 (CH3), 20.4 (CH2), 30.1 (CH2), 31.5 (CH3),
34.2 (C), 47.4 (CH2), 119.7 (CH), 125.4 (CH), 136.9 (C), 145.2 (C),
164.1 (C), 165.1 (C). Anal. Calcd for C31H46N6: C, 74.06; H, 9.22; N,
16.72. Found: C, 73.97; H, 9.07; N, 16.84.
2,4-Bis(butylamino)-6-dibutylamino-1,3,5-triazine (3g). 1-Ami-
nobutane (1 mL) was added dropwise to a solution of cyanuric chloride
(0.21 g, 1.125 mmol) in THF (10 mL). The solution was stirred at
room temperature for 24 h, and then HCl (1 M, 20 mL) was added.
The resulting precipitate was filtered, washed with HCl (1 M, 10 mL)
and H2O (10 mL), and dried under vacuum. The solid was then
(55) Mathias, J. P.; Seto, C. T.; Simanek, E. E.; Whitesides, G. M. J.
Am. Chem. Soc. 1994, 116, 1725-1736.