Novel Hydrogen-Bonded Assemblies
MS (FAB): m/z 315.2 ([M + H+], calcd 314.2). Anal. Calcd for
2-N,N-Diben zylam in o-4,6-bis[N-(10-N-(4-N-bu tylam in o-
6-N,N-dibu tylam in o-1,3,5-tr iazin -2-yl)am in odecyl)am in o]-
1,3,5-tr ia zin e (4). Compound 4 was obtained from 10 as a
transparent oil in 60% yield. 1H NMR (300 MHz, CDCl3) δ 7.4-
7.2 (m, 10H), 4.9 (br s, 6H), 4.7 (s, 4H), 3.6-3.4 (m, 8H), 3.4-
3.3 (m, 12H), 1.7-1.2 (m, 56H), 1.0-0.9 (m, 18H). 13C NMR
(75 MHz, CDCl3) δ 138.2, 127.7, 127.3, 126.2, 47.4, 45.8, 40.1,
39.7, 31.4, 29.6, 29.3, 28.8, 28.7, 26.3, 19.6, 19.5, 13.4, 13.2.
MS (FAB): m/z 1171.9 ([M + H+], calcd 1172.0). Anal. Calcd
for C67H114N18: C 68.68, H 9.81, N 21.52. Found: C 68.34, H
9.60, N, 20.98.
Gen er a l P r oced u r e for th e Syn th esis of Mela m in es 6
a n d 7. To an ice-cold solution of cyanuric chloride (1.4 g, 7.5
mmol) and DIPEA (5.2 mL, 3.0 mmol) in THF (100 mL) was
added dropwise the appropriate primary amine (1.0 equiv) and
the solution was stirred for 2 h at 0 °C. Upon increasing the
temperature to 30 °C the secondary amine (dibenzylamine and
dibutylamine, respectively) was added (4.0 equiv) and the
solution was stirred for another 24 h at 90 °C. Then, the
solvent was removed under reduced pressure and the residue
was partitioned between CH2Cl2 and 1 N HCl. The organic
layer was washed with H2O and brine and the solvent was
removed under reduced pressure.
C
15H28N5Cl: C 57.40, H 8.99, N 22.31. Found: C 57.66, H 8.83,
N, 21.60.
Gen er a l P r oced u r e for th e Syn th esis of Mela m in es 8,
9, a n d 10. To a solution of compound 5 (833 mg, 2.6 mmol) in
THF (10 mL) was added dropwise an excess of the appropriate
diamine (30 equiv) and the solution was refluxed for 24 h at
90 °C. The solvent was removed under reduced pressure and
the residue was partitioned between CH2Cl2 and 1 N HCl. The
organic layer was washed with water, 1 N NaOH, and brine.
The solvent was removed under reduced pressure. The result-
ing yellow oil was purified by column chromatography (SiO2;
CH2Cl2/MeOH/NH4OH 90/8/2).
2-N-(3-(Am in om eth yl)p h en yl)a m in o-4-N-bu tyla m in o-
6-N,N-d ibu tyla m in o-1,3,5-tr ia zin e (8). Compound 8 was
obtained from 5 and m-xylylene diamine as a transparent oil
1
in 95% yield. H NMR (300 MHz, CDCl3) δ 7.3-7.1 (m, 4H),
5.1 (br s, 1H), 4.72 (br s, 1H), 4.50 (d, 2H, J HH ) 6.0 Hz), 3.78
(s, 2H), 3.4-3.3 (m, 4H), 3.3-3.2 (m, 2H), 1.5-1.4 (m, 6H),
1.3-1.2 (m, 6H), 0.9-0.8 (m, 9H). 13C NMR (75 MHz, CDCl3)
δ 128.1, 125.6, 125.5, 125.1, 45.9, 44.0, 39.9, 31.5, 29.6, 19.7,
19.6, 13.4, 13.3. MS (FAB): m/z 414.3 ([M + H+], calcd 414.3).
2-N-(7-Am in oh ep t yl)a m in o-4-N-b u t yla m in o-6-N,N-d i-
bu tyla m in o-1,3,5-tr ia zin e (9). Compound 9 was obtained
from 5 and 1,7-diaminoheptane as transparent oil in 90% yield.
1H NMR (300 MHz, CDCl3) δ 4.68 (br s, 2H), 3.48 (t, 2H, J HH
) 7.2 Hz), 3.4-3.3 (m, 4H), 2.7 (t, 2H, J HH ) 6.9 Hz), 1.6-1.3
(m, 22H), 1.0-0.9 (m, 9H). MS (FAB): m/z 408.5 ([M + H+],
calcd 408.4).
2-Ch lor o-4-N,N-d iben zyla m in e-6-N-((S)-r-m eth ylben z-
yl)a m in o-1,3,5-tr ia zin e (6). The resulting yellow solid was
purified by flash column chromatography (SiO2; CH2Cl2/
MeOH/NH4OH 98/1.7/0.3) to yield 6 as a yellow oil in 84%
yield. 1H NMR (300 MHz, CDCl3) δ 7.4-7.1 (m, 15H), 5.73 (d,
1H, J HH ) 6.9 Hz), 5.1-5.0 (m, 1H), 4.9-4.5 (m, 4H), 1.53 (d,
3H, J HH ) 6.9 Hz). MS (FAB): m/z 430.5 ([M + H+], calcd
430.2). Anal. Calcd for C25H24N5Cl: C 69.84, H 5.63, N 16.29.
Found: C 69.88, H 5.46, N, 15.89.
2-N-(10-Am in od ecyl)a m in o-4-N-bu tyla m in o-6-N,N-d i-
bu tyla m in o-1,3,5-tr ia zin e (10). Compound 10 was obtained
from 5 and 1,10-diaminodecane as a transparent oil in 99%
yield. 1H NMR (300 MHz, CDCl3) δ 4.71 (br s, 2H), 3.5-3.4
(m, 4H), 3.4-3.3 (m, 4H), 2.71 (t, 2H J HH ) 6.6 Hz), 1.7-1.3
(m, 28H), 1.0-0.9 (m, 9H). MS (FAB): m/z 450.4 ([M + H+],
calcd 450.4).
2-Ch lor o-4-N,N-d ibu tyla m in o-6-N-(p yr en em eth yl)a m i-
n o-1,3,5-tr ia zin e (7). The resulting yellow oil was purified
by flash column chromatography (SiO2; hexane/EtOAc 250/8)
1
to yield 7 as a white solid in 70% yield. H NMR (300 MHz,
CDCl3) δ 8.5-8.0 (m, 9H), 6.03 (br s, 1H), 5.31 (d, 2H, J HH
)
Gen er a l P r oced u r e for th e Syn th esis of Mela m in es 2a ,
3, a n d 4. To an ice-cold solution of cyanuric chloride (30 mg,
0.16 mmol) and DIPEA (0.27 mL, 1.0 mmol) in THF (10 mL)
was dropwise added dibenzylamine (0.031 mL, 0.16 mmol) and
the solution was stirred for 2 h at 0 °C. Upon increasing the
temperature to 30 °C the appropriate compound 8, 9, or 10
was added (4.0 equiv) and the solution was stirred for another
24 h at 90 °C. The solvent was removed under reduced
pressure and the residue was partitioned between CH2Cl2 and
1 N HCl. The organic layer was washed with H2O and brine
and the solvent was removed under reduced pressure. The
resulting yellow oil was purified by column chromatography
(SiO2; CH2Cl2/MeOH/NH4OH 98/1.7/0.3).
5.4 Hz), 3.6-3.4 (m, 4H), 1.6-0.9 (m, 8H), 1.0-0.7 (m, 6H).
MS (FAB): m/z 472.5 ([M + H+], calcd 472.5). Anal. Calcd for
C
28H30N5Cl: C 71.25, H 6.41, N 14.84. Found: C 71.36, H 6.26,
N 14.51.
Gen er a l P r oced u r e for th e Syn th esis of Mela m in es 11
a n d 12. An excess of m-xylylenediamine (30 equiv) was added
dropwise to a solution of the appropriate melamine (6 or 7) in
THF (10 mL) and the solution was refluxed for 24 h at 90 °C.
The solvent was removed under reduced pressure and the
residue was partitioned between CH2Cl2 and 1 N HCl. The
organic layer was washed with H2O, 1 N NaOH, and brine.
The solvent was removed under reduced pressure.
2-N -(3-(Am in om e t h yl)p h e n ylm e t h yl)a m in o-4-N ,N -
d iben zyla m in o-6-N-((S)-R-m eth ylben zyla m in o)-1,3,5-tr i-
a zin e (11). The resulting yellow oil was obtained from 6 and
m-xylylene diamine and was purified by flash column chro-
matography (SiO2; CH2Cl2/MeOH/NH4OH 92/6/2). Compound
11 was obtained as a transparent oil in 90% yield. 1H NMR
(300 MHz, CDCl3) δ 7.2-7.1 (m, 19H), 5.10 (br s, 3H), 4.8-
2-N ,N -D ib e n zy la m in o -4,6-b is [N -(3-(N -(4-N -b u t y l-
amino-4-N,N-dibutylamino-1,3,5-triazin-2-yl)aminomethyl)-
p h en ylm eth yl)a m in o]-1,3,5-tr ia zin e (2a ). Compound 2a
was obtained from 8 as a transparent oil in 74% yield. 1H NMR
(300 MHz, CDCl3) δ 7.4-7.1 (m, 18H), 5.5, 5.1, and 4.8 (3 br
s, 6H), 4.7 (s, 4H), 4.5 (br s, 8H), 3.5-3.4 and 3.4-3.3 (2m,
20H), 1.7-1.5 and 1.5-1.2 (2m, 24H), 1.0-0.9 (m, 18H). 13C
NMR (75 MHz, CDCl3) δ 166.0, 165.5, 165.4, 165.3, 164.4,
139.9, 138.5, 128.6, 128.3, 128.2, 127.9, 127.8, 126.9, 48.1, 46.6,
44.7, 44.5, 40.4, 32.0, 30.1, 20.2, 20.1, 14.0, 13.8. MS (FAB):
m/z 1099.8 ([M + H+], calcd 1099.8).
4.6 (br m, 2H), 4.8 (m, 4H), 3.74 (br s, 2H), 1.42 (d, 3H, J HH
)
5.7 Hz). 13C NMR (75 MHz, CDCl3) δ 165.7, 165.6, 164.8, 144.4,
142.9, 139.5, 138.0, 128.2, 127.9, 127.8, 127.4, 126.4, 126.2,
125.7, 125.5, 125.3, 49.6, 47.5, 45.8, 44.2, 22.4. MS (FAB): m/z
530.3 ([M + H+], calcd 530.3). Anal. Calcd for C33H35N7: C
74.83, H 6.66, N 18.51. Found: C 74.79, H 6.54, N 18.46.
2-N-(3-(Am in om et h yl)p h en ylm et h yl)a m in o-4-N,N-d i-
bu tyla m in o-6-N-(pyr en em eth yl)a m in o-1,3,5-tr ia zin e (12).
The resulting yellow oil was obtained from 7 and m-xylylene
diamine and was purified by column chromatography (SiO2;
hexane/EtOAc 250/8) to yield 12 as a white solid in 80% yield.
Mp 118-122 °C. 1H NMR (300 MHz, CDCl3) δ 8.35 (d, 1H,
J HH ) 9.8 Hz), 8.19 (d, 1H, J HH ) 10.0 Hz), 8.1-8.0 (m, 7H),
7.3-7.2 (m, 4H), 5.29 (br, 2H), 5.28 (br s, 2H), 5.31 (br s, 2H),
3.84 (s, 2H), 3.5-3.4 (m, 4H), 1.6-0.4 (br m, 4H), 1.3-1.1 (br
m, 4H), 0.9-0.7 (m, 6H). 13C NMR (75 MHz, CDCl3) δ 165.5,
2-N,N-Diben zyla m in o-4,6-bis[N-(7-N-(4-N-bu tyla m in o-
6-N,N-d ibu tyla m in o-1,3,5-tr ia zin -2-yl)a m in oh ep tyl)a m i-
n o]-1,3,5-tr ia zin e (3). Compound 3 was obtained from 9 as
a white solid in 80% yield. Mp 202-203 °C. 1H NMR (300 MHz,
CDCl3) δ 7.3-7.2 (m, 10H), 4.78 (br s, 6H), 4.76 (s, 4H), 3.5-
3.4 (m, 8H), 3.3-3.1 (m, 12H), 1.6-1.5 (m, 20H), 1.3-1.2 (m,
24), 1.0-0.9 (m, 18H). 13C NMR (75 MHz, CDCl3) δ 166.0,
165.6, 165.4, 164.4, 138.3, 127.8, 127.3, 126.3, 47.5, 45.9, 40.2,
40.1, 39.8, 31.6, 29.7, 29.4, 29.3, 28.6, 26.4, 19.7, 13.5. MS
(FAB): m/z 1087.8 ([M + H+], calcd 1087.9). Anal. Calcd for
C
61H102N18: C 67.37, H 9.45, N 23.18. Found: C 66.91, H 9.26,
N, 22.84.
J . Org. Chem, Vol. 68, No. 3, 2003 1105