B. Kolesinska, Z.J. Kaminski / Tetrahedron 65 (2009) 3573–3576
3575
4. Experimental
4.1. General
diethylamino)-1,3,5-triazine (4d) (2.92 g, yield 99%), mp¼44–47 ꢀC,
lit.16 mp¼46–47 ꢀC. 1H NMR (CDCl3):
d¼1.40 (q, J¼7.0 Hz, 18H), 3.55
(t, J¼7.0 Hz, 12H). 13C NMR (CDCl3):
d
¼13.4, 40.8, 164.6. IR (film/
NaCl):
n
¼2970, 2940, 2650, 2610, 2500, 1610, 1540, 1485, 1440,
Melting points were determined on a Bu¨chi apparatus, model
510. IR spectra were recorded as KBr pellets or film on an Infracord
137 E spectrometer. Intensities of signals were estimated as
vs¼very strong, s¼strong, m¼medium, w¼weak, br¼broad.
1H NMR and 13C NMR spectra were recorded on a Bruker Avance
DPX 250 (250 MHz) spectrometer. Chemical shifts (ppm) are rela-
tive to TMS used as an internal standard. The multiplicity were
marked as s¼singlet, d¼doublet, t¼triplet, q¼quartet, qu¼quintet,
sext¼sextet, m¼multiplet.
1375, 1340, 1295, 1245, 1190 [cmꢁ1]. Anal. for C15H30N6: (294.5).
Calcd: C, 61.19%; H, 10.27%; N, 28.54%. Found: C, 61.17%; H, 10.30%;
N, 28.57%.
The liquid in the cold trap was identified as chloroethane (6d)
(0.88 g, 68%) bp¼12 ꢀC (determined by capillary method), lit.22
bp¼12 ꢀC; n5D¼1.3751. 1H NMR (CDCl3):
3.50 (q, J¼7.2 Hz, 2H).
d
¼1.49 (t, J¼7.2 Hz, 3H),
4.6. Synthesis of 2,4,6-tris-(N,N-dipropylamino)-1,3,5-
triazine (4e)
4.2. Synthesis of 2,4,6-tris-(morpholin-4-yl)-1,3,5-
triazine (4a). Typical procedure
Product: 2,4,6-tris-(N,N-dipropylamino)-1,3,5-triazine (4e)
(3.71 g, yield 98%), mp¼68–70 ꢀC, lit.17 mp¼75 ꢀC. 1H NMR (CDCl3):
The vigorously stirred solution of cyanuric chloride (1) (0.37 g,
2 mmol) in dichloromethane (5 ml) was cooled to 0 ꢀC, NMM (5a)
(0.66 mL, 6 mmol) was added dropwise and stirring was continued
for additional 30 min until evolution of gases was ceased. The
solution was diluted with dichloromethane (20 mL) and then
washed with water, 1 M aqueous KHSO4, water, dried with MgSO4,
filtered, and concentrated to dryness yielding 2,4,6-tris-(morpho-
lin-4-yl)-1,3,5-triazine (4a) (1.29 g, yield 96%), mp¼264–266 ꢀC,
d
¼0.87 (t, J¼7.0 Hz, 18H), 1.62 (m, 12H), 3.44 (m, 12H). 13C NMR
(CDCl3):
d
¼13.8, 21.2, 50.3, 165.4. IR (film/NaCl): ¼2960, 2925,
n
2870, 1655, 1590, 1510, 1500, 1430, 1395, 1330, 1230, 1200 [cmꢁ1].
Anal. for C21H42N6: (378.6). Calcd: C, 66.62%; H, 11.18%; N, 22.20%.
Found: C, 66.61%; H, 11.19%; N, 22.22%.
By repeating these synthesis in toluene (20 mL), 1-chloro-
propane (6e) (1.41 g, 90%) was isolated from the distillate collected
in the cold trap, bp¼45–48 ꢀC, lit.23 bp¼46–47 ꢀC; n2D0¼1.3875. 1H
lit.14 mp¼263–264 ꢀC. 1H NMR (CDCl3):
d
¼3.71 (t, J¼5.5 Hz, 12H),
NMR (CDCl3):
3.51 (t, J¼6.5 Hz, 2H).
d
¼1.23 (t, J¼7.0 Hz, 3H), 1.80 (br sext, J¼7.0 Hz, 2H),
3.76 (t, J¼5.5 Hz, 12H). 13C NMR (CDCl3):
d
¼43.5, 66.7, 165.2. IR
(film/NaCl):
n
¼2970, 2900, 2860, 1560, 1515, 1495, 1460, 1440, 1360,
1250, 1240, 1230, 1115 [cmꢁ1]. Anal. for C15H24N6O3 (336.4). Calcd:
C, 53.56%; H, 7.19%; N, 24.98%. Found: C, 53.55%; H, 7.24%; N, 24.99%.
The evolved gas was absorbed in ice-cold CDCl3 and then identified
4.7. Synthesis of 2,4,6-tris-(N,N-dibutylamino)-1,3,5-
triazine (4f)
as chloromethane (6a) by 1H NMR (CDCl3):
d
¼3.71 (s, CH3Cl).
Product: 2,4,6-tris-(N,N-dibutylamino)-1,3,5-triazine (4f) was
obtained (4.44 g, yield 96%), mp¼112 ꢀC, lit.14 mp¼112 ꢀC. 1H NMR
4.3. Synthesis of 2,4,6-tris-(pyrrolidin-1-yl)-1,3,5-triazine (4b)
(CDCl3):
d
¼0.92 (t, J¼7.5 Hz, 18H), 1.32 (m, 12H), 1.56 (m, 12H), 3.46
(m, 12H). 13C NMR (CDCl3):
NaCl):
d
¼13.6, 19.7, 29.9, 51.9, 165.4. IR (film/
Starting materials: cyanuric chloride (1) (1.84 g, 10 mmol),
1-methyl-pyrrolidine (5b) (2.89 mL, 30 mmol), dichloro-
methane (20 mL). Product: 2,4,6-tris-(pyrrolidin-1-yl)-1,3,5-tri-
azine (4b) was obtained (2.74 g, yield 95%), mp¼175–177 ꢀC,
n
¼2970, 2930, 2880, 1675,1575, 1540, 1500, 1425, 1375, 1340,
1240, 1205 [cmꢁ1]. Anal. for C27H54N6: (462.8). Calcd: C, 70.08%; H,
11.76%; N, 18.16%. Found: C, 70.05%; H, 11.75%; N, 18.21%.
From the distillate, 1-chlorobutane (6f) was isolated (1.50 g,
lit.14 mp¼176–179 ꢀC. 1H NMR (CDCl3):
d
¼1.70 (qu, J¼8.0 Hz,
81%); bp¼77 ꢀC, lit.24 bp¼74–77 ꢀC; nD20¼1.4025. 1H NMR (CDCl3):
12H), 3.52 (t, J¼8.0 Hz, 12H). 13C NMR (CDCl3):
d
¼24.7, 44.2,
d
¼0.94 (t, J¼7 Hz, 3H), 1.47 (sext, J¼7 Hz, 2H), 1.76 (qw, J¼7 Hz, 2H),
165.2. IR (film/NaCl):
n
¼2938, 2866, 2568, 2512, 2408, 2152,
3.54 (t, J¼7 Hz).
1536, 1504, 1434, 1399, 1375, 1320, 1216, 1161, 1121, 1055
[cmꢁ1]. Anal. for C15H24N6 (288.4). Calcd: C, 62.47%; H, 8.39%;
N, 29.14%. Found: C, 62.45%; H, 8.35%; N, 29.11%.
4.8. Synthesis of 2,4,6-tris(N-methylphenylamino)-1,3,5-
triazine (4g)
4.4. Synthesis of 2,4,6-tris-(piperidin-1-yl)-1,3,5-triazine (4c)
2,4,6-Tris(N-methylphenylamino)-1,3,5-triazine
(4g)
was
obtained (3.01 g, yield 76%), mp¼113–115 ꢀC, lit.18 mp¼117.5 ꢀC. 1H
Product: 2,4,6-tris-(piperidin-1-yl)-1,3,5-triazine (4c) was obtained
(3.11 g, yield 94%), mp¼216–217 ꢀC, lit.14 mp¼215–216 ꢀC. 1H NMR
NMR (CDCl3):
d
¼3.47 (s, 9H), 7.24–7.61 (m, 15H). 13C NMR (CDCl3):
d
¼37.9, 126.1, 126.2, 128.6, 143.5, 164.9. IR (film/NaCl): ¼3062,
n
(CDCl3):
d
¼1.49–1.69 (m, 12H), 1.81–1.98 (m, 6H), 3.70 (t, J¼6.5 Hz,
3038, 2942, 2794, 1951, 1774, 1679, 1600, 1536, 1481, 1446, 1386,
1320, 1263, 1169, 1098, 1026 [cmꢁ1]. Anal. for C24H24N6 (396.5).
Calcd: C, 72.70%; H, 6.10%; N, 21.20%. Found: C, 72.61%; H, 6.15%; N,
21.11%.
12H). 13CNMR(CDCl3):
d
¼20.7, 23.5, 50.0,163.2. IR (film/NaCl): ¼3015,
n
2942, 2857, 2737, 1617, 1530, 1481, 1446, 1376, 1298, 1272, 1233, 1217,
1127,1064,1025 [cmꢁ1]. Anal. for C18H30N6 (330.5). Calcd: C, 65.42%; H,
9.15%; N, 25.43%. Found: C 65.45%; H 9.12%; N 25.41%.
4.9. Synthesis of 2,4,6-tris(dimethylamino)-1,3,5-triazine (4h)
4.5. Synthesis of 2,4,6-tris-(N,N-diethylamino)-1,3,5-
triazine (4d)
To the vigorously stirred solution of cyanuric chloride (1) (1.84 g,
10 mmol) in dichloromethane (20 mL), N,N-dimethylbenzylamine
(5h) (4.51 mL, 30 mmol) was added dropwise. Then, the mixture
was heated under reflux for additional 30 min and dichloro-
methane was distilled off. The residue was heated for additional
60 min and benzyl chloride was distilled off. The residue was dis-
solved in chloroform (30 mL) and then washed with 1 M aqueous
KHSO4 (40 mL) and water (40 mL). The organic layer was dried with
Na2SO4, filtered, and concentrated to dryness. After crystallization
Starting materials: cyanuric chloride (1) (1.84 g, 10 mmol),
N,N,N-triethylamine (5d) (4.18 mL, 30 mmol), dichloromethane
(10 mL). Evolved gaseous products passed through the condenser
were trapped in ice-cold washer. After ceasing of gas evolution,
residue was diluted with dichloromethane (10 ml), cooled to room
temperature, washed with 1 M aqueous KHSO4 (10 mL) then water
(10 mL), dried with MgSO4, and evaporated yielding 2,4,6-tris-(N,N-