Jan-Feb 2007
Synthesis of 1,4-Disubstituted 1,2,3-Triazoles
91
ꢄ1
proved to promote other three-component reactions
catalyzed by CuX. These aqueous medium reactions do
not require any special precautions or existence of a
reducing agent. Hence, the process is convenient and
environmentally benign.
IR (KBr): ꢃ (cm ) 3238vs, 3120s, 3074m, 2959m, 2870m,
1
1
7
633w, 1550w, 1498w, 1464m, 1436m, 1377w, 1434m, 1219s,
132m, 1107w, 1063m, 1040s, 1017s, 861w, 846w, 805w,
69m, 747s, 711w, 679w, 652w. Anal. Calcd. for C H N O:
C, 64.99; H, 6.45; N, 20.68. Found: C, 64.96; H, 6.43; N, 20.87.
1-(2-Chlorobenzyl)-1H-1,2,3-triazol-4-yl)methanol (8a).
1
1
13
3
(
1
White solid, m.p. 110-112ºC. H NMR (300 MHz, CDCl ): ꢂ
3
2
7
.30 (b, 1H, OH), 4.72 (s, 2H, CH ), 5.59 (s, 2H, CH ), 7.15-
2
2
EXPERIMENTAL
.25 (m, 3H, C H ), 7.36-7.39 (m, 1H, C H ), 7.49 (s, 1H, CH).
6
4
6
4
1
3
C NMR (75.5 MHz, CDCl ): ꢂ 51.56, 56.49, 122.19, 127.75,
30.07, 130.43, 130.56, 132.47, 133.65. IR (KBr): ꢃ (cm )
3
1
13
H and C NMR spectra were recorded on a Bruker Avance
00 NMR spectrometer at ambient temperature and the chemical
ꢄ1
1
3
1
1
3
223vs, 3121m, 3072m, 2940m, 2867m, 1626w, 1549w, 1477m,
447m, 1376w, 1352w, 1224m, 1193w, 1122m, 1106w, 1041vs,
1
13
shifts of H and C NMR spectra are referenced to internal
solvent resonances. IR spectra were recorded on a Bruker
VECTOR-22 spectrometer. Elemental analyses were performed
by the Analytical Center of University of Science and
Technology of China. o-MeC H CH Cl, m-MeC H CH Cl,
016m, 861w, 837w, 802w, 759s, 681m.
Anal. Calcd. for
C H ClN O: C, 53.80; H, 4.52; N, 18.83. Found: C, 53.77; H,
4.51; N, 19.02.
1
0
10
3
6
4
2
6
4
2
1-Benzyl-4-phenoxymethyl-1H-1,2,3-triazole
(9a)
[1].
1
o-ClC H CH Cl, p-ClC H CH Cl, o-(ClCH ) C H , m-
White solid, m.p. 118-120ºC. H NMR (300 MHz, CDCl ): ꢂ
6
4
2
6
4
2
2
2
6
4
3
(
ClCH ) C H and PhOCH CꢀCH were prepared according to
5.12 (s, 2H, CH ), 5.47 (s, 2H, CH ), 6.88-6.91 (m, 3H, Ph),
7.19-7.31 (m, 7H, Ph), 7.50 (s, 1H, CH). C NMR (75.5 MHz,
2
2
6
4
2
2
2
1
3
reported procedures [12,13]. Other reagents were commercially
obtained and used without further purification.
General Procedure. A mixture of alkyl halide (5 mmol for
monohalides or 2.5 mmol for o- and m-bis(chloromethyl)-
CDCl ): ꢂ 54.18, 62.04, 114.82, 121.27, 122.70, 128.10, 128.78,
3
ꢄ1
129.13, 129.54, 134.56, 144.63, 158.25. IR (KBr): ꢃ (cm )
3133m, 3095w, 3065w, 3033w, 3012w, 2993vw, 2957vw,
2922m, 2872m, 1599vs, 1585s, 1560w, 1495vs, 1489vs, 1466s,
1456s, 1429m, 1384s, 1361w, 1351w, 1332m, 1292wm, 1243vs,
1222vs, 1179s, 1152m, 1120s, 1080s, 1054vs, 1030vs, 1006vs,
988vs, 890m, 857s, 818s, 757vs, 717vs, 705s, 694s, 640w,
benzene), alkyne (5 mmol), NaN (5 mmol) and CuX (X = I, Cl)
3
(0.01- 0.125 mmol) in distilled water (5 mL) was stirred at 65-
1
00ºC (bath temperature) for 5-24h. After cooling to room
temperature, the precipitate was collected by filtration and
washed successively with dilute NH OH (3 mL), cold water (2 ꢁ
614vw. Anal. Calcd. for C16
5.84. Found: C, 72.59; H, 5.53; N, 15.97.
1,1'-(o-Phenylenedimethylene)bis[4-phenyl-1H-1,2,3-
H N O: C, 72.43; H, 5.70; N,
15 3
4
1
5
mL) and petroleum ether (3 mL), and dried in air. In addition,
reactions carried out in tap water gave the same results.
-Benzyl-4-phenyl-1H-1,2,3-triazole (1a). Off-white solid,
1
triazole] (10a) [17,18]. White solid, m.p. 180-182ºC. H NMR
(300 MHz, CDCl ): ꢂ 5.64 (s, 4H, CH ), 7.25-7.35 (m, 10H,
1
1
m.p. 120-122ºC (lit. [14]: 126-127ºC). H NMR (300 MHz,
3
2
1
3
Ph+C H ), 7.48 (s, 2H, CH), 7.65-7.68 (m, 4H, Ph). C NMR
CDCl ): ꢂ 5.52 (s, 2H, CH ), 7.23-7.35 (m, 8H, Ph), 7.60 (s, 1H,
6
4
3
2
(
75.5 MHz, CDCl ): ꢂ 51.49, 119.85, 125.84, 128.42, 128.94,
CH), 7.73 (d, J = 7.3 Hz, 2H, Ph).
-(2-Methylbenzyl)-4-phenyl-1H-1,2,3-triazole (2a). White
3
ꢄ1
1
30.06, 130.32, 130.82, 133.49, 148.54. IR (KBr): ꢃ (cm )
3124m, 3080m, 3028m, 1609m, 1483m, 1463s, 1435m, 1357w,
221s, 1078s, 1045m, 977w, 941w, 814w, 765vs, 735vs, 695vs.
Anal. Calcd. for C H N : C, 73.45; H, 5.14; N, 21.41. Found:
1
1
powder, m.p. 94-95ºC (lit. [15]: 92-94ºC). H NMR (300 MHz,
1
CDCl ): ꢂ 2.25 (s, 3H, Me), 5.53 (s, 2H, CH ), 7.15-7.33 (m, 7H,
3
2
2
4
20
6
Ph+C H ), 7.47 (s, 1H, CH), 7.72 (d, J = 7.2Hz, 2H, Ph).
6
4
C, 73.26; H, 5.32; N, 21.45.
1
-(3-Methylbenzyl)-4-phenyl-1H-1,2,3-triazole (3a). White
1
1,1'-(m-Phenylenedimethylene)bis[4-phenyl-1H-1,2,3-
powder, m.p. 95-96ºC (lit. [15]: 200-202ºC). H NMR (300
1
triazole] (11a) [17,18]. White solid, m.p. 158-160ºC. H NMR
MHz, CDCl ): ꢂ 2.28 (s, 3H, Me), 5.47 (s, 2H, CH ), 7.03-7.36
3
2
(
300 MHz, CDCl ) ꢂ 5.51 (s, 4H, CH ), 7.21-7.36 (m, 10H,
3
2
(
m, 7H, Ph+C H ), 7.60 (s, 1H, CH), 7.74 (d, J = 7.4Hz, 2H,
6 4
13
Ph+C H ), 7.63 (s, 2H, CH), 7.72-7.75 (m, 4H, Ph). C NMR
6
4
Ph).
(
75.5 MHz, CDCl ) ꢂ 53.88, 119.77, 125.82, 127.47, 128.36,
3
1
-(2-Chlorobenzyl)-4-phenyl-1H-1,2,3-triazole (4a). White
ꢄ1
1
3
1
8
28.40, 128.97, 130.13, 130.46, 148.48. IR (KBr): ꢃ (cm )
130s, 3089m, 2923m, 2853vw, 1610m, 1483m, 1461m, 1435m,
356w, 1222m, 1192m, 1157vw, 1075s, 1048m, 976w, 915vw,
21w, 764vs, 742s, 695vs. Anal. Calcd. for C H N : C, 73.45;
1
powder, m.p. 90-91ºC (lit. [15]: 89-90ºC). H NMR (300 MHz,
CDCl ): ꢂ 5.72 (s, 2H, CH ), 7.26-7.440 (m, 7H, Ph+C H ), 7.77
3
2
6
4
(s, 1H, CH), 7.80-7.83 (m, 2H, Ph).
2
4
20
6
1
-(4-Chlorobenzyl)-4-phenyl-1H-1,2,3-triazole (5a). White
H, 5.14; N, 21.41. Found: C, 73.15; H, 5.31; N, 21.55.
-(2-Methylallyl)-4-phenyl-1H-1,2,3-triazole (12a). Yellowish
1
powder, m.p.143-144ºC (lit. [15]: 146-147ºC). H NMR (300
1
MHz, CDCl ): ꢂ 5.48 (s, 2H, CH ), 7.17-7.36 (m, 7H, Ph+C H ),
1
3
2
6
4
solid, m.p. 78-79ºC. H NMR (300 MHz, CDCl ): ꢂ 1.67 (s, 3H,
3
7
.59 (s, 1H, CH), 7.72 (d, J = 7.8Hz, 2H, Ph).
1-Benzyl-1H-1,2,3-triazol-4-yl)methanol (6a). Off-white
Me), 4.88 (s, 2H, CH ), 4.90 (s, 1H, =CH), 5.00 (s, 1H, =CH),
2
(
7
.24-7.30 (m, 1H, Ph), 7.36 (t, J = 7.1 Hz, 2H, Ph), 7.69 (s, 1H,
1
1
3
solid, m.p. 73-75ºC (lit.[16]: 76-77ºC). H NMR (300 MHz,
CH), 7.76-7.79 (m, 2H, Ph). C NMR (75.5 MHz, CDCl ) ꢂ
3
CDCl ): ꢂ 2.22 (b, 1H, OH), 4.75 (d, J = 4.3Hz, 2H, CH ), 5.50
3
2
19.78, 56.44, 115.50, 119.65, 125.78, 128.22, 128.89, 130.71,
139.51, 148.10. IR (KBr disk) ꢀ (cm ) 3126m, 3090w, 2980w,
ꢄ1
(
s, 2H, CH ), 7.24-7.37 (m, 5H, Ph), 7.42 (s, 1H).
2
(
1-(2-Methylbenzyl)-1H-1,2,3-triazol-4-yl)methanol (7a).
2925w, 2854w, 1656m, 1610w, 1462s, 1439vs, 1360w, 1225s,
1201m, 1156w, 1078m, 1049m, 1022w, 975w, 894s, 825m,
767vs, 696vs. Anal. Calcd. for C H N : C, 72.34; H, 6.58; N,
1
White powder, m.p. 116-118ºC. H NMR (300 MHz, CDCl ): ꢂ
.10 (t, J = 5.0 Hz, 1H, OH), 2.21 (s, 3H, Me), 4.68 (d, J =
.0Hz, 2H, CH ), 5.46 (s, 2H, CH ), 7.08-7.23 (m, 4H, C H ),
.25 (s, 1H, CH). C NMR (75.5 MHz, CDCl ): ꢂ 19.07, 52.45,
3
2
5
7
5
1
2
13
3
2
2
6
4
21.09. Found: C, 72.19; H, 6.41; N, 20.92.
1
3
3
Synthesis of 1-methyl-4-phenyl-1H-1,2,3-triazole (13a).
1
6.40, 121.72, 126.77, 129.29, 129.58, 131.15, 132.48, 137.03.
White powder, m.p. 126-127ºC (lit.[19]: 127ºC). H NMR (300