884 Yang et al.
Asian J. Chem.
νmax, cm-1): 3118, 1721, 1515, 1200, 1108. Elemental anal.
calc. (%) for C12H13N3O2 (Mr = 231.25): C 62.33, H 5.67, N
18.17; found (%): C 62.42, H 5.70, N 18.21.
peaks and holes are 1360 e/nm3 and -753 e/nm3, respectively.
S = 1.062 and (∆/s)max = 0.006. Atomic scattering factors and
anomalous dispersion correction were taken from International
Table for X-Ray Crystallography15. A summary of the key
crystallographic information is given in Table-1.
(1H-1,2,4-Triazol-1-yl)methyl 4-ethylbenzoate (3b):
Yield: 75 %; m.p.: 61-63 °C: 1H NMR (CDCl3, 600 MHz), δ:
8.49 (s, 1H, Tr-H), 7.99 (s, 1H, Tr-H), 7.69-7.26 (m, 4H, Ar -
H), 6.30 (s, 2H, Tr-CH2), 2.71(q, 2H, Ar-CH2), 1.25 (t, 3H,
CH3). IR (KBr, νmax, cm-1): 3101, 1717, 1514,1272, 1084. El-
emental anal. calc. (%) for C12H13N3O2 (Mr = 231.25): C 62.33,
H 5.67, N 18.17; found (%): C 62.45, H 5.72, N 18.26.
(1H-1,2,4-Triazol-1-yl)methyl 3-(2,4-dichlorophenyl)-
TABLE-1
CRYSTAL DATAAND STRUCTURE
REFINEMENT FOR THE COMPOUND 3c
Empirical formula
m.w.
C12H11N3O2Cl2
300.14
Crystal systerm
Space group
Monoclinic
P2(1)/c
1
propanoate (3c): Yield: 72.0 %; m.p.: 61-63 °C: H NMR
(CDCl3, 600 MHz), δ: 8.37 (s, 1H, Tr-H); 8.00 (s, 1H, Tr-H),
7.27-6.78 (m, 3H, Ar-H); 6.18 (s, 2H, Tr-CH2), 4.66-4.65 (m,
4H,Ar-CH2CH2). IR (KBr, νmax, cm-1): 3125, 1738, 1516, 1252,
1092. Elemental anal. calc. (%) for C12H11N3O2Cl2 (Mr =
300.14): C 48.02, H 3.69, N 14.00; found (%): C 48.13, H
3.73, N 14.38.
Unit cell dimensions
a = 1.0814(2) nm α = 90º
b = 0.64514(13) nm β = 101.05(3)º
c = 1.8698(4) nm γ = 90º
1.2802(4) nm3
Volume
Z, Calculated density
Absorption coefficient
Crystal size
4, 1.557 Mg/m3
0.508 mm-1
0.74 × 0.22 × 0.05 mm
616
1.92º to 27.36º
(1H-1,2,4-Triazol-1-yl)methyl 2-(4-bromophenoxy)-
acetate (3d): Yield: 68.0 %; m.p.: 165-167 °C: 1H NMR (CDCl3,
600 MHz), δ: 8.51 (s, 1H, Tr-H), 8.02 (s, 1H, Tr-H), 7.29-6.77
(m, 4H, Ar-H), 6.17 (s, 2H, Tr-CH2), 4.67 (s, 2H, ArO-CH2).
IR (KBr, νmax, cm-1): 3132, 1728, 1510, 1269, 1089. Elemental
anal. calc. (%) for C11H10N3O3Br (Mr = 311.00): C 42.33, H
3.23, N 13.46; found (%): C 42.45, H 3.17, N 13.39.
(1H-1,2,4-Triazol-1-yl)methyl 2-(4-nitrophenoxy)-
F(000)
θ angle for data collection
Limiting indices
-13 ≤ h ≤ 3, -8 ≤ k ≤ 8, -24 ≤ l ≤ 23
Reflections collected/ unique 11868 / 2899 [R(int) = 0.0427]
Data/restraints/parameters
Final R indices [I>2σI)]
Largest diff. peak and hole
2899 / 0 / 172
R1 = 0.0700, wR2 = 0.2202
1360 e/nm3 and -753 e/nm3
1
acetate (3e): Yield: 65.5 %; m.p.: 120-121°C: H NMR
RESULTS AND DISCUSSION
(CDCl3, 600 MHz), δ: 8.40 (s, 1H, Tr-H), 8.03 (s, 1H, Tr-H),
7.42-6.74 (m, 4H, Ar-H), 6.30 (s, 2H, Tr-CH2), 4.71 (s, 2H,
ArO-CH2). (KBr, νmax, cm-1): 3124, 1760, 1512, 1188, 1074.
Elemental anal. calc. (%) for C11H10N4O5 (Mr = 278.07): C
47.49, H 3.62, N 20.14; found (%): C 47.40, H 3.71, N 20.08.
(1H-1,2,4-Triazol-1-yl)methyl 2-(4-chlorophenoxy)-
Design idea of the target compounds: The triazole com-
pounds inducting ester group, reported in literature16-18, are
mostly oxime esters that are prepareed by means of α-triazolyl
ketoxime reacting with acyl chloride. Also, some of them are
obtained via triazole reacting with halogenated aliphatic ester.
We made (1H-1,2,4-triazol-1-yl)methanol (intermediates 1)
react with aryl chlorides (intermediates 2) to get six novel
triazole compounds containing ester group. The structure of
the synthetical compounds is reported for the first time although
the synthesis method is classical.
Spectral characterization of the target compounds:The
1H NMR, IR, elemental analysis results for the target comp-
ounds are good agreement with their structure. In the IR
spectrum, there are medium or weak absorption bands for the
benzene ring and the triazole ring at 3100 cm-1. The strong
absorption at 1760-1717, 1272-1188 and 1108-1074 cm-1 are
attributed to C=O and C-O-C stretching vibration absorption
in the ester group, respectively. In the 1H NMR spectrum, the
chemical shifts for the two protons of the triazole ring appears
at 8.51-8.37 and 8.03-7.99, respectively. The chemical shifts
for the two protons of the CH2 group connecting with a triazole
ring at 6.30-6.17. The chemical shifts for the protons of the
benzene ring at 7.69-6.74.
1
acetate (3f): Yield: 86.5 %; m.p.: 146-150 °C: H NMR
(CDCl3, 600 MHz), δ: 8.37 (s, 1H, Tr-H), 8.00 (s, 1H, Tr-H),
7.27-6.78 (m, 4H, Ar-H), 6.17 (s, 2H, Tr-CH2), 4.65 (s, 2H,
ArO-CH2). IR (KBr, νmax, cm-1): 3123, 1756, 1518, 1193,
1078. Elemental anal. calc. (%) for C11H10N3O3Cl (Mr =
267.04): C 49.36, H 3.77, N 15.70; found (%): C 49.45, H
3.63, N 15.62.
X-ray crystallographic analysis: The single crystal of
the compound 3c was obtained from a methanol solution by
slow evaporation at room temperature. The colorless crystal
with the dimension 0.74 mm × 0.22 mm × 0.05 mm was
selected for X-ray diffraction analysis. The data was collected
by Rigaku R-axis Rapid IPArea Detector diffractometer using
graphite monochromated MoKα radiation (λ = 0.071073 nm),
in the range 1.92º < θ < 27.36º, 2899 independent reflections
were obtained.
The structure was solved by direct methods using SHELXS-
97 program14. All the non-hydrogen atoms were refined on F2
anistropically by full-matrix least squares method. Hydrogen
atoms were located from the difference Fourier map and added
to the structure calculation, but their positions were not refined.
The contributions of these hydrogen atoms were included in
structure-factor calculations. The final least-square cycle gave
R1 = 0.0700, ωR2 = 0.2202 for 2185 reflections with I > 2σ(I);
The weighting scheme, ω = 1/[σ2 (Fo2) + (0.1466P)2 + 1.164P],
where P = (F2o + 2F2c)/3. The maximum and minimum difference
Description of the crystal structure of the compound 3c:
Fig. 1 and 2 show the molecular structure and the perspective
view of the crystal packing in the unit cell of the compound
3c. The selected bond lengths, angles and hydrogen-bonding
geometry of compound 3c are listed in Tables 2 and 3, respec-
tively.
The compound of 3c crystallizes as monoclinic system.
The bond lengths and angles are generally normal in the phenyl