Synthesis and characterization of novel arylaldehyde (arylketone)-(4- substituted phenyl-5-substituted phenoxy-methyl-4H-1,2,4-triazole-3-yl)-thiol acetyl hydrazones

Article abstract of DOI:10.1002/jccs.200900172

Fourteen novel arylaldehyde (arylketone)-(4-substituted phenyl-5-substituted phenoxy-methyl-4H-1,2,4-triazole-3-yl)-thiol acetyl hydrazone derivatives (5a-5g, 6a-6g) were synthesized by 4-substituted phenyl-5-substituted phenoxy-methyl-1,2,4-triazole-3-th

Full text of DOI:10.1002/jccs.200900172

Journal of the Chinese Chemical Society, 2009, 56, 1191-1197
1191
Synthesis and Characterization of Novel Arylaldehyde
(Arylketone)-(4-substituted phenyl-5-substituted
phenoxy-methyl-4H-1,2,4-triazole-3-yl)-thiol Acetyl Hydrazones
Heng-Wen Zhang (
Hai-Long Li (
Key Laboratory of Oil and Gas Fine Chemicals of Ministry of Education,
), Yan-Ping Li* (
), Chen-Jiang Liu (
),
) and Wen-Li Sun (
)
College of Chemistry and Chemical Engineering, Xinjiang University, Urumqi Xinjiang 830046, P. R. China
Fourteen novel arylaldehyde (arylketone)-(4-substituted phenyl-5-substituted phenoxy-methyl-4H-
1,2,4-triazole-3-yl)-thiol acetyl hydrazone derivatives (5a-5g, 6a-6g) were synthesized by 4-substituted
phenyl-5-substituted phenoxy-methyl-1,2,4-triazole-3-thione as starting material according to substruc-
ture link principle, followed by thioetherification, hydrazide hydrazone reaction. The structures of these
compounds were confirmed by IR, 1H NMR and elemental analysis. Crystal structure of compounds 1b
and 6d were determined by the X-ray diffraction.
Keywords: Hydrazone derivatives; 1,2,4-Triazole; Synthesis; Crystal structureas.
Scheme I
INTRODUCTION
Acyl hydrazone is a special type of schiff base, it has
been shown to exhibit a variety of interesting biological ac-
tions, including pesticide, antibacterial, anticancer, antimi-
crobial, herbicidal and anti-trypanosome activities1-6 due to
the presence of (-CONHN=CH-) moiety. It is also exten-
sively used in coordination chemistry and the metal com-
plexes and it was reported to possess excellent physical and
chemical properties,7-9 which is the hotspot in medicine and
materials chemistry areas. In addition, 1,2,4-triazoles have
been reported to possess antibacterial, antifungal, antitu-
bercular, antiviral, herbicidal, antihypertensive and insecti-
cidal properties.10-15
arylaldehyde. The datas of physical properties and elemen-
tal analysis of all new compounds are listed in Table 1.
In the IR spectra, all new compounds exhibited me-
dium-strong bands at 3200-3100 cm-1, which assigned to
their N-H stretches. The strong bands appeared at around
3000 cm-1 were assigned to the group of phenyl and the
strong bands appeared at around 1680 cm-1 were assigned
to the carbonyl group. The bands appeared at around 1620
cm-1 were assigned to the C=N in triazole ring.
In the 1H NMR spectra, because of coupling with the
carbonyl, the proton of NH appeared at around d 11.7. The
signal of N=CH appeared at around d 8.2, multiple peaks at
d 6.7-8.0 ascribable to aromeric protons, the signal of
OCH2 appeared at around d 5.0 and S-CH2 appeared at
around d 3.9, the signal of methyl group protons which
Some compounds consisting of 1,2,4-triazole rings
and acyl hydrazone moiety which have been synthesized
by Bayrak16 showed antimicrobial activities. Prompted by
these observations we designed the synthesis of a series of
novel arylaldehyde (arylketone)-(4-substituted phenyl-5-
substituted phenoxy-methyl-4H-1,2,4-triazole-3-yl)-thiol
acetyl hydrazones (5a-5g, 6a-6g) and two single-crystal
structures of compounds 1b and 6d were obtained. The
route of synthesis is shown in Scheme I.
RESULTS AND DISCUSSION
In the process of the synthesis of these all new com-
pounds, we found that the reaction of acetyl hydrazine with
the arylketone could take more time than reaction with the

1192 J. Chin. Chem. Soc., Vol. 56, No. 6, 2009
Zhang et al.
Table 1. Physical datas and Elemental analysis of compounds
Elemental analysis (Calcd.)/%
H
Yield
(%)
No
Formula
m.p. /°C
C
N
1a
1b
2a
2b
3a
3b
5a
5b
5c
5d
5e
5f
C15H12ClN3OS
C17H17N3OS
C19H18ClN3O3S
C21H23N3O3S
C18H20ClN5O2S
C19H21N5O2S
C24H20ClN5O2S
C22H18ClN5O3S
C26H22ClN5O2S
C24H20ClN5O3S
C26H20BrClN8O2S
C25H22ClN5O2S
C26H24ClN5O3S
C26H25N5O2S
84
99
80
76
80
84
80
70
86
80
75
80
72
74
70
83
97
77
80
82
176-177
178-179
96-97
56.71 (56.69)
65.61 (65.57)
56.52 (56.50)
63.43 (63.45)
53.22 (53.26)
59.52 (59.51)
60.30 (60.31)
56.44 (56.47)
61.96 (61.96)
58.38 (58.36)
50.04 (50.05)
61.03 (61.03)
59.84 (59.82)
66.23 (66.22)
62.44 (62.46)
67.59 (67.58)
64.03 (64.05)
54.44 (54.46)
66.77 (66.78)
65.24 (65.22)
3.85 (3.84)
5.45 (5.46)
4.48 (4.49)
5.84 (5.83)
4.96 (4.97)
5.52 (5.52)
4.21 (4.22)
3.89 (3.88)
4.41 (4.40)
4.07 (4.08)
3.22 (3.23)
4.50 (4.51)
4.62 (4.63)
5.35 (5.34)
5.03 (5.02)
5.48 (5.47)
5.18 (5.17)
4.08 (4.08)
5.61 (5.60)
5.66 (5.67)
13.29 (13.22)
13.54 (13.49)
10.39 (10.40)
10.58 (10.57)
17.31 (17.28)
18.25 (18.26)
14.67 (14.65)
14.99 (14.97)
13.92 (13.90)
14.17 (14.18)
17.99 (17.96)
14.24 (14.23)
13.41 (13.42)
14.84 (14.85)
15.19 (15.17)
14.06 (14.07)
14.38 (14.36)
18.17 (18.15)
14.41 (14.42)
13.57 (13.58)
84-85
177-179
147-148
148-149
144-146
180-181
191-192
202-203
175-176
133-135
186-187
168-169
174-176
194-195
202-203
167-168
205-206
5g
6a
6b
6c
6d
6e
6f
C24H23N5O3S
C28H27N5O2S
C26H25N5O3S
C28H25BrN8O2S
C27H27N5O2S
6g
C28H29N5O3S
connect with benzene ring appeared at around d 2.3. The
datas of the 1H NMR and IR spectra of the new compounds
are listed in Table 2.
shown in Fig. 3. The packing diagram of the unit cell of
compound 1b is shown in Fig. 2, and 6d is shown in Fig. 4.
Complete crystallographic datas for the structural analysis
of compounds have been deposited in the Cambridge Crys-
tallographic Data Centre, CCDC numbers of 1b and 6d
were 710323, 730920 respectively.
Two single crystals of compounds 1b and 6d were
gained by slow evaporation of solvent in their diluted etha-
nol and trichloromethane solution. The datas of crystals of
the compounds are listed in Table 3, Table 4 and Table 5.
The molecular structure of 1b is shown in Fig. 1, and 6d is
X-ray single crystal diffraction analysis indicates that
the crystal 1b belongs to triclinic system with space group
P-1, Atoms in triazole rings [N(1), N(2), C(10), N(3), C(9)]
Fig. 1. Molecular structure of compound 1b. The
bonds length (Å): S(1)-C(10), 1.6988(18);
N(2)-C(10), 1.515(2).
Fig. 2. Packing diagram of the unit cell of compound
1b. Two intermolecular hydrogen bonds are
shown.

1,2,4-Triazole-3-yl-thiol Acetyl Hydrazones
Table 2. 1H NMR, IR data of compounds
J. Chin. Chem. Soc., Vol. 56, No. 6, 2009 1193
No.
1H NMR ä
IR (KBr) n/cm-1
1a 11.40 (s, br, 1H, S-H), 7.42-6.87 (m, 9H, Ar-H), 4.91 (s, 2H, CH2)
3075, 3020, 2890, 2550, 1590
1b 11.38 (s, br, 1H, S-H), 7.42-6.46 (m, 8H, Ar-H), 4.52 (s, 2H, CH2), 2.28 (s, 3079, 3032, 2891, 2593, 1583
3H, CH3), 2.17 (s, 3H, CH3)
2a 7.32-6.78 (m, 9H, Ar-H), 5.00 (s, 2H, OCH2), 4.21 (q, 2H, COOCH2), 4.07 (s,
2H, SCH2), 1.28 (t, 3H, CH3)
3041, 1746, 1610
3044, 1745, 1614
2b 7.31-6.77 (m, 8H, Ar-H), 5.01 (s, 2H, OCH2), 4.20 (q, 2H, COOCH2), 4.08 (s,
2H, SCH2), 2.42 (s, 3H, CH3), 2.26 (s, 3H, CH3), 1.27 (t, 3H, CH3)
3a 6.86-7.50 (m, 9H, Ar-H), 5.05 (s, 2H, OCH2), 3.86 (s, 2H, SCH2)
3b 6.87-7.53 (m, 8H, Ar-H), 5.07 (s, 2H, OCH2), 3.89 (s, 2H, SCH2), 2.44 (s, 3H,
CH3), 2.27 (s, 3H, CH3)
3331, 3241, 1680, 1619
3333, 3245, 1681, 1621
5a 11.70 (s, 1H, NH), 8.19 (s, 1H, N=CH), 6.74-7.80 (m, 14H, Ar-H), 5.03 (s,
2H, OCH2), 3.96 (s, 2H, SCH2)
5b 11.80 (s, 1H, NH), 8.22 (s, 1H, N=CH), 6.72-7.55 (m, 12H, Ar-H and furan-
CH), 5.01 (s, 2H, OCH2), 3.98 (s, 2H, SCH2)
5c 11.48 (s, 1H, NH), 7.92 (s, 1H, N=CH), 6.85-7.52 (m, 16H, Ar-H and
CH=CH), 5.07 (s, 2H, OCH2), 3.93 (s, 2H, SCH2)
5d 11.82 (s, 1H, NH), 11.15 (s, 1H, OH), 8.17 (s, 1H, N=CH), 6.87-7.36 (m, 13H,
Ar-H), 5.04 (s, 2H, OCH2), 3.92 (s, 2H, SCH2)
3190, 3076, 1685, 1620
3186, 3005, 1674, 1625
3177, 3000, 1681, 1622
3270, 3069, 1679, 1618
3178, 3061, 1681, 1624
3190, 3076, 1685, 1614
3201, 3069, 1692, 1620
3190, 3076, 1685, 1616
3186, 3005, 1674, 1619
3177, 3000, 1681, 1628
5e 11.81 (s, 1H, NH), 8.40 (s, 1H, triazole-CH), 8.32 (s, 1H, N=CH), 6.82-7.99
(m, 13H, Ar-H), 5.08 (s, 2H, OCH2), 3.94 (s, 2H, SCH2)
5f
11.33 (s, 1H, NH), 8.6 (s, 1H, N=CH), 6.81-7.98 (m, 14H, Ar-H), 5.07 (s, 2H,
OCH2), 3.98 (s, 2H, SCH2), 2.41 (s, 3H, CH3)
5g 11.33 (s, 1H, NH), 8.5 (s, 1H, N=CH), 6.81-7.98 (m, 13H, Ar-H), 5.07 (s, 2H,
OCH2), 3.96 (s, 2H, SCH2), 2.40 (s, 3H, OCH3), 2.25 (s, 3H, CH3)
6a 11.65 (s, 1H, NH), 8.15 (s, 1H, N=CH), 6.76-7.79 (m, 13H, Ar-H), 5.02 (s,
2H, OCH2), 3.94 (s, 2H, SCH2), 2.43 (s, 3H, CH3), 2.26 (s, 3H, CH3)
6b 11.80 (s, 1H, NH), 8.12 (s, 1H, N=CH), 6.69-7.52 (m, 11H, Ar-H and furan-
CH), 5.02 (s, OCH2), 4.00 (s, 2H, SCH2), 2.44 (s, 3H, CH3), 2.26 (s, 3H, CH3)
6c 11.52 (s, 1H, NH), 8.02 (s, 1H, N=CH), 6.75-7.51 (m, 15H, Ar-H and
CH=CH), 5.03 (s, 2H, OCH2), 3.90 (s, 2H, SCH2), 2.43 (s, 3H, CH3), 2.26 (s,
3H, CH3)
6d 11.84 (s, 1H, NH), 6.77-7.34 (m, 12H, Ar-H), 5.03 (s, 2H, OCH2), 2.27 (s, 3H,
CH3), 3.92 (s, 2H, SCH2), 2.43 (s, 3H, CH3), 2.27 (s, 3H, CH3)
6e 11.80 (s, 1H, NH), 8.32 (s, 1H, triazole-CH), 8.12 (s, 1H, N=CH), 6.88-7.99
(m, 12H, Ar-H), 5.05 (s, 2H, OCH2), 3.92 (s, 2H, SCH2), 2.45 (s, 3H, CH3),
2.26 (s, 3H, CH3)
3270, 3069, 1694, 1616
3268, 3065, 1692, 1621
6f
11.21 (s, 1H, NH), 6.84-8.02 (m, 13H, Ar-H), 5.04 (s, 2H, OCH2), 3.92 (s, 2H,
SCH2), 2.41 (s, 3H, CH3), 2.33 (s, 3H, CH3)
3274, 3064, 1690, 1617
3271, 3073, 1695, 1622
6g 11.36 (s, 1H, NH), 6.81-7.80 (m, 12H, Ar-H), 5.01 (s, 2H, OCH2), 3.83 (s, 2H,
SCH2), 2.41 (s, H, OCH3), 2.24 (s, 3H, CH3)
…
…
…
are quite planar, and the deviation from the least squares
plane through the ring atom is 0.0039 Å, the plane equation
is 4.440 x + 3.447 y + 13.541 z = 6.9493. And atoms in ben-
zene ring [C(11), C(12), C(14), C(15), C(16), C(17)] are
also quite planar, the deviation from the least squares plane
through the ring atom is 0.0011 Å, the plane equation is
0.748 x + 6.425 y – 2.350 z = 1.4534. The dihedral angle
between the plane of triazole group and the plane of the
benzene ring [C(11), C(12), C(14), C(15), C(16), C(17)] is
92.2°. Some kinds of hydrogen bonds of intermolecular
H-bond (C-H S, N-H S and C-H N) exist in the crys-
tal lattice, and the structure is stabilized by the hydrogen
bond. The molecule exists in the thione tautomeric form
with an S(1)–C(10) distance of 1.6988(18) Å, which indi-
cates substantial double bond character whereas bond
N(2)–C(10) distance of 1.515(2) Å is typical for a single
bond. Bond lengths observed in the thione fragment are in
agreement with the values found in analogues com-
pounds.17,18
X-ray single crystal diffraction analysis indicates that

1194 J. Chin. Chem. Soc., Vol. 56, No. 6, 2009
Zhang et al.
Table 3. Crystal data and structure refinement for 1b and 6d
Compound
1b
6d
Empirical formula
Formula weight
Temperature
C17H17N3OS
311.40
293(2) K
C26H25N5O3S
487.57
293(2) K
Wavelength
Crystal system, space group
0.71073 Å
triclinic, P-1
0.71073 Å
triclinic, P-1
a = 10.060(2) Å,
b = 11.077(2) Å,
c = 21.546(4) Å
a = 90.00(3)°,
b = 90.04(3)°,
g = 90.00(3)°
2401.0(8) Å3
4, 1.349 Mg/m3
0.174 mm-1
1024
a = 7.4017(15) Å,
b = 7.4516(15) Å,
c = 16.587(3) Å
a = 77.08(3)°,
Unit cell dimensions
b = 88.40(3)°,
g = 62.17(3)°
Volume
785.5(3) Å3
Z, Calculated density
Absorption coefficient
F(000)
2, 1.317 Mg/m3
0.211 mm-1
328
Crystal size
Theta range for data collection
0.79 ´ 0.54 ´ 0.18 mm
3.12 to 30.69 deg
-8 £ h £ 9, -9 £ k £9,
-21 £ l £ 21
0.241 ´ 0.188 ´ 0.034 mm
3.32 to 27.47 deg
-12 £ h £ 11, -14 £ k £ 14,
-27 £ l £ 27
Limiting indices
Reflections collected / unique
Completeness to theta = 27.47
Refinement method
Data / restraints / parameters
Goodness-of-fit on F2
7751 / 3568 [R(int) = 0.0208]
73.3%
20485 / 10214 [R(int) = 0.0839]
92.9%
Full-matrix least-squares on F2
3568 / 0 / 225
Full-matrix least-squares on F2
10214 / 0 / 772
1.079
0.901
Final R indices [I > 2sigma(I)]
R indices (all data)
Extinction coefficient
R1 = 0.0447, wR2 = 0.1296
R1 = 0.0483, wR2 = 0.1330
0.086(8)
R1 = 0.0707, wR2 = 0.0839
R1 = 0.2032, wR2 = 0.1092
0.0035(3)
Largest diff. peak and hole
0.393 and -0.446 e.Å-3
0.215 and -0.189 e.Å-3
Table 4. Selected bond lengths (Å) for the compound 1b and 6d
1b
S(1)-C(10)
N(1)-N(2)
N(1)-C(9)
N(2)-C(10)
1.6988(18)
1.3375(19)
1.409(2)
N(3)-C(9)
N(3)-C(10)
N(3)-C(17)
O(1)-C(7)
1.481(2)
1.342(2)
1.608(2)
1.2630(19)
O(1)-C(8)
C(3)-C(4)
C(8)-C(9)
C(14)-C(13)
1.518(2)
1.382(3)
1.430(2)
1.684(3)
1.515(2)
6d
S(1)-C(17)
S(1)-C(18)
O(1)-C(7)
O(1)-C(8)
O(2)-C(19)
O(3)-C(26)
N(2)-N(3)
1.740(3)
1.797(4)
1.383(5)
1.424(5)
1.218(3)
1.374(4)
1.409(3)
N(4)-N(5)
N(1)-C(9)
N(1)-C(10)
N(1)-C(17)
N(2)-C(9)
N(3)-C(17)
N(4)-C(19)
1.382(3)
1.367(4)
1.442(4)
1.372(4)
1.299(4)
1.305(4)
1.351(4)
N(5)-C(20)
C(3)-C(4)
C(8)-C(9)
C(13)-C(14)
C(18)-C(19)
C(20)-C(21)
1.269(4)
1.516(6)
1.499(5)
1.509(5)
1.502(5)
1.459(4)
the crystal 6d belongs to triclinic system with space group
P-1, Atoms in triazole rings [N(1), C(9), N(2), N(3), C(17)]
are quite planar, the deviation from the least squares plane
through the ring atom is 0.0032 Å, the plane equation is
0.794 x – 1.940 y + 15.425 z = 6.5830. And atoms in ben-
zene ring [C(10), C(11), C(12), C(14), C(15), C(16)] are
also quite planar, the deviation from the least squares plane
through the ring atom is 0.0039 Å, the plane equation is
-6.662 x – 2.480 y + 15.419 z = 3.3448. The dihedral angle
between the plane of triazole group and the plane of the

1,2,4-Triazole-3-yl-thiol Acetyl Hydrazones
J. Chin. Chem. Soc., Vol. 56, No. 6, 2009 1195
Table 5. Selected bond angles (°) for the compound 1b and 6d
1b
S(1) -C(10)-N(2)
S(1)-C(10)-N(3)
O(1)-C(7)-C(1)
O(1)-C(7)-C(6)
O(1)-C(8)-C(9)
N(1)-N(2)-C(10)
N(2)-N(1)-C(9)
133.05(12)
118.83(14)
110.47(16)
119.84(16)
108.81(14)
115.55(14)
96.52(14)
N(1)-C(9)-N(3)
N(2)-C(10)-N(3)
N(1)-C(9)-C(8)
N(3)-C(17)-(11)
N(3)-C(17)-(16)
N(3)-C(9)-C(8)
C(7)-O(1)-C(8)
120.62(13)
108.13(14)
120.68(16)
129.28(13)
118.67(15)
118.68(16)
114.08(14)
C(10)-N(3)-C(9)
C(9)-N(3)-C(17)
C(10)-N(3)-C(17)
C(2)-C(4)-C(3)
C(12)-C(14)-C(13)
C(13)-C(14)-C(15)
99.17(14)
135.14(12)
125.62(14)
114.4(2)
121.32(17)
129.87(15)
6d
S(1)-C(17)-N(1)
S(1)-C(17)-N(3)
S(1)-C(18)-C(19)
O(1)-C(7)-C(1)
O(1)-C(7)-C(6)
O(1)-C(8)-C(9)
O(2)-C(19)-N(4)
O(2)-C(19)-C(18)
O(3)-C(26)-C(21)
O(3)-C(26)-C(25)
N(1)-C(9)-N(2)
N(1)-C(17)-N(3)
121.1(3)
127.6(3)
109.0(3)
125.9(4)
114.9(4)
113.2(4)
123.6(3)
123.8(3)
122.2(3)
117.9(3)
111.3(3)
111.2(3)
N(2)-N(3)-C(17)
N(3)-N(2)-C(9)
N(4)-N(5)-C(20)
N(5)-N(4)-C(19)
N(1)-C(9)-C(8)
N(1)-C(10)-C(11)
N(1)-C(10)-C(16)
N(2)-C(9)-C(8)
N(4)-C(19)-C(18)
N(5)-C(20)-C(21)
C(17)-S(1)-C(18)
C(7)-O(1)-C(8)
106.4(3)
107.1(3)
119.0(3)
117.7(3)
125.1(3)
120.0(3)
119.9(3)
123.5(3)
112.6(3)
119.9(3)
96.84(17)
117.7(3)
C(9)-N(1)-C(10)
C(9)-N(1)-C(17)
C(10-N(1)-C(17)
C(7)-O(1)-C(8)
C(2)-C(4)-C(3)
C(3)-C(4)-C(5)
C(12)-C(14)-C(13)
C(13)-C(14)-C(15)
C(20)-C(21)-C(22)
C(20)-C(21)-C(26)
130.6(3)
104.0(3)
125.4(3)
117.7(3)
121.9(4)
121.0(5)
122.0(4)
120.7(4)
119.6(3)
121.7(3)
analogues compounds.22
EXPERIMENTAL
General Method
The 1H NMR spectra were recorded on an Inova-400
(using TMS as internal standard, CDCl3 as solvent). The IR
spectra were recorded in KBr pellets on a Bruker FT-IR
Equinox apparatus. Elemental analyses were performed on
a Thermo Flash EA-1112 analyzer. Melting points were
measured on a Büchi B-540 and were uncorrected. The
boiling point range of petroleum ether was 60-90 °C. The
TLC was performed by GF254 and 0.5% CMC. X-ray sin-
gle-crystal diffraction datas for compounds 1b and 6d
were collected on a Bruker Smart 1000 CCD diffractome-
ter at 293(2) K with Mo-Ka radiation (l = 0.71073 Å) by
w-j scan mode. The structures were solved by direct meth-
ods using the SHELXS program of the SHELXTL package
and refined by full-matrix least-squares methods with
SHELXL.
Fig. 3. Molecular structure of compound 6d. The
bonds length (Å): C(19)-O(2), 1.218(3); N(5)-
C(20), 1.269(4): N(4)-C(19), 1.351(4); C(20)-
C(21), 1.459(4); O(3)-C(26), 1.374(4).
benzene ring [C(10), C(11), C(12), C(14), C(15), C(16)] is
84°. In the crystal lattice, there exist some intermolecular
…
…
…
hydrogen bonds (C-H N, N-H O and C-H O hydro-
gen bonds) interactions, and the structure is stabilized by
the hydrogen bond.19-21 The bonds C(19)–O(2) of 1.218(3)
Å and N(5)–C(20) Å of 1.269(4) have a double bond char-
acter, whereas bonds N(4)-C(19) of 1.351(4) Å, C(20)-
C(21) of 1.459(4) Å and O(3)-C(26) of 1.374(4) Å are typi-
cal for a single bond. Bond lengths observed in the hydra-
zones fragment are in agreement with the values found in
1. Preparation of 4-substituted phenyl-5-substituted
phenoxy-methyl-4H-1,2,4-triazole-3-thione (1a, 1b)
A solution of corresponding thiosemicarbazide (10
mmol) in 2 N NaOH was refluxed for 5 h. The resulting so-
lution was cooled to room temperature and acidified to pH
3-4 with 33% HCl. The precipitate formed was filtered,

1196 J. Chin. Chem. Soc., Vol. 56, No. 6, 2009
Zhang et al.
Fig. 4. Packing diagram of the unit cell of compound 6d. Four intermolecular hydrogen bonds are shown.
washed with water and recrystallized from ethanol to af-
ford the desired compounds.
aldehyde (aryketone) (4a-4g) (1 mmol) for 5-20 h. After
cooling the mixture to room temperature, a white solid ap-
peared. This crude product was recrystallized from ethanol
to afford the desired products.
2. Preparation of (4-substituted phenyl-5-substituted
phenoxy-methyl-4H-1,2,4-triazol-3-yl)-thiol ethyl
acetate (2a, 2b)
The physical datas of new compounds are listed in
Table 1. The datas of 1H NMR and IR are listed in Table 2.
To a mixture of 1 (2 mmol) and ethyl chloroacetate
(2.5 mmol) in ethanol (30 mL), KOH (132 mg, in 10 mL
H2O) was added slowly. The mixture was stirred at room
temperature overnight, H2O was added and the separated
solid was filtered off, washed with water and crystallized
from ethanol to afford the desired compounds.
3. Preparation of (4-substituted phenoxy-5-substituted
phenoxy-methyl-4H-1,2,4-triazol-3-yl)-thiol acetohy-
drazide (3a, 3b)
Received May 21, 2009.
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