Synthesis and fungicidal activity of 5-aryl-1-(aryloxyacetyl)-3-(tert-butyl or phenyl)-4-(1h-1,2,4-triazol-1-yl)-4,5-dihydropyrazole

Article abstract of DOI:10.1002/jhet.934

A series of novel 5-aryl-1-(aryloxyacetyl)-3-(tert-butyl or phenyl)-4-(1H-1,2,4-triazol-1-yl)-4,5-dihydropyrazole - were synthesized by the annulation of 2-aryloxyacetohydrazides with 3-aryl-1-t-butyl (or phenyl)-2-(1H-1,2,4-triazol-1-yl)prop-2-en-1-ones

Full text of DOI:10.1002/jhet.934

216
Synthesis and Fungicidal Activity of 5‐Aryl‐1‐(aryloxyacetyl)‐3‐
(tert‐butyl or phenyl)‐4‐(1H‐1,2,4‐triazol‐1‐yl)‐4,5‐
Vol 50
dihydropyrazole
a
Hui‐Yu Mao,a,b Hong Song,a,b and De‐Qing Shi
*
aKey Laboratory of Pesticide & Chemical Biology of Ministry of Education, College of Chemistry,
Central China Normal University, Wuhan 430079, People’s Republic of China
bWuhan Bioengineering Institute, Yangluo District, Wuhan 430415, People’s Republic of China
*
E-mail: chshidq@mail.ccnu.edu.cn
Received December 17, 2010
DOI 10.1002/jhet.934
Published online 7 March 2013 in Wiley Online Library (wileyonlinelibrary.com).
A series of novel 5‐aryl‐1‐(aryloxyacetyl)‐3‐(tert‐butyl or phenyl)‐4‐(1H‐1,2,4‐triazol‐1‐yl)‐4,5‐dihydro-
pyrazole 3a–3n were synthesized by the annulation of 2‐aryloxyacetohydrazides with 3‐aryl‐1‐t‐butyl (or
phenyl)‐2‐(1H‐1,2,4‐triazol‐1‐yl)prop‐2‐en‐1‐ones (2) in the presence of a catalytic amount of acetic acid.
Compounds 2 were obtained by the Knoevenagel reactions of 1‐t‐butyl (or phenyl)‐2‐(1H‐1,2,4‐triazol‐1‐
yl)ethanone (1) with aromatic aldehydes in the presence of piperidine. Their structures were confirmed by
1
IR, H‐NMR, ESI‐MS, and elemental analyses. The preliminary bioassay indicated that some compounds
displayed moderate to excellent fungicidal activity. For example, compounds 3l, 3m, and 3n possessed
100% inhibition against Cercospora arachidicola Hori at the concentration of 50 mg/L.
J. Heterocyclic Chem., 50, 216 (2013).
INTRODUCTION
ethanol medium at room temperature afforded 5‐aryl‐1‐
(aryloxyacetyl)‐3‐(tert‐butyl or phenyl)‐4‐(1H‐1,2,4‐triazol‐
1‐yl)‐4,5‐dihydropyrazole 3 in moderate to excellent yields.
Their structures were deduced from their spectral data
(IR, 1H‐NMR, and ESI‐MS) and elemental analyses, which
were listed in the experimental part. In the 1H‐NMR spectra of
3, the t‐butyl protons displayed as a singlet with chemical shift
δ between 0.79 and 1.21; the methylene protons showed as a
singlet, sometimes as AB system with chemical shifts δ 4.4,
the two methine protons of pyrazoline ring exhibited as two
doublets with coupling constants of about 9.0 Hz in δ 4.8
and 5.7, respectively; whereas the 1,2,4‐triazole protons
showed two singlets with chemical shifts δ 8.0 and 8.6,
respectively. IR spectra of compounds 3 showed normal
stretching absorption bands, indicating the existence Ar‐H
(~2960 cm−1), C═O (~1690 cm−1), C═N (~1640 cm−1),
C─O─C (~1050 cm−1). The ESI mass spectra of compounds
3 revealed the existence of the molecular ion peaks and strong
M+K‐1 or M+Na‐1 peaks, which were in good accordance
with the given structures of products.
Many arylpyrazole and pyrazoline derivatives were widely
used as agrochemicals such as fungicides, herbicides and
insecticides in plant protection or in pharmaceuticals [1–7].
Recently, the triazole fungicides, as an important class of agro-
chemicals, have played a major role in crop protection [8–10].
The introduction of these sterol biosynthesis inhibitors repre-
sented a significant progress in the chemical control of fungal
diseases. More than 30 triazole fungicides such as Unicona-
zole, Diniconazole and Paclobutrazol, have been commercial-
ized. To find novel triazole fungicides with high activity and
low toxicity, we designed and synthesized a series of novel
target compounds 3 via the annulation of 2‐aryloxyacetohy-
drazides with 3‐aryl‐1‐t‐butyl (or phenyl)‐2‐(1H‐1,2,4‐tria-
zol‐1‐yl)prop‐2‐en‐1‐ones, in which the triazole ring was
linking with a pyrazoline ring in the same molecular skeleton.
Herein, we would like to report the synthesis and fungicidal
activities of the title compounds 3 in this article (Scheme 1).
RESULTS AND DISCUSSION
Fungicidal activity. The preliminary fungicidal activity of
the target compounds 3 was evaluated by the classic plate
method at the concentration of 50 mg/L, which was
described in the experimental part. The five fungi used,
Fusarium oxysporium, Physalospora piricola Nose,
Alternaria solani, Cercospora arachidicola Hori, and
Gibberella sanbinetti, belong to the group of field fungi
1‐(t‐Butyl or phenyl)‐2‐(1H‐1,2,4‐triazol‐1‐yl)ethanone
(1) reacted with aromatic aldehydes in the presence of
piperidine to obtain 3‐aryl‐1‐t‐butyl(or phenyl)‐2‐(1H‐
1,2,4‐triazol‐1‐yl)prop‐2‐en‐1‐ones (2) as Z‐ and E‐isomer
mixtures. Treatment of 2 with 2‐aryloxyacetohydrazides in
the presence of a catalytic amount of glacial acetic acid in
© 2013 HeteroCorporation

March 2013
Synthesis and Fungicidal Activity of 5‐Aryl‐1‐(aryloxyacetyl)‐3‐(tert‐butyl or phenyl)‐
4‐(1H‐1,2,4‐triazol‐1‐yl)‐4,5‐dihydropyrazole
217
Scheme 1. Synthetic route to compounds 3a–3n.
and were isolated from corresponding crops. The activities
data were also listed in Table 1. The preliminary bioassay
(in vitro) indicated that some of the title compounds 3
exhibited moderate to good inhibitory activities against
the above five fungi. For example, compounds 3i, 3l, and
3n possessed 81.8%, 81.8%, and 95.5% inhibition against
Fusarium oxysporium, respectively, and compound 3n
exhibited 89.3% inhibition against Physalospora piricola
Nose. Moreover, compounds 3l, 3m, and 3n possessed
100% inhibition against Cercospora arachidicola Hori as
well as the control drug‐difenoconazole did at the
concentration of 50 mg/L. However, most of compounds
3 exhibited weaker fungicidal activities against the tested
fungi than the control drug—difenoconazole did. As for
the preliminary structure‐activity relationships, first, the
compounds whose R is tert‐butyl showed better activities
than those whose R is phenyl did. Secondly, when Ar
and Ar′ are both 2,4‐dichlorophenyl, the compound
showed the best activities against those fungi. Further
exploring of structure‐activity relationships needs more
experimental results to support. Further biological activity
(in vivo) investigations are on the way.
In conclusion, a series of novel 5‐aryl‐1‐(aryloxyacetyl)‐
3‐(tert‐butyl or phenyl)‐4‐(1H‐1,2,4‐triazol‐1‐yl)‐4,5‐dihy-
dropyrazole 3a–3n were synthesized by the annulation of
2‐aryloxyacetohydrazides with 3‐aryl‐1‐t‐butyl (or phenyl)‐
2‐(1H‐1,2,4‐triazol‐1‐yl)prop‐2‐en‐1‐ones (2) in the presence
of a catalytic amount of acetic acid. The preliminary bioassay
indicated that some of the title compounds exhibited good fun-
gicidal activities against five fungi used, and the compounds
3l, 3m, and 3n possessed 100% inhibition against Cercospora
arachidicola Hori at the concentration of 50 mg/L.
EXPERIMENTAL
Melting points were determined with a WRS‐1B digital melting
point apparatus and are uncorrected. 1H‐NMR spectra was recorded
with a Varian Mercury PLUS 600 (600 MHz) spectrometer with
TMS as the internal reference and CDCl3 as the solvent, while mass
spectra were obtained with an Applied Biosystems API 2000 LC/
MS/MS (ESI‐MS) spectrometer. IR spectra were measured by a
Nicolet NEXUS470 spectrometer. Elemental analyses were per-
formed with an Elementar Vario ELШ CHNSO elemental analyzer.
3‐Aryl‐1‐t‐butyl (or phenyl)‐2‐(1H‐1,2,4‐triazol‐1‐yl)prop‐2‐en‐1‐
one (2) were prepared by the Knoevenagel reactions of 1‐tert‐butyl
Table 1
Fungicidal activity of compounds 3a–3n (in vitro, 50 mg/L, relative inhibitory rate %).
Fusarium
oxysporium
Physalospora piricola
Alternaria
solani
Cercospora arachidicola
Gibberella
sanbinetti
Compd.
Nose
Hori
3a
3b
3c
3d
3e
3f
3g
3h
3i
3j
3k
3l
3m
3n
31.8
22.7
18.2
45.5
22.7
27.3
63.6
77.3
81.8
27.3
0.0
25.0
17.9
0
39.3
39.3
7.1
25.0
7.1
0.0
50.0
17.9
78.6
78.6
89.3
100
25.0
14.3
21.4
46.4
25.0
21.4
21.4
10.7
7.1
46.4
14.3
71.4
67.9
67.9
100
38.5
15.4
23.1
69.2
53.8
30.8
46.2
76.9
61.5
61.5
46.2
100
41.4
27.6
15.5
51.7
39.7
20.7
32.8
32.8
15.5
51.7
24.1
87.9
87.9
86.2
98.3
81.8
77.3
95.5
100
100
100
100
Difenoconazole
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

218
H.‐Y. Mao, H. Song, and D.‐Q. Shi
Vol 50
(or phenyl)‐2‐(1H‐1,2,4‐triazol‐1‐yl)‐ethanone (1) with aromatic alde-
hydes in the presence of piperidine according to the literature proce-
dure [11]. 2‐Aryloxyacetohydrazides were synthesized using the
reported method [12]. All of the solvents and materials were reagent
grade and purified as required.
General procedure for the synthesis of 5‐aryl‐1‐
(aryloxyacetyl)‐3‐(tert‐butyl or phenyl)‐4‐(1H‐1,2,4‐triazol‐1‐yl)‐
4,5‐dihydropyrazole 3. 3‐aryl‐1‐t‐butyl (or phenyl)‐2‐(1H‐1,2,
4‐triazol‐1‐yl)prop‐2‐en‐1‐one 2 (2.0 mmol), 2‐aryloxyacetohydrazides
(2.4 mmol), anhydrous ethanol (20 mL) and several drops of glacial
acetic acid were added to a 50 mL three‐necked flask, the mixture was
stirred at room temperature for 6–10 h till the reaction was completed
(monitored by TLC). The solid was filtered and recrystallized by
anhydrous ethanol to give the target compounds 3a–3n in 56–87%
yields.
7.20 (d, J = 9.0 Hz, 2H, ArH), 7.25 (d, J = 9.0 Hz, 2H, ArH), 7.30
(d, J = 8.4 Hz, 2H, ArH), 7.96 (s, 1H, triazole‐H), 8.55 (s, 1H, tria-
zole‐H); IR (KBr) υ: 3115, 2973 (ArH), 1700 (C═O), 1659
(C═N), 1580, 1492, 1368 (Ar), 1273, 1224, 1093 (C─O─C) cm−1;
ESI‐MS m/z (%): 514 (M+K+4, 35), 512 (M+K+2, 100), 510 (M
+K, 40). Anal. calcd for C23H23Cl2N5O2: C 58.48, H 4.91, N
14.83; found C 58.40, H 5.06, N 14.98.
3f (R = t‐butyl, Ar = 4‐ClC6H4, Ar′ = 2,4‐Cl2C6H3): white
crystals, yield: 87%, m.p. 155.5–157.2°C; 1H‐NMR (CDCl3,
600 MHz) δ: 0.83 (s, 9H, 3CH3), 4.40 (AB, J = 14.4 Hz, 2H,
CH2), 4.87 (d, J = 9.6 Hz, 1H, CH), 5.69 (d, J = 9.0 Hz, 1H,
CH), 6.68 (d, J = 8.4 Hz, 1H, ArH), 7.14 (d, J = 8.4 Hz, 1H,
ArH), 7.15 (d, J = 8.4 Hz, 2H, ArH), 7.32 (d, J = 8.4 Hz, 2H,
ArH), 7.61 (s, 1H, ArH), 7.96 (s, 1H, triazole‐H), 8.51 (s, 1H, tria-
zole‐H); IR (KBr) υ: 3128, 2974 (ArH), 1712 (C═O), 1656
3a (R = t‐butyl, Ar = 2,4‐Cl2C6H3, Ar′ = C6H5): white crystals,
yield: 56%, m.p. 141.2–141.5°C; 1H‐NMR (CDCl3, 600 MHz) δ:
1.21 (s, 9H, 3CH3), 4.47 (s, 2H, CH2), 5.23 (d, J = 9.0 Hz, 1H,
CH), 5.96 (d, J = 9.0 Hz, 1H, CH), 6.82 (d, J = 7.8 Hz, 2H,
ArH), 7.02–7.30 (m, 5H, ArH), 7.79(s, 1H, triazole‐H), 7.84 (s,
1H, Ar─H), 8.05 (s, 1H, triazole‐H); IR (KBr) υ: 3071, 2971
(ArH), 1715 (C═O), 1652 (C═N), 1592, 1495, 1477 (Ar),
1218, 1061(C─O─C) cm−1; ESI‐MS m/z (%): 512 (M+K+2,
100), 510 (M+K, 85), 494 (M+Na, 16), 472 (M++1, 8), 347
(26). Anal. calcd for C23H23Cl2N5O2: C 58.48, H 4.91, N
14.83; found C 58.30, H 4.84, N 14.97.
(C═N), 1579, 1477, 1321 (Ar), 1232, 1071 (C─O─C) cm−1
;
ESI‐MS m/z (%): 548 (M+K+4), 546 (M+K, 100), 381 (25),
379 (17). Anal. calcd for C23H22Cl3N5O2: C 54.51, H 4.38, N
13.82; found C 54.71, H 4.44, N 13.69.
3g (R = t‐butyl, Ar = C6H5, Ar′ = C6H5): white solid, yield:
1
75%, m.p. 129.3–131.8°C; H‐NMR (CDCl3, 600 MHz) δ: 0.79
(s, 9H, 3CH3), 4.38 (s, 2H, CH2), 4.86 (d, J = 8.4 Hz, 1H, CH),
5.73 (d, J = 9.0 Hz, 1H, CH), 6.75 (d, J = 8.4 Hz, 2H, ArH),
6.99 (t, J = 8.4 Hz, 1H, ArH), 7.24–7.42 (m, 7H, ArH), 7.96 (s,
1H, triazole‐H), 8.56 (s, 1H, triazole‐H); IR (KBr) υ: 3113,
2971 (ArH), 1705 (C═O), 1655 (C═N), 1582, 1496, 1364 (Ar),
1270, 1226, 1084 (C─O─C) cm−1; ESI‐MS m/z (%): 444 (M+K+2,
35), 442 (M+K, 36), 277 (86). Anal. calcd for C23H25N5O2: C
68.47, H 6.25, N 17.36; found C 68.61, H 6.18, N 17.50.
3b (R = t‐butyl, Ar = 2,4‐Cl2C6H3, Ar′ = 4‐ClC6H4): white solid,
yield: 80%, m.p. 144.6–146.4°C; 1H‐NMR (CDCl3, 600 MHz)
δ: 1.13 (s, 9H, 3CH3), 4.44 (s, 2H, CH2), 5.19 (d, J = 8.4 Hz, 1H,
CH), 5.93 (d, J = 9.0 Hz, 1H, CH), 6.75 (d, J = 8.4 Hz, 2H, ArH),
7.09–7.30 (m, 4H, ArH), 7.76 (s, 1H, triazole‐H), 7.82 (s, 1H,
Ar─H), 8.09 (s, 1H, triazole‐H); IR (KBr) υ: 3123, 2972 (ArH),
1716 (C═O), 1643 (C═N), 1508, 1491, 1368 (Ar), 1276, 1220,
1057(C─O─C) cm−1; ESI‐MS m/z (%): 547.6 (M+K+2, 100), 546
(M+K, 89), 507 (M++2, 8), 505 (5). Anal. calcd for C23H22Cl3N5O2:
C 54.51, H 4.38, N 13.82; found C 54.73, H 4.24, N 13.67.
3h (R = t‐butyl, Ar = C6H5, Ar′ = 4‐ClC6H4): white solid,
1
yield: 74%, m.p. 140.1–141.8°C; H‐NMR (CDCl3, 600 MHz)
δ: 0.80 (s, 9H, 3CH3), 4.36 (s, 2H, CH2), 4.84 (d, J = 8.4 Hz,
1H, CH), 5.73 (d, J = 9.0 Hz, 1H, CH), 6.68 (d, J = 8.4 Hz,
2H, ArH), 7.19 (d, J = 8.4 Hz, 2H, ArH), 7.31–7.36 (m, 5H,
ArH), 7.96 (s, 1H, triazole‐H), 8.62 (s, 1H, triazole‐H); IR
(KBr) υ: 3115, 2977 (ArH), 1699 (C═O), 1655 (C═N), 1582,
1491, 1329 (Ar), 1276, 1221, 1059 (C─O─C) cm−1; ESI‐MS
m/z (%): 479 (88), 477 (M+K+1, 100), 311 (97). Anal. calcd for
C23H24ClN5O2: C 63.08, H 5.52, N 15.99; found C 63.24, H
5.77, N 16.13.
3c (R = t‐butyl, Ar = 2,4‐Cl2C6H3, Ar′ = 2,4‐Cl2C6H3): white crys-
tals, yield: 72%, m.p. 156.1–156.5°C; 1H‐NMR (CDCl3, 600 MHz) δ:
1.15 (s, 9H, 3CH3), 4.50 (s, 2H, CH2), 5.26 (d, J = 9.0 Hz, 1H, CH),
5.94 (d, J = 9.0 Hz, 1H, CH), 6.71 (d, J = 8.4 Hz, 1H, ArH), 7.17
(d, J = 8.4 Hz, 2H, ArH), 7.29 (d, J = 8.4 Hz, 1H, ArH), 7.38 (s,
1H, ArH), 7.80 (s, 1H, triazole‐H), 7.94 (s, 1H, ArH), 8.05 (s, 1H,
triazole‐H); IR (KBr) υ: 3126, 2974 (ArH), 1718 (C═O), 1636
(C═N), 1588, 1476, 1363 (Ar), 1236, 1071(C─O─C) cm−1; ESI‐
MS m/z (%): 582 (M+K+2, 86), 580 (M+K, 100), 543 (M++2, 4),
541 (3). Anal. calcd for C23H21Cl4N5O2: C 51.04, H 3.91, N 12.94;
found C 51.23, H 4.07, N 12.70.
3i (R = t‐butyl, Ar = C6H5, Ar′ = 2,4‐Cl2C6H3): white solid,
1
yield: 67%, m.p. 154.2–155.8°C; H‐NMR (CDCl3, 600 MHz)
δ: 0.79 (s, 9H, 3CH3), 4.40 (AB, J = 15.0 Hz, 2H, CH2), 4.88
(d, J = 9.6 Hz, 1H, CH), 5.74 (d, J = 9.6 Hz, 1H, CH), 6.66 (d,
J = 9.0 Hz, 1H, ArH), 7.12 (d, J = 9.0 Hz, 1H, ArH), 7.28–7.33
(m, 5H, ArH), 7.64 (s, 1H, ArH), 7.96 (s, 1H, triazole‐H), 8.58
(s, 1H, triazole‐H); IR (KBr) υ: 3134, 2972 (ArH), 1720
(C═O), 1652 (C═N), 1531, 1500, 1473, 1348 (Ar), 1292,
1230, 1074 (C─O─C) cm−1; ESI‐MS m/z (%): 512 (M+K+2,
100), 510 (M+K, 26). Anal. calcd for C23H23Cl2N5O2: C 58.48,
H 4.91, N 14.83; found C 58.31, H 4.75, N 14.62.
3d (R = t‐butyl, Ar = 4‐ClC6H4, Ar′ = C6H5): white solid,
1
yield: 78%, m.p. 130.0–131.8°C; H‐NMR (CDCl3, 600 MHz)
δ: 0.84 (s, 9H, 3CH3), 4.40 (s, 2H, CH2), 4.87 (d, J = 9.0 Hz,
1H, CH), 5.69 (d, J = 8.4 Hz, 1H, CH), 6.76 (d, J = 6.6 Hz,
2H, ArH), 7.00 (t, J = 7.2 Hz, 1H, ArH), 7.28–7.41 (m, 6H,
ArH), 7.98 (s, 1H, triazole‐H), 8.60 (s, 1H, triazole‐H); IR
(KBr) υ: 3124, 2972 (ArH), 1715 (C═O), 1639 (C═N), 1586,
1477, 1365 (Ar), 1233, 1067 (C─O─C) cm−1; ESI‐MS m/z
(%): 478 (M+K+1, 89), 437 (M+, 5), 311 (100), 190 (45). Anal.
calcd for C23H24ClN5O2: C 63.08, H 5.52, N 15.99; found C
62.95, H 5.37, N 15.72.
3j (R = t‐butyl, Ar = 4‐CH3OC6H4, Ar′ = 4‐ClC6H4): white
solid, yield: 75%, m.p. 115.8–116.9°C; 1H‐NMR (CDCl3, 600
MHz) δ: 0.80 (s, 9H, 3CH3), 3.73 (s, 3H, CH3O), 4.55 (s, 2H,
CH2), 4.79 (d, J = 9.6 Hz, 1H, CH), 5.69 (d, J = 9.0 Hz, 1H,
CH), 6.68 (d, J = 9.0 Hz, 2H, ArH), 6.84 (d, J = 9.0 Hz, 2H,
ArH), 7.19–7.23 (m, 4H, ArH), 7.95 (s, 1H, triazole‐H), 8.55 (s,
1H, triazole‐H); IR (KBr) υ: 3120, 2967 (ArH), 1717 (C═O),
1681 (C═N), 1631, 1513, 1490 (Ar), 1250, 1218, 1061
(C─O─C) cm−1; ESI‐MS m/z (%): 507.6 (M+K+1, 100), 507
(M+K, 87), 340.6 (52). Anal. calcd for C24H26ClN5O3: C 61.60,
H 5.60, N 14.97; found C 61.73, H 5.66, N 14.82.
3e (R = t‐butyl, Ar = 4‐ClC6H4, Ar′ = 4‐ClC6H4): white crystals,
1
yield: 65%, m.p. 168.1–169.2°C; H‐NMR (CDCl3, 600 MHz) δ:
0.83 (s, 9H, 3CH3), 4.36 (s, 2H, CH2), 4.82 (d, J = 9.0 Hz, 1H,
CH), 5.68 (d, J = 9.0 Hz, 1H, CH), 6.68 (d, J = 9.0 Hz, 2H, ArH),
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

March 2013
Synthesis and Fungicidal Activity of 5‐Aryl‐1‐(aryloxyacetyl)‐3‐(tert‐butyl or phenyl)‐
4‐(1H‐1,2,4‐triazol‐1‐yl)‐4,5‐dihydropyrazole
219
3k (R = t‐butyl, Ar = 4‐CH3OC6H4, Ar′ = 2,4‐Cl2C6H3): white
solid, yield: 84%, m.p. 149.5–151.5°C; 1H‐NMR (CDCl3, 600 MHz)
δ: 0.81 (s, 9H, 3CH3), 3.80 (s, 3H, CH3O), 4.40 (AB, J = 15.0 Hz, 2H,
CH2), 4.83 (d, J = 9.6 Hz, 1H, CH), 5.71 (d, J = 9.0 Hz, 1H, CH), 6.66
(d, J = 9.0 Hz, 1H, ArH), 6.85 (d, J = 9.0 Hz, 2H, ArH), 7.14 (d, J = 8.4
Hz, 1H, ArH), 7.24 (d, J = 8.4 Hz, 2H, ArH), 7.31 (s, 1H, ArH), 7.96
(s, 1H, triazole‐H), 8.53 (s, 1H, triazole‐H); IR (KBr) υ: 3076, 2969
(ArH), 1720 (C═O), 1662 (C═N), 1515, 1476, 1392 (Ar), 1249,
1232, 1076 (C─O─C) cm−1; ESI‐MS m/z (%): 542 (M+K+2, 100),
541 (M+K+1, 67), 520 (45), 508 (21), 353 (35). Anal. calcd for
C24H25Cl2N5O3: C 57.38, H 5.02, N 13.94; found C 57.20, H 4.93,
N 14.07.
The synthesized target compounds were dissolved in 0.5–1.0 mL of
DMF to the concentration of 500 mg/L. The solutions (1 mL) were
mixed rapidly with thawed potato glucose agar culture medium
(9 mL) under 50°C. The mixtures were poured into Petri dishes.
After the dished were cooled, the solidified plates were incubated
with 4 mm mycelium disk, inverted, and incubated at 28°C for 48 h.
Distilled water was used as the blank control and the commercially
available fungicide difenoconazole as the control drug. Three
replicates of each test were carried out. The mycelial elongation
radius (mm) of fungi settlements was measured after 48 h of culture.
The growth inhibitory rates were calculated with the following
equation: I = [(C‐T)/C] × 100%. Here, I is the growth inhibitory rate
(%), T is the treatment group fungi settlement radius (mm) and C is
the radius of the blank control. The results are listed in Table 1.
3l (R = C6H5, Ar = 2,4‐Cl2C6H3, Ar′ = C6H5): white solid,
1
yield: 68%, m.p. 121.9–123.4°C; H‐NMR (CDCl3, 600 MHz)
δ: 4.25 (AB, J = 15.0 Hz, 2H, CH2), 5.21 (d, J = 6.6 Hz, 1H,
CH), 5.45 (d, J = 6.0 Hz, 1H, CH), 6.79–7.04 (m, 5H, ArH),
7.27–7.73 (m, 7H, ArH), 7.79 (s, 1H, triazole‐H), 8.03(s, 1H,
ArH), 8.81 (s, 1H, triazole‐H); IR (KBr) υ: 3061, 2959 (ArH),
1694 (C═O), 1598 (C═N), 1494, 1448, 1332 (Ar), 1251, 1140,
1057 (C─O─C) cm−1; ESI‐MS m/z (%): 530 (M+K, 100), 510
(63), 377 (75). Anal. calcd for C25H19Cl2N5O2: C 60.99, H
3.89, N 14.22; found C 60.84, H 4.05, N 14.13.
Acknowledgments. This work was supported by the Natural
Science Foundation of China (No. 20872046) and the Natural
Science Foundation of Hubei Province (No. 2008CDB086).
3m (R = C6H5, Ar = 2,4‐Cl2C6H3, Ar′ = 4‐ClC6H4): white
crystals, yield: 66%, m.p. 118.6–120.5°C; 1H‐NMR (CDCl3,
600 MHz) δ: 4.24 (AB, J = 15.6 Hz, 2H, CH2), 5.43 (d, J = 6.6
Hz, 1H, CH), 6.42 (d, J = 6.6 Hz, 1H, CH), 6.71 (d, J = 8.4 Hz,
2H, ArH), 6.81 (d, J = 9.0 Hz, 1H, ArH), 7.02 (d, J = 9.0 Hz,
1H, ArH), 7.22–7.63 (m, 5H, ArH), 7.70 (s, 1H, ArH), 7.80 (s,
1H, triazole‐H), 8.03 (d, J = 8.4 Hz, 2H, ArH), 8.83 (s, 1H, tria-
zole‐H); IR (KBr) υ: 3068, 2963 (ArH), 1696 (C═O), 1564
(C═N), 1495, 1442, 1336 (Ar), 1250, 1144, 1052 (C─O─C)
cm−1; ESI‐MS m/z (%): 566 (M+K+2, 52), 549 (M+Na+1, 100),
528 (82). Anal. calcd for C25H18Cl3N5O2: C 57.00, H 3.44, N
13.29; found C 57.17, H 3.56, N 13.48.
REFERENCES AND NOTES
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Journal of Heterocyclic Chemistry
DOI 10.1002/jhet