Synthesis, Structure, and Biological Activities of [5-(Arylthio/sulfinyl/sulfonyl)-3-methyl-1-phenyl-1 H -pyrazol-4-yl]-arylmethanones

Article abstract of DOI:10.1080/10426507.2014.919503

A series of novel N-phenylpyrazolyl aryl methanones derivatives containing the arylthio/sulfinyl/sulfonyl group have been synthesized via multi-step reactions from 3-methyl-1-phenyl-1H-pyrazol-5(4H)-one and characterized by melting point, ¹H NM

Full text of DOI:10.1080/10426507.2014.919503

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Phosphorus, Sulfur, and Silicon and the
Related Elements
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Synthesis, Structure, and Biological
Activities of [5-(Arylthio/Sulfinyl/
Sulfonyl)-3-Methyl-1-Phenyl-1H-
Pyrazol-4-yl]-Arylmethanones
Bao-Lei Wanga, Jing Wua, Qiao-Xia Liua, Yong-Hong Lia, Hai-Bin Songa
& Zheng-Ming Lia
a State-Key Laboratory of Elemento-Organic Chemistry, Collaborative
Innovation Center of Chemical Science and Engineering (Tianjin),
Nankai University, Tianjin, China
Click for updates
Accepted author version posted online: 27 Jun 2014.Published
online: 31 Dec 2014.
To cite this article: Bao-Lei Wang, Jing Wu, Qiao-Xia Liu, Yong-Hong Li, Hai-Bin Song & Zheng-Ming
Li (2014): Synthesis, Structure, and Biological Activities of [5-(Arylthio/Sulfinyl/Sulfonyl)-3-Methyl-1-
Phenyl-1H-Pyrazol-4-yl]-Arylmethanones, Phosphorus, Sulfur, and Silicon and the Related Elements,
DOI: 10.1080/10426507.2014.919503
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Phosphorus, Sulfur, and Silicon, 190:1–13, 2015
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2014.919503
SYNTHESIS, STRUCTURE, AND BIOLOGICAL ACTIVITIES
OF [5-(ARYLTHIO/SULFINYL/SULFONYL)-3-METHYL-1-
PHENYL-1H-PYRAZOL-4-YL]-ARYLMETHANONES
Bao-Lei Wang, Jing Wu, Qiao-Xia Liu, Yong-Hong Li,
Hai-Bin Song, and Zheng-Ming Li
State-Key Laboratory of Elemento-Organic Chemistry, Collaborative Innovation
Center of Chemical Science and Engineering (Tianjin), Nankai University, Tianjin,
China
GRAPHICAL ABSTRACT
Abstract A series of novel N-phenylpyrazolyl aryl methanones derivatives containing the
arylthio/sulfinyl/sulfonyl group have been synthesized via multi-step reactions from 3-methyl-
1-phenyl-1H-pyrazol-5(4H)-one and characterized by melting point, 1H NMR, 13C NMR, FT-
IR, and HRMS. The crystal structure of (5-(4-chlorophenylsulfonyl)-3-methyl-1-phenyl-1H-
pyrazol-4-yl)(2,4-dichlorophenyl)methanone containing the arylsulfonyl moiety is reported.
The biological activity results showed that some of the title compounds exhibit favorable
herbicidal and insecticidal activities.
Keywords Pyrazole; sulfoxide; sulfone; synthesis; crystal structure; biological activities
INTRODUCTION
Sulfur-containing compounds, such as sulfoethers, sulfoxides, and sulfones play
important roles in research areas of organic chemistry, medicinal chemistry, and pesticide
chemistry.1–6 It has been demonstrated that these groups are important pharmacophores
of many pesticides, such as Fipronil7 and KIH-4858, and are often introduced into some
bioactive heterocycles to enhance the possible activities during the pesticide design.
Received 7 March 2014; accepted 25 April 2014.
Address correspondence to Bao-Lei Wang and Zheng-Ming, State-Key Laboratory of Elemento-Organic
Chemistry, Nankai University, Tianjin 300071, China. E-mail: wangbaolei@126.com, nkzml@vip.163.com
1

2
B.-L. WANG ET AL.
It is known that many pyrazole derivatives possess significant antiinflammatory,9,10
antibacterial,11 anti-Alzheimer,12 antioxidant,13 and anticancer14 properties. Also, the herbi-
cidal,15 insecticidal,16 and fungicidal17 activities of some multi-substituted pyrazoles have
been reported. Although there are many reports of the modification of substituents on
the pyrazole ring, structures containing a 4-arylacyl and 5-arylthio, or 5-arylsulfinyl, or
5-arylsulfonyl on the pyrazole ring have been seldom reported. Thus a series of [5-(4-
substituted phenylsulfinyl/sulfonyl)-1,3-dimethyl-1H-pyrazol-4-yl]-arylmethanones were
synthesized successfully in our recent study,18 which encouraged us to synthesize some
other novel compounds with such modified structures.
In continuation of our research on the synthesis of bioactive heterocyclic compounds,
a series of title new pyrazole derivatives were synthesized and structures characterized, also
their biological activities were investigated by herbicidal and insecticidal tests in this paper.
RESULTS AND DISCUSSION
Synthesis
The intermediates and the title compounds were synthesized as shown in Scheme 1.
Referring to the literature reported by us for the synthesis of (substituted phenyl)(5-
hydroxy-1,3-dimethyl-1H-pyrazol-4-yl)methanone,18 intermediate 3 was prepared success-
fully (yield 72∼85%) via a two-step method involving a Scotten-Baumann acylation of
pyrazolinone (1) with 4-chlorobenzoyl chloride or 2,4-dichlorobenzoyl chloride and then
a Fries rearrangement reaction of the product ester catalyzed by K2CO3 in dioxane at
80–90◦C (1.5 h). Intermediate 3 reacted with POCl3 to easily form intermediate 4.
Scheme 1 Reagents and conditions: (i) EtOH, reflux, 5 h; (ii) 4-Chlorobenzoyl chloride or 2,4-dichlorobenzoyl
chloride, triethylamine, ethylidene chloride, 50∼60◦C; (iii) Potassium carbonate, 1,4-dioxane, 80∼90◦C, 1.5 h;
(iv) phosphorus oxychloride, reflux, 3 h; (v) Substituted thiophenol, NaH, THF, r.t.; (vi) Hydrogen peroxide,
AcOH, r.t.; (vii) Hydrogen peroxide, AcOH, 80◦C’.

SYNTHESIS AND BIOACTIVITIES OF NOVEL PYRAZOLES
3
Figure 1 Molecular structure of compound 7d.
The sulfoether compounds 5 can be synthesized from pyrazole chlorides 4 and
substituted thiophenols in THF using NaH as a base at room temperature with yields
51∼87%. In this step, the substrates didn’t convert to the sulfoether products completely,
which may be due to the weakened reactivity of the Cl atom caused by a p–π conjugative
effect of pyrazole ring with Cl atom.18 The sulfoxide compounds 6 were synthesized from
the oxidation of sulfoethers with H2O2 in acetic acid for 1–2 h at room temperature, but
some amount of substrate sulfoethers existed in the products; sulfone compounds 7 were
obtained in the same reaction system at 80◦C, and likewise a small amount of substrate
sulfoxides also existed in the products. These experimental results indicate that oxidation is
not complete under these conditions. According to our similar results reported previously,18
this probably originated from the electronic effect of the substituents on the structures of
these compounds such as the 4-arylacyl, or 5-arylthio, or 5-arylsulfinyl group on the
pyrazole ring, and from the existence of steric hindrance because two bulky aryl groups
(phenylpyrazole and benzene ring) are located on same sulfur atom.
Spectroscopic Characterization
In the 1H NMR spectra of 5–7, the CH3 proton signals in pyrazole ring of sulfoether
were observed at δ 2.34–2.49 ppm; sulfoxide were observed at δ 2.24–2.50 ppm and
δ 2.20–2.48 ppm as sulfone, respectively. The difference of the chemical shift values of
the CH3 proton signals in pyrazole ring between these three kinds of sulfur-containing
derivatives 5, 6, and 7 is little. The other peaks observed were the aromatic protons at δ
6.53–7.93 ppm and an additional singlet at δ 2.13–2.23 ppm in compounds 5a, 5c, 5d,
6a, 6b, 6d, 7a, and 7c, respectively due to –CH3 group attached to phenyl ring. In the 13
C
NMR spectra of 5–7, the typical carbon resonance at δ 188.2–190.2 ppm was indicative of
a carbonyl group. The methyl carbon in pyrazole ring appeared at δ 12.44–14.41 ppm and
the aromatic carbon of benzene and pyrazole rings appeared at δ 117.9–156.0 ppm.

4
B.-L. WANG ET AL.
Table 1 Crystal structure and data refinement parameters
Compound
7d
Empirical Formula
Formula Weight
C23H15Cl3N2O3S
505.78
Crystal System / Space Group
a/Å
b/Å
Monoclinic, P2(1)/n
10.266(2) Å
13.960(3) Å
15.514(4) Å
90◦
c/Å
α/ ◦
β/ ◦
91.073(5) ◦
γ / ◦
90◦
V/Å3
2223.1(9) Å3
4
Z
Dcalc (g/cm3)
1.511 Mg/m3
0.536
μ (mm−1
)
Crystal size (mm)
Color / Shape
Temp (K)
Theta range for collection
Reflections collected
Independent reflections
Data/restraints/parameters
Goodness of fit on F2
Final R indices [I > 2σ(I)]
R indices (all data)
0.16 × 0.10 × 0.10
Colorless, prism
294(2)
1.96–26.35◦
12613
4528 [R(int) = 0.0725]
4528/0/290
0.989
R1 = 0.0477, wR2 = 0.0781
R1 = 0.1363, wR2 = 0.0978
0.310 and −0.270 e/A3
Largest difference peak/hole
The infrared spectra of compounds 5–7 showed the absorption band at
1639∼1676 cm−1 for C O stretching, and 1010∼1103 cm−1 for C S stretching.
In the cases of sulfoxide compounds 6, it showed the strong peak at 1261∼1289 cm−1
for S O stretching, while the characteristic stretching vibration ν (O S O) of sulfone
compounds 7 appears at 1335∼1362 cm−1 and 1163∼1199 cm−1 as strong peaks.
In addition, the ESI-FTMS (HRMS) of new compounds 5, 6, and 7 showed molecular
ion peak of [M+H]+ or [M+Na]+ clearly, and were consistent with those of calculated
ones.
Crystal Structure
The structure of compound 7d was further confirmed by single crystal X-ray diffrac-
tion analysis (Figure 1). The crystal structure and data refinement parameters are shown in
Table 1. The selected bond lengths and bond angles are shown in Table 2. Selected torsion
angles are shown in Table 3.
Compound 7d belongs to monoclinic system with space group P21/n. There are three
aromatic rings, the average bond lengths and bond angles of each ring are in agreement
with the literature data.19 The C N and C C bond lengths of pyrazole ring range between
the single and double bonds (1.388(4) ∼ 1.399(4)), and the interior angles of the five-
membered ring are 105.5(2) ∼ 111.4(3)◦, close to the ideal 108◦ for pentagon.20 The bond
angles of C1–S1–C7 and C8–C17–C18 is 102.20(14)◦ and 118.0(3)◦, respectively. From
the molecular structure, it can be seen that the pyrazole ring (N1, N2, C7, C8, C9) and

SYNTHESIS AND BIOACTIVITIES OF NOVEL PYRAZOLES
5
Table 2 Selected bond lengths (Å) and angles (◦) for the compound 7d
Bond lengths
Å
Bond angles
(◦)
S(1)–O(1)
S(1)–O(2)
S(1)–C(1)
S(1)–C(7)
1.424(2)
1.4280(19)
1.749(3)
1.764(3)
1.716(4)
1.727(3)
1.725(3)
1.213(3)
1.359(3)
1.368(3)
1.435(4)
1.338(4)
1.379(4)
1.399(4)
1.499(4)
1.490(4)
1.373(4)
1.486(4)
1.392(4)
C(1)–S(1)–C(7)
N(2)–N(1)–C(7)
N(2)–N(1)–C(11)
C(7)–N(1)–C(11)
C(9)–N(2)–N(1)
C(6)–C(1)–S(1)
C(2)–C(1)–S(1)
N(1)–C(7)–C(8)
N(1)–C(7)–S(1)
C(8)–C(7)–S(1)
C(7)–C(8)–C(9)
C(7)–C(8)–C(17)
C(9)–C(8)–C(17)
N(2)–C(9)–C(8)
N(2)–C(9)–C(10)
C(8)–C(9)–C(10)
C(16)–C(11)–N(1)
C(12)–C(11)–N(1)
C(18)–C(17)–C(8)
102.20(14)
110.9(2)
118.3(2)
129.8(3)
105.5(2)
120.0(3)
118.9(3)
107.2(3)
123.9(2)
128.9(2)
105.1(3)
126.9(3)
127.1(3)
111.4(3)
119.8(3)
128.8(3)
118.3(3)
120.8(3)
118.0(3)
Cl(1)–C(4)
Cl(2)–C(23)
Cl(3)–C(21)
O(3)–C(17)
N(1)–N(2)
N(1)–C(7)
N(1)–C(11)
N(2)–C(9)
C(7)–C(8)
C(8)–C(9)
C(8)–C(17)
C(9)–C(10)
C(11)–C(12)
C(17)–C(18)
C(18)–C(23)
benzene ring (C11, C12, C13, C14, C15, C16) are not coplanar and have a dihedral angle
63.8◦. The X-ray analysis also reveals that in this typical compound 7d, the torsion angle of
C(1)–S(1)–C(7)–C(8) is 108◦. This is probably because the existence of two bulky groups
(5-arylsulfonyl and 4-aryloyl) leads to the aromatic ring at the 1-position of pyrazole not
being coplanar with the pyrazole ring (the steric effect). The crystal structure of this kind
of pyrazole sulfone compound has not been reported before, and so will provide useful
information for the structural studies of novel pyrazole derivatives.
Biological Activities
From Table S 1 (Supplemental Materials), we can see that most of the new compounds
showed weak herbicidal activity for the inhibition of the rape root growth at 100 μg/mL.
However, compounds 5b and 6e possessed inhibition rates of 33.6% and 67.0% in rape
root test, respectively, and the latter still had 56.1% inhibitory activity at 10 μg/mL, yet
Table 3 Selected torsion angles (◦) for the compound 7d
Torsion angles
(◦)
Torsion angles
(◦)
C(7)–S(1)–C(1)–C(6)
C(7)–S(1)–C(1)–C(2)
N(2)–N(1)–C(7)–S(1)
C(11)–N(1)–C(7)–S(1)
C(1)–S(1)–C(7)–N(1)
C(1)–S(1)–C(7)–C(8)
S(1)–C(7)–C(8)–C(17)
C(17)–C(8)–C(9)–N(2)
−102.9(3)
74.3(3)
−178.6(2)
−10.3(4)
70.9(3)
N(2)–N(1)–C(11)–C(16)
C(7)–N(1)–C(11)–C(16)
N(2)–N(1)–C(11)–C(12)
C(7)–N(1)–C(11)–C(12)
C(7)–C(8)–C(17)–C(18)
C(9)–C(8)–C(17)–C(18)
C(8)–C(17)–C(18)–C(23)
C(8)–C(17)–C(18)–C(19)
63.8(4)
−103.8(4)
−116.0(3)
76.4(4)
−129.1(3)
−108.1(3)
63.3(4)
9.6(5)
−163.8(3)
19.7(4)
168.7(3)

6
B.-L. WANG ET AL.
it was less effective than the control (Chlorsulfuron, 76.0%). For the inhibition of growth
of the barnyardgrass stems and leaves, both pyrazole sulfides 6 and pyrazole sulfones 7
showed weak herbicidal activity at 100 μg/mL, while pyrazole sulfoethers 5c and 5d held
44.8% and 52.8% inhibition activity in baryardgrass cup test at 100 μg/mL, which are more
effective than Chlorsulfuron (29.9%).
From the same table, it was found that most of compounds exhibited apparent lar-
vicidal activity against oriental armyworm with the lethality rate 10∼30% at 200 mg/L,
in which the activity difference between sulfides 6 and sulfones 7 is little. Interestingly,
sulfoether 5f exhibited 70% larvicidal activity at 200 mg/L.
EXPERIMENTAL
Melting points were determined using a Taike X-4 apparatus and were uncorrected.
Infrared spectra were recorded on a BRUKER EQUINOX 55 spectrophotometer as KBr
1
tablets. H NMR and 13C NMR spectra were measured on a Bruker AVANCE-300 MHz
or a Varian Mercury Vx400MHz instrument using TMS as an internal standard and CDCl3
(or DMSO-d6) as solvent. HRMS data were obtained on a FTICR-MS instrument (Ionspec
7.0T). Crystallographic data of the compound were collected on a Rigaku MM-07 Saturn
724 CCD diffractometer.
Synthesis of the Intermediate 3-Methyl-1-phenyl-1H-pyrazol-5(4H)-one (1)
3-Methyl-1-phenyl-1H-pyrazol-5(4H)-one (1) was synthesized according to Ref.21
Synthesis of the Intermediates 3-Methyl-1-phenyl-1H-pyrazol-5-yl
substituted-benzoate (2)
Intermediates 2 were synthesized according to Ref.18
3-Methyl-1-phenyl-1H-pyrazol-5-yl 4-chlorobenzoate (2a): white solid, yield
96%, m.p. 88–90◦C (Lit.22 m.p. 95–96◦C); 3-methyl-1-phenyl-1H-pyrazol-5-yl 2,4-
dichlorobenzoate (2b): white solid, yield 88%, m.p. 113–114◦C.
Synthesis of the Intermediates (Substituted-phenyl)(5-hydroxy-
3-methyl-1-phenyl-1H-pyrazol-4- yl)methanone (3)
Intermediates 3 were synthesized according to Ref.18
(4-Chlorophenyl)(5-hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)methanone
(3a): white solid, yield 72%, m.p. 103–105◦C (Lit.23 m.p. 105–107◦C); (2,4-
dichlorophenyl)(5-hydroxy-3-methyl-1-phenyl- 1H-pyrazol-4-yl)methanone (3b):
white solid, yield 85%, m.p. 151–153◦C.
Synthesis of the Intermediate Pyrazole Chloride (4)
Referring to the literature18 method, intermediates pyrazole chloride (4) were suc-
cessfully synthesized. A mixture of POCl3 (9.25 g, 0.06 mol) and intermediate 3 (0.03 mol)
was stirred at reflux condition for 3∼4 h. After cooling, the reaction solution was slowly
poured into crushed ice and the mixture was adjusted to pH 7∼8 with 10% sodium

SYNTHESIS AND BIOACTIVITIES OF NOVEL PYRAZOLES
7
hydroxide solution. The mixture was extracted with ethyl acetate (3 × 25 mL), the or-
ganic layers were combined, washed with brine, and dried over anhydrous Na2SO4. The
solvent was evaporated and the residue was recrystallized with a mixed solvent of ethyl
acetate and petroleum ether to give intermediate 2.
5-Chloro-3-methyl-1-phenyl-1H-pyrazol-4-yl)(4-chlorophenyl)methanone
(4a): white solid, yield 88%, m.p. 120–122◦C. 1H NMR (400 MHz, DMSO-d6):
7.85 (d, J = 8.4 Hz, 2H), 7.41–7.75 (m, 7H), 2.30 (s, 3H); 13C NMR (101 MHz,
DMSO-d6): 188.7 (C O), 151.01 (Pyrazole-C), 138.5 (Ph-C), 137.5 (Ph-C), 136.9
(Ph-C), 131.6 (2C, Ph-C), 129.8 (2C, Ph-C), 129.7 (Ph-C), 129.5 (Pyrazole-C),
129.3 (2C, Ph-C), 126.2 (2C, Ph-C), 117.8 (Pyrazole-C), 14.2 (Pyrazole-CH3);
5-chloro-3-methyl-1-phenyl-1H-pyrazol-4-yl)(2,4-dichlorophenyl)methanone (4b):
1
white solid, yield 82%, m.p. 165–168◦C. H NMR (400 MHz, CDCl3): 7.02–7.87 (m,
8H), 2.48 (s, 3H); 13C NMR (101 MHz, CDCl3): 187.4 (C O), 152.6 (Pyrazole-C), 137.9
(Ph-C), 137.2 (Ph-C), 136.7 (Ph-C), 132.0 (Ph-C), 131.3 (Pyrazole-C), 129.9 (Ph-C),
129.7 (Ph-C), 129.2 (3C, Ph-C), 127.5 (Ph-C), 125.5 (2C, Ph-C), 117.7 (Pyrazole-C), 14.7
(Pyrazole-CH3).
Synthesis of (5-Arylthio-3-methyl-1-phenyl-1H-pyrazol-4-yl)-
arylmethanones (5a–5f)
To a mixture of NaH (50%, 15 mmol) in THF (10 mL) was added dropwise, a solution
of substituted thiophenol (10 mmol) in THF (5 mL) at 0◦C. After being stirred at room
temperature for 1∼2 h, the mixture was then added dropwise a solution of intermediate 4
(10 mmol) in THF (10 mL). The mixture was further stirred at room temperature for 4∼6 h,
then water (25 mL) was added and extracted with ethyl acetate (3 × 15 mL). The organic
layers were combined and dried over anhydrous Na2SO4. The solvent was evaporated in
vacuo and the residue was purified by recrystallization with a mixed solvent of ethyl acetate
and petroleum ether to give the pyrazole sulfoether (5a–5f).
(4-Chlorophenyl)(3-methyl-1-phenyl-5-(p-tolylthio)-1H-pyrazol-4-yl)
methanone (5a): white solid, yield 60%, m.p. 110–112◦C; IR (υ, cm−1): 3010 (m,
1
Ph-H), 2920 (m, CH3), 1644 (vs, C O), 1590, 1501, 1463 (s, Ar), 1086 (vs, C S); H
NMR (400 MHz, CDCl3): 7.68 (d, J = 8.4 Hz, 2H, Ph-H), 7.39–7.45 (m, 7H, Ph-H), 6.85
(d, J = 7.6 Hz, 2H, Ph-H), 6.68 (d, J = 8.0 Hz, 2H, Ph-H), 2.37 (s, 3H, pyrazol-CH3), 2.20
(s, 3H, Ph-CH3); 13C NMR (101 MHz, CDCl3): 190.3 (C O), 150.8 (Pyrazole-C), 139.2
(Ph-C), 138.7 (Ph-C), 137.4 (Ph-C), 137.0 (Ph-C), 136.2 (Ph-C), 130.9 (2C, Ph-C), 130.0
(Pyrazole-C), 129.8 (2C, Ph-C), 129.7 (2C, Ph-C), 128.8 (Ph-C), 128.6 (2C, Ph-C), 128.6
(2C, Ph-C), 126.0 (2C, Ph-C), 124.1 (Pyrazole-C), 21.0 (Ph-CH3), 13.6 (Pyrazole-CH3).
ESI-FTMS for C24H19ClN2OS [M+H]+: Calcd. 419.0979, Found 419.0986.
(4-Chlorophenyl)(5-(4-chlorophenylthio)-3-methyl-1-phenyl-1H-pyrazol-4-yl)
methanone (5b): white solid, yield 51%, m.p. 143◦C; IR (υ, cm−1): 3066 (m, Ph-H), 2964
1
(m, CH3), 1650 (vs, C O), 1594, 1502, 1474, 1457 (s, Ar), 1090 (vs, C S); H NMR
(400 MHz, CDCl3): 7.71 (d, J = 8.4 Hz, 2H, Ph-H), 7.41–7.44 (m, 7H, Ph-H), 7.03 (d,
J = 8.4 Hz, 2H, Ph-H), 6.74 (d, J = 8.4 Hz, 2H, Ph-H), 2.37 (s, 3H, pyrazol-CH3); 13C
NMR (101 MHz, CDCl3): 190.1 (C O), 150.8 (Pyrazole-C), 139.4 (Ph-C), 138.5 (Ph-C),
136.8 (Ph-C), 133.3 (Ph-C), 132.2 (Ph-C), 130.9 (2C, Ph-C), 130.5 (2C, Ph-C), 130.5
(Pyrazole-C), 129.2 (2C, Ph-C), 128.9 (2C, Ph-C), 128.8 (2C, Ph-C), 128.8 (Ph-C), 125.9
(2C, Ph-C), 124.6 (Pyrazole-C), 13.7 (Pyrazole-CH3). ESI-FTMS for C23H16Cl2N2OS
[M+H]+: Calcd. 439.0433, Found 439.0425.

8
B.-L. WANG ET AL.
(2,4-Dichlorophenyl)(3-methyl-1-phenyl-5-(m-tolylthio)-1H-pyrazol-4-yl)
methanone (5c): white solid, yield 71%, m.p. 99–102◦C; IR (υ, cm−1): 3091 (m, Ph-H),
1
2920 (m, CH3), 1661 (vs, C O), 1584, 1508, 1471 (s, Ar), 1103 (vs, C S); H NMR
(300 MHz, CDCl3): 7.17–7.68 (m, 12H, Ph-H), 2.34 (s, 3H, pyrazol-CH3), 2.22 (s, 3H,
Ph-CH3); 13C NMR (101 MHz, CDCl3): 189.0 (C O), 152.8 (Pyrazole-C), 138.9 (Ph-C),
138.5 (Ph-C), 138.2 (Ph-C), 136.9 (Ph-C), 136.4 (Ph-C), 133.6 (Ph-C), 132.3 (Ph-C),
130.0 (Ph-C), 129.6 (Ph-C), 129.0 (Ph-C), 128.9 (Ph-C), 128.8 (Ph-C), 128.8 (Ph-C),
127.7 (Ph-C), 126.9 (Ph-C), 126.1 (2C, Ph-C), 125.4 (Ph-C), 123.8 (Pyrazole-C), 121.4
(Pyrazole-C), 21.2 (Ph-CH3), 14.4 (Pyrazole-CH3). ESI-FTMS for C24H18Cl2N2OS
[M+H]+: Calcd. 453.0590, Found 453.0592.
(2,4-Dichlorophenyl)(3-methyl-1-phenyl-5-(p-tolylthio)-1H-pyrazol-4-yl)
methanone (5d): white solid, yield 87%, m.p. 82–85◦C; IR (υ, cm−1): 3070 (m, Ph-H),
1
2962 (m, CH3), 1660 (vs, C O), 1584, 1505, 1466 (s, Ar), 1052 (vs, C S); H NMR
(300 MHz, CDCl3): 7.19–7.28 (m, 6H, Ph-H), 7.08–7.14 (m, 2H, Ph-H), 6.80 (d, J =
8.1 Hz, 2H, Ph-H), 6.53 (d, J = 8.1 Hz, 2H, Ph-H), 2.42 (s, 3H, pyrazol-CH3), 2.15 (s,
3H, Ph-CH3); 13C NMR (101 MHz, CDCl3): 189.0 (C O), 152.7 (Pyrazole-C), 138.5
(Ph-C), 138.3 (Ph-C), 136.6 (Pyrazole-C), 136.5 (Ph-C), 134.0 (Ph-C), 132.2 (Ph-C),
130.0 (Ph-C), 129.7 (Ph-C), 129.0 (Ph-C), 128.9 (2C, Ph-C), 128.8 (2C, Ph-C), 128.2 (2C,
Ph-C), 127.0 (Ph-C), 126.9 (Ph-C), 126.0 (2C, Ph-C), 123.9 (Pyrazole-C), 21.2 (Ph-CH3),
14.4 (Pyrazole-CH3). ESI-FTMS for C24H18Cl2N2OS [M+H]+: Calcd. 453.0590, Found
453.0585.
(5-(3-Chlorophenylthio)-3-methyl-1-phenyl-1H-pyrazol-4-yl)
(2,4-dichlorophenyl)methanone (5e): white solid, yield 81%, m.p. 98–101◦C; IR
(υ, cm−1): 3074 (m, Ph-H), 2923 (m, CH3), 1664 (vs, C O), 1581, 1504, 1459 (s, Ar),
1
1071 (vs, C S); H NMR (300 MHz, CDCl3): 7.30–7.39 (m, 6H, Ph-H), 7.20–7.26 (m,
2H, Ph-H), 6.68-6.70 (m, 2H, Ph-H), 6.66 (m, 2H, Ph-H), 2.49 (s, 3H, pyrazol-CH3); 13
C
NMR (101 MHz, CDCl3): 188.7 (C O), 152.8 (Pyrazole-C), 138.3 (Ph-C), 138.1 (Ph-C),
136.7 (Ph-C), 135.7 (Ph-C), 134.8 (Ph-C), 132.3 (Ph-C), 130.0 (Ph-C), 129.9 (Ph-C), 129.8
(Ph-C), 129.5 (Ph-C), 129.1 (Ph-C), 128.9 (2C, Ph-C), 128.0 (Ph-C), 127.1 (Ph-C), 126.3
(Ph-C), 126.0 (2C, Ph-C), 124.0 (Pyrazole-C), 121.4 (Pyrazole-C), 14.3 (Pyrazole-CH3).
ESI-FTMS for C23H15Cl3N2OS [M+Na]+: Calcd. 494.9863, Found 494.9858.
(5-(4-Chlorophenylthio)-3-methyl-1-phenyl-1H-pyrazol-4-yl)
(2,4-dichlorophenyl)methanone (5f): white solid, yield 62%, m.p. 105–106◦C; IR
(υ, cm−1): 3075 (m, Ph-H), 2923 (m, CH3), 1660 (vs, C O), 1586, 1503, 1464 (s, Ar),
1
1087 (vs, C S); H NMR (400 MHz, CDCl3): 7.33–7.38 (m, 4H, Ph-H), 7.18–7.22 (m,
4H, Ph-H), 7.04 (d, J = 8.4 Hz, 2H, Ph-H), 6.67 (d, J = 8.8 Hz, 2H, Ph-H), 2.47 (s, 3H,
pyrazol-CH3); 13C NMR (101 MHz, CDCl3): 188.7 (C = O), 152.7 (Pyrazole-C), 138.3
(Ph-C), 138.2 (Ph-C), 136.7 (Ph-C), 136.1 (Pyrazole-C), 133.1 (Ph-C), 132.3 (Ph-C), 132.2
(Ph-C), 130.0 (Ph-C), 129.8 (Ph-C), 129.7 (2C, Ph-C), 129.1 (2C, Ph-C), 129.0 (2C, Ph-C),
128.9 (Ph-C), 127.1 (Ph-C), 126.0 (2C, Ph-C), 124.0 (Pyrazole-C), 14.3 (Pyrazole-CH3).
ESI-FTMS for C23H15Cl3N2OS [M+H]+: Calcd. 473.0038, Found 473.0033.
Synthesis of (5-Arylsulfinyl-3-methyl-1-phenyl-1H-pyrazol-4-yl)-
arylmethanones (6a–6e)
To a stirred solution of 5 (2 mmol) in glacial acetic acid (10 mL), solution of H2O2
(30%, 4 mmol) was added dropwise. Reaction mixture was then stirred at room temperature

SYNTHESIS AND BIOACTIVITIES OF NOVEL PYRAZOLES
9
with monitoring by TLC (about 1∼2 h) and poured into H2O. The mixture was extracted
with ethyl acetate (15 mL × 3). The organic layer was combined and dried over anhydrous
Na2SO4. The solvent was removed and the residue was purified by recrystallization with a
mixed solvent of ethyl acetate and petroleum ether to give the product 6.
(4-Chlorophenyl)(3-methyl-1-phenyl-5-(m-tolylsulfinyl)-1H-pyrazol-4-yl)
methanone (6a): white solid, yield 51%, m.p. 73–75◦C; IR (υ, cm−1): 3057 (m, Ph-H),
2922 (m, CH3), 1649 (vs, C O), 1589, 1507, 1472 (s, Ar), 1277 (vs, S O), 1085 (vs,
1
C-S); H NMR (400 MHz, CDCl3): 7.65 (d, J = 8.4 Hz, 2H, Ph-H), 7.37-7.46 (m, 7H,
Ph-H), 6.95 (t, J = 8.0 Hz, 1H, Ph-H), 6.87 (d, J = 7.6 Hz, 1H, Ph-H), 6.62 (d, J = 8.0 Hz,
1H, Ph-H), 6.54 (s, 1H, Ph-H), 2.39 (s, 3H, pyrazol-CH3), 2.13 (s, 3H, Ph-CH3); 13C
NMR (101 MHz, CDCl3): 190.2 (C O), 151.0 (Pyrazole-C), 139.1 (Ph-C), 138.9 (Ph-C),
138.7 (Ph-C), 136.9 (Ph-C), 136.0 (Pyrazole-C), 133.2 (Ph-C), 130.8 (2C, Ph-C), 129.9
(Ph-C), 128.9 (Ph-C), 128.8 (2C, Ph-C), 128.7 (2C, Ph-C), 128.6 (Ph-C), 128.0 (Ph-C),
126.4 (Ph-C), 126.0 (2C, Ph-C), 123.9 (Pyrazole-C), 21.2 (Ph-CH3), 13.7 (Pyrazole-CH3).
ESI-FTMS for C24H19ClN2O2S [M+Na]+: Calcd. 457.0748, Found 457.0455.
(4-Chlorophenyl)(3-methyl-1-phenyl-5-(p-tolylsulfinyl)-1H-pyrazol-4-yl)
methanone (6b): white solid, yield 71%, m.p. 198–200◦C; IR (υ, cm−1): 3055 (m, Ph-H),
2931 (m, CH3), 1640 (vs, C O), 1586, 1502, 1452 (s, Ar), 1261 (vs, S O), 1085 (vs,
1
C-S); H NMR (400 MHz, CDCl3): 7.86 (d, J = 8.4 Hz, 2H, Ph-H), 7.35–7.51 (m, 8H,
Ph-H), 6.99–7.04 (m, 3H, Ph-H), 2.28 (s, 3H, pyrazol-CH3), 2.16 (s, 3H, Ph-CH3); 13C
NMR (101 MHz, CDCl3): 189.1 (C O), 149.0 (Pyrazole-C), 144.5 (Ph-C), 141.1 (Ph-C),
140.2 (Ph-C), 138.4 (Ph-C), 136.5 (Ph-C), 131.2 (2C, Ph-C), 129.4 (2C, Ph-C), 129.1
(2C, Ph-C), 128.7 (2C, Ph-C), 128.4 (Pyrazole-C), 127.5 (Ph-C), 126.3 (2C, Ph-C), 124.5
(2C, Ph-C), 123.7 (Pyrazole-C), 21.3 (Ph-CH3), 13.3 (Pyrazole-CH3). ESI-FTMS for
C24H19ClN2O2S [M+H]+: Calcd. 435.0929, Found 435.0933.
(4-Chlorophenyl)(5-(3-chlorophenylsulfinyl)-3-methyl-1-phenyl-1H-pyrazol-4-
yl)methanone (6c): white solid, yield 73%, m.p. 156–158◦C; IR (υ, cm−1): 3085, 3069
(m, Ph-H), 2939 (m, CH3), 1639 (vs, C O), 1586, 1574, 1503, 1457 (s, Ar), 1262 (vs,
1
S O), 1083 (vs, C S); H NMR (400 MHz, CDCl3): 7.88 (d, J = 8.4 Hz, 2H, Ph-H),
7.54 (d, J = 8.4 Hz, 2H, Ph-H), 7.43 (d, J = 7.6 Hz, 1H, Ph-H), 7.36 (t, J = 8.0 Hz, 2H,
Ph-H), 7.31 (d, J = 8.0 Hz, 2H, Ph-H), 7.23 (d, J = 8.4 Hz, 1H, Ph-H), 7.16 (t, J = 8.0 Hz,
1H, Ph-H), 7.10 (s, 1H, Ph-H), 7.05 (d, J = 7.2Hz, 1H, Ph-H), 2.29 (s, 3H, pyrazol-CH3);
13C NMR (101 MHz, CDCl3): 188.8 (C O), 149.0 (Pyrazole-C), 143.8 (Ph-C), 142.1
(Ph-C), 140.5 (Ph-C), 138.1 (Pyrazole-C), 136.3 (Ph-C), 135.1 (Ph-C), 131.2 (2C, Ph-C),
130.8 (Ph-C), 129.8 (Ph-C), 129.7 (Ph-C), 129.2 (2C, Ph-C), 128.8 (2C, Ph-C), 126.5 (2C,
Ph-C), 124.8 (Ph-C), 124.4 (Pyrazole-C), 122.6 (Ph-C), 13.4 (Pyrazole-CH3). ESI-FTMS
for C23H16Cl2N2O2S [M+H]+: Calcd. 455.0382, Found 455.0374.
(2,4-Dichlorophenyl)(3-methyl-1-phenyl-5-(p-tolylsulfinyl)-1H-pyrazol-4-yl)
methanone (6d): white solid, yield 88%, m.p. 128–130◦C; IR (υ, cm−1): 3057 (m, Ph-H),
2924 (m, CH3), 1662 (vs, C O), 1583, 1532, 1504, 1441 (s, Ar), 1280 (vs, S O), 1063
1
(vs, C-S); H NMR (400 MHz, CDCl3): 7.31–7.38 (m, 6H, Ph-H), 7.14–7.18 (m, 2H,
Ph-H), 7.05 (d, J = 8.0 Hz, 2H, Ph-H), 6.87 (d, J = 8.0 Hz, 2H, Ph-H), 2.50 (s, 3H,
pyrazol-CH3), 2.23 (s, 3H, Ph-CH3); 13C NMR (101 MHz, CDCl3): 189.0 (C O), 152.6
(Pyrazole-C), 138.5 (Ph-C), 138.3 (Ph-C), 137.1 (Ph-C), 136.5 (Ph-C), 132.3 (Ph-C), 130.2
(Ph-C), 130.0 (Ph-C), 129.7 (Ph-C), 129.7 (Ph-C), 129.5 (Ph-C), 128.8 (Ph-C), 128.7
(Ph-C), 128.7 (Ph-C), 128.1 (Ph-C), 127.7 (Pyrazole-C), 127.0 (Ph-C), 126.1 (2C, Ph-C),
121.4 (Ph-C), 117.9 (Pyrazole-C), 21.0 (Ph-CH3), 14.3 (Pyrazole-CH3). ESI-FTMS for
C24H18Cl2N2O2S [M+H]+: Calcd. 469.0539, Found 469.0547.

10
B.-L. WANG ET AL.
(5-(3-Chlorophenylsulfinyl)-3-methyl-1-phenyl-1H-pyrazol-4-yl)(2,4-dichloro-
phenyl)methanone (6e): white solid, yield 75%, m.p. 100–102◦C; IR (υ, cm−1): 3062
(m, Ph-H), 2930 (m, CH3), 1657 (vs, C O), 1587, 1506, 1460 (s, Ar), 1289 (vs, S O),
1
1010 (vs, C S); H NMR (300 MHz, CDCl3): 7.27–7.74 (m, 12H, Ph-H), 2.24 (s, 3H,
pyrazol-CH3); 13C NMR (101 MHz, CDCl3): 189.0 (C O), 152.6 (Pyrazole-C), 138.5
(Ph-C), 138.3 (Ph-C), 137.3 (Pyrazole-C), 137.1 (Ph-C), 136.5 (Ph-C), 132.3 (Ph-C),
130.2 (Ph-C), 130.0 (Ph-C), 129.7 (2C, Ph-C), 129.7 (Ph-C), 128.8 (Ph-C), 128.7 (Ph-C),
128.7 (2C, Ph-C), 127.0 (Ph-C), 126.1 (2C, Ph-C), 123.8 (Pyrazole-C), 121.4 (Ph-C),
14.3 (Pyrazole-CH3). ESI-FTMS for C23H16Cl3N2O2S [M+H]+: Calcd. 488.9993, Found
488.9993.
Synthesis of (5-Arylsulfonyl-3-methyl-1-phenyl-1H-pyrazol-4-yl)-
arylmethanones (7a–7d)
The synthetic and purified procedures were similar to those of compound 6, in addition
to a reaction temperature of 80◦C.
(4-Chlorophenyl)(3-methyl-1-phenyl-5-(m-tolylsulfonyl)-1H-pyrazol-4-yl)
methanone (7a): white solid, yield 47%, m.p. 143–145◦C; IR (υ, cm−1): 3087 (m,
Ph-H), 2935 (m, CH3), 1670 (vs, C O), 1595, 1549, 1508, 1465 (s, Ar), 1362, 1199 (vs,
O S O), 1068 (vs, C S); 1H NMR (300 MHz, CDCl3): 7.07–7.89 (m, 13H, Ph-H), 2.30
(s, 3H, pyrazol-CH3), 2.17 (s, 3H, Ph-CH3); 13C NMR (101 MHz, CDCl3): 189.28 (C O),
153.73 (Pyrazole-C), 142.37 (Ph-C), 138.85 (Ph-C), 137.15 (Ph-C), 136.92 (Ph-C), 133.08
(Pyrazole-C), 132.54 (Ph-C), 130.57 (2C, Ph-C), 129.86 (Ph-C), 128.78 (Ph-C), 128.65
(2C, Ph-C), 128.48 (2C, Ph-C), 128.24 (Ph-C), 128.03 (Ph-C), 127.13 (Ph-C), 126.34
(2C, Ph-C), 124.68 (Pyrazole-C), 22.13 (Ph-CH3), 13.48 (Pyrazole-CH3). ESI-FTMS for
C24H19ClN2O3S [M+H]+: Calcd. 451.0878, Found 451.0883.
(4-Chlorophenyl)(5-(4-chlorophenylsulfonyl)-3-methyl-1-phenyl-1H-pyrazol-
4-yl)methanone (7b): white solid, yield 50%, m.p. 155–157◦C; IR (υ, cm−1): 3092 (m,
Ph-H), 2934 (m, CH3), 1669 (vs, C O), 1583, 1523, 1497, 1476, 1452 (s, Ar), 1343,
1170 (vs, O S O), 1089 (vs, C S); 1H NMR (400 MHz, CDCl3): 7.93 (d, J = 8.0 Hz,
2H, Ph-H), 7.31–7.54 (m, 11H, Ph-H), 2.20 (s, 3H, pyrazol-CH3); 13C NMR (101 MHz,
CDCl3): 189.5 (C O), 147.1 (Pyrazole-C), 141.0 (Ph-C), 140.7 (Ph-C), 140.1 (Ph-C),
137.8 (Ph-C), 137.8 (Ph-C), 137.6 (Ph-C), 135.9 (Pyrazole-C), 131.2 (2C, Ph-C), 130.2
(Ph-C), 129.8 (2C, Ph-C), 129.3 (Ph-C), 129.3 (2C, Ph-C), 128.9 (2C, Ph-C), 127.5
(2C, Ph-C), 124.3 (Pyrazole-C), 12.4 (Pyrazole CH3). ESI-FTMS for C23H16Cl2N2O3S
[M+H]+: Calcd. 471.0322, Found 471.0331.
(2,4-Dichlorophenyl)(3-methyl-1-phenyl-5-tosyl-1H-pyrazol-4-yl)methanone
(7c): white solid, yield 48%, m.p. 137–138◦C; IR (υ, cm−1): 3081, 3040 (m, Ph-H), 2964
(m, CH3), 1670 (vs, C O), 1597, 1584, 1502, 1458 (s, Ar), 1335, 1163 (vs, O S O),
1
1088 (vs, C S); H NMR (300 MHz, CDCl3): 7.06–7.74 (m, 12H, Ph-H), 2.39 (s,
3H, pyrazol-CH3), 2.22 (s, 3H, Ph-CH3); 13C NMR (101 MHz, CDCl3): 188.4 (C O),
156.0 (Pyrazole-C), 148.0 (Ph-C), 141.1 (Ph-C), 138.8 (Ph-C), 138.0 (Ph-C), 136.2
(Pyrazole-C), 134.2 (Ph-C), 133.0 (Ph-C), 131.1 (Ph-C), 130.0 (Ph-C), 128.7 (2C, Ph-C),
128.6 (2C, Ph-C), 127.5 (2C, Ph-C), 127.3 (Ph-C), 127.0 (2C, Ph-C), 125.1 (Ph-C), 124.8
(Pyrazole-C), 23.6 (Ph-CH3), 12.53 (Pyrazole-CH3). ESI-FTMS for C24H18Cl2N2O3S
[M+H]+: Calcd. 485.0488, Found 485.0493.
(5-(4-Chlorophenylsulfonyl)-3-methyl-1-phenyl-1H-pyrazol-4-yl)(2,4-dichloro
phenyl)methanone (7d): white solid, yield 80%, m.p. 116–117◦C; IR (υ, cm−1): 3066

SYNTHESIS AND BIOACTIVITIES OF NOVEL PYRAZOLES
11
(m, Ph-H), 2929 (m, CH3), 1676 (vs, C O), 1580, 1546, 1520, 1463 (s, Ar), 1343,
1171 (vs, O S O), 1086 (vs, C S); 1H NMR (400 MHz, CDCl3): 7.36 (m, 6H, Ph-H),
7.22 (d, J = 7.2 Hz, 2H, Ph-H), 7.05 (d, J = 8.8 Hz, 2H, Ph-H), 6.67 (d, J = 8.4 Hz,
2H, Ph-H), 2.48 (s, 3H, pyrazol-CH3); 13C NMR (101 MHz, CDCl3): 188.2 (C = O),
148.0 (Pyrazole-C), 141.0 (Ph-C), 140.3 (Pyrazole-C), 139.1 (Ph-C), 137.9 (Ph-C), 137.6
(Ph-C), 135.9 (Ph-C), 134.2 (Ph-C), 133.0 (Ph-C), 131.1 (Ph-C), 130.2 (Ph-C), 130.0
(2C, Ph-C), 129.2 (2C, Ph-C), 128.9 (2C, Ph-C), 127.5 (2C, Ph-C), 127.4 (Ph-C), 125.2
(Pyrazole-C), 12.6 (Pyrazole-CH3). ESI-FTMS for C23H15Cl3N2O3S [M+Na]+: Calcd.
526.9761, Found 526.9753.
Crystal Structure Determination
Compound 7d was dissolved in a mixed solvent of ethyl acetate and petroleum ether
and the resulting solution was allowed to stand in air at room temperature to give single
crystal of 7d. A colorless crystal of 7d suitable for X-ray diffraction with dimensions of
0.16 mm × 0.10 mm × 0.10 mm was mounted on a Rigaku MM-07 Saturn 724 CCD
diffractometer with Mo-Kα radiation (λ = 0.71073 Å) for data collection. A total of 12613
reflections were collected in the range of 1.96 < θ < 26.35 by using a phi and scan modes
at 294(2) K, of which 4528 were independent with Rint = 0.0725. All calculations were
refined anisotropically (SHELXS-97).24 All hydrogen atoms were located from a difference
Fourier map, placed at calculated positions, and included in the refinements in the riding
mode with isotropic thermal parameters. A summary of the key crystallgraphic information
were given in Table 1.
Herbicidal Activity Tests
Herbicidal activities in vivo of compounds 5, 6, and 7 were determined by rape root
test (Brassica campestris) and barnyardgrass cup test (Echinochloa crusgalli) according to
the reported method.25
Insecticidal Activity Test
Insecticidal activity of compounds against oriental armyworm (Mythimna separate
Walker) was performed in the greenhouse.16
CONCLUSION
A series of novel [5-(arylthio/sulfinyl/sulfonyl)-3-methyl-1-phenyl-1H-pyrazol-4-
yl]-arylmethanones have been synthesized successfully via multi-step reactions with
3-methyl-1-phenyl-1H-pyrazol-5(4H)-one as starting material and characterized by melt-
ing point and organic spectroscopy. The crystal structure of (5-(4-chlorophenylsulfonyl)-
3-methyl-1-phenyl-1H-pyrazol-4-yl)(2,4-dichlorophenyl)methanone (7d) is reported. The
biological activity results showed that some of the title compounds exhibit favorable her-
bicidal and insecticidal activities.

12
B.-L. WANG ET AL.
ACKNOWLEDGMENT
We thank Mrs. Li-Xia Xiong of the Biological Assay Center, Nankai University, for
insecticidal test of compounds.
FUNDING
This work was supported by the National Basic Research Program of China (No.
2010CB126106), the National Natural Science Foundation of China (Nos. 21372133 and
21272129) and Specialized Research Fund for the Doctorial Program of Higher Education
(20110031110017).
SUPPLEMENTAL MATERIAL
Supplementary data for this article can be accessed on the publisher’s website at
http://dx.doi.org/10.1080/10426507.2014.919503
CCDC-999266 contains the supplementary crystallographic data for this paper. These
data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html or from
the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK;
fax: +44-1223-336033; e-mail: deposit@ccdc.cam.ac.uk.
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