Synthesis and insecticidal activities of O,O-dialkyl-2-[3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carbonyloxy] (aryl) methylphosphonates

Article abstract of DOI:10.1080/10426507.2016.1206103

A series of novel O,O-Dialkyl-2-[3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carbonyloxy](aryl) methy-lphosphonates I-1–14 were designed and synthesized. The structures of all the title compounds were confirmed by ¹H-NMR, ¹³C-NMR, ³¹P-NMR, IR and elemental analysis. Their insecticidal activities against Mythimna separata and Plutella xylostella were evaluated. The results of bioassays indicated that the title compounds exhibited 20–80% larvicidal activity against Mythimna separata at 1000?mg/L.

Full text of DOI:10.1080/10426507.2016.1206103

Phosphorus, Sulfur, and Silicon and the Related Elements
ISSN: 1042-6507 (Print) 1563-5325 (Online) Journal homepage: http://www.tandfonline.com/loi/gpss20
Synthesis and insecticidal activities of O,O-
dialkyl-2-[3-bromo-1-(3-chloropyridin-2-
yl)-1H-pyrazole-5-carbonyloxy] (aryl)
methylphosphonates
Wei Wang, Lie-Ping Wang, Bin-Ke Ning, Ming-Zhen Mao, Chao Xue & Hai-
Yang Wang
To cite this article: Wei Wang, Lie-Ping Wang, Bin-Ke Ning, Ming-Zhen Mao, Chao
Xue & Hai-Yang Wang (2016) Synthesis and insecticidal activities of O,O-dialkyl-2-[3-
bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carbonyloxy] (aryl) methylphosphonates,
Phosphorus, Sulfur, and Silicon and the Related Elements, 191:10, 1362-1367, DOI:
10.1080/10426507.2016.1206103
To link to this article: http://dx.doi.org/10.1080/10426507.2016.1206103
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Date: 20 September 2016, At: 06:44

PHOSPHORUS, SULFUR, AND SILICON
, VOL. , NO. , –
http://dx.doi.org/./..
Synthesis and insecticidal activities of O,O-dialkyl--[-bromo--(-chloropyridin--yl)
-H-pyrazole--carbonyloxy] (aryl) methylphosphonates
Wei Wanga,b, Lie-Ping Wanga,b, Bin-Ke Ninga,b, Ming-Zhen Maoa,b, Chao Xuea,b, and Hai-Yang Wanga,b
aState Key Laboratory of Fluorine & Nitrogen Chemicals, Xi’an, Shaanxi, P. R. China; bXi’an Modern Chemistry Research Institute, Xi’an, Shaanxi, P. R.
China
ABSTRACT
ARTICLE HISTORY
Received  February 
Accepted  June 
A series of novel O,O-Dialkyl-2-[3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carbonyloxy](aryl) methy-
lphosphonates I-1–14 were designed and synthesized. The structures of all the title compounds were con-
firmedby1H-NMR, 13C-NMR, 31P-NMR, IRandelementalanalysis. TheirinsecticidalactivitiesagainstMythimna
separata and Plutella xylostella were evaluated. The results of bioassays indicated that the title compounds
exhibited 20–80% larvicidal activity against Mythimna separata at 1000 mg/L.
KEYWORDS
Synthesis; insecticidal
activity; pyridylpyrazole;
phosphonate
GRAPHICAL ABSTRACT
synthesis of O,O-Dialkyl-2-[3-bromo-1-(3-chloropyridin-2-yl)-
1H-pyrazole-5-carbonyloxy](aryl)-methylphosphonates I-1–
14. Their insecticidal activities against Mythimna separata and
Plutella xylostella were evaluated accordingly.
Introduction
Heterocyclic compounds display a wide range of biological
activities and have attracted considerable attention as the main
source of lead compounds in agrochemicals. Among various
biologically nitrogen-containing heterocycles, pyrazole, pyri-
dine, and their derivatives have occupied important posi-
tions in pesticide chemistry and are often introduced in the
Results and discussion
design of bioactive compounds.1-3 Some of these compounds Synthesis
have been developed as commercial pesticides, such as Chlo-
The synthetic procedures for the title compounds I are shown in
rantraniliprole (A),4 Cyantraniliprole (B),5 and Pyriprole (C)6
(Figure 1).
Schemes 1-3. According to the literature,1g the key intermedi-
ate pyrazole carboxylic acid 5 was synthesized from 3-chloro-2-
hydrazinylpyridine 1 which was used directly as obtained com-
mercially. Pyrazole-5-carbonyl chloride 6 could be prepared by
the reaction of pyrazole carboxylic acid 5 with thionyl chlo-
ride under reflux for 5–6 h11. The intermediate compounds 7
were synthesized via reaction of several aldehydes with dimethyl
phosphite or diethyl phosphite in dichloromethane using tri-
ethylamine as a catalyst in yields of 80–90%.10,11 Then, com-
pound 6 was reacted with compounds 7 to afford the title com-
pounds I. The structures of these newly synthesized compounds
were confirmed by 1H-NMR, 13C-NMR, 31P–NMR, IR, and ele-
mental analysis. The 1H-NMR, 13C-NMR, 31P–NMR of the title
On the other hand, organic phosphorus compounds repre-
sent another important type of bioactive compounds and have
received special attention in agrochemicals.7-13 Some novel
phosphonate derivatives are widely employed as fungicides and
herbicides, such as Dufulin (D)8 and Clacyfos (E)9(Figure 2).
In our previous work, it was shown that some alkylphospho-
nate derivatives possessed good herbicide activities3,10-12 and
some α-aminophosphonate derivatives exhibited high cyto-
tocity.13 In order to find new phosphonates with improved
pesticide activity, a series of novel phosphonate derivatives
were designed by introducing the N-pyridylpyrazole struc-
tural unit into the phosphonate molecule. Here, we describe the
CONTACT Wei Wang
wangwei@aliyun.com, Bin-Ke Ning
bkning@.com
Xi’an Modern Chemistry Research Institute, Xi’an, Shaanxi, P. R. China.
Supplemental data for this article can be accessed on the publisher’s website at http://dx.doi.org/./..
©  Taylor & Francis Group, LLC

PHOSPHORUS, SULFUR, AND SILICON
1363
Figure . Chemical structures of chlorantraniliprole (A), cyantraniliprole (B), and pyriprole (C).
compounds I-1–14 (Figures S1–S42) are presented in the Sup- separata at 1000 mg/L. Compounds (such as I-4, I-9–11) with
plemental Materials.
2-CH3, 4-CH3, 2-OCH3, 4-OCH3 as R1 show 40–70% larvici-
In the 1H-NMR spectra of the title compounds I-1–14, the dal activity against Mythimna separata at 1000 mg/L. It can be
chemical shifts of aromatic protons appeared at 6.86–8.50 ppm found that the electronic factor does not seem to play a signif-
and the proton signal corresponding to OCHP displayed dou- icant role as compounds with electron-rich and electron-poor
blets at 6.10–6.71 ppm. The proton signal corresponding to substituents, respectively. Interestingly, when CH3 as R, com-
the two methoxy groups (-OCH3) attached with phosphorus pounds with Cl or F or CH3 as R1 at ortho in phenyl ring
appears as two doublets at 3.60 0.06 and 3.72 0.06 ppm, show better larvicidal activities against Mythimna separata and
respectively. IR spectra of the title compounds I-1–14 showed Plutella xylostella at 500 mg/L compared to that substituted at
normal stretching absorption bands, indicating the existence para position.
of P═O (∼1246 cm−1), P–C (750–840 cm−1), P–O–C (1010–
Experimental details and the insecticidal activities (Table S 1)
1084 cm−1), C═O (∼1760 cm−1), C–O (∼1180 cm−1), Ar- are presented in the Supplemental Materials, together with sam-
H (∼3130 cm−1), and C–H (2954–3002 cm−1). The typi- ple 1H, 13C, and 31P NMR spectra for the products (Figures S1–
cal phosphorus resonance at 15.5–19.2 ppm in the 31P–NMR S42)
spectra of I-1–14 reveals the presence of a phosphorus cen-
ter coupled to an adjacent CH. The EI mass spectra of the
title compounds I-1–4 revealed the existence of the molecu-
lar ion peaks, which were in good accordance with the given
structures of title compounds. The elemental analysis of all
target compounds are in good agreement with the theoretical
data.
Conclusions
In summary, a series of phosphonates derivatives containing N-
pyridylpyrazole structural unit were synthesized with moder-
ate to good yields and screened for their insecticidal activity.
Chlorantraniliprol was slected as a positive control. A prelim-
inary bioassay shows that some of the title compounds exhib-
ited certain insecticidal activities against Mythimna separata and
Plutella xylostella.
Insecticidal activity
The preliminary results of insecticidal activity assessment indi-
cate that the title compounds I exhibited 20–80% larvicidal
activities against Mythimna separata at 1000 mg/L and the data
are shown in Table S 1 (Supplemental Materials). Some of
the title compounds were then selected for further test against
Mythimna separata and Plutella xylostella at 500 mg/L using
Chlorantraniliprol as a positive control. The subsequent results
show that the title compounds I-1, I-3, I-4, I-5, I-7, I-8 and I-11
have certain insecticidal activity against Mythimna separata with
10–50% death rates and Plutella xylostella with 0–17.5% death
rates at 500 mg/L. As shown in Table S1, compounds (such as
I-1–3, I-6–8, I-12, I-14) with 2-Cl, 2-F, 4-Cl, 4-F, 2,4-Cl2, 4-CF3,
4-Br as R1 show 30–80% larvicidal activity against Mythimna
Experimental
All the reagents were of analytical grade. Melting points were
determined using an X-4 apparatus and uncorrected. 1H NMR,
31P NMR, 13C NMR spectra were measured on a Bruker AC-
P500 (500 Hz) instrument using TMS as an internal stan-
dard and CDCl3 as solvent. MS spectra were analyzed on
a Finnigen TRACE spectrometer and API2000LC/MS. Ele-
mental analyses were performed by a Vario EL III elemental
analyzer.
Synthesis of the intermediate 3-bromo-1-(3-chloropyridin-
2-yl)-1H-pyrazole-5-carbonyl chloride 6
The intermediate compound 5 was synthesized according to the
literature.1g A mixture containing the intermediate compound 5
(3.5 mmol) and thionyl chloride (3 mL) was added into a 25 mL
flask and refluxed for 5–6 h. Excess thionyl chloride was evap-
orated off under reduced pressure, and a light yellow oil 6 was
obtained in a yield of 94%.
Figure . Chemical structures of dufulin (D) and clacyfos (E).

1364
W. WANG ET AL.
Scheme . Synthesis of Compounds 6. Reagents and conditions: (a) diethyl maleate, NaOEt, EtOH, reflux, (b) POBr, MeCN,  °C, (c) KSO, HSO, MeCN, reflux, (d) (i)
aqueous NaOH, MeOH and (ii) aqueous HCl, (e) SOCl, reflux.
Scheme . Synthesis of compounds 7.
Synthesis of the intermediate O,O-dialkyl-1-hydroxyalk
ylphosphonates 7
(20 mL) at 0–5 °C. The resulting mixture was stirred for 3–
5 h at room temperature and then for 1–2 h at 40 °C. The
dichloromethane layer was washed with 0.1 M hydrochlo-
ric acid, saturated sodium hydrogen carbonate solution, and
brine, dried, and concentrated. The residue was purified by col-
umn chromatography on silica gel and elution with petroleum
ether/acetone (4:1, v/v) to give the corresponding pure title com-
pounds I-1–14 in 66–90% yields.
The intermediate compounds 7 could be prepared by the
reaction of several aldehydes (4 mmol) and dimethyl phos-
phite or diethyl phosphite (4 mmol) in dichloromethane (15
mL) using triethylamine (2 mmol) as a catalyst in yields of
80–90%10,11
.
General procedure for the synthesis of the title compounds O,O-Dimethyl-2-[3-bromo-1-(3-chloropyridin-2-yl)-1H-
I-1–14
pyrazole-5-carbonyloxy](2-chlorophenyl)methylp-
hosphonate I-1:
A solution of pyrazole carbonyl chloride 6 (3.3 mmol) in
dichloromethane (15 mL) was added to a stirred mixture of White solid; yield, 82%; mp, 95–96 °C; H NMR (500 MHz,
7 (3 mmol) and triethylamine (3.3 mmol) in dichloromethane CDCl3): δ 3.61 (d, 3H, J = 10.5 Hz, P-O-CH3), 3.78 (d, 3H,
1
Scheme . Synthesis of the target compounds I.

PHOSPHORUS, SULFUR, AND SILICON
1365
1080, 1064, 1046, 961, 759; EI-MS m/z (%): 513 (M+, 8); Anal.
Calcd for C19H18BrClN3O5P: C, 44.34; H, 3.52; N, 8.16; Found:
C, 44.38; H, 3.92; N, 8.29.
J = 10.5 Hz, P-O-CH3), 6.70 (d, 1H, J = 13.5 Hz, P-CH),
7.19 (s, 1H, 4H-Pyrazole), 7.26–8.50 (m, 7H, 3,4,5,6H-Ar, 4,5,6H-
1
Py); 13C NMR (125 MHz, CDCl3): δ 53.9, 67.4 (d, JC-P
=
168.99 Hz), 115.0, 126.4, 127.3, 128.3, 129.1, 129.6, 130.4, 133.4,
134.9, 139.3, 147.1, 148.3, 155.6, 155.7; 31P NMR (202 MHz,
CDCl3): δ 17.9; IR (KBr)/cm−1: 3456, 3119, 3071, 2963, 2938,
2906, 1741, 1580, 1511, 1469, 1358, 1291, 1255, 1226, 1134, 1073,
1040, 1025, 960, 759; EI-MS m/z (%): 532 (M+, 8); Anal. Calcd
for C18H15BrCl2N3O5P: C, 40.40; H, 2.83; N, 7.85. Found: C,
40.48; H, 2.92; N, 7.59.
O,O-Dimethyl-2-[3-bromo-1-(3-chloropyridin-2-yl)-1H-
pyrazole-5-carbonyloxy](2,2-difluorobenzo[d][1,3]dioxole-
4-yl)methylphosphonate I-5:
White solid; yield, 68%; mp, 121–123 °C; 1H NMR (500 MHz,
CDCl3): δ 3.64 (d, 3H, J = 11.0 Hz, P-O-CH3), 3.76 (d, 3H,
J = 11.0 Hz, P-O-CH3), 6.31 (d, 1H, J = 13.5 Hz, P-CH),
7.02–8.50 (m, 7H, 4H-Pyrazole, 4,5,6H-Ar, 4,5,6H-Py); 13C NMR
O,O-Diethyl-2-[3-bromo-1-(3-chloropyridin-2-yl)-1H-
pyrazole-5-carbonyloxy](2- chlorophenyl)methylp-
hosphonate I-2:
1
1
(125 MHz, CDCl3): δ 53.8, 64.9 (d, JC-P = 163.6 Hz), 109.0,
White solid; yield, 79%; mp, 85–87 °C; H NMR (500 MHz,
109.1, 115.1, 119.9, 122.4, 123.7, 123.8, 126.2, 128.4, 131.5, 134.6,
136.8, 137.7, 139.3, 140.9, 141.0, 143.3, 147.1, 148.3, 155.6, 155.8;
31P NMR (202 MHz, CDCl3): δ 16.9; IR (KBr)/cm−1: 3454, 3131,
3090, 2976, 2911, 2868, 1749, 1643, 1575, 1466, 1358, 1291,
1256, 1239, 1185, 1149, 1082, 1063, 1046, 960, 758; Anal. Calcd
for C19H14BrClF2N3O7P: C, 39.30; H, 2.43; N, 7.24; Found: C,
39.38; H, 2.52; N, 7.28.
CDCl3): δ 1.16 (t, 3H, J = 7.0 Hz, P-O-CH2CH3), 1.30 (t,
3H, J = 7.0 Hz, P-O-CH2CH3), 3.85–4.18 (m, 2×2H, 2×P-O-
4
CH2CH3), 6.67 (d, 1H, J = 13.5Hz, P-CH), 7.19(s, 1H, H-
Pyrazole), 7.26–8.47 (m, 7H, 3,4,5,6H-Ar, 4,5,6H-Py); 13C NMR
1
(125 MHz, CDCl3): δ 16.5, 63.6, 67.8 (d, JC-P = 171.9 Hz),
114.9, 126.3, 127.2, 128.3, 129.2, 129.6, 129.8, 130.3, 133.6, 135.1,
139.3, 147.1, 148.4, 155.7, 155.8; 31P NMR (202 MHz, CDCl3): δ
15.5; IR (KBr)/cm−1: 3457, 3119, 3073, 2988, 2963, 2939, 2906,
1738, 1575, 1510, 1469, 1358, 1291, 1255, 1226, 1134, 1076,
1043, 960, 759; EI-MS m/z (%):561 (M+, 4); Anal. Calcd for
C20H19BrCl2N3O5P: C, 42.65; H, 3.40; N, 7.46; Found: C, 42.88,
H, 3.82, N, 7.49.
O,O-Dimethyl-2-[3-bromo-1-(3-chloropyridin-2-yl)-1H-
pyrazole-5-carbonyloxy](2,4-dichlorophenyl)
methylphosphonate I-6:
White solid; yield, 88%; mp, 117–119 °C; 1H NMR (500 MHz,
CDCl3): δ 3.64 (d, 3H, J = 11.0 Hz, P-O-CH3), 3.78 (d, 3H, J =
10.5 Hz, P-O-CH3), 6.60 (d, 1H, J = 13.5 Hz, P-CH), 7.18(s, 1H,
4H-Pyrazole), 7.26–8.50 (m, 6H, 3,5,6H-Ar, 4,5,6H-Py); 13C NMR
O,O-Dimethyl-2-[3-bromo-1-(3-chloropyridin-2-yl)-1H-
pyrazole-5-carbonyloxy](4-chlorophenyl)methylp-
hosphonate I-3:
White solid; yield, 84%; mp, 109–111 °C; 1H NMR (500 MHz,
CDCl3): δ 3.63 (d, 3H, J = 11.0 Hz, P-O-CH3), 3.69 (d, 3H,
J = 11.0 Hz, P-O-CH3), 6.13 (d, 1H, J = 13.5 Hz, P-CH),
1
(125 MHz, CDCl3): δ 54.2, 67.0 (d, JC-P = 172.3 Hz), 115.1,
126.3, 127.7, 128.0, 128.4, 129.2, 129.3, 129.6, 130.6, 134.3, 134.8,
135.9, 139.3, 147.1, 148.3, 155.5, 155.6; 31P NMR (202 MHz,
CDCl3): δ 17.6; IR (KBr)/cm−1: 3449, 3113, 3088, 2976, 2911,
2869, 1747, 1640, 1576, 1468, 1357, 1290, 1258, 1236, 1185, 1150,
1083, 1065, 1046, 960, 759; Anal. Calcd for C18H14BrCl3N3O5P:
C, 37.96; H, 2.48; N, 7.38; Found: C, 38.08; H, 2.72; N, 7.69.
7.19(s, 1H, 4H-Pyrazole), 7.32–8.50 (m, 7H, 2,3,5,6H-Ar, 4,5,6H-
1
Py); 13C NMR (125 MHz, CDCl3): δ 53.9, 70.4 (d, JC-P
=
169.8 Hz), 115.0, 126.3, 128.4, 128.9, 129.2, 130.7, 134.9, 139.2,
147.1, 148.4, 155.8, 155.9; 31P NMR (202 MHz, CDCl3): δ 18.1;
IR (KBr)/cm−1: 3443, 3132, 3097, 2956, 2918, 2851, 1739, 1650,
1578, 1469, 1358, 1292, 1256, 1239, 1184, 1149, 1084, 1063,
1047, 960, 759; EI-MS m/z (%): 532 (M+, 6); Anal. Calcd for
C18H15BrCl2N3O5P: C, 40.40; H, 2.83; N, 7.85; Found: C, 40.42;
H, 2.86; N, 7.89.
O,O-Dimethyl-2-[3-bromo-1-(3-chloropyridin-2-yl)-1H-
pyrazole-5-carbonyloxy](2-fluorophenyl)methyl-
phosphonate I-7:
O,O-Dimethyl-2-[3-bromo-1-(3-chloropyridin-2-yl)-1H-
pyrazole-5-carbonyloxy](4-methyl-phenyl)methylp-
hosphonate I-4:
White solid; yield, 86%; mp, 101–103 °C; 1H NMR (500 MHz,
CDCl3): δ 3.64 (d, 3H, J = 11.0 Hz, P-O-CH3), 3.76 (d, 3H,
J = 11.0 Hz, P-O-CH3), 6.52 (d, 1H, J = 13.0 Hz, P-CH),
1
White solid; yield, 77%; mp, 68–70 °C; H NMR (500 MHz, 7.03–8.48 (m, 8H, 4H-Pyrazole, 3,4,5,6H-Ar, 4,5,6H-Py); 13C NMR
1
CDCl3): δ 2.33 (s, 3H, Ar-CH3), 3.60 (d, 3H, J = 11.0 Hz, P- (125 MHz, CDCl3): δ 54.1, 64.2 (d, JC-P = 173.3 Hz), 105.1,
O-CH3), 3.68 (d, 3H, J = 10.5 Hz, P-O-CH3), 6.14 (d, 1H, J 115.0, 115.6, 115.7, 119.9, 120.0, 124.6, 126.3, 128.3, 129.2, 129.3,
= 13.0 Hz, P-CH), 7.14–8.50 (m, 8H, 4H-Pyrazole, 2,3,5,6H-Ar, 129.4, 131.0, 131.1, 134.9, 139.2, 147.1, 148.4, 155.7, 155.8; 31
P
4,5,6H-Py); 13C NMR (125 MHz, CDCl3): δ 21.3, 54.1, 70.9 (d, NMR (202 MHz, CDCl3): δ 17.9; IR (KBr)/cm−1: 3451, 3123,
1JC-P = 170.5 Hz), 105.4, 113.9, 114.9, 126.3, 127.1, 127.8, 128.9, 3097, 2986, 2909, 2860, 1750, 1645, 1576, 1466, 1358, 1290, 1257,
129.4, 135.8, 139.3, 147.0, 156.4, 156.5; 31P NMR (202 MHz, 1238, 1180, 1152, 1081, 1065, 1044, 960, 758; Anal. Calcd for
CDCl3): δ 18.8; IR (KBr)/cm−1: 3441, 3112, 3087, 2966, 2908, C18H15BrClFN3O5P: C, 41.68; H, 2.92; N, 8.10; Found: C, 42.08;
2860, 1741, 1647, 1577, 1468, 1358, 1290, 1255, 1237, 1183, 1150, H, 3.02; N, 8.19.

1366
W. WANG ET AL.
129.3, 130.6, 135.3, 136.6, 139.2, 147.1, 148.5, 155.9, 156.1; 31
P
O,O-Dimethyl-2-[3-bromo-1-(3-chloropyridin-2-yl)-1H-
pyrazole-5-carbonyloxy](4-fluorophenyl)methylp-
hosphonate I-8:
NMR (202 MHz, CDCl3): δ 19.2; IR (KBr)/cm−1: 3441, 3150,
3054, 2955, 2852, 1740, 1645, 1579, 1472, 1358, 1297, 1263,
1240, 1174, 1151, 1078, 1057, 1027, 961, 763; Anal. Calcd for
C19H18BrClN3O5P: C, 44.34; H, 3.52; N, 8.16; Found: C, 44.38;
H, 3.92; N, 8.29.
White solid; yield, 79%; mp, 131–133 °C; 1H NMR (500 MHz,
CDCl3): δ 3.61 (d, 3H, J = 11.0 Hz, P-O-CH3), 3.70 (d, 3H,
J = 10.5 Hz, P-O-CH3), 6.14 (d, 1H, J = 13.5 Hz, P-CH),
7.01–8.50 (m, 8H, 4H-Pyrazole, 2,3,5,6H-Ar, 4,5,6H-Py); 13C NMR
1
(125 MHz, CDCl3): δ 53.7, 69.9 (d, JC-P = 160.5 Hz), 105.2,
115.2, 115.3, 115.4, 126.3, 128.7, 128.8, 128.9, 129.0, 132.4, 136.9,
137.7, 139.3, 147.1, 159.4, 161.6, 163.6; 31P NMR (202 MHz,
CDCl3): δ 18.4; IR (KBr)/cm−1: 3455, 3119, 3094, 2970, 2906,
2863, 1742, 1649, 1578, 1465, 1358, 1291, 1256, 1236, 1180, 1150,
1081, 1065, 1045, 960, 759; Anal. Calcd for C18H15BrClFN3O5P:
C, 41.68; H, 2.92; N, 8.10; Found: C, 41.81; H, 3.13; N, 8.11.
O,O-Dimethyl-2-[3-bromo-1-(3-chloropyridin-2-yl)-1H-
pyrazole-5-carbonyloxy](4-trifluoromethylphenyl)
methylphosphonate I-12:
White solid; yield, 70%; mp, 138–140 °C; 1H NMR (500 MHz,
CDCl3): δ 3.66 (d, 3H, J = 10.5 Hz, P-O-CH3), 3.70 (d, 3H, J
= 11.0 Hz, P-O-CH3), 6.22 (d, 1H, J = 14.0 Hz, P-CH), 7.21
4
(s, 1H, H-Pyrazole), 7.44–8.50 (m, 7H, 2,3,5,6H-Ar, 4,5,6H-Py);
13C NMR (125 MHz, CDCl3): δ 53.9, 70.4 (d, 1JC-P = 168.0 Hz),
115.1, 125.6, 125.7, 125.8, 126.3, 127.9, 128.0, 129.2, 130.8, 131.0,
131.1, 131.3, 131.4, 131.6, 134.7, 136.2, 139.3, 147.1, 148.4, 155.8,
O,O-Dimethyl-2-[3-bromo-1-(3-chloropyridin-2-yl)-1H-
pyrazole-5-carbonyloxy](2-methoxyphenyl)methylp-
hosphonate I-9:
155.9; 31P NMR (202 MHz, CDCl3): δ 17.8; IR (KBr)/cm−1
:
White solid; yield, 66%; mp, 126–128 °C; 1H NMR (500 MHz,
CDCl3): δ 3.55 (d, 3H, J = 10.5 Hz, P-O-CH3), 3.68 (d, 3H,
J = 11.0 Hz, P-O-CH3), 3.77 (s, 3H, -OCH3), 6.73 (d, 1H, J
= 12.5 Hz, P-CH), 6.81–8.42 (m, 8H, 4H-Pyrazole, 3,4,5,6H-Ar,
4,5,6H-Py); 13C NMR (125 MHz, CDCl3): δ 53.8, 55.8, 64.6 (d,
1JC-P = 172.0 Hz), 105.1, 110.9, 114.9, 120.8, 126.2, 128.2, 129.2,
135.4, 137.0, 137.7, 139.2, 147.0, 148.4, 155.9, 156.7; 31P NMR
(202 MHz, CDCl3): δ 16.9; IR (KBr)/cm−1: 3441, 3121, 3099,
2969, 2905, 2862, 1748, 1644, 1576, 1468, 1355, 1291, 1256,
1236, 1181, 1152, 1080, 1065, 1047, 957, 758; Anal. Calcd for
C19H18BrClN3O6P: C, 43.00; H, 3.42; N, 7.92; Found: C, 43.08;
H, 3.52; N, 8.09.
3440, 3130, 3044, 2965, 2858, 1741, 1645, 1578, 1471, 1358, 1296,
1261, 1239, 1173, 1150, 1079, 1055, 1030, 960, 762; Anal. Calcd
for C19H15BrClF3N3O5P: C, 40.13; H, 2.66; N, 7.39; Found: C,
40.38; H, 2.72; N, 7.41.
O,O-Dimethyl-2-[3-bromo-1-(3-chloropyridin-2-yl)-1H-
pyrazole-5-carbonyloxy](phenyl)methylphosphonate
I-13:
White solid; yield, 90%; mp, 141–143 °C; 1H NMR (500 MHz,
CDCl3): δ3.60 (d, 3H, J = 11.0 Hz, P-O-CH3), 3.67 (d, 3H, J
= 11.0 Hz, P-O-CH3), 6.18 (d, 1H, J = 13.0 Hz, P-CH), 7.20
O,O-Dimethyl-2-[3-bromo-1-(3-chloropyridin-2-yl)-1H-
pyrazole-5-carbonyloxy](4-methoxyphenyl)methylphos-
phonate I-10:
4
(s, 1H, H-Pyrazole), 7.33–8.50 (m, 8H, Ar-H, 4,5,6H-Py); 13C
1
NMR (125 MHz, CDCl3): δ 53.9, 71.0 (d, JC-P = 169.3 Hz),
105.2, 114.9, 126.3, 127.8, 128.3, 128.7, 129.3, 135.1, 137.7, 139.2,
147.1, 155.9, 156.0; 31P NMR (202 MHz, CDCl3): δ 18.6; IR
(KBr)/cm−1: 3443, 3122, 3054, 2961, 2855, 1740, 1646, 1579,
1474, 1358, 1295, 1260, 1237, 1174, 1150, 1081, 1054, 1033, 961,
759; Anal. Calcd for C18H16BrClN3O5P: C, 43.18; H, 3.22; N,
8.39; Found: C, 43.31; H, 3.52; N, 8.44.
White solid; yield, 72%; mp, 117–119 °C; 1H NMR (500 MHz,
CDCl3): δ 3.59 (d, 3H, J = 10.5 Hz, P-O-CH3), 3.69 (d, 3H,
J = 10.5 Hz, P-O-CH3), 3.79 (s, 3H, -OCH3), 6.11 (d, 1H, J
= 13.0 Hz, P-CH), 6.86–8.49 (m, 8H, 4H-Pyrazole, 2,3,5,6H-Ar,
4,5,6H-Py); 13C NMR (125 MHz, CDCl3): δ 53.9, 55.3, 70.7 (d,
1JC-P = 171.9 Hz), 114.2, 114.9, 126.2, 128.3, 129.3, 129.6, 135.3,
139.2, 147.1, 148.5, 156.0, 156.1, 160.3; 31P NMR (202 MHz,
CDCl3): δ 18.9; IR (KBr)/cm−1: 3440, 3129, 3082, 2955, 2930,
2851, 1736, 1644, 1611, 1578, 1514, 1471, 1360, 1293, 1246, 1180,
1134, 1047, 959, 815, 762; Anal. Calcd for C19H18BrClN3O6P: C,
43.00; H, 3.42; N, 7.92; Found: C, 43.13; H, 3.47; N, 8.11.
O,O-Dimethyl-2-[3-bromo-1-(3-chloropyridin-2-yl)-1H-
pyrazole-5-carbonyloxy](4-bromophenyl)
methylphosphonate I-14:
White solid; yield, 71%; mp, 148–150 °C; 1H NMR (500 MHz,
CDCl3): δ 3.63 (d, 3H, J = 10.5 Hz, P-O-CH3), 3.69 (d, 3H, J
= 10.5 Hz, P-O-CH3), 6.12 (d, 1H, J = 13.5 Hz, P-CH), 7.19
O,O-Dimethyl-2-[3-bromo-1-(3-chloropyridin-2-yl)-1H-
pyrazole-5-carbonyloxy](2-methylphenyl)methylphos-
phonate I-11:
4
(s, 1H, H-Pyrazole), 7.24–8.50 (m, 7H, 2,3,5,6H-Ar, 4,5,6H-Py);
13C NMR (125 MHz, CDCl3): δ 53.9, 70.4 (d, 1JC-P = 169.5 Hz),
White solid; yield, 83%; mp, 125–127 °C; 1H NMR (500 MHz, 115.0, 123.5, 126.3, 128.4, 129.2, 129.4, 131.2, 131.9, 134.9, 139.2,
CDCl3): δ 2.41 (s, 1H, Ar-CH3), 3.57 (d, 3H, J = 10.5 Hz, P- 147.1, 148.4, 155.8, 155.9; 31P NMR (202 MHz, CDCl3): δ 18.0;
O-CH3), 3.69 (d, 3H, J = 10.5 Hz, P-O-CH3), 6.40 (d, 1H, IR (KBr)/cm−1: 3437, 3131, 3096, 2954, 2920, 2851, 1740, 1651,
4
J = 13.5Hz, P-CH), 7.14–8.50 (m, 8H, H-Pyrazole, 3,4,5,6H- 1578, 1512, 1469, 1358, 1238, 1184, 1135, 1062, 1047, 960, 815,
Ar, 4,5,6H-Py); 13C NMR (125 MHz, CDCl3): δ 19.5, 53.9, 67.8 763; Anal. Calcd for C18H15Br2ClN3O5P: C, 37.30; H, 2.61; N,
1
(d, JC-P = 170.9 Hz), 114.9, 126.2, 126.4, 128.0, 128.3, 129.1, 7.25; Found: C, 37.51; H, 3.02; N, 7.46.

PHOSPHORUS, SULFUR, AND SILICON
1367
Phosphorus Sulfur Silicon Relat. Elem., 2002, 177, 1597–1600. (c)
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