Synthesis and herbicidal activities of sodium hydrogen 1-(substituted phenoxyacetoxy)alkylphosphonates

Article abstract of DOI:10.1080/10426507.2012.717147

A series of sodium hydrogen 1-(substituted phenoxyacetoxy) alkylphosphonates was designed and synthesized. The test for herbicidal activity indicated that most of the phosphonates (8) possessed excellent postemergence herbicidal activities against broadleaf weeds. Especially, 8f and 8g showed the best herbicidal activity against rape and amaranth with more than 95% inhibitory rate. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.

Full text of DOI:10.1080/10426507.2012.717147

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Synthesis and Herbicidal Activities
of Sodium Hydrogen 1-(Substituted
Phenoxyacetoxy)Alkylphosphonates
Qingwu Long a , Xiaoyan Deng a , Yujiao Gao a , Huayong Xie a , Hao
Peng a & Hongwu He a
a The Key Laboratory of Pesticide & Chemical Biology, Ministry of
Education, College of Chemistry , Central China Normal University ,
Wuhan , P. R. China
Accepted author version posted online: 09 Aug 2012.Published
online: 05 Jul 2013.
To cite this article: Qingwu Long , Xiaoyan Deng , Yujiao Gao , Huayong Xie , Hao Peng &
Hongwu He (2013) Synthesis and Herbicidal Activities of Sodium Hydrogen 1-(Substituted
Phenoxyacetoxy)Alkylphosphonates, Phosphorus, Sulfur, and Silicon and the Related Elements, 188:7,
819-825, DOI: 10.1080/10426507.2012.717147
To link to this article: http://dx.doi.org/10.1080/10426507.2012.717147
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Phosphorus, Sulfur, and Silicon, 188:819–825, 2013
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2012.717147
SYNTHESIS AND HERBICIDAL ACTIVITIES OF SODIUM
HYDROGEN 1-(SUBSTITUTED
PHENOXYACETOXY)ALKYLPHOSPHONATES
Qingwu Long, Xiaoyan Deng, Yujiao Gao, Huayong Xie,
Hao Peng, and Hongwu He
The Key Laboratory of Pesticide & Chemical Biology, Ministry of Education,
College of Chemistry, Central China Normal University, Wuhan, P. R. China
GRAPHICAL ABSTRACT
Abstract A series of sodium hydrogen 1-(substituted phenoxyacetoxy) alkylphosphonates was
designed and synthesized. The test for herbicidal activity indicated that most of the phos-
phonates (8) possessed excellent postemergence herbicidal activities against broadleaf weeds.
Especially, 8f and 8g showed the best herbicidal activity against rape and amaranth with more
than 95% inhibitory rate.
Supplemental materials are available for this article. Go to the publisher’s online edition of
Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.
Keywords Synthesis; herbicidal activity; phosphonate
INTRODUCTION
Alpha-substituted alkylphosphonate derivatives have received considerable attention
in medicine and pesticide chemistry due to their biological activities over the past two
Received 29 June 2012; accepted 20 July 2012.
This work was supported by the National Basic Research Program of China (2010CB126100), the National
Key Technologies R & D Program of China (No.2011BAE06B03), and the National Natural Science Foundation
of China (No. 21172090 and No. 21002037). The research was supported in part by the PCSIRT (No. IRT0953)
Address correspondence to Hao Peng, or Hongwu He, The Key Laboratory of Pesticide & Chemical Biology,
Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, 430079,
P. R. China. E-mail: penghao@mail.ccnu.edu.cn, he1208@mail.ccnu.edu.cn
819

820
Q. LONG ET AL.
decades.1–5 Especially, α-(substituted phenoxyacetoxy)alkylphosphonates, as potent pyru-
vate dehydrogenase complex (PDHc) inhibitors,6,7 possess notable herbicidal activities.8
Based on the bioisosterism, their phosphonic acids were assumed to have better herbici-
dal activity, because phosphonic acid is more analogous to the pyruvic acid, which acts
as the substrate of pyruvate dehydrogenase complex.9 So we are interested in extending
our investigations to design some α-(substituted phenoxyacetoxy)alkylphosphonic acids.
However, as strong acids, these phosphonic acids themselves would lead the cleavage of
carboxylate ester group in the structures.10 Therefore, monosalts of α-(substituted phenoxy-
acetoxy)alkylphosphonic acids were designed, which are almost neutral salts with higher
stability than the corresponding phosphonic acids. Herein, 13 novel sodium hydrogen
1-(substituted phenoxyacetoxy)alkylphosphonates were synthesized and their herbicidal
activities were evaluated.
RESULTS AND DISCUSSION
Syntheses
The multistep procedure for the synthesis of the title phosphonates 8 is outlined
in Scheme 1. The methods for the synthesis of substituted phenoxyacetyl chloride
X
X
O
C
O
C
SOCl2
+
Y
O
CH2
OH
Y
O
CH2
Cl
1
2
O
P
O
RCHO
KF/Al2O3
H
OCH3
OCH3
OCH3
OCH3
HO
C
R
HP
4
3
X
X
X
O
Pyridine
O
P
O
C
H
O
OCH3
OCH3
H
C
OCH3
OCH3
+
HO
O
C
R
P
Y
Y
O
O
CH2
5
O
O
Y
O
CH2
C
Cl
X
R
4
2
O
P
O
O
C
CH3OH
Me3SiCl/NaI
CH3CN
H
C
R
H
C
R
OH
OH
OSiMe3
OSiMe3
CH2
Y
O
CH2
C
O
P
6
7
X
O
NaOH
O
H
OH
Y
O
CH2
8
C
O
P
C
R
ONa
Scheme 1 Synthesis of the title compounds 8.
2, dimethyl 1-hydroxyalkylalkylphosphonates 4, and dimethyl 1-(substituted phenoxy-
acetoxy)alkylphosphonates 5 were adopted, according to the previous work reported in

SYNTHESIS AND HERBICIDAL ACTIVITIES
821
Table 1 Preparation of sodium hydrogen 1-(substituted phenoxyacetoxy)alkylphosphonates 8a–8m
Compound
X
Y
R
Appearance
mp (◦C)
Yield (%)
8a
8b
8c
8d
8e
8f
8g
8h
8i
Cl
Cl
Cl
Cl
Cl
Cl
Cl
CH3
CH3
CH3
CH3
CH3
CH3
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
CH3
C2H5
White solid
White solid
White solid
White solid
White solid
White solid
White solid
White solid
White solid
White solid
White solid
White solid
White solid
150–151
133–134
173–175
157–158
179–181
145–146
135–136
140–141
130–131
185–187
110–111
175–177
108–109
88
92
86
84
91
87
56
89
89
83
93
87
83
n-C3H7
i-C3H7
n-C4H9
Phenyl
Thien-2-yl
CH3
C2H5
8j
8k
8l
n-C3H7
i-C3H7
n-C4H9
Phenyl
8m
our group.11–13 The phosphonates 5 reacted with chlorotrimethylsilane in acetonitrile us-
ing sodium iodide as a catalyst to provide bis(trimethylsilyl) 1-(substituted phenoxyace-
toxy)alkylphosphonates 6, which were further transformed into 1-(substituted phenoxyace-
toxy)alkylphosphonic acids 7 by reaction with methanol. The title phosphonates 8 were
then obtained by the reaction with sodium hydroxide (Table 1).
The structures of the phosphonates 8 were confirmed by IR, 1H NMR, and elemental
analysis; 8a and 8h were also identified via MS. The IR displayed a weak and wide P-O-
H combination peak at 2300–2250 cm−1, P O stretching vibration at ∼1200 cm−1, and
1
the two strong absorption bands at ∼1080 cm−1. In the H NMR spectra, the signal of
methylene group flanked by the phenoxy and carbonyl appeared as a symmetric quartet,
which belongs to the AB coupled system, such as the compound 8f (Figure S3 in the
supplemental material available online).
Herbicidal Activities
The herbicidal activities of the title phosphonates 8 were evaluated at the dosage of
150 g ai/ha in a set of experiments in a greenhouse. They were tested for postemergence in-
hibitory effect against Echinochloa crusgalli Beava (barnyard grass), Digitaria sanguinalis
Scop (ascendant crabgrass), Brassica napus L. (rape), Amaranthus retroflerus L. (ama-
ranth), Setaria viridis (green bristlegrass) and Chenopodium serotinum (small goosefoot).
It was found that 8 displayed higher herbicidal activities against dicotyledonous weeds
than monocotyledon. The phosphonates 8f (R = phenyl) and 8g (R = thien-2-yl) showed
the best herbicidal activity against rape and amaranth with more than 95% inhibitory rate.
Experimental details and the table of activities (Table S1 and S2) are presented in the
supplemental materials available online.
CONCLUSIONS
In conclusion, a series of sodium hydrogen 1-(substituted phenoxyacetoxy)
alkylphosphonates were designed and synthesized via the key intermediate 1-(substituted
phenoxyacetoxy)alkylphosphonic acids with satisfactory yields. The test for herbicidal

822
Q. LONG ET AL.
activity indicated that most of the title compounds possessed excellent postemergence
herbicidal activities against broadleaf weeds, and they displayed higher herbicidal
activities against dicotyledonous weeds than monocotyledon. Especially, sodium hydrogen
1-(2,4-dichlorophenoxyacetoxy)-1-phenylmethylphosphonate and sodium hydrogen 1-
(2,4-dichlorophenoxyacetoxy)-1-thien-2’-ylmethylphosphonate showed the best herbicidal
activity against rape and amaranth with more than 95% inhibitory rate, which provided
some indications for further studies on structure modification.
EXPERIMENTAL
Mass spectra were measured on API2000LC/MS. Infrared spectra were recorded in
potassium bromide pellets with a Nicolet Avatar 360 Fourier transform infrared (FTIR)
1
spectrophotometer. H NMR spectra were recorded in D2O solution using sodium 3-
(trimethylsilyl)propane-1-sulfonate (DSS) as an internal standard with a Varian Mercury-
Plus 400 (400 MHz) spectrometer. Elemental analysis was performed with an Elementar
Vario EL III elementary analyzer. Melting points were measured with an electrothermal
mp apparatus and are uncorrected.
Synthesis
All of the compounds 1–5 were synthesized (Scheme 1) according to the methods
described in the literature.14–17
General Procedure for 5
To a solution of dimethyl (1-hydroxyalkyl)phosphonates 4 (10 mmol) and pyridine
(14 mmol) in CH2Cl2 (25 mL), a solution of substituted phenoxyacetyl chloride 2 (10 mmol)
◦
was added dropwise in CH2Cl2 (15 mL) at below 5 C, and the mixture was stirred
for 4 h, which was monitored by TLC. The oily residue was purified by flash column
chromatography on silica gel with the mixture of acetone/petroleum ether (v:v 1:4) as
eluent to furnish 5.
General Procedure for 6
Under a nitrogen atmosphere and in a dark environment, to a solution of 5 (10 mmol)
and sodium iodide (22 mmol) in ac◦etonitrile (25 mL), was added all of trimethylchlorosilane
(22 mmol) in one portion at 30 C, then the reaction mixture was stirred for 2 h. The
resultant mixture was purified by flash column chromatography on silica gel with a mixture
of petroleum ether/n-propanol (v:v 3:1) as eluent to furnish 6 as a colorless oil.
General Procedure for 7
To a solution of 6 (10◦mmol) in anhydrous methanol (25 mL), the reaction mixture
was stirred for 2–3 h at 30 C, which was monitored by TLC. The solvent was removed
under reduced pressure followed by column chromatography on silica gel with a mixture
of petroleum ether/n-propanol (v:v 1:3) as eluent to yield 7.

SYNTHESIS AND HERBICIDAL ACTIVITIES
823
General Procedure for Compounds (8a–8m)
To a solution of 7 (5.5 mmol) in methanol (20 mL) was added sodium hydroxide
(5 mmol) and the mixture was stirred at r.t. for 2 h. Removal of the solvent under reduced
pressure, gave the crude product as a white solid, which was recrystallized from acetonitrile
to afford 8.
Sodium hydrogen 1-(2,4-dichlorophenoxyacetoxy)ethylphosphonate (8a). White
solid, Yield 88%; 1H NMR (D2O) δ: 1.43 (dd, 3H, 3JHH = 7.0 Hz, 3JPH = 15.0 Hz, P-CH-
CH3), 4.93 (s, 2H, O-CH2-C), 5.13–5.17 (m, 1H, P-CH), 7.00 (d, 1H, 3Jo = 8.8 Hz, H6-Ph),
4
4
7.30 (dd, 1H, 3Jo = 8.8 Hz, Jm = 2.0 Hz, H5-Ph), 7.52 (d, 1H, Jm = 2.0 Hz, H3-Ph);
ESI-MS(m/z): positive: 351 (M+1, 12.83%), 259 (21.71%), 107 (100%), 90 (28.58%), 85
(20.97%); negative: 327 (M-23, 100%), 219 (58.74%); IR (KBr, ν/cm−1): 3425, 2986, 2938,
1756, 1481, 1439, 1391, 1207, 1083, 921, 871, 802, 720; elemental anal. C10H10Cl2NaO6P:
C, 34.21, H, 2.87; found C, 34.26, H, 2.96.
Sodium hydrogen 1-(2,4-dichlorophenoxyacetoxy)propylphosphonate (8b).
1
3
White solid, Yield 92%; H NMR (D2O) δ: 0.91 (t, 3H, JHH = 6.8 Hz, CH2CH3),
1.75–1.95 (m, 2H, CH2CH3), 4.93 (s, 2H, O-CH2-C), 5.04–5.09 (m, 1H, P-CH), 7.00
(d, 1H, 3Jo = 8.8 Hz, H6-Ph), 7.29 (dd, 1H, 3Jo = 8.8 Hz, 4Jm = 2.4 Hz, H5-Ph), 7.51 (d,
1H, 4Jm = 2.4 Hz, H3-Ph); IR (KBr, ν/cm−1): 3419, 2971, 2934, 1747, 1629, 1481, 1436,
1394, 1214, 1082, 936, 893, 799; elemental anal. C11H12Cl2NaO6P: C, 36.19, H, 3.31;
found C, 36.36, H, 3.67.
Sodium hydrogen 1-(2,4-dichlorophenoxyacetoxy)butylphosphonate (8c). White
1
3
solid, Yield 86%; H NMR (D2O) δ: 0.87 (t, 3H, JHH = 6.8 Hz, CH2CH3), 1.21–1.41
(m, 2H, CH2CH3), 1.75–1.80 (m, 2H, P-CH-CH2), 4.97 (s, 2H, O-CH2-C), 5.14–5.20 (m,
1H, P-CH), 7.00 (d, 1H, 3Jo = 8.8 Hz, H6-Ph), 7.30 (dd, 1H, 3Jo = 8.8 Hz, 4Jm = 2.4 Hz,
4
H5-Ph), 7.53 (d, 1H, Jm = 2.4 Hz, H3-Ph); IR (KBr, ν/cm−1): 3431, 2962, 2933, 2874,
2314, 1748, 1650, 1481, 1436, 1393, 1290, 1206, 1082, 917, 871, 802, 720; elemental anal.
C12H14Cl2NaO6P: C, 38.02, H, 3.72; found C, 37.90, H, 4.18.
Sodium hydrogen 1-(2,4-dichlorophenoxyacetoxy)-2-methylpropylphosphonate
1
3
4
(8d). White solid, Yield 84%; H NMR (D2O) δ: 0.97 (t, 6H, JHH = 6.8 Hz, JPH
= 6.8 Hz, P-CH-CH(CH3)2), 2.15–2.22 (m, 1H, P-CH-CH), 4.95–5.05 (m, 2H, O-
CH2-C; 1H, P-CH), 7.00 (d, 1H, Jo = 8.8 Hz, H6-Ph), 7.30 (dd, 1H, Jo = 8.8 Hz,
3
3
4Jm = 2.4 Hz, H5-Ph), 7.52 (d, 1H, Jm = 2.4 Hz, H3-Ph); IR (KBr, ν/cm−1): 3419,
4
2966, 2933, 2354, 1747, 1650, 1480, 1438, 1391, 1291, 1215, 1079, 1049, 921, 870,
801, 718; elemental anal. C12H14Cl2NaO6P: C, 38.02, H, 3.72; found C, 38.10, H,
3.49.
Sodium hydrogen 1-(2,4-dichlorophenoxyacetoxy)pentylphosphonate (8e).
1
3
White solid, Yield 91%; H NMR (D2O) δ: 0.89 (t, 3H, JHH = 6.8 Hz, CH2CH3),
1.23–1.27 (m, 4H, CH2CH2), 1.75–1.80 (m, 2H, P-CH-CH2), 4.98 (s, 2H, O-CH2-C),
5.13–5.17 (m, 1H, P-CH), 7.01 (d, 1H, Jo = 8.8Hz, H6-Ph), 7.31 (d, 1H, Jo = 8.8 Hz,
H5-Ph), 7.54 (s, 1H, H3-Ph); IR (KBr, ν/cm−1): 3430, 2958, 2931, 1749, 1482, 1436,
1392, 1290, 1216, 1079, 923, 869, 801, 719; elemental anal. C13H16Cl2NaO6P: C, 39.72,
H, 4.10; found C, 39.67, H, 4.05.
3
3
Sodium hydrogen 1-(2,4-dichlorophenoxyacetoxy)-1-phenylmethylphosphonate
1
2
(8f). White solid, Yield 87%; H NMR (D2O) δ: 5.00, 5.02 (q, AB system, 2H, JAB
=
16.4 Hz, O-CH2-C), 5.89 (d, 1H, 3JPH = 12.4 Hz, P-CH), 6.85 (d, 1H, 3Jo = 8.8 Hz, H6-
Ph-O), 7.17 (dd, 1H, 3Jo = 8.8 Hz, 4Jm = 2.4 Hz, H5-Ph-O), 7.33–7.44 (m, 5H, C6H5-CH),
7.47 (d, 1H, Jm = 2.4 Hz, H3-Ph-O); IR (KBr, ν/cm−1): 3420, 2930, 1747, 1634, 1480,
4

824
Q. LONG ET AL.
1453, 1394, 1218, 1081, 912, 871, 802, 720; elemental anal. C15H12Cl2NaO6P: C, 43.61,
H, 2.93; found C, 43.97, H, 3.17.
Sodium hydrogen 1-(2,4-dichlorophenoxyacetoxy)-1-thien-2’-ylmethylphospho-
nate (8g). White solid, Yield 56%; 1H NMR (D2O) δ: 4.94 (m, 2H, O-CH2-C), 6.30 (d, 1H,
3JPH = 12.4 Hz, P-CH), 6.75–6.80 (m, 1H, H6-Ph-O; 1H, 3-thienyl-H), 7.03–7.22 (m, 1H,
H5-Ph-O; 1H, 4-thienyl-H), 7.36–7.44 (m, 1H, H3-Ph-O; 5-thienyl-H); IR (KBr, ν/cm−1):
3417, 3103, 2929, 1757, 1625, 1480, 1434, 1392, 1196, 1080, 912, 802, 707; elemental
anal. C13H10Cl2NaO6PS: C, 37.25, H, 2.40, S, 7.65; found C 37.12, H, 2.32, S, 7.78.
Sodium hydrogen 1-(4-chloro-2-methylphenoxyacetoxy)ethylphosphonate (8h).
White solid, Yield 89%; 1H NMR (D2O) δ: 1.42 (dd, 3H, 3JHH = 6.8 Hz, 3JPH = 15.2 Hz,
P-CH-CH3), 2.24 (s, 3H, C6H3-CH3), 4.86 (s, 2H, O-CH2-C), 5.13–5.16 (m, 1H, P-CH),
3
6.84 (d, 1H, Jo = 8.8 Hz, H6-Ph), 7.18 (t, 1H, 3Jo = 8.8 Hz, H5-Ph), 7.26 (s, 1H, H3-
Ph); IR (KBr, ν/cm−1): 3423, 2958, 1759, 1634, 1493, 1444, 1380, 1219, 1186, 1138,
1074, 997, 919, 876, 800; ESI-MS(m/z): positive: 353(M+23, 100%), 330(M+, 7.91%),
301(77.68%), 250(11.64%), 245(20.43%), 136(4.03%); negative: 309(M-23+2, 31.31%),
307(M-23, 100%), 199(8.10%), 165(3.47%), 141(6.34%), 125(28.92%), 107(68.95%),
63(66.92%); elemental anal. C11H13ClNaO6P: C, 39.96, H, 3.96; found: C, 39.78, H,
3.87.
Sodium hydrogen 1-(4-chloro-2-methylphenoxyacetoxy)propylphosphonate
1
3
(8i). White solid, Yield 89%; H NMR (D2O) δ: 0.91 (t, 3H, JHH = 6.8 Hz, CH2CH3),
1.75–1.89 (m, 2H, CH2CH3), 2.24 (s, 3H, C6H3-CH3), 4.90 (s, 2H, O-CH2-C), 5.05–5.10
(m, 1H, P-CH), 6.85 (d, 1H, 3Jo = 8.8 Hz, H6-Ph), 7.18 (d, 1H, 3Jo = 8.8 Hz, H5-Ph), 7.26
(s, 1H, H3-Ph); IR (KBr, ν/cm−1): 3422, 2973, 2934, 2878, 2361, 1748, 1651, 1492, 1438,
1383, 1216, 1186, 1072, 941, 800; elemental anal. C12H15ClNaO6P: C, 41.82, H, 4.39;
found C, 41.69, H, 4.31.
Sodium hydrogen 1-(4-chloro-2-methylphenoxyacetoxy)butylphosphonate (8j).
White solid, Yield 83%; 1H NMR (D2O) δ: 0.85 (t, 3H, 3JHH = 6.8 Hz, CH2CH3), 1.18–1.33
(m, 2H, CH2CH3), 1.77–1.81 (m, 2H, P-CH-CH2), 2.15 (s, 3H, C6H3-CH3), 4.68–4.82 (m,
2H, O-CH2-C), 5.15–5.20 (m, 1H, P-CH), 6.68 (d, 1H, 3Jo = 8.8 Hz, H6-Ph), 7.03 (d, 1H,
3Jo = 8.8 Hz, H5-Ph), 7.05 (s, 1H, H3-Ph); IR (KBr, ν/cm−1): 3419, 2962, 2874, 2315, 1742,
1634, 1492, 1294, 1223, 1187, 1138, 1070, 912, 801; elemental anal. C13H17ClNaO6P: C,
43.53, H, 4.78; found: C, 43.26, H, 4.72.
Sodium hydrogen 1-(4-chloro-2-methylphenoxyacetoxy)-2-methylpropyl phos-
3
phornate (8k). White solid, Yield 93%; 1H NMR (D2O) δ: 0.97 (t, 6H, JHH
=
6.8 Hz, CH(CH3)2), 2.20–2.24 (m, 1H, P-CH-CH), 2.24 (s, 3H, C6H3-CH3), 4.91–5.00 (m,
2H, O-CH2-C; 1H, P-CH), 6.84 (d, 1H, 3Jo = 8.4 Hz, H6-Ph), 7.19 (d, 1H, 3Jo = 8.4 Hz,
H5-Ph), 7.25 (s, 1H, H3-Ph); IR (KBr, ν/cm−1): 3421, 2965, 2931, 2327, 1748, 1651, 1493,
1386, 1300, 1218, 1187, 1138, 1071, 920, 800; elemental anal. C13H17ClNaO6P: C, 43.53,
H, 4.78; found C, 43.32, H, 4.65.
Sodium hydrogen 1-(4-chloro-2-methylphenoxyacetoxy)pentylphosphonate (8l).
White solid, Yield 87%; 1H NMR (D2O) δ: 0.83 (t, 3H, 3JHH = 6.4 Hz, CH2CH3), 1.18–1.28
(m, 4H, CH2CH2), 1.75–1.80 (m, 2H, P-CH-CH2), 2.24 (s, 3H, C6H3-CH3), 4.90 (s, 2H,
O-CH2-C), 5.11–5.16 (m, 1H, P-CH), 6.85 (d, 1H, 3Jo = 8.8 Hz, H6-Ph), 7.19 (d, 1H, 3Jo
= 8.8 Hz, H5-Ph), 7.26 (s, 1H, H3-Ph); IR (KBr, ν/cm−1): 3424, 2958, 2930, 2322, 1734,
1651, 1492, 1438, 1383, 1297, 1220, 1187, 1137, 1069, 923, 874, 800; elemental anal.
C14H19ClNaO6P: C, 45.12, H, 5.14; found C, 44.78, H, 5.11.
Sodium hydrogen 1-(4-chloro-2-methylphenoxyacetoxy)-1-phenylmethyl phos-
1
phonate (8m). White solid, Yield 83%; H NMR (D2O) δ: 2.04 (s, 3H, C6H3-CH3),

SYNTHESIS AND HERBICIDAL ACTIVITIES
825
4.71–4.74 (m, 2H, O-CH2-C), 5.99 (d, 1H, 3JPH = 12.8 Hz, P-CH), 6.47 (s, 1H, H6-Ph-O),
6.85 (s, 1H, H5-Ph-O), 6.97 (s, 1H, H3-Ph-O), 7.30–7.38 (m, 5H, C6H5-CH); IR (KBr,
ν/cm−1): 3432, 2927, 1748, 1635, 1492, 1454, 1186, 1137, 1073, 927, 881, 801; elemental
anal. C16H15ClNaO6P: C, 48.94, H, 3.85; found C, 48.67, H, 3.67.
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