Synthesis and herbicidal activity of [(Substituted Phenoxyacetoxy) (Substituted Phenyl)Methyl](Methyl) phosphinates containing fluorine

Article abstract of DOI:10.1080/10426507.2012.710680

A series of [(substituted phenoxyacetoxy)(substituted phenyl)methyl] (methyl)phos- phinates containing fluorine were designed and synthesized. All the synthesized compounds were identified by elemental analysis, IR, ¹H NMR, mass spectrometry. O-methyl [(2-fluorophenoxyacetoxy)(2,4- dichlorophenyl)methyl](methyl)phosphinate was further analyzed by X-ray single-crystal diffraction. Their herbicidal activity against a set of weed species was examined. Some of the compounds showed potential herbicidal activity, which provided some indications for further studies on structure modification. 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:10.1080/10426507.2012.710680

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Synthesis and Herbicidal Activity
of [(Substituted Phenoxyacetoxy)
(Substituted Phenyl)Methyl](Methyl)
Phosphinates Containing Fluorine
Xiaoyan Deng a , Guihong Liao a , Qingwu Long a , Yujiao Gao a , Hao
Peng a & Hongwu He a
a Key Laboratory of Pesticide & Chemical Biology, Ministry of
Education, College of Chemistry , Central China Normal University ,
Wuhan, Hubei , P. R. , China
Accepted author version posted online: 17 Jul 2012.Published
online: 31 May 2013.
To cite this article: Xiaoyan Deng , Guihong Liao , Qingwu Long , Yujiao Gao , Hao Peng & Hongwu He
(2013): Synthesis and Herbicidal Activity of [(Substituted Phenoxyacetoxy) (Substituted Phenyl)Methyl]
(Methyl) Phosphinates Containing Fluorine, Phosphorus, Sulfur, and Silicon and the Related Elements,
188:6, 663-671
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Phosphorus, Sulfur, and Silicon, 188:663–671, 2013
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2012.710680
SYNTHESIS AND HERBICIDAL ACTIVITY
OF [(SUBSTITUTED PHENOXYACETOXY)
(SUBSTITUTED PHENYL)METHYL](METHYL)
PHOSPHINATES CONTAINING FLUORINE
Xiaoyan Deng, Guihong Liao, Qingwu Long, Yujiao Gao,
Hao Peng, and Hongwu He
Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of
Chemistry, Central China Normal University, Wuhan, Hubei, P. R., China
GRAPHICAL ABSTRACT
Abstract A series of [(substituted phenoxyacetoxy)(substituted phenyl)methyl](methyl)phos-
phinates containing fluorine were designed and synthesized. All the synthesized compounds
were identified by elemental analysis, IR, 1H NMR, mass spectrometry. O-methyl [(2-
fluorophenoxyacetoxy)(2,4-dichlorophenyl)methyl](methyl)phosphinate was further analyzed
by X-ray single-crystal diffraction. Their herbicidal activity against a set of weed species was
examined. Some of the compounds showed potential herbicidal activity, which provided some
indications for further studies on structure modification.
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 Herbicidal activity; phosphinate; fluorine
Received 17 May 2012; accepted 30 June 2012.
This work was supported by the National Basic Research Program of China (No. 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 Hongwu He and Hao Peng, College of Chemistry, Central China Normal
University, 152 Luoyu Road, Wuhan 430079, P. R. China. E-mail: he1208@mail.ccnu.edu.cn; penghao@mail.
ccnu.edu.cn
663

664
X. DENG ET AL.
INTRODUCTION
Many phosphorus-containing agrochemicals have been developed and widely used all
over the world due to their high efficacy and low persistency in the natural environment.1
Recent studies on α-substituted phosphonates revealed that some of them had a wide
range of biological effects, including herbicidal activity,2 enzyme-inhibiting properties,3
anti-HIV activity,4 antitumor properties,5 and hapten activity for catalytic antibodies.6 In
our previous work, a series of α-(substituted phenoxyacetoxy)alkylphosphonate derivatives
were synthesized and shown to be endowed with notable herbicidal activities,7,8 and some
of them have been demonstrated as inhibitors of PDHc E1.9–11
Bioisosterism is an important concept of bioactive compound design.12,13 The phos-
phinate group is often used for bioisosteric replacement of phosphonate group in bioactive
molecules to obtain more bioactivity or safety. On the other hand, fluorine-containing
pesticides have become the subject of the creation of new pesticides due to the unique
properties of fluorine, such as the highest electronegativity of any element, its small size,
and high thermal stability.14 All of these above findings encouraged us to replace the
phosphonate group with phosphinate group and introduce fluorine to the structure of phos-
phinate. Herein, 13 novel fluorine-containing [(substituted phenoxyacetoxy)(substituted
phenyl)methyl](methyl)phosphinates were synthesized and their herbicidal activities were
evaluated.
RESULTS AND DISCUSSION
Syntheses
O-methyl methylphosphinate 1 was accomplished in two-step sequence starting from
phosphorus trichloride, methyl iodide, and aluminium trichloride according to the lit-
erature.15,16 O-methyl [hydroxy(substituted phenyl)methyl](methyl)phosphinates 3 were
prepared by the addition of 1 and several kinds of aromatic aldehydes 2 using triethylamine
as catalyst and gave yields of 48–87%. Different fluorine-containing phenoxyacetic acids 7
were prepared in satisfactory yields by the reaction of corresponding phenols with ethyl bro-
moacetate in the presence of K2CO3 in dimethyl sulfoxide followed by alkaline hydrolysis,
and the fluorine-containing phenoxyacetyl chlorides 8 could be easily obtained by treated
compounds 7 with thionyl chloride.8,17 The title compounds 9a–9m can be obtained by the
condensation of compounds 3 with different fluorine-containing phenoxyacetyl chlorides
8 (Table 1). The synthetic route is shown in Scheme 1.
The structures of 9a–9m were established by comprehensive elemental analysis, IR,
1
1H NMR, and mass spectrometry (MS). The H NMR spectrum shows that the proton
signals corresponding to methyl, methoxy, and methylidyne attached with phosphorus
appear as two doublets, respectively. For example, the CH3 signals of compound 9a appear
at δ 1.41 (d), 1.50 (d), and the CH3O signals at δ 3.60 (d), 3.77 (d), respectively (Figure
S1 Supplemental Materials). The magnetic nucleus phosphorus makes these proton signals
split into a doublet, and the low rate of environment exchange caused by the slow rotation
of the P–C bond is the probable reason for two doublets signals. And the signal strength
of these two doublets is different, which indicates that the ratio of two conformations is
different. However, at the extreme, when two doublets are partly overlaid, they merge into
an irregular triplet, exemplified by compound 9b (Figure S2 Supplemental Materials). The
signal corresponding to the methylene group (CH2) flanked by the phenoxy group and

(METHYL)PHOSPHINATES CONTAINING FLUORINE
665
Table 1 Physical constants of compound 9
No.
X
Y
Appearance
mp/ ◦C or n2D0
Yield/%
9a
9b
9c
9d
9e
9f
9g
9h
9i
2-F
2-F
2, 4-F2
2-F
2-F
2, 4-F2
2-F
2, 4-F2
3-CF3
3-CF3
4-F
4-F
4-F
2-ClPh
4-FPh
2-ClPh
4-CH3Ph
Ph
4-CH3Ph
2, 4-Cl2Ph
2, 4-Cl2Ph
2, 4-Cl2Ph
2-ClPh
2-ClPh
2, 4-Cl2Ph
Ph
Yellow oil
White solid
Yellow oil
Yellow oil
White solid
Yellow oil
White solid
White solid
White solid
White solid
White solid
White solid
White solid
1.5482
89.2–91.0
1.5392
1.5239
106.4–107.3
1.5088
106.1–106.8
109.1–110.6
92.1–92.9
88.2–89.7
93.6–95.2
90.8–92.2
88.6–89.2
82
54
86
57
78
56
82
71
81
72
86
77
66
9j
9k
9l
9m
KCl/Fe
CH3PCl2
PCl3 CH Cl
CH3PCl3
AlCl3I
+
+
2AlCl3
3
O
Et3N
H3C
2CH3OH
CH3PCl2
+
PH
H3CO
1
3a:white solid, 68%,Y= 2-Cl
3b
O
O
H
C
H3C
H3C
H3CO
1
: yellow liquid, 52%,Y= 4-F
3c: white solid, 48%,Y= 4-CH3
3d
Et3N
P
+
PH
OHC
Y
H3CO
Y
OH
: white solid, 64%,Y= H
3e: white solid, 87%,Y= 2,4-Cl2
2
3
X
X
K2CO3/KI
DMSO
OH +
BrCH2COOEt
OCH2COOEt
5
4
6
8a:
2-F
8b: 4-F
8c:
X
X
(1)2N NaOH
(2)2N HCl
SOCl2
OCH2COCl
OCH2COOH
3-CF3
8d: 2,4-F2
7
8
O
O
X
H
Et3N
H3C
X
P
C
CH3
OCH3
OCH2COCl
+
OCH2COOCHP
H3CO
Y
OH
Y
8
3
9a-9m
Scheme 1

666
X. DENG ET AL.
Figure 1 Molecular structure of the title compound 9g, with 50% probability thermal ellipsoids.
carbonyl group appears as a quartet, the outside lines smaller in size, which belongs to the
AB system with the difference in chemical shift between the two mutually coupled protons
A and B.
The structure of 9g was further identified by a single-crystal X-ray diffraction analysis
(Figure 1). Analysis of the crystal structure showed that the bond lengths and bond angles
of nonhydrogen atoms are normal, but the tetrahedron of P atom is distorted greatly. The
◦
minimum bond angle◦in the tetrahedron is 96.72 (O(2)–P(1)–C(3)), but the maximum
bond angle is 116.72 (O(1)–P(1)–O(2)), which are similar to the angles of the reported
compound.18 The selected bond angles, lengths, and torsion angles are listed in Table 2.
Herbicidal Activity
The herbicidal activities of title compounds 9a–9m were evaluated at a dose of 900
a.i.g/ha in a set of experiments in a greenhouse. They were tested for pre-emergence and
post-emergence inhibitory effect against Echinochloa crusgalli (barnyard grass), Digiatria
sanguinalis (ascendant crabgrass), Setaria faberii (big bristlegrass), Brassica juncea (brown
mustard), Amaranthus retroflexus (amaranth), and Abuliton theophrasti (velvet leaf). Com-
pounds 9j, 9c, 9f, and 9i showed post-emergence inhibitory effect against A. theophrasti
Table 2 Selected bond angles, lengths, and torsion angles of compound 9g
Selected angles
(Deg.)
Selected bonds
(Å)
Selected torsion angle
(Deg.)
O(1)–P(1)–C(1)
O(2)–P(1)–C(1)
C(1)–P(1)–C(3)
O(1)–P(1)–C(3)
O(2)–P(1)–C(3)
O(1)–P(1)–O(2)
P(1)–C(1)–H(1A)
P(1)–C(1)–H(1B)
P(1)–C(1)–H(1C)
P(1)–C(3)–H(3)
F(1)–C(13)–C(14)
F(1)–C(13)–C(12)
113.5 (2)
107.7 (2)
105.5 (2)
114.9 (2)
96.72 (19)
116.7 (2)
109.5
109.5
109.5
109.9
118.1(5)
119.1(4)
P(1)–O(1)
P(1)–O(2)
P(1)–C(1)
P(1)–C(3)
O(2)–C(2)
C(1)–H(1A)
C(1)–H(1B)
C(1)–H(1C)
C(3)–H(3)
C(3)–O(3)
C(3)–C(4)
C(13)–F(1)
1.476 (4)
1.570 (4)
1.769 (5)
1.841 (4)
1.433 (6)
0.9600
0.9600
0.9600
0.9800
O(1)–P(1)–O(2)–C(2)
C(1)–P(1)–O(2)–C(2)
C(3)–P(1)–O(2)–C(2)
O(1)–P(1)–C(3)–O(3)
O(2)–P(1)–C(3)–O(3)
C(1)–P(1)–C(3)–O(3)
O(1)–P(1)–C(3)–C(4)
O(2)–P(1)–C(3)–C(4)
C(1)–P(1)–C(3)–C(4)
O(5)–C(12)–C(13)–F(1)
C(17)–C(12)–C(13)–F(1)
F(1)–C(13)–C(14)–C(15)
−53.3 (5)
75.7 (5)
−175.5 (5)
62.8 (4)
−173.6 (3)
−63.1 (3)
−57.2 (4)
66.4 (3)
177.0 (3)
−1.3 (8)
1.448 (5)
1.506 (6)
1.320 (7)
178.4 (6)
−176.6 (7)

(METHYL)PHOSPHINATES CONTAINING FLUORINE
667
of 100%, 90%, 80%, and 80%, respectively, while 9c and 9i against B. juncea of 80% and
80%.
By comparison of herbicidal activities among compounds 9 in Table S1, substituent
X on the benzene ring greatly affected activity when Y was kept the same, 4-F as X on
the phenoxy benzene ring was the most promotive followed by 3-CF3, 2,4-F2, and 2-F. For
example, the inhibitory rates of compounds 9l (X = 4-F), 9i (X = 3-CF3), 9h (X = 2,4-F2),
and 9g (X = 2-F) against B. juncea were 90%, 80%, 70%, and 0, respectively. On the other
hand, it is very interesting that the introduction of 4-F as X probably contributes to the
activity for pre-emergence. For example, the inhibitory rates of compound 9k against A.
theophrasti, compound 9l against E. crusgalli, and compound 9m against Setaria viridis,
B. juncea, and A. theophrasti for pre-emergence are all more than 80%.
Experimental details and the activities (Table S1) are presented in the Supplemental
Materials.
CONCLUSION
In conclusion, a series of novel [(substituted phenoxyacetoxy)(substituted phenyl)
methyl](methyl)phosphinates containing fluorine were synthesized by the condensation of
O-methyl [hydroxy(substituted phenyl)methyl](methyl)phosphinates and substituted phe-
noxyacetyl chlorides. The test for herbicidal activity in a greenhouse showed that some of
the synthesized compounds possessed good herbicidal activity and the introduction of 4-F
as X is beneficial to herbicidal activity. As for the active compounds, the inhibitory effect
for post-emergence is higher than that for pre-emergence.
EXPERIMENTAL
Column chromatography was carried out with Merck silica gel (230–400 mesh).
Thin-layer chromatography was performed on silica gel GF-254. Melting points (mp) were
measured on a WRS-IB electrothermal melting-point apparatus and uncorrected. IR spectra
were recorded in potassium bromide disks with an AVATAR360 FTIR spectrophotometer;
only the most significant absorption bands were recorded. 1H NMR was recorded on a Varian
XL-400 spectrometer using tetramethylsilane as internal standard and deuterochloroform
as solvent. Chemical shifts (δ) are given in parts per million, and coupling constants (J) in
hertz, and multiplicities are indicated by s (singlet), d (doublet), t (triplet), q (quartet), and m
(multiplet). MS was performed on a Finnigen TRACE spectrometer and API2000LC/MS.
Elemental analysis (C, H, and N) were analyzed on a Vario EL III CHNSO elemental
analyzer. The results were within 0.5% of the theoretical values.
General Procedure for the Synthesis of Compounds 9a–9m
To a three-necked flask, O-methyl [hydroxy(substituted phenyl)methyl](methyl)
phosphinates 3 (0.005 mol), triethylamine (0.008 mol), and anhydrous dichloromethane
(15 mL) were added. Then anhydrous dichloromethane (10 mL) containing◦substituted
phenoxyacetyl 8 (0.006 mol) was added dropwise to the mixture at below 5 C. The re-
sulting mixture was stirred at room temperature about 6–8 h, then washed with diluted
hydrochloric acid, saturated sodium bicarbonate, saturated sodium chloride, then dried
over anhydrous sodium sulfate, and filtered. The filtrate was concentrated under reduced
pressure to give the crude product. Further flash-column chromatography on silica gel using

668
X. DENG ET AL.
a mixture of petroleum ether and acetone (3:2) afforded the title compounds as oils or white
solids.
O-methyl [(2-fluorophenoxyacetoxy)(2-chlorophenyl)methyl](methyl)
phosphinate (9a). Yellow oil: 1H NMR (CDCl3): δ = 1.41, 1.50 (d, 3H, CH3,
J = 14.0 Hz), 3.60, 3.77 (d, 3H, OCH3, J = 10.4 Hz), 4.81, 4.88 (q, AB system, 2H,
OCH2CO , JAB = 16.4 Hz), 6.63, 6.70 (d, 1H, OCHP, J = 8.4 Hz), 6.91–7.49 (m,
8H, Ar–H); MS (m/z,%): 386 (M+ 0.06), 233 (1.18), 219 (0.77), 153 (0.86), 125 (34.69),
111 (28.11), 97 (11.80), 93 (14.00), 77 (22.24), 63 (22.75), 47 (4.31); IR (υ/cm−1):
2966 (Ph–H), 1771 (C O), 1238 (P O), 1172 (C O C), 1038 (P O C); calcd. for
C17H17ClFO5P: C 52.80, H 4.43; found: C 52.41, H 4.64.
O-methyl
[(2-fluorophenoxyacetoxy)(4-fluorophenyl)methyl](methyl)
1
phosphinate (9b). White solid: H NMR (CDCl3): δ = 1.35, 1.38 (d, 3H, CH3,
J = 12.4 Hz), 3.60, 3.64 (d, 3H, OCH3, J = 10.8 Hz), 4.82, 4.88 (q, AB system, 2H,
OCH2CO , JAB = 16.4 Hz), 6.13, 6.21 (d, 1H, OCHP, J = 11.2 Hz), 6.92–7.39 (m,
8H, Ar–H); MS (m/z,%): 370 (M+ 2.09), 278 (1.37), 218 (13.46), 202 (38.72), 153 (1.18),
125 (100), 111 (19.43), 97 (59.60), 93 (71.73), 77 (62.72), 63 (22.75), 47 (17.63); IR
(υ/cm−1): 3071 (Ph–H), 1759 (C O), 1228 (P O), 1185 (C O C), 1039 (P O C);
calcd. for C17H17F2O5P: C 55.14, H 4.59; found: C 55.39, H 4.70.
O-methyl [(2,4-difluorophenoxyacetoxy)(2-chlorophenyl)methyl](methyl)
1
phosphinate (9c). Yellow oil: H NMR (CDCl3): δ = 1.44, 1.55 (d, 3H, CH3,
J = 14.4 Hz), 3.62, 3.80 (d, 3H, OCH3, J = 10.4 Hz), 4.77, 4.84 (q, AB system, 2H,
OCH2CO , JAB = 16.4 Hz), 6.64, 6.68 (d, 1H, OCHP, J = 8.4 Hz), 6.76–7.51 (m,
7H, Ar–H); MS (m/z,%): 405 (M+ 3.25), 233 (14.11), 217 (22.65), 171 (3.88), 143 (100),
129 (10.78), 113 (51.94), 94 (7.30), 93 (72.56), 77 (70.10), 63 (45.45), 47 (17.24); IR
(υ/cm−1): 3057 (Ph–H), 1771 (C O), 1245 (P O), 1173 (C O C), 1040 (P O C);
Calcd. for C17H16ClF2O5P: C 50.45, H 3.98; found: C 50.52, H 3.94.
O-methyl [(2-fluorophenoxyacetoxy)(4-methylphenyl)methyl](methyl)
1
phosphinate (9d). Yellow oil: H NMR (CDCl3): δ = 1.37, 1.45 (d, 3H, CH3,
J = 14.4 Hz), 2.35 (s, 3H, Ar CH3), 3.63, 3.66 (d, 3H, OCH3, J = 10.8 Hz), 4.84, 4.93
(q, AB system, 2H, OCH2CO , JAB = 16.4 Hz), 6.22 (d, 1H, OCHP, J = 11.2 Hz),
6.95–7.33 (m, 8H, Ar H); MS (m/z,%): 366 (M+ 10.6), 273 (26.20), 213 (54.95), 197
(4.51), 153 (2.74), 125 (100), 111 (2.22), 97 (40.39), 93 (52.65), 77 (42.39), 63 (17.02),
47 (7.29); IR (υ/cm−1): 3066 (Ph H), 1751 (C O), 1264 (P O), 1171 (C O C), 1042
(P O C); calcd. for C18H20FO5P: C 59.02, H 5.50; found: C 59.39, H 5.70.
O-methyl [2-fluorophenoxyacetoxy)(phenyl)methyl](methyl)phosphi-
nate (9e). White solid: 1H NMR (CDCl3): δ = 1.36, 1.40 (d, 3H, CH3, J = 14.4 Hz),
3.59, 3.61 (d, 3H, OCH3, J = 10.8 Hz), 4.84, 4.90 (q, AB system, 2H, OCH2CO ,
JAB = 16.8 Hz), 6.17, 6.19 (d, 1H, OCHP, J = 8.0 Hz), 6.95 7.38 (m, 9H, Ar H);
MS (m/z,%): 352 (M+ 10.23), 259 (2.98), 199 (34.87), 183 (3.70), 153 (5.16), 125 (100),
111 (4.24), 96 (43.90), 93 (58.07), 77 (74.76), 63 (20.30), 47 (11.97); IR (υ/cm−1):
3057 (Ph H), 1766 (C O), 1214 (P O), 1182 (C O C), 1036 (P O C); calcd. for
C17H18FO5P: C 57.96, H 5.15; found: C 58.71, H 5.33.
O-methyl [(2,4-difluorophenoxyacetoxy)(4-methylphenyl)methyl](methyl)
1
phosphinate (9f). Yellow oil: H NMR (CDCl3): δ = 1.36, 1.44 (d, 3H, CH3,
J = 14.0 Hz), 2.32 (s, 3H, Ar CH3), 3.62, 3.66 (d, 3H, OCH3, J = 10.4 Hz), 4.85, 4.92
(q, AB system, 2H, OCH2CO , JAB = 16.4 Hz), 6.22 (d, 1H, OCHP, J = 11.2 Hz),
6.95–7.33 (m, 7H, Ar H); MS (m/z,%): 385 (M+ 6.24), 291 (32.88), 213 (48.16), 197
(71.48), 171 (4.01), 143 (98.94), 129 (96.83), 111 (13.09), 96 (51.57), 93 (78.11), 77

(METHYL)PHOSPHINATES CONTAINING FLUORINE
669
(56.63), 63 (79.85), 47 (33.43); IR (υ/cm−1): 3057 (Ph H), 1724 (C O), 1264 (P O),
1178 (C–O–C), 1045 (P–O C); calcd. for C18H19F2O5P: C 56.25, H 4.98; found: C 56.62,
H 4.64.
O-methyl [(2-fluorophenoxyacetoxy)(2,4-dichlorophenyl)methyl](methyl)
1
phosphinate (9g). White solid: H NMR (CDCl3): δ = 1.48, 1.51 (d, 3H, CH3,
J = 14.4 Hz), 3.60, 3.62 (d, 3H, OCH3, J = 10.8 Hz), 4.84, 4.85 (q, AB system, 2H,
OCH2CO , JAB = 16.4 Hz), 6.60, 6.62 (d, 1H, OCHP, J = 8.0 Hz), 6.90–7.45 (m,
7H, Ar H); MS (m/z,%): 421 (M+ 0.90), 328 (0.71), 268 (7.28), 252 (7.25), 153 (7.37),
125 (100), 111 (27.91), 96 (78.74), 93 (98.09), 77 (67.64), 63 (94.40), 47 (44.60); IR
(υ/cm−1): 3071 (Ph H), 1782 (C O), 1233 (P O), 1176 (C O C), 1049 (P O C);
calcd. for C17H16Cl2FO5P: C 48.48, H 3.83; found: C 48.75, H 3.89.
O-methyl
[(2,4-difluorophenoxyacetoxy)(2,4-dichlorophenyl)methyl]
1
(methyl)phosphinate (9h). White solid: H NMR (CDCl3): δ = 1.43, 1.53 (d, 3H,
CH3, J = 14.4 Hz), 3.60, 3.77 (d, 3H, OCH3, J = 10.8 Hz), 4.76, 4.82 (q, AB system,
2H, OCH2CO , JAB = 16.4 Hz), 6.55, 6.60 (d, 1H, OCHP, J = 8.0 Hz), 6.76–7.45
(m, 6H, Ar H); MS (m/z,%): 440 (M+ 2.07), 345 (1.11), 268 (11.58), 253 (20.37), 197
(71.48), 173 (58.60), 143 (90.19), 129 (20.50), 111 (17.10), 95 (32.65), 93 (98.82), 77
(52.09), 63 (100), 47 (40.54); IR (υ/cm−1): 3092 (Ph H), 1756 (C O), 1244 (P O),
1173 (C O C), 1068 (P O C); calcd. for C17H15Cl2F2O5P: C 46.49, H 3.44; found: C
46.93, H 3.80.
O-methyl [(3-trifluoromethylphenoxyacetoxy)(2,4-dichlorophenyl)methyl]
1
(methyl)phosphinate (9i). White solid: H NMR (CDCl3): δ = 1.42, 1.50 (d, 3H,
CH3, J = 14.4 Hz), 3.59, 3.77 (d, OCH3, J = 10.8 Hz), 4.81, 4.85 (q, AB system,
2H, OCH2CO , JAB = 16.0 Hz), 6.56, 6.60 (d, 1H, OCHP, J = 8.0 Hz), 7.07–7.45
(m, 7H, Ar H); MS (m/z,%): 471 (M+ 0.07), 252 (0.55), 239 (11.70), 203 (0.85), 175
(90.87), 161 (7.60), 145 (95.69), 93 (100), 77 (58.64), 63 (84.61), 47 (36.20); IR (υ/cm−1):
3036 (Ph H), 1776 (C O), 1233 (P O), 1173 (C O C), 1066 (P O C); calcd. for
C18H16Cl2F3O5P: C 45.88, H 3.42; found: C 46.46, H 3.32.
O-methyl [(3-trifluoromethylphenoxyacetoxy)(2-chlorophenyl)methyl]
1
(methyl)phosphinate (9j). White solid: H NMR (CDCl3): δ = 1.41, 1.50 (d, 3H,
CH3, J = 14.4 Hz), 3.58, 3.78 (d, 3H, OCH3, J = 10.8 Hz), 4.82, 4.88 (q, AB system,
2H, OCH2CO , JAB = 16.4 Hz), 6.64, 6.69 (d, 1H, OCHP, J = 8.4 Hz), 7.07–7.50
(m, 8H, Ar H); MS (m/z,%): 436.5 (M+ 7.67), 233 (14.44), 217 (84.64), 203 (2.73),
175 (95.54), 161 (16.93), 145 (92.04), 93 (100), 77 (82.88), 63 (80.50), 47 (31.77); IR
(υ/cm−1): 3073 (Ph H), 1764 (C O), 1236 (P O), 1186 (C O C), 1049 (P O C);
calcd. for C18H17ClF3O5P: C 49.50, H 3.92; found: C 49.69, H 3.94.
O-methyl [(4-fluorophenoxyacetoxy)(2-chlorophenyl)methyl](methyl)
phosphinate (9k). White solid: 1H NMR (CDCl3): δ = 1.40, 1.50 (d, 3H, CH3,
J = 14.4 Hz), 3.57, 3.77 (d, 3H, OCH3, J = 10.8 Hz), 4.71, 4.77 (q, AB system, 2H,
OCH2CO , JAB = 16.4 Hz), 6.60, 6.67 (d, 1H, OCHP, J = 7.6 Hz), 6.83–7.46 (m,
8H, Ar H); MS (m/z,%): 386 (M+ 19.17), 233 (7.15), 218 (27.24), 153 (1.17), 124
(93.85), 110 (17.94), 97 (19.19), 92 (100), 76 (35.75), 62 (36.69), 46 (14.35); IR (υ/cm−1):
2980 (Ph H), 1772 (C O), 1236 (P O), 1177 (C O C), 1052 (P O C); calcd. for
C17H17ClFO5P: C 52.80, H 4.43; found: C 52.62, H 4.50.
O-methyl [(4-fluorophenoxyacetoxy)(2,4-dichlorophenyl)methyl](methyl)
1
phosphinate (9l). White solid: H NMR (CDCl3): δ = 1.41, 1.50 (d, 3H, CH3,
J = 14.4 Hz), 3.58, 3.76 (d, 3H, OCH3, J = 10.8 Hz), 4.70, 4.76 (q, AB system, 2H,
OCH2CO , JAB = 16.4 Hz), 6.55, 6.59 (d, OCHP, J = 8.0 Hz), 6.83–7.45 (m, 7H,

670
X. DENG ET AL.
Ar H); IR (υ/cm−1): 3064 (ph H), 1740 (C O), 1216 (P O), 1158 (C O C), 1042
(P O C); calcd. for C17H16Cl2FO5P: C 48.48, H 3.83; found: C 48.81, H 3.56.
O-methyl [(4-fluorophenoxyacetoxy)(phenyl)methyl](methyl)phosphi-
nate (9m). White solid: 1H NMR (CDCl3): δ = 1.33, 1.37 (d, 3H, CH3, J = 14.2 Hz),
3.61, 3.64 (d, 3H, OCH3, J = 10.8 Hz), 4.76, 4.80 (q, AB system, 2H, OCH2CO ,
JAB = 16.4 Hz), 6.22, 6.24 (d, 1H, OCHP, J = 8.4 Hz), 6.84–7.39 (m, 9H, Ar H); IR
(υ/cm−1): 3066 (Ph H), 1735 (C O), 1221 (P O), 1169 (C O C), 1050 (P O C);
calcd. for C17H18FO5P: C 57.96, H 5.15; found: C 57.62, H 5.50.
X-Ray Diffraction
Compound 9g was recrystallized from trichloromethane and petroleum ether
(60 ◦C 90 ◦C) to give colorless crystals (0.44 × 0.18 × 0.14 mm) suitable for X-ray single-
crystal diffraction. The crystal structures of compound 9g were recorded on a Smart Apex
CCD diffractometer using graphite monochromated Mo Kα-radiation (λ = 0.71073 Å) at
293 2K. Three thousand three hundred and nine independent reflections (Rint = 0.0234)
of which 2358 contributing reflection had I > 2σ(I). The structure was solved by direct
methods using SHELXS-97; all other calculations were performed with Bruker SAINT
system and Bruker SMART programs. Full-matrix least-squares refinement gave final
values of R1 = 0.0695, R2 = 0.1784. Max/min residual electron density = 0.798/−0.278e
Å-3. Hydrogen atoms were observed and refined with a fixed value of their isotropic
displacement parameter. The molecular structure of compound 9g is shown in Figure 1,
and a summary of data collection statistics is given in Table 3. CCDC 882176 contains
the supplementary crystallographic data for this article. These data can be obtained free of
Table 3 Crystal structure and data refinement parameters of 9g
Compound
9g
Empirical formula
Formula weight
C17H16Cl2FO5P
420.01
Crystal system/space group
Triclinic
a/Å
b/Å
8.9124 (10)
9.3109 (11)
11.4420 (13)
87.575 (2)
87.734 (2)
83.993 (2)
942.84 (19)
2
1.484
c/Å
α/◦
β/◦
γ /◦
V/Å3
Z
Dcalc (g/m3)
μ/(mm−1
)
0.464
Crystal size (mm3)
0.44 × 0.18 × 0.14
Color/shape
Colorless
Temp (K)
293 (2)
Theta range for collection
Reflections collected
Independent reflections
Final R indices [I > 2σ(I)]
Largest difference peak/hole
1.78 to 27.00 ◦
2358
3309[R(int) = 0.0234]
R1 = 0.0695, ωR2 = 0.1784
0.798 and −0.278e Å-3

(METHYL)PHOSPHINATES CONTAINING FLUORINE
671
charge via www.ccdc.cam.ac.uk/retrieving.html (or from the Cambridge Crystallographic
Data Centre, 12, Union Road, Cambridge B2 1EZ, UK; fax +44 1223 336033; or deposit@
ccdc.cam.ac.uk).
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