An efficient synthesis of α-(2,4-dichlorophenoxyacetoxy)aryl methyl phosphonate monosodium salts

Article abstract of DOI:10.1081/SCC-120030691

A series of α-(2,4-dichlorophenoxyacetoxy)aryl methyl phosphonate monosodium salts 6 were synthesized by the reaction of the intermediate 5 with sodium iodide under moderate condition. This method was applied to the synthesis of novel phosphonate derivati

Full text of DOI:10.1081/SCC-120030691

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An Efficient Synthesis of
α‐(2,4‐Dichloro‐phenoxyacetoxy)aryl Methyl
Phosphonate Monosodium Salts
Tao Wang a & Hong Wu He a
a Institute of Organic Synthesis , Central China Normal University , Wuhan, Hubei,
430079, P.R. China
Published online: 21 Aug 2006.
To cite this article: Tao Wang & Hong Wu He (2004) An Efficient Synthesis of α‐(2,4‐Dichloro‐phenoxyacetoxy)aryl
Methyl Phosphonate Monosodium Salts, Synthetic Communications: An International Journal for Rapid Communication of
Synthetic Organic Chemistry, 34:8, 1415-1423, DOI: 10.1081/SCC-120030691
To link to this article: http://dx.doi.org/10.1081/SCC-120030691
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SYNTHETIC COMMUNICATIONSw
Vol. 34, No. 8, pp. 1415–1423, 2004
An Efficient Synthesis of a-(2,4-Dichloro-
phenoxyacetoxy)aryl Methyl Phosphonate
Monosodium Salts
*
Tao Wang and Hong Wu He
Institute of Organic Synthesis, Central China Normal University,
Wuhan, Hubei, P.R. China
ABSTRACT
A series of a-(2,4-dichlorophenoxyacetoxy)aryl methyl phosphonate
monosodium salts 6 were synthesized by the reaction of the intermediate
5 with sodium iodide under moderate condition. This method was applied
to the synthesis of novel phosphonate derivatives containing sensitive
groups such as carboxylic ester to acid, base, or water.
Key Words: Phosphonate monosodium salt; Synthesis; Pyruvate dehydro-
genase; Carboxylic ester.
*
Correspondence: Hong Wu He, Institute of Organic Synthesis, Central China
Normal University, Wuhan, Hubei 430079, P.R. China; E-mail: hel208@public.
wh.hb.cn.
1415
DOI: 10.1081/SCC-120030691
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com
Copyright # 2004 by Marcel Dekker, Inc.

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Wang and He
INTRODUCTION
Pyruvate dehydrogenase complex is already known to be a site of pesticide
action.[1] For a number of years, we have been engaged in attempts to design
agrochemicals using biochemical reasoning. Some substituted phenoxyacetoxy-
aryl methyl phosphonates have shown herbicidal activities.[2,3] The biological
activity of its corresponding phosphonate monosodium salts would be of better
herbicidal activity, because the structure of a-oxophosphonate salt is more
analogous to the pyruvate which act as the substrate of pyruvate dehydro-
genase complex. Recently, we are interested in the synthesis of biologically
active a-oxophosphonate monosodium salts. However, they cannot be pre-
pared by using the general method described in the literature.[4] Here, we
wish to report a very mild and efficient method to synthesize a-(2,4-
dichlorophenoxyacetoxy)aryl methyl phosphonate monosodium salts 6 from
the corresponding aryl methyl phosphonates 5. The title compounds 6 were pre-
pared by the method shown in Sch. 1 and Table 1.
RESULTS AND DISCUSSIONS
Generally, according to the literature,[4] Baillie et al. reported that
phosphonate monosodium salts could be obtained by a direct means of con-
verting phosphonate esters in butanone (Sch. 2). However, this method is
Scheme 1.

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Synthesis of Phosphonate Monosodium Salts
Table 1. Preparation of the title compounds 6.
1417
Compounds
R
Ar
Condition (598C)
Yield (%)
6a
6b
6c
6d
6e
6f
CH3
CH3
CH3
CH3
CH3
CH3
CH3
C2H5
C2H5
C2H5
C2H5
C2H5
C2H5
C6H5
2h
2h
86
82
88
86
79
78
85
72
66
72
68
79
71
2,4-Cl2C6H3
p-CH3OC6H4
3,4-OCH2OC6H3
p-FC6H4
4h
4h
3h
2h
p-CH3C6H4
m-NO2C6H4
C6H5
6g
6h
6i
3h
14h
19h
18h
22h
16h
10h
2,4-Cl2C6H3
3,4-OCH2OC6H3
p-FC6H4
6j
6k
6l
p-CH3C6H4
m-NO2C6H4
6m
not applicable to the phosphonates containing sensitive groups such as
carboxylic ester to acid, base, water, or temperature.
Attempts to prepare 6a by direct reaction of sodium monomethyl-
1-hydroxy phenyl methyl phosphonate with 2,4-dichloro phenoxy acetic
chloride 4 in the presence of pyridine were unsuccessful (Sch. 3).
As described in the literature,[5] we attempted to prepare disodium salt 6a0
by the reaction of C2H5ONa with 8, which can be prepared by dealkylation of
o,o-dimethyl-a-(2,4-dichlorophenoxyacetoxy)phenyl methyl phosphonate 7
(Sch. 4). Unfortunately, in this case, the ester bond in the phosphonic acid 8
is still too delicate to survive the harsh basic condition by using C2H5ONa
at higher temperature.
Based on the above considerations, the synthetic route was chosen to pre-
pare the phosphonate monosodium salts 6 (Sch. 1). The experiments showed
that the reactions of the compounds 5a–m with sodium iodide were affected
by reaction temperature, base, solvent, and water. We observed that carboxy-
lic ester bond in compounds 5 was easy to cleave by hydrolysis in the presence
of base and water at about 608C. For example, when the title compound 6a was
prepared under basic condition (pH ¼ 9–10) by the reaction in Sch. 1, both
by-products 6x and 6y were found, which were identified as 2,4-dichloro-
Scheme 2.

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Wang and He
Scheme 3.
phenoxy acetic acid 6x and sodium monomethyl-1-hydroxy phenyl methyl
phosphonate 6y, respectively. The reactions were examined in different con-
ditions (Sch. 5, e.g., 1). When refluxing of compound 5g with oven-dried
sodium iodide at 838C in the presence of butanone, we did not find the corre-
sponding 6g, but got both by-product 6x and 6y0 (R ¼ CH3, Ar ¼ 3-
NO2C6H4).
We attempted to prepare 6h by the reaction of 5h with oven-dried sodium
iodide in the presence of butanone for 48 hr, but no 6h was found, producing
both by-product 6x and by-product 6y00 identified as sodium monoethyl-1-
hydroxy phenyl methyl phosphonate instead. However, when the compound
5h and sodium iodide were dissolved in acetone and stirred and refluxed
only for 14 hr, the title compound 6h was obtained.
Therefore, in the molecular structure of a-(2,4-dichlorophenoxyacetoxy)-
aryl methyl phosphonate 5, the carboxylic ester bond may be more delicate to
cleave than phosphonate ester bond in such a hard condition. The formation of
the title compounds 6 can be rationalized in terms of direct reaction of the
phosphonates 5 with oven-dried sodium iodide in the presence of molecular
sieve (4A) in dried acetone under nitrogen for 2–22 hr. The method of the
preparation shows following advantageous features: (a) the title compounds
6 can be obtained from 5 in one-step; (b) the reactions only need short time
under mild condition by a simple procedure.
EXPERIMENTAL
Melting points (m.p.) were measured on an electrothermal melting-
point apparatus and uncorrected; Elemental analysis was performed by
Vario EL III elemental analysis; IR spectra were obtained with a Avatar 360
spectrometer; 1H NMR were measured with a Varian XL-300 spectrometer at
Scheme 4.

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Synthesis of Phosphonate Monosodium Salts
1419
Scheme 5.
300 MHz. Tetramethyl silane (TMS) was used as an internal standard, and
chemical shift values are expressed in d(DMSO) ppm. MS were measured
on a Finnigen Trace 2000 spectrometer.
Compounds 3 and 4 were prepared according to the literature.[6,7]
General Procedure for the Synthesis of o,o-Dialkyl-a-(2,4-
dichlorophenoxyacetoxy)aryl Methyl Phosphonates (5a–m)
A solution of 2,4-dichlorophenoxy acetic chloride 4 (0.022 mol) in
trichloromethane (10 mL) was added to stirred mixture of 1-hydroxy aryl
methyl phosphonate 3 (0.02 mol) and pyridine (0.022 mol) in trichlorometh-
ane (25 mL) at 2–48C. The resultant mixture was stirred at ambient tem-
perature for 3–5 hr, then all stirred at 408C for 1–2 hr, washed with 0.1 M
hydrochloric acid, saturated sodium hydrogen carbonate solution and brine,
dried and evaporated. The residue was chromatographed on silica with 20%
acetone in petroleum ether as eluent to give the compound 5 as a yellow liquid
or white solid, which was recrystallized from DCM/petroleum ether. Yield:
58–91%.
General Procedure for the Synthesis of Sodium
Monomethyl-a-(2,4-dichlorophenoxyacetoxy)aryl
Methyl Phosphonates (6a–g)
A solution of o,o-dimethyl-a-(2,4-dichlorophenoxyacetoxy)aryl methyl
phosphonate (0.02 mol) and oven-dried sodium iodide (0.02 mol) in molecular
sieve (4A) dried acetone (40 mL) was stirred and refluxed under nitrogen for
2–4 hr, The solution was evaporated at reduced pressure. The residual solid
was recrystallized from dichloromethane to afford the pure product as white
solid or crystal (the product was very deliquescent). The salts were isolated
directly in 78–88% yields.

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Wang and He
6a. White crystal, m.p. 164–1658C; 1H NMR: 3.29–3.34 (d, 3H,
–OCH3, J ¼ 10.0 Hz), 4.90–5.09 (q, 2H, –OCH2CO–, J ¼ 12.6 Hz), 5.77–
5.83 (d, 1H, –OCHP, J ¼ 12.0 Hz), 6.98–7.53 (m, 8H, –C6H5, –C6H3). IR
(KBr) ymax (cm21): 3042 (Ph–H), 2952, 2846 (C– H), 1715 (C55O), 1601,
1601, 1490 (Ph), 1244 (P55O), 1077 (C–O–C), 1045, 930 (P–O–C), 722
(P–C). MS (m/z): 426 (Mþ 0.1%), 234 (14.35%), 220 (15.98%), 199
(43.15%), 185 (4.30%), 175 (70.19%), 162 (77.72%), 133 (41.88%),
109 (85.39%), 105 (52.92%), 94 (3.78%), 93 (100%), 77 (63.71%), 63
(93.51%). Anal. calcd for C16H14Cl2NaO6P: C, 44.99; H, 3.30. Found: C,
44.51; H, 3.52.
6b. White solid, m.p. 151–1528C; 1H NMR: 3.35–3.40 (d, 3H, –OCH3,
J ¼ 10.0 Hz), 4.98 (s, 2H, –OCH2CO–), 6.06–6.12 (d, 1H, –OCHP,
J ¼ 12.0 Hz), 6.95–7.60 (m, 6H, –C6H3, –C6H3). IR (KBr) ymax (cm21):
3087 (Ph–H), 2952, 2846 (C–H), 1743 (C55O), 1643, 1585, 1485 (Ph),
1217 (P55O), 1079 (C–O–C), 1051, 928 (P–O–C), 744 (P–C). MS (m/z):
494 (Mþ 0.1%), 234 (28.65%), 220 (3.89%) 199 (48.38%), 175 (74.41%),
173 (61.47%), 162 (100%), 133 (28.65%), 109 (36.44%), 94 (1.91%), 93
(3.99%), 63 (72.35%). Anal. calcd for C16H12Cl4NaO6P: C, 38.74; H, 3.31.
Found: C, 38.92; H, 3.28.
6c. White solid, m.p. 109–1108C; 1H NMR: 3.27–3.31 (d, 3H, –OCH3,
J ¼ 8.7 Hz), 3.72 (s, 3H, CH3O–Ph), 4.85–5.04 (q, 2H, –OCH2CO–, J ¼
11.6 Hz), 5.69–5.75 (d, 1H, –OCHP, J ¼ 13.6 Hz), 6.76–7.54 (m, 7H,
–C6H4, –C6H3). IR (KBr) ymax (cm21): 3076 (Ph–H), 2947, 2829 (C–H),
1736 (C55O), 1611, 1514, 1485 (Ph), 1226 (P55O), 1080 (C–O–C), 1051,
932 (P–O–C), 734 (P–C). MS (m/z): 456 (Mþ 0.05%), 234 (32.20%),
220 (13.78%), 199 (57.55%), 175 (44.58%), 162 (100%), 135 (60.88%),
133 (27.57%), 109 (24.13%), 93 (2.04%), 63 (62.19%). Anal. calcd for
C17H16Cl2NaO7P: C, 44.66; H, 3.53. Found: C, 44.58; H, 3.59.
1
6d. White solid, m.p. 83–858C; H NMR: 3.29–3.34 (d, 3H, –OCH3,
J ¼ 9.7 Hz), 4.86–5.07 (q, 2H, –OCH2CO–, J ¼ 13.6 Hz), 5.67–5.73
(d, 1H, –OCHP, J ¼ 10.7 Hz), 5.93 (s, 2H, –OCH2OPh), 6.76–7.53
(m, 6H, –C6H3, –C6H3). IR (KBr) ymax (cm21): 3092 (Ph–H), 2941, 2840
(C–H), 1735 (C55O), 1615, 1503, 1485 (Ph), 1245 (P55O), 1079 (C–O–
C), 1038, 934 (P–O–C), 761 (P–C). MS (m/z): 470 (Mþ 0.3%), 234
(15.55%), 220 (9.29%), 199 (28.68%), 175 (35.56%), 162 (28.86%), 149
(24.92%), 133 (69.41%), 109 (86.58%), 94 (1.60%), 93 (10.55%), 63
(83.23%). Anal. calcd for C17H14Cl2NaO8P: C, 43.34; H, 2.98. Found: C,
43.21; H, 3.07.
6e. White crystal, m.p. 143–1448C; 1H NMR: 3.31–3.36 (d, 3H, –OCH3,
J ¼ 9.7 Hz), 4.98–5.01 (q, 2H, –OCH2CO–, J ¼ 4.9 Hz), 5.76–5.83 (d, 1H,
–OCHP, J ¼ 12.6 Hz), 7.01–7.52 (m, 7H, –C6H4, –C6H3). IR (KBr) ymax
(cm21): 3065 (Ph–H), 2941, 2835 (C–H), 1742 (C55O), 1629, 1559, 1484

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Synthesis of Phosphonate Monosodium Salts
1421
(Ph), 1197 (P55O), 1076 (C–O–C), 1035, 931 (P–O–C), 768 (P–C). MS
(m/z): 444 (Mþ 0.05%), 234 (35.34%), 220 (9.86%), 199 (66.23%),
175 (79.06%), 162 (68.35%), 133 (37.95%), 123 (72.38%), 109 (100%), 94
(6.15%), 93 (80.78%), 63 (66.55%). Anal. calcd for C16H13Cl2FNaO6P: C,
43.17; H, 2.94. Found: C, 43.08; H, 3.23.
1
6f. White solid, m.p. .1088C (decompound); H NMR: 2.25 (s, 3H,
–CH3Ph), 3.31–3.35 (d, 3H, –OCH3, J ¼ 9.7 Hz), 4.98 (s, 2H,
–OCH2CO–), 5.76–5.82 (d, 1H, –OCHP, J ¼ 12.6 Hz), 7.03–7.51 (m, 7H,
–C6H4, –C6H3). IR (KBr) ymax (cm21): 3077 (Ph–H), 2978, 2845 (C–H),
1757 (C55O), 1612, 1537, 1487 (Ph), 1213 (P55O), 1122 (C–O–C), 1122,
930 (P–O–C), 765 (P–C). MS (m/z): 440 (Mþ 0.8%), 234 (25.20%), 220
(19.40%), 199 (29.57%), 175 (60.62%), 162 (100%), 133 (19.29%), 119
(10.64%), 109 (35.91%), 94 (3.93%), 93 (9.61%), 63 (33.03%). Anal. calcd
for C17H16Cl2NaO6P: C, 46.28; H, 3.66. Found: C, 46.19; H, 3.58.
6g. White crystal, m.p. 98–998C; 1H NMR: 3.36–3.41 (d, 3H, –OCH3,
J ¼ 9.7 Hz), 5.04–5.09 (q, 2H, –OCH2CO–, J ¼ 11.7 Hz), 5.89–5.95 (d, 1H,
–OCHP, J ¼ 12.6 Hz), 7.03–8.16 (m, 7H, –C6H4, –C6H3). IR (KBr) ymax
(cm21): 3076 (Ph–H), 2958, 2857 (C–H), 1759 (C55O), 1632, 1535, 1484
(Ph), 1217 (P55O), 1075 (C–O–C), 1040, 932 (P–O–C), 728 (P–C). MS
(m/z): 471 (Mþ 0.3%), 234 (33.09 %), 220 (15.49%), 199 (61.55%), 175
(48.66%), 162 (100%), 150 (51.60%), 133 (33.49%), 109 (32.25%), 94
(1.38%), 93 (2.91%), 63 (64.93%). Anal. calcd for C16H13Cl2NNaO8P: C,
40.70; H, 2.78; N, 2.97. Found: C, 40.61; H, 2.89; N, 3.01.
General Procedure for the Synthesis of Sodium
Monoethyl-a-(2,4-dichlorophenoxyacetoxy)aryl
Methyl Phosphonates (6h–m)
A solution of o,o-diethyl-a-(2,4-dichlorophenoxyacetoxy)aryl methyl
phosphonate (0.02 mol) and oven-dried sodium iodide (0.02 mol) was refluxed
for 10–22 hr in molecular sieve (4A) dried acetone (40 mL) under nitrogen.
The solution was evaporated at reduced pressure. The residual solid was
recrystallized from dichloromethane to afford the pure product as white
solid or crystal (the product was very deliquescent). The salts were isolated
directly in 66–79% yields.
6h. White solid, m.p. . 2618C (decompound); 1H NMR: 1.01–1.07
(t, 3H, –OCH2CH3, J ¼ 7.0 Hz), 3.64–3.76 (m, 2H, –OCH2CH3), 4.91–
5.07 (q, 2H, –OCH2CO–, J ¼ 16.8 Hz), 5.72–5.76 (d, 1H, –OCHP,
J ¼ 12.2 Hz), 7.01–7.67 (m, 8H, –C6H5, –C6H3). IR (KBr) ymax (cm21):
3072 (Ph–H), 2947, 2858 (C–H), 1732 (C55O), 1617, 1530, 1487 (Ph),
1242 (P55O), 1081 (C–O–C), 1081, 946 (P–O–C), 741 (P–C). MS (m/z):

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Wang and He
440 (Mþ 0.60%), 220 (3.67%), 133 (4.21%), 127 (100.0%), 75 (6.75%), 73
(9.78%). Anal. calcd for C17H16Cl2NaO6P: C, 46.28; H, 3.66. Found: C,
46.09; H, 3.73.
1
6i. White crystal, m.p. . 2588C (decompound); H NMR: 1.12–1.17
(t, 3H, –OCH2CH3, J ¼ 7.1 Hz), 3.82–3.91 (m, 2H, –OCH2CH3), 5.00
(s, 2H, –OCH2CO–), 5.05–5.10 (d, 1H, –OCHP, J ¼ 13.5 Hz), 7.01–7.77
(m, 6H, –C6H3, –C6H3). IR (KBr) ymax (cm21): 3054 (Ph–H), 2952, 2862
(C–H), 1712 (C55O), 1613, 1539, 1450 (Ph), 1224 (P55O), 1066 (C–O–
C), 1032, 943 (P–O–C), 760 (P–C). MS (m/z): 508 (Mþ 0.18%), 220
(5.69%), 133 (8.90%), 127 (100.0%), 75 (8.691%), 73 (23.78%). Anal.
calcd for C17H14Cl4NaO6P: C, 40.03; H, 2.77. Found: C, 39.91; H, 2.64.
6j. White solid, m.p. 201–2038C; 1H NMR: 1.20–1.25 (t, 3H,
–OCH2CH3, J ¼ 7.6 Hz), 3.62–3.67 (d, 3H, –OCH2CH3), 4.84–4.98
(q, 2H, –OCH2CO–, J ¼ 14.8 Hz), 5.67–5.71 (d, 1H, –OCHP, J ¼
12.2 Hz), 5.96 (s, 2H, –OCH2OPh), 6.86–7.63 (m, 6H, –C6H3, –C6H3). IR
(KBr) ymax (cm21): 3078 (Ph–H), 2958, 2846 (C–H), 1729 (C55O), 1627,
1534, 1489 (Ph), 1232 (P55O), 1080 (C–O–C), 1035, 946 (P–O–C), 765
(P–C). MS (m/z): 484 (Mþ 0.80%), 220 (4.67%), 133 (6.31%), 127
(100.0%), 75 (9.55%), 73 (7.78%). Anal. calcd for C18H16Cl2NaO8P: C,
44.56; H, 3.32. Found: C, 44.47; H, 3.21.
6k. White solid, m.p. .2768C (decompound); 1H NMR: 1.00–1.05
(t, 3H, –OCH2CH3, J ¼ 7.0 Hz), 3.63–3.73 (m, 2H, –OCH2CH3),
4.93–5.11 (q, 2H, –OCH2CO–, J ¼ 17.6 Hz), 5.78–5.82 (d, 1H, –OCHP,
J ¼ 12.5 Hz), 7.03–7.61 (m, 7H, –C6H4, –C6H3). IR (KBr) ymax (cm21):
3078 (Ph–H), 2941, 2847 (C–H), 1730 (C55O), 1611, 1528, 1484 (Ph),
1219 (P55O), 1070 (C–O–C), 1034, 943 (P–O–C), 772 (P–C). MS (m/z):
458 (Mþ 0.18%), 220 (2.69%), 133 (2.97%), 127 (100.0%), 75 (7.51%), 73
(24.78%). Anal. calcd for C17H15Cl2FNaO6P: C, 44.47; H,3.29. Found: C,
44.28; H, 3.38.
6l. White solid, m.p. .2658C (decompound); 1H NMR: 0.98–1.03
(t, 3H, –OCH2CH3, J ¼ 7.1 Hz), 2.26 (s, 3H, –CH3Ph), 3.60–3.70 (m, 2H,
–OCH2CH3), 4.90–5.06 (q, 2H, –OCH2CO–, J ¼ 16.3 Hz), 5.73–5.77
(d, 1H, –OCHP, J ¼ 12.5 Hz), 7.03–7.59 (m, 7H, –C6H4, –C6H3). IR
(KBr) ymax (cm21): 3056 (Ph–H), 2947, 2841 (C–H), 1729 (C55O), 1629,
1536, 1482 (Ph), 1281 (P55O), 1077 (C–O–C), 1032, 948 (P–O–C),
759 (P–C). MS (m/z): 454 (Mþ 1.32%), 220 (1.69%), 133 (4.59%), 127
(100.0%), 75 (18.51%), 73 (31.21%). Anal. calcd for C18H18Cl2NaO6P:
C, 47.49; H,3.99. Found: C, 47.28; H, 4.12.
6m. White solid, m.p. 192–1938C; 1H NMR: 1.01–1.06 (t, 3H,
–OCH2CH3, J ¼ 7.0 Hz), 3.67– 3.75 (m, 2H, –OCH2CH3), 4.98–5.20
(q, 2H, –OCH2CO–, J ¼ 19.9 Hz), 5.89–5.93 (d, 1H, –OCHP, J ¼
13.1 Hz), 7.07–8.18 (m, 7H, –C6H4, –C6H3). IR (KBr) ymax (cm21): 3043

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Synthesis of Phosphonate Monosodium Salts
1423
(Ph–H), 2971, 2859 (C–H), 1730 (C55O), 1624, 1530, 1482 (Ph), 1222
(P55O), 1077 (C–O–C), 1047, 946 (P–O–C), 699 (P–C). MS (m/z): 485
(Mþ 0.09%), 220 (5.19%), 199 (1.55%), 175 (8.06%), 162 (12.84%), 150
(6.30%), 145 (29.10%), 133 (9.09%), 127 (100.0%), 111 (6.31%), 109
(8.25%), 75 (18.51%), 74 (31.21%), 63 (49.93%). Anal. calcd for
C17H15Cl2NNaO8P: C, 42.00; H, 3.11; N, 2.88. Found: C, 41.87; H, 3.20;
N, 3.01.
ACKNOWLEDGMENTS
We gratefully acknowledge financial support of this work by National
Natural Science Foundation of China (Project No: 29572045, 20072008,
20372023).
REFERENCES
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Received in Japan August 18, 2003

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