Simple and improved preparation of α-oxophosphonate monolithium salts

Article abstract of DOI:10.1080/10426500490474941

Some α-OxoPhosphonate monolithium salts were synthesized by a facile one-step procedure. In this way, α-(2,4-dichlorophenoxyacetoxy)alkyl phosphonic acid dimethyl esters 5 can be transformed into the corresponding phosophonate monolithium salts 6 without influence on the carboxylic ester group under mild conditions.

Full text of DOI:10.1080/10426500490474941

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Phosphorus, Sulfur, and Silicon and the Related
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SIMPLE AND IMPROVED PREPARATION OF α-
OXOPHOSPHONATE MONOLITHIUM SALTS
Tao Wang a & Hong Wu He a
a Institute of Pesticide Chemistry, Central China Normal University Wuhan , Hubei, P.R. China
Published online: 16 Aug 2010.
To cite this article: Tao Wang & Hong Wu He (2004) SIMPLE AND IMPROVED PREPARATION OF α-OXOPHOSPHONATE
MONOLITHIUM SALTS, Phosphorus, Sulfur, and Silicon and the Related Elements, 179:10, 2081-2089, DOI:
10.1080/10426500490474941
To link to this article: http://dx.doi.org/10.1080/10426500490474941
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Phosphorus, Sulfur, and Silicon, 179:2081–2089, 2004
ꢀC
Copyright Taylor & Francis Inc.
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500490474941
SIMPLE AND IMPROVED PREPARATION
OF α-OXOPHOSPHONATE MONOLITHIUM SALTS
Tao Wang and Hong Wu He
Institute of Pesticide Chemistry, Central China Normal
University Wuhan, Hubei, P.R. China
(Received December 13, 2003; accepted March 23, 2004)
Some α-OxoPhosphonate monolithium salts were synthesized by
a
facile one-step procedure. In this way, α-(2,4-dichlorophen-
oxyacetoxy)alkyl phosphonic acid dimethyl esters 5 can be transformed
into the corresponding phosophonate monolithium salts 6 without in-
fluence on the carboxylic ester group under mild conditions.
Keywords: Phosphonate monolithium salt; synthesis
In continuation of our work on the synthesis of substituted phenoxy ace-
toxy alkyl phosphonic acid derivatives with good biological activities,1
we are interested in the preparation of phosphonate salts because its
corresponding salts would be of greater biological interest, such as for
herbicidal activities.2 A. C. Baillie reported that some phosphinate
monolithium salts could be obtained by directly converting a phos-
phinate ester (a) into the corresponding salts (b) in a 0.5 M solution
of anhydrous lithium iodide in methyl isobutyl ketone3 (Scheme 1).
SCHEME 1
We gratefully acknowledge financial support of this work by National Natural Science
Foundation of China (Project No. 29572045, 20072008, 20372023) and National Key Basic
Research Development Program of China (“973” Project No. 2003CB114400).
Address correspondence to Hong Wu He, Institute of Pesticide Chemistry, Central
China Normal University, Wuhan, Hubei, 430079, P.R. China. E-mail: hel208@public.
wh.hb.cn
2081

2082
T. Wang and H. W. He
However, this method is not applicable to prepare the title compounds
under harsher conditions. This was probably due to the cleavage of the
carboxylate ester bond in substituted phenoxy acetoxy alkyl phosphonic
acid derivative in methyl isobutyl ketone.
An alternative method,3 by reaction of a phosphonate ester (c) with
lithium bromide in butanone giving the corresponding phosphonate
monolithium salt (d), was reported (Scheme 2). However, attempts to
prepare the title compounds in butanone according to these conditions
were also unsuccessful.
SCHEME 2
Herein we report the reaction of α-(2,4-dichlorophenoxyacetoxy)
alkyl phosphonic acid dimethyl esters with lithium bromide in acetone
to produce the corresponding phosphonate monolithium salts. The reac-
tion under mild conditions resulted in high yields of the products 6a–p
(Table I) as shown in Scheme 3.
SCHEME 3 Syntheses of title compounds 6.
Initially, we prepared the title compounds 6 (Scheme 3) from α-(2,4-
dichlorophenoxyacetoxy) alkyl phosphonic acid dimethyl esters accord-
ing to the method in Scheme 2. The experiment showed that the reaction
of compounds 5a–p with lithium bromide was affected by reaction tem-
perature, base, solvent, and water. We attempted to prepare the title
compound 6d by the reaction of 5d with lithium bromide, which was
dried in the presence of butanone for 36 h, but no title compound 6d
was found. Instead, only 2,4-dichloro phenoxy acetic acid lithium salt
and the methyl-1-hydroxy phenyl phosphonate monolithium salt as a
by-product were found.

OxoPhosphonate Monolithium Salts
2083
TABLE I Preparation of α-OxoPhosphonate Monolithium Salts
Compd.
R
Formula
Color
m.p. (C) rt (h) Yield (%)
6a
6b
6c
6d
6e
6f
6g
6h
6i
6j
6k
6l
6m
6n
6o
6p
H
CH3
C10H10Cl2LiO6P
C11H12Cl2LiO6P
C13H16Cl2LiO6P
C16H14Cl2LiO6P
White 138–139
White 103–105
White 151–152
White 244–245
3
3
4
3
3
3
76
74
67
79
69
70
91
73
91
81
84
80
78
82
93
95
n-C3H7
Ph
o-ClPh
p-ClPh
p-FPh
p-CH3OPh
p-CH3Ph
2,4-Cl2Ph
C
16H13Cl3LiO6P
White
76–78
C16H13Cl3LiO6P
C16H13Cl2FLiO6P White 236–237 2.5
C17H16Cl2LiO7P
C17H16Cl2LiO6P
C16H12Cl4LiO6P
White 187–189
White 202–203
White 131–133
White 259–262
4
3
3
3,4-OCH2OPh C17H14Cl2LiO8P
White 238–239 2.5
m-NO2Ph
p-NO2Ph
o-Fural
o-Thiophenyl
o-Pyridyl
C16H13Cl2LiNO8P White 227–228 3
C16H13Cl2LiNO8P White 216–218
C14H12Cl2LiO7P White 132–134
14H12Cl2LiO6PS
C15H13Cl2LiNO6P White 227–228
3
2
C
White 171–172 1.5
1
Therefore, in the molecular structure of 0,0-dimethyl-α-(2,4-
dichlorophenoxyacetoxy)alkyl phosphonate, the carboxylate ester bond
may be easier to cleave than phosphonate ester bond under such
harsh conditions. Based on the above results, we needed milder con-
ditions for selective cleavage of phosphonate ester bond without cleav-
age carboxylate ester group. Consequently, the formation of the ti-
tle compounds 6 can be rationalized in terms of direct reaction of
TABLE II Preparation of the Intermediates 5a–p
Compd.
R
Formula
Color
n2D0
m.p. (◦C) Yield (%)
5a
5b
5c
5d
5e
5f
5g
5h
5i
5j
5k
5l
5m
5n
5o
5p
H
CH3
C11H13Cl2O6P
C12H15Cl2O6P
C14H19Cl2O6P
C17H17Cl2O6P
Yellow 1.5448
Yellow 1.5178
Yellow 1.4859
Yellow 1.5069
White
Yellow 1.5634
White
White
75.8
90.7
66.0
58.9
n-C3H7
Ph
o-ClPh
p-ClPh
p-FPh
p-CH3OPh
p-CH3Ph
2,4-Cl2Ph
C
17H16Cl3O6P
76–78
58.5
58.9
81.5
67.8
79.2
83.2
84.2
73.8
79.5
81.4
86.2
82.5
C17H16Cl3O6P
C17H16Cl2FO6P
C18H19Cl2O7P
C18H19Cl2O6P
C17H15Cl4O6P
90–91
96–97
Yellow 1.5429
White
White
103–104
120–121
92–93
126–127
62–63
3,4-OCH2OPh C18H17Cl2O8P
m-NO2Ph
p-NO2Ph
o-Fural
o-Thiophenyl
o-Pyridyl
C17H16Cl2NO8P White
C17H16Cl2NO8P White
C
15H15Cl2O7P
White
White
C15H15Cl2O6PS
C16H16Cl2NO6P White
92–93
86–87

2084
T. Wang and H. W. He
TABLE III 1H NMR Chemical Shifts (TMS, DMSO) of 6 and Coupling
Constants J(Hz)
Compd.
1H NMR
6a
3.36 (d, 3H, OCH3, J = 4.8 Hz), 4.13 (d, 2H, OCH2P, J = 8.6 Hz), 5.13
(s, 2H, OCH2CO ), 7.07–7.59 (m, 3H, C6H3)
6b
6c
1.32 (q, 3H, CH3, J = 6.75 Hz), 3.41 (d, 3H, OCH3, J = 9.81 Hz), 4.75
(d, 1Ha, OCH2CO , J = 16.53 Hz), 4.89 (d, 1Hb, OCH2CO , J =
16.54 Hz), 5.01 (d, 1H, OCHP, J = 15.63 Hz), 7.06–7.58 (m, 3H, C6H3)
0.88 (t, 3H, CH2CH2CH2, J = 7.4 Hz), 1.25–1.47 (m, 2H, CH2CH2CH3),
1.82–2.05 (m, 2H, CH2CH2CH3), 3.67 (d, 3H, OCH3, J = 9.90 Hz), 4.96
(d, 1Ha, OCH2CO , J = 16.50 Hz), 5.00 (d, 1Hb, OCH2CO , J =
16.50 Hz), 5.30 (d, 2H, OCHP, J = 8.40 Hz), 7.04–7.42 (m, 3H, C6H3)
3.31 (d, 3H, OCH3, J = 9.84 Hz), 4.94 (d, 1Ha, OCH2CO , J = 16.59 Hz),
5.05 (d, 1Hb, OCH2CO , J = 16.56 Hz), 5.80 (d, 1H, OCHP, J =
12.81 Hz), 7.05–7.59 (m, 8H, C6H5, C6H3)
6d
6e
6f
3.31 (d, 3H, OCH3, J = 9.94 Hz), 4.91 (d, 1Ha, OCH2CO , J = 16.56 Hz),
4.98 (d, 1Hb, OCH2CO , J = 16.59 Hz), 6.18 (d, 1H, OCHP,
J = 12.06 Hz), 6.98–7.64 (m, 7H, C6H4, C6H3)
3.31 (d, 3H, OCH3, J = 9.9 Hz), 4.90 (d, 1Ha, OCH2CO , J = 16.56 Hz),
4.96 (d, 1Hb, OCH2CO , J = 16.56 Hz), 6.15 (d, 1H, OCHP,
J = 12.20 Hz), 7.02–7.57 (m, 7H, C6H4, C6H3)
6g
6h
6i
3.32 (d, 3H, OCH3, J = 9.30 Hz), 4.93 (d, 1Ha, OCH2CO , J = 16.80 Hz),
5.03 (d, 1Hb, OCH2CO , J = 16.80 Hz), 5.80 (d, 1H, OCHP,
J = 12.80 Hz), 7.04–7.58 (m, 7H, C6H4, C6H3)
3.29 (d, 3H, OCH3, J = 9.90 Hz), 3.74 (s, 3H, CH3OPh), 4.88 (d, 1Ha,
OCH2CO , J = 16.50 Hz), 5.01 (d, 1Hb, OCH2CO , J = 16.56 Hz),
5.67–5.73 (d, 1H, OCHP, J = 13.6 Hz), 6.86–7.58 (m, 7H, C6H4, C6H3)
2.26 (s, 3H, CH3Ph), 3.30 (d, 3H, OCH3, J = 9.82 Hz), 4.91 (d, 1Ha,
OCH2CO , J = 16.56 Hz), 5.03(d, 1Hb, OCH2CO , J = 16.57 Hz), 5.76
(d, 1H, OCHP, J = 12.57 Hz), 7.03–7.59 (m, 7H, C6H4, C6H3)
3.38 (d, 3H, OCH3, J = 9.00 Hz), 4.94 (d, 1Ha, OCH2CO , J = 16.56 Hz),
4.99 (d, 1Hb, OCH2CO , J = 16.62 Hz), 6.12 (d, 1H, OCHP,
J = 12.21 Hz), 6.99–7.65 (m, 6H, C6H3, C6H3)
6j
6k
6l
3.34 (d, 3H, OCH3, J = 9.90 Hz), 4.91 (d, 1Ha, OCH2CO , J = 16.50 Hz),
5.03 (d, 1Hb, OCH2CO , J = 16.56 Hz), 5.74 (d, 1H, OCHP,
J = 12.42 Hz), 5.97 (s, 2H, OCH2OPh), 6.77–7.59 (m, 6H, C6H3, C6H3)
3.37 (d, 3H, OCH3, J = 10.02 Hz), 4.99 (d, 1Ha, OCH2CO , J = 16.62 Hz),
5.13 (d, 1Hb, OCH2CO , J = 16.62 Hz), 5.91 (d, 1H, OCHP,
J = 13.02 Hz), 7.07–8.22 (m, 7H, C6H4, C6H3)
6m
6n
6o
6p
3.36 (d, 3H, OCH3, J = 10.02 Hz), 4.94 (d, 1Ha, OCH2CO , J = 16.60 Hz),
5.13 (d, 1Hb, OCH2CO , J = 16.50 Hz), 5.90 (d, 1H, OCHP,
J = 12.80 Hz), 7.06–8.10 (m, 7H, C6H4, C6H3)
3.35 (d, 3H, OCH3, J = 9.7 Hz), 4.91 (d, 1Ha, OCH2CO , J = 16.80 Hz),
4.96 (d, 1Hb, OCH2CO , J = 16.80 Hz), 5.84 (d, 1H, OCHP, J = 12.6 Hz),
6.37–7.27 (m, 3H, C4H3O ), 7.03–7.65 (m, 3H, C6H3)
3.37 (d, 3H, OCH3, J = 8.40 Hz), 4.90 (d, 1Ha, OCH2CO , J = 16.80 Hz),
4.97(d, 1Hb, OCH2CO , J = 16.40 Hz), 6.06 (d, 1H, OCHP, J = 12.40 Hz),
6.38–7.05 (m, 3H, C4H3S), 7.07–7.58 (m, 3H, C6H3)
3.34 (d, 3H, OCH3, J = 10.40 Hz), 5.01 (d, 1Ha, OCH2CO , J = 16.80 Hz),
5.06 (d, 1Hb, OCH2CO , J = 16.80 Hz), 5.85 (d, 1H, OCHP,
J = 13.20 Hz), 7.13–7.65 (m, 3H, C6H3), 7.15–8.45 (m, 4H, C5H4N)

OxoPhosphonate Monolithium Salts
2085
the phosphonates 5a–p with lithium bromide in acetone which was
˚
dried by molecular sieves (4 A) under nitrogen for 1–4 h. Thereby,
we could obtain the title compound 6p by the reaction of com-
pound 5p and lithium and 1 h at reflux. The preliminary biolog-
ical tests showed that most of the title compounds 6a–p have ex-
cellent inhibitory activities against Echinochloa crusgalli, Brassica
napus, Digitaria adscendens, Amaranthus retroflexus, and Medicago
sativa.
EXPERIMENTAL
Instruments
Melting points (m.p.) were measured on an Electrothermal melting-
point apparatus and uncorrected; Elemental analysis were performed
by Vario EL III elemental analysis; IR spectra were obtained with a
1
Avatar 360 spectrometer; H NMR were measured with a Varian XL-
300 spectrometer at 300 MHZ, Tetramethyl Silane (TMS) was used
as an internal standard, and chemical shift values are expressed in
δ (DMSO) ppm. MS were measured on a Finnigen TRACE spectrome-
ter and API2000LC/MS.
Compounds 3 and 4 were prepared according to the literature.4,5
TABLE IV IR Data of Compounds 6
ν
ν
ν
ν
ν
ν
ν
ν
Compd. ph
H
C
H
C
O
Ph
P
O
C
O
C
P
O
C
P C
6a
6b
6c
6d
6e
6f
6g
6h
6i
6j
6k
6l
6m
6n
6o
6p
3036 2953, 2847 1783 1662, 1583, 1481 1226
3028 2952, 2857 1759 1633, 1548, 1484 1205
3029 2961, 2875 1759 1638, 1586, 1481 1203
3098 2947, 2846 1723 1648, 1590, 1487 1243
3078 2956, 2852 1733 1643, 1590, 1480 1242
3086 2944, 2852 1750 1638, 1599, 1480 1240
3068 2958, 2852 1748 1637, 1511, 1480 1224
3038 2948, 2852 1758 1638, 1501, 1480 1226
3098 2950, 2857 1746 1646, 1516, 1481 1218
3104 2958, 2852 1727 1649, 1587, 1485 1234
3059 2947, 2896 1718 1633, 1504, 1482 1235
3068 2964, 2857 1740 1635, 1538, 1479 1228
3048 2952, 2846 1739 1638, 1548, 1452 1226
3064 2957, 2852 1741 1645, 1601, 1465 1216
3101 2930, 2848 1761 1654, 1543, 1481 1224
3020 2953, 2856 1754 1599, 1575, 1480 1228
1092
1082
1081
1099
1078
1105
1106
1086
1080
1083
1082
1104
1081
1078
1101
1085
1045, 932 775
1055, 928 717
1046, 948 719
1049, 943 726
1052, 948 745
1049, 941 788
1052, 958 787
1052, 938 727
1052, 933 716
1057, 953 760
1040, 949 719
1052, 923 730
1050, 943 731
1053, 918 732
1046, 928 728
1053, 932 721

2086
T. Wang and H. W. He
Preparation of Intermediate 5
A solution of 2,4-dichlorophenoxy acetyl chloride 4 (0.022 mol)
in trichloromethane (10 ml) was added to stirred mixture of 1-
hydroxyalkyl phosphonate 3 (0.02 mol) and organic base (0.022 mol)
in trichloromethane (25 ml) at 20–25◦C. The mixture was stirred at
TABLE V Elemental Analysis and MS Data of Compound 6
Calcd. (found)
Compd.
C
H
N/Li
MS/LC-MS
6a
35.85
3.01
334 (M+), 175, 162, 133, 127, 109, 75, 63, 45 (100%)
(35.80) (3.49)
37.85 3.47
(37.88) (3.43)
41.41 4.28
(41.01) (4.61)
46.75 3.43
(46.38) (3.65) (1.89)
43.13 2.94
(42.87) (2.86)
43.13 2.94
(42.91) (2.89)
44.79 3.05
6b
6c
6d
6e
6f
348 (M+), 199, 175, 162, 133, 127, 109, 94, 93, 75, 63,
45 (100%)
37634 (M+), 175, 162, 133, 127, 109, 75, 63, 45
(100%)
1.71 410 (M+), 175, 162, 133, 127, 109, 94, 93, 77, 63,
45 (100%)
444 (M+), 175, 162, 133, 127, 111, 109, 94, 93, 75, 63,
45 (100%)
444 (M+), 175, 162, 133, 127, 111, 109, 94, 93, 75, 63,
45 (100%)
6g
1.64 428 (M+), 175, 162, 133, 127, 109, 95, 94, 93, 75, 63,
(44.38) (2.92) (1.72)
45 (100%); LC-MS: 421 (M+–7, 100%, negative);
431 (M++7, 92.51%, positive), 428 (M+, 60.43%,
positive)
6h
6i
46.29
(46.07) (3.58)
48.03 3.79
3.66
440 (M+), 175, 162, 133, 127, 109, 107, 94, 93, 75, 63,
45 (100%)
1.65 424 (M+), 199, 175, 162, 133, 127, 109, 94, 93, 91, 75,
(48.30) (3.64) (1.57) 63, 45 (100%); LC-MS: 417 (M+–7, 100%, negative);
431 (M++7, 89.77%, positive), 424 (M+, 18.98%,
positive)
6j
40.04
(39.55) (2.80)
44.86 3.10
(45.14) (3.35)
42.13 2.87
2.52
478 (M+), 199, 175, 162, 145, 133, 127, 109, 94, 93,
75, 63, 45, 42 (100%)
6k
6l
454 (M+), 199, 175, 162, 133, 127, 121, 109, 94, 93,
75, 63, 45 (100%)
3.07 455 (M+), 175, 162, 133, 127, 122, 109, 94, 93, 75, 63,
(41.71) (2.90) (2.97)
42.13 2.87
3.07 455 (M+), 175, 162, 133, 127, 122, 109, 94, 93, 75, 63,
(41.83) (2.88) (2.98)
41.93 3.02
(41.68) (2.86)
40.31 2.90
45 (100%)
6m
6n
6o
45 (100%)
400 (M+), 199, 175, 162, 133, 127, 109, 94, 93, 75, 67,
63, 45 (100%)
1.68 416 (M+), 175, 162, 133, 127, 109, 94, 93, 83, 63, 45
(40.02) (2.72) (1.79)
(100%); LC-MS: 409 (M+−7, 100%, negative);
423 (M++7, 92.87%, positive), 416 (M+, 10.38%,
positive)
6p
43.72
3.18
3.40 411 (M+), 175, 162, 133, 127, 109, 94, 93, 78, 63, 45
(43.63) (3.18) (3.39)
(100%)

OxoPhosphonate Monolithium Salts
2087
ambient temperature for 4 h and then at 40◦C for 1 h, washed with
0.1 M hydrochloric acid, saturated sodium hydrogen carbonate solu-
tion, and brine. The resultant mixture was dried and evaporated. The
residue was chromatographed on silica with 20% acetone in petroleum
ether as eluent to give the compound 5 as a liquid or solid, which was
recrystallized from DCM/petroleum ether. Yield, 58–91%. The interme-
diates 5a–p are listed in Table II.
General Preparation of Lithium
Monomethyl-α-(2,4-Dichlorophenoxy Acetoxy) Alkyl
Phosphonate Salts 6
A solution of 0,0-dimethyl-α-(2,4-dichlorophenoxyacetoxy)alkyl phos-
phonate (0.02 mol) and lithium bromide (0.02 mol) in acetone (50 ml)
˚
dried over molecular sieves (4 A) was stirred and refluxed under
nitrogen for 1–4 h. The solution was evaporated at reduced pressure.
The residual solid was recrystallized from dichloromethane/petroleum
to afford the pure product as a white crystals 6a–p (the product was very
deliquescent). The salts were isolated directly in 67–95.2% yields. The
structures of compounds 6a–p were confirmed by 1H NMR, IR spectra,
LC-MS, and elemental analyses.
In the 1H NMR spectra of 6, the proton in the P C moiety and the pro-
ton in the P OCH3 moiety each displays doublets. The IR spectra of all
compounds showed normal stretching absorption bands, indicating the
existence of the Ph H (∼3050 cm−1), C H (∼2950 cm−1, ∼2860 cm−1),
C O (∼1720 cm−1), C C (∼1620, ∼1450 cm−1), P O (∼1260 cm−1),
C O C (∼1080 cm−1), P O C (∼1050 cm−1, ∼930 cm−1) and P C
(∼750 cm−1). The EI mass spectra of compound 6 gave weak molec-
ular ion peaks. All the fragmentation ions were consistent with the
structure and can be clearly assigned. All results are listed in Tables I
and III–V.
REFERENCES
[1] H. W. He and Z. J. Liu, Chinese J. Org. Chem., 21(11), 878 (2001).
[2] A. C. Baillie, K. Wright, B. J. Wright, and C. G. Earnshaw, Pestic. Biochem. Physiol.,
30, 103 (1988).
[3] H. Krawczyk, Synth. Commun., 27(18), 3151 (1997).
[4] a) F. T. Boullet and A. Foucaud, Synthesis, 916 (1982); b) D. A. Evans, K. M. Hurst,
and J. M. Tabaks, J.A.C.S., 100, 3467 (1978).
[5] P. Coutrot et al., Synthesis, 661 (1986).

2088
T. Wang and H. W. He
APPENDIX
TABLE AI 1H NMR Chemical Shifts (TMS, CDCl3) of Compounds 5a–p
Compd.
1H NMR
5a
3.80 (dd, 6H, OCH3, J = 9.80 Hz), 4.30 (d, 2H, OCH2P, J = 8.28 Hz), 4.75
(s, 2H, OCH2CO ), 6.89–7.55 (m, 3H, C6H3)
5b
5c
1.53 (q, 3H, CH3, J = 6.75 Hz), 3.81 (dd, 6H, OCH3, J = 9.86 Hz), 4.75
(s, 1H, OCH2CO ), 5.25–5.40 (m, 1H, OCHP), 6.89–7.56 (m, 3H, C6H3)
0.92 (t, 3H, CH2CH2CH3, J = 7.20 Hz), 1.40–1.86 (m, 2H, CH2CH2CH3),
3.85 (dd, 3H, OCH3, J = 9.90 Hz), 4.80 (d, 1H, OCH2CO ), 5.35
(m, 2H, OCHP), 6.80–7.46 (m, 3H, C6H3)
5d
5e
5f
3.70 (dd, 6H, OCH3, J = 9.54 Hz), 4.89 (s, 1H, OCH2CO ), 6.24 (d, 1H,
OCHP,J = 11.60 Hz), 6.72–7.42 (m, 3H, C6H3)
3.85 (dd, 6H, OCH3, J = 9.80 Hz), 4.81 (s, 1H, OCH2CO ), 6.40 (d, 1H,
OCHP, J = 11.80 Hz), 6.80–7.40 (m, 7H, C6H4, C6H3)
3.75 (dd, 6H, OCH3, J = 9.80 Hz), 5.10 (s, 1H, OCH2CO ), 6.20 (d, 1H,
OCHP, J = 11.20 Hz), 7.12–7.67 (m, 7H, C6H4, C6H3)
3.85 (dd, 6H, OCH3, J = 9.58 Hz), 4.90 (s, 1H, OCH2CO ), 6.40 (d, 1H,
OCHP, J = 11.80 Hz), 6.94–7.50 (m, 7H, C6H4, C6H3)
3.10 (s, 3H, CH3OPh), 3.80 (dd, 6H, OCH3, J = 9.80 Hz), 4.86 (s, 2H,
OCH2CO ), 6.20 (d, 1H, OCHP, J = 11.6 Hz), 6.80–7.68 (m, 7H, C6H4,
C6H3)
5g
5h
5i
2.30 (s, 3H, CH3Ph), 3.74 (dd, 6H, OCH3, J = 9.80 Hz), 4.70 (s, 1H,
OCH2CO ), 6.26 (d, 1H, OCHP, J = 11.80 Hz), 6.77–7.42 (m, 7H,
C6H4, C6H3)
5j
3.76 (dd, 6H, OCH3, J = 9.80 Hz), 4.98 (s, 1H, OCH2CO ), 6.12 (d, 1H,
OCHP, J = 11.22 Hz), 7.20–7.60 (m, 6H, C6H3, C6H3)
3.72 (dd, 6H, OCH3, J = 9.80 Hz), 4.97 (s, 1H, OCH2CO ), 5.67 (d, 1H,
OCHP, J = 11.80 Hz), 5.97 (s, 2H, OCH2OPh), 6.76–7.53 (m, 6H,
C6H3, C6H3)
5k
5l
3.88 (dd, 6H, OCH3, J = 9.80 Hz), 5.09 (s, 1H, OCH2CO ), 5.95 (d, 1H,
OCHP, J = 11.60 Hz), 7.03–8.16 (m, 7H, C6H4, C6H3)
3.86 (dd, 6H, OCH3, J = 9.80 Hz), 5.01 (s, 1H, OCH2CO ), 5.92 (d, 1H,
OCHP, J = 11.60 Hz), 7.00–8.02 (m, 7H, C6H4, C6H3)
3.80 (dd, 6H, OCH3, J = 9.80 Hz), 4.76 (d, 1Ha, OCH2CO , J = 16.54 Hz),
4.78 (d, 1Hb, OCH2CO , J = 16.54 Hz), 6.38 (d, 1H, OCHP,
J = 14.83 Hz), 6.42–6.76 (m, 3H, C4H3O ), 7.12–7.47 (m, 3H, C6H3)
5m
5n
5o
5p
3.74 (dd, 6H, OCH3, J = 10.50 Hz), 4.74 (d, 1Ha, OCH2CO
,
J = 16.54 Hz), 4.77 (d, 1Hb, OCH2CO , J = 16.54 Hz), 6.48–6.53 (d, 1H,
OCHP, J = 13.50 Hz), 6.68–7.01 (m, 3H, C4H3S ), 6.98–7.36 (m, 3H,
C6H3)
3.76 (dd, 6H, OCH3, J = 9.95 Hz), 4.88 (s, 2H, OCH2CO ), 6.36 (d, 1H,
OCHP, J = 13.76 Hz), 6.81–7.39 (m, 3H, C6H3), 7.27–8.63 (m, 4H,
C5H4N)

OxoPhosphonate Monolithium Salts
TABLE AII IR Data of Compounds 5a–p
2089
ν
ν
ν
ν
ν
ν
ν
ν
Compd. ph
H
C
H
C
O
Ph
P
O
C
O
C
P
O
C
P C
5a
5b
5c
5d
5e
5f
5g
5h
5i
5j
5k
5l
5m
5n
5o
5p
3020 2990, 2850 1760 1580, 1490 1226
3030 2980, 2860 1745 1580, 1480 1260
3010 2980, 2850 1740 1590, 1480 1240
3020 2956, 2854 1772 1580, 1480 1265
3020 2950, 2849 1750 1580, 1490 1250
3096 2958, 2855 1773 1587, 1476 1262
3018 2952, 2850 1758 1590, 1457 1258
3020 2980, 2850 1752 1590, 1490 1245
3018 2974, 2857 1750 1585, 1479 1262
3035 2962, 2850 1746 1562, 1474 1248
3015 2929, 2875 1760 1585, 1470 1260
3028 2952, 2845 1774 1580, 1460 1235
3043 2958, 2858 1773 1578, 1472 1257
3074 2971, 2852 1765 1583, 1483 1285
3072 2972, 2852 1763 1582, 1483 1275
3056 2963, 2852 1766 1591, 1478 1265
1092
1170
1180
1176
1180
1175
1101
1170
1187
1164
1180
1170
1176
1188
1190
1190
1045, 929 770
1060, 937 751
1050, 941 739
1032, 943 747
1030, 937 742
1051, 928 768
1040, 958 752
1040, 939 757
1036, 930 732
1063, 946 754
1052, 940 754
1035, 927 758
1056, 948 751
1036, 934 753
1038, 946 732
1027, 926 755