Synthesis and biological activity of O,O-Dimethyl-2,6-Pyridinyl diformyloxy alkyl phosphonates

Article abstract of DOI:10.1080/10426500802583553

In an attempt to discover novel compounds with high activity and low toxicity, a series of new O,O-dimethyl-2,6-pyridinyl diformyloxy alkyl phosphonates 4a-4p has been designed and synthesized by the reaction of 2,6-pyridinyl diformyloxy chloride with α-hydroxyalkyl phosphonate. The structures of all new compounds were characterized by elementary analysis, IR, ¹H NMR, and MS spectroscopies. The results of a preliminary bioassay indicate that some of the target compounds have obviously promotive action for plant growth against the stalk of barnyard grass.

Full text of DOI:10.1080/10426500802583553

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Synthesis and Biological
Activity of O,O-Dimethyl-2,6-
Pyridinyl Diformyloxy Alkyl
Phosphonates
Tao Wang a , Da You Lei a , Ying Huang a & Li Hua Ao
a
a College of Chemistry and Chemical Engineering,
Jiangxi Normal University, Nanchang, P. R. China
Published online: 03 Nov 2009.
To cite this article: Tao Wang , Da You Lei , Ying Huang & Li Hua Ao (2009): Synthesis
and Biological Activity of O,O-Dimethyl-2,6-Pyridinyl Diformyloxy Alkyl Phosphonates,
Phosphorus, Sulfur, and Silicon and the Related Elements, 184:11, 2777-2785
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Phosphorus, Sulfur, and Silicon, 184:2777–2785, 2009
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500802583553
Synthesis and Biological Activity of
O,O-Dimethyl-2,6-Pyridinyl Diformyloxy Alkyl
Phosphonates
Tao Wang, Da You Lei, Ying Huang, and Li Hua Ao
College of Chemistry and Chemical Engineering, Jiangxi Normal
University, Nanchang, P. R. China
In an attempt to discover novel compounds with high activity and low toxicity, a
series of new O,O-dimethyl-2,6-pyridinyl diformyloxy alkyl phosphonates 4a–4p
has been designed and synthesized by the reaction of 2,6-pyridinyl diformyloxy
chloride with α-hydroxyalkyl phosphonate. The structures of all new compounds
were characterized by elementary analysis, IR, 1H NMR, and MS spectroscopies.
The results of a preliminary bioassay indicate that some of the target compounds
have obviously promotive action for plant growth against the stalk of barnyard
grass.
Keywords Biological activities; O,O-dimethyl-2,6-pyridinyl diformyloxy alkyl phospho-
nates; synthesis
INTRODUCTION
We have reported the synthesis of a series of substituted phenoxy ace-
toxy alkyl phosphonates.1–3 He and Wang1–3 have demonstrated that
some phosphonates and their derivatives exhibit notable herbicidal ac-
tivity due to their inhibition against pyruvate dehydrogenase complex
(PDHC). In order to find new phosphonates with better pesticide activ-
ity, the pyridine structural unit was introduced into their molecules,
so O,O-dimethyl-2,6-pyridinyl diformyloxy alkyl phosphonates were
synthesized by the reaction of 2,6-pyridinyl diformyloxy chloride with
α-hydroxyalkyl phosphonate under mild conditions. The synthetic route
is shown in Scheme 1.
Received 3 September 2008; accepted 27 October 2008.
We are grateful to the National Natural Science Foundation of China (No. 20862007)
and Natural Science Foundation of Jiangxi Province (No. 2007GZH1399).
Address correspondence to Tao Wang, College of Chemistry and Chemical Engi-
neering, Jiangxi Normal University, Nanchang 330022, P. R. China. E-mail: wang-
tao1962@sohu.com
2777

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T. Wang et al.
SCHEME 1 R: 4a: H; 4b: CH3; 4c: CCl3; 4d: CH3CH2; 4e: CH3CH2CH2; 4f:
(CH3)2CH; 4g: Ph; 4h: 2-ClPh; 4i: 4-ClPh; 4j: 2,4-2ClPh; 4k: 3-NO2Ph; 4l: 4-
CH3OPh; 4m: 4-CH3Ph; 4n: 3,4-OCH2OPh; 4o: 2-Furyl; 4p: 2-Thiophenyl.
RESULTS AND DISCUSSION
Preparation of α-Hydroxyalkylphosphonates 2 and
O,O-Dimethyl-2,6-pyridinyl Diformyloxy Alkyl Phosphonates 4
The reaction of dialkyl phosphates 1 with aldehydes is a conve-
nient method used to synthesize α-hydroxyphosphonates 2. There
are some reports on the synthesis of α-hydroxyphosphonates.4, 5 How-
ever, there are few reports on the reaction of dimethylphosphonate
with 2-thiophenecarboxaldehyde. Herein we report the reaction of
dimethylphosphonate with 2-thiophenecarboxaldehyde to produce α-
hydroxy phosphonates 2p. The reaction under mild conditions (room
temperature) resulted in high yields of the products as shown in Scheme
1.
However, the addition of a base (triethylamine) was essential to
the addition reaction. Without the use of the triethylamine as a cat-
alyst, the reaction rate was greatly slowed and the yields were very
low. We tried to synthesize compound 2p by the addition reaction of
dimethylphosphonate with 2-thiophene-carboxaldehyde in the pres-
ence of KF/Al2O3, but only byproducts were found. Therefore we ob-
tained the title compound 2p by the reaction of compound 1 with 2-
thiophenecarboxaldehyde in the presence of the triethylamine.
The compounds 4 were prepared from the compounds 2 and 2,6-
pyridinyl diformyloxy chloride 3 in the presence of triethylamine. As the
target phosphonate derivatives contain groups sensitive to acid, base,
or water, such as carboxylic esters, so the reaction required conditions
near room temperature and the use of anhydrous solvents.

O,O-Dimethyl-2,6-Pyridinyl Diformyloxy Alkyl Phosphonates
2779
The Structures of O,O-Dimethyl-2,6-pyridinyl Diformyloxy
Alkyl Phosphonates 4
The molecular structures of all new compounds obtained were con-
firmed by 1H NMR, IR spectra, MS, and elemental analyses. In the 1H
NMR spectra of 4, the proton in the P C moiety exhibits a doublet,
while the proton in the P-OCH3 moiety displays a doublet of doublets.
The IR spectra of all compounds showed normal stretching absorp-
tion bands, indicating the existence of the Ph H (–2950 cm−1), C O
(–1730 cm−1), C C (–1620, –1450 cm−1), P O (–1260 cm−1), P O C
(–1050 cm−1), and P C (–750 cm−1). The EI mass spectra of compounds
4a–p gave the anticipated molecular ion peaks.
Herbicidal Activities
As seen from Table I, the compound 4c exhibited notable herbicidal
activity on the root of barnyard grass and rape at 100 ppm, while the
compounds 4b, 4e, 4f, 4h, 4i, 4k, 4l, 4n, 4o, and 4p have an obviously
promotive action for plant growth against a stalk of barnyard grass at
100 ppm.
EXPERIMENTAL
Melting points are uncorrected. MS were measured with a Finnigan
Trace MS spectrometer. IR were recorded with a PE-983 infrared spec-
trometer as KBr pellets. NMR were recorded in CDCl3 or [d6]DMSO
with a Varian Mercury 400 spectrometer and resonances relative to
TMS. Elementary analyses were taken with a Vario EL III elementary
analysis instrument. The reagents and solvents were available com-
mercially and purified according to conventional methods before use.
Compounds 1, 2, and 3 were prepared according to the literature.6–10
Synthesis of O,O-Dimethyl-2,6-pyridinyl Diformyloxy Alkyl
Phosphonates General Procedure
A solution of 2,6-pyridinyl diformyloxy chloride 3 (0.022 mol) in
dichloromethane (10 mL) was added to a stirred mixture of α-hydroxy
alkyl phosphonate 2 (0.01 mol) and triethylamine (0.022 mol) in
dichloromethane (25 mL) at 20–25◦C. The mixture was stirred at am-
bient temperature for 4 h, and then at 40◦C for 1 h, and was washed
with 0.1 M hydrochloric acid, saturated sodium hydrogen carbonate
solution, and brine in that order. The resulting mixture was dried, and
the solvent used was evaporated. The residue was chromatographed on

2780

O,O-Dimethyl-2,6-Pyridinyl Diformyloxy Alkyl Phosphonates
2781
silica with 20% acetone in petroleum ether as eluent to give the title
compounds 4.
O,O-Dimethyl-2,6-pyridinyl Diformyloxy Methyl Phosphonate
(4a)
Light yellow liquid (yield 38%); nD20: 1.4619; IR (KBr)υ: 3095 (w,
Ph H), 2953, 2854 (m, C H), 1739 (s, C O), 1583, 1478, 1437 (s,
Ph), 1246 (s, P O), 1182 (s, C O C), 1042, 898 (s, P O C), 756 (s,
P C) cm−1; 1H NMR(CHCl3, 400Hz)δ: 3.88 (dd, 4 × 3H, 2 × ( OCH3),
J = 10.4 Hz), 4.74 (d, 2 × 2H, OCH2P, J = 5.28 Hz), 8.02–8.34 (m, 3H,
C5H3N). 31P NMR(CHCl3, 400 Hz)δ: 15.77 ppm. MS (70 eV) m/z (%):
411 (M+ +1 12); Anal. Calcd. (%) for C13H19NO10P2: C 37.97, H 4.66, N
3.41; Found C 37.73, H 4.57, N 3.70.
O,O-Dimethyl-2,6-pyridinyl Diformyloxy Ethyl Phosphonate
(4b)
Light yellow liquid (yield 39%); nD20: 1.4687; IR (KBr)υ: 3091 (w,
Ph H), 2956, 2852 (m, C H), 1736 (s, C O), 1584, 1473, 1433 (s,
Ph), 1243 (s, P O), 1182 (s, C O C), 1044, 894 (s, P O C), 754 (s,
P C) cm−1; 1H NMR(CHCl3, 400Hz)δ: 1.63 (q, 2 × 3H, 2 × ( CH3), J =
5.40 Hz), 3.90 (dd, 4 × 3H, 2 × ( OCH3), J = 7.60 Hz), 5.58 (q, 2 × H,
OCHP, J = 2.80 Hz), 8.01–8.33 (m, 3H, C5H3N). 31P NMR (CHCl3,
400Hz) δ: 16.32 ppm. MS (70eV) m/z (%): 439 (M+ +1 22); Anal. Calcd.
(%) for C15H23NO10P2: C 41.01, H 5.28, N 3.19; Found C 41.22, H 5.51,
N 3.42.
O,O-Dimethyl-2,6-pyridinyl Diformyloxy Trichloromethylmethyl
Phosphonate (4c)
White crystal (yield 73%); mp: 144–146; IR (KBr)υ: 3092 (w, Ph H),
2962, 2851 (m, C H), 1733 (s, C O), 1583, 1473, 1432 (s, Ph), 1242 (s,
P O), 1184 (s, C O C), 1044, 895 (s, P O C), 754 (s, P C) cm−1; 1H
NMR (CHCl3, 400Hz) δ: 3.92 (dd, 4 × 3H, 2 × ( OCH3), J = 4.58 Hz),
6.21 (d, 2 × H, OCHP, J = 7.78 Hz), 8.12–8.49 (m, 3H, C5H3N). 31
P
NMR (CHCl3, 400 Hz) δ: 12.39 ppm. MS (70 eV) m/z (%): 645 (M+ +1
14); Anal. Calcd. (%) for C15H17Cl6NO10P2: C 27.89, H 2.65, N 2.17;
Found C 27.65, H 2.74, N 2.42.
O,O-Dimethyl-2,6-pyridinyl Diformyloxy Ethylmethyl
Phosphonate (4d)
Light yellow liquid (yield 65%); nD20: 1.4710; IR (KBr)υ: 3112 (w,
Ph H), 2959, 2855 (m, C H), 1732 (s, C O), 1586, 1476, 1436 (s,
Ph), 1245 (s, P O), 1185 (s, C O C), 1045, 895 (s, P O C), 755 (s,
1
P C) cm−1; H NMR(CHCl3, 400Hz) δ: 1.07 (t, 2 × 3H, 2 × ( CH3),

2782
T. Wang et al.
J = 6.80 Hz), 1.97–2.11 (m, 2 × 2H, 2 × ( CH2CH3)), 3.87 (dd, 4 ×
3H, 2 × ( OCH3), J = 6.20 Hz), 5.51 (q, 2 × H, OCHP, J = 2.82 Hz),
8.01–8.33 (m, 3H, C5H3N). 31P NMR (CHCl3, 400 Hz) δ: 16.46 ppm.
MS (70 eV) m/z (%): 467 (M+ +1 13); Anal. Calcd. (%) for C17H27NO10P2:
C 43.69, H 5.82, N 3.00; Found C 43.43, H 5.98, N 3.27.
O,O-Dimethyl-2,6-pyridinyl Diformyloxy n-Propylmethyl
Phosphonate (4e)
Light yellow liquid (yield 43%); nD20: 1.4564; IR (KBr)υ: 3098 (w,
Ph H), 2960, 2850 (m, C H), 1735 (s, C O), 1580, 1477, 1439 (s,
Ph), 1246 (s, P O), 1162 (s, C O C), 1044, 894 (s, P O C), 753 (s,
P C) cm−1; 1H NMR(CHCl3, 400Hz)δ: 0.98 (t, 2 × 3H, 2 × ( CH3), J =
6.80 Hz), 1.39–1.54 (m, 2 × 2H, 2 × ( CH2CH2CH3)), 1.93–2.16 (m, 2 ×
2H, 2 × (-CH2CH2CH3)), 3.87 (dd, 4 × 3H, 2 × ( OCH3), J = 6.20Hz),
5.59 (q, 2 × H, OCHP, J = 2.80Hz), 8.00–8.32 (m, 3H, C5H3N). 31P
NMR (CHCl3, 400Hz) δ: 16.62 ppm. MS (70eV) m/z (%): 495 (M+ +1
17); Anal. Calcd. (%) for C19H31NO10P2: C 46.06, H 6.31, N 2.83; Found
C 46.38, H 6.60, N 3.07.
O,O-Dimethyl-2,6-pyridinyl Diformyloxy i-Propylmethyl
Phosphonate (4f)
Light yellow liquid (yield 43%); nD20: 1.4604; IR (KBr)υ: 3089 (w,
Ph H), 2960, 2856 (m, C H), 1737 (s, C O), 1587, 1475, 1436 (s,
Ph), 1247 (s, P O), 1182 (s, C O C), 1046, 897 (s, P O C), 755 (s,
P C) cm−1; 1H NMR(CHCl3, 400 Hz)δ: 1.06 (d, 4 × 3H, 4 × ( CH3), J
= 4.27 Hz), 1.08–1.51 (m, 2 × H, 2 × (-CH(CH3)2), 3.86 (dd, 4 × 3H, 2 ×
( OCH3), J = 6.80Hz), 5.43 (q, 2 × H, OCHP, J = 2.80 Hz), 8.02–8.34
(m, 3H, C5H3N). 31P NMR (CHCl3, 400Hz) δ: 16.95 ppm. MS (70eV)
m/z (%): 495 (M+ +1 19); Anal. Calcd. (%) for C19H31NO10P2: C 46.06,
H 6.31, N 2.83; Found C 46.22, H 6.55, N 3.11.
O,O-Dimethyl-2,6-pyridinyl Diformyloxy Benzyl Phosphonate
(4g)
White crystal (yield 73%); mp: 102–105; IR (KBr)υ: 3074 (w, Ph H),
2959, 2857 (m, C H), 1737 (s, C O), 1587, 1476, 1457 (s, Ph), 1267 (s,
P O), 1156 (s, C O C), 1037, 835 (s, P O C), 757 (s, P C) cm−1; 1H
NMR (CHCl3, 400Hz) δ: 3.81 (dd, 4 × 3H, 2 × ( OCH3), J = 3.20 Hz),
6.47 (d, 2 × H, OCHP, J = 5.00 Hz), 7.36–7.66 (m, 2 × 5H, 2 ×
( C6H5)), 8.02–8.37 (m, 3H, C5H3N). 31P NMR (CHCl3, 400 Hz) δ:
18.56 ppm. MS (70eV) m/z(%): 563 (M+ +1 26); Anal. Calcd. (%) for
C25H27NO10P2: C 53.29, H 4.83, N 2.49; Found C 53.08, H 4.96, N 2.66.

O,O-Dimethyl-2,6-Pyridinyl Diformyloxy Alkyl Phosphonates
2783
O,O-Dimethyl-2,6-pyridinyl Diformyloxy 2-Chlorobenzyl
Phosphonate (4h)
White crystal (yield 48%); mp: 119–122; IR (KBr)υ: 3087 (w, Ph H),
2956, 2856 (m, C H), 1736 (s, C O), 1585, 1498, 1457 (s, Ph), 1267 (s,
P O), 1157 (s, C O C), 1069, 836 (s, P O C), 754 (s, P C) cm−1; 1H
NMR(CHCl3, 400 Hz)δ: 3.84 (dd, 4 × 3H, 2 × ( OCH3), J = 4.00 Hz),
6.94 (d, 2 × H, OCHP, J = 5.50Hz), 7.30–7.86 (m, 2 × 4H, 2 × ( C6H4)),
8.02–8.34 (m, 3H, C5H3N). 31P NMR (CHCl3, 400 Hz) δ: 18.26 ppm. MS
(70eV) m/z (%): 632 (M+ +1 20); Anal. Calcd. (%) for C25H25Cl2NO10P2:
C 47.49, H 3.99, N 2.22; Found C 47.58, H 4.18, N 2.51.
O,O-Dimethyl-2,6-pyridinyl Diformyloxy 4-Chlorobenzyl
Phosphonate (4i)
Light yellow liquid (yield 80%); nD20: 1.4855; IR (KBr)υ: 3089 (w,
Ph H), 2959, 2853 (m, C H), 1736 (s, C O), 1584, 1494, 1457(s,
Ph), 1266 (s, P O), 1154 (s, C O C), 1035, 835 (s, P O C), 755 (s,
P C) cm−1; 1H NMR (CHCl3, 400 Hz) δ: 3.82 (dd, 4 × 3H, 2 × ( OCH3),
J = 2.80 Hz), 6.40 (q, 2 × H, OCHP, J = 5.25 Hz), 7.34–7.59 (m, 2
× 4H, 2 × ( C6H4)), 8.03–8.35 (m, 3H, C5H3N). 31P NMR (CHCl3,
400 Hz) δ: 18.34ppm. MS (70 eV) m/z(%): 632 (M+ +1 13); Anal. Calcd.
(%) for C25H25Cl2NO10P2: C 47.49, H 3.99, N 2.22; Found C 47.60, H
4.21, N 2.45.
O,O-Dimethyl-2,6-pyridinyl Diformyloxy 2,4-Dichlorobenzyl
Phosphonate (4j)
White crystal (yield 38%); mp: 199–201; IR (KBr)υ: 3088 (w, Ph H),
2959, 2857 (m, C H), 1734 (s, C O), 1585, 1496, 1455 (s, Ph), 1268
(s, P O), 1151 (s, C O C), 1051, 832 (s, P O C), 754 (s, P C) cm−1
;
1H NMR (CHCl3, 400 Hz) δ: 3.87 (dd, 4 × 3H, 2 × ( OCH3), J =
4.80 Hz), 6.83 (d, 2 × H, OCHP, J = 6.00 Hz), 7.31–7.76 (m, 2 × 3H,
2 × ( C6H3)), 8.01–8.34 (m, 3H, C5H3N). 31P NMR (CHCl3, 400 Hz)
δ: 17.76 ppm. MS (70eV) m/z (%): 701 (M+ +1 14); Anal.Calcd.(%) for
C25H23Cl4NO10P2: C 42.82, H 3.31, N 2.00; Found C 42.88, H 3.53, N
2.28.
O,O-Dimethyl-2,6-pyridinyl Diformyloxy 3-Nitrobenzyl
Phosphonate (4k)
Light yellow crystal (yield 56%); mp: 127–128; IR (KBr)υ: 3124 (w,
Ph H), 2959, 2855 (m, C H), 1732 (s, C O), 1586, 1496, 1454 (s,
Ph), 1268 (s, P O), 1151 (s, C O C), 1039, 831 (s, P O C), 753 (s,
P C) cm−1; 1H NMR (CHCl3, 400 Hz)δ: 3.88 (dd, 4 × 3H, 2 × ( OCH3),
J = 6.75 Hz), 6.52 (d, 2 × H, OCHP, J = 7.25 Hz), 7.60–8.47 (m, 2 × 4H,

2784
T. Wang et al.
2 × ( C6H4)), 8.08–8.38 (m, 3H, C5H3N). 31P NMR (CHCl3, 400 Hz)
δ: 17.31 ppm. MS (70 eV) m/z (%): 653 (M+ +1 24); Anal.Calcd.(%) for
C25H25N3O14P2: C 45.95, H 3.86, N 6.43; Found C 46.16, H 4.03, N 6.61.
O,O-Dimethyl-2,6-pyridinyl Diformyloxy 4-Methyloxybenzyl
Phosphonate (4l)
Light yellow liquid (yield 46%); nD20: 1.4740; IR (KBr)υ: 3084 (w,
Ph H), 2956, 2856 (m, C H), 1737 (s, C O), 1588, 1498, 1455 (s,
Ph), 1263 (s, P O), 1154 (s, C O C), 1036, 834 (s, P O C), 757 (s,
P C) cm−1; 1H NMR (CHCl3, 400 Hz)δ: 3.73 (s, 2 × 3H, 2 × CH3OPh),
3.82 (dd, 4 × 3H, 2 × ( OCH3), J = 4.50 Hz), 6.40 (d, 2 × H, OCHP,
J = 4.00 Hz), 6.91–7.59 (m, 2 × 4H, 2 × ( C6H4)), 7.99–8.32 (m, 3H,
C5H3N). 31P NMR (CHCl3, 400Hz) δ: 18.76 ppm. MS (70eV) m/z (%):
623 (M+ +1 21); Anal. Calcd. (%) for C27H31NO12P2: C 52.01, H 5.01, N
2.25; Found C 52.25, H 5.22, N 2.38.
O,O-Dimethyl-2,6-pyridinyl Diformyloxy 4-Methyl Benzyl
Phosphonate (4m)
Light yellow liquid (yield 79%); nD20: 1.4985; IR (KBr)υ: 3099 (w,
Ph H), 2949, 2854 (m, C H), 1736 (s, C O), 1584, 1494, 1455 (s,
Ph), 1264 (s, P O), 1154 (s, C O C), 1036, 832 (s, P O C), 752(s,
1
P C) cm−1; H NMR(CHCl3, 400 Hz) δ: 2.32 (s, 2 × 3H, 2 × CH3Ph),
3.80 (dd, 4 × 3H, 2 × ( OCH3), J = 4.80 Hz), 6.42 (d, 2 × H, OCHP,
J = 6.50 Hz), 7.06–7.54 (m, 2 × 4H, 2 × ( C6H4)), 8.00–8.32 (m, 3H,
C5H3N). 31P NMR (CHCl3, 400Hz) δ: 18.62 ppm. MS (70 eV) m/z(%):
591 (M+ +1 17); Anal.Calcd. (%) for C27H31NO10P2: C 54.83, H 5.28, N
2.37; Found C 54.99, H 5.47, N 2.43.
O,O-Dimethyl-2,6-pyridinyl Diformyloxy 3,4-Methylenedioxy
Benzyl Phosphonate (4n)
Light yellow liquid (yield 61%); nD20: 1.4971; IR (KBr)υ: 3124 (w,
Ph H), 2959, 2855 (m, C H), 1732 (s, C O), 1586, 1496, 1454 (s,
Ph), 1268 (s, P O), 1151 (s, C O C), 1039, 831 (s, P O C), 753 (s,
P C) cm−1; 1H NMR(CHCl3, 400 Hz) δ: 3.82 (dd, 4 × 3H, 2 × ( OCH3),
J = 4.25 Hz), 5.98 (s, 2 × 2H, 2 × ( OCH2OPh)), 6.35 (d, 2 × H, OCHP,
J = 4.50 Hz), 6.81–7.16 (m, 2 × 3H, 2 × ( C6H3)), 8.00–8.34 (m, 3H,
C5H3N). 31P NMR (CHCl3, 400 Hz) δ: 18.64 ppm. MS (70 eV) m/z (%):
651 (M+ +1 15); Anal. Calcd. (%) for C27H27NO14P2: C 49.78, H 4.18, N
2.15; Found C 49.89, H 4.32, N 2.33.

O,O-Dimethyl-2,6-Pyridinyl Diformyloxy Alkyl Phosphonates
2785
O,O-Dimethyl-2,6-pyridinyl Diformyloxy 2-Furyl Methyl
Phosphonate (4o)
Yellow crystal (yield 54%); mp: 92–94; IR (KBr)υ: 3124 (w, Ph H),
2959, 2855 (m, C H), 1732 (s, C O), 1586, 1496, 1454 (s, Ph), 1268 (s,
P O), 1151 (s, C O C), 1039, 831 (s, P O C), 753 (s, P C) cm−1; 1H
NMR (CHCl3, 400Hz) δ: 3.92 (dd, 4 × 3H, 2 × ( OCH3), J = 4.80 Hz),
6.57 (q, 2 × H, OCHP, J = 9.50 Hz), 6.41–7.48 (m, 2 × 3H, C4H3O),
8.00–8.33 (m, 3H, C5H3N). 31P NMR (CHCl3, 400 Hz) δ: 17.44 ppm.
MS (70 eV) m/z (%): 543 (M+ +1 23); Anal. Calcd. (%) for C21H23NO12P2:
C 46.42, H 4.27, N 2.58; Found C 46.31, H 4.53, N 2.76.
O,O-Dimethyl-2,6-pyridinyl Diformyloxy 2-Thiophenyl Methyl
Phosphonate (4p)
Light yellow crystal (yield 57%); mp: 93–95; IR (KBr)υ: 3091 (w,
Ph H), 2956, 2853 (m, C H), 1729 (s, C O), 1585, 1452, 1423 (s,
Ph), 1248 (s, P O), 1185 (s, C O C), 1039, 842 (s, P O C), 757 (s,
P C) cm−1; 1H NMR(CHCl3, 400 Hz) δ: 3.85 (dd, 4 × 3H, 2 × ( OCH3),
J = 4.50 Hz), 6.70 (q, 2 × H, OCHP, J = 6.50 Hz), 6.99–7.37 (m, 2 ×
3H, C4H3S), 7.98–8.31 (m, 3H, C5H3N). 31P NMR (CHCl3, 400 Hz)
δ: 17.84 ppm. MS (70 eV) m/z(%): 575 (M+ +1 19); Anal. Calcd. (%) for
C21H23NO10P2 S2: C 43.83, H 4.03, N 2.43; Found C 43.99, H 4.33, N
2.62.
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