A synthesis of phosphorylated 2,4-dioxothiazolidine derivatives

Article abstract of DOI:10.1080/10426507.2010.526672

The zwitterionic 1:1 intermediates generated from trialkyl phosphites and dialkyl acetylenedicarboxylates are trapped by 2,4-thiazolidinedione and 5-arylidene-2,4-thiazolidinediones to produce dialkyl 2-(2,4-dioxothiazolidin-3- yl)-3-(dialkoxyphosphoryl)

Full text of DOI:10.1080/10426507.2010.526672

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Phosphorus, Sulfur, and Silicon and the
Related Elements
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A Synthesis of Phosphorylated 2,4-
Dioxothiazolidine Derivatives
Issa Yavari a , Tayebeh Sanaeishoar a , Mohammad Piltan a & Leila
Azad a
a Chemistry Department, Islamic Azad University, Science and
Research Branch, Ponak, Tehran, Iran
Published online: 04 Aug 2011.
To cite this article: Issa Yavari , Tayebeh Sanaeishoar , Mohammad Piltan & Leila Azad (2011) A
Synthesis of Phosphorylated 2,4-Dioxothiazolidine Derivatives, Phosphorus, Sulfur, and Silicon and the
Related Elements, 186:7, 1612-1619, DOI: 10.1080/10426507.2010.526672
To link to this article: http://dx.doi.org/10.1080/10426507.2010.526672
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Phosphorus, Sulfur, and Silicon, 186:1612–1619, 2011
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2010.526672
A SYNTHESIS OF PHOSPHORYLATED
2,4-DIOXOTHIAZOLIDINE DERIVATIVES
Issa Yavari, Tayebeh Sanaeishoar, Mohammad Piltan,
and Leila Azad
Chemistry Department, Islamic Azad University, Science and Research Branch,
Ponak, Tehran, Iran
GRAPHICAL ABSTRACT
Abstract The zwitterionic 1:1 intermediates generated from trialkyl phosphites and
dialkyl acetylenedicarboxylates are trapped by 2,4-thiazolidinedione and 5-arylidene-
2,4-thiazolidinediones to produce dialkyl 2-(2,4-dioxothiazolidin-3-yl)-3-(dialkoxyphosphoryl)
succinates and dialkyl 2-(5-arylidene-2,4-dioxothiazolidin-3-yl)-3-(dialkoxyphosphoryl)
succinates in good yields.
Keywords Acetylenic esters; MCR; phosphites; phosphonates; 2,4-thiazolidinedione
INTRODUCTION
Multicomponent reactions (MCRs), with three or more reactants combining in a one-
pot procedure to give a single product, are powerful building tools in organic synthesis.1,2
Organophosphorus compounds are widely used in agriculture as insecticides and fungicides
and to some extent as herbicides.3,4 In research laboratories, organophosphorus compounds
find important applications in organic synthesis (Wittig, Staudinger, organocatalysis).5,6
Furthermore, organophosphorus compounds can be used as flame retardants for fabrics and
plastics, plasticizing and stabilizing agents in the plastics industry, selective extractants for
metal salts from ores, additives for petroleum products, and corrosion inhibitors.7,8
As part of our study on the development of new routes to heterocyclic and carbocyclic
systems,9–13 we now report an efficient synthesis of dialkyl 2-(2,4-dioxothiazolidin-3-yl)-
3-(dialkoxyphosphoryl)succinates 4a–d and dialkyl 2-(5-arylidene-2,4-dioxothiazolidin-
3-yl)-3-(dialkoxyphosphoryl)succinates 4e–l from the reaction of trialkyl phosphites
Received 22 August 2010; accepted 21 September 2010.
Address correspondence to Issa Yavari, Chemistry Department, Islamic Azad University, Science and
Research Branch, P.O. Box 14115-175, Ponak, Tehran, Iran. E-mail: yavarisa@modares.ac.ir
1612

SYNTHESIS OF 2,4-DIOXOTHIAZOLIDINE DERIVATIVES
1613
Table 1 Reaction of (RO)3P, acetylenic esters, and 2,4-thiazolidinediones
O
O
CO2R'
CO2R'
P(O)(OR)2
CO2R'
4a-l
Z
S
Et2O
rt
Z
S
NH
(RO)3P +
+
N
CO2R'
O
O
2a,b
1a,b
3a-e
Acetylenic
Phosphite 1
ester 2
Thiazolidinedione 3
R
R’
Z
Product 4
Yield (%)
1a
1a
1b
1b
1a
1a
1a
1a
1a
1a
1a
1a
Me
Me
Ph
2a
2b
2a
2b
2a
2b
2a
2b
2a
2b
2a
2b
Me
Et
Me
Et
Me
Et
Me
Et
Me
Et
Me
Et
3a
CH2
CH2
CH2
CH2
4a
4b
4c
4d
4e
4f
4g
4h
4i
70
73
82
84
85
83
93
91
90
88
90
86
3a
3a
3a
3b
3b
3c
3c
3d
3d
3e
3e
Ph
Me
Me
Me
Me
Me
Me
Me
Me
Ph CH
Ph CH
p-Tolyl CH
p-Tolyl CH
2-Thienyl CH
2-Thienyl CH
2-Furyl CH
2-Furyl CH
C
C
C
C
C
C
C
4j
4k
4l
C
1, dialkyl acetylenedicarboxylates 2, and 2,4-thiazolidinedione 3a or 5-arylidene-2,4-
thiazolidinediones 3b–e in good yields (Table 1).
RESULTS AND DISCUSSION
The reactions were carried out by mixing phosphate 1 with 3 and then adding the
acetylenic ester 2 slowly at r.t. The reactions were complete within 1–3 h. The structures of
compounds 4a–l as 1:1:1 adducts were apparent from their mass spectra, which displayed,
1
in each case, the molecular ion peak at appropriate m/z values. The H- and 13C-NMR
spectroscopic data, as well as infrared (IR) spectra, are in agreement with the proposed
1
structures. The H-NMR spectrum of 4a exhibited two doublets readily recognized as
arising from the two diastereotopic methoxy (δ = 3.73 ppm, 3JHP = 11.0 Hz and δ = 3.78
3
ppm, JHP = 11.0 Hz) groups. The two singlets at δ = 3.75 and 3.85 ppm belong to the
ester methoxy protons. The proton-decoupled 13C-NMR spectrum of 4a showed 11 distinct
resonances in agreement with the proposed structure.
3
Observation of JHH = 11.4 Hz for the vicinal methine protons in 4a indicates the
dominance of the anti arrangement. Because compound 4a possesses two stereogenic
centers, two diastereomers with anti HCCH arrangement are possible (Scheme 1). The
3
observation of JCP = 17.6 Hz for the carbonyl carbon atom of CO2Me group is in
agreement with the (2S,3R) or (2R,3S) diastereomer. However, as long as the coupling
constant of at least one other diastereomer is not known, the assignment remains uncertain.
Although we have not established the mechanism of the reaction between phosphites
1, dialkyl acetylenedicarboxylates 2, and 2,4-thiazolidinedione in an experimental manner,

1614
I. YAVARI ET AL.
O
Z
CO2Me
H
H
(MeO)2(O)P
H
(MeO)2(O)P
S
N
Z =
CO2Me
CO2Me
Z
H
CO2Me
O
(2S, 3R)-4a or (2R, 3S)-4a (2S, 3S)-4a or (2R, 3R)-4a
Scheme 1 Diastereoisomers of compound 4a.
O
NH
S
O
P(OR)3
P(OR)3
O
3
CO2R'
1
2
+
+
N
CO2R'
R'O2C
S
R'O2C
O
5
6
7
O
N
O
CO2R'
CO2R'
moisture
-ROH
P(OR)3
CO2R'
N
S
S
P(O)(OR)2
CO2R'
O
O
8
4
Scheme 2 Plausible mechanism for formation of compounds 4.
a possible explanation is proposed in Scheme 2. The first step may involve addition of phos-
phite to acetylenic ester and formation of the 1:1 adducts 5 and its subsequent protonation
by 2,4-thiazolidinedione. Then, the positively charged ion 6 is attacked by the anion of the
NH-acidic 7 to produce ylide 8, which is hydrolyzed to give 4. Because the reactions were
carried out under an ordinary atmosphere, the conversion of 8 to 4 is presumably accom-
plished by the moisture from the air. When the reaction was carried out in the absence of
air, a complex mixture was obtained.
The reaction of trimethyl phosphite (1a), acetylenedicarboxylates 2, and 5-arylidene-
2,4-thiazolidinediones 3b–e (prepared by a Knoevenagel condensation of thiazolidine-2,4-
dione with aromatic aldehydes)14 proceeded smoothly to afford functionalized phospho-
1
nated 4e–l in good yields. The structures of compounds were again confirmed by H ,
3
13C , and 31P-NMR data and IR spectra. Observation of JHH = 11.0 Hz for the vicinal
methine protons in 4e indicates the dominance of the anti arrangement (see Scheme 1). The
observation of 3JCP = 17.8 Hz for the CO2Me group is in agreement with the presence of
a single diastereoisomer, namely, (2S,3R) and its enantiomer (2R,3S).

SYNTHESIS OF 2,4-DIOXOTHIAZOLIDINE DERIVATIVES
1615
CONCLUSIONS
In summary, the reaction of dialkyl acetylenedicarboxylates with phosphites in the
presence of 2,4-thiazolidinedione or 5-arylidene-2,4-thiazolidinediones provides a simple
one-pot synthesis of stable dialkyl(aryl) phosphorylsuccinates of potential synthetic and
pharmaceutical interest. The present procedure has the advantage that the reaction is per-
formed under neutral conditions, and the starting material can be used without any activation
or modification.
EXPERIMENTAL
5-Arylidene-2,4-thiazolidinediones 3b–e were prepared according to the literature.14
Other compounds were purchased from Merck and used without further purification. IR
spectra were recorded on a Shimadzu IR-460 spectrometer. 1H-, 13C-, and 31P-NMR spectra
were recorded on a Bruker DRX-300 Avance instrument with CDCl3 as solvent at 300.1,
75.5, and 121.5 MHz, respectively. Electron impact–mass spectrometry (EI-MS) (70 eV)
was used to obtain mass spectra (in m/z) using a Finnigan-MAT-8430 mass spectrometer.
Elemental analyses (C, H, N) were obtained with a Heraeus CHN-O rapid analyzer.
General Procedure for the Preparation of Compounds 4
To a stirred solution of 1 (1 mmol) and 3 (1 mmol) in Et2O (5 mL) was added a
solution of 2 (1 mmol) in Et2O (2 mL) at r.t. over 10 min. After completion of the reaction
(1–3 h; thin-layer chromatography [TLC; AcOEt/hexane 1:1]), the reaction mixture was
purified by column chromatography (silica gel [230–240 mesh; Merck], hexane/AcOEt
4:1).
Dimethyl 2-(dimethoxyphosphoryl)-3-(2,4-dioxothiazolidin-3-yl)succin
ate (4a). Pale yellow oil, yield: 0.26 g (70%). Anal. Calcd. for C11H16NO9PS (369.3):
C, 35.78; H, 4.37; N, 3.79%. Found: C, 35.5; H, 4.3; N, 3.9%. IR (KBr, cm−1): 1748 and
1
3
1695 (C O), 1258 (P O); H-NMR (300 MHz, CDCl3, δ/ppm): 3.73 (3 H, d, JHP
=
3
11.0 Hz, MeO), 3.75 (3 H, s, MeO), 3.78 (3 H, d, JHP = 11.0 Hz, MeO), 3.85 (3 H, s,
MeO), 4.03 (2 H, s, CH2S), 4.17 (1 H, dd, 3JHH = 11.4 Hz, 2JHP = 20.4 Hz, CH), 5.61 (1
H, dd, JHH = 11.4 Hz, JHP = 4.4 Hz, CH); 13C-NMR (75 MHz, CDCl3, δ/ppm): 33.8
3
3
1
2
(CH2S), 42.7 (d, JCP = 128.2 Hz, CH), 52.0 (d, JCP = 5.4 Hz, CH), 52.9 (MeO), 53.3
(MeO), 53.8 (d, 2JPC = 5.3 Hz, MeO), 54.5 (d, 2JPC = 5.9 Hz, MeO), 164.8 (C O), 166.7
(d, 2JCP = 7.5 Hz, C O), 167.0 (d, 3JCP = 17.6 Hz, C O), 170.9 (C O); 31P-NMR (121
MHz, CDCl3, δ/ppm): 18.7; MS (EI, 70 eV): m/z (%) = 369 (M+, 8), 338 (18), 296 (27),
222 (35), 193 (20), 124 (16), 109 (86), 31 (80).
Diethyl 2-(dimethoxyphosphoryl)-3-(2,4-dioxothiazolidin-3-yl)succinate
(4b). Pale yellow oil, yield: 0.29 g (73%). Anal. Calcd. for C13H20NO9PS (397.3): C,
39.30; H, 5.07; N, 3.53%. Found: C, 39.6; H, 5.0; N, 3.6%. IR (KBr, cm−1): 1740 and 1705
(C O), 1255 (P O); 1H-NMR (300 MHz, CDCl3, δ/ppm): 1.23 (3 H, t, 3JHH = 7.2 Hz,
Me), 1.34 (3 H, t, 3JHH = 7.2 Hz, Me), 3.74 (3 H, d, 3JHP = 11.1 Hz, MeO), 3.80 (3 H, d,
3JHP = 11.1 Hz, MeO), 4.02 (2 H, s, CH2S), 4.18–4.34 (5 H, m, 2 CH2O, CH), 5.58 (1 H,
dd, 3JHH = 11.4 Hz, 3JHP = 4.5 Hz, CH); 13C-NMR (75 MHz, CDCl3, δ/ppm): 14.3 (Me),
1
2
2
14.4 (Me), 42.8 (d, JCP = 127.3 Hz, CH), 52.2 (d, JCP = 5.4 Hz, CH), 53.9 (d, JPC
=
5.3 Hz, MeO), 54.4 (d, 2JPC = 5.8 Hz, MeO), 62.5 (CH2O), 63.2 (CH2O), 163.8 (C O),
166.8 (d, 2JCP = 7.5 Hz, C O), 167.2 (d, 3JCP = 17.6 Hz, C O), 171.2 (C O); 31P-NMR

1616
I. YAVARI ET AL.
(121 MHz, CDCl3, δ/ppm): 15.3; MS (EI, 70 eV): m/z (%) = 397 (M+, 5), 348 (18), 324
(25), 235 (35), 207 (20), 135 (22), 109 (100), 44 (38).
Dimethyl 2-(2,4-dioxothiazolidin-3-yl)-3-(diphenoxyphosphoryl)succinate
(4c). Colorless oil, yield: 0.40 g (82%). Anal. Calcd. for C21H20NO9PS (493.4): C, 51.12;
H, 4.09; N, 2.84%. Found: C, 51.3; H, 4.0; N, 2.7%. IR (KBr, cm−1): 1745 and 1710
1
(C O), 1279 (P O); H-NMR (300 MHz, CDCl3, δ/ppm): 3.78 (3 H, s, MeO), 3.90 (3
3
2
H, s, MeO), 4.02 (2 H, s, CH2S), 4.46 (1 H, dd, JHH = 11.4 Hz, JHP = 21.1 Hz, CH),
5.88 (1 H, dd, 3JHH = 11.4 Hz, 3JHP = 4.5 Hz, CH), 7.12–7.23 (6 H, m, 6 CH), 7.29–7.34
(4 H, m, 4 CH); 13C-NMR (75 MHz, CDCl3, δ/ppm): 34.0 (CH2S), 43.9 (d, 1JCP = 133.0
Hz, CH), 52.1 (d, 2JCP = 4.1 Hz, CH), 53.8 (MeO), 54.1 (MeO), 120.7 (d, 3JCP = 4.5 Hz,
2 CHortho), 121.0 (d, 3JCP = 4.5 Hz, 2 CHortho), 126.1 (CHpara), 126.2 (CHpara), 130.3 (m,
4 CHmeta), 149.7 (d, 2JCP = 8.5 Hz, Cipso), 150.4 (d, 2JCP = 8.2 Hz, Cipso), 165.5 (C O),
166.7 (d, 3JCP = 9.4 Hz, C O), 167.6 (d, 2JCP = 18.9 Hz, C O), 171.2 (C O); 31P-NMR
(121 MHz, CDCl3, δ/ppm): 11.7; MS (EI, 70 eV): m/z (%) = 493 (M+, 4), 462 (16), 420
(26), 346 (20), 318 (16), 233 (100), 93 (56).
Diethyl 2-(2,4-dioxothiazolidin-3-yl)-3-(diphenoxyphosphoryl)succinate
(4d). Colorless oil, yield: 0.44 g (84%). Anal. Calcd. for C23H24NO9PS (521.5): C, 52.97;
H, 4.64; N, 2.69%. Found: C, 52.7; H, 4.6; N, 2.6%. IR (KBr, cm−1): 1740 and 1969 (C O),
1282 (P O); 1H-NMR (300 MHz, CDCl3, δ/ppm): 1.29 (3 H, t, 3JHH = 7.2 Hz, Me), 1.34
3
3
(3 H, t, JHH = 7.2 Hz, Me), 4.00 (2 H, s, CH2S), 4.22 (2 H, q, JHH = 7.2 Hz, CH2O),
4.32 (2 H, q, 3JHH = 7.2 Hz, CH2O), 4.46 (1 H, dd, 3JHH = 11.4 Hz, 2JHP = 21.1 Hz, CH),
5.86 (1 H, dd, 3JHH = 11.4 Hz, 3JHP = 4.8 Hz, CH), 7.13–7.27 (6 H, m, 6 CH), 7.29–7.36
(4 H, m, 4 CH); 13C-NMR (75 MHz, CDCl3, δ/ppm): 14.3 (Me), 14.4 (Me), 34.0 (CH2S),
44.1 (d, 1JCP = 132.6 Hz, CH), 52.2 (d, 2JCP = 4.4 Hz, CH), 62.9 (CH2O), 63.4 (CH2O),
3
3
120.7 (d, JCP = 4.3 Hz, 2 CHortho), 121.0 (d, JCP = 4.3 Hz, 2 CHortho), 126.0 (CHpara),
126.1 (CHpara), 130.2 (m, 4 CHmeta), 149.7 (d, 2JCP = 8.5 Hz, Cipso), 150.3 (d, 2JCP = 8.2
Hz, Cipso), 163.7 (C O), 166.0 (d, 3JCP = 8.0 Hz, C O), 167.2 (d, 2JCP = 19.2 Hz, C O),
171.8 (C O); 31P-NMR (121 MHz, CDCl3, δ/ppm): 11.1; MS (EI, 70 eV): m/z (%) = 521
(M+, 8), 472 (23), 448 (20), 374 (35), 332 (28), 233 (100), 93 (86), 77 (42).
Dimethyl 2-(5-benzylidene-2,4-dioxothiazolidin-3-yl)-3-(dimethoxyphos
phoryl)succinate (4e). Colorless oil, yield: 0.39 g (85%). Anal. Calcd. for
C18H20NO9PS (457.4): C, 47.27; H, 4.41; N, 3.06%. Found: C, 47.0; H, 4.3; N,
3.1%. IR (KBr, cm−1): 1746 and 1699 (C O), 1269 (P O); 1H-NMR (300 MHz, CDCl3,
δ/ppm): 3.68 (3 H, d, 3JHP = 11.0 Hz, MeO), 3.73 (3 H, d, 3JHP = 11.0 Hz, MeO), 3.75 (3
H, s, MeO), 3.81 (3 H, s, MeO), 4.13 (1 H, dd, 3JHH = 11.7 Hz, 2JHP = 20.7 Hz, CH), 5.66
3
3
(1 H, dd, JHH = 11.7 Hz, JHP = 4.5 Hz, CH), 7.48–7.71 (5 H, m, 5 CH), 8.00 (1 H, s,
CH); 13C-NMR (75 MHz, CDCl3, δ/ppm): 43.2 (d, 1JCP = 128.5 Hz, CH), 52.2 (d, 2JCP
=
5.6 Hz, CH), 53.3 (MeO), 53.8 (d, 2JPC = 6.1 Hz, MeO), 54.0 (MeO), 54.3 (d, 2JPC = 6.2
Hz, MeO), 120.9 (C), 129.6 (2 CH), 130.7 (2 CH), 131.1 (CH), 133.4 (C), 135.2 (CH),
2
3
165.7 (C O), 167.7 (d, JCP = 8.2 Hz, C O), 167.9 (d, JCP = 17.8 Hz, C O), 171.3
(C O); 31P-NMR (121 MHz, CDCl3, δ/ppm): 20.1; MS (EI, 70 eV): m/z (%) = 457 (M+,
3), 352 (27), 296 (33), 222 (21), 193 (18), 134 (100), 109 (18).
Diethyl 2-(5-benzylidene-2,4-dioxothiazolidin-3-yl)-3-(dimethoxyphos
phoryl)succinate (4f). Pale yellow oil, yield: 0.40 g (83%). Anal. Calcd. for
C20H24NO9PS (485.4): C, 49.48; H, 4.98; N, 2.89%. Found: C, 49.2; H, 5.1; N, 2.8%. IR
(KBr, cm−1): 1730 and 1695 (C O), 1254 (P O); 1H-NMR (300 MHz, CDCl3, δ/ppm):
1.22 (3 H, t, 3JHH = 7.2 Hz, Me), 1.35 (3 H, t, 3JHH = 7.2 Hz, Me), 3.72 (3 H, d, 3JHP
=

SYNTHESIS OF 2,4-DIOXOTHIAZOLIDINE DERIVATIVES
1617
3
11.1 Hz, MeO), 3.77 (3 H, d, JHP = 11.0 Hz, MeO), 4.19–4.35 (5 H, m, 2 CH2O, CH),
3
3
5.58 (1 H, dd, JHH = 11.4 Hz, JHP = 4.5 Hz, CH), 7.46–7.52 (5 H, m, 5 CH), 7.94 (1
1
H, s, CH); 13C-NMR (75 MHz, CDCl3, δ/ppm): 14.3 (Me), 14.4 (Me), 43.4 (d, JCP
=
2
2
128.2 Hz, CH), 52.4 (d, JCP = 6.4 Hz, CH), 53.9 (d, JPC = 6.5 Hz, MeO), 54.2 (d,
2JPC = 6.2 Hz, MeO), 62.6 (CH2O), 63.5 (CH2O), 121.0 (C), 129.6 (2 CH), 130.8 (2
CH), 131.1 (CH), 133.4 (C), 135.0 (CH), 165.6 (C O), 167.2 (d, 2JCP = 7.2 Hz, C O),
3
167.5 (d, JCP = 17.8 Hz, C O), 170.7 (C O); 31P-NMR (121 MHz, CDCl3, δ/ppm):
19.2; MS (EI, 70 eV): m/z (%) = 485 (M+, 5), 436 (16), 380 (55), 235 (35), 207 (20), 134
(100), 109 (30).
Dimethyl 2-(dimethoxyphosphoryl)-3-(5-(4-methylbenzylidene)-2,4-dio
xothiazolidin-3-yl)succinate (4g). Pale yellow oil, yield: 0.44 g (93%). Anal. Calcd.
for C19H22NO9PS (471.4): C, 48.41; H, 4.70; N, 2.97%. Found: C, 48.6; H, 4.8; N, 2.9%.
1
IR (KBr, cm−1): 1724 and 1700 (C O), 1246 (P O); H-NMR (300 MHz, CDCl3,
δ/ppm): 2.42 (3 H, s, Me), 3.68 (3 H, d, 3JHP = 11.1 Hz, MeO), 3.73 (3 H, d, 3JHP = 11.1
Hz, MeO), 3.75 (3 H, s, MeO), 3.80 (3 H, s, MeO), 4.07 (1 H, dd, 3JHH = 11.4 Hz, 2JHP
20.5 Hz, CH), 5.67 (1 H, dd, 3JHH = 11.4 Hz, 3JHP = 4.5 Hz, CH), 7.42 (2 H, d, 3JHH
=
=
8.1 Hz, 2 CH), 7.58 (2 H, d, 3JHH = 8.1 Hz, 2 CH), 7.95 (1 H, s, CH); 13C-NMR (75 MHz,
CDCl3, δ/ppm): 22.0 (Me), 43.2 (d, 1JCP = 128.5 Hz, CH), 52.2 (d, 2JCP = 4.5 Hz, CH),
2
2
53.6 (MeO), 53.9 (d, JPC = 6.3 Hz, MeO), 54.0 (MeO), 54.3 (d, JPC = 6.3 Hz, MeO),
119.6 (C), 130.4 (2 CH), 130.6 (C), 130.8 (2 CH), 136.3 (C), 142.0 (CH), 165.7 (C O),
167.7 (d, 2JCP = 7.2 Hz, C O), 168.0 (d, 3JCP = 18.0 Hz, C O), 170.9 (C O); 31P-NMR
(121 MHz, CDCl3, δ/ppm): 19.7; MS (EI, 70 eV): m/z (%) = 471 (M+, 5), 439 (22), 352
(15), 222 (25), 148 (100), 124 (22), 109 (20).
Diethyl
2-(dimethoxyphosphoryl)-3-(5-(4-methylbenzylidene)-2,4-dio
xothiazolidin-3-yl)succinate (4h). Pale yellow oil, yield: 0.45 g (91%). Anal. Calcd.
for C21H26NO9PS (499.5): C, 50.50; H, 5.25; N, 2.80%. Found: C, 50.3; H, 5.1; N, 2.7%.
1
IR (KBr, cm−1): 1722 and 1700 (C O), 1252 (P O); H-NMR (300 MHz, CDCl3,
δ/ppm): 1.24 (3 H, t, 3JHH = 7.2 Hz, Me), 1.35 (3 H, t, 3JHH = 7.2 Hz, Me), 2.41 (3 H, s,
Me), 3.71 (3 H, d, 3JHP = 11.4 Hz, MeO), 3.81 (3 H, d, 3JHP = 11.4 Hz, MeO), 4.18–4.35
(5 H, m, 2 CH2O, CH), 5.72 (1 H, dd, 3JHH = 11.4 Hz, 3JHP = 4.2 Hz, CH), 7.28 (2 H, d,
3JHH = 7.8 Hz, 2 CH), 7.42 (2 H, d, 3JHH = 7.8 Hz, 2 CH), 7.90 (1 H, s, CH); 13C-NMR
1
(75 MHz, CDCl3, δ/ppm): 14.3 (Me), 14.4 (Me), 22.0 (Me), 43.6 (d, JCP = 127.7 Hz,
CH), 52.3 (d, 2JCP = 7.1 Hz, CH), 53.8 (d, 2JPC = 6.7 Hz, MeO), 54.2 (d, 2JPC = 5.9 Hz,
MeO), 62.6 (CH2O), 63.2 (CH2O), 119.8 (C), 130.4 (2 CH), 130.7 (C), 130.8 (2 CH),
2
3
135.1 (C), 141.9 (CH), 165.8 (C O), 167.1 (d, JCP = 7.2 Hz, C O), 167.5 (d, JCP
=
22.4 Hz, C O), 171.0 (C O); 31P-NMR (121 MHz, CDCl3, δ/ppm): 20.8; MS (EI, 70
eV): m/z (%) = 499 (M+, 6), 434 (12), 324 (14), 235 (14), 207 (16), 148 (100), 135 (12),
109 (13), 96 (14).
Dimethyl 2-(dimethoxyphosphoryl)-3-(2,4-dioxo-5-(thiophen-2-ylmethy
lene)thiazolidin-3-yl)succinate (4i). Pale yellow oil, yield: 0.41 g (90%). Anal. Calcd.
for C16H18NO9PS2 (463.4): C, 41.47; H, 3.92; N, 3.02%. Found: C, 41.2; H, 3.8; N, 3.1%.
IR (KBr, cm−1): 1735 and 1691 (C O), 1260 (P O); 1H-NMR (300 MHz, CDCl3, δ/ppm):
3
3
3.72 (3 H, d, JHP = 11.7 Hz, MeO), 3.74 (3 H, s, MeO), 3.78 (3 H, d, JHP = 11.7 Hz,
MeO), 3.87 (3 H, s, MeO), 4.26 (1 H, dd, 3JHH = 11.4 Hz, 2JHP = 20.3 Hz, CH), 5.73 (1
H, dd, 3JHH = 11.4 Hz, 3JHP = 4.5 Hz, CH), 7.20 (1 H, dd, 3JHH = 4.8 Hz, 3JHH = 3.6 Hz,
3
3
CH), 7.42 (1 H, d, JHH = 3.6 Hz, CH), 7.68 (1 H, d, JHH = 4.8 Hz, CH), 8.01 (1 H, s,
CH); 13C-NMR (75 MHz, CDCl3, δ/ppm): 43.2 (d, 1JCP = 128.6 Hz, CH), 52.3 (d, 2JPC
=
2
2
7 Hz, CH), 53.2 (d, JPC = 5.3 Hz, MeO), 53.7 (MeO), 54.0 (MeO), 54.3 (d, JPC = 5.3

1618
I. YAVARI ET AL.
Hz, MeO), 118.8 (C), 127.7 (C), 129.0 (CH), 132.8 (CH), 134.1 (CH), 137.9 (CH), 165.3
(C O), 167.2 (d, 2JCP = 7.4 Hz, C O), 167.9 (d, 3JCP = 17.5 Hz, C O), 171.0 (C O);
31P-NMR (121 MHz, CDCl3, δ/ppm): 20.5; MS (EI, 70 eV): m/z (%) = 463 (M+, 4), 296
(27), 193 (40), 139 (100), 109 (55).
Diethyl 2-(dimethoxyphosphoryl)-3-(2,4-dioxo-5-(thiophen-2-ylmethy
lene)thiazolidin-3-yl)succinate (4j). Pale yellow oil, yield: 0.43 g (88%). Anal.
Calcd. for C18H22NO9PS2 (491.5): C, 43.99; H, 4.51; N, 2.85%. Found: C, 43.7; H, 4.4; N,
2.8%. IR (KBr, cm−1): 1732 and 1690 (C O), 1246 (P O); 1H-NMR (300 MHz, CDCl3,
δ/ppm): 1.23 (3 H, t, 3JHH = 7.2 Hz, Me), 1.36 (3 H, t, 3JHH = 7.2 Hz, Me), 3.72 (3 H, d,
3JHP = 11.0 Hz, MeO), 3.79 (3 H, d, 3JHP = 11.0 Hz, MeO), 4.19–4.33 (5 H, m, 2 CH2O,
CH), 5.72 (1 H, dd, 3JHH = 11.4 Hz, 3JHP = 4.5 Hz, CH), 7.20 (1 H, dd, 3JHH = 4.5 Hz,
3JHH = 3.2 Hz, CH), 7.42 (1 H, d, 3JHH = 3.2 Hz, CH), 7.68 (1 H, d, 3JHH = 4.5 Hz, CH),
8.11 (1 H, s, CH); 13C-NMR (75 MHz, CDCl3, δ/ppm): 14.3 (Me), 14.4 (Me), 43.4 (d,
1JCP = 128.1 Hz, CH), 52.5 (d, 2JPC = 6.6 Hz, CH), 53.9 (d, 2JPC = 6.9 Hz, MeO), 54.2
2
(d, JCP = 5.9 Hz, MeO), 62.6 (CH2O), 63.2 (CH2O), 118.9 (C), 127.5 (C), 129.0 (CH),
132.7 (CH), 134.1 (CH), 137.9 (CH), 165.4 (C O), 167.1 (d, 2JCP = 7.4 Hz, C O), 167.5
(d, 3JCP = 19.5 Hz, C O), 170.6 (C O); 31P-NMR (121 MHz, CDCl3, δ/ppm): 21.1; MS
(EI, 70 eV): m/z (%) = 491 (M+, 5), 442 (25), 380 (36), 324 (22), 235 (20), 139 (100), 109
(17).
Dimethyl 2-(dimethoxyphosphoryl)-3-(5-(furan-2-ylmethylene)-2,4-dio
xothiazolidin-3-yl)succinate (4k). Pale yellow oil, yield: 0.40 g (90%). Anal. Calcd.
for C16H18NO10PS (447.3): C, 42.96; H, 4.06; N, 3.13%. Found: C, 42.7; H, 4.1; N,
3.0%. IR (KBr, cm−1): 1730 and 1705 (C O), 1257 (P O); 1H-NMR (300 MHz, CDCl3,
3
3
δ/ppm): 3.75 (3 H, d, JHP = 11.7 Hz, MeO), 3.78 (3 H, s, MeO), 3.79 (3 H, d, JHP
=
11.7 Hz, MeO), 3.87 (3 H, s, MeO), 4.25 (1 H, dd, 3JHH = 11.1 Hz, 2JHP = 20.6 Hz, CH),
5.72 (1 H, dd, 3JHH = 11.1 Hz, 3JHP = 4.5 Hz, CH), 6.60 (1 H, dd, 3JHH = 4.2 Hz, 3JHH
=
3.2 Hz, CH), 6.81 (1 H, d, 3JHH = 3.2 Hz, CH), 7.68 (1 H, d, 3JHH = 4.2 Hz, CH), 7.80 (1
H, s, CH); 13C-NMR (75 MHz, CDCl3, δ/ppm): 43.2 (d, 1JCP = 128.5 Hz, CH), 52.2 (d,
2JPC = 4.3 Hz, CH), 53.2 (MeO), 53.9 (MeO), 54.2 (d, 2JPC = 6.2 Hz, MeO), 54.7 (d, 2JCP
= 5.9 Hz, MeO), 113.6 (CH), 118.5 (C), 118.7 (C), 120.8 (CH), 147.1 (CH), 150.0 (CH),
2
3
165.5 (C O), 167.7 (d, JCP = 7.2 Hz, C O), 168.0 (d, JCP = 18.0 Hz, C O), 170.9
(C O); 31P-NMR (121 MHz, CDCl3, δ/ppm): 22.4; MS (EI, 70 eV): m/z (%) = 447 (M+,
4), 416 (24), 352 (31), 296 (24), 193 (31), 124 (100), 109 (36), 31 (96).
Diethyl
2-(dimethoxyphosphoryl)-3-(5-(furan-2-ylmethylene)-2,4-dio
xothiazolidin-3-yl)succinate (4l). Pale yellow oil, yield: 0.41 g (86%). Anal. Calcd.
for C18H22NO10PS (475.4): C, 45.48; H, 4.66; N, 2.95%. Found: C, 45.3; H, 4.5; N,
2.8%. IR (KBr, cm−1): 1725 and 1690 (C O), 1262 (P O); 1H-NMR (300 MHz, CDCl3,
δ/ppm):1.22 (3 H, t, 3JHH = 7.2 Hz, Me), 1.34 (3 H, t, 3JHH = 7.2 Hz, Me), 3.72 (3 H, d,
3JHP = 11.4 Hz, MeO), 3.79 (3 H, d, 3JHP = 11.4 Hz, MeO), 4.18–4.36 (5 H, m, 2 CH2O,
CH), 5.70 (1 H, dd, 3JHH = 11.4 Hz, 3JHP = 4.2 Hz, CH), 6.59 (1 H, dd, 3JHH = 4.8 Hz,
3JHH = 3.3 Hz, CH), 6.80 (1 H, d, 3JHH = 3.3 Hz, CH), 7.68 (1 H, d, 3JHH = 4.8 Hz, CH),
7.78 (1 H, s, CH); 13C-NMR (75 MHz, CDCl3, δ/ppm): 14.3 (Me), 14.4 (Me), 43.4 (d,
1JCP = 128.2 Hz, CH), 52.3 (d, 2JPC = 4.8 Hz, CH), 53.8 (d, 2JPC = 6.6 Hz, MeO), 54.2
2
(d, JCP = 6.0 Hz, MeO), 62.5 (CH2O), 63.2 (CH2O), 113.6 (CH), 118.5 (C), 118.7 (C),
120.6 (CH), 147.0 (CH), 150.1 (CH), 165.3 (C O), 167.1 (d, 2JCP = 7.4 Hz, C O), 167.4
(d, 3JCP = 17.8 Hz, C O), 169.3 (C O); 31P-NMR (121 MHz, CDCl3, δ/ppm): 21.9; MS
(EI, 70 eV): m/z (%) = 475 (M+, 4), 426 (18), 380 (47), 235 (26), 124 (100), 109 (26).

SYNTHESIS OF 2,4-DIOXOTHIAZOLIDINE DERIVATIVES
1619
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