Synthesis of dialkyl 2-(dialkoxyphosphoryl)-3-(4-oxo-4,5-dihydro-thiazole- 2-yl sulfanyl) succinates

Article abstract of DOI:10.1080/00397911.2011.555904

A three-component reaction of trialkyl(aryl) phosphites, dialkyl acetylenedicarboxylates and rhodanine is described as a simple and efficient route for synthesis of dialkyl 2-(dialkoxyphosphoryl)-3-(4-oxo-4,5-dihydro- thiazole-2-yl sulfanyl) succinates in good yields. Protonation of the reactive 1:1 intermediate produced in the reaction between dialkyl acetylenedicarboxylate and triphenylphosphine by N′-formylbenzohydrazide leads to vinylphosphonium salts, which undergo Michael addition with the conjugate base of the NH acid to produce highly functionalized, salt-free phosphorus ylides in excellent yields.

Full text of DOI:10.1080/00397911.2011.555904

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Synthesis of Dialkyl 2-
(Dialkoxyphosphoryl)-3-(4-oxo-4,5-
dihydro-thiazole-2-yl Sulfanyl)
Succinates
Alireza Hassanabadi a , Mohammad H. Mosslemin b , Shabnam Salari b
& Mahnoush Momeni Landi b
a Department of Chemistry, Islamic Azad University, Zahedan Branch,
Zahedan, Iran
b Department of Chemistry, Islamic Azad University, Yazd Branch,
Yazd, Iran
Accepted author version posted online: 19 Dec 2011.Published
online: 09 Apr 2012.
To cite this article: Alireza Hassanabadi , Mohammad H. Mosslemin , Shabnam Salari & Mahnoush
Momeni Landi (2012) Synthesis of Dialkyl 2-(Dialkoxyphosphoryl)-3-(4-oxo-4,5-dihydro-thiazole-2-yl
Sulfanyl) Succinates, Synthetic Communications: An International Journal for Rapid Communication of
Synthetic Organic Chemistry, 42:15, 2309-2317, DOI: 10.1080/00397911.2011.555904
To link to this article: http://dx.doi.org/10.1080/00397911.2011.555904
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Synthetic Communications1, 42: 2309–2317, 2012
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397911.2011.555904
SYNTHESIS OF DIALKYL 2-(DIALKOXYPHOSPHORYL)-
3-(4-OXO-4,5-DIHYDRO-THIAZOLE-2-YL SULFANYL)
SUCCINATES
Alireza Hassanabadi,1 Mohammad H. Mosslemin,2
Shabnam Salari,2 and Mahnoush Momeni Landi2
1Department of Chemistry, Islamic Azad University, Zahedan Branch,
Zahedan, Iran
2Department of Chemistry, Islamic Azad University, Yazd Branch,
Yazd, Iran
GRAPHICAL ABSTRACT
Abstract A three-component reaction of trialkyl(aryl) phosphites, dialkyl acetylenedicar-
boxylates and rhodanine is described as a simple and efficient route for synthesis of dialkyl
2-(dialkoxyphosphoryl)-3-(4-oxo-4,5-dihydro-thiazole-2-yl sulfanyl) succinates in good
yields. Protonation of the reactive 1:1 intermediate produced in the reaction between dialkyl
acetylenedicarboxylate and triphenylphosphine by N0-formylbenzohydrazide leads to vinyl-
phosphonium salts, which undergo Michael addition with the conjugate base of the NH acid
to produce highly functionalized, salt-free phosphorus ylides in excellent yields.
Keywords Dialkyl acetylenedicarboxylates; NH acids; phosphorus ylides; trialkyl(aryl)
phosphites; triphenylphosphine
Received November 22, 2010.
Address correspondence to Alireza Hassanabadi, Department of Chemistry, Islamic Azad
University, Zahedan Branch, P.O. Box 98135-978, Zahedan, Iran. E-mail: ar_hasanabadi@yahoo.com
2309

2310
A. HASSANABADI ET AL.
INTRODUCTION
Organophosphonates have been used as substitutes for the corresponding
esters and acids with high biological activity.[1,2] As a result, a large number of meth-
ods have appeared describing novel syntheses of organophosphorus compounds.
The attack by nucleophilic trivalent phosphorus on a carbon atom is facilitated when
the latter is part of, or conjugated with, a carbonyl group or when it is part of an
unsaturated bond otherwise activated.[3–9] The reaction of trimethyl phosphite and
dimethyl acetylenedicarboxylate (DMAD) in the presence of alcohols is reported
to produce phosphite ylide derivatives, which are stable at low temperatures but
are converted to phosphonate derivatives warming or by treatment with water.[10]
There are some other recent reports on the reaction between phosphites and acety-
lenic esters in the presence of an acidic organic compound, all of them proceeding
through a phosphite ylide intermediate.[11–24] In continuation of our previous works
on the reaction of trivalent phosphorus nucleophiles and acetylenic esters in the pres-
ence of organic NH, OH, or CHacids,[19–25] here we report the results of our study on
the reaction between dialkyl acetylenedicarboxylates (DAADs) and trialkyl(aryl)
phosphites in the presence of rhodanine.
The reaction of DAAD 2 with trialkyl(aryl) phosphite 3 in the presence of rho-
danine 1 leads to dialkyl 2-(dialkoxyphosphoryl)-3-(4-oxo-4,5-dihydro-thiazole-2-yl
sulfanyl) succinates 4 in good yields (Scheme 1).
Products 4a–e were all new compounds, and their structures were deduced
from their elemental analyses and spectral data. The mass spectrum of compound
1
4a showed the molecular ion peak at 385. The H NMR spectrum of compound
4a displayed two doublets (JHP ¼ 11 Hz) at 3.71 and 3.76 ppm for two POCH3
Scheme 1. Synthesis of dialkyl 2-(dialkoxyphosphoryl)-3-(4-oxo-4,5-dihydro-thiazole-2-yl sulfanyl) succi-
nates by reaction of DAAD and trialkyl(aryl) phosphites in the presence of rhodanine.

REACTION OF DAADs AND TRIALKYL(ARYL) PHOSPHITES
2311
Scheme 2. Suggested mechanism for formation of compound 4.
groups and two singlets at 3.70 and 3.81 ppm for two methoxycarbonyl groups. Two
3
2
signals were absorbed at 4.32 (dd, JHH ¼ 11 Hz, JHP ¼ 21 Hz) and 4.54 ppm (dd,
3
3JHH ¼ 11 Hz, JHP ¼ 5 Hz) for two vicinal methine protons. One signal was
absorbed at 3.68 for two methylene protons. The 13C NMR spectrum of compound
4a showed 11 distinct resonances in agreement with the proposed structure. The
structural assignments made on the basis of the NMR spectra of compound 4a were
supported by its infared (IR) spectrum; the ester carbonyl groups exhibited strong
absorption bands at 1736 and 1700 cmꢀ1. The 31P NMR spectrum of compound
4a displays a signal at 19.22 ppm.
A reasonable mechanism for the formation of compound 4 is presented in
Scheme 2. The initial addition of trialkyl(aryl) phosphite on DAAD leads to a diio-
nic intermediate that is protonated by rhodanine to produce the vinyl phosphonium
5. It is well known that thioamide usually undergoes nucleophilic addition from the
sulfur atom, because sulfur is more nucleophilic than the nitrogen atom. Also in the
13CNMR spectrum of compound 4 we do not observe any signal at magnetic fields
=
lower than 172 ppm, and the C S carbon is expected to be observed at about
Scheme 3. Three-component reaction of triphenylphosphine, dialkyl acetylenedicarboxylate, and
N0-formylbenzohydrazide.

2312
A. HASSANABADI ET AL.
Scheme 4. Suggested mechanism for formation of compound 9.
195 ppm. So, we can conclude that compound 4 is formed by the conjugate addition
of anion 6 from the sulfur atom on phosphonium cation 5, which afforded the phos-
phite ylide 7, which then hydrolyzed to product 4.
The reaction of acetylenic ester 2 with triphenylphosphine in the presence of
N0-formylbenzohydrazide 8 leads to functionalized phosphoranes 9 in excellent
yields (Scheme 3).
The 1H NMR spectrum of 9a exhibits two sharp lines at d ¼ 3.03 and 3.76 ppm
for the protons of two methoxy groups and a doubled signal for the methine proton
at 4.96 ppm (3JHP ¼ 16 Hz). One single signal is absorbed at 9.05 ppm, and disap-
peared after addition of a few drops of D2O to solution of compound 9a. This signal
is related to the NH proton. Aromatic protons resonate between 7.37 and 7.96 ppm
as multiplets and a single signal at 8.35 ppm for the CH O proton. 13C NMR spec-
=
tra of compound 9a shows 16 distinct signals, which is consistent with the proposed
structure. The 31P NMR spectrum of compound 9a consists of one signal at 24.37.
This shift is similar to those absorbed for other stable phosphorus ylides.[26,27] The
structural assignments made on the basis of the NMR spectra of compounds 9a–c
are supported by their IR spectra. The carbonyl groups exhibited strong absorption
bands at 1717, 1691, and 1618 cmꢀ1 and showed the stretching absorption bond
related to NH bond.
It is reasonable to assume that ylide 9 results from the initial addition of triphe-
nylphosphine to DAAD and subsequent protonation of the 1:1 adduct by the
NH-acidic N0-formylbenzohydrazide. The positively charged ion 10 is then attacked
by anion 11 to form the phosphorane 9 (Scheme 4).
In summary, we report herein that the three-component reaction of trialkyl-
(aryl) phosphites, dialkyl acetylenedicarboxylates, and rhodanine provides a simple
and efficient one-pot route for the synthesis of dialkyl 2-(dialkoxyphosphoryl)-3-
(4-oxo-4,5-dihydro-thiazole-2-yl sulfanyl)succinates in good yields, and the reaction
between
dialkyl
acetylenedicarboxylate
and
triphenylphosphine
by
N0-formylbenzohydrazide produces highly functionalized, salt-free phosphorus
ylides in excellent yields.
EXPERIMENTAL
Melting points were determined with an Electrothermal 9100 apparatus.
Elemental analyses were performed at the analytical laboratory of the Science and
Researches Unit of Islamic Azad University. Mass spectra were recorded on a
Finnigan-MAT 8430 mass spectrometer operating at an ionization potential of
1
70 eV. IR spectra were recorded on a Shimadzu IR-470 spectrometer. H, 13C, and

REACTION OF DAADs AND TRIALKYL(ARYL) PHOSPHITES
2313
31P NMR spectra were recorded on a Bruker DRX-500 Avance spectrometer in
CDCl3 and dimethylsulfoxide (d6-DMSO) using tetramethylsilane (TMS) as internal
standard or 85% H3PO4 as external standard. The chemicals used in this work were
purchased from Fluka (Buchs, Switzerland) and were used without further
purification.
Compounds 4a–e
General procedure. A mixture of dialkyl acetylenedicarboxylate (2 mmol) in
acetone (3 mL) was added dropwise at room temperature to a magnetically stirred
solution of trialkyl(aryl) phosphite (2 mmol) and rhodanine (2 mmol) in acetone
(15 mL) over 2 min. The reaction mixture was then stirred for 3 h at reflux tempera-
ture. The solvent was removed under reduced pressure, and the residue was purified
by column chromatography on silica gel (60, 230–400 mesh) using ethyl acetate–hex-
ane (2:1) mixture as eluent.
Dimethyl 2-(dimethoxyphosphoryl)-3-(4-oxo-4,5-dihydro-thiazole-2-yl
sulfanyl) succinate (4a). Yield: 91%; yellow oil. IR (KBr) (nmax, cmꢀ1): 1736,
=
=
(C O, ester), 1700 (C O, amide), Analyses: calcd. for C11H16NO8PS2: C, 34.28;
H, 4.19; N, 3.63%. Found: C, 34.2; H, 4.15; N, 3.7%. MS (m=z, %): 385 (Mþ, 3),
-
-
1
=
353 (M CH3OH, 65), 109 [(CH3O)2P O, 80], 294 (353 CO2CH3, 100). H NMR
(500 M Hz, CDCl3): d 3.68 (2H, s, CH2), 3.70 and 3.81 (6 H, 2 s, 2 OCH3), 3.71
and 3.76 (6 H, d 3JPH ¼ 11 Hz, 2POCH3), 4.32 (1 H, dd, 2JHP ¼ 21 Hz, 3JHH ¼ 12 Hz,
P-CH), 4.54 (1 H, dd, 3JHP ¼ 5 Hz, 3JHH ¼ 12 Hz, P-C-CH). 13C NMR (125.8 M Hz,
1
CDCl3): d 40.20 (d, Jcp ¼ 137 Hz, P-C), 45.08 (CH2), 53.89 (m, CH), 54.38 (m, 2
2
=
=
POCH3), 53.64 and 53.68 (2 OCH3), 156.2 (SC N), 167.43 (d, JCP ¼ 7 Hz, C O),
167.86 (C O), 172.88 (d, JCP ¼ 21 Hz, C O). 31P NMR (202.5 MHz, CDCl3): d
3
=
=
19.22.
Dimethyl
2-(diethoxyphosphoryl)-3-(4-oxo-4,5-dihydro-thiazole-2-yl
sulfanyl) succinate (4b). Yield: 89%; yellow oil. IR (KBr) (nmax, cmꢀ1): 1732,
=
=
(C O, ester), 1700 (C O, amide). Analyses: calcd. for C13H20NO8PS2: C, 37.77;
H, 4.88; N, 3.39%. Found: C, 37.9; H, 5.00; N, 3.3%. MS (m=z, %): 413 (Mþ, 8),
-
-
1
381 (M CH3OH, 55), 137 [(EtO)2P O, 74], 322 (381 CO2CH3, 100). H NMR
=
3
(500 M Hz, CDCl3): d 1.23 and 1.30 (6 H, 2 t JHH ¼ 7 Hz, 2 CH3), 3.64 (2 H, s,
CH2), 3.76 and 3.98 (6 H, 2 s, 2 OCH3), 4.00 –4.13 (5H, m, 2 OCH2 and CH),
3
3
4.32 (1 H, dd, JHH ¼ 11 Hz, JHP ¼ 4 Hz, CH). 13C NMR (125.8 M Hz, CDCl3): d
1
16.52 and 16.61 (2 CH3), 42.38 (d, Jcp ¼ 132 Hz, P-C), 45.03 (CH2), 53.38 and
2
53.41 (2 OCH3), 53.80 (d, JCP ¼ 3 Hz, CH), 63.51–63.93 (m, 2 POCH2), 156.5
2
3
=
=
=
(SC N), 167.87 (C O), 167.56 (d, JCP ¼ 7 Hz, C O), 171.95 (d, JCP ¼ 21 Hz,
C O). 31P NMR (202.5 MHz, CDCl3): d 19.35.
=
Dimethyl
2-(dibutoxyphosphoryl)-3-(4-oxo-4,5-dihydro-thiazole-2-yl
sulfanyl) succinate (4c). Yield: 87%; yellow oil. IR (KBr) (nmax cmꢀ1): 1739,
=
=
(C O, ester), 1701 (C O, amide). Analyses: calcd. for C17H28NO8PS2: C, 43.49;
H, 6.01; N, 2.98%. Found: C, 43.4; H, 6.1, N, 3.00%. MS (m=z, %): 469 (Mþ, 6),
-
-
1
=
433 (M CH3OH, 62), 193 [(n-BuO)2P O, 48], 374 (433 CO2CH3, 100). H NMR
(500 MHz, d6-DMSO-Me4Si): d 0.82, and 0.86 (6 H, 2 t, 2 CH3), 1.32 (4 H, m, 2

2314
A. HASSANABADI ET AL.
CH2), 1.56 (4 H, m, 2 CH2), 3.64 (2 H, s, CH2), 3.68 and 3.74 (6 H, 2 s, 2 OCH3),
3
3
3.94–4.04 (4 H, m, 2 OCH2), 4.22 (1 H, dd, JHP ¼ 6 Hz, JHH ¼ 11 Hz, CH), 4.36
2
3
(1 H, dd, JHP ¼ 21 Hz, JHH ¼ 12 Hz, P-CH). 13C NMR (125.8 MHz, d6-
DMSO-Me4Si): d 13.89 and 13.91 (2 CH3), 18.92 and 18.99 (2 CH2), 32.64 and
3
1
32.74 (2d, JCP ¼ 7 Hz, 2 CH2), 45.01 (d, Jcp ¼ 127 Hz, P-C), 45.19 (CH2), 53.78
2
(d, Jcp ¼ 4 Hz, P-C-C), 53.15 and 53.31 (2 OCH3), 66.85–67.54 (m, 2 POCH2),
2
3
=
=
=
156.2 (SC N), 167.51 (d, JCP ¼ 7 Hz, C O), 167.94 (C O), 171.85 (d, JCP ¼ 21 Hz,
Hz, C O). 31P NMR (202.5 MHz, d6-DMSO): d 19.24.
=
Diethyl
2-(dimethoxyphosphoryl)-3-(4-oxo-4,5-dihydro-thiazole-2-yl
sulfanyl) succinate (4d). Yield: 90%; yellow oil. IR (KBr) (nmax, cmꢀ1): 1742,
=
=
(C O, ester), 1712 (C O, amide); Analyses: calcd. for C13H20NO8PS2: C, 37.77;
H, 4.88; N, 3.39%. Found: C, 37.9; H, 5.00; N, 3.3%. MS (m=z, %): 413 (Mþ, 3),
-
-
367 (M C2H5OH, 58), 109 [(CH3O)2P O, 68], 294 (367 CO2C2H5, 100). H NMR
1
=
3
(500 MHZ, CDCl3): d 1.18 and 1.28 (6 H, 2 t JHH ¼ 7 Hz, 2 CH3), 3.62 (2 H, s,
CH2), 3.71–3.78 (6 H, m, 2 POCH3), 4.12–4.27 (4 H, m, 2 OCH2), 4.55 (1 H, dd,
2JHP ¼ 21 Hz, JHH ¼ 12 Hz, P-CH), 4.68 (1 H, dd, JHP ¼ 5 Hz, JHH ¼ 12 Hz,
3
3
3
P-C-CH).13C NMR (125.8 M Hz, CDCl3): d 14.26 and 14.42 (2 CH3), 45.12
1
2
(CH2), 48.46 (d, Jcp ¼ 137 Hz, P-C), 53.58 (d, JCP ¼ 3 Hz, CH), 54.32 (m, 2
2
=
POCH3), 62.50 and 62.18 (2 OCH2), 153.8 (SC N), 166.97 (d, JCP ¼ 7 HZ,
C O), 167.25 (C O), 172.43 (d, JCP ¼ 21 Hz, C O). 31P NMR (202.5 MHz,
3
=
=
=
CDCl3): d 19.28.
Dimethyl 2-(diphenoxyphosphoryl)-3-(4-oxo-4,5-dihydro-thiazole-2-yl
sulfanyl) succinate (4e). Yield: 90%; Yellow oil. IR (KBr) (nmax, cmꢀ1): 1739,
=
=
(C O, ester), 1706 (C O, amide). Analyses: calcd. for C21H20NO8PS2: C, 49.51;
H, 3.96; N, 2.75%. Found: C, 49.6; H, 3.8; N, 2.7%. MS (m=z, %): 509 (Mþ, 7),
-
477 (M CH3OH, 35), 233 [(PhO)2P O, 100], 418 (477 CO2CH3, 100). H NMR
-
1
=
(500 M Hz, CDCl3): d 3.71 (2 H, s, CH2), 3.89 and 3.99 (6 H, 2 s, 2 OCH3), 4.32
3
3
2
(1 H, dd, JHP ¼ 5 Hz, JHH ¼ 12 Hz, P-C-CH), 4.53(1 H, dd, JHP ¼ 21 Hz,
3JHH ¼ 12 Hz, P-CH), 7.13–7.34 (10 H, m, 10 CH aromatic). 13C NMR
1
(125.8 M Hz, CDCl3): d 45.08 (CH2), 45.57 (d, Jcp ¼ 137 Hz, P-C), 53.47 (d,
2JCP ¼ 3 Hz, CH), 53.78 and 53.85 (2 OCH3), 120.77 (d, JCP ¼ 5 Hz, 4 CHortho),
3
126.04 (s, 2 CHpara), 130.24 (d, 4Jcp ¼ 8 Hz, 4 CHmeta), 150.33 (d, 2Jcp ¼ 10 Hz, Cipso),
150.44 (d, 2Jcp ¼ 10 Hz, Cipso), 156.03 (SC N), 166.71 (d, JCP ¼ 7 Hz, C O), 167.45
2
=
=
(C O), 171.08 (d, JCP ¼ 21 Hz, C O). 31P NMR (202.5 MHz, CDCl3): d 19.33.
3
=
=
Compounds 9a–c
General procedure. DAAD (2 mmol) in 10 mL acetone was added to a
magnetically stirred solution of N0-[2-(phenyl)-acetyl]-formic acid hydrazide (2 mmol)
and triphenylphosphine (2 mmol) in acetone (15 mL) at room temperature over 2 min.
The reaction mixture was then allowed to stir for 6 h. The solvent was evaporated at
reduced pressure. The residue was precipitated in a solution of diethyl ether–hexane.
The solid was filtered and washed with diethyl ether to give the pure product.
Compound 9a. White powder; mp 171–173 ꢁC. IR (KBr) (nmax, cmꢀ1): 3365
=
(NH), 1717, 1691, 1618 (C O). Analyses: calcd. for C32H29N2O6P: C, 67.60; H, 5.14;

REACTION OF DAADs AND TRIALKYL(ARYL) PHOSPHITES
2315
N, 4.93%. Found: C, 67.8; H, 5.3; N, 4.8%. MS (m=z, %): 568 (Mþ, 3), 105 (COPh,
80), 262 (PPh3, 85), 77 (Ph, 100).1H NMR (500 MHz, d6-DMSO): d 3.03 (3H, s,
3
OCH3), 3.76 (3H, s, OCH3), 4.98 (1H, d, JPH ¼ 16 Hz), 7.37–7.96 (20H, m, aro-
matic), 8.35 (1H, s, CH O), 9.05 (1H, s, NH). 13C NMR (125.8 MHz, d6-DMSO):
=
1
2
=
d 40.67 (d, JPC ¼ 128 Hz, C P), 49.91, 53.16 (2 OCH3), 58.91 (d, JPC ¼ 17 Hz,
1
2
4
CH), 126.2 (d, JPC ¼ 91 Hz), 129.15 (d, JPC ¼ 12 Hz), 132.68 (d, JPC ¼ 2 Hz),
3
134.14 (d, JPC ¼ 10 Hz), 128.31, 129.0, 132.26 and 132.88 (ph), 164.38, 168.42
(2C O), 168.6 (d, JPC ¼ 12 Hz C O), 172.44 (d, JPC ¼ 12 Hz C O). 31P NMR
2
3
=
=
=
(202.5 MHz, d6-DMSO): d 24.37.
Compound 9b. White powder; mp 157–159 ꢁC. IR (KBr) (nmax, cmꢀ1): 3425
=
(NH), 1762, 1690, 1619 (C O). Analyses: calcd. for C34H33N2O6P: C, 68.45; H, 5.58;
N, 4.70%. Found: C, 68.3; H, 5.7; N, 4.9%. MS (m=z, %): 568 (Mþ, 7), 105 (COPh,
100), 262 (PPh3, 74), 77 (Ph, 95).1H NMR (500 MHz, d6-DMSO): d 0.35 (3H, d
3
3JHH ¼ 7 Hz, CH3), 1.32 (3H, d JHH ¼ 7 Hz, CH3), 3.51–3.61 (2H, m, OCH2),
4.13–4.32 (2H, m, OCH2), 4.99 (1H, d, 3JPH ¼ 16 Hz), 7.37–7.98 (20H, m, aromatic),
8.22 (1H, s, CH O), 8.97 (1H, s, NH). 13C NMR (125.8 MHz, d6-DMSO): d 14.34
=
1
=
and 14.74 (2CH3), 40.50 (d, JPC ¼ 128 Hz, C P), 58.51, 61.99 (2OCH2), 58.89 (d,
1
2
2JPC ¼ 17 Hz, CH), 126.49 (d, JPC ¼ 91 Hz), 129.04 (d, JPC ¼ 12 Hz), 132.60 (d,
3
4JPC ¼ 2 Hz), 134.21 (d, JPC ¼ 10 Hz), 128.34, 129.2, 132.36 and 132.71
2
3
=
=
(ph),164.37,168.40 (2C O), 171.55 (d, JPC ¼ 12 Hz C O), 171.77 (d, JPC ¼ 12 Hz
C O). 31P NMR (202.5 MHz, d6-DMSO): d 24.12.
=
Compound 9c. White powder; m.p. 180–182 ꢁC. IR (KBr) (nmax, cmꢀ1): 3410
=
(NH), 1730, 1697, 1613 (C O). Analyses: calcd. for C38H41N2O6P: C, 69.92; H, 6.33;
N, 4.29%. Found: C, 70.1; H, 6.5; N, 4.4%. MS (m=z, %): 652 (Mþ, 15), 105 (COPh,
84), 262 (PPh3, 70), 77 (Ph, 100).1H NMR (500 MHz, d6-DMSO): d 0.79 (9H, s,
3CH3), 1.54 (9H, s, 3CH3), 4.86 (1H, d, 3JPH ¼ 16 Hz,), 7.33-8.03 (20H, m, aromatic),
8.23 (1H, s, CH O), 9.05 (1H, s, NH). 13C NMR (125.8 MHz, d6-DMSO): d 28.65
=
and 28.67 (6CH3), 40.10 (d, 1JPC ¼ 128 Hz, C P), 59.58 (d, JPC ¼ 17 Hz, CH), 78.29
2
=
1
2
and 81.80 (2C), 127.08 (d, JPC ¼ 91 Hz), 128.88 (d, JPC ¼ 12 Hz), 132.47 (d,
3
4JPC ¼ 2 Hz), 134.24 (d, JPC ¼ 10 Hz), 128.56, 129.0, 132.33 and 132.63 (ph),
2
3
=
=
164.27, 168.27 (2C O), 170.65 (d, JPC ¼ 12 Hz C O), 171.38 (d, JPC ¼ 12HZ
C O). 31P NMR (202.5 MHz, d6-DMSO): d 23.94.
=
ACKNOWLEDGMENTS
We gratefully acknowledge financial support from the Research Council of
Islamic Azad University of Yazd and the Islamic Azad University of Zahedan of
Iran.
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3. Engel, R. Synthesis of Carbon–Phosphorus Bonds; CRC Press: Boca Raton, FL, 1988.

2316
A. HASSANABADI ET AL.
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