Synthesis of new phosphonato esters by reaction between triphenyl or trialkyl phosphite and acetylenic diesters in the presence of NH-containing compounds

Article abstract of DOI:10.1002/hc.20725

The reaction between triphenyl or trialkyl phosphite and acetylenic esters in the presence of some heterocyclic or aromatic NH compounds such as thiazolidine-2,4-dione, 2-methyl indole, 5-bromoisatine, 3-nitroacetanilide, saccharin, 5,5-dimethylhydantoin,

Full text of DOI:10.1002/hc.20725

Heteroatom Chemistry
Volume 22, Number 5, 2011
Synthesis of New Phosphonato Esters by
Reaction between Triphenyl or Trialkyl
Phosphite and Acetylenic Diesters in the
Presence of NH-Containing Compounds
Ghasem Marandi,1 Malek Taher Maghsoodlou,1 Nourallah Hazeri,1
Reza Heydari,1 Sayyed Mostafa Habibi-Khorassani,1 Niloufar
Akbarzadeh Torbati,1 Seyed Sajad Sajadikhah,1 Danial Saravani,1
Mansoureh Rakhshanipour,1 Samira Gholamipour,1 Faramarz
Rostami-Charati,2 Brian W. Skelton,3 Mohamed Makha,3 Zeynab
Zare,1 and Mojtaba Lashkari1
1Department of Chemistry, The University of Sistan & Baluchestan, P. O. Box: 98135-674,
Zahedan, Iran
2Department of Chemistry, Faculty of Science, Gonbad Kavous University, P.O. Box 163,
Gonbad, Iran
3Chemistry, School of Biomedical, Biomolecular and Chemical Sciences,
M313, University of Western Australia, Perth, WA 6009, Australia
Received 18 November 2010; revised 19 February 2011
INTRODUCTION
ABSTRACT: The reaction between triphenyl or
trialkyl phosphite and acetylenic esters in the pres-
ence of some heterocyclic or aromatic NH com-
pounds such as thiazolidine-2,4-dione, 2-methyl in-
dole, 5-bromoisatine, 3-nitroacetanilide, saccharin,
5,5-dimethylhydantoin, 2-nitroaniline, 4-nitroaniline,
benzophenon hydrazine, and anthranilic acid led to
the formation of phosphonato esters in high yield.
2011 Wiley Periodicals, Inc. Heteroatom Chem 22:630–
639, 2011; View this article online at wileyonlineli-
brary.com. DOI 10.1002/hc.20725
Heterocyclic systems with oxygen, nitrogen, sulfur,
and other heteroatoms in five- and six-membered
rings, and also phosphorus compounds, are of in-
terest due to their pharmaceutical and biological
activities such as anti-inflammatory, cardiotonic,
inotropic, antihypertensive, antimicrobial, and an-
tibacterial properties [1–15]. Numerous studies have
been previously reported using the reaction be-
tween trivalent phosphorus nucleophiles and defi-
cient carbonyl compounds, in the presence of a pro-
ton source, such as CH, NH, OH, or SH compounds
[16–30].
ꢀ
C
Continuing a series of investigations made on
the development of organophosphorus heterocyclic
compound synthesis [22–30], we now describe a one-
pot synthesis of heterocyclic and aromatic phos-
phonato ester derivatives 4a–f, 5a–g, and 7, using
Correspondence
mt maghsoodlou@yahoo.com.
Contract grant sponsor: Research Council of the University of
Sistan & Baluchestan.
to:
M.
T.
Maghsoodlou;
e-mail:
c
ꢀ
2011 Wiley Periodicals, Inc.
630

Synthesis of New Phosphonato Esters by Reaction between Triphenyl or Trialkyl Phosphite and Acetylenic Diesters 631
1H, 13C, and 31P NMR, and mass spectra. The mass
spectra of these compounds displayed molecular ion
peaks at appropriate m/z values, in addition to molec-
ular fragmentation peaks involving the loss of the
ester and phenoxy or alkoxy moieties. No products
other than 4a–f, 5a–f, and 7 could be detected by
NMR spectroscopy.
triphenyl or trialkyl phosphite 1 and acetylenic di-
esters 2 in the presence of NH heterocyclic or aro-
matic compounds 3 and6.
RESULTS AND DISCUSSION
The aim of this work was to undertake the reac-
tions between triphenyl or ethyl phosphite 1 and
acetylenic diesters 2 in the presence of heterocyclic
or aromatic NH compounds 3 in appropriate sol-
vents. These reactions preceded smoothly at room
temperature and were completed within 2–48 h and
resulted in high yields. TLC monitoring and 1H NMR
spectra of the crude products clearly indicated for-
mation of phosphonate esters 4 (see Schemes 1
and 2).
1
The H NMR spectra of 4a showed two singlets
(at δ = 3.75 and 3.87 ppm) for methoxy protons, an
AB quartet (δ = 3.97, 2 JHH = 17.3 Hz) for the methy-
lene group and a multiplet (δ = 7.10–7.37 ppm) for
aromatic protons. In addition, two doublet of dou-
blets were observed for the vicinal methine protons
3
2
of 4a (δ = 4.45, JHH = 11.5, JHP = 21.1 Hz, and
δ = 5.87, JHH = 11.5, JHP = 4.8 Hz), respectively.
The vicinal proton–proton coupling constant (3 JHH
3
3
)
The essential structures of the products 4a–f, 5a–
f, and 7 were deduced from elemental analysis, IR,
can be obtained from the Karplus equation as a func-
tion of the torsion angle [31–35]. Typically Jgauche
H
(RO)2OP
CO2R'
CO2R′
C
Solvent
r.t.
Z
(RO)3P
+
+
Z
H
CO2R'
C
H
4
CO2R'
1
2
3
% Yield
97
4
a
Solvent
R
R′
Z
Ph
Diethyl ether
Me
S
O
N
O
Diethyl ether
b
c
94
Et
Ph
CH3
Me
Ph
Ph
90
93
DMF
DMF
N
H
O
Br
d
Me
Me
Me
O
N
O
N
e
Et
91
94
EtoAc
NO2
O
S
O
N
1 : 1
Ether : EtoAc
f
Me
O
SCHEME 1
CH3
N
H
N
N
CO2Me
C
CH3
MeO2C
CH3
+ H2O
−PhOH
H
4c
+
(PhO)3P
MeO2C
H
C
(PhO)3P
CO2Me
CO2Me
(PhO)3P CO2Me
SCHEME 2
Heteroatom Chemistry DOI 10.1002/hc

632 Marandi et al.
H
1:1:1 adducts displayed fairly weak molecular ion
peaks (Scheme 4).
H
3
3
RO2C
PO(OPh)2
RO2C
*
PO(OPh)2
S
S
*
O
O
When the reaction between triphenyl phos-
phite and acetylenic esters in the presence of 2-
nitroaniline was conducted, only one diastereoiso-
mer was obtained for compounds 5 (a,b, e, and f),
since compounds 5 (c,d, and g) and 7 consist of a
mixture of two diastereoisomers (see the Experimen-
tal section).
N
RO2C
CO2R
2
O
N
2
*
H
H
O
(2R, 3R)-4a or (2S, 3S)-4a
(2S, 3R)-4a or (2R, 3S)-4a
The observation of 3 JHH = 3.6 and 3.7 Hz for the
vicinal protons in compounds 5a and 5b confirms a
gauche-arrangement for these protons, respectively.
Since compounds 5a and 5b possess two stereogenic
centers, two diastereoisomers, [(2R, 3R) or (2S, 3S)]
and [(2R, 3S) or (2S, 3R)] with a gauche HCCH ar-
rangement are possible (Scheme 5). For example,
the 1H NMR spectrum of 5c displays double doublets
and a double doublets of doublets for the vicinal pro-
tons of the major isomer and also a double doublets
and a multiplet for the vicinal protons of the minor
SCHEME 3
and Janti configurations give rise to distinct coupling
constants, which vary between 1.5–5 and 10–14 Hz,
respectively [31–35]. The observation of 3 JHH = 11.5
Hz for the vicinal methine protons in compound
4a confirms an anti arrangement for these protons.
Since compounds possess two stereogenic centers,
two diastereoisomers [(2R, 3R)-4 or (2S, 3S)-4 and
(2S, 3R)-4 or (2R, 3S)-4] with an anti HCCH arrange-
ment are possible (Scheme 3). In addition, com-
pound 4d showed two broad peaks for vicinal me-
thine protons (P-CH-CH), such that we were unable
to recognize the configuration of these protons.
The presence of phosphorus (31P) nucleus in the
compounds 4 assist in identifying their configura-
tion by analysis of the long-range spin–spin coupling
signals of phosphorus (31P) nucleus with the neigh-
boring protons (1H) and carbon (13C) nuclei (see the
Experimental section).
3
2
isomer: (δ = 4.22, JHH = 3.6, JHP = 25.4 Hz, and
3
3
δ = 4.96, JHH = 3.6, JHP = 7.7 Hz) and (δ =
3
2
4.10, JHH = 5.1, JHP = 24.4 Hz, and δ = 5.10),
respectively.
In addition, two diastereoisomers in compound
7 with anti and gauche HCCH arrangement are pos-
sible (Scheme 6 and 7). Attempts to separate the ma-
jor and the minor compounds 5 (c, d, and g) and
7 were unsuccessful. Single-crystal X-ray diffraction
was used to authenticate the structure of compound
5e (Fig. 1). Prismatic colorless crystals of 5e were
prepared by slow evaporation of a saturated solu-
tion of dichloromethane.
The carbon–phosphorus three bond range cou-
pling constant JCP is associated with the anti or cis
3
configuration (transoid coupling being larger than
cisoid coupling) [31]. The Karplus relationship can
be derived from the literature data for organophos-
phorus compounds with tetra- or pentavalent phos-
phorus environments [32]. The observation of
3 JCP = 19.1 Hz at δ = 166.28 ppm for the ester
carbonyl group of compounds 4a is in agreement
with an anti-arrangement along the P-CH-CH-CO
bond. This assignment was reinforced in 4a with
the smaller coupling of the phosphorus to the prox-
On the basis of the proposed mechanism in the
literature [36–40], it is reasonable to assume that
the heterocyclic phosphonato ester 4 results from
the initial addition of triphenyl phosphite 1 to the
acetylenic ester 2 (1:1 adduct or zwitterionic A),
with subsequent protonation of the 1:1 adduct by
the NH compound 3 to generate the intermediate
phosphonium ion B, which was followed by q re-
action with the conjugate base (Z−) to produce the
ylide C. It is converted to D in the presence of
moisture and with subsequent loss of PhOH (see
Scheme 8).
2
imal ester carbon group, JCP = 8.1 Hz at δ =
165.18 ppm.
In a series of other experiments, from reactions
between triphenyl phosphite and acetylenic diesters
in the presence of 2-nitroaniline, 4-nitroaniline, an-
thranilic acid, o-trifluoromethylaniline, diphenylhy-
drazone, or 5,5-dimethylhydantoin, the hitherto un-
known butanedioates 5 and 7 were generated in
91–95% yield. All compounds are stable, with the
proposed structures being fully supported by ele-
In conclusion, the reaction between triphenyl
or triethyl phosphite and acetylenic esters in the
presence of NH compounds, such as thiazolidine-
2,4-dione, 2-methyl indole, 5-bromoisatine, 3-
nitroacetanilide, saccharin, 5,5-dimethylhydantoin,
2-nitroaniline, 4-nitroaniline, benzophenon hy-
drazine, and anthranilic acid, provides a simple one-
pot entry into the synthesis of stable phosphonato es-
ters of potential interest. The present procedure has
the advantage that not only is the reaction performed
1
mental analyses and IR, H, 13C, and 31P NMR, and
mass spectroscopy data. The mass spectra of these
Heteroatom Chemistry DOI 10.1002/hc

Synthesis of New Phosphonato Esters by Reaction between Triphenyl or Trialkyl Phosphite and Acetylenic Diesters 633
PO(OR)2
CO2R′
C
H
Z
CO2R′
H
i: Solvent
r.t.
(RO)3P
+
+
Z
H
C
R′O2C
1
CO2R′
2
3
5
% Yield
5
a
b
Solvent
R
Z
R′
95a
91a
NH
Ph
Ph
Me
Et
NO2
EtoAc
Et2O
NH
93b
92b
c
d
Me
Et
Et2O
Ph
Ph
1:1
Et2O/n-Hexane
NO2
NH
NH
CO2H
95a
95a
e
f
Me
Me
Acetone
EtOAc
Ph
Ph
CF3
NH
N
EtOAc
93b
g
Ph
Me
a
b
Only one isomer with gauche HCCH arrengement.
Mixture of two isomer with gauche HCCH arrengement.
SCHEME 4
PO(OPh)2
CO2Me
Avance instrument (Germany) with CDCl3 as a
solvent at 400.1, 100.6, and 161.9 MHz, respec-
tively. Elemental analyses for C, H, and N were
performed using a Heraeus CHN-O-Rapid analyzer
(Germany). The mass spectra were recorded on
a Shimadzu GCMS-QP5050A (Japan) mass spec-
trometer operating at an ionization potential of
70 eV. Triphenyl phosphite, dialkyl acetylendicar-
boxylate, thiazolidine-2,4-dione, 2-methyl indole,
5-bromoisatine, 3-nitroacetanilide, saccharin, 5,5-
dimethylhydantoin, 2-nitroaniline, 4-nitroaniline,
benzophenon hydrazine, and anthranilic acid were
purchased from Merck (Darmstadt, Germany),
Fluka (Buchs, Switzerland), and Acros (Geel, Bel-
gium), and used without further purifications.
PO(OPh)2
H
H
CO2Me
CO2Me
NH
H
H
NH
NO2
MeO2C
NO2
(2R,3R)-5a or (2S,3S)-5a
(2S,3R)-5a or (2R,3S)-5a
SCHEME 5
under neutral conditions but also the substances can
be mixed without any activation or modifications.
EXPERIMENTAL
General Procedure (Exemplified by 4a)
Melting points and IR spectra were measured on
an Electrothermal 9100 apparatus (England) and
a JASCO FT-IR 460 plus spectrometer (Japan),
respectively. The 1H, 13C, and 31P NMR spectra
were recorded on a Bruker DRX-300 and 400
To a stirred solution of thiazolidine-2,4-dione (1
mmol) and dimethyl acetylendicarboxylate (1 mmol)
in 10 mL diethyl ether, a mixture of triphenyl phos-
phite (1 mmol) in 5 mL diethyl ether was added drop
Heteroatom Chemistry DOI 10.1002/hc

634 Marandi et al.
R'O2C
PO(OPh)2
CO2R'
CO2R'
C
O
O
N
HN
CH3
CH3
(PhO)3P +
H3C
H3C
MDF
r.t.
+
C
R' = Me
O
N
N
O
1
CO2R'
H
H
7
With major (67%) and minor (33%) diastereoisomers
2
6
SCHEME 6
PO(OPh)2
PO(OPh)2
H
MeO2C
CO2Me
H
H
O
H
O
CH3
CH3
CH3
CH3
N
N
MeO2C
MeO2C
N
N
O
O
H
H
(2R, 3R)-7 or (2S, 3S)-7
(2S, 3R)-7 or (2R, 3S)-7
Minor
Major
SCHEME 7
wise at −5◦C over 10 min. The mixture was then
allowed to warm up to room temperature and was
stirred for 5 h. The solvent was removed under re-
duced pressure, and the residue was washed by di-
ethyl ether (2×3) mL to afford the pure product.
FIGURE 1 Crystal structure of 5e with ellipsoids depicted at
the 50% probability level. Hydrogen atoms have been drawn
with arbitrary radii.
(2R, 3S)-Dimethyl 2-(2,4-thiazolindione-N-yl)-3-
(diphenoxyphosphoryl)butandioate (4a)
White powder; yield: 97% (0.48 g), mp = 85–88◦C.
−1
=
IR (KBr) (νmax, cm ): 1766, 1745, and 1690 (C O),
+
3
3
=
1288 (P O). MS (m/z, %): 493 (M , 1), 462 (4), 434
PCHCH), 5.87 (1H, dd, JHH = 11.5, JPH = 4.8 Hz,
PCHCH), 7.10–7.37 (10H, m, 2OPh).
(1), 400 (100), 376 (7), 346 (4), 285 (30), 94 (16), 77
(51). Anal. Calcd for C21H20NO9PS (493.42): C, 51.12;
H, 4.09; N, 2.84. Found: C, 51.25; H, 4.03; N, 2.93.
13C NMR (100.6 MHz, CDCl3): δC 32.51 (s,
SCH2CO), 42.43 (d, 1 JPC = 133.8 Hz, PCHCH), 50.64
1H NMR (400.1 MHz, CDCl3): δH 3.75 and 3.87
(d, JPC = 4.2 Hz, PCHCH), 52.35 and 52.66 (2s,
2
2
(6H, 2s, 2 OCH ), 3.97, (AB quartet JHH = 17.3 Hz,
2OCH3), 119.24 (d, 3 JPC = 4.4 Hz, 2Cortho), 119.50 (d,
3 JPC = 4.2 Hz, 2Cortho), 124.67 and 124.80 (2s, 2Cpara),
3
SCH CO), 4.45 (1H, dd, 3 JHH = 11.5, 2 JPH = 21.1 Hz,
2
CO2R
CO2R
C
C
CO2R
(PhO)3P
RO2C
3
H
(PhO)3P
+
P(OPh)3
Z
RO2C
CO2R
B
A
1
2
CO2R
CO2R
H
Moisture
H
4
H
(PhO)3P
RO2C
(PhO)3P
Z
Z
RO2C
C
D
SCHEME 8
Heteroatom Chemistry DOI 10.1002/hc

Synthesis of New Phosphonato Esters by Reaction between Triphenyl or Trialkyl Phosphite and Acetylenic Diesters 635
128.81 and 128.84 (2s, 4Cmeta), 148.25 (d, 2 JPC = 10.2
129.47 (2s, 4Cmeta), 149.78 and 152.59 (2d, 2 JPC = 9.1
2
2
Hz, Cipso), 148.80 (d, JPC = 8.5 Hz, Cipso), 165.18 (d,
Hz, 2Cipso), 152.65 (Carom), 168.66 (d, JPC = 5.0 Hz,
3
2 JPC = 8.1 Hz, CO), 166.28 (d, JPC = 19.1 Hz, CO),
CO), 172.69 (d, 3 JPC = 22.8 Hz, CO). 31P NMR (161.9
MHz, CDCl3): δP 13.42.
167.88 (s, NCO), 169.73 (s, SCON). 31P NMR (161.9
MHz, CDCl3): δP 9.44.
(2R, 3S)-Dimethyl 2-(5-bromo-2,3-dioxoindolin-
1-yl)-3-(diphenoxyphosphoryl)butandioate (4d)
(2R, 3S)-Dimethyl 2-(2,4-thiazolindione-N-yl)-3-
(diphenoxyphosphoryl)butandioate (4b)
Brown viscous oil; yield: 93% (0.56 g), IR (in CCl4)
−1
=
=
White powder; yield: 94% (0.49 g), mp = 103.5–
(νmax, cm ): 1750 and 1609 (C O), 1235 (P O). MS
(m/z, %): 604 (M++2, 5), 603 (M+ +1, 3), 602 (M+,
5), 510 (72), 508 (67), 377 (8), 349 (8), 285 (25), 250
(91), 94 (100), 77 (78). Anal. Calcd for C26H21BrNO9P
(602.32): C, 51.85; H, 3.51; N, 2.33. Found: C, 51.96;
H, 3.44; N, 2.19.
−1
106◦C. IR (KBr) (νmax, cm ): 1749 and 1696 (C O),
=
+
+
=
1273 (P O). MS (m/z, %): 522 (M +1, 3), 521 (M ,
1), 476 (10), 428 (100), 380 (19), 311 (60), 297 (2),
255 (94), 227 (5), 94 (26), 77 (58). Anal. Calcd for
C23H24NO9PS (521.48): C, 52.97; H, 4.64; N, 2.69.
Found: C, 53.08; H, 4.59; N, 2.74.
1H NMR (400.1 MHz, CDCl3): δH 3.75 and 3.88
1H NMR (400.1 MHz, CDCl3): δH 1.27 (3H, t,
(6H, 2s, 2 OCH ), 5.33 and 6.53 (2H, 2 br s,
3
3 JHH = 7.1 Hz, OCH2CH ), 1.35 (3H, t, JHH = 7.1
PCHCH and PCHCH), 6.56–7.63 (13H, m, 2OPh and
3CHarom).
3
3
Hz, OCH2CH ), 3.96–4.04 (2H, m, SCH CO), 4.16–
3
2
3
4.34 (3H, m, OCH CH3), 4.36 (1H, q, JHH = 7.1 Hz,
13C NMR (100.6 MHz, CDCl3): δC 42.11 (d, 1 JPC
=
2
OCH CH3), 4.45 (1H, dd, 3 JHH = 11.5, 2 JPH = 21.1 Hz,
133.7 Hz, PCHCH), 48.16 (d, 2 JPC = 5.3 Hz, PCHCH),
2
3
3
PCHCH), 5.87 (1H, dd, JHH = 11.5, JPH = 4.7 Hz,
PCHCH), 7.14–7.36 (10H, m, 2OPh).
53.54 and 53.87 (2s, 2OCH3), 117.03 and 119.27 (2s,
3
2CHarom), 120.15 (d, JPC = 4.8 Hz, 2Cortho), 120.26
3
13C NMR (100.6 MHz, CDCl3): δP 13.96 and 14.00
(d, JPC = 4.8 Hz, 2Cortho), 124.00 (s, 2Cpara), 125.70
(2s, 2 OCH2CH3), 33.57 (s, SCH2CO), 43.71 (d, 1 JPC
=
and 125.82 (2s, CH and Carom), 125.22 and 125.24
(2s, 2Cpara), 126.61 (Carom), 129.45 and 129.53 (2s,
133.1 Hz, PCHCH), 51.86 (d, 2 JPC = 4.5 Hz, PCHCH),
3
2
62.52 and 63.03 (2s, 2OCH2CH3), 120.33 (d, JPC
=
4Cmeta), 129.94 (s, Carom), 149.13 (d, JPC = 9.3 Hz,
3
2
4.3 Hz, 2Cortho), 120.61 (d, JPC = 4.3 Hz, 2Cortho),
Cipso), 151.28 (d, JPC = 9.1 Hz, Cipso), 156.00 (CO),
2
3
125.64 and 125.77 (2s, 2Cpara), 129.85 and 129.87 (2s,
167.85 (d, JPC = 7.5 Hz, CO), 168.14 (d, JPC = 21.5
Hz, CO), 180.12 (CO). 31P NMR (161.9 MHz, CDCl3):
δP 10.05.
2
4Cmeta), 149.41 (d, JPC = 10.3 Hz, Cipso), 150.00 (d,
2 JPC = 8.5 Hz, Cipso), 165.72 (d, JPC = 7.9 Hz, CO),
2
3
166.74 (d, JPC = 19.1 Hz, CO), 170.53 (br s, NCO),
170.85 (s, SCON). 31P NMR (161.9 MHz, CDCl3): δP
(2S, 3R)-Dimethyl 2-[N-(3-nitrophenyl)acetam-
9.81.
ido]-3-(diethoxyphosphoryl)butandioate (4e)
Yellow crystalline; yield: 91% (0.42 g), mp = 126–
(2S, 3R)-Dimethyl 2-(2-methyl-1H-indol-3-yl)-3-
(diphenoxyphosphoryl)butandioate (4c)
−1
129◦C. IR (KBr) (νmax, cm ): 1740 and 1734 (C O),
=
+
+
=
1229 (P O). MS (m/z, %): 461 (M +1, 4), 460 (M ,
1), 429 (3), 414 (2), 400 (4), 359 (82), 281 (26), 265
(3), 235 (13), 221 (100). Anal. Calcd for C18H25N2O10P
(460.37): C, 46.96; H, 5.47; N, 6.08. Found: C, 46.89;
H, 5.51; N, 6.13.
Brown viscous oil; yield: 90% (0.46 g), IR (in CCl4)
−1
=
(νmax, cm ): 3309 (NH), 1743 and 1691 (C O), 1254
=
+
(P O). MS (m/z, %): 507 (M , 3), 475 (1), 411 (7),
376 (2), 351 (1), 326 (88), 94 (100). Anal. Calcd
for C27H26NO7P (507.47): C, 63.90; H, 5.16; N, 2.76.
Found: C, 63.84; H, 5.11; N, 2.84.
1H NMR (400.1 MHz, CDCl3): δH 1.16 and 1.25
(6H, 2t, JHH = 7.1 Hz, 2OCH2CH ), 1.93 (3H, s,
3
3
1H NMR (400.1 MHz, CDCl3): δH 2.38 (3H, s,
NCOCH ), 3.79 and 3.82 (6H, 2s, 2OCH ), 3.97–4.17
3
3
CH3), 3.60 and 3.80 (6H, 2s, 2OCH ), 4.56 (1H, dd,
(4H, 2m, 2ABX3 system, 2OCH CH3), 4.44 (1H, dd,
3
2
3 JHH = 11.9, 2 JPH = 22.5 Hz, PCHCH), 4.93 (1H, 3 JHH
3 JHH = 10.0, JPH = 20.7 Hz, PCHCH), 4.81 (1H, dd,
2
3
= 11.9, JPH = 9.4 Hz, PCHCH), 6.50–7.72 (14H, m,
3 JHH = 10.0, 3 JPH = 4.4 Hz, PCHCH), 6.64 (1H, t, J =
8.1 Hz, CH), 8.07 (1H, d, J = 7.9 Hz, CH), 8.24 (1H,
dd, J = 8.2 and 1.6 Hz, CH), 8.53 (1H, t, J = 2.0 Hz,
CH).
2 OPh and 4 CHarom).
13C NMR (100.6 MHz, CDCl3): δC 11.93 (s, -CH3),
2
1
41.86 (d, JPC = 4.0 Hz, PCHCH), 47.23 (d, JPC
=
136.9 Hz, PCHCH), 52.60 and 53.10 (2s, 2OCH3),
13C NMR (100.6 MHz, CDCl3): δC 15.74 (d,
3
3
118.42 and 119.72 (2CHarom), 119.75 (d, JPC = 4.8
3 JPC = 6.3 Hz, POCH2CH3), 15.84 (d, JPC = 6.4 Hz,
Hz, 2Cortho), 120.13 (d, 3 JPC = 4.8 Hz, 2Cortho), 120.24,
120.72, 123.71 and 124.88 (2CH and 3Carom), 125.22
and 125.24 (2s, 2Cpara), 126.61 (Carom), 129.43 and
POCH2CH3), 22.60 (s, NCOCH3), 44.78 (d, JPC
=
1
130.0 Hz, PCHCH), 51.89 (d, 2 JPC = 6.3 Hz, PCHCH),
52.63 and 53.00 (2s, 2OCH3), 62.70 (d, 2 JPC = 7.1 Hz,
Heteroatom Chemistry DOI 10.1002/hc

636 Marandi et al.
2
POCH2CH3), 63.25 (d, JPC = 6.4 Hz, POCH2CH3),
(2R,3R)-Diethyl 2-(2-nitrophenylamino)-3-
(diphenoxyphosphoryl)butandioate (5b)
112.56, 123.19, 129.84, 134.28, 144.82 and 148.38
2
(6s, CH and Carom), 167.90 (d, JPC = 6.9 Hz, CO),
Yellow powder; yield: 91% (0.49 g), mp = 84–86◦C. IR
169.46 (d, JPC = 18.1 Hz, CO), 171.10 (NCO). 31P
3
−1
=
(KBr) (νmax, cm ): 3359 (NH), 1726 and 1707 (C O),
NMR (161.9 MHz, CDCl3): δP 17.80.
+
=
1268 (P O). MS (m/z, %): 542 (M , 10), 469 (100),
423 (51), 331 (20), 275 (35), 138 (63), 92 (36), 77
(40), 65 (43). Anal. Calcd for C26H27N2O9P (542.47):
C, 57.57; H, 5.02; N, 5.16. Found: C, 57.49; H, 5.11;
N, 5.24.
(2S, 3R)-Dimethyl 2-(1,2-dihydro-1λ6-benzol[d]-
isothiazol-3-one-2-yl)–3-(dimethoxyphosphoryl)
butandioate (4f)
1H NMR (300.1 MHz, CDCl3): δH 1.19 (3H, t,
White powder; yield: 94% (0.41 g), mp = 125–127◦C.
J = 7.1 Hz, OCH2CH ), and 1.41 (3H, t, J = 7.2
3
−1
=
IR (KBr) (νmax, cm ): 1738 and 1721 (C O), 1259
Hz, OCH2CH ), 4.12–4.18 (2H, m, OCH CH3), 4.26
3
2
+
=
(P O). MS (m/z, %): 436 (M +1, 3), 435 (M , 2), 404
3
2
(1H, dd, JHH = 3.7, JPH = 25.6 Hz, PCHCH), 4.34–
(9), 376 (73), 221 (76), 193 (100), 109 (95), 59 (24).
Anal. Calcd for (435.34): C15H18NO10PS: C, 41.38; H,
4.17; N, 3.22. Found: C, 41.23; H, 4.10; N, 3.31.
1H NMR (400.1 MHz, CDCl3): δH 3.71–3.86 (12H,
3
4.47 (2H, m, OCH CH3), 5.09 (1H, ddd, JHH = 3.6,
JPH = 7.7, JHH =2 10.9 Hz, PCHCH), 6.70 (1H, dt,
3
3
JHH = 1.0, JHH = 7.15 Hz, CHarom), 6.93–7.43 (12H,
m, 2OPh and 2CHarom), 8.08 (1H, dd, JHH = 1.36,
JHH = 8.6 Hz, CHarom), 9.06 (1H, br d, JHH = 10.9 Hz,
NH).
m, 4OCH ), 4.40 (1H, dd, 3 JHH = 11.4, 2 JPH = 21.1 Hz,
3
3
2
PCHCH), 5.53 (1H, dd, JHH = 11.4, JPH = 7.3 Hz,
PCHCH), 7.82–8.11 (4H, m, CHarom).
13C NMR (75.5 MHz, CDCl3): δC 13.59 and 14.10
(2s, 2OCH2CH3), 47.21 (d, 1 JPC = 136.3 Hz, PCHCH),
13C NMR (100.6 MHz, CDCl3): δC 43.49 (d, 1 JPC
=
129.7 Hz, PCHCH), 50.82 (d, 2 JPC = 4.6 Hz, PCHCH),
53.18, 53.45, 53.54 and 53.72 (4s, 4OCH3), 121.09,
125.51, 126.71, 134.41, 135.10, and 137.90 (6s, CH
2
54.09 (d, JPC = 3.3 Hz, PCHCH), 62.90 and 62.47
(2s, 2OCH2CH3), 115.02 and 117.02 (2s, 2CHarom),
120.02 (d, JCP = 4.8 Hz, 2CHortho), 120.78 (d, 3 JCP
=
3
2
and Carom), 159.40 (s, SCON), 167.34 (d, JPC = 7.2
4.3 Hz, 2CHortho), 126.53 (CHarom), 125.81 and 125.93
(2s, 2Cpara), 129.41 and 129.97 (2s, 4Cmeta), 133.66 and
135.87 (2s, CH and Carom), 144.14 (s, Carom), 149.75 (d,
Hz, CO), 167.56 (d, JPC = 7.5 Hz, CO). 31P NMR
3
(161.9 MHz, CDCl3): δP 18.57.
2 JCP = 8.2 Hz, Cipso), 149.82 (d, JCP = 8.3 Hz, Cipso),
2
2
3
(2R,3R)-Dimethyl 2-(2-nitrophenylamino)-3-
(diphenoxyphosphoryl)butandioate (5a)
166.40 (d, JPC = 5.4 Hz, CO), 170.01 (d, JPC = 18.4
Hz, CO). 31P NMR (121.5 MHz, CDCl3): δP 12.24.
Yellow powder; yield: 95% (0.49 g), mp = 97–100◦C.
IR (KBr) (νmax, cm−1): 3339 (NH), 1731 and 1711
Dimethyl 2-(4-nitrophenylamino)-3-(dipheno-
xyphosphoryl)butandioate (5c)
+
=
=
(C O), 1282 (P O). MS (m/z, %): 514 (M , 11), 455
(59), 423 (47), 376 (29), 317 (21), 283 (76), 223 (83),
138 (100), 92 (43), 77 (64), 65 (69). Anal. Calcd for
C24H23N2O9P (514.42): C, 56.04; H, 4.51; N, 5.45.
Found: C, 55.98; H, 4.42; N, 5.61.
Pale yellow powder; yield: 93% (0.48 g), mp = 129–
132◦C. IR (KBr) (νmax, cm−1): 3368 and 3286 (2NH),
=
=
1733 and 1730 (C O), 1266 (P O). MS (m/z, %): 514
(M+, 11), 455 (24), 423 (15), 376 (31), 283 (73), 223
(100), 138 (40), 77 (64). Anal. Calcd for C24H23N2O9P
(514.42): C, 56.04; H, 4.51; N, 5.45. Found: C, 56.13;
H, 4.66; N, 5.31.
1H NMR (300.1 MHz, CDCl3): δH 3.59 and 3.72
3
2
(6H, 2s, 2OCH ), 4.28 (1H, dd, JHH = 3.6, JPH
=
=
=
3
3
3
25.5 Hz, PCHCH), 5.15 (1H, ddd, JHH = 3.6, JPH
3
8.0, JHH = 10.5 Hz, PCHCH), 6.71 (1H, dt, JHH
1.2, JHH = 7.6 Hz, CHarom), 6.94–7.44 (12H, m, 2OPh
and 2CHarom), 8.10 (1H, dd, JHH = 1.5, JHH = 8.5 Hz,
CHarom), 9.12 (1H, d, JHH = 10.5 Hz, NH).
Major isomer (69%): 1H NMR (300.1 MHz,
CDCl3): δH 3.73 and 3.92 (6H, 2s, 2OCH ), 4.22 (1H,
3
3
2
dd, JHH = 3.6, JPH = 25.4 Hz, PCHCH), 4.96 (1H,
ddd, 3 JHH = 3.6, 3 JPH = 7.7, 3 JHH = 10.9 Hz, PCHCH),
5.73 (1H, d, 3 JHH = 10.9 Hz, NH), 6.55–8.05 (14H, m,
2OPh and 4CHarom).
13C NMR (75.5 MHz, CDCl3): δC 47.05 (d, JPC
1
= 136.2 Hz, PCHCH), 53.39 and 53.53 (2s, 2OCH3),
53.80 (d, 2 JPC = 3.1 Hz, PCHCH), 114.71 and 117.03
3
(2s, 2CHarom), 120.00 (d, JCP = 4.8 Hz, 2CHortho),
13C NMR (75.5 MHz, CDCl3): δC 47.00 (d,
1 JPC = 138.5 Hz, PCHCH), 53.35 and 53.55 (2s,
3
120.71 (d, JCP = 4.5 Hz, 2CHortho), 126.60 (CHarom),
2
125.29 and 125.88 (2s, 2Cpara), 129.46 and 130.00 (2s,
4Cmeta), 133.58 and 135.97 (2s, CH and Carom), 143.88
2OCH3), 54.31 (d, JPC = 3.2 Hz, PCHCH), 112.77
3
(s, CHarom), 120.21 and 120.59 (2d, JPC = 4.5 Hz,
2
(s, Carom), 149.71 (d, JCP = 8.8 Hz, 2Cipso), 167.09
4Cortho), 125.57 and 125.96 (2s, 2Cpara), 125.98 (s,
CHarom), 129.73 and 130.00 (2s, 4Cmeta), 139.48 (s,
Carom), 149.61 and 149.84 (2d, 2 JPC = 8.8 Hz, 2 Cipso),
2
3
(d, JPC = 5.4 Hz, CO), 170.55 (d, JPC = 18.2 Hz,
CO). 31P NMR (121.5 MHz, CDCl3): δP 11.74.
Heteroatom Chemistry DOI 10.1002/hc

Synthesis of New Phosphonato Esters by Reaction between Triphenyl or Trialkyl Phosphite and Acetylenic Diesters 637
2OCH2CH3), 112.40 (s, CHarom), 120.21 and 120.35
151.87 (s, Carom), 168.08 (d, 2 JPC = 5.3 Hz, CO), 170.67
3
(d, 3 JPC = 18.2 Hz, CO). 31P NMR (121.5 MHz, CDCl3):
δP 11.29.
(2d, JPC = 4.6 Hz, 4Cortho), 125.61 and 125.85 (2s,
2Cpara), 126.32 (s, CHarom), 129.80 and 129.98 (2s,
2
Minor isomer (31%): 1H NMR (300.1 MHz,
4Cmeta), 139.06 (s, Carom), 149.68 (d, JPC = 8.3 Hz,
Cipso), 149.79 (d, 2 JPC = 8.7 Hz, Cipso), 151.25 (s, Carom),
CDCl3): δH 3.72 and 3.82 (6H, 2s, 2OCH ), 4.10 (1H,
3
2
3
dd, 3 JHH = 5.1, 2 JPH = 24.4 Hz, PCHCH), 5.06 (1H, m,
PCHCH), 5.50 (1H, d, 3 JHH = 8.6 Hz, NH), 6.55–8.05
(14H, m, 2OPh and 4CHarom).
165.92 (d, JPC = 5.2 Hz, CO), 169.55 (d, JPC = 7.2
Hz, CO). 31P NMR (121.5 MHz, CDCl3): δP 11.41.
13C NMR (75.5 MHz, CDCl3): δC 47.34 (d,
1 JPC = 136.1 Hz, PCHCH), 53.30 and 53.55 (2s,
Dimethyl 2-(2-amino-N-yl-benzoic acid)-3-
(diphenoxyphosphoryl)butandioate (5e)
2
2OCH3), 54.51 (d, JPC = 3.0 Hz, PCHCH), 112.33
3
Colorless crystalline; yield: 95% (0.49 g), mp = 152–
(s, CHarom), 120.28 and 120.56 (2d, JPC = 5.4 Hz,
154◦C. IR (KBr) (νmax, cm−1): 3297 (NH), 1750 and
4Cortho), 125.63 and 125.95 (2s, 2Cpara), 126.11 (s,
CHarom), 129.83 and 130.12 (2s, 4Cmeta), 139.48 (s,
+
=
=
1730 (C O), 12,890 (P O). MS (m/z, %): 513 (M ,
9), 453 (2), 421 (12), 376 (38), 137 (100), 77 (45).
Anal. Calcd for C25H24NO9P (513.43): C, 58.48; H,
4.71; N, 2.73. Found: C, 58.56; H, 4.63; N, 2.67. H
NMR (500.1 MHz, CDCl3): δH 3.75 and 3.90 (6H,
2
Carom), 149.67 and 149.96 (2d, JPC = 8.9 Hz, 2Cipso),
151.09 (s, Carom), 166.50 (d, 2 JPC = 5.2 Hz, CO), 170.08
(d, 3 JPC = 6.7 Hz, CO). 31P NMR (121.5 MHz, CDCl3):
δP 11.04.
1
3
2
2s, 2OCH ), 4.25 (1H, dd, JHH = 4.4, JPH = 25.0
3
3
3
Hz, PCHCH), 5.15 (1H, ddd, JHH = 4.4, JPH = 9.5,
Diethyl 2-(4-nitrophenylamino)-3-(diphenoxyp-
hosphoryl)butandioate (5d)
3 JHH = 10.4 Hz, PCHCH), 6.70 (14H, m, Ar), 8.80
(1H, d, JHH = 10.4 Hz, NH). 13C NMR (125.7 MHz,
3
Yellow powder; yield: 92% (0.50 g), mp = 112–114◦C.
CDCl3): δC 47.32 (d, 1 JPC = 137.3 Hz, PCHCH), 53.03
and 53.21 (2s, 2OCH3), 54.04 (s, PCHCH), 110.93,
112.62, 115.39, 116.63 (4s, C7H6NO2), 120.34, (d,
IR (KBr) (νmax, cm−1): 3368 and 3285 (2NH), 1730
=
=
and 1700 (C O), 1265 (P O). MS (m/z, %): 542
(M+, 2), 404 (25), 331 (54), 285 (52), 255 (73), 138
(100), 108 (54), 65 (81). Anal. Calcd for C26H27N2O9P
(542.14): C, 57.57; H, 5.02; N, 5.16. Found: C, 57.43;
H, 4.96; N, 5.22.
3 JCP = 4.4 Hz, 2CHortho), 120.79 (d, JCP = 4.4 Hz,
3
2CHortho), 125.24, 125.65 (2s, 2Cpara), 129.48 and
129.87 (2s, 4Cmeta), 132.48, 135.48 (2s, C7H6NO2),
2
2
149.94 (d, JCP = 8.3 Hz, Cipso), 150.04 (d, JCP
=
2
Major isomer (70%): 1H NMR (300.1 MHz,
8.3 Hz, Cipso), 166.78 (d, JPC = 4.7 Hz, CO), 171.25
CDCl3): δH 1.21 and 1.39 (6H, 2t, JHH = 7.1 Hz,
(d, JPC = 16.2 Hz, CO), 172.99 (s, CO2H). 31P NMR
3
3
2OCH2CH ), 4.17–4.31 (4H, m, 2OCH CH3), 4.38
(202.4 MHz, CDCl3): δP 11.76.
3
2
3
2
(1H, dd, JHH = 7.2, JPH = 16.4 Hz, PCHCH), 4.93
3
3
3
(1H, ddd, JHH = 3.6, JPH = 7.6, JHH = 10.7 Hz,
Diethyl 2-(2-triflourophenylamino)-3-(dipheno-
xyphosphoryl)butandioate (5f)
3
PCHCH), 5.75 (1H, d, JHH = 10.7 Hz, NH), 6.57–
8.08 (14H, m, 2OPh and 4CHarom).
13C NMR (75.5 MHz, CDCl3): δC 14.03 and 14.09
(2s, 2OCH2CH3), 47.10 (d, 1 JPC = 137.8 Hz, PCHCH),
54.41 (d, 2 JPC = 3.5 Hz, PCHCH), 62.50 and 62.85 (2s,
2 OCH2CH3), 112.79 (s, CHarom), 120.21 and 120.57
White powder; yield: 95% (0.51 g), mp = 92–93◦C. IR
−1
=
(KBr) (νmax, cm ): 3394 (NH), 1764 and 1734 (C O),
+
=
1264 (P O). MS (m/z, %): 537 (M , 83), 505 (21),
478 (100), 446 (35), 406 (9), 380 (13), 303 (26), 275
(31), 243 (10), 212 (16), 172 (20), 145 (13), 77 (49),
51 (13). Anal. Calcd for C25H23F3NO7P (537.42): C,
55.87; H, 4.31; N, 2.61. Found: C, 55.82; H, 4.22; N,
2.69. 1H NMR (500.1 MHz, CDCl3): δH 3.73 and 3.90
3
(2d, JPC = 4.4 Hz, 4Cortho), 125.51 and 125.92 (2s,
2Cpara), 126.06 (s, CHarom), 129.71 and 129.98 (2s,
2
4Cmeta), 139.46 (s, Carom), 149.91 (d, JPC = 9.1 Hz,
Cipso), 149.94 (d, 2 JPC = 9.0 Hz, Cipso), 152.06 (s, Carom),
2
3
3
2
167.54 (d, JPC = 5.3 Hz, CO), 170.11 (d, JPC = 18.2
Hz, CO). 31P NMR (121.5 MHz, CDCl3): δP 11.66.
Minor isomer (30%): 1H NMR (300.1 MHz,
(6H, 2s, 2OCH ), 4.21 (1H, dd, JHH = 4.0, JPH
=
3
3
3
25.2 Hz, PCHCH), 5.08 (1H, ddd, JHH = 4.0, JPH
3
= 9.1 Hz, JHH = 10.5 Hz, PCHCH), 5.89 (1H, d,
3
CDCl3): δH 1.21 and 1.29 (6H, 2t, JHH = 7.1 Hz,
3 JHH = 10.5 Hz), 6.79–7.49 (14H, m, Ar). 13C NMR
1
2OCH2CH ), 4.23–4.43 (4H, m, 2OCH CH3), 4.35
(125.7 MHz, CDCl3): δC 47.23 (d, JPC = 137.2 Hz,
3
2
3
2
(1H, dd, JHH = 3.6, JPH = 16.3 Hz, PCHCH), 5.02
PCHCH), 52.89 and 53.23 (2s, 2OCH3), 54.96 (d,
3
2
(1H, m, PCHCH), 5.46 (1H, d, JHH = 6.1 Hz, NH),
2 JPC = 3.0 Hz, PCHCH), 115.14 (q, JCF = 32.0 Hz,
6.57–8.08 (14H, m, 2OPh and 4CHarom).
C7H6F3N), 115.26, 117.82 (2s, C7H6F3N), 120.37 (d,
13C NMR (75.5 MHz, CDCl3): δC 13.95 and 14.03
(2s, 2 OCH2CH3), 47.51 (d, 1 JPC = 137.7 Hz, PCHCH),
54.68 (d, 2 JPC = 3.5 Hz, PCHCH), 62.67 and 62.75 (2s,
3 JCP = 4.0 Hz, 2CHortho), 120.62 (d, JCP = 4.0 Hz,
3
1
2CHortho), 124.82 (q, JCF = 272.6 Hz, CF3), 125.32
3
and 125.65 (2s, 2Cpara), 126.58 (q, JCF = 5.5 Hz,
Heteroatom Chemistry DOI 10.1002/hc

638 Marandi et al.
C7H6F3N), 129.47 and 129.82 (2s, 4Cmeta), 133.00 (s,
C, 54.76; H, 5.00; N, 5.55. Found: C, 54.87; H, 4.93;
N, 5.62.
2
C7H6F3N), 149.83(d, JCP = 9.6 Hz, Cipso), 149.71 (d,
2 JCP = 9.6 Hz, Cipso), 155.96 (s, C7H6F3N), 167.34 (d,
Major isomer (67%): 1H NMR (400.1 MHz,
3
2 JPC = 5.0 Hz, CO), 171.14 (d, JPC = 17.0 Hz, CO).
CDCl3): δH 1.35 and 1.37 (6H, 2s, 2CH ), 3.76 and
3
31P NMR (121.5 MHz, CDCl3): δP 11.72.
3.86 (6H, 2s, 2OCH ), 4.53 (1H, dd, 3 JHH = 11.5, 2 JPH
3
3
3
= 21.2 Hz, PCHCH), 5.70 (1H, dd, JHH = 11.5, JPH
= 5.3 Hz, PCHCH), 6.63–7.32 (10H, m, 2 OPh), 9.31
(1H, s, NH).
Dimethyl 2-[1-(diphenylmethylene)hydrazine-N-
yl]-3-(diphenoxyphosphoryl)butandioate (5g)
13C NMR (100.6 MHz, CDCl3): δC 24.40 and 24.70
Dark yellow viscous oil; yield: 93% (0.53 g), IR
1
(2s, 2CH3), 40.69 (d, JPC = 134.4 Hz, PCHCH),
(in CHCl3) (νmax, cm−1): 3317 (NH), 1746 and 1660
2
43.97 (d, JPC = 4.5 Hz, PCHCH), 53.28 and 53.60
+
=
=
(C O), 1277 (P O). MS (m/z, %): 572 (M , 2), 392
(15), 326 (13), 223 (20), 196 (52), 105 (100), 77 (88),
51 (40). Anal. Calcd for C31H29N2O7P (572.54): C,
65.03; H, 5.11; N, 4.89. Found: C, 64.97; H, 5.17;
N, 4.81.
3
(2s, 2OCH3), 60.34 (s, CMe2), 120.13 (d, JPC = 4.8
Hz, 2Cortho), 120.19 (d, 3 JPC = 4.9 Hz, 2Cortho), 123.75
(s, 2Cpara), 129.42 and 129.67 (2s, 4Cmeta), 149.47 (d,
2 JPC = 7.2 Hz, Cipso), 149.58 (d, JPC = 7.5 Hz, Cipso),
2
152.45 (CMe2CO), 156.66 (NCON), 166.65 (d, 2 JPC
=
Major isomer (56%): 1H NMR (300.1 MHz,
CDCl3): δH 3.72 and 3.79 (6H, 2s, 2 OCH ), 4.10 (1H,
7.6 Hz, CO), 168.12 (d, 3 JPC = 18.9 Hz, CO). 31P NMR
(161.9 MHz, CDCl3): δP 10.23.
s, NH), 4.16 (1H, dd, JHH = 5.4, JPH 3= 24.7 Hz,
PCHCH), 5.08 (1H, m, PCHCH), 6.77–7.84 (20H, m,
2OPh and 2Ph).
3
2
Minor isomer (33%): 1H NMR (400.1 MHz,
CDCl3): δH 1.35 and 1.37 (6H, 2s, 2CH ), 3.74 and
3
3
2
3.86 (6H, 2s, 2OCH ), 4.34 (1H, dd, JHH = 3.1, JPH
3
13C NMR (75.5 MHz, CDCl3): δC 47.40 (d, JPC
1
= 9.1 Hz, PCHCH), 5.62 (1H, br s, PCHCH), 6.63–
7.32 (10H, m, 2OPh), 9.03 (1H, s, NH).
= 137.3 Hz, PCHCH), 52.71 and 53.03 (2s, 2OCH3),
60.81 (d, 2 JPC = 3.2 Hz, PCHCH), 120.51 and 120.58
13C NMR (100.6 MHz, CDCl3): δC 24.40 and 24.70
(2s, 2CH3), 40.69 (d, 1 JPC = 134.4 Hz, PCHCH), 43.97
3
(2d, JPC = 5.4 Hz, 4Cortho), 125.32 and 125.66 (2s,
2Cpara), 128.77 (s, 4CHarom), 129.27 and 129.64 (2s,
4Cmeta), 130.33 (s, Carom), 131.43, 132.47, 138.05 and
2
(d, JPC = 4.5 Hz, PCHCH), 53.26 and 53.53 (2s,
3
2OCH3), 59.35 (s, CMe2), 120.42 (d, JPC = 4.7 Hz,
148.92 (4s, 6CHarom and 2Carom), 150.07 and 150.21
3
2Cortho), 120.60 (d, JPC = 4.5 Hz, 2Cortho), 125.67 (s,
2
=
(d, JPC = 9.4 Hz, Cipso), 156.43 (s, C N), 167.27 (d,
2Cpara), 129.84 and 129.88 (2s, 4Cmeta), 149.94 (d, 2 JPC
= 7.2 Hz, Cipso), 150.40 (d, 2 JPC = 7.5 Hz, Cipso), 152.53
(CMe2CO), 156.74 (NCON), 166.60 (d, 2 JPC = 6.6 Hz,
CO), 168.06 (d, 3 JPC = 18.5 Hz, CO). 31P NMR (161.9
MHz, CDCl3): δ 11.63.
2 JPC = 5.2 Hz, CO), 171.13 (d, JPC = 15.4 Hz, CO).
3
31P NMR (121.5 MHz, CDCl3): δP 11.62.
Minor isomer (44%): 1H NMR (300.1 MHz,
CDCl3): δH 3.66 and 3.75 (6H, 2s, 2OCH ), 4.03 (1H,
s, NH), 4.46 (1H, dd, JHH = 8.9, JPH 3= 22.4 Hz,
3
2
3
2
PCHCH), 4.91 (1H, dd, JHH = 8.9, JPH = 11.5 Hz,
PCHCH), 6.77–7.84 (20H, m, 2OPh and 2Ph).
Crystal Structure Determination
13C NMR (75.5 MHz, CDCl3): δC 47.55 (d, JPC
Crystallographic data for the structure were col-
lected at 100(2) K on an Oxford Diffraction (Ox-
fordshire, UK) Xcalibur diffractometer fitted with
graphite-monochromated Mo Kα radiation. Follow-
ing multi-scan absorption corrections and solution
by direct methods, the structure was refined against
F2 with full-matrix least squares using the pro-
gram SHELXL-97 [41]. The hydroxyl hydrogen atom
H(311) was allowed to refine without restraints.
All other H-atoms were added at calculated posi-
tions and refined by use of a riding model with
isotropic displacement parameters based on those
of the parent atoms. Anisotropic displacement pa-
rameters were employed throughout for the non-
hydrogen atoms.
1
= 138.7 Hz, PCHCH), 52.79 and 53.40 (2s, 2OCH3),
60.01 (d, 2 JPC = 3.3 Hz, PCHCH), 120.14 and 120.75
3
(2d, JPC = 4.7 Hz, 4Cortho), 125.27 and 125.50 (2s,
2Cpara), 128.77 (s, 4CHarom), 129.40 and 129.70 (2s,
4Cmeta), 130.47 (s, Carom), 131.45, 132.70, 138.41, and
147.68 (4s, 6CHarom and 2Carom), 150.00 and 150.14
2
=
(d, JPC = 7.4 Hz, Cipso), 158.11 (s, C N), 167.00 (d,
2 JPC = 4.7 Hz, CO), 171.84 (d, JPC = 14.3 Hz, CO).
3
31P NMR (121.5 MHz, CDCl3): δP 12.52.
Dimethyl 2-(4,4-dimethyl-2,5-dioxoimidazoli-
din-1-yl)-3-(diphenoxyphosphoryl)butandioate
(7)
Yellow viscous oil; yield: 91% (0.46 g), IR (in CCl4)
−1
=
(νmax , cm ): 3068 (NH), 1748 and 1590 (C O), 1204
=
Crystal Data
+
+
(P O). MS (m/z, %): 505 (M +1, 1), 504 (M , 2), 473
(2), 411 (41), 377 (2), 326 (100), 285 (9), 128 (27), 94
(92), 77 (61). Anal. Calcd for C23H25N2O9P (504.43):
C25H24NO9P, M = 513.42, monoclinic, space group
P21/n, a = 8.8905(3), b = 20.7227(7), c = 13.8954(5)
Heteroatom Chemistry DOI 10.1002/hc

Synthesis of New Phosphonato Esters by Reaction between Triphenyl or Trialkyl Phosphite and Acetylenic Diesters 639
◦
3
˚
˚
Noshiranzadeh, N.; Souldozi, A. Curr Org Chem
2008, 12, 59–82.
[22] Maghsoodlou, M. T.; Habibi Khorassani, S. M.;
Hazeri, N.; Nassiri, M. Phosphorus Sulfur Silicon
2006, 181, 1363.
[23] Maghsoodlou, M. T.; Hazeri, N.; Habibi-Khorassani,
S. M.; Saghatforoush, L.; Rofouei, M. K.; Rezaie, M.
Arkivoc 2006, xiii, 117.
A, β = 105.083(4) , V = 2471.83(15) A , Z = 4,
μ = 0.166 mm–1, 23,047 reflections collected, 6739
unique (R = 0.0652). Final R indices R = 0.0526,
int
1
wR2 = 0.0952 [I > 2σ I)]; R = 0.1238, wR2 = 0.1104
1
(all data). CCDC deposition code: 798758.
[24] Maghsoodlou, M. T.; Habibi-Khorassani, S. M.;
Rofouei, M. K.; Adhamdoust, S. R.; Nassiri, M.
Arkivoc 2006, xii, 145.
REFERENCES
[25] Maghsoodlou, M. T.; Habibi-Khorassani, S. M.;
Heydari, R.; Hassankhani, A.; Marandi, G.;
Nassiri, M.; Mossadegh, E. Mol Diversity 2007,
11, 87.
[1] Bagley, M. C.; Dale, J. W.; Bower, J. Chem Commun
2002, 1682.
[2] Li, Y. X.; Wang, S. H.; Li, Z. M.; Su, N.; Zhao, W. G.
Carbohydr Res 2006, 341,2867.
[26] Maghsoodlou, M. T.; Hazeri, N.; Habibi-Khorassani,
S. M.; Nassiri, M.; Marandi, G.; Afshari, G.;
Niroumand, U. J Sulfur Chem 2005, 26, 261.
[27] Saghatforoush, L.; Maghsoodlou, M. T.; Aminkhani,
A.; Marandi, G.; Kabiri, R. J Sulfur Chem 2006, 27,
583.
[28] Habibi-Khorassani, S. M.; Maghsoodlou M. T.;
Ebrahimi A.; Zakarianejad M.; Fattahi, M. J Solution
Chem 2007, 36, 1117.
[29] Habibi-Khorassani, S. M.; Maghsoodlou, M. T.;
Ebrahimi, A.; Roohi, H.; Zakarianejad, M.; Moradian,
M. Prog React Kinet Mech 2005, 30, 127.
[30] Habibi-Khorassani, S. M.; Maghsoodlou, M. T.;
Zakarianejad, M.; Kazemian, M. A.; Nassiri, M.;
Karimi, P. Heteroat Chem 2008, 19, 723.
[31] Yavari, I.; Anary-Abbasinejad, M.; Hossaini, Z. Org
Biomol Chem 2003, 1, 560.
[3] Tenorio, R. P.; Carvalho, C. S.; Pessanha, C. S.; de
Lima, J. G.; de Faria, A. R.; Alves, A. J.; de Melo, E.
J. T.; Goes, A. J. S. Bioorg Med Chem Lett 2005, 15,
2575.
[4] Kucukguzel, S. G.; Oruc, E. F.; Rollas, S.; Shahin, F.;
Ozbek, A. Eur J Med Chem 2002, 37, 197.
[5] Kato, T.; Ozaki, T.; Tamura, K.; Suzuki,Y.; Akima,
M.; Ohi, N. J Med Chem 1999, 442, 3134.
[6] Do¨mling, A. Chem Rev 2006, 106.
[7] Do¨mling, A.; Ugi, I. Angew Chem, Int Ed Engl 2000,
39, 3168.
[8] Toskoparan, B.; Ertan, M.; Kelicen, P.; Demirdamar,
R. Farmaco 1999, 30, 588.
[9] Jeanneau-Nicolle, E.; Benoti-Guyod, M.; Namil, A.;
Leclerc, G. J Med Chem 1992, 27, 115.
[10] Sayed, H. H.; Shamroukh, A. H.; Rashad, A. E. Acta
Pharm 2006, 56, 231.
[32] Breitmaier, E.; Voelter, W. Carbon-13 NMR Spec-
troscopy, 3rd ed.; VCH: NewYork, 1990, pp. 247–254.
[33] Mander, L. N. Stereochemistry of Organic Com-
pounds; Wiley: NewYork, 1994.
[34] Karplus, M. J Am Chem Soc 1963, 85, 2870.
[35] Hanoot, A. G.; Leeuw, F. A. M.; Altona, C. Tetrahe-
dron 1980, 36, 783.
[11] Coburn, R. A.; Glennon, R. A. J Pharm Sci 1973, 62,
1785.
[12] Engel, R. Chem Rev 1977, 77, 349.
[13] Arduago, A. J.; Stewart, C. A. Chem Rev 1994, 94,
1215.
[14] Pietrusiewiewiz, K. M.; Zabloka, M. Chem Rev 1994,
94, 1375.
[36] Holmes, R. R. Acc Chem Res 2004, 37, 746.
[37] Maryanoff, B. E.; Reitz, A. B. Chem Rev 1989, 89,
863.
[38] Yavari, I.; Kowsari, E. Dyes Pigm 2008, 77, 103.
[39] Rostami Charati, F.; Maghsoodlou, M. T.; Habibi-
Khorassani, S. M.; Makha, M. Tetrahedron Lett 2008,
49, 343.
[40] Maghsoodlou, M. T.; Rostami Charati, F.; Habibi-
Khorassani, S. M.; Ghasemzadeh, M.; Makha, M.
Chem Res 2008, 55.
[15] Bestmann, H. J.; Vostrowsky, O. Top Curr Chem
1983, 109, 85.
[16] Yavari, I.; Alizadeh, A. Tetrahedron 2001, 57,
9873.
[17] Yavari, I.; Adib, M.; Jahani-Moghaddam, F.; Bijan-
zadeh, H. R. Tetrahedron 2002, 58, 6901.
[18] Balaraman, E.; Kumaraswamy, K. C. Synthesis 2004,
3037.
[19] Kolodiazhnyi, O. I. Tetrahedron 1996, 52, 1855.
[20] Hughes, A. N. Heterocycles 1981, 15, 637.
[21] Ramazani, A.; Kazemizadeh, A. R.; Ahmadi, E.;
[41] Sheldrick, G. M. Acta Crystallogr A 2008, 64, 112.
Heteroatom Chemistry DOI 10.1002/hc