Solvent-free conditions as an eco-friendly strategy for synthesis of organophosphorus compounds

Article abstract of DOI:10.1080/10426507.2012.690116

A series of diverse NH- and CH-acids are used for a one-pot synthesis of stable phosphorus ylides and 1,4-diionic organophosphorus compounds by trapping of the zwitterionic intermediate from the reaction between triphenylphosphine and dialkyl acetylenedic

Full text of DOI:10.1080/10426507.2012.690116

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Phosphorus, Sulfur, and Silicon and the
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Solvent-Free Conditions as an Eco-
Friendly Strategy for Synthesis of
Organophosphorus Compounds
Ghasem Marandi a , Niloufar Akbarzadeh Torbati b , Reza Heydari c
, Nourallah Hazeri c , Sayyed Mostafa Habibi-Khorassani d , Malek
Taher Maghsoodlou c , Belghais Adrom c , Brian W. Skelton e &
Mohamed Makha e
a Shahid Bakeri High Education Center of Miandoab, Urmia
University, Urmia, Iran
b Department of Inorganic Chemistry, Faculty of Science, The
University of Sistan and Baluchestan, Zahedan, Iran
c Department of Organic Chemistry, Faculty of Science, The
University of Sistan and Baluchestan, Zahedan, Iran
d Department of Physical Organic Chemistry, Faculty of Science, The
University of Sistan and Baluchestan, Zahedan, Iran
e Chemistry School of Biomedical, Biomolecular and Chemical
Science, University of Western Australia, Perth, Western Australia,
M313, Australia
Accepted author version posted online: 09 May 2012.Published
online: 10 Sep 2012.
To cite this article: Ghasem Marandi , Niloufar Akbarzadeh Torbati , Reza Heydari , Nourallah Hazeri ,
Sayyed Mostafa Habibi-Khorassani , Malek Taher Maghsoodlou , Belghais Adrom , Brian W. Skelton
& Mohamed Makha (2012) Solvent-Free Conditions as an Eco-Friendly Strategy for Synthesis of
Organophosphorus Compounds, Phosphorus, Sulfur, and Silicon and the Related Elements, 187:12,
1450-1461, DOI: 10.1080/10426507.2012.690116
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Phosphorus, Sulfur, and Silicon, 187:1450–1461, 2012
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2012.690116
SOLVENT-FREE CONDITIONS AS AN ECO-FRIENDLY
STRATEGY FOR SYNTHESIS OF ORGANOPHOSPHORUS
COMPOUNDS
Ghasem Marandi,1 Niloufar Akbarzadeh Torbati,2
Reza Heydari,3 Nourallah Hazeri,3 Sayyed Mostafa
Habibi-Khorassani,4 Malek Taher Maghsoodlou,3
Belghais Adrom,3 Brian W. Skelton,5 and Mohamed Makha5
1Shahid Bakeri High Education Center of Miandoab, Urmia University, Urmia,
Iran
2Department of Inorganic Chemistry, Faculty of Science, The University of Sistan
and Baluchestan, Zahedan, Iran
3Department of Organic Chemistry, Faculty of Science, The University of Sistan
and Baluchestan, Zahedan, Iran
4Department of Physical Organic Chemistry, Faculty of Science, The University of
Sistan and Baluchestan, Zahedan, Iran
5Chemistry School of Biomedical, Biomolecular and Chemical Science, M313,
University of Western Australia, Perth, Western Australia, Australia
GRAPHICAL ABSTRACT
CO2R
H
PPh3
H
Z
Z
3
CO2R
4
CO2R
C
solvent-free
r.t.
Ph3P
+
C
X
X
1
CO2R
R'
R'
R'
R'
N
N
N
N
2
O
O
X: O, S
5
O
C
O
CO2R
7
CH
RO2CHC
PPh3
Abstract A series of diverse NH- and CH-acids are used for a one-pot synthesis of stable phos-
phorus ylides and 1,4-diionic organophosphorus compounds by trapping of the zwitterionic
Received 25 December 2011; accepted 21 April 2012.
We gratefully acknowledge financial support from the Research Council of The University of Sistan and
Baluchestan, Iran.
Address correspondence to Ghasem Marandi, Shahid Bakeri High Education Center of Miandoab, Urmia
University, Urmia, Iran. E-mail: g.marandi@urmia.ac.ir
1450

SYNTHESIS OF ORGANOPHOSPHORUS COMPOUNDS
1451
intermediate fromthe reaction between triphenylphosphine and dialkyl acetylenedicarboxylates
under solvent-free conditions. The structural geometry for one of the products was confirmed
by single crystal X-ray diffraction analysis.
Supplemental materials are available for this article. Go to the publisher’s online edition of
Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.
Keywords Solvent-free conditions; acetylenic ester; Ph3P; stable phosphorus ylides; 1,4-
diionic compounds
INTRODUCTION
The design of new environmentally safe synthetic methodologies for preparation
of organic compounds is a major task for organic chemists.1–3 One strategy to achieve
this goal involves the development of reactions in which reactants are combined, without
any solvent, together.4,5 Among the proposed protocols for the reduction of solvent in
reactions, solvent-free conditions have a specific position. Hence, it can be argued that
“the best solvent is no solvent.”6 The solid-state technique often leads to a large reduction
in reaction time, increased yields, and easy work-up. This technique matches with green
chemistry protocols, and it may enhance the regio- and stereo-selectivity of reactions.6–8
Most often, phosphonium salts are prepared from the reaction between a desired phosphine
and an alky halide, and then addition of a base to the salt yields the required phosphorus
ylide.9,10 Also, they can be obtained by the Michael addition of a phosphorus nucleophile
to activated olefins.11–14 Traditionally, the preparation of the required phosphorus ylides
often occurs in organic solvents, such as diethyl ether or tetrahydrofuran. The mechanical
generation of phosphonium salts and phosphorus ylides in the solid state followed by the
Wittig reaction have been described in the absence of a solvent.15,16 To deploy the green
chemistry approaches in organic reactions, we were encouraged to use no solvent in our
works for the synthesis of stable phosphorus compounds.
RESULTS AND DISCUSSION
Reaction of malonitrile, ethyl cyanoacetate, benzanilide, indole, 2-methyl in-
dole, 2-benzoxazolinone, indazole, thiazoline-2-thiol, 1,2,3,4-tetrahydrocarbazole, and
1-(3-chlorobenzylidene)semicarbazide as NH-, CH-, and SH-acid source 3 with dialkyl
acetylenedicarboxylates, in the presence of triphenylphosphine, proceeds under solvent-
free conditions to generate stable phosphorus ylides 4 at room temperature (see Scheme 1).
Compounds 4 are stable solids whose structures are fully characterized and supported by
spectroscopic data.
CO2R
CO2R
C
C
H
Z
CO2R
H
Ph3P
solvent-free
r.t.
PPh3
CO2R
Z H
+
Ph3P
+
+
Z
RO2C
1
3
CO2R
4
2
Scheme 1
1
The H, 13C, and 31P NMR spectra of ylides 4a–v are consistent with the presence
of two isomers. The ylide moieties of these compounds are strongly conjugated with the

1452
G. MARANDI ET AL.
adjacent carbonyl group, and rotation around the partial double bond in (E)-4 and (Z)-4
geometrical isomers is slow on the NMR time scale at ambient temperature (Table 1).17–24
The assignment of 4-(E)- and 4-(Z)-rotamers as the major and minor components
1
in phosphorus ylides have been reported previously in the literature.25–27 The H NMR
Table 1 Synthesis of stable phosphorus ylides in solvent-free conditions at room temperature
Entry
1
Z
Product
R
Yield (%)
96
mp (◦C)
182–185
mp (◦C)ref
182–18520
4a
Me
Et
NC
CN
2
3
4
4b
4c
4d
94
95
94
169–172
158–161
142–145
169–17220
158–16020
143–14520
t-butyl
Me
O
NC
Ph
OEt
Ph
5
6
7
4e
4f
4g
Et
t-butyl
Me
92
95
90
120–123
144–147
180–183
120–12320
144–14620
182–18421
O
N
8
9
10
4h
4i
4j
Et
t-butyl
Me
83
93
93
183–185
189–192
152–155
183–18521
190–19221
154–15622
N
S
S
11
12
13
4k
4l
4m
Et
t-butyl
Me
90
95
95
115–117
104–106
160–162
113–11522
105–10722
163–16423
O
N
O
14
15
16
4n
4o
4p
Et
t-butyl
Me
89
92
95
155–157
189–192
198–200
158–15923
189–19023
198–20014
N
17
18
19
4q
4r
4s
Et
t-butyl
t-butyl
89
92
92
136–138
158–160
188–191
134–13614
158–16014
188–19014
CH3
N
20
21
4t
t-butyl
t-butyl
92
89
164–166
120–123a
165–16724
N
N
4u
–
N
22
4v
Me
93
163–166a
–
O
N
H2N
N
Cl
aNew compounds.

SYNTHESIS OF ORGANOPHOSPHORUS COMPOUNDS
1453
spectrum of compound 4m exhibits two sharp lines (δ 3.17 and 3.84) arising from the
methoxy group in the Z-rotamer and two single sharp resonances at 3.74 and 3.89 ppm for
methoxy groups in the E-rotamer. The shift at 3.17 of the methoxy group of the Z-rotamer
is shielded, due to the anisotropic effect of the phenyl groups of triphenylphosphine. This
effect confirms why the 4-E and 4-Z rotamers could appear as the minor and major forms,
respectively, as reported in the Experimental section (available online in the Supplemental
Material).
1
The H NMR spectra of the synthesized ylides exhibit the E/Z proportion of the
ylides. The major and minor rotamers of these ylides are rapidly interchangeable at room
temperature, and for this reason, the separation of E- and Z-isomers is impossible and we are
unable to perform single crystal X-ray structural analysis. However, in t-butyl derivatives,
because of the bulky group, t-butyl, one of the rotamers, (Z-isomer) is produced in such
an excellent ratio (over 95%) that we are able to perform single crystal X-ray structural
analysis.
All ylides from the reaction between triphenylphosphine and acetylenic diesters in
the presence of CH-, NH-, or SH-acids exist as E/Z rotamers. A major factor for the
1
determination of E/Z rotamers is the abundance (integration) of these rotamers in the H
and 13C NMR spectrum.
Explicit structural elucidation of resulting phosphorus ylide was accomplished by
single crystal X-ray diffraction (Figure 1).
On the basis of the results obtained from X-ray crystallography,28 it is noticeable
that the adjacent carbonyl group in the ylide moiety of compound 4o (C321 O321, see
Figure 1) has a resonance with C32 P1 bond. In the present work, single crystal X-ray
diffraction of stable phosphorus ylide 4o (prepared from solution involving 95% of one
isomer) recognizes this as the Z-structure for this isomer since the X-ray crystal structure
indicates that the tert-butoxy group along with triphenylphosphine has been placed on the
same side of the carbon–carbon double bond (see Scheme 2 and Figure 1).
Crystallographic data and the refinement procedures are given in Table 2 and also,
selected bond lengths, bond angles, and torsion angles of compound 4o are listed in Tables 3
and S1 (available online in Supplemental Materials).
Figure 1 ORTEP representation of the compound 4o (thermal ellipsoids are at the 50% probability level).

1454
G. MARANDI ET AL.
OBut
O
O
Ph3P
Ph3P
OBut
ButO2C CH
N
ButO2C CH
N
O
O
O
O
E-isomer
Z-isomer
Minor
Major
Scheme 2
On the other hand, the synthesis of stable 1,4-diionic phosphorus compounds A and B
from the reaction between triphenylphosphine and ethyl propiolate in the presence of CH-
acids has been described previously.29–34 With the purpose of the preparation of betaines,
having two vicinal stereogenic centers, such as B (see Scheme 3, previous work),29,31 the
reaction between triphenylphosphine 1 and dialkyl acetylenedicarboxylates 2 with 1,3-
diethyl-2-thiobarbituric acid 5 was undertaken for the generation of 1,4-diionic 7 while
Table 2 Crystallographic data and structure refinement details for compound 4o
Compound
4o
Empirical formula
Formula weight
C37H38NO6P
623.65
Crystal system/space group
Monoclinic P21/n
11.5967(7)
a (Å)
b (Å)
c (Å)
17.5150(10)
16.6369(7)
α (◦)
90◦
β (◦)
67.719(4)◦
γ (◦)
90◦
V (Å3)
Z
3348.5(3) Å3
4
Dcalc (g/cm3)
1.237 mg/m3
0.128 mm−1
0.44 × 0.21 × 0.18 mm3
Colorless hexagonal rod
100(2)
µ (mm−1
)
Crystal size (mm)
Color/shape
Temp (K)
Theta range for collection
Reflections collected
Independent reflections
Data/restraints/parameters
Goodness of fit on F2
Final R1, wR2a (obs. data)
Final R1, wR2a (all data)
Largest difference peak/hole
2.92–32.27◦
41,153
11,138 [R(int) = 0.0554]
4870/0/412
0.882
0.0453, 0.0914
0.0842, 0.0982
0.502/−0.319
aR1 = ꢀꢁFo| − |Fcꢁ/ꢀ|Fo|, wR2 = [ꢀ(w(Fo2 − Fc2)2)/ꢀw(Fo2)2]1/2.

SYNTHESIS OF ORGANOPHOSPHORUS COMPOUNDS
1455
Table 3 Selected bond lengths (Å) and bond angles (◦) for compound 4o
111.24(10)
O(322)–C(321)–C(32)
1.2263(14)
O(321)–C(321)
122.27(11)
126.48(11)
118.03(9)
121.15(9)
119.72(10)
108.92(9)
124.20(12)
109.19(10)
O(321)–C(321)–O(322)
O(321)–C(321)–C(32)
P(1)–C(32)–C(321)
P(1)–C(32)–C(31)
C(31)–C(32)–C(321)
N(3)–C(31)–C(311)
O(311)–C(311)–C(31)
O(312)–C(311)–C(31)
1.3702(14)
1.7230(12)
1.4198(17)
1.4990(17)
1.4715(15)
1.5387(18)
1.1966(16)
1.3324(15)
O(322)–C(321)
P(1)–C(32)
C(32)–C(321)
C(31)–C(32)
N(3)–C(31)
C(31)–C(311)
O(311)–C(311)
O(312)–C(311)
stable phosphorus ylides 4 were obtained from reactions between 1, 2, and 3 in excellent
yields (see Scheme 1).
The thiobarbituric acid moiety and its derivatives have important pharmaceutical
property and have been used for medicinal chemistry purposes.35
O
O
O
O
CH3
N
O
N
CH3
Ph3P CH2
CH
EtO2C
Ph3P CH2
CH
EtO2C
O
O
CH3
CH3
B
A
Previous work
S
CO2R
Et
Et
O
RO2C
Ph3P
C
N
N
solvent free
+
PPh3
+
C
CO2R
O
1
CO2R
2
5
S
S
Et
Et
O
S
N
N
Et
Et
N
H
RO2C
Ph3P
N
H
[1,3] H shift
Et
Et
O
N
N
O
C
O
C
O
CO2R
CH
O
CO2R
RO2CHC
CH
CO2R
RO2CC
PPh3
7
PPh3
6
S
Et
Et
O
N
N
O
P
H
CO2R
H
CO2R
8
not formed
Scheme 3

1456
G. MARANDI ET AL.
Table 4 Synthesis of 1,4-diionic phosphorus compounds in solvent-sfree conditions at room temperature
Entry
Z
Product
R
Yield (%)
mp (◦C)
mp (◦C)
1
2
3
7a
7b
7c
Me
Et
t-butyl
92
90
93
160–163
162–164
176–179
160–16230
162–16430
176–17830
4
5
6
7d
7e
7f
Me
Et
t-butyl
90
83
93
159–161
153–155
159–162
153–15829
151–15629
162–16429
O
H3C
O
CH3
O
N
N
The reaction between 1, 2, and 5 produces the hitherto unknown butanedioates 7a–f
in 90–93% yield. All the compounds are stable crystalline solids whose structures are
fully supported by infrared (IR) and 1H NMR spectra as well as melting points (see Table
4). Structure 8 with an additional six-membered ring as an alternative structure instead
1
of 7 is unlikely because it requires several chemical shift coincidences in the H and 13C
NMR spectra, and hence, we would expect to see a doublet at about δ 160 for the C–O–P
moiety in the 13C NMR spectra.29–37 On the basis of the chemistry of trivalent phosphorus
nucleophiles9–14,17 it is reasonable to assume compound 7 results from the initial addition
of triphenylphosine to the acetylenic ester and subsequent protonation of the 1:1 adduct by
CH-acid 5. Then, the positively charged ion is attacked by the enolate anion of the CH-acid
to generate ylide 6. Compound 6, under the reaction conditions, apparently isomerizes to
produce the 1,4-diionic compound 7.
1
The H NMR (300 MHz) spectra of compounds 7a–f displayed signals for vicinal
methine protons at δ 4.81–5.91, which appear as two sets of double doublets for the
major and minor diastereoisomers. The vicinal proton–proton coupling constant (3JHH
)
as a function of torsion angle can be obtained from the Karplus equation.38,39 Typically,
3
Jgauche varies between 1.5 and 5 Hz and Janti between 9 and 14 Hz. Observation of JHH
10.2–12.1 Hz for the vicinal protons in major and minor diastereoisomers of compounds
7a–f indicates an antiarrangement for these protons. The assignments of the (2S∗, 3S∗)-7
and (2R∗, 3S∗)-7 configurations of 7a–f are based on the triple-bond carbon–phosphorus
coupling, 3JPC. Vicinal carbon–phosphorus coupling depends on configuration, as expected,
trans couplings being larger than cis ones. The Karplus relation can be derived from the
data for organophosphorus compounds with tetra- and penta-valent phosphorus.40,41
On the basis of the reported literature,38–42 it is postulated that phosphorus ylide 4
results from the initial addition of triphenylphosphine to the acetylenic ester and subsequent
protonation of the 1:1 adduct by the NH- and CH-acids to form phosphoranes 4 (see
Scheme 1).
In conclusion, we have found that the reaction between dialkyl acetylenedicar-
boxylates and 1,3-dimethylbarbituric acid, 1,3-diethyl-2-thiobarbituric acid, malononitrile,
ethyl cyanoacetate, benzanilide, indole, 2-methyl indole, 2-benzoxazolinone, indazole,
thiazoline-2-thiol, 1,2,3,4-tetrahydrocarbazole, and 1-(3-chlorobenzylidene)semicarbazide

SYNTHESIS OF ORGANOPHOSPHORUS COMPOUNDS
1457
in the presence of triphenylphosphine leads to the facile synthesis of highly function-
alized 1,4-diionic organophosphorus compounds 7a–f and also stable phosphorus ylides
3a–t in excellent yields. In addition, our reported work carries advantages because in
comparison with other procedures with low yield, prolonged reaction time, use of excess
reagents/catalyst, and use of toxic organic solvents, this methodology provides for improved
yield, short reaction time, and safe reaction condition.
EXPERIMENTAL
Dialkyl acetylenedicarboxylates, 1,3-dimethylbarbituric acid, 1,3-diethyl-2-
thiobarbituric acid, malonitrile, ethyl cyanoacetate, benzanilide, indole, 2-methyl indole,
2-benzoxazolinone, indazole, thiazoline-2-thiol, 1,2,3,4-tetrahydrocarbazole, and triph-
enylphosphine were purchased from Fluka (Buchs, Switzerland) and used without further
purification. Melting points and IR spectra of all compounds were obtained using an
Electrothermal 9100 apparatus and a Shimadzu IR-460 spectrometer, respectively. Also,
the 1H, 13C, and 31P NMR spectra were recorded on a BRUKER DRX-300 AVANCE spec-
trometer at 300.1, 75.5, and 121.5 MHz, respectively. The X-ray diffraction measurements
of compound 4o were obtained using an Oxford Diffraction Gemini diffractometer 100K
(Mo-Kα radiation, graphite monochromator, λ = 0.71073 Å).
General Procedures for Preparation of Stable Phosphorus Ylides
(Exemplified by 4a)
In a mortar, a mixture of malonitrile (0.06 g, 1 mmol) and triphenylphosphine
(0.26 g, 1 mmol) was crushed vigorously to give a homogeneous mass, and then dimethyl
acetylenedicarboxylate (0.14 g, 1 mmol) was added dropwise. Thereafter, the mixture
was thoroughly grounded with a pestle at room temperature for 30 min until the reaction
was completed by thin-layer chromatography (TLC) monitoring. The precipitate was thor-
oughly washed with diethyl ether (2 × 3 mL) and recrystallized from ethyl acetate to obtain
compound (4a).
Di-tert-butyl 2-(1,2,3,4-tetrahydrocarbazole-N-yl)-
3-(triphenylphosphoranylidene)butanedioate (4u)
◦
White powder, yield: 0.62 g (95%). mp 120–123 C, IR (KBr) (vmax, cm−1): 1714
and 1622 (s, 2 C O). MS (m/z,%): 659 (M+, 3), 527 (30), 490 (24), 377 (100), 262 (65),
183 (77), 108 (34), 57 (19), 44 (40). Anal calcd. for C42H46NO4P (659.79): C, 76.46; H,
7.03; N, 2.12%; Found: C, 76.33; H, 7.11; N, 2.07%.
1
Major isomer (Z)-4u: H NMR (300.1 MHz, CDCl3): δ 1.08 and 1.61 (18H, 2s,
2OCMe3), 1.69–1.73 (4H, m, 2CH2, C12H12N), 2.62–2.66 (4H, m, 2CH2, C12H12N), 4.85
(1H, br s, P C-CH), 6.79–7.74 (2H, m, 2CH, C12H12N), 7.68–7.75 (2H, m, 2CH, C12H12N),
7.39–7.61 (15H, m, 3C6H5). 13C NMR (75.5 MHz, CDCl3): δ 21.09, 22.23, 22.96, and
1
23.50 (4s, 4CH2, C12H12N), 28.32 and 28.54 (2s, 2OCMe3), 40.72 (d, JPC = 122.9 Hz,
P C), 58.53 (d, 2JPC = 15.9 Hz, P C-CH), 77.43 and 80.19 (2s, 2OCMe3), 108.80, 109.23,
116.63, 116.96, 117.82, and 119.48 (6s, 4CH, and 2C, C12H12N), 127.72 (d, 1JPC = 91.1 Hz,
Cipso), 128.44 (d, 3JPC = 12.2 Hz, Cmeta), 128.59 (s, C, C12H12N), 131.77 (Cpara), 133.64

1458
G. MARANDI ET AL.
2
2
(d, JPC = 9.6 Hz, Cortho), 136.16 (s, C, C12H12N), 168.29 (d, JPC = 10.9 Hz, P-C C),
171.14 (d, 3JPC = 15.4 Hz, C O). 31P NMR (121.5 MHz, CDCl3): δ 23.73 (Ph3P+-C).
Dimethyl 2-[2-(3-chlorobenzylidene)hydrazinecarboxamide-1-yl]-
3-(triphenylphosphoranylidene)butanedioate (4v)
Pale white powder, yield: 0.54 g (90%). mp 163–166 ◦C, IR (KBr) (vmax, cm−1): 3276
and 3205 (NH2), 1758, 1687, and 1633 (s, 3C O). MS (m/z,%): 603 (M+ + 2, 1), 601
(M+, 4), 570 (7), 542 (2), 538 (3), 523 (6), 428 (14), 376 (33), 262 (13), 183 (30), 108 (11),
77 (100). Anal calcd. for C32H29ClN3O5P (602.02): C, 63.84; H, 4.86; N, 6.98%; Found:
C, 63.96; H, 4.73; N, 7.05%.
Major isomer (Z)-4v (80%): 1H NMR (300.1 MHz, CDCl3): δ 3.05 and 3.80 (6H, 2s,
2OCH3), 5.33 (2H, br s, NH2), 5.76 (1H, d, 3JPH = 16.6 Hz, P C-CH), 7.38–7.61 (18H,
m, 3CHchlorophen, and 3C6H5), 7.72 (1H, s, CHchlorophen), 8.42 (1H, s, N = CH). 13C NMR
1
(75.5 MHz, CDCl3): δ 38.03 (d, JPC = 125.3 Hz, P C), 49.23 and 52.62 (2s, 2OCH3),
57.76 (d, 2JPC = 15.4 Hz, P C-CH), 125.87 (s, CHchlorophen), 126.02 (d, 1JPC = 91.7 Hz,
Cipso), 128.73 (d, 3JPC = 12.3 Hz, Cmeta), 129.04, 129.84, 131.90 (3s, 3CHchlorophen), 132.16
2
(Cpara), 133.50 (d, JPC = 9.7 Hz, Cortho), 134.62 and 137.84 (2s, 2Cchlorophen), 146.50 (s,
C N), 156.10 (s, CONH2), 169.25 (d, 2JPC = 12.6 Hz, P-C C), 171.99 (d, 3JPC = 16.4 Hz,
C O). 31P NMR (121.5 MHz, CDCl3): δ 23.03 (Ph3P+-C).
1
Minor isomer (E)-4v (20%): H NMR (300.1 MHz, CDCl3): δ 3.79 and 3.80 (6H,
2s, 2OCH3), 4.58 (2H, br s, NH2), 5.73 (1H, d, 3JPH = 15.8 Hz, P C-CH), 7.39–7.67
(18H, m, 3CHchlorophen, and 3C6H5), 8.07 (1H, s, CHchlorophen), 8.34 (1H, s, N = CH). 13
C
1
NMR (75.5 MHz, CDCl3): δ 37.19 (d, JPC = 125.3 Hz, P C), 49.18 and 52.62 (2s,
2OCH3), 57.64 (d, 2JPC = 15.3 Hz, P C-CH), 125.67 (d, 1JPC = 92.9 Hz, Cipso), 126.15
(s, CHchlorophen), 128.50 (d, 3JPC = 12.2 Hz, Cmeta), 129.28 and 129.76 (2s, 2CHchlorophen),
132.03 (Cpara), 133.78 (d, 2JPC = 8.4 Hz, Cortho), 134.59 and 137.40 (2s, 2Cchlorophen), 145.88
2
3
(s, C N), 154.11 (s, CONH2), 169.03 (d, JPC = 12.1 Hz, P-C C), 171.53 (d, JPC
16.3 Hz, C O). 31P NMR (121.5 MHz, CDCl3): δ 22.77 (Ph3P+-C).
=
General Procedures for Preparation of 1,4-diionic Compounds
(Exemplified by 7a)
In a mortar, a mixture of 1,3-diethyl-2-thiobarbituric acid (0.20 g, 1 mmol) and
triphenylphosphine (0.26 g, 1 mmol) was crushed vigorously to give a homogeneous mass,
and then dimethyl acetylenedicarboxylate (0.14 g, 1 mmol) was added dropwise and the
mixture was thoroughly ground with a pestle at room temperature for 30 min until the
reaction was complete by TLC monitoring. The precipitate was thoroughly washed with
diethyl ether (2 × 3 mL) and recrystallized from (dry ethyl acetate/n-hexane 95:5) to obtain
compound (7a).
Crystal Structure of 4o
Crystallographic data and the refinement procedures are given in Table 1. The single
crystals were grown from a CHCl3/Et2O solution. Crystallographic data for the structure
were collected at 100(2) K on an Oxford Diffraction Xcalibur diffractometer fitted with
graphite-monochromated Mo-Kα (λ = 0.71073 Å) radiation. The structure was solved by

SYNTHESIS OF ORGANOPHOSPHORUS COMPOUNDS
1459
using direct methods and refined by full-matrix least squares on F2 (SHELXL-97).28 Ab-
sorption correction, data collection, cell refinement, and data reduction have been carried
out using Oxford Diffraction Ltd.43 ORTEP (molecular graphics)44 and WinGX (publica-
tion material).45 All H-atoms were added at calculated positions and refined by using a
riding model with isotropic displacement parameters based on the isotropic displacement
parameter of the parent atom. Anisotropic displacement parameters were employed for all
non-H atoms.
Supplementary Data
CCDC 760455 contains the supplementary crystallographic data for this paper. These
data can be obtained free of charge from the Cambridge Crystallographic Data Center.
Copies of the data can be obtained, free of charge, on application to CCDC, 12 Union Road,
Cambridge CB2 1EZ, UK, (fax: +44-(0)1223–336033, E-mail: deposit@ccdc.cam.ac.uk),
or via http://www.ccdc.cam.ac.uk/data request/cif.
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