A practical method for synthesis of stable phosphorus ylides in the presence of polyacrylamide in aqueous media

Article abstract of DOI:10.1080/10426500801967914

Equation Presented Stable crystalline phosphorus ylides were obtained in good to excellent yields from the 1:1:1 addition reaction between triphenylphosphine, dialkyl acetylenedicarboxylates and -dicarbonyl or heterocyclic compounds such as, diethyl malon

Full text of DOI:10.1080/10426500801967914

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Phosphorus, Sulfur, and Silicon
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A Practical Method for
Synthesis of Stable Phosphorus
Ylides in the Presence of
Polyacrylamide in Aqueous
Media
Reza Heydari a , Malek Taher Maghsoodlou a & Razieh
Nejat Yami a
a Department of Chemistry, The University of Sistan
and Baluchestan, Zahedan, Iran
Published online: 24 Sep 2008.
To cite this article: Reza Heydari , Malek Taher Maghsoodlou & Razieh Nejat Yami
(2008) A Practical Method for Synthesis of Stable Phosphorus Ylides in the Presence
of Polyacrylamide in Aqueous Media, Phosphorus, Sulfur, and Silicon and the Related
Elements, 183:10, 2578-2583, DOI: 10.1080/10426500801967914
To link to this article: http://dx.doi.org/10.1080/10426500801967914
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Phosphorus, Sulfur, and Silicon, 183:2578–2583, 2008
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500801967914
A Practical Method for Synthesis of Stable Phosphorus
Ylides in the Presence of Polyacrylamide
in Aqueous Media
Reza Heydari, Malek Taher Maghsoodlou,
and Razieh Nejat Yami
Department of Chemistry, The University of Sistan and Baluchestan,
Zahedan, Iran
Stable crystalline phosphorus ylides were obtained in good to excellent yields from
the 1:1:1 addition reaction between triphenylphosphine, dialkyl acetylenedicarboxy-
lates and β-dicarbonyl or heterocyclic compounds such as, diethyl malonate, acetyl
acetone, 1, 3-dimethylbarbituric acid, meldrum’s acid, 2-benzoxazolinone, pyrrole-
2-carboxaldehyde, benzotriazole, 5-methyl benzotriazole, and 5-chloro benzotria-
zole, in the presence of polyacrylamide in water. The green and mild reaction con-
ditions, medium to short reaction time, low cost, ready preparation are the main
advantages of this method.
Keywords Acetylenic esters; water; triphenylphosphine; stable phosphorus
ylides; polyacrylamide
Received 15 November 2007; accepted 22 January 2008.
We gratefully acknowledge financial support from the Research Council of University
of Sistan and Balouchestan.
Address correspondence to Reza Heydari, Department of Chemistry, The Uni-
versity of Sistan and Baluchestan, P.O. Box 98135-674, Zahedan, Iran. E-mail:
heydari@chem.usb.ac.ir
2578

Synthesis of Phosphorus Ylides in Aqueous Media
2579
INTRODUCTION
Recently, organic reactions in water have attracted much attention
because water as a solvent is not only inexpensive and environmen-
tally benign, but also shows completely different reactivity to organic
solvents.1−5 Various reactions that are traditionally carried out in or-
ganic solvents have been equally successful or even more effective in
aqueous media.6−12 If water could also replace organic solvents more
often on the industrial scale, it would save money, increase the safety
of chemical facilities, and reduce stress on the environment. Another
advantage is that after the reaction, the organic and aqueous phases
separate, eliminating the need for complex isolation steps to obtain the
product. In recent years there has been increasing interest in the syn-
thesis of organophosphorus compounds having a carbon atom bonded
directly to the phosphorus atom.13−15 This interest has resulted from
the recognition of the value of such compounds in a variety of biological,
industrial, and chemical synthetic uses. A large number of methods
have appeared describing novel syntheses of organophosphorus com-
pounds. The preparation of phosphorus ylides generally involves the
initial addition of a desired phosphine to an alkyl halide to provide a
phosphonium salt. Subsequently, addition of a base to the salt affords
the required phosphorus ylide.14,16
Thus, the preparation of the required phosphorus ylide often needs
two steps that involve the formation of phosphonium salts as interme-
diates and the addition of a base to convert these salts to ylides. Tra-
ditionally, these steps often occur in organic solvents, such as diethyl
ether, tetrahydrofuran, and toluene. Phosphorus ylides have earlier
been prepared in several steps using a basic aqueous solution.17 The
mechanical generation of phosphonium salts and phosphorus ylides in
the solid state followed by the Wittig reaction in the absence of a sol-
vent has been described.18,19 In the course of our investigation devoted
to the development of synthetic methods for the preparation of organic
compounds using phosphorus compounds, we found that the addition of
polyacrylamide to water provided an efficient system for the synthesis
of stable phosphorus ylides in aqueous media.
RESULTS AND DISCUSSION
We found that the reaction of triphenylphosphine with acetylenic esters
(1) and β-dicarbonyl or heterocyclic compounds (2), in water (without
additives of organic solvents) afforded the corresponding stable phos-
phorus ylides (3) in good to excellent yields (Scheme 1).

2580
R. Heydari et al.
TABLE I Synthesis of Stable Phosphorus Ylides in the Presence of
Polyacrylamide in Water at Room Temperature
Entry
Z
Product
R
1
2
3a
3b
Me
Et
85
75
192–194
164–166
3
4
5
3c
3d
3e
Me
Et
t-Bu
85
76
85
174–175
165–166
146–148
6
7
8
3f
3g
3h
Me
Et
t-Bu
86
75
90
154–156
153-155
161–163
9
10
11
3i
3j
3k
Me
Et
t-Bu
89
78
90
181–183
163–165
182–183
12
13
14
3l
3m
3n
Me
Et
t-Bu
95
89
92
160–162
185–187
190–193
15
16
17
3o
3p
3q
Me
Et
t-Bu
83
71
85
178–180
154–156
191–193
18
19
20
3r
3s
3t
Me
Et
t-Bu
91
73
83
143—145
147–149
155–157
21
22
3u
3v
Me
Et
86
71
163–165
147–149
23
24
3w
3x
t-Bu
t-Bu
82
85
165–167
170–172
Based on the well-studied chemistry of trivalent phosphorus
nucleophiles,20,21 it is reasonable to assume that phosphorus ylide
(3) is formed due to the initial addition of triphenylphosphine to the
acetylenic ester (1) and concomitant protonation of the 1:1 adduct
by the β-dicarbonyl or heterocyclic compounds such as diethyl mal-
onate, acetyl acetone, 1,3-dimethylbarbituric acid Meldrum’s acid,
2-benzoxazolinone, pyrrole-2-carboxaldehyde, benzotriazole, 5-methyl

Synthesis of Phosphorus Ylides in Aqueous Media
2581
SCHEME 1
benzotriazole, and 5-chloro benzotriazole, to form phosphoranes (3)
were obtained in good to excellent yields. The results are summarized
in Table I.
The spectral data and physical properties of the phosphoranes 3a–x
were in agreement with those of literature reported.22−27
CONCLUSION
In conclusion, we showed that polyacrylamide could be used for a conve-
nient and rapid synthesis of organophosphorus compounds in aqueous
media. Although, the yields of corresponding products are not better
than those for organic solvents, but the reaction times are shorter and
water as a solvent has advantages, including its low cost, low flamma-
bility, and most important, that it is non-toxic.
EXPERIMENTAL
Dialkyl acetylenedicarboxylates, triphenylphosphine, diethyl mal-
onate, acetyl acetone, 1,3-dimethylbarbituric acid, Meldrum’s acid,
2-benzoxazolinone, pyrrole-2-carboxaldehyde, benzotriazole, 5-methyl
benzotriazole, and 5-chloro benzotriazole, were obtained from Fluka or
Merck companies. Melting points were measured on an Electrother-
mal 9100 apparatus. IR spectra were recorded on a Shimadzu IR-460
1
spectrometer (pellets with KBr). H NMR spectra were measured on
a Bruker DRX-500 AVANCE spectrometer instrument with CDCl3 as
solvent.

2582
R. Heydari et al.
Preparation of Stable Phosphorus Ylides—General Procedures
To a magnetically stirred solution of a C-H or N-H acid (1 mmol)
and polyacrylamide (0.0025 g) in water (10 mL), Ph3P (0.26 g, 1
mmol) was added. Dimethyl acetylenedicarboxylate (0.14 g, 1 mmol)
was added dropwise at room temperature over 10 min. After approxi-
mately 1–5 h of stirring, the solution was filtered and was washed with
dichloromethane. The solvent was evaporated under reduced pressure,
and the precipitate was thoroughly washed with cold diethyl ether.
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