A simple and an efficient method for preparation of new phosphorus ylides containing several functional groups using aryl thiourea

Article abstract of DOI:10.1080/10426500701542890

New phosphorus ylides were prepared in a convenient way using the addition of Pb(OAc)2 to aryl thiourea followed by condensation of the resulted compounds with acetylenic esters in the presence of triphenylphosphine. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/10426500701542890

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Phosphorus, Sulfur, and Silicon
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A Simple and an Efficient
Method for Preparation of New
Phosphorus Ylides Containing
Several Functional Groups
Using Aryl Thiourea
Mohammad Reza Islami a & Moazameh Yazdi Rouh-
Alamini a
a Department of Chemistry , Shahid Bahonar
University of Kerman , Kerman, Iran
Published online: 03 Dec 2007.
To cite this article: Mohammad Reza Islami & Moazameh Yazdi Rouh-Alamini (2007) A
Simple and an Efficient Method for Preparation of New Phosphorus Ylides Containing
Several Functional Groups Using Aryl Thiourea, Phosphorus, Sulfur, and Silicon and the
Related Elements, 182:12, 2919-2924, DOI: 10.1080/10426500701542890
To link to this article: http://dx.doi.org/10.1080/10426500701542890
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Phosphorus, Sulfur, and Silicon, 182:2919–2924, 2007
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500701542890
A Simple and an Efficient Method for Preparation of New
Phosphorus Ylides Containing Several Functional Groups
Using Aryl Thiourea
Mohammad Reza Islami
Moazameh Yazdi Rouh-Alamini
Department of Chemistry, Shahid Bahonar University of Kerman,
Kerman, Iran
New phosphorus ylides were prepared in a convenient way using the addition of
Pb(OAc)2 to aryl thiourea followed by condensation of the resulted compounds with
acetylenic esters in the presence of triphenylphosphine.
Keywords Acetylenic compounds; phosphorus ylides; thiourea
INTRODUCTION
The synthesis and chemistry of phosphorus ylides have been attracted
considerable attention due to their applications in the preparation of
organic compounds.1–4 Also, these compounds are an interesting class
of materials that have been used as building blocks in the synthe-
sis of heterocyclic systems such as pyrazoloisoindole, pyrrolizine and
pyrroloisoindole derivatives.5–7 Some stable phosphorus ylides were
used as precursors in the preparation of drugs.8 On the other hand, most
of the phosphorus ylides are unstable systems and they are known to
react easily with other compounds such as, halogens,9,10 peroxyacids,11
and carbonyl compounds.12–15
In recent years, the synthesis of succinic esters connected to phos-
phorus atom has drawn much more attention.16–22 Since the synthetic
application of these compounds has increased enormously in organic
synthesis, we now wish to report a method for the synthesis of new
phosphorus ylides containing several functional groups by reaction of
Received May 5, 2007; accepted June 5, 2007.
The authors express appreciation to Shahid Bahonar University for generous financial
support by a Grant-in-Aid for Scientific Research.
Address correspondence to Mohammad Reza Islami, Department of Chemistry,
Shahid Bahonar University of Kerman, P.O. Box 76169-133, Kerman, Iran. E-mail:
mrislami@mail.uk.ac.ir
2919

2920
M. R. Islami and M. Z. Rouh-Alamini
Pb(OAc)2 with aryl thiourea and then condensation of the resulted com-
pounds with acetyletic esters in the presence of triphenylphosphine as
a good nucleophile.
RESULTS AND DISCUSSION
At first, N-aryl cyanamides were obtained from the reaction between N-
phenyl or N-naphthyl urea and Pb(OAc)2 in the presence of potassium
hydroxide solution as a base under reflux23 (Scheme 1).
SCHEME 1
The results presented here are based on the proposed sequence below
(Scheme 2). It is known that the reaction of acetylenic esters and Ph3P
produces the carbene-ylide intermediate I which is sufficiently stabi-
lized by resonance.24,25 Thus, compounds 3a–c are apparently obtained
from the initial addition of triphenylphosphine as a good nucleophile
to acetylenic esters as a Michael acceptor26 and concomitant protona-
tion of the carbene-ylide intermediate I by the NH-acid. Then positively
charged ion is attacked by the nitrogen of the conjugated base of the

Phosphorus Ylides Using Aryl Thiorea
2921
SCHEME 2
NH-acid to form stable phosphorus ylides containing several functional
groups 3.
The product structures 3a–c were identified by IR, 1H, and 13C NMR
1
spectra. The H NMR and 13C NMR spectral data of new ylides 3a–c
exhibited a mixture of two conformational isomers. The ylide moiety
of these compounds is strongly conjugated with the adjacent carbonyl
group and rotation about the partial double bond in 3-(E), 3-(Z) geo-
metrical isomer is low on the NMR time scale at ambient temperature
(Scheme 2). Conformational isomers in phosphoranes have been previ-
ously established and reported in the literature.27–29
Insertion of nitrogen in the chain was characterized by disappear-
ance of band at near 3300 cm−1 of N H and appearance of new peaks
1
near 1740 and 1645 cm−1 for C O stretching. The H NMR spectra of
3a showed four sharp signals due to methoxy protons of ester groups

2922
M. R. Islami and M. Z. Rouh-Alamini
at δ = 3.18, 3.62, 3.72, and 3.75 ppm. Methine protons appeared as two
doublet peaks at δ = 4.12 and 4.14 ppm for the Z and E geometrical
isomers. The aromatic protons appeared as a multiplet at δ = 6.56–
7.44 ppm. The 13C NMR spectrum of 3a displayed signals in agreement
with the mixture of two geometrical isomers of Z and E. Although the
presence of the 31P nucleus has complicated both the 1H and 13C NMR
spectra of 3a, it helps in assignment of signals by long range spin-spin
couplings with 1H and 13C nuclei.
1
The H and 13C NMR spectra of compound 3b are similar to those
of 3a, except for the signals from the aromatic ring of naphthaline,
which appear as characteristic resonance lines with the corresponding
chemical shifts. The 1H and 13C NMR spectroscopic data for compounds
3c are also consistent with the proposed structures.
In conclusion, we have presented an efficient synthetic method for
formation of new stable phosphorus ylides. The simplicity of experimen-
tal procedure and availability of the starting materials thus render this
method, an experimental attractive approach for the synthesis of these
compounds.
EXPERIMENTAL
All common reagents and solvents were used as obtained from com-
1
mercial suppliers without further purification. The H, and 13C NMR
spectra were recorded on a Bruker BRUKER DRX-500 AVANCE (1H
at 500 MHz, and 13C at 125.77 MHz,). Melting points were obtained
on a Gallenkamp melting point apparatus and are uncorrected. Ele-
mental analyses for C, H and N for compound 3c as an example were
performed by University of Tarbiat Moalem using a Heracus CHN-O-
Rapid analyzer. IR spectra were measured on a Mattson 1000 FT-IR
spectrometer. Phenyl cyanamide 1a and Naphthyl cyanamide 1b were
obtained as described in the literature.23
Dimethyl 2-(cyanoanilino)-3-(1,1,1-triphenyl-λ5
phosphanylidene) Succinate (3a)
At ambient temperature (0.24 ml, 2 mmol) of dimethyl acetylenedicar-
boxylate was added dropwise to a stirred solution of (0.53 g, 2 mmol)
of triphenylphosphine and (0.24 g, 2 mmol) of phenyl cyanamide in a
10 mL ethyl acetate. After the addition was complete (approximately
60 minutes), the mixture was stirred for another 10 h and filtered. The
solid collected in the filter was washed thoroughly with ethyl acetate
to give a white powder. (0.81 g, m.p. 132–134◦C, yield 76%); IR (KBr)
1
(νmax, cm−1): 2237 (CN), 1741 and 1666 (C O). Isomer (E) (57%) H

Phosphorus Ylides Using Aryl Thiorea
2923
NMR: δ 3.62, 3.72 (6H, 2s, 2 OCH3), 4.14 (1H, d, 3JPH18.2 Hz, P C CH),
1
6.56–7.44 (40 H, m, arm).30,13C NMR: δ 42.45 (d, JPC137.4 Hz, P C),
50.44, 52.60 (2 OCH3), 62.05 (d, 2JPC 15.6 Hz, P C CH) ,115.49 (C N),
2
116.04–133.75 (carbons of aromatic rings),15–18,30 170.19 (d, JPC17.7
Hz, C O), 171.13 (d, 3JPC 13.9 Hz, C O). Isomer (Z) (43%), 1H NMR: δ
3
3.18, 3.75 (6H, 2s, 2 OCH3), 4.13 (1H, d, JPH13.9 Hz, P C CH ). 13C
NMR: δ 40.73 (d, 1JPC127.7 Hz, P C), 49.44 and 52.79 (2OCH3), 63.08
(d, 2JPC16.2Hz, P C-CH), 112.93 (C N), 169.05 (d, 2JPC12.7 Hz, C O),
171.24(d, 3JPC13.8 Hz, C O).
Dimethyl 2-[cyano(1-naphthyl)amino]-3-(1,1,1-triphenyl-
λ5phosphanylidene) Succinate (3b)
(0.88 g, m.p. 168–170◦C, yield 76%); IR (KBr) (νmax, cm−1): 2212
1
(CN),1765 and 1619 (C O). Isomer (Z) (57 %) H NMR: δ 3.00, 3.54
3
(6H, 2s, 2 OCH3), 4.58 (1H, d, JPH19.6 Hz, P C CH), 7.04-7.99 (44
1
H, m, arm) .30,13C NMR: δ 41.40 (d, JPC125.6 Hz, P C), 45.86 (d,
2JPC12.8 Hz, P C CH), 48.71, 51.70 (2 OCH3), 112.50 (C N),121.44–
2
133.72(carbons of aromatic rings),30 169.02 (d, JPC13.1 Hz, C O),
170.20 (d, 3JPC18.1 Hz, C O). Isomer (E) (43%), 1H NMR: δ 3.643, 3.55
(6H, 2s, 2 OCH3), 4.42 (1H, d, 3JPH20.0 Hz, P C CH). 13C NMR: δ 41.73
1
2
(d, JPC134.04 Hz, P C), 45.19 (d, JPC13.6Hz, P C CH), 49.71 and
2
51.90 (2 OCH3),111.00 (C N), 174.25 (d, JPC7.4Hz, C O), 174.65(d,
3JPC8.0Hz, C O).
Diethyl 2-[cyano(1-naphthyl)amino]-3-(1,1,1-triphenyl-
λ5phosphanylidene) Succinate (3c)
(0.92 g, m.p. 170–172◦C, yield 75%); IR (KBr) (νmax, cm−1): 2237 (CN),
1716,1641 (C O). Anal. Calcd. for C37H33N2O4P (600.64): C,73.99; H,
1
5.54;N, 4.66%. Found: C,73.54; H, 5.66;N, 4.65%. Isomer (Z) (63%), H
3
NMR: δ 0. 37 (3H, t, JHH6.9 Hz, CH3), 1.17 (3H, t,3JHH7.1 Hz, CH3),
3
3.53–4.09 (8 H, m, 4 OCH2),30 4.56 (1H, d, JPH20.0 Hz, P C CH),
7.02–7.99 (44H, m, arm).30,13C NMR: 13.88 and 14.16 (2 CH3), 41.17 ( d,
,1JPC 124.9Hz, P C), 45.08(d, 2JPC 12.2 Hz P C CH), 56.89 and 60.03
(2 OCH2), 113.04 (C N), 121.39–133.24 (carbons of aromatic rings),30
168.57 (d, 2JPC 12.9 Hz, C O), 173.84 (d, 2JPC 7.7 Hz, C O). Isomer (E)
(37%), 1H NMR: δ 1.04(3H, t, 3JHH6.8 Hz, CH3), 1.19 (3H, t, 3JHH 6.5 Hz,
3
CH3), 4.34 (1H, d, JPH20.2 Hz, P C CH) .13C NMR: 14.11 and 14.90
(CH3), 41.58 ( d, ,1JPC 132.7 Hz, P C), 45.08 (d,2JPC 12.2 Hz, P C H),
57.32 and 60.11 (2 OCH2), 111.12 (C N),169.88 (d, 2JPC 19.1 Hz, C O),
173.67 (d, 2JPC 9.5Hz, C O).

2924
M. R. Islami and M. Z. Rouh-Alamini
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