Three-component reaction of triphenylphosphine, acetylenic esters, and arylsulfonyl hydrazides or aryl hydrazines: An efficient one-pot synthesis of stable β-nitrogen-substituted phosphorus ylides

Article abstract of DOI:10.1080/00397910801997785

The three-component reaction between dialkyl acetylenedicarboxylates and triphenylphosphine in the presence of arylsulfonyl hydrazides or aryl hydrazines produces highly functionalized, salt-free phosphorus ylides in excellent yields. Copyright Taylor & F

Full text of DOI:10.1080/00397910801997785

This article was downloaded by: [University of Windsor]
On: 12 November 2014, At: 10:47
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954
Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH,
UK
Synthetic Communications: An
International Journal for Rapid
Communication of Synthetic
Organic Chemistry
Publication details, including instructions for
authors and subscription information:
http://www.tandfonline.com/loi/lsyc20
Three-Component Reaction
of Triphenylphosphine,
Acetylenic Esters, and
Arylsulfonyl Hydrazides or
Aryl Hydrazines: An Efficient
One-Pot Synthesis of Stable
β-Nitrogen-Substituted
Phosphorus Ylides
Hossein Anaraki-Ardakani a , Shirin Sadeghian a ,
Foroghossadat Rastegari a , Alireza Hassanabadi a &
Mohammad Anary-Abbasinejad a
a Department of Chemistry , Islamic Azad
University , Yazd, Iran
Published online: 12 Jun 2008.
To cite this article: Hossein Anaraki-Ardakani , Shirin Sadeghian , Foroghossadat
Rastegari , Alireza Hassanabadi & Mohammad Anary-Abbasinejad (2008) Three-
Component Reaction of Triphenylphosphine, Acetylenic Esters, and Arylsulfonyl
Hydrazides or Aryl Hydrazines: An Efficient One-Pot Synthesis of Stable β-Nitrogen-
Substituted Phosphorus Ylides, Synthetic Communications: An International Journal
for Rapid Communication of Synthetic Organic Chemistry, 38:12, 1990-1999, DOI:
10.1080/00397910801997785
To link to this article: http://dx.doi.org/10.1080/00397910801997785

PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the
information (the “Content”) contained in the publications on our platform.
However, Taylor & Francis, our agents, and our licensors make no
representations or warranties whatsoever as to the accuracy, completeness,
or suitability for any purpose of the Content. Any opinions and views
expressed in this publication are the opinions and views of the authors, and
are not the views of or endorsed by Taylor & Francis. The accuracy of the
Content should not be relied upon and should be independently verified with
primary sources of information. Taylor and Francis shall not be liable for any
losses, actions, claims, proceedings, demands, costs, expenses, damages,
and other liabilities whatsoever or howsoever caused arising directly or
indirectly in connection with, in relation to or arising out of the use of the
Content.
This article may be used for research, teaching, and private study purposes.
Any substantial or systematic reproduction, redistribution, reselling, loan,
sub-licensing, systematic supply, or distribution in any form to anyone is
expressly forbidden. Terms & Conditions of access and use can be found at
http://www.tandfonline.com/page/terms-and-conditions

Synthetic Communications1, 38: 1990–1999, 2008
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910801997785
Three-Component Reaction of
Triphenylphosphine, Acetylenic Esters, and
Arylsulfonyl Hydrazides or Aryl Hydrazines: An
Efficient One-Pot Synthesis of Stable
b-Nitrogen-Substituted Phosphorus Ylides
Hossein Anaraki-Ardakani, Shirin Sadeghian, Foroghossadat
Rastegari, Alireza Hassanabadi, and Mohammad
Anary-Abbasinejad
Department of Chemistry, Islamic Azad University, Yazd, Iran
Abstract: The three-component reaction between dialkyl acetylenedicarboxy-
lates and triphenylphosphine in the presence of arylsulfonyl hydrazides or aryl
hydrazines produces highly functionalized, salt-free phosphorus ylides in excellent
yields.
Keywords: Acetylenic esters; Aryl hydrazines; Arylsulfonyl hydrazides; Phos-
phorus ylides; Triphenylphosphine
Phosphorus ylides are reactive systems that take part in many valuable
reactions in organic synthesis.[1–7] Several methods have been developed
for the preparation of phosphorus ylides. These ylides are usually pre-
pared by treatment of an appropriate phosphonium salt with a base;
the corresponding phosphonium salts are usually obtained from the
phosphine and an alkyl halide.[1,2] Phosphonium salts are also prepared
by Michael addition of phosphorus nucleophiles to activated olefins.[1]
The phosphonium salts are most often converted to the ylides by treat-
ment with a strong base, though weaker bases can be used if the salt is
acidic enough. Reaction of acetylenic esters with triphenylphosphine in
Received in the U.K. June 27, 2007
Address correspondence to Mohammad Anary-Abbasinejad, Department of
Chemistry, Islamic Azad University, Yazd Branch, P.O.Box 89195-155, Yazd,
Iran. E-mail: mohammadanary@yahoo.com
1990

b-Nitrogen-Substituted Phosphoranes
1991
the presence of an organic acid has also been reported to produce phos-
phorus ylides.[8] In continuation of our work on the reaction between
trivalent phosphorus nucleophiles and electron-deficient acetylenic
compounds in the presence of organic N-H, O-H, or C-H acids,[9] we
herein report an efficient synthetic route to stable phosphorus ylides
using triphenylphosphine, dialkyl acetylenedicarboxylates, and arylsulfo-
nyl hydrazides or aryl hydrazines. Thus, the reaction of the arylsulfonyl
hydrazide 1 with the acetylenic ester 2 in the presence of triphenylpho-
sphine leads to the corresponding ylide 3a in good yields (Scheme 1).
The mass spectra of the ylides 3 are fairly similar and display molecu-
lar ion peaks. The NMR spectra of ylides 3a–f are consistent with the
presence of two isomers. The ylide moiety of these compounds is strongly
conjugated with the adjacent carbonyl group, and rotation about the C-C
bond due to partial double bond character is slow on the NMR timescale
at room temperature (Scheme 2).
The 1H NMR spectrum of 3a shows two sharp lines (d ¼ 3.06,
3.73 ppm) for the methyl groups of the major isomer, along with a signal
for the methine proton at 4.62 ppm, which appears as a doublet
(3JPH ¼ 8.65 Hz). Two single signals are observed at d ¼ 6.63 and
6.68 ppm, which disappear after addition to CDCl3 solution of 3a a
few drops of D2O. These signals are related to two NH protons. The aro-
matic protons show multiplets at d ¼ 7.37–7.99 ppm. The corresponding
signals for the minor isomer appear at d ¼ 3.42, 3.82 ppm for methyl
Scheme 1. Three-component reaction between triphenylphosphine, acetylenic
esters, and arylsulfonyl hydrazides.

1992
H. Anaraki-Ardakani et al.
Scheme 2. Two rotational isomers for ylides 3a–f.
groups and at d ¼ 4.39 ppm (3JPH ¼ 8.7 HZ,) for the methine proton.
The 31P NMR spectrum of compound 3a displays two signals at 24.49
and 24.85 ppm for major and minor isomers, respectively. These shifts
are similar to those observed for other stable phosphorus ylides.[10,11]
The structural assignments made on the basis of the NMR spectra of
compound 3a are supported by its IR spectrum. The ester carbonyl
groups exhibit absorption bands at 1736 and 1619cmꢀ1. The N-H
stretching absorption bands appear at 3295–3150cmꢀ1
.
On the basis of the well-established chemistry of trivalent phos-
phorus nucleophiles,[1–7] it is reasonable to assume that ylides 3 result
from the initial addition of triphenylphosphine to the acetylenic ester
and subsequent protonation of the 1:1 adduct by the NH-acid. Then,
the positively charged ion is attacked by the anion of the NH-acid to
form the phosphorane 3.
The three-component reaction of acetylenic esters, triphenylpho-
sphine, and aryl hydrazines also leads to the similar phosphorus
ylides 3g–i (Scheme 3). As for ylides 3a–f, the NMR spectra of ylides
3g–i are consistent with the presence of two isomers.
In summary, phosphorus ylides may be prepared by a simple,
one-pot, three-component reaction of dialkyl acetylenedicarboxylates,
Scheme 3. Three-component reaction between triphenylphosphine, acetylenic
esters, and aryl hydrazines.

b-Nitrogen-Substituted Phosphoranes
1993
triphenylphosphine, and arylsulfonyl hydrazides or aryl hydrazines. The
present method has the advantage that not only the reaction is performed
under neutral conditions but also the substances can be mixed without
any activation or modification.
EXPERIMENTAL
All melting points were determined on an Electrothermal 9100 apparatus
and are uncorrected. Elemental analyses were performed using a Heraeus
CHN-O-Rapid analyzer. Mass spectra were recorded on a Finnigan-Mat
8430 mass spectrometer operating at an ionization potential of 70 eV. IR
1
spectra were recorded on a Shimadzu IR-470 spectrometer. H, 13C, and
31P NMR spectra were recorded on a Bruker DRX-300 Avance spec-
trometer at 300.1, 75.46, and 121.49 MHz, respectively. 1H, 13C, and
31P NMR spectra were obtained in CDCl3 solution using TMS as internal
standard (1H, 13C) or 85% H3PO4 as external standard (31P). The
chemicals used in this study were purchased from Fluka and were used
without further purification.
General Procedure
To a magnetically stirred solution of triphenylphosphine (0.52 g, 2 mmol)
and arylsulfonyl hydrazide (2 mmol) in ethyl acetate (10 ml), a mixture of
dialkyl acetylenedicarboxylate (2 mmol) in ethyl acetate (3 ml) was added
dropwise at room temperature over 2 min. The reaction mixture was then
stirred for 30 min, and the product was removed by filtration and washed
with ethyl acetate (10 ml).
Dimethyl 2-[2-(Phenylsulfonyl)hydrazino]-3-(triphenylphosphanylidene)
Succinate (3a)
Yield: 90%; colorless crystals; mp 119–120 ꢁC. IR (KBr) (nmax, cmꢀ1):
=
3295, 3150 (NH), 1736, 1619 (C O). Calcd. for C30H29N2O6PS: C,
62.49; H, 5.07; N, 4.86%. Found: C, 62.52; H, 5.01; N, 4.87%. MS
1
(m=z, %): 576 (M, 3). Major isomer (80%): H NMR (CDCl3): d 3.06
3
(s, 3 H, OCH3), 3.73 (s, 3 H, OCH3), 4.62 (d, JPH ¼ 8.65 Hz, 1 H,
=
P C-CH), 6.63 (s, 1 H, NH), 6.68 (s, 1 H, NH), 7.37–7.99 (m, 40 H,
arom)ꢂ (ꢂfor two conformational isomers). 13C NMR (CDCl3): d 42.83
1
2
=
(d, JPC ¼ 125 Hz, C P), 49.02, 52.16 (2 OCH3), 60.41 (d, JPC
¼
14.6 Hz, CH), 125.90 (d, 1JPC ¼ 92.25Hz, Cipso), 128.86 (d, 3JPC ¼ 12.0 Hz,
Cmeta), 132.03 (d, JPC ¼ 2.4 Hz, Cpara)ꢂ, 133.65 (d, JPC ¼ 9.82 Hz,
4
2

1994
H. Anaraki-Ardakani et al.
2
Cortho), 128.10, 128.70, 132.66, 138.43 (CH, arom), 169.82 (d, JPC
¼
12.15 Hz, C O) , 175.34 (d, JPC ¼ 11.32 Hz, C O) . 31P NMR
3
ꢂ
ꢂ
=
=
1
(CDCl3): d 24.49 Minor isomer (20%): H NMR (CDCl3): d 3.42 (s,
3
3 H, OCH3), 3.82 (s, 3 H, OCH3), 4.39 (d, JPH ¼ 8.7 Hz, 1 H,
P C-CH), 6.57 (s, 1 H, NH), 6.88 (s, 1 H, NH). 13C NMR (CDCl3):
=
1
=
d 41.16 (d, JPC ¼ 122 Hz, C P), 49.96, 52.52 (2 OCH3), 63.59 (d,
2JPC ¼ 14.25 Hz, CH), 125.34 (d, JPC ¼ 91.5 Hz, Cipso), 128.43 (d,
1
3JPC ¼ 11 Hz, Cmeta), 133.18 (d, JPC ¼ 9.74 Hz, Cortho), 128.22,
2
128.34, 132.71, 139.01 (CH, arom). 31P NMR (CDCl3): d 24.85.
Diethyl 2-[2-(Phenylsulfonyl)hydrazino]-3-(triphenylphosphanylidene)
Succinate (3b)
Yield: 95%; colorless crystals; mp 133–134 ꢁC. IR (KBr) (nmax, cmꢀ1):
=
3335, 3150 (NH) 1735, 1619 (C O). Calcd. for C32H33N2O6PS: C,
63.56; H, 5.50; N, 4.63%. Found: C, 63.61; H, 5.52; N, 4.58%. MS
1
(m=z, %): 604 (M, 1). Major isomer (70%): H NMR (CDCl3): d 0.40
3
3
(t, JHH ¼ 7.05 Hz, 3 H, CH3), 1.27 (t, JHH ¼ 7.11 Hz, 3 H, CH3), 3.59
3
(m, 2 H, OCH2), 4.28 (m, 2 H, OCH2), 4.68 (d, JPH ¼ 9 Hz, 1 H,
=
P C-CH), 6.25 (s, 1 H, NH), 6.87 (s, 1 H, NH) 7.39–7.93 (m, 40 H,
¼
arom)ꢂ. 13C NMR (CDCl3): d 13.87, 14.28 (2CH3), 41.83 (d, JPC
1
2
=
126 Hz, C P), 57.56, 61.26 (2 OCH2), 63.48 (d, JPC ¼ 15.2 Hz, CH),
126.16 (d, JPC ¼ 92.25 Hz, Cipso), 128.65 (d, JPC ¼ 12 Hz, Cmeta),
1
3
132.06 (d, JPC ¼ 2.2 Hz, Cpara), 133.75 (d, JPC ¼ 9.83 Hz, Cortho),
4
2
2
128.11, 129.25, 132.60, 138.53 (CH, arom), 169.45 (d, JPC ¼ 12.52 Hz,
C O) , 174.93 (d, JPC ¼ 11 Hz, C O) . 31P NMR (CDCl3): d 23.41.
3
ꢂ
ꢂ
=
=
1
3
Minor isomer (30%): H NMR (CDCl3) d 0.45 (t, JHH ¼ 7.08 Hz, 3 H,
3
CH3), 1.35 (t, JHH ¼ 7.11 Hz, 3 H, CH3), 3.81 (m, 2 H, OCH2), 4.08
3
=
(m, 2 H, OCH2), 4.71 (d, JPH ¼ 9 Hz, 1 H, P C-CH), 6.22 (s, 1 H,
NH), 6.71 (s, 1 H, NH). 13C NMR (CDCl3): d 14.03, 14.12 (2CH3),
1
=
43.36 (d, JPC ¼ 126 Hz, C P), 57.79, 61.34 (2 OCH2), 63.72
(d, JPC ¼ 15.2 Hz, CH), 126.72 (d, JPC ¼ 92 Hz, Cipso), 128.55
2
1
(d, JPC ¼ 12 Hz, Cmeta), 131.94 (d, JPC ¼ 2.2 Hz, Cpara), 133.19 (d,
2JPC ¼ 9.83 Hz, Cortho), 128.43, 129.81, 132.16, 138.57 (CH, arom). 31P
NMR (CDCl3): d 25.12.
3
4
Dimethyl 2-[2-((4-Methylphenyl)sulfonyl)hydrazino]-3
(triphenylphosphanylidene) Succinate (3c)
ꢁ
Yield: 92%; colorless crystals; mp 140–142 C. IR (KBr) (nmax, cmꢀ1):
=
3255, 3180 (NH), 1730, 1670 (C O). Calcd. for C31H31N2O6PS: C,

b-Nitrogen-Substituted Phosphoranes
1995
63.04; H, 5.29; N, 4.74%. Found: C, 63.10; H, 5.21; N, 4.75%. MS (m=z,
1
%): 590 (M, 1). Major isomer (80%): H NMR (CDCl3): d 2.46 (s, 3 H,
CH3), 3.06 (s, 3 H, OCH3), 3.73 (s, 3 H, OCH3), 4.59 (d, 3JPH ¼ 9 Hz, 1 H,
=
P C-CH), 6.60 (s, 1 H, NH), 7.24 (s, 1 H, NH), 7.27–8.00 (m, 38 H,
arom)ꢂ. 13C NMR (CDCl3): d 21.60 (CH3), 41.84 (d, JPC ¼ 125.5 Hz,
1
2
ꢂ
=
C P) , 48.99, 52.11 (2 OCH3), 63.55 (d, JPC ¼ 14.2 Hz, CH), 125.91
(d, JPC ¼ 91.8 Hz, Cipso), 128.68 (d, JPC ¼ 12.3 Hz, Cmeta), 132.13 (d,
1
3
4JPC ¼ 2 Hz, Cpara), 133.76 (d, JPC ¼ 9.75 Hz, Cortho), 128.14, 129.31,
2
2
=
135.39, 144.07 (CH, arom), 169.81 (d, JPC ¼ 12.7 Hz, C O), 175.33
(d, JPC ¼ 12.52 Hz, C O). 31P NMR (CDCl3): d 23.79 Minor isomer
3
=
1
(20%): H NMR (CDCl3): d 1.65 (s, 3 H, CH3), 3.42 (s, 3 H, OCH3),
3
=
3.83 (s, 3 H, OCH3), 4.37 (d, JPH ¼ 9 Hz, 1 H, P C-CH), 6.28 (s, 1 H,
NH), 6.88 (s, 1 H, NH). 13C NMR (CDCl3): d 21.77 (CH3), 49.90,
2
52.36 (2 OCH3), 62.81 (d, JPC ¼ 14.2 Hz, CH), 125.31 (d,
1JPC ¼ 91.8 Hz, Cipso), 128.44 (d, JPC ¼ 12.3 Hz, Cmeta), 131.96 (d,
3
4JPC ¼ 2 Hz, Cpara), 133.41 (d, JPC ¼ 10 Hz, Cortho), 128.29, 129.73,
2
2
=
135.43, 144.12 (CH, arom), 169.86 (d, JPC ¼ 12.7 Hz, C O), 175.65
(d, JPC ¼ 12.50 Hz, C O). 31P NMR (CDCl3): d 24.85.
3
=
Diethyl 2-[2-((4-Methylphenyl)sulfonyl)hydrazino]-3-
(triphenylphosphanylidene) Succinate (3d)
ꢁ
Yield: 93%; colorless crystals; mp 150–152 C. IR (KBr) (nmax, cmꢀ1):
=
3285, 3170 (NH), 1733, 1625 (C O). Calcd. for C33H35N2O6PS: C,
64.06; H, 5.70; N, 4.53%. Found: C, 64.11; H, 5.68; N, 4.55%. MS
1
(m=z, %): 618 (M, 1). Major isomer (80%): H NMR (CDCl3): d 0.40
3
3
(t, JHH ¼ 7 Hz, 3 H, CH3), 1.26 (t, JHH ¼ 7.08 Hz, 3 H, CH3), 2.45
(s, 3H, CH3), 3.59 (m, 2 H, OCH2), 4.11 (m, 2 H, OCH2), 4.65
=
3
(d, JPH ¼ 9 Hz, 1 H, P C-CH), 6.64 (s, 1 H, NH), 7.23 (s, 1 H, NH),
7.26–7.94 (m, 38 H, arom)ꢂ. 13C NMR (CDCl3): d 13.89, 14.29
1
=
(2CH3), 21.58 (CH3), 41.99 (d, JPC ¼ 126.3 Hz, C P), 57.50, 60.76
2
1
(2 OCH2), 63.62 (d, JPC ¼ 15 Hz, CH), 126.15 (d, JPC ¼ 92 Hz,
Cipso), 128.60 (d, JPC ¼ 12 Hz, Cmeta), 132.09 (d, JPC ¼ 2.3 Hz, Cpara),
3
4
133.67 (d, JPC ¼ 9.82 Hz, Cortho), 128.16, 129.45, 135.49, 143.31 (CH,
2
2
3
ꢂ
=
arom), 169.26 (d, JPC ¼ 12.52 Hz, C O) , 174.77 (d, JPC ¼ 11.77 Hz,
C O) . 31P NMR (CDCl3): d 23.64. Minor isomer (30%): H NMR
1
ꢂ
=
3
3
(CDCl3) d 1.05 (t, JHH ¼ 6.95 Hz, 3 H, CH3), 1.35 (t, JHH ¼ 7 Hz,
3 H, CH3), 2.41 (s, 3 H, CH3), 3.65 (m, 2 H, OCH2), 4.21 (m, 2 H,
=
3
OCH2) 4.41 (d, JPH ¼ 9 Hz, 1 H, P C-CH), 6.65 (s, 1 H, NH), 6.86 (s,
1 H, NH). 13C NMR (CDCl3): d 14.12, 14.87 (2CH3), 21.61 (CH3),
1
=
42.01 (d, JPC ¼ 126.3 Hz, C P), 57.94, 61.22 (2 OCH2), 62.90
(d, JPC ¼ 15 Hz, CH), 125.47 (d, JPC ¼ 92 Hz, Cipso), 128.44
2
1

1996
H. Anaraki-Ardakani et al.
3
4
(d, JPC ¼ 12 Hz, Cmeta), 131.99 (d, JPC ¼ 2.3 Hz, Cpara), 133.14 (d,
2JPC ¼ 10 Hz, Cortho), 128.28, 129.66, 135.52, 143.40, (CH, arom). 31P
NMR (CDCl3): d 24.14.
Dimethyl 2-[2-((4-nitrophenyl)sulfonyl)hydrazino]-3-
(triphenylphosphanylidene) Succinate (3e)
ꢁ
Yield: 90%; colorless crystals; mp 142–1143 C. IR (KBr) (nmax, cmꢀ1):
=
3400, 3130 (NH), 1733, 1615 (C O). Calcd. for C30H28N3O8PS: C,
57.97; H, 4.54; N, 6.76%. Found: C, 57.90; H, 4.48; N, 6.80%. MS
1
(m=z, %): 621 (M, 1). Major isomer (80%): H NMR (CDCl3): d, 3.07
3
(s, 3 H, OCH3), 3.70 (s, 3 H, OCH3), 4.88 (d, JPH ¼ 9 Hz, 1 H,
=
P C-CH), 6.87 (s, 1 H, NH), 7.18 (s, 1 H, NH), 7.33–8.28 (m, 38 H,
=
arom)ꢂ. 13C NMR (CDCl3): d 42.83 (d, JPC ¼ 125.5 Hz, C P) , 49.14,
1
ꢂ
2
1
52.34 (2 OCH3), 63.42 (d, JPC ¼ 14.5 Hz, CH), 125.72 (d, JPC ¼ 92 Hz,
Hz, Cipso), 128.77 (d, JPC ¼ 12.2 Hz, Cmeta), 132.12 (d, JPC ¼ 2 Hz,
3
4
Cpara), 133.73 (d, JPC ¼ 10 Hz, Cortho), 123.90, 129.41, 144.44, 150.06
2
2
3
ꢂ
=
(CH, arom), 169.92 (d, JPC ¼ 12.6 Hz, C O) , 175.01 (d, JPC
¼
11.76 Hz, C O) . 31P NMR (CDCl3): d 25.49. Minor isomer (20%):
ꢂ
=
1H NMR (CDCl3): d, 3.45 (s, 3 H, OCH3), 3.82 (s, 3 H, OCH3), 4.51
3
=
(d, JPH ¼ 9 Hz, 1 H, P C-CH), 6.69 (s, 1 H, NH), 7.21 (s, 1 H, NH).
13C NMR (CDCl3): d 51.86, 52.18, (2 OCH3), 62.67 (d, JPC ¼ 14.2 Hz,
2
CH), 126.40 (d, JPC ¼ 92 Hz, Cipso), 128.94 (d, JPC ¼ 12.3 Hz, Cmeta),
1
3
131.62 (d, JPC ¼ 2 Hz, Cpara), 133.01 (d, JPC ¼ 10 Hz, Cortho), 124.15,
4
2
129.76, 144.59, 150.32 (CH, arom). 31P NMR (CDCl3): d 26.85.
Diethyl 2-[2-((4-Nitrophenyl)sulfonyl)hydrazino]-3-
(triphenylphosphanylidene) Succinate (3f)
ꢁ
Yield: 94%; colorless crystals; mp 152–154 C. IR (KBr) (nmax, cmꢀ1):
=
3270, 3110 (NH), 1726, 1609, (C O). Calcd. for C32H32N3O8PS: C,
59.16; H, 4.96; N, 6.47%. Found: C, 59.21; H, 4.94; N, 6.39%. MS
1
(m=z, %): 649 (M, 1). Major isomer (80%): H NMR (CDCl3): d 0.42
3
3
(t, JHH ¼ 6.9 Hz, 3 H, CH3), 1.26 (t, JHH ¼ 7.1 Hz, 3 H, CH3), 3.56
3
(m, 4 H, OCH2)ꢂ, 4.14 (m, 4 H, OCH2)ꢂ, 4.96 (d, JPH ¼ 9.9 Hz,1 H,
=
P C-CH), 6.60 (s, 1 H, NH), 7.19 (s, 1 H, NH), 7.24–8.2 (m, 38 H,
d 13.86, 14.25 (2CH3), 42.43 (d,
arom)ꢂ. 13C NMR (CDCl3):
1
2
=
JPC ¼ 126.3 Hz, C P), 57.70, 60.38 (2 OCH2), 63.47 (d, JPC ¼ 14 Hz,
CH), 126.07 (d, JPC ¼ 91.8 Hz, Cipso), 128.65 (d, JPC ¼ 12 Hz, Cmeta),
1
3
132.03 (d, JPC ¼ 2.1 Hz, Cpara), 133.66 (d, JPC ¼ 9.83 Hz, Cortho),
4
2
2
123.75, 129.42, 144.68, 149.95 (CH, arom), 169.51 (d, JPC ¼ 12.67 Hz,

b-Nitrogen-Substituted Phosphoranes
1997
3
C O) , 174.53 (d, JPC ¼ 11.78 Hz, C O) . 31P NMR (CDCl3): d 24.27.
ꢂ
ꢂ
=
=
1
3
Minor isomer (30%): H NMR (CDCl3) d 1.06 (t, JHH ¼ 7 Hz, 3 H,
3
3
CH3), 1.32 (t, JHH ¼ 7.1 Hz, 3 H, CH3), 4.54 (d, JPH ¼ 9 Hz, 1 H,
P C-CH), 6.57 (s, 1 H, NH), 7.16 (s, 1 H, NH). 13C NMR (CDCl3): d
=
1
=
1
13.84, 14.20 (2CH3), 41.35 (d, JPC ¼ 126.3 Hz, C P), 58.01, 60.84 (2
2
OCH2), 62.96 (d, JPC ¼ 15.2 Hz, CH), 125.29 (d, JPC ¼ 92 Hz, Cipso),
128.23 (d, JPC ¼ 12 Hz, Cmeta), 131.96 (d, JPC ¼ 2.1 Hz, Cpara), 133.57
3
4
(d, JPC ¼ 10 Hz, Cortho), 123.81, 129.03, 144.61, 149.84 (CH, arom).
2
31P NMR (CDCl3): d 25.81.
Dimethyl 2-[2-(2,4-Dinitrophenyl)hydrazino]-3-(triphenylphosphanylidene)
Succinate (3g)
ꢁ
Yield: 90%; colorless crystals; mp 153–155 C. IR (KBr) (nmax, cmꢀ1):
=
3350 (NH), 1734, 1616 (C O). Calcd. for C30H29N4O8P: C, 59.60; H,
4.84; N, 9.27%. Found: C, 59.65; H, 4.78; N, 9.31%. MS (m=z, %):
1
604 (M, 3). Major isomer (75%): H NMR (CDCl3): d 3.17 (s, 3 H,
3
=
OCH3), 3.81 (s, 3 H, OCH3), 5.54 (d, JPH ¼ 10.18 Hz, 1 H, P C-CH),
7.28–8.01 (m, 36 H, arom)ꢂ, 9.00 (s, 1 H, NH), 9.97 (s, 1 H, NH).
13C NMR (CDCl3): d 37.4 (d, JPC ¼ 122 Hz, C P), 49.3, 52.34
1
=
2
1
(2 OCH3), 62.28 (d, JPC ¼ 14.52 Hz, CH), 125.64 (d, JPC ¼ 91.5 Hz,
Cipso), 128.43 (d, JPC ¼ 12 Hz, Cmeta), 132.01 (d, JPC ¼ 2.3 Hz, Cpara),
3
4
133.52 (d, JPC ¼ 9.75 Hz, Cortho), 115.35, 123.84, 129.41, 132.14,
2
2
ꢂ
=
135.91, 149.4 (CH, arom), 165.38 (d, JPC ¼ 12.32 Hz, C O) , 169.95
(d, JPC ¼ 11.52 Hz, C O) . 31P NMR (CDCl3): d 23.36. Minor
3
ꢂ
=
isomer (25%): 1H NMR (CDCl3): d 3.57 (s, 3 H, OCH3), 3.79 (s,
3
=
3 H, OCH3), 5.05 (d, JPH ¼ 9.21 Hz, 1 H, P C-CH), 9.04 (s, 1 H,
NH), 10.02 (s, 1 H, NH). 13C NMR (CDCl3): d 36.5 (d, JPC
¼
1
2
=
1
121.7 Hz, C P), 50.1, 53.42 (2 OCH3), 62.53 (d, JPC ¼ 14.52 Hz, CH),
125.04 (d, JPC ¼ 91 Hz, Cipso), 128.80 (d, JPC ¼ 11.92 Hz, Cmeta),
3
132.41 (d, JPC ¼ 2.2 Hz, Cpara), 133.40 (d, JPC ¼ 10 Hz, Cortho),
115.48, 123.75, 129.91, 131.80, 136.42, 150.3 (CH, arom). 31P NMR
(CDCl3): d 23.43.
4
2
Dimethyl 2-[2-(4-Nitrophenyl)hydrazino]-3-(triphenylphosphanylidene)
Succinate (3h)
ꢁ
Yield: 91%; colorless crystals; mp 148–150 C. IR (KBr) (nmax, cmꢀ1):
=
3335, 3300, (NH), 1779, 1637 (C O). Analyses: calcd. for C30H29N3O6P:
C, 64.51; H, 5.23; N, 7.52%. Found: C, 64.49; H, 5.29; N, 7.56%. MS
1
(m=z, %): 558 (M, 5). Major isomer (80%): H NMR (CDCl3): d 3.13

1998
H. Anaraki-Ardakani et al.
3
=
(s, 3 H, OCH3), 3.79 (s, 3 H, OCH3), 5.05 (d, JPH ¼ 8.8 Hz, 1 H, P
C-CH), 6.51–7.93 (m, 38 H, arom)ꢂ, 7.93 (s, 1 H, NH), 9.97 (s, 1 H,
NH). 13C NMR (CDCl3): d 40.59 (d, JPC ¼ 125 Hz, C P) , 49.64,
1
ꢂ
=
2
52.69 (2 OCH3), 62.34 (d, JPC ¼ 14.52 Hz, CH), 126.27 (d,
1JPC ¼ 91.65 Hz, Cipso), 129.08 (d, JPC ¼ 12.15 Hz, Cmeta), 132.67 (d,
3
4JPC ¼ 2.7 Hz, Cpara)ꢂ, 133.88 (d, JPC ¼ 9.75 Hz, Cortho), 110.87,
2
2
ꢂ
=
126.49, 138.38, 155.74 (CH, arom), 170.73 (d, JPC ¼ 12.82 Hz, C O) ,
175.87 (d, JPC ¼ 11.25 Hz, C O) . 31P NMR (CDCl3): d 23.66. Minor
3
ꢂ
=
1
isomer (20%): H NMR (CDCl3): d 3.56 (s, 3 H, OCH3), 3.76 (s, 3 H,
3
=
OCH3), 4.79 (d, JPH ¼ 9.92 Hz, 1 H, P C-CH), 9.04 (s, 1 H, NH),
10.02 (s, 1 H, NH). 13C NMR (CDCl3): d 39.5 (d, JPC ¼ 122 Hz,
1
2
=
C P), 50.57, 52.51 (2 OCH3), 61.87 (d, JPC ¼ 15.2 Hz, CH), 125.70 (d,
1JPC ¼ 93.97 Hz, Cipso), 128.63 (d, JPC ¼ 11 Hz, Cmeta), 134.10 (d,
3
2JPC ¼ 9.74 Hz, Cortho), 110.57, 126.53, 138.27, 154.97 (CH, arom). 31P
NMR (CDCl3): d 23.92.
Diethyl 2-[2-(4-Nitrophenyl)hydrazino]-3-(triphenylphosphanylidene)
Succinate (3i)
ꢁ
Yield: 94%; colorless crystals; mp 152–154 C. IR (KBr) (nmax, cmꢀ1):
=
3335, 3270 (NH), 1741, 1620 (C O). Calcd. for C32H33N3O6P: C,
65.52; H, 5.67; N, 7.16%. Found: C, 65.61; H, 5.67; N, 7.22%. MS
1
(m=z, %): 586 (M, 3). Major isomer (80%): H NMR (CDCl3): d 0.44
3
3
(t, JHH ¼ 7.08 Hz, 3 H, CH3), 1.31 (t, JHH ¼ 7.08 Hz, 3 H, CH3), 3.66
3
3
(q, JHH ¼ 7 Hz, 2 H, OCH2), 4.14 (q, JHH ¼ 7 Hz, 2 H, OCH2), 5.29
3
ꢂ
=
(d, JPH ¼ 9 Hz, 1 H, P C-CH), 6.55–7.93 (m, 38 H, arom) , 9.00 (s,
1 H, NH), 9.97 (s, 1 H, NH). 13C NMR (CDCl3): d 14.38, 14.72
1
=
(2CH3), 40.45 (d, JPC ¼ 126 Hz, C P), 58.72, 61.83 (2 OCH2), 62.42
(d, JPC ¼ 14.63 Hz, CH), 126.44 (d, JPC ¼ 92 Hz, Cipso), 128.96 (d,
2
1
3JPC ¼ 12 Hz, Cmeta), 132.60 (d, JPC ¼ 2.6 Hz, Cpara)ꢂ, 133.94 (d,
4
2JPC ¼ 9.82 Hz, Cortho), 110.88, 126.50, 138.26, 156.04 (CH, arom),
170.39 (d, JPC ¼ 12.52 Hz, C O), 175.52 (d, JPC ¼ 11 Hz, C O). 31P
2
3
=
=
NMR (CDCl3): d 23.74. Minor isomer (20%): 1H NMR (CDCl3) d
3
3
0.49 (t, JHH ¼ 7.08 Hz, 3 H, CH3), 1.19 (t, JHH ¼ 7.08 Hz, 3 H, CH3),
3
3
3.33 (q, JHH ¼ 7 Hz, 2 H, OCH2), 4.32 (q, JHH ¼ 7 Hz, 2 H, OCH2),
3
=
5.05 (d, JPH ¼ 9 Hz, 1 H, P C-CH), 9.00 (s, 1 H, NH), 9.97 (s, 1 H,
NH). 13C NMR (CDCl3): d 14.76, 15.42, (2CH3), 41.54 (d, JPC
¼
1
2
=
1
133 Hz, C P), 53.89, 58.72 (2 OCH2), 61.83 (d, JPC ¼ 14.63 Hz, CH),
125.87 (d, JPC ¼ 92 Hz, Cipso), 129.28 (d, JPC ¼ 12 Hz, Cmeta), 134.17
3
2
(d, JPC ¼ 9.82 Hz, Cortho), 110.50, 126.65, 138.49, 155.06 (CH, arom),
170.46 (d, JPC ¼ 12.52 Hz, C O), 175.39 (d, JPC ¼ 11 Hz, C O). 31P
2
3
=
=
NMR (CDCl3): d 25.12.

b-Nitrogen-Substituted Phosphoranes
1999
REFERENCES
1. Corbridge, D. E. C. Phosphorus: An Outline of the Chemistry, Biochemistry,
and Uses, 5th ed.; Elsevier: Amsterdam, 1995.
2. Engel, R. Synthesis of Carbon-Phosphorus Bonds; CRC Press: Boca Raton,
FL, 1988.
3. Kolodiazhnyi, O. I. Methods of preparation of C-substituted phosphorus
ylides and their application in organic synthesis. Russ. Chem. Rev. 1997,
66, 225.
4. Bestmann, H. J.; Zimmermann, R. Selected topics of the Wittig reaction in
the synthesis of natural products. Top. Curr. Chem. 1983, 109, 85.
5. Maryano, B. E.; Reits, A. B. The Wittig olefination reaction and
modification involving phosphoryl-stabilized carbanions. Stereochemistry,
mechanism, and selected synthetic aspects. Chem. Rev. 1989, 89, 863.
6. Pietrusiewiz, K. M.; Zablocka, M. Preparation of scalemic p-chiral
phosphines and their derivatives. Chem. Rev. 1994, 94, 1375.
7. Aitken, R. A.; Herion, H.; Janosi, A.; Karodia, N.; Raut, S.; Seth, V. S.;
Shannon, I. J.; Smith, F. C. Flash vacuum pyrolysis of stabilised phosphorus
ylides. Part 5. Selective extrusion of PH3PO from b,c,b0 -trioxo ylides to give
diacylalkynes. J. Chem. Soc., Perkin Trans. 1 1994, 2467.
8. (a) Yavari, I.; Maghsoodlou, M. T.; Djahaniani, H.; Hazeri, N. A facile syn-
thesis of stable heterocyclic phosphorus ylides. J. Chem. Res., Synop. 1999,
216; (b) Adib, M.; Mostofi, M.; Ghanbary, K.; Bijanzadeh, H. Vinyltriphe-
nylphosphonium salt-mediated efficient synthesis of iminophosphoraneds
derived from 2-aminothiazoles. Synthesis 2005, 10, 1663.
9. (a) Yavari, I.; Anary-Abbasinejad, M. Reaction between naphthols and
dimethyl acetylenedicarboxylate in the presence of phosphites. Synthesis of
stable oxa-2k5-phosphaphenanthrenes, and benzochromene derivatives.
Org. Biomol. Chem. 2003, 3, 560; (b) Anary-Abbasinejad, M.; Ascarrian,
N. Stereoselective one-pot synthesis of functionalised phosphonates by
three-component reaction between trimethylphosphite, dialkyl acetylenedi-
carboxylates and aldehyde semicarbazones. J. Chem. Res. 2007, 1, 831; (c)
Anary-Abbasinejad, M.; Tahan, S. Three-component reaction of triphenyl-
phosphine, acetylenic esters, and aromatic amides: The synthesis of stable
nitrogen-containing phosphorus ylides. Phosphorus, Sulfur Silicon Relat.
Elem. 2007, 2, 315.
10. Tebby, J. C. In Phosphorus-31 NMR Spectroscopy in Stereochemical Analysis;
J. C. Verkade, L. D. Quin (Eds.); VCH: Weinheim, 1987; chap. 1, pp. 1–60.
11. Vedejs, E.; Snoble, K. A. J. Direct observation of oxaphosphetanes from
typical Wittig reactions. J. Am. Chem. Soc. 1973, 95, 5778.