Study of reaction between triphenylphosphine and activated acetylenic esters in the presence of benzanilide and some its derivatives

Article abstract of DOI:10.3184/030823408X293675

Triphenylphosphine reacts with dialkyl acetylenedicarboxylates in the presence of NH-acids, such as benzanilide, 2-cyanobenzanilide, N-(2-acetylphenyl)benzamide, 3-nitrobenzanilide and methyl 2-benzamidobenzoate to generate stable phosphorus ylides. These stable ylides exist in solution as a mixture of two geometrical isomers as a result of restricted rotation around the carbon-carbon partial double bond resulting from conjugation of the ylide moiety with the adjacent carbonyl group.

Full text of DOI:10.3184/030823408X293675

JOURNAL OF CHEMICAL RESEARCH 2008
FEBRUARY, 97–100
RESEARCH PAPER 97
Study of reaction between triphenylphosphine and activated acetylenic
esters in the presence of benzanilide and some its derivatives
Nourollah Hazeria, Malek Taher Maghsoodloua*, Sayyed Mostafa Habibi Khorassania,
Mahmoud Nassirib and Zahra Afarinia
aDepartment of Chemistry, The University of Sistan and Balouchestan, PO Box 98135-674, Zahedan, Iran
bDepartment of Maritime, The University of Chabahar, Chabahar, Iran
Triphenylphosphine reacts with dialkyl acetylenedicarboxylates in the presence of NH-acids, such as benzanilide,
2-cyanobenzanilide, N-(2-acetylphenyl)benzamide, 3-nitrobenzanilide and methyl 2-benzamidobenzoate to generate
stable phosphorus ylides. These stable ylides exist in solution as a mixture of two geometrical isomers as a result
of restricted rotation around the carbon–carbon partial double bond resulting from conjugation of the ylide moiety
with the adjacent carbonyl group.
Keywords: activated acetylenic esters, NH-acids, triphenylphosphine, stable phosphorus ylides, geometrical isomers
Z
Trivalent phosphorus compound is known to be a nucleophile,
whereas it behaves as an electron donor toward good electron
acceptor both in the ground and excited state.1,2 In recent
years, there has been increasing interest in the synthesis of
organophosphorus compounds, that is, those bearing a carbon
atom bound directly to a phosphorus atom.3-38 This interest has
resulted from the recognition of the value of such compounds
in variety of biological, industrial and chemical synthetic
uses.3-7 A large number of methods have appeared describing
novel synthesis of organophosphorus compounds.6,7
There are many studies on the reaction between trivalent
phosphorus nucleophiles and α, β-unsaturated carbonyl
compounds in the presence of a proton source such as alcohol
or phenol.7 As part of our current studies on the development
of new routes in stable phosphorus ylides synthesis,19-24 we
describe the reaction between triphenylphosphine 1 and
activated acetylenic esters 2 in the presence of benzanilide and
some its derivatives 3 which leads to the corresponding stable
phosphorus ylides 4 in fairly high yield (see Scheme 1).
PPh3
Solvent
r.t
PPh +
1
RO2C
4
C
2
C
CO2R +
3
Z-H
3
RO2C
CO2R
4
%Yield
Z
R
a
b
c
O
Me
Et
93
91
96
N
C
But
O
C OCH3
O
d
e
f
Me
Et
94
91
96
N
C
But
O2N
g
h
O
Me 94
Et
92
N
C
CN
O
C
i
j
Me
But
92
96
N
Results and discussion
O
C
We now report a simple synthesis of stable phosphorus
ylides from reaction between triphenylphosphine 1 and
dialkyl acetylenedicarboxylate 2 in the presence of N-H
acids 3, such as benzanilide, 2-cyanobenzanilide, N-(2-
acetylphenyl)benzamide, 3-nitrobenzanilide and methyl
2-benzamidobenzoate which led to 4 in fairly high yield
(see Scheme 1). The reactions 4a–k were carried out in
ethyl acetate solvent at room temperature and were finished
CH3
O
k
N
C
Me 95
Scheme 1
1
within a few minutes. The H and 13C NMR spectra of the
H
H
CO2R
CO2R
OR
O
Z
crude product clearly indicated the formation of compounds
4a–k. Any products other than 4a–k could not be detected
by NMR spectroscopy. The structures of compounds 4a–k
Z
O
Ph3P
Ph3P
OR
1
were deduced from their IR, H, 13C and 31P NMR spectra.
Although the presence of the 31P nucleus complicates both
minor: (Z)-4
major: (E)-4
1
the H and 13C NMR spectra of 4a, it helps in assignment
1
of the signals by long-range couplings with the H and 13C
Scheme 2
nuclei (see Experimental). The 1H, 13C, and 31P NMR spectra
of ylides 4a–k are consistent with the presence of two
isomers. The ylides moiety of these compounds are strongly
conjugated with the adjacent carbonyl group and rotation
around the partial double bond in (E)-4 and (Z)-4 geometrical
isomers is slow on the NMR timescale at ambient temperature
(see Scheme 2). As can be seen, only one geometrical isomer
was observed for di-tert-butyl derivatives of 4, presumably,
because of the bulky tert-butyl groups. On the basis of the well
established chemistry of trivalent phosphorus nucleophiles,3-7
it is reasonable to assume that phosphorus ylide 4 results from
the initial addition of triphenylphosphine to the acetylenic
esters and subsequent protonation of the 1:1 adduct by
the NH-acid to form phosphoranes 4 (see Scheme 3).
The 1H NMR spectrum of 4a showed four sharp lines at
δ = 3.18, 3.85, 2.95 and 3.89 ppm arising from methoxy
protons. Methine protons appeared as two doublet peaks at
δ = 5.57 ppm (1H, d, 3JPH = 20.1 Hz, P–C–CH) and 5.66 ppm
3
(1H, d, JPH = 18.4 Hz, P–C–CH) respectively for the E and
Z geometrical isomers. The aromatic protons appeared as a
multiplet at δ = 6.82–7.91 ppm. The 13C NMR spectrum of 4a
* Correspondent. E-mail: MT_maghsoodlou@ yahoo.com
PAPER: 07/4901

98 JOURNAL OF CHEMICAL RESEARCH 2008
C13H10NO), 128.65 (d, 3JPC = 12.7 Hz, Cmeta), 132.19 (Cpara), 128.75,
131.75 and 132.06 (3C, C13H10NO), 133.74 (d, JPC = 9.8 Hz,
Ph P
+ RO2C
C
C
CO R
3
+
Z-H
2
2
1
2
3
Cortho), 137.30, 140.44 and 165.87 (3C, C13H10NO), 169.92 (N-C=O),
3
2
170.36 (d, JPC = 18.2 Hz, C=O ester), 172.90 (d, JPC = 14.2 Hz,
P-C=C). 31P NMR (202.5 MHz, CDCl3): δ 24.06 (Ph3P+-C).
Ph3P
C
CHCO2R +
Z
4
Minor rotamer: (%48), 1H NMR (500.1 MHz, CDCl3): δ 2.95 and
3.89 (6H, 2 s, 2OCH3), 5.66 (1H, d, 3JPH = 18.4 Hz, P =C–CH), 6.82–
7.91 (25Harom, m, 5C6H5). 13C NMR (125.8 MHz, CDCl3): δ 40.97
(d, 1JPC = 134.1 Hz, P =C), 49.52 and 52.18 (2OCH3), 60.49 (d, 2JPC
= 16.5 Hz, P =C–CH), 124.12, 126.06 and 126.80 (3C, C13H10NO),
126.95 (d, 1JPC = 91.9 Hz, Cipso), 127.28, 128.14, 128.53 and 128.76
(4C, C13H10NO), 128.80 (d, 3JPC = 12.2 Hz, Cmeta), 131.48 and 132.04
RO2C
Scheme 3
displayed 46 distinct resonances in a good agreement with the
mixture of two conformational isomers. The 1H and 13C NMR
spectra of compounds 4b–k are similar to those of 4a, except
for signals from the ester group which appear as characteristic
resonance lines with the corresponding chemical shifts.
The structural assignments for compounds 4a–k were made on
the basis of the 1H and 13C NMR spectra that were supported
by their IR spectra. The carbonyl region of the spectra exhibits
absorption bands for each compound. Of special interest is
the ester absorption of these compounds at 1761–1612 cm-1.
Conjugation with negative charge accounts for the reduction
of the wave unmbers of the carbonyl absorption bands.
Briefly, we have prepared novel phosphorus ylides
using a one-pot reaction between triphenylphosphine and
dialkyl acetylenedicarboxylates in the presence of strong
NH-acids such as benzanilide, 2-cyanobenzanilide, N-
(2-acetylphenyl)benzamide, 3-nitrobenzanilide, and methyl
2-benzamidobenzoate. The present method carries the
advantage that, not only the reaction is performed under
neutral conditions, but also the substances can be mixed
without any activation or modifications. Benzanilide and some
of its derivatives containing phosphorus ylides 4a–k may
be considered as potentially useful synthetic intermediates.
It seems that the procedure described here may be employed
as an acceptable method for the preparation of phosphoranes
with variable functionalities.
2
(2C, C13H10NO), 132.12 (Cpara), 133.55 (d, JPC = 9.7 Hz, Cortho),
3
137.55, 140.97 and 165.91 (3C, C13H10NO), 168.90 (d, JPC = 12.9
2
Hz, C=O), 169.66 (N–C=O), 173.15 (d, JPC = 14.8 Hz, P–C=C).
31P NMR (202.5 MHz, CDCl3): δ 24.87 (Ph3P+–C).
Diethyl 2-(N-phenylbenzamido)-3-(triphenylphosphanylidene)butane
dioate (4b): White powder, m.p 183–185°C, yield 0.57 g, 91%. IR
(KBr) (νmax, cm-1): 1749, 1736 and 1629 (C=O). MS (m/z, %): 629
(M+, 3), 567 (M-2OCH3, 39), 433 (M-C13H10NO, 42), 262 (PPh3,
33), 183 (PPh2, 30), 108 (PPh, 17), 77 (Ph, 100). Anal. calcd. for
C39H36NO5P (629): C, 74.37; H, 5.77; N, 2.22%. Found: C, 73.95;
H, 5.79; N, 2.18%.
Major rotamer: (%53). 1H NMR (500.1 Hz, CDCl3 δ 0.36 and
3
0.97 (6H, 2t, JHH = 7.0 Hz, 2OCH2CH3), 3.47 and 4.32 (4 H, 2 m,
2ABX3system, 2OCH2CH3), 5.65 (1H, d, 3JPH = 18.7 Hz, P =C–CH),
7.06–7.73 (25Harom, m, 5C6H5). 13C NMR (125.8 MHz, CDCl3):
1
δ 14.35 and 14.44 (2OCH2CH3), 39.56 (d, JPC = 124.8 Hz, P =C),
59.78 and 59.92 (2OCH2CH3), 61.13 (d, 2JPC = 13.8 Hz, P =C–CH),
120.82 and 123.77(2C, C13H10NO), 125.92 (d, 1JPC = 92.0 Hz, Cipso),
126.60, 127.51, 127.69 and 128.09 (4C, C13H10NO), 128.19 (d, 3JPC
= 12.1 Hz, Cmeta), 128.58 and 131.06 (2C, C13H10NO), 132.49 (Cpara),
133.64 (d, 2JPC = 9.7 Hz, Cortho), 137.67, 138.84, 141.01 and 166.06
(4C, C13H10NO), 169.39 (d, 3JPC = 13.4 Hz, C=O), 169.67(N-C=O),
172.50 (d, 2JPC = 14.6 Hz, P–C=C). 31P NMR (202.5 MHz, CDCl3):
δ 25.07 (Ph3P+–C).
Minor rotamer: (%47). 1H NMR (500.1 MHz, CDCl3): δ 1.34
3
and 1.44 (6H. 2t. JHH = 7.1, 2OCH2CH3), 3.75 and 4.45 (4H, 2 m,
2ABX3system, 2OCH2 CH3), 5.54 (1H, d, 3JPH = 20.5 Hz, P =C–CH),
7.06–7.73 (25Harom, m, 5C6H5). 13C NMR (125.8 MHz, CDCl3):
1
δ 13.86 and 13.97 (2OCH2CH3), 40.06 (d, JPC = 135.1 Hz, P =C),
60.53 and 60.66 (2OCH2CH3), 61.24 (d, 2JPC = 14.3 Hz, P =C–CH),
120.68 and 123. 84 (2C, C13H10NO), 125.87 (d, 1JPC = 92.2 Hz, Cipso),
126.76, 127.33, 128.09 and 128.24 (4C, C13H10NO), 128.31 (d, 3JPC
= 12.0 Hz, Cmeta), 128.77 and 131.23 (2C, C13H10NO), 132.49 (Cpara),
133.64 (d, 2JPC = 9.7 Hz, Cortho), 137.39, 138.84, 140,49 and 164.94
(4C, C13H10NO), 169.97 (N–C=O), 170.19 (d, 3JPC = 18.1 Hz, C=O),
172.16 (d, 2JPC = 14.1 Hz, P–C=C), 31P NMR (202.5 MHz, CDCl3):
δ 23.94 (Ph3P+–C).
Experimental
Melting points and IR spectra of all compounds were measured on an
Electrothermal 9100 apparatus and a Shimadzu IR-460 spectrometer
respectively. Also, the 1H, 13C, and 31P NMR spectra were obtained
from a Bruker DRX-500 AVANCE instrument with CDCl3 as an
solvent at 500.1, 202.5, and 125.8 MHz respectively. Elemental
analyses for C, H, N were performed using a Heraeus CHN–O–Rapid
analyser (for 4a, 4b, 4c, 4d, 4f, 4g, 4h, 4i, 4j and 4k) and also new
equipment (CHNF–O–Perkin elemer 2004 II) for 4e. In addition, the
mass spectra were recorded on a Shimadzu GCMS-QP 5050A mass
spectrometer operating at an ionisation potential of 70 eV. Benzanilide
and some of its derivatives 3 were prepared using benzoylchlorid,
aniline, 2-cyanoaniline, 3-nitroaniline, 2-aminoacetophenone and
methyl-2-aminobenzoate. Dialkyl acetylenedicarboxylates and
triphenylphosphine, were purchsed from Fluka, (Buchs, Switzerland)
and used without further purifications.
Di-tert-butyl
2-(N-phenylbenzamido)-3-(triphenylphosphanylidene)
butanedioate (4c): White powder, m.p 190–192°C, yield 0.66 g,
96%. IR (KBr) (νmax, cm-1) 1751, 1735 and 1629 (C=O). MS (m/z,
%): 685 (M+, 3), 584 (M–CO2Me3, 29), 571 (M–2CO2CMe3, 21),
262 (PPh3, 64), 183 (PPh2, 78), 108 (PPh, 56). Anal. calcd. for
C43H44NO5P (685): C, 75.29; H, 6.47; N, 2.04%. Found: C, 75.64;
H, 6.51; N, 1.98%.
Major rotamer: 1H NMR (500.1 MHz, CDCl3): δ 0.82 and 1.66
(18H, 2 s, 2OCMe3), 5.51 (1H, d, 3JPH = 19.5 Hz, P =C–CH) 7.04–7.70
(25Harom, m, 5C6H5). 13C NMR (75.5 MHz, CDCl3): δ 28.14 and 28.48
General procedures (exemplified by 4a)
Dimethyl
2-(N-phenylbenzamido)-3-(triphenylphosphanylidene)
1
2
(2OCMe3), 38.15 (d, JPC = 125.6 Hz, P =C), 61.06 (d, JPC = 17.1
Hz, P =C–CH), 76.70 and 80.37 (2OCMe3), 125.68 and 126.65 (2C,
C13H10NO), 126.70 (d, 1JPC = 92.1 Hz, Cipso), 127.15, 127.23, 127.76,
127.94 and 128.09 (5C, C13H10NO), 128.32 (d, 3JPC = 11.9 Hz, Cmeta),
129.86, 130.14 and 130.40 (3C, C13H10NO), 131.77 (Cpara), 133.78
(d, 2JPC = 9.2 Hz, Cortho), 137.80 and 141.46 (2C, C13H10NO), 167.68
(d, 3JPC = 12.4 Hz, C=O), 170.91 (d, 2JPC = 14.4 Hz, P-C=C), 169.19
(N–C=O).31P NMR (202.5 MHz, CDCl3):δ 23.39 (Ph3P+–C).
butanedioate (4a): To a magnetically stirred solution of triphenyl-
phosphine (0.26 g or 1 mmol) and benzanilide (0.2 g or 1 mmol) in
10 ml of dry ethyl acetate was added, dropwise, a mixture of dimethyl
acetylenedicarboxylate (0.14 g or 1 mmol) in 4 ml of dry ethyl acetate
over 10 min. After a few minutes stirring at room temperature, the
product was filtered and washed with cold diethyl ether (3 × 5 ml).
White powder. m.p 182–184°C, yield 0.56 g, 93%. IR (KBr)
(νmax, cm-1) 1753, 1731 and 1620 (C=O). MS (m/z, %): 601 (M+,4),
483 (M-2CO2Me, 34), 405 (M-C13H10NO, 23), 262 (PPh3, 28), 183
(PPh2, 37), 108 (PPh, 19), 77 (Ph, 100). Anal. calcd. for C37H32NO5P
(601): C, 73.85; H, 5.36; N, 2.33%. Found: C, 74.27; H, 5.21;
N, 2.40%.
Dimethyl 2-[N-(2-methoxycarbonylphenyl)benzamido]-3-(triphenyl-
phosphanylidene)butanedioate (4d): White powder. m.p 202–204°C,
yield 0.60 g, 94%. IR (KBr) (νmax, cm-1) 1750, 1725 and 1620 (C=O).
MS (m/z, %): 643 (M+, 3), 584 (M–CO2Me, 41), 389 (M–C15H12NO3,
27), 262 (PPh3, 64), 183 (PPh2, 59), 108 (PPh, 21), 77 (Ph, 100). Anal.
calcd. for C39H34NO7P (659): C, 70.99; H, 5.20; N, 2.12%. Found: C,
70.81; H, 5.19; N, 2.20%.
Major rotamer: (%52), 1H NMR (500.1 MHz, CDCl3): δ 3.18
and 3.85 (6H, 2 s, 2OCH3), 5.57 (1H, d, 3JPH = 20.1 Hz, P =C–CH),
6.82–7.91 (25Harom, m, 5C6H5). 13C NMR (125.8 MHz, CDCl3):
δ 38.69 (d,1JPC = 126.3 Hz, P=C), 49.86 and 52.53 (2OCH3), 59.79 (d,
2JPC =17.4Hz, P=C–CH), 124.08, 126.03and126.76(3C, C13H10NO),
Major rotamer: (%60), 1H NMR (500.1 MHz, CDCl3): δ 2.69, 3.18
and 3.91 (9H, 3 s, 3OCH3), 5.73 (1H, d, 3JPH = 19.4 Hz, P =C–CH),
1
126.81 (d, JPC = 91.4 Hz, Cipso), 127.33, 128.01 and 128,49 (3C,
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JOURNAL OF CHEMICAL RESEARCH 2008 99
6.97–8.34 (24Harom, m, 5C6H5). 13C NMR (125.8 MHz, CDCl3):
δ 40.16 (d, 1JPC = 127.6 Hz, P =C), 48.45, 51.25 and 52.22 (3OCH3),
60.01 (d, 2JPC = 18.1 Hz, P =C–CH), 126.04 (d, 1JPC = 92.0 Hz, Cipso),
127.34 and 128.02 (2C, C13H9NO), 128.46 (Cmeta), 128.76, 129.14,
130.06 and 130.99 (4C, C13H9NO), 131.79 (d, 4JPC = 2.2 Hz, Cpara),
Dimethyl 2-[N-(2-nitrophenyl)benzamido]-3-(triphenylphosphanyl-
idene)butanedioate (4g): Yellow powder. m.p 198–200°C, yield
0.61 g, 94%. IR (KBr) (νmax, cm-1) 1750, 1734 and 1632 (C=O). MS
(m/z, %): 646 (M+, 3), 615 (M–OMe, 44), 528 (M–2CO2Me), 405
(M–C13H9N2O3, 27), 262 (PPh3, 60), 183 (PPh2, 40), 108 (PPh, 27),
77 (Ph, 100). Anal. calcd. for C37H31N2O7P (646): C, 68.70; H, 4.83;
N, 4.33%. Found: C, 68.98; H, 4.78; N, 4.37%.
2
131.98 (1C, C13H10NO), 133.70 (d, JPC = 9.6 Hz, Cortho), 134.83,
137.58, 142.19, 164.71 and 165.69 (5C, C13H9NO), 169.06 (N–C=O),
Major rotamer: (%60), 1H NMR (500.1 MHz, CDCl3): δ 2.91 and
3.89 (6H, 2 s, 2OCH3), 5.58 (1H, d, 3JPH = 20.5 Hz, P =C–CH), 7.08–
8.04 (24Harom, m, 4C6H5 and C6H4). 13C NMR (125.8 MHz, CDCl3):
δ 38.85 (d, 1JPC = 123.9 Hz, P =C), 49.09 and 52.72 (2OCH3), 60.01
3
2
169.47 (d, JPC = 13.9 Hz, C=O ester), 174.01 (d, JPC = 12.7 Hz,
P–C=C). 31P NMR (202.5 MHz, CDCl3): δ 26.00 (Ph3P+-C).
Minor rotamer: (%40), 1H NMR (500.1 MHz, CDCl3): δ 3.04, 3.16
and 3.85 (9H, 3 s, 3OCH3), 5.88 (1H, d, 3JPH = 21.2 Hz, P =C–CH),
6.97–8.34 (24Harom, m, 5C6H5). 13C NMR (125.8 MHz, CDCl3):
δ 41.48 (d, 1JPC = 134.7 Hz, P =C), 49.28, 52.18 and 51.96 (3OCH3),
59.92 (d, 2JPC = 18.4 Hz, P =C–CH), 127.25 (1C, C13H9NO), 126.19
2
(d, JPC = 18.1 Hz, P =C–CH), 121.22, 121.78 and 125.60 (3C,
C13H9NO), 125.91 (d, 1JPC = 92.0 Hz, Cipso), 127.84 and 127.96 (2C,
C13H9NO), 128.89 (d, 3JPC = 12.0 Hz, Cmeta), 129.23 (1C, C13H9NO),
2
132.45 (Cpara), 133.40 (d, JPC = 9.7 Hz, Cortho), 136.26, 136.33,
1
(d, JPC = 91.8 Hz, Cipso), 128.24 (1C, C13H9NO), 128.62 (Cmeta),
137.08, 142.21, 142.50 and 147.04 (6C, C13H9NO), 169.06 (N–C=O),
128.83, 129.02, 130.38 and 131.07 (4C, C13H9NO), 131.79 (d, 4JPC
=
2
169.73 (d, 3JPC = 18.5 Hz, C=O ester), 172.59 (d, JPC = 13.4 Hz,
2.2 Hz, Cpara), 132.12 (1C, C13H9NO), 133.85 (d, 2JPC = 9.8 Hz, Cortho),
134.66, 137.75, 141.84, 164.42 and 165.34 (5C, C13H9NO), 169.06
(N–C=O), 170.09 (d, 3JPC = 9.1 Hz, C=O), 174.05 (d, 2JPC = 12.3 Hz,
P–C=C). 31P NMR (202.5 MHz, CDCl3): δ 26.48 (Ph3P+-C).
P–C=C). 31P NMR (202.5 MHz, CDCl3): δ 23.96 (Ph3P+-C).
Minor rotamer: (%40), 1H NMR (500.1 MHz, CDCl3): δ 3.12 and
3.82 (6H, 2 s, 2OCH3), 5.64 (1H, d, 3JPH = 18.9 Hz, P =C–CH), 7.08–
8.04 (24Harom, m, 4C6H5 and C6H4). 13C NMR (125.8 MHz, CDCl3):
δ 40.89 (d, 1JPC = 133.7 Hz, P =C), 49.72 and 52.45 (2OCH3), 59.92
2
(d, JPC = 18.4 Hz, P =C–CH), 121.26, 121.84 and 125.66 (3C,
Diethyl 2-[N-(2-methoxycarbonylphenyl)benzamido]-3-(triphenyl-
phosphanylidene)butanedioate (4e): White powder, m.p 141–143°C,
yield 0.63 g, 91%. IR (KBr) (νmax, cm-1): 1758, 1690 and 1656 (C=O).
MS (m/z, %): 687 (M+, 4), 629 (M–2Et, 30), 628 (M–OCH3, 40), 614
(M–CO2Et, 53), 262 (PPh3, 67), 183 (PPh2, 77), 108 (PPh, 37), 77
(Ph, 100). Anal. calcd. for C41H38NO7P (687): C, 71.58; H, 5.57; N,
2.04%. Found: C, 71.97; H, 5.57; N, 1.97%.
C13H9NO), 126.37 (d, 1JPC = 91.7 Hz, Cipso), 127.79 and 128.02 (2C,
3
C13H9NO), 129.05 (d, JPC = 11.6 Hz, Cmeta), 132.45 (Cpara), 133.61
2
(d, JPC = 9.9 Hz, Cortho), 136.21, 136.37, 136.14, 137.14, 142.25,
142.56 and 147.08 (7C, C13H9NO), 169.06 (N–C=O), 169.03 (d,
3JPC = 12.8 Hz, C=O), 169.97 (d, 2JPC = 18.3 Hz, P–C=C). 31P NMR
(202.5 MHz, CDCl3): δ 25.14 (Ph3P+-C).
Major rotamer: (%61). 1H NMR (500.1 Hz, CDCl3 δ 0.24 and 1.39
(6H, 2t, 3JHH = 7.1 Hz, 2OCH2CH3), 3.15 (1 s, OCH3), 3.47 and 4.30
(4 H, 2 m, 2ABX3system, 2OCH2CH3), 5.73 (1H, d, 3JPH = 19.6 Hz,
P =C–CH), 6.86–8.44 (24Harom, m, 4C6H5 and C6H4). 13C NMR
(125.8 MHz, CDCl3): δ 13.82 and 14.47 (2OCH2CH3), 40.13 (d, 1JPC
= 125.9 Hz, P =C), 51.23 (OCH3), 57.23 (OCH2CH3), 61.00 (d, 2JPC
= 18.2 Hz, P =C–CH), 61.05 (OCH2CH3), 126.22(1C, C13H9NO),
Diethyl 2-[N-(2-nitrophenyl)benzamido]-3-(triphenyl phosphanylidene)
butanedioate (4h): Yellow powder, m.p 179–181°C, yield 0.62 g,
92%. IR (KBr) (νmax, cm-1): 1745, 1731 and 1617 (C=O). MS (m/z,
%): 674 (M+, 3), 601 (M–CO2Et, 38), 584 (M–2OEt, 31), 433 (M–
C13H9N2O3t, 26), 262 (PPh3, 53), 183 (PPh2, 80), 108 (PPh, 45), 77
(Ph, 100). Anal. calcd. for C39H35N2O5P (674): C, 69.41; H, 5.23; N,
4.15%. Found: C, 70.01; H, 5.15; N, 4.20%.
1
Major rotamer: (%65). 1H NMR (500.1 Hz, CDCl3 δ 0.34 and
126.67 (d, JPC = 91.9 Hz, Cipso), 127.24, 127.98 and 128.19 (3C,
3
3
C13H9NO), 128.40 (d, JPC = 11.9 Hz, Cmeta), 128.73, 129.22,
1.39 (6H, 2t, JHH = 7.1 Hz, 2OCH2CH3), 3.45 and 4.3o (4 H, 2 m,
129.91, 130.04 and 131.14 (5C, C13H9NO), 131.87 (Cpara), 133.64
2ABX3system, 2OCH2CH3), 5.62 (1H, d, 3JPH = 18.7 Hz, P =C–CH),
7.08–8.04 (24Harom, m, 4C6H5 and C6H4). 13C NMR (125.8 MHz,
CDCl3): δ 13.89 and 14.38 (2OCH2CH3), 39.07 (d, 1JPC = 125.7 Hz,
P =C), 57.75 (OCH2CH3), 60.63 (d, 2JPC = 17.7 Hz, P =C–CH), 61.36
(OCH2CH3), 115.43, 121.26 and 121.76 (3C, C13H9NO), 126.63
(d, 2JPC = 9.3 Hz, Cortho), 134.81, 137.72 and 142.22(3C, C13H9NO),
3
164.71(CH3O–C=O), 168.95 (d, JPC = 13.9 Hz, C=O), 170.14 (N–
2
C=O), 173.38 (d, JPC = 12.6 Hz, P–C=C). 31P NMR (202.5 MHz,
CDCl3): δ 25.68 (Ph3P+–C).
1
1
(d, JPC = 91.8 Hz, Cipso), 127.64, 127.78, 127.98 and 128.42 (4C,
Minor rotamer: (%39). H NMR (500.1 MHz, CDCl3): δ 1.09 and
C13H9NO), 128.81 (d, 3JPC = 12.4 Hz, Cmeta), 129.19 and 129.82 (2C,
1.42 (6H. 2t. 3JHH = 7.1, 2OCH2CH3), 3.01(1 s, OCH3), 4.21 and 4.44
2
C13H9NO), 132.37 (Cpara), 133.52 (d, JPC = 9.7 Hz, Cortho), 133.71,
3
(4H, 2 m, 2ABX3system, 2OCH2CH3), 5.85 (1H, d, JPH = 21.4 Hz,
142.26 and 142.56 (3C, C13H9NO), 169.63 (N–C=O), 169.92 (d,
3JPC = 17.8 Hz, C=O), 172.08 (d, 2JPC = 13.8 Hz, P–C=C). 31P NMR
(202.5 MHz, CDCl3): δ 24.01 (Ph3P+–C).
P =C–CH), 6.86–8.44 (24Harom, m, 4C6H5 and C6H4). 13C NMR (125.8
MHz, CDCl3): δ 14.40 and 14.76 (2OCH2CH3), 40.27 (d, 1JPC = 134.8
Hz, P =C), 51.18 (OCH3), 57.60 (OCH2CH3), 59.91 (d, 2JPC = 18.3 Hz,
P =C–CH), 61.02 (OCH2CH3), 126.30 (1C, C13H9NO), 126.85 (d, 1JPC
Minor rotamer: (%35). 1H NMR (500.1 MHz, CDCl3): δ 1.27
3
and 1.42 (6H. 2t. JHH = 7.1, 2OCH2CH3), 4.16 and 4.37 (4H, 2 m,
3
= 92.0 Hz, Cipso), 127.29 (1C, C13H9NO), 128.54 (d, JPC = 12.0 Hz,
2ABX3system, 2OCH2CH3), 5.53 (1H, d, 3JPH = 21.7 Hz, P =C–CH),
7.08–8.04 (24Harom, m, 4C6H5 and C6H4). 13C NMR (125.8 MHz,
CDCl3): δ 14.27 and 14.38 (2OCH2CH3), 40.98 (d, 1JPC = 132.5 Hz,
P =C), 58.16 (OCH2CH3), 60.02 (d, 2JPC = 17.3 Hz, P =C–CH), 61.27
(OCH2CH3), 116.21, 121.54 and 122.03 (3C, C13H9NO), 126.24
(d, 1JPC = 92.0 Hz, Cipso), 126.42, 127.91, 128.18 and 128.64 (4C,
C13H9NO), 128.89 (d, 3JPC = 12.6 Hz, Cmeta), 129.37 and 130.11 (2C,
Cmeta), 128.93, 128.26, 128.73, 129.33, 129.91, 130.12 and 131.19 (7C,
2
C13H9NO), 131.87 (Cpara), 133.85 (d, JPC = 9.1 Hz, Cortho), 134.88,
137.85 and 142.93 (3C, C13H9NO), 164.46 (CH3O–C=O), 169.04 (d,
2
3JPC = 13.2 Hz, C=O), 169.88 (N–C=O), 173.51 (d, JPC = 12.5 Hz,
P–C=C), 31P NMR (202.5 MHz, CDCl3): δ 26.68 (Ph3P+–C).
2
C13H9NO), 132.37 (Cpara), 133.65 (d, JPC = 9.7 Hz, Cortho), 133.84,
Di-tert-butyl 2-[N-(2-methoxycarbonylphenyl)benzamido]-3-(triphenyl-
phosphanylidene)butanedioate (4f): White powder, m.p 47–149°C,
yield 0.71 g, 96%. IR (KBr) (νmax, cm-1) 1761, 1737 and 1624 (C=O).
MS (m/z, %): 743 (M+, 5), 684 (M–CO2Me, 47), 560 (M–PPh2, 20),
489 (M–C15H12NO3, 17), 262 (PPh3, 80), 183 (PPh2, 73), 108 (PPh,
57). Anal. calcd. for C45H46NO7P (743): C, 72.64; H, 6.24; N, 1.88%.
Found: C, 72.95; H, 6.29; N, 2.01%.
142.48 and 142.93 (3C, C13H9NO), 168.53 (d, 3JPC = 13.1 Hz, C=O),
2
169.88 (N–C=O), 171.83 (d, JPC = 16.6 Hz, P–C=C), 31P NMR
(202.5 MHz, CDCl3): δ 25.50 (Ph3P+–C).
Dimethyl 2-[N-(2-cyanophenyl)benzamido]-3-(triphenylphosphanylidene)
butanedioate (4i): Yellow powder. m.p 205–207°C, yield 0.58 g, 92%.
IR (KBr) (νmax, cm-1) 1729, 1641 and 1612 (C=O). MS (m/z, %):
626 (M+, 5), 595 (M–OMe, 29), 508 (M–2CO2Me, 32), 262 (PPh3,
78), 183 (PPh2, 86), 108 (PPh, 54), 77 (Ph, 100). Anal. calcd. for
C38H31N2O5P (626): C, 72.81; H, 4.99; N, 4.47%. Found: C, 72.65;
H, 5.04; N, 4.53%.
1
Major rotamer: H NMR (500.1 MHz, CDCl3): δ 0.69 and 1.63
3
(18H, 2 s, 2OCMe3), 5.47 (1H, d, JPH = 20.2 Hz, P =C–CH) 6.93–
8.56 (24Harom, m, 4C6H5 and C6H4). 13C NMR (75.5 MHz, CDCl3):
1
δ 28.07 and 28.55 (2OCMe3), 39.21 (d, JPC = 127.4 Hz, P =C),
2
51.28 (OMe), 61.95 (d, JPC = 18.4 Hz, P =C-CH), 76.69 and 80.34
Major rotamer: (%65), 1H NMR (500.1 MHz, CDCl3): δ 2.81 and
3.92 (6H, 2 s, 2OCH3), 5.56 (1H, d, 3JPH = 19.0 Hz, P =C–CH), 7.09–
8.45 (24Harom, m, 4C6H5 and C6H4). 13C NMR (125.8 MHz, CDCl3):
δ 40.23 (d, 1JPC = 125.3 Hz, P =C), 48.80 and 52.70 (2OCH3), 61.63
(d, 2JPC = 17.6 Hz, P =C–CH), 114.48 (1C, C13H9NO), 117.71 (CN),
122.22, 124.55 and 125.20 (3C, C13H9NO), 125.84 (d, 1JPC = 92.0 Hz,
Cipso), 127.73 and 128.60 (2C, C13H9NO), 128.84 (d, 3JPC = 12.5 Hz,
Cmeta), 129.18 (1C, C13H9NO), 132.26 (Cpara), 133.55 (d, 2JPC = 9.5 Hz,
(2OCMe3), 126.36 and 126.42 (2C, C13H9NO), 126.51 (d, 1JPC = 92.0
Hz, Cipso), 127.43 (1C, C13H9NO), 128.13 (d, 3JPC = 11.8 Hz, Cmeta),
128.60, 129.96, and 131.58 (3C, C13H9NO), 133.15 (Cpara), 133.87
(d, 2JPC = 9.2 Hz, Cortho), 134.87, 137.73 and 142.59 (3C, C13H9NO),
3
164.80 (MeO–C=O), 168.08 (d, JPC = 13.3 Hz, C=O), 169.87 (N–
2
C=O), 171.68 (d, JPC = 12.4 Hz, P–C=C). 31P NMR (202.5 MHz,
CDCl3):δ 25.06 (Ph3P+–C).
PAPER: 07/4901

100 JOURNAL OF CHEMICAL RESEARCH 2008
Cortho), 133.87, 136.37, 144.21 and 165.62 (4C, C13H9NO), 169.22 (d,
3JPC =13.4Hz,C=Oester),169.76(N–C=O),173.36(d,2JPC =13.7Hz,
P–C=C). 31P NMR (202.5 MHz, CDCl3): δ 26.10 (Ph3P+-C).
We gratefully acknowledge financial support from the
Research Council of University of Sistan and Balouchestan.
Minor rotamer: (%35), 1H NMR (500.1 MHz, CDCl3): δ 3.24 and
3.87 (6H, 2 s, 2OCH3), 5.68 (1H, d, 3JPH = 20.5 Hz, P =C–CH), 7.09–
8.45 (24Harom, m, 4C6H5 and C6H4). 13C NMR (125.8 MHz, CDCl3):
δ 41.68 (d, 1JPC = 132.4 Hz, P =C), 49.40 and 52.51 (2OCH3), 60.53
(d, 2JPC = 18.6 Hz, P =C–CH), 115.67 (1C, C13H9NO), 117.67 (CN),
Received 19 October 2007; accepted 15 February 2008
Paper 07/4901
doi: 10.3184/030823408X293675
References
1
122.28, 125.28 and 125.39 (4C, C13H9NO), 125.96 (d, JPC = 91.2
1
M. Nakamura, M. Miki and T. Majima, J. Chem. Soc. Perkin Trans 2.,
3
Hz, Cipso), 127.41 and 128.70 (2C, C13H9NO), 128.75 (d, JPC
=
2000, 1447.
12.1 Hz, Cmeta), 129.78 (1C, C13H9NO), 132.26 (Cpara), 132.51(1C,
C13H9NO), 133.81 (d, 2JPC = 9.8 Hz, Cortho), 134.10, 136.42, 143.49
and 165.39 (4C, C13H9NO), 169.70 (N–C=O), 169.84 (d, 3JPC = 12.1
Hz, C=O), 173.44 (d, 2JPC = 12.9 Hz, P–C=C). 31P NMR (202.5 MHz,
CDCl3): δ 26.46 (Ph3P+–C).
2
3
S. Yasui, S. Tojo and T. Majima,. J. Org. Chem., 2005, 70, 1276.
D.E.C. Corbridge, Phosphorus, an outline of the chemistry, biochemistry,
and uses, Elsevier Amsterdam, 5th edn 1995.
4
R. Engel, Synthesis of carbon–phosphorus bonds, CRC Press, Boca
Raton, FL, 1988.
5
6
A.W. Johnson, Ylide chemistry, Academic Press, London, 1966.
J.I.G. Cadogan, Organophosphorus reagents in organic synthesis,
Academic Press, New York, 1979.
H.R. Hudson, Chemistry of organophosphorus compounds: primary
secondary and tertiary phosphines and heterocyclic organophosphorus
(III) compounds, ed. Hantely, F.R., Wiley, New York, 1990.
I. Yavari, M. Anary-Abbasinejad and Z. Hossaini, Org. Biomol. Chem.,
2003, 1, 560.
Di-tert-butyl 2-[N-(2-cyanophenyl)benzamido]-3-(triphenylphosph
anylidene)butanedioate (4j): White powder, m.p 189–191°C, yield
0.71 g, 96%. IR (KBr) (νmax, cm-1) 1741, 1735 and 1620 (C=O).
MS (m/z, %): 710 (M+, 4), 609 (M–CO2CMe3, 34), 560 (M–2OCMe3,
53), 262 (PPh3, 77), 183 (PPh2, 80), 108 (PPh, 69). Anal. calcd. for
C44H43N2O5P (710): C, 74.33; H, 6.10; N, 3.94%. Found: C, 74.68;
H, 5.99; N, 4.02%.
7
8
9
I. Yavari, M. Adib and L. Hojabri, Tetrahedron, 2002, 58, 6895.
1
Major rotamer: H NMR (500.1 MHz, CDCl3): δ 0.74 and 1.63
10 I. Yavari, A. Alizadeh and M. Anary-Abbasinejad, Phosphorus, sulfur
silicon, 2003, 178, 269.
3
(18H, 2 s, 2OCMe3), 5.38 (1H, d, JPH = 19.7 Hz, P =C–CH), 7.04–
8.61 (24Harom, m, 4C6H5 and C6H4). 13C NMR (75.5 MHz, CDCl3):
11 I. Yavari and A. Alizadeh, Synthesis, 2004, 2, 237.
12 I. Yavari, M. Adib and L. Hojabri, Tetrahedron, 2001, 57, 7537.
13 I. Yavari and F. Feiz-Javadian, Phosphorus, sulfur silicon, 2006, 181, 1011.
14 I. Yavari, N. Zabarjad-Shiraz and T. Partovi, Synth Commun., 2002, 32,
2763.
δ 28.07 and 28.47 (2OCMe3), 39.58 (d, 1JPC = 126.0 Hz, P =C), 62.55
2
(d, JPC = 17.9 Hz, P =C–CH), 76.96 and 80.61 (2OCMe3), 114.48
(1C, C13H9NO), 117.91 (CN), 121.73 and 124.45 (3C, C13H9NO),
126.62 (d, 1JPC = 91.8 Hz, Cipso), 126.85 and 127.33 (2C, C13H9NO),
128.52 (d, 3JPC = 12.1 Hz, Cmeta), 129.01 and 129.16 (2C, C13H9NO),
15 I. Yavari, A. Alizadeh and M. Anary-Abbasinejad, Tetrahedron Lett.,
2003, 44, 2877.
2
132.01 (Cpara), 132.32 (1C, C13H9NO), 132.84 (d, JPC = 9.2 Hz,
Cortho), 133.18, 133.67, 136.60 and 144.67 (4C, C13H9NO), 167.88 (d,
3JPC = 12.6 Hz, C=O), 169.32 (N–C=O), 171.29 (d, 2JPC = 13.4 Hz,
P–C=C). 31P NMR (202.5 MHz, CDCl3):δ 25.19 (Ph3P+–C).
16 I. Yavari and E. Karimi, Phosphorus, sulfur silicon, 2007, 182, 595.
17 I. Yavari and F. Noumohammadian Tetrahedron, 2000, 56, 5221.
18 I. Yavari and A. Ramazani, Phosphorus, sulfur silicon, 1997, 130, 73.
19 N. Hazeri, S.M. Habibi-Khorasani, M.T. Maghsoodlou, G. Marandi,
M. Nassir and A.G. Shahzadeh, J. Chem. Res., 2006, 215.
20 M.T. Maghsoodlou, S.M. Habibi-Khorasani, N. Hazeri, M. Nassiri,
R. Kakaei and G. Marandi, Phosphorus, sulfur silicon, 2006, 181, 553.
21 M.T. Maghsoodlou, R. Heydari, S.M. Habibi-Khorasani, M.K. Rofouei,
M. Nassiri, E. Mosaddegh and A. Hassankhani, J. Sulfur Chem., 2006, 27,
341.
22 M.T. Maghsoodlou, N. Hazeri, S.M. Habibi-Khorasani, L. Saghatforoush,
M.K. Rofouei and M. Rezaie, Arkivoc., 2006, xiii, 117.
23 M.T. Maghsoodlou, S.M. Habibi-Khorasani, R. Heydari and F.R. Charati,
J. Chem. Res., 2006, 364.
24 M.T. Maghsoodlou, S.M. Habibi-Khorasani, M.K. Rofouei,
S.R. Adhamdoust and M. Nassiri, Arkivoc., 2006, xii, 145.
25 N. Khir-el-Din, A.A. Nada, M. Ramla and M.F. Zayed, Synth. Commun.,
2002, 32, 591.
Dimethyl 2-[N-(2-acetylphenyl)benzamido-3-(triphenylphosphanyl-
idene)butanedioate (4k): Yellow powder. m.p 150–152°C, yield
0.61 g, 95%. IR (KBr) (νmax, cm-1) 1743, 1634 and 1618 (C=O).
MS (m/z, %): 643 (M+, 4), 581 (M–2OMe, 21), 525 (M–2CO2Me,
36), 262 (PPh3, 33), 183 (PPh2, 38), 108 (PPh, 100). Anal. calcd. for
C39H34NO6P (643): C, 72.75; H, 5.32; N, 2.18%. Found: C, 73.12; H,
5.38; N, 2.22%.
Major rotamer: (%56), 1H NMR (500.1 MHz, CDCl3): δ 2.73 (1H,
s, CH3), 3.07 and 3.80 (6H, 2 s, 2OCH3), 5.72 (1H, d, 3JPH = 19.4 Hz,
P =C–CH), 7.00–8.38 (24Harom, m, 4C6H5 and C6H4). 13C NMR
1
(125.8 MHz, CDCl3): δ 28.66 (CH3), 40.08 (d, JPC = 123.9 Hz,
P =C), 48.48 and 52.35 (2OCH3), 61.22 (d, 2JPC = 16.8 Hz, P =C–CH),
120.79, 122.53, 125.15 and 127.48 (4C, C13H9NO), 127.63 (d, 1JPC
90.2 Hz, Cipso), 128.22 (1C, C13H9NO), 128.50 (d, JPC = 12.1 Hz,
=
3
26 J.J. Kiddle, Synth. Commun., 2001, 21, 3377.
27 M.R. Islami, Z. Hassani and K. Saidi, Synth Commun., 2003, 33, 65.
28 Z. Hassani, M.R. Islami, H. Sheibani, M. Kalantari and K. Saidi, Arkivoc.,
2006, i, 89.
29 M. Kalantari, M.R. Islami, Z. Hassani and K. Saidi, Arkivoc., 2006, x, 55.
30 M.R. Islami, F. Mollazehi, A. Badiei and H. Sheibani, Arkivoc., 2005,
xy, 25.
31 A. Alizadeh and H.R. Bijanzadeh, Synthesis., 2004, 18, 3023.
32 M. Adib, M. Mostofi, K. Ghanbary and H.R. Bijanzadeh, Synthesis, 2005,
10, 1663.
33 K. Moonen, E.V. Meenen, A. Verwee and C.V. Stevens, Angew. Chem.
Int. Ed. Eng., 2005, 44, 7407.
34 K. Moonen, I. Laureyn and C.V. Stevens, Chem. Rev., 2004, 104, 6177.
35 P.J. Murphy and S.E. Lee, J. Chem. Soc. Perkin Trans. 1., 1999, 3049.
36 H. Krawczyk, W.M. Wolf and M. Sliwinski, J. Chem. Soc. Perkin Trans.
1., 2002, 2794.
37 V.K. Brel, Synthesis, 2002, 13, 1829.
38 R. Robiette, J. Richardson, V.K. Aggarwal and J.N. Harvey, J. Am. Chem.
Soc., 2005, 127, 13468.
Cmeta), 129.01, 130.15, 131.03, 131.88 and 133.24 (5C, C13H9NO),
2
133.41 (Cpara), 134.15 (d, JPC3 = 9.0 Hz, Cortho), 141.43 and 166.13
(2C, C13H9NO), 169.35 (d, JPC = 13.6 Hz, C=O ester), 169.62
2
(N–C=O), 172.18 (d, JPC = 13.9 Hz, P–C=C), 203.33 (O=C–CH3).
31P NMR (202.5 MHz, CDCl3): δ 26.11 (Ph3P+–C).
Minor rotamer: (%44), 1H NMR (500.1 MHz, CDCl3): δ 2.71 (1H,
s, CH3), 3.82 and 3.88 (6H, 2 s, 2OCH3), 5.89 (1H, d, 3JPH = 20.0 Hz,
P =C–CH), 7.00–8.38 (24Harom, m, 4C6H5 and C6H4). 13C NMR
1
(125.8 MHz, CDCl3): δ 28.66 (CH3), 41.25 (d, JPC = 135.4 Hz,
2
P =C), 49.36 and 52.35 (2OCH3), 60.41 (d, JPC = 16.5 Hz,
P =C–CH), 120.63, 121.96 and 125.19 (3C, C13H9NO), 126.83
(d, 1JPC = 91.3 Hz, Cipso), 127.54 and 128.42 (2C, C13H9NO), 128.50
(d, 3JPC = 12.1 Hz, Cmeta), 129.27, 130.33, 131.22, 131.92 and 133.05
(5C, C13H9NO), 133.41(Cpara), 134.15(d, 2JPC =9.0Hz, Cortho), 140.73
and 165.38 (2C, C13H9NO), 168.76 (d, 3JPC = 14.2 Hz, C=O), 169.45
2
(N–C=O), 171.92 (d, JPC = 14.0 Hz, P–C=C), 203.33 (O=C–CH3).
31P NMR (202.5 MHz, CDCl3): δ 26.52 (Ph3P+–C).
PAPER: 07/4901