Three-component reaction between triphenylphosphine, acetylenic esters and 4-hydroxycoumarin, 4-(phenylamino)coumarin, 4-hydroxyquinolin-2(1H)-one or 4-hydroxy-1-methylquinolin-2(1H)-one

Article abstract of DOI:10.3184/030823407X256154

Three-component reaction between dialkyl acetylenedicarboxylates and triphenylphosphine in the presence of 4-hydroxycoumarin, 4-(phenylamino) coumarin, 4-hydroxyquinolin-2(1H)-one or 4-hydroxy-1-methylquinolin-2(1H)-one is described.

Full text of DOI:10.3184/030823407X256154

JOURNAL OF CHEMICAL RESEARCH 2007
OCTObER, 605–608
RESEARCH PAPER 605
Three-component reaction between triphenylphosphine, acetylenic
esters and 4-hydroxycoumarin, 4-(phenylamino)coumarin,
4-hydroxyquinolin-2(1Hꢀ)-one or 4-hydroxy-1-methylquinolin-2(1Hꢀ)-one
Mohammad Anary-Abbasinejada*, Hossein Anaraki-Ardakanib, Ali Ezadia and
Alireza Hassanabadia
aDepartment of Chemistry, Islamic Azad University, Yazd Branch, PO Box 89195-155, Yazd, Iran
bDepartment of Chemistry, Islamic Azad University, Mahshahr Branch, Mahshahr, Iran
Three-component reaction between dialkyl acetylenedicarboxylates and triphenylphosphine in the presence of
4-hydroxycoumarin, 4-(phenylamino)coumarin, 4-hydroxyquinolin-2(1H)-one or 4-hydroxy-1-methylquinolin-2(1H)-
one is described.
Keywords: acetylenic esters, 4-hydroxycoumarin, 4-(phenylamino)coumarin, 4-hydroxyquinolin-2(1H)-one, triphenylphosphine,
phosphorus ylides
The nucleophilic addition of triphenylphosphine to electron-
deficient triple bonds leads to a highly reactive zwitterionic
intermediate which may be trapped by various electrophiles.
The reaction of triphenylphosphine with dimethyl
acetylenedicarboxylate (DMAD) in the presence of different
organic acidic compounds, in order to trap the diionic
intermediate, has been extensively investigated.1–2,11 In the
most of these reactions, the phosphorus ylides were reported
as intermediates or the final product. However, there are also
many reports of the reaction between triphenylphosphine and
acetylenic esters in the presence of an electrophile in which
triphenylphosphine acted as catalyst.3-6 In fact, in these
reactions nucleophilic triphenylphosphine connected together
the two electrophilic substrates. In continuation of our
previous works on the reaction between trivalent phosphorus
nucleophiles with acetylenic esters in the presence of organic
acidic compounds,7-11 we report here the results of our study on
the reaction between triphenylphosphine and electron-deficient
acetylenic esters in the presence of 4-hydroxycoumarin, 4-
(phenylamino)coumarin, 4-hydroxyquinolin-2(1H)-one or
4-hydroxy-1-methylquinolin-2(1H)-one. Thus the reaction
between DMAD or diethyl acetylendicarboxylate (DEAD)
with 4-hydroxyquinolin-2(1H)-one in the presence of
triphenylphosphine afforded dialkyl 2-(4-hydroxy-2-oxo-1,2-
dihydroquinolin-3-yl)-3-(triphenylphosphanylidene)succinate
4a, b in excellent yields (Scheme 1).
4-(Z) geometrical isomers is low on the NMR time scale at
ambient temperature (Scheme 2). Conformational isomers in
phosphoranes have been previously established and reported
in the literature.12-14
The 1H NMR spectrum of 4a shows two sharp lines (d = 2.82,
3.52 ppm) for the methyl groups of the major isomer, along
with a signal for the methine proton at 5.13 ppm, which appears
as a doublet (3JPH = 11 Hz). Two single signals are observed at
d = 9.63 and 9.68 ppm which disappear after addition to DMSO
solution of 4a a few drops of D2O. These signal are related to
NH and OH protons. The aromatic protons show multiplets at
d = 6.99-7.58 ppm. The corresponding signals for the minor
isomer appear at d = 3.42, 3.82 ppm for methyl groups and
at d = 4.39 ppm (3JPH = 9 Hz) for the methine proton. The
31P NMR spectrum of compound 4a displays two signals
at 24.49 and 24.85 ppm for the major and minor isomers,
respectively. These shifts are similar to those observed for
other stable phosphorus ylides.15,16 The structural assignments
made on the basis of the NMR spectra of compound 4a
are supported by its IR spectrum. The ester carbonyl
groups exhibit absorption bands at 1736 and 1619 cm-1.
TheN-Hstretchingabsorptionbandsappearat3295–3150cm-1.
On the basis of the well-established chemistry of trivalent
phosphorus nucleophiles2,15 it is reasonable to assume that
ylides 4 result from the initial addition of triphenylphosphine
to the acetylenic ester and subsequent protonation of the 1:1
adduct by 4-hydroxyquinolin-2(1H)-one. Then, the positively
charged ion intermediate 5 is attacked by the conjugate anion
of 4-hydroxyquinolin-2(1H)-one 6 to form the phosphorane 4
(Scheme 3).
The structures of compounds 4a, b result from their IR,
1H, 13C, and 31P NMR spectra. The mass spectra of the ylides
4 are fairly similar and display molecular ion peaks. The
NMR spectra of ylides 4a, b are consistent with the presence
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 4-(E),
Under similar conditions as for the reactions above,
triphenylphosphine reacted with DMAD in the presence of
4-(phenylamino)coumarin to produce phosphorane 8 in 90%
OH CO2R
PPh3
OH
RO2C
CO2R
2
+
CO2R
N
H
O
N
H
O
PPh3
4
3
1
%Yield
92
2,4
a
b
R
Me
Et
95
Scheme 1
* Correspondent. E-mail: mohammadanary@yahoo.com
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606 JOURNAL OF CHEMICAL RESEARCH 2007
_
subsequent elimination of triphenylphosphine (Scheme 6).
Compound 11 may be obtained from the intermediate ylide
12 by losing of triphenylphosphine (Scheme 7). The 1H NMR
spectrum of compound 10 showed two singlets at 3.87
and 6.79 ppm for methoxy and methine protons, respectively.
The 13C NMR spectrum of compound 10 showed 14 distinct
signals in accordance with the proposed structure.
O
OH CO2R
OH CO2R
OR
_
OR
O
+
+
PPh3
PPh3
N
H
O
N
H
O
When 4-hydroxy-1-methylquinolin-2(1H)-one 14 treated
with dimethyl acetylenedicarboxylate in the presence of
triphenylphosphine, dimethyl 2-(1,2-dihydro-4-hydroxy-1-
methyl-2-oxoquinolin-3-yl)fumarate 15 were formed in 90%
yield (Scheme 8).
Scheme 2
H
H
N
RO2C
O
1
The H NMR spectrum of 15 exhibited three single sharp
4
lines readily recognised as arising from methyl (d = 3.55
ppm) and methoxy (d = 3.57 and 3.68 ppm) protons, along
with a single signal for the methine proton at 6.89 ppm. The
aromatic protons appeared as multiplets at d = 7.26–8.02 ppm.
A singlet was observed at d = 10.72 ppm which arises from
OH proton and disappeared after addition of D2O to DMSO
solution of compound 15.
+
CO2R
Ph3P
O
_
5
6
Scheme 3
In summary phosphorus ylides may be prepared by a
simple, one-pot, three-component reaction of acetylenic
esters, triphenylphosphine and 4-(phenylamino)coumarin
or 4-hydroxyquinolin-2(1H)-one. Similar reaction between
triphenylphosphine, DMAD and 4-hydroxy-1-methylquinolin-
2(1H)-one produces dimethyl 2-(1,2-dihydro-4-hydroxy-1-
methyl-2-oxoquinolin-3-yl)fumarate. 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 modification.
yield (Scheme 4). NMR spectra of compound 8 in d6-DMSO
show that for this compound, in contrast to ylides 4a and 4b,
the rate of conversion of two rotational isomers is too fast in
the NMR time scale so that only one set of signals is observed
in the 1H and 13C NMR spectra of this compound.
Reaction between triphenylphosphine and acetylenic esters
was also carried out in the presence of 4-hydroxycoumarin.
When DMAD was used, the only isolated product was methyl
2,5-dioxo-2H,5H-pyrano[3,2-c]chromene-4-carboxylate 10
which obtained in 89% yield (Scheme 5). However, three-
component reaction between triphenylphosphine, DEAD and
4-hydroxycoumarin afforded diethyl 2-(4-hydroxy-2-oxo-2H-
chromen-3-yl)fumarate 11 in 90% yield. The chemical shift of
Experimental
All melting points were determined on an Electrothermal 9100
apparatus and are uncorrected. Elemental analyses were performed
using a Heraeus CHN-O-Rapid analyser. Mass spectra were recorded
on a Finnigan-Mat 8430 mass spectrometer operating at an ionisation
potential of 70 eV. IR spectra were recorded on a Shimadzu IR-
1
6.99 ppm of the olefinic proton in the H NMR spectrum of
compound 11 is consistent with the E-geometry of the carbon–
carbon double bond.16 It is reasonable to assume that compound
10 was produced from phosphorane 12 by lactonisation and
1
470 spectrometer. H, 13C, and 31P NMR spectra were recorded on
bruker DRX-300 Avance spectrometer at 300.1, 75.46, and 121.49
H
Ph
H
Ph
N
O
N
O
CO2Me
PPh3
CO2Me
+
PPh3
+
CO2Me
O
O
CO2Me
8
7
Scheme 4
OH CO2Et
H
R=CO2Et
CO2Et
O
O
11
OH
CO2R
+
PPh3
+
O
O
O
CO2R
9
O
O
OMe
R=CO2Me
O
O
10
Scheme 5
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JOURNAL OF CHEMICAL RESEARCH 2007 607
OMe
OMe
+
O
O
_
O
OH
PPh3
OMe
PPh3
-PPh3, -CH3OH
10
OMe
H
O
O
O
O
O
O
12
13
Scheme 6
(d6-DMSO): d 14.15, 14.35 (2 CH3), 42.32 (d, 1JPC = 126 HZ, C = P),
_
57.39, 60.20 (2 OCH2), 63.48 (d, 2JPC = 15 HZ, CH), 126.16 (d, 1JPC
=
O
CO2Me
H
+
92 HZ,C ipso), 128.65 (d, 3JPC = 12 HZ, C meta), 132.06 (d, 4JPC = 2.2 HZ,
PPh3
-PPh3
2
para), 133.75 (d, JPC = 10 HZ, C ortho), 118.88, 119.29, 123.50,
11
C
123.96, 128.11, 129.25, 139.32, 139.63 (aromatic), 166.93 (HO–C=)*,
CO2Me
O
O
167.09 (C=O)*, 169.45 (d, JPC = 13 HZ, C=O)*, 174.93 (d, JPC
=
2
3
11 HZ, C=O)*. 31P NMR (CDCl3): d 23.41. Minor isomer (30%): H
1
13
NMR (d6-DMSO) d 0.45 (t, 3JHH = 7 HZ, 3 H, CH3), 1.35 (t, 3JHH
=
7 HZ, 3 H, CH3), 3.81 (m, 2 H, OCH2), 4.08 (m, 2 H, OCH2), 4.71 (d,
Scheme 7
3JPH = 9 HZ, 1 H, P =C–CH), 9.22 (s, 1 H, NH), 9.71 (s, 1 H, OH).
13C NMR (d6-DMSO): d 14.03, 14.12, (2 CH3), 43.36 (d, JPC
1
2
OH
OH CO2Me
= 126 HZ, C = P), 57.79, 61.34 (2 OCH2), 63.72 (d, JPC = 15 HZ,
CO2Me
+
1
3
CH), 126.72 (d, JPC = 92 HZ,
C
ipso), 128.55 (d, JPC = 12 HZ,
H
4
2
C
C
meta), 131.94 (d, JPC = 2.2 HZ, C para), 133.19 (d, JPC = 9.83 HZ,
PPh3
+
ortho), 119.10, 119.63, 123.11, 124.21, 128.43, 129.81, 138.57,
CO2Me
N
O
N
O
139.54 (aromatic). 31P NMR (d6-DMSO): d 25.12.
CO2Me
CH3
CH3
Dimethyl 2-(2-oxo-4-phenylamino-2H-chromen-3-yl)-3-(triphenyl-
phosphanylidene)succinate (8): Yield: 90%; Colourless crystals;
m.p. 136–137°C. IR (Kbr) (νmax, cm-1): 3145 (NH), 1734, 1702,
(C=O). Calcd. for C39H32NO6P: C, 73.00; H, 5.03; N, 2.18%. Found:
15
14
Scheme 8
1
C, 72.83; H, 5.21; N, 2.25%. MS (m/z,%): 641 (M, 3). H NMR
(d6-DMSO): d 3.06 (s, 3 H, OCH3), 3.18 (s, 3 H, OCH3), 4.23 (d,
1
MHz, respectively. H, 13C and 31P NMR spectra were obtained in
d6-DMSO solution using TMS as internal standard or 85% H3PO4 as
external standard. 4-(phenylamino)coumarin prepared as a previously
reported method.17 The chemicals used in this study were purchased
from Fluka and were used without further purification
3JPH = 18 HZ, 1 H, P =C–CH), 6.92–7.77 (m, 24 H, aromatic), 9.78
1
(s, 1 H, NH).13C NMR (d6-DMSO): d 42.21 (d, JPC = 123 HZ,
2
C = P), 43.36 (d, JPC = 16 HZ, CH), 49.71, 52.24 (2 OCH3), 116.84
(d, 3JPC = 5 HZ, C=C-NHPh), 126.70 (d, 1JPC = 91 HZ, C ipso), 128.92
3
4
(d, JPC = 12 HZ, C meta), 132.32 (d, JPC = 3 HZ, Cpara), 134.34 (d,
2JPC = 10 HZ, C ortho), 117.97, 117.07, 118.18, 120.61, 123.20, 127.50,
129.16, 130.82, 144.23, 148.70 (aromatic), 153.03 (C=C–NHPh),
163.76 (C=O), 171.72 (d, 2JPC = 13 HZ, C=O), 174.20 (d, 3JPC = 7 HZ,
C=O). 31P NMR (d6-DMSO): d 24.49.
Dimethyl 2-(4-hydroxy-2-oxo-1,2-dihydroquinolin-3-yl)-3-(triphenyl-
phosphanylidene)succinate (4a): Typical procedure for preparation of
compounds 4a, b, 8, 10, 11 and 15: To a magnetically stirred solution
of triphenylphosphine (2 mmol) and 4-hydroxyquinolin-2(1H)-
one (2 mmol) in acetone (10 ml) was added dropwise a mixture of
dimethyl acetylenedicarboxylate (2 mmol) in acetone (3 ml) at room
temperature over 2 min. The reaction mixture was then stirred for
24 h. Solvent was evaporated and the residue was crystallised from
ethyl acetate–hexane mixture. Yield: 92%; Colourless crystals; m.p.
119–120°C. IR (Kbr) (νmax, cm-1): 3295, 3125, (NH, OH), 1736,
1708 (C=O). Calcd. for C33H28NO6P: C, 70.08; H, 4.99; N, 2.48%.
Found: C, 70.21; H, 4.62; N, 2.45;%. MS (m/z,%): 565 (M, 3). Major
isomer (80%): 1H NMR (d6-DMSO): d 2.82 (s, 3 H, OCH3), 3.52 (s,
3 H, OCH3), 5.13 (d, 3JPH = 11 HZ, 1 H, P =C–CH), 6.99–7.58 (m, 38
H, aromatic*–*for two conformational isomers), 9.63 (s, 1 H, NH),
9.68 (s, 1 H, OH) 13C NMR (d6-DMSO): d 42.83 (d, 1JPC = 125 HZ,
C = P), 48.74, 51.48 (2 OCH3), 55.67 (d, 2JPC = 14.6 HZ, CH), 125.90
Diethyl 2-(4-hydroxy-2-oxo-2H-chromen-3-yl)fumarate (11):
Yield: 90%; Colourless crystals; m.p. 130–131°C. IR (Kbr) (νmax
,
cm-1): 3045 (OH), 1721, 1696, (C=O). Calcd. for C17H16O7: C, 61.44;
H, 4.85%. Found: C, 61.75; H, 5.01%. MS (m/z,%): 332 (M, 10). 1H
NMR (DMSO): d 1.06 (t, 3JHH = 7 HZ, 3 H, CH3), 1.21 (t, 3JHH = 7 HZ,
3 H, CH3), 4.06 (q, 3JHH = 7 HZ, 2 H, OCH2), 4.21 (q, 3JHH = 7 HZ,
2 H, OCH2) 6.99 (s, 1 H, CH), 7.11–7.99 (m, 5 H, aromatic and
OH). 13C NMR (d6-DMSO): d 13.83, 14.61 (2 CH3), 60.48, 61.33
(2 OCH2), 110.99, 116.87, 117.86, 124.99, 129.78, 137.16, 137.52,
137.62, 153.37, 161.45 (aromatic and olefinic carbons), 162.23,
164.81, 165.86 (3 C=O).
Methyl 2,5-dioxo-2H,5H-pyrano[3,2-c]chromen-4-carboxylate (10):
(d, JPC = 92 HZ,C ipso), 128.79 (d, JPC = 12 HZ, C meta), 132.32 (d,
4JPC = 2 HZ,C para)*, 134.07 (d, 2JPC = 10 HZ, C ortho), 119.27, 119.54,
123.58, 124.02, 129.29, 129.39, 139.04, 139.56 (aromatic), 166.85
1
3
Yield: 89%; Colourless crystals; m.p. 146–147°C. IR (Kbr) (νmax
,
cm-1): 1728 (C=O). Calcd. for C14H8O6: C, 61.77; H, 2.96%. Found:
C, 61.54; H, 2.72%. MS (m/z,%): 272 (M, 3). 1H NMR (d6-DMSO):
3.87 (s, 3 H, OCH3), 6.79 (s, 1 H, CH), 7.53–8.02 (m, 4 H, aromatic).
13C NMR (d6-DMSO): d 52.97 (OCH3), 113.51, 117.53, 124.04,
125.73, 128.87, 129.02, 132.12, 132.25, 135.47, 154.04 (aromatic
and oleficic carbons), 157.56, 163.75, 164.91 (3C=O).
(HO–C = )*, 166.99 (C=O), 168.99 (d, JPC = 12 HZ, C=O)*, 174.70
2
(d, 3JPC = 11 HZ, C=O)*. 31P NMR (d6-DMSO): d 24.49. Minor isomer
1
(20%): H NMR (d6-DMSO): d 3.42 (s, 3 H, OCH3), 3.82 (s, 3 H,
OCH3), 4.39 (d, 3JPH = 8.7 HZ,1 H, P =C–CH), 9.57 (s, 1 H, NH), 9.89
(s, 1 H, OH).13C NMR (d6-DMSO): d 41.16 (d, 1JPC = 122 HZ, C = P),
49.96, 52.52 (2 OCH3), 63.59 (d, 2JPC = 14 HZ, CH), 125.34 (d, 1JPC
= 91 HZ,C ipso), 128.43 (d, 3JPC = 11 HZ, C meta), 133.18 (d, 2JPC = 10
HZ, C ortho), 118.83, 119.37, 123.62, 124.23, 128.22, 128.34, 138.71,
139.01 (aromatic), 167.12 (C=O). 31P NMR (CDCL3): d 24.85.
Diethyl 2-(4-hydroxy-2-oxo-1,2-dihydro-quinolin-3-yl)-3-(triphenyl-
phosphanylidene)succinate (4b): Yield: 95%; Colourless crystals;
m.p. 133–134°C. IR (Kbr) (νmax, cm-1): 3266, 3050 (NH, OH) 1732,
1705 (C=O). Calcd. for C35H32NO6P: C, 70.82; H, 5.43; N, 2.36%.
Found: C, 70.68; H, 5.65; N, 2.15%. MS (m/z,%): 593 (M, 1). Major
Dimethyl 2-(1,2-dihydro-4-hydroxy-1-methyl-2-oxoquinolin-3-yl)
fumarate (15): Yield: 90%; Colourless crystals; m.p. 119–120°C.
IR (Kbr) (νmax, cm-1): 3305 (OH), 1733, 1712, (C=O). Calcd. for
C16H15NO6: C, 60.57; H, 4.77; N, 4.41%. Found: C, 60.35 H, 4.99;
1
N, 4.38%. MS (m/z,%): 317 (M, 3). H NMR (DMSO): d 3.55 (s,
3 H, CH3), 3.57 (s, 3 H, OCH3), 3.68 (s, 3 H, OCH3), 6.89 (s, 1 H,
CH), 7.26–8.02 (m, 4 H, aromatic),10.72 (s, 1 H, OH). 13C NMR
(d6-DMSO): d 29.33 (CH3), 52.12, 53.02 (2 OCH3), 106.44, 115.02,
116.36, 122.01, 124.12, 130.31, 131.93, 138.58, 139.59, 157.68
(aromatic and olefinic carbons), 161.35, 164.86, 166.72 (3 C=O).
isomer (70%): H NMR (d6-DMSO): d 0.26 (t, 3JHH = 7 HZ, 3 H,
1
CH3), 1.08 (t, 3JHH = 7 HZ, 3 H, CH3), 3.50 (m, 2 H, OCH2), 3.99 (m,
3
Received 28 September 2007; accepted 30 October 2007
2 H, OCH2), 5.17 (d, JPH = 11 HZ,1 H, P =C–CH), 6.97–7.62 (m,
38 H, aromatic)*, 9..83 (s, 1 H, NH), 9.86 (s, 1 H, OH). 13C NMR
Paper 07/4858
doi: 10.3184/030823407X256154
PAPER: 07/4858

608 JOURNAL OF CHEMICAL RESEARCH 2007
9
M. Anary-Abbasinejad, A. Hassanabadi and H. Anaraki-Ardakani,
J. Chem. Res., 2007, in press.
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