Regioselective synthesis of novel functionalized phosphanylidene anthra[2,1-b]furan derivatives under solvent-free conditions

Article abstract of DOI:10.1080/10426500902797053

A convenient and efficient, regioselective, solvent-free procedure has been developed to react 2,6-dihydroxyanthraquinone, dialkyl acetylenedicarboxylates, and triphenylphosphine in one-pot, to afford novel phosphanylidene anthracenyl derivatives 3a-c, which at 90°C due to intramolecular nucleophilic attack formed novel phosphanylidene anthra[2,1-b]furans 4a-c in good yield.

Full text of DOI:10.1080/10426500902797053

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Phosphorus, Sulfur, and Silicon and the
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Regioselective Synthesis of Novel
Functionalized Phosphanylidene
Anthra[2,1-b]furan Derivatives Under
Solvent-Free Conditions
Farahnaz Nourmohammadian a & Mahnaz Davoudzadeh Gholami a
a Department of Organic Colorant , Institute for Colorants , Paint
and Coatings, Tehran, Iran
Published online: 03 Feb 2010.
To cite this article: Farahnaz Nourmohammadian & Mahnaz Davoudzadeh Gholami (2010)
Regioselective Synthesis of Novel Functionalized Phosphanylidene Anthra[2,1-b]furan Derivatives
Under Solvent-Free Conditions, Phosphorus, Sulfur, and Silicon and the Related Elements, 185:2,
340-346
To link to this article: http://dx.doi.org/10.1080/10426500902797053
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Phosphorus, Sulfur, and Silicon, 185:340–346, 2010
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500902797053
REGIOSELECTIVE SYNTHESIS OF NOVEL
FUNCTIONALIZED PHOSPHANYLIDENE
ANTHRA[2,1-b]FURAN DERIVATIVES UNDER
SOLVENT-FREE CONDITIONS
Farahnaz Nourmohammadian and Mahnaz Davoudzadeh
Gholami
Department of Organic Colorant, Institute for Colorants, Paint and Coatings,
Tehran, Iran
A convenient and efficient, regioselective, solvent-free procedure has been developed to react
2,6-dihydroxyanthraquinone, dialkyl acetylenedicarboxylates, and triphenylphosphine in
one-pot, to afford novel phosphanylidene anthracenyl derivatives 3a-c, which at 90◦C due to
intramolecular nucleophilic attack formed novel phosphanylidene anthra[2,1-b]furans 4a–c
in good yield.
Keywords 2,6-Dihydroxyanthraquinone; hydroxyfuran; phosphanylidene anthracenyls; triph-
enyl phosphine
INTRODUCTION
The building blocks in organic pigments are molecules that determine, directly or
indirectly, important performance properties of them.1 From the beginning of modern
structural theory of organic chemistry, quinones have been intimately associated with the
chemistry of aromatic compounds.2,3 Hydroxyanthraquinones (HAQs) as dyes, liquid crys-
tals, and key intermediates with a variety of biological effects, such as interesting antitumor
and antiviral activities and pharmaceutical properties,4–12 could serve as a nucleophile
in a three-component reaction such as the reaction of 2,6-dihydroxyanthraquinon (2,6-
DHAQ), triphenylphosphine (PPh3), and dialkyl acetylene dicarboxylates in one-pot and
under solvent-free conditions to produce some novel phosphanylidene anthracenyl (3a–c)
and phosphanylidene anthra[2,1-b]furan derivatives (4a–c).
Although the synthesis of stable phosphorus ylides, coumarins, and chromones via
solvent-mediated reactions of phenols and naphthols,13,14 and under solvent free con-
ditions15–22 were also reported previously, DHAQ-mediated reactions do not frequently
produce anthra [2,1-b] furan derivatives, and 2-hydroxyfuran as a known tautomer of 2-
furanone was also not commonly detected in the solution. Actually, stable 2-hydroxyfuran
derivatives were reported only in limited numbers of studies.22,23
Received 18 August 2008; accepted 4 February 2009.
Address correspondence to Farahnaz Nourmohammadian, Department of Organic Colorant, Institute for
Colorants, Paint and Coatings, P.O. Box 16765-654, Tehran, Iran. E-mail: nour@icrc.ac.ir
340

PHOSPHANYLIDENE ANTHRA[2,1-b]FURAN DERIVATIVES
341
In this context, and in continuation of our current interest in the application of
PPh3 and activated acetylenes in organic synthesis,24–32 the current study sought to obtain
stable anthra[2,1-b]furans with a 2-hydroxyfuran moiety. Therefore, under solvent-free
conditions, as an optimal alternative for the insoluble HAQs such as 2,6-DHAQ, some
novel phosphanylidene anthracenyl derivatives (3a–c) have been synthesized (Scheme 1).
Even with considerable stability of 3a–c at room temperature, an intramolecular
nucleophilic attack occurred under solvent-free conditions by heating at 90◦C for 2 h, and
novel phosphanylidene anthra[2,1-b]furan derivatives 4a–c (Scheme 2) were produced.
PPh3
RO2C
CO2R
HC
CO2R
O
O
OH
OH
Solvent.free
PPh3
+
+
HO
HO
O
O
2
CO2R
1
CO2R
C
CO2R
H
3
% Yields of 3
1,3
a
R
Me
Et
85
80
68
b
ipr
c
Scheme 1 Functionalized phosphanylidene anthracenyl derivatives 3a–c.
+
PPh3
CO2R
Ph3P
CO2R
CO2R
+
RO2C
-
1
5
PPh3
CO2R
O
CO2R
O
-
O
O
+
CO2R
Ph3P
CH
O
CO2R
O
-
O
O
7
CO2R
CO2R
8
6
PPh3
PPh3
PPh3
CO2R
O
CO2R
O
CO2R
OH
CO2R
OH
-PPh3
HO
HO
O
CO2R
O
CO2R
-
CO2R
CO2R
+
PPh3
H
9
3
Scheme 2 Plausible mechanism for formation of 3.

342
F. NOURMOHAMMADIAN AND M. D. GHOLAMI
RESULTS AND DISCUSSION
The reaction of activated acetylenes 1 with PPh3 in the presence of 2,6-
DHAQ 2 under solvent-free conditions led to the corresponding functionalized
dialkyl (E)-2-{2,6-dihydroxy-5-[3-alkoxy-1-(alkoxycarbonyl)-3-oxo-(1,1,1-triphenyl-λ5-
phosphanylidene)propyl]-9,10-dioxo-9,10-dihydro-2-anthracenyl}-2-butenedioate 3a–c
(Scheme 1) in less than 20 min. The structures of compounds 3a–c were deduced from
their elemental analyses and their IR, 1H, 13C, and 31P NMR spectroscopic data.
1
The H NMR of the products 3 exhibited a C CH proton signal at about 7.0–7.4
ppm. Additionally, the carbons of C CH moiety in 13C NMR spectra appear in 127 ppm,
which is in agreement with the E configuration for the vinyl moiety.6 The mechanism
for the reaction between PPh3 and 1 in the presence of 2 in a possible explanation is
proposed in Scheme 2.17,33,34 It is reasonable to assume that the zwitterionic intermediate35
5 formed from PPh3 and dialkyl acetylenedicarboxylate is protonated by 2,6-DHAQ to
furnish intermediate 6, which then is attacked by the conjugate base 7 to produce ylide 8.
This intermediate undergoes proton transfer to furnish the 1,3-diionic structure 9, which is
converted to the final product by loss of PPh3.
In spite of the considerable stability of 3a–c at room temperature, novel, highly
functionalized dialkyl (E)-2-{2,8-dihydroxy-1-[2-alkoxy-2-oxo-1-(1,1,1-triphenyl-λ5-
phosphanylidene)ethyl]-6,11-dioxo-6,11-dihydroanthra[2,1-b]furan-7-yl}-2-butenedioates
4a–c were produced under solvent-free conditions in good yields by heating at 90◦C for
2 h (Scheme 3).
PPh3
PPh3
OH
O
RO2C
O
RO2C
O
CO2R
OH
0
C /
2 Hour
90
Solvent free.
HO
HO
O
O
CO2R
CO2R
C
C
CO2R
CO2R
H
H
4
3
%Yields of 4
4
a
b
c
R
Me
Et
65
62
59
iPr
Scheme 3 Phosphanylidene anthra[2,1-b]furan derivatives 4a–c.
The structures of compounds 4a–c were also deduced from their elemental analyses
and their IR, 1H, 13C, and 31P NMR spectroscopic data. For example the 1H NMR spectrum
of 4a exhibited three singlets for the methoxy groups arising from the two methoxy groups
on E butanedioate (as discussed above for 3) and a methoxy group on furan moiety
(Scheme 3). In 13C NMR, the carbons of the furan moiety on 4a appeared at 105.2 (d,
2JPC 12.0 Hz, C), 128.6 (d, 3JPC 11.7 Hz, C), 134.3 (d, 4JPC 2.6 Hz, C), and 166.2 (d, 3JPC
18.9 Hz, C), and the carbons of methoxy groups appeared at 50.6, 52.0, and 52.2.

PHOSPHANYLIDENE ANTHRA[2,1-b]FURAN DERIVATIVES
343
Table I Summarized fluorescence spectroscopic data for 2, 3a–c, and 4a–c
Compound∗
λabs (nm)
ε (M−1cm−1
)
λex (nm)
λem (nm)
2
350
380
376
370
344
340
334
0.84 × 104
1.8 × 104
1.48 × 104
1.4 × 104
1.39 × 104
1.28 × 104
1.2 × 104
230
230
230
230
230
230
230
448
441
440
438
491
488
480
3a
3b
3c
4a
4b
4c
λabs: Maximum absorption wavelength for peaks and; ε: corresponding molar absorption coefficient; λex
:
maximum excitation wavelength and shoulders; λem: maximum emission and shoulders.
∗The concentrations for all compounds are 1.9 × 10 −4 mol lit−1
.
These reactions are regioselective, since ortho CH of the anthraquinone moieties
revealed two doublets at δ 7.02 to 7.92 ppm, with 3JHH 7.0–8.1 Hz in the 1H NMR spectra
for 3a–c and 4a–c.
Thefluorescencepropertiesofthereactant 2(2,6-DHAQ)andinitialandfinalproducts
were evaluated by means of fluorescence spectroscopy, and showed that the maximum
intensity of fluorescence emission (λmax) was found in the 456 20 nm region (Table I).
EXPERIMENTAL
2,6-DHAQ, dialkyl acetylenedicarboxylates, and PPh3 were obtained from Fluka
(Buchs, Switzerland) and used without further purification. Melting points were measured
on a Buchi melting point B-545 apparatus. 1H, 13C, and 31P NMR spectra were measured
at 500, 125.7, and 202.4 MHz, respectively, on a Bruker 500-Avance FT-NMR instrument
with DMSO as solvent. Elemental analyses for C, H, and N were performed using a Heraeus
CHN-O-Rapid analyzer. IR spectra were measured on a Perkin Elmer Spectrum One BX FT-
IR spectrometer. Luminescence spectra were measured on a Luminescence spectrometer,
Perkin-Elmer Ls5. UV/vis spectra were recorded on an UV/vis spectrophotometer, Cecil
CE 9200.
General Procedure for the Preparation of Compounds 3
The 2,6-dihydroxyanthraquinone (1 mmol) and triphenylphosphine (2 mmol) were
mixed and grinded for 2 min, and then dimethyl acetylenedicarboxylate was added dropwise
(2 mmol) over a period of 10 min. The reaction mixture was allowed to stand at room tem-
perature for 8 min. The products 3a–c were purified by silica gel thin layer chromatography
using n-hexane:EtOAc (1:1) as eluent.
Dimethyl (E)-2-{2,6-Dihydroxy-5-[3-methoxy-1-(methoxy carbonyl)-3-
oxo-(1,1,1-triphenyl-λ5-phosphanylidene)propyl]-9,10-dioxo-9,10-dihydro-
2-anthracenyl}-2-butenedioate (3a). Yellow powder; yield (85%); mp 200–202◦C;
IR (KBr) (υmax/cm−1): 3437 (OH); 2947 (CH ); 1749, 1738, 1684, and 1641 (C O).
1H NMR (500 MHz, DMSO): δH 3.08 (3H, S, OCH3); 3.30 (3H, S, OCH3); 3.52 (3H,
3
S, OCH3); 3.70 (3H, S, OCH3); 3.78 (1H, d, JPH 13.5 Hz, CH); 7.01 (1H, S, CH); 7.02
(2H, d, 3JHH 7.9 Hz, 2CH); 7.59–7.65 (15 H, m, PPh3); 7.76 (2H, d, 3JHH 7.9 Hz, 2CH);
10.99 and 11.06 (2H, S, 2OH). 13C NMR (125.7 MHz, DMSO): δC 50.1, 51.4, 51.5 and

344
F. NOURMOHAMMADIAN AND M. D. GHOLAMI
1
2
3
51.9 (4OCH3); 70.0 (d, JPC 118.1 Hz, C); 86.8 (d, JPC 11.8 Hz, CH); 107.3 (d, JPC
10.6 Hz, C); 116.6 (C); 123.4 (d, 1JPC 91.7 Hz, C); 127.5 (CH); 127.7 (CH); 127.8 (CH);
130.0 (d, 3JPC 12.5 Hz, C); 132.6 (C); 133.1 (C); 133.9 (CH); 134.2 (d, 2JPC 10.5 Hz, C);
4
2
134.6 (CH); 134.8 (C); 134.9 (C); 135.0 (d, JPC 2.6 Hz, C); 136.1 (C); 160.8 (d, JPC
12.5 Hz, C); 162.5 (d, 3JPC 5.2 Hz, C); 167.1 (C), 167.6 (C); 167.8 (C); 168.6 (C); 188.2
(C); 194.7 (C). 31P NMR (202.4 MHz, DMSO): δp 20.69. Anal. Calcd for C44H35O12P
(786): C, 67.17; H, 4.45%. Found C, 67.10; H, 4.38%.
Diethyl (E)-2-{2,6-Dihydroxy-5-[3-ethoxy-1-(ethoxy carbonyl)-3-oxo-(1,1,
1-triphenyl-λ5-phosphanylidene)propyl]-9,10-dioxo-9,10-dihydro-2-anthracen
yl}-2-butenedioate (3b). Deep yellow powder; yield (80%); mp 173–175◦C; IR (KBr)
(υmax/cm−1): 3434 (OH); 2919 (CH ); 1736, 1729, 1692 and 1657 (C O). 1H NMR (500
MHz, DMSO): δH 0.78 (3H, t, 3JHH 7.1 Hz, CH3); 0.88 (3H, t, 3JHH 7.1Hz, CH3); 1.22 (3H,
3
3
3
t, JHH 7.1 Hz, CH3); 1.36 (3H, t, JHH 7.1 Hz, CH3); 3.57 (2H, q, JHH 7.1 Hz, OCH2);
3.77 (1H, d, 3JPH 13.8 Hz, CH); 3.78 (2H, q, 3JHH 7.1 Hz, OCH2); 3.90 (2H, q, 3JHH 7.1
Hz, OCH2); 4.04 (2H, q, 3JHH 7.1 Hz, OCH2); 7.02 (1H, S, CH); 7.03 (2H, d, 3JHH 8.1 Hz,
2CH); 7.23–7.73 (15H, m, PPh3); 7.78 (2H, d, 3JHH 8.1 Hz, 2CH); 10.97 and 11.06 (2H,
S, 2OH). 13C NMR (125.7 MHz, DMSO): δC 13.1, 13.9 and 14.0 and 14.1 (4CH3); 58.6,
60.6, 61.4 and 61.5 (4OCH2); 69.2 (d, 1JPC 116.7 Hz, C); 88.3 (d, 2JPC 10.1 Hz, CH); 106.0
(d, 3JPC 9.8 Hz, C); 117.1 (C); 122.5 (d, 1JPC 90.8 Hz, C); 127.1 (CH); 127.4 (CH); 127.6
(CH); 129.3 (d, 3JPC 12.5 Hz, Cmeta); 131.8 (CH), 131.9 (C); 132.0 (C); 132.8 (C); 133.1
(CH); 133.4 (C); 133.5 (d, 2JPC 9.6 Hz, C); 133.7 (d, 2JPC 3.0 Hz, C); 134.1 (C); 163.2 (d,
2JPC 11.12 Hz, C); 165.1 (d, 3JPC 6.2 Hz, C); 166.5 (C); 167.3 (C); 168.5 (C); 169.6 (C);
188.3 (C) 194.7(C). 31P NMR (202.4 MHz, DMSO): δp 20.61. Anal. Calcd for C48H43O12P
(842): C, 68.41; H, 5.10%. Found C, 68.36; H, 5.01%.
Diisopropyl (E)-2-{2,6-Dihydroxy-5-[3-isopropoxy-1-(isopropoxy carbon
yl)-3-oxo-(1,1,1-triphenyl-λ5-phosphanylidene)propyl]-9,10-dioxo-9,10-dihydro-
2-anthracenyl}-2-butenedioate (3c). Pale yellow powder; yield (68%); mp
166–168◦C; IR (KBr) (υmax/cm−1): 3434 (OH); 2980 (CH ); 1732, 1721, 1693 and 1660
1
3
(C O). H NMR (500 MHz, DMSO): δH 0.79 (6H, d, JHH 6.0 Hz, 2CH3); 1.05 (6H, d,
3JHH 6.0 Hz, 2CH3); 1.30 (6H, d, JHH 6.0 Hz, 2CH3); 1.56 (6H, d, JHH 6.0 Hz, 2CH3)
3
3
3
3.70 (1H, d, JPH 15.0 Hz, CH); 4.38 (1H, m, OCH); 4.82 (1H, m, OCH); 4.94 (1H, m,
OCH); 5.36 (1H, m, OCH); 7.01 (1H, S, CH); 7.08 (2H, d, 3JHH 7.8 Hz, 2CH); 7.12–7.90
(15 H, m, PPh3); 7.94 (2H, d, JHH 7.8 Hz, 2CH); 11.82 and 12.64 (2H, S, 2OH). 13C
3
NMR (125.7 MHz, DMSO): δC 21.2, 21.57, 21.8 and 21.9 (8CH3); 66.5, 69.2, 70.5 and
1
2
3
70.55 (4OCH); 70.1 (d, JPC 116.0 Hz, C); 84.6 (d, JPC 10.2 Hz, CH); 104.5 (d, JPC
1
9.5 Hz, C); 116.9 (C); 122.5 (d, JPC 91.0 Hz, C); 127.2 (CH); 127.5 (CH); 127.6 (CH);
128.8 (d, 3JPC 12.5 Hz, C); 129.4 (CH); 131.5 (C); 132.0 (C); 132.1 (C); 132.2 (CH); 133.0
2
4
2
(C); 133.1 (d, JPC 9.8 Hz, C); 134.1 (d, JPC 2.8 Hz, C); 134.2 (C); 160.1 (d, JPC 11.7
Hz, C); 163.7 (d, 3JPC 5.0 Hz, C); 166.1 (C); 166.3 (C); 166.9 (C); 167.8 (C); 188.1 (C);
194.7 (C). 31P NMR (202.4 MHz, DMSO): δp 21.01. Anal. Calcd for C52H51O12P (898):
C, 69.48; H, 5.68%. Found C, 69.39; H, 5.73%.
General Procedure for the Preparation of Compounds 4
3a–c were heated at 90◦C for 2 h in the solid phase under solvent-free conditions.
The reaction mixture was allowed to stand at room temperature for 8 min. The products

PHOSPHANYLIDENE ANTHRA[2,1-b]FURAN DERIVATIVES
345
4a–c were purified by silica gel thin layer chromatography using n-hexane:EtOAc (1:1) as
eluent.
Dimethyl (E)-2-{2,8-Dihydroxy-1-[2-methoxy-2-oxo-1-(1,1,1-triphenyl-λ5-
phosphanylidene)ethyl]-6,11-dioxo-6,11-dihydroanthra[2,1-b]furan-7-yl}-2-
butenedioate (4a). Orange powder; yield (65%); mp 173–175◦C; IR (KBr) (υmax/cm−1):
1
3435(OH); 2953(CH ); 1740, 1662 and 1640 (C O). H NMR (500 MHz, DMSO): δH
3.00, 3.33 and 3.85 (9H, S, 3OCH3); 7.03 (1H, S, CH); 7.04 (2H, d, 3JHH 7.0 Hz, 2CH);
7.29–7.75 (15 H, m, PPh3); 7.78 (2H, d, 3JHH 7.0 Hz, 2CH); 11.05 and 11.11 (2H, S, 2OH).
13C NMR(125.7 MHz, DMSO): δC 50.6; 52.0 and 52.2 (3OCH3); 51.0 (d,1JPC 117.1 Hz,
C); 105.2 (d, 2JPC 12.1 Hz, C); 116.8 (C); 123.4 (d, 1JPC 91.8 Hz, C); 127.3 (CH); 127.6
3
3
(CH); 127.7 (CH); 128.5 (d, JPC 12.7 Hz, C); 128.7 (d, JPC 11.8 Hz, C); 131.5 (CH);
2
132.0 (C); 132.2 (C); 132.9 (C); 133.1 (CH); 133.4 (C); 134.1(d, JPC 9.6 Hz, C); 134.4
4
2
4
(d, JPC 2.6 Hz, C); 135.1 (C); 163.7 (d, JPC 11.8 Hz, C); 165.1 (d, JPC 2.6 Hz, C);
166.2 (d, JPC 19.6 Hz, C); 166.8 (C); 167.5 (C); 188.2 (C); 194.2 (C). 31P NMR (202.4
3
MHz, DMSO): δp 21.49. Anal. Calcd for C43H31O11P (754): C, 68.43; H, 4.11%. Found
C, 68.35; H, 4.02%.
Diethyl
(E)-2-{2,8-Dihydroxy-1-[2-ethoxy-2-oxo-1-(1,1,1-triphenyl-λ5-
phosphanylidene)ethyl]-6,11-dioxo-6,11-dihydroanthra[2,1-b]furan-7-yl}-2-
butenedioate (4b). Deep yellow powder; yield (62%); mp 150–152◦C; IR (KBr)
(υmax/cm−1): 3432 (OH); 2924 (CH ); 1728, 1678 and 1630 (C O). 1H NMR(500 MHz,
DMSO): δH 0.70, 1.43 and 1.49 (9H, d, 3JHH 7.1 Hz, 3CH3); 3.49, 4.38 and 4.45 (6H, q,
3JHH 7.1 Hz, 3OCH2); 7.00 (1H, S, CH); 7.02 (2H, d, JHH 7.1 Hz, 2CH); 7.05–7.75 (15
3
H, m, PPh3); 7.79 (2H, d, JHH 7.1 Hz, 2CH); 11.12 and 11.20 (2H, S, 2OH). 13C NMR
3
1
(125.7 MHz, DMSO): δC 13.1, 14.3 and 14.7 (3CH3); 50.6 (d, JPC 117.0 Hz, C); 58.7,
62.0 and 62.6 (3OCH2); 105.0 (d, 2JPC 12.0 Hz, C); 117.1 (C); 122.4 (d, 1JPC 90.8 Hz, C);
127.0 (CH); 127.2 (CH); 127.5 (CH); 127.9 (d, 3JPC 12.5 Hz, C); 128.4 (d, 3JPC 12.4 Hz,
2
C); 131.1 (CH); 131.9 (C); 132.2 (C); 132.5 (C); 132.8 (CH); 133.1 (C); 133.3 (d, JPC
4
2
9.6 Hz, C); 133.6 (d, JPC 3.0 Hz, C); 134.2 (C); 164.0 (d, JPC 11.12 Hz, C); 165.2 (d,
4JPC 2.8 Hz, C); 165.8(d, JPC 18.7 Hz, C); 167.1 (C); 188.3 (C); 194.1(C). 31P NMR
3
(202.4 MHz, DMSO): δp 21.17. Anal. Calcd for C46H37O11P (796): C, 69.34; H, 4.65%.
Found C, 69.25; H, 4.59%.
Diisopropyl (E)-2-{2,8-Dihydroxy-1-[2-isopropoxy-2-oxo-1-(1,1,1-triphen
yl-λ5-phosphanylidene)ethyl]-6,11-dioxo-6,11-dihydroanthra[2,1-b]furan-7-yl}-
2-butenedioate (4c). Yellow powder; yield (59%); mp 146–148◦C. IR (KBr)
(υmax/cm−1): 3432 (OH); 2985 (CH ); 1724, 1673 and 1641 (C O). 1H NMR (500 MHz,
DMSO): δH 0.71 (6H, d, 3JHH 6.0 Hz, 2CH3); 1.65 (6H, d, 3JHH 6.0 Hz, 2CH3); 1.75 (6H,
3
d, JHH 6.0 Hz, 2CH3); 4.30 (1H, m, OCH); 5.33 (1H, m, OCH); 5.49 (1H, m, OCH);
7.01 (1H, S, CH); 7.07 (2H, d, 3JHH 7.0 Hz, 2CH); 7.10–7.90 (15 H, m, PPh3); 7.93 (2H,
3
d, JHH 7.0 Hz, 2CH); 12.68 and 12.74 (2H, S, 2OH). 13C NMR(125.7 MHz, DMSO):
δC 21.3, 22.5 and 22.9 (6CH3); 50.9 (d,1JPC 116.0 Hz, C); 66.6, 70.5 and 71.2 (3OCH);
104.8 (d, 2JPC 11.8Hz, C); 116.6 (C); 122.5 (d, 1JPC 91.0 Hz, C); 127.1 (CH); 127.3 (CH);
3
3
127.4 (CH); 127.8 (d, JPC 12.5 Hz, C); 128.5 (d, JPC 12.0 Hz, C); 129.4 (CH); 130.6
2
(C); 131.8 (C); 132.1 (C); 132.6 (CH); 132.9 (C); 133.1 (d, JPC 9.8 Hz, C); 133.6 (d,
4JPC 2.8 Hz, C); 134.1 (C); 163.0 (d, JPC 11.6 Hz, C); 165.3 (d, JPC 2.8 Hz, C); 166.8
2
4
(d, JPC18.5 Hz, C); 167.5 (C); 188.1 (C); 194.2 (C). 31P NMR (202.4 MHz, DMSO):
2
δp 21.95. Anal. Calcd for C49H43O11P (838): C, 70.17; H, 5.13%. Found C, 70.10; H,
5.17%.

346
F. NOURMOHAMMADIAN AND M. D. GHOLAMI
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