A facile, one-pot synthesis of azoic compounds and anthraquinone derivatives containing dialkyl phosphoryl moieties in multicomponent reactions

Article abstract of DOI:10.1080/10426500903061517

Protonation of the reactive 1:1 intermediates produced in the reactions between triphenylphosphine and dialkyl acetylenedicarboxylates by 1-amino-anthraquinone or 1,5-diphenylcarbazone as a core dye leads to vinyl phosphonium salts, which undergo Michael addition with conjugate base of NH compounds to produce stable phosphorus ylides as novel dyes in fairly good yields. These ylides can exist in two geometrical isomers (Z) and (E) for 3, because the negative charge of the ylide moiety of these compounds are strongly conjugated with the adjacent carbonyl group. Rotation around the carbon-carbon double bond is slow in the (Z) and (E) geometrical isomers on the NMR time scale at ambient temperature. These compounds are assigned by their IR, 1H, 13C NMR spectral data as well as their mass spectroscopic data. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/10426500903061517

This article was downloaded by: [Pennsylvania State University]
On: 21 May 2013, At: 01:11
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
Phosphorus, Sulfur, and Silicon and the
Related Elements
Publication details, including instructions for authors and
subscription information:
http://www.tandfonline.com/loi/gpss20
A Facile, One-Pot Synthesis of Azoic
Compounds and Anthraquinone
Derivatives Containing Dialkyl
Phosphoryl Moieties in Multicomponent
Reactions
Ghasem Marandi a , Malek Taher Maghsoodlou a , Reza Heydari
a , Sayyed Mostafa Habibi-Khorassani a , Roya Kabiri b , Zahra
Gharechahi a , Mahbobe Ghahramaninezhad a & Belghais Adrom a
a Chemistry Department, The University of Sistan and Baluchestan,
Zahedan, Iran
b Faculty of Chemistry, The University of Tabriz, Tabriz, Iran
Published online: 03 Jul 2010.
To cite this article: Ghasem Marandi , Malek Taher Maghsoodlou , Reza Heydari , Sayyed Mostafa
Habibi-Khorassani , Roya Kabiri , Zahra Gharechahi , Mahbobe Ghahramaninezhad & Belghais Adrom
(2010): A Facile, One-Pot Synthesis of Azoic Compounds and Anthraquinone Derivatives Containing
Dialkyl Phosphoryl Moieties in Multicomponent Reactions, Phosphorus, Sulfur, and Silicon and the
Related Elements, 185:7, 1395-1403
To link to this article: http://dx.doi.org/10.1080/10426500903061517
PLEASE SCROLL DOWN FOR ARTICLE
Full terms and conditions of use: http://www.tandfonline.com/page/terms-and-conditions
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.
The publisher does not give any warranty express or implied or make any representation
that the contents will be complete or accurate or up to date. The accuracy of any
instructions, formulae, and drug doses should be independently verified with primary
sources. The publisher shall not be liable for any loss, actions, claims, proceedings,

demand, or costs or damages whatsoever or howsoever caused arising directly or
indirectly in connection with or arising out of the use of this material.

Phosphorus, Sulfur, and Silicon, 185:1395–1403, 2010
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500903061517
A FACILE, ONE-POT SYNTHESIS OF AZOIC COMPOUNDS
AND ANTHRAQUINONE DERIVATIVES CONTAINING
DIALKYL PHOSPHORYL MOIETIES IN
MULTICOMPONENT REACTIONS
Ghasem Marandi,1 Malek Taher Maghsoodlou,1 Reza Heydari,1
Sayyed Mostafa Habibi-Khorassani,1 Roya Kabiri,2
Zahra Gharechahi,1 Mahbobe Ghahramaninezhad,1 and
Belghais Adrom1
1Chemistry Department, The University of Sistan and Baluchestan, Zahedan, Iran
2Faculty of Chemistry, The University of Tabriz, Tabriz, Iran
Protonation of the reactive 1:1 intermediates produced in the reactions between
triphenylphosphine and dialkyl acetylenedicarboxylates by 1-amino-anthraquinone or
1,5-diphenylcarbazone as a core dye leads to vinyl phosphonium salts, which undergo
Michael addition with conjugate base of NH compounds to produce stable phosphorus
ylides as novel dyes in fairly good yields. These ylides can exist in two geometrical isomers
(Z) and (E) for 3, because the negative charge of the ylide moiety of these compounds are
strongly conjugated with the adjacent carbonyl group. Rotation around the carbon–carbon
double bond is slow in the (Z) and (E) geometrical isomers on the NMR time scale at
ambient temperature. These compounds are assigned by their IR, 1H, 13C NMR spectral
data as well as their mass spectroscopic data.
Keywords 1-Amino-anthraquinone; azoic dyes; dialkyl acetylenedicarboxylate; 1,5-
diphenylcarbazone; geometrical isomers; stable phosphorus ylides
INTRODUCTION
Dyes have been the subject of much interest in recent years because of increasingly
stringent restriction on the organic content of industrial effluents. Many industries (plas-
tics, paper, textile, and cosmetics) use dyes in order to color their products. Over 100,000
commercially available dyes exist, and more than 7 × 105 tons are produced annually.1, 2
Azoic dyes, 9,10-anthraquinone, and its derivatives constitute the largest group of com-
monly available dyes and pigments.3–5 Due to their colors, azoic dyes are used as pigments,
indicators of solvent polarity, of molecular environments, and of chemical environments;
they are also widely used as histological stains and in the colorimetric analysis of pharma-
ceuticals.6–11 The widespread applications of the azoic dyes as chromophoric and metallo
Received 28 February 2009; accepted 22 May 2009.
We gratefully acknowledge financial support from the Research Council of the University of Sistan and
Baluchestan, Iran.
Address correspondence to Malek Taher Maghsoodlou, Chemistry Department, The University of Sistan
and Baluchestan, 98135-674, Zahedan, Iran. E-mail: mt maghsoodlou@yahoo.com
1395

1396
G. MARANDI ET AL.
chromic reagents,12–17 photochromic materials,18, 19 colorants,20, 21 nonlinear optics,22–25
photosensitizers,26 and sensors27, 28 have attracted the interest of many electrochemists.29–33
Amino anthraquinones are the basic structural units of disperse dyes,34, 35 which are
an important class of dye, characterized by good fastness properties and brightness on hy-
drophobic fibers, such as poly(ethylene terephthalate), on which they provide mostly bright
red to blue hues; also are included acylamino-anthraquinones, which furnish mainly yellow
and orange dyes. In addition, anthraquinones have become recently very important due to
their application in high technology electronics. Some amino anthraquinone derivatives are
used in transfer printing toners, and others are used in thermal printing.36, 37
In continuation of our current interest in the development of new routes to heterocyclic
and carbocyclic systems,38–45 in this article we report a simple, one-pot synthesis of stable
azo compounds and also anthraquinone derivatives containing dialkyl phosphoryl groups
as novel dyes in fairly good yields (see Scheme 1).
Scheme 1
RESULTS AND DISCUSSION
The reactions of 1-amino-anthraquinone or 1,5-diphenylcarbazone with dialkyl
acetylenedicarboxylates 1 in the presence of triphenylphosphine were carried out in Et2O
solvent at room temperature and were finished within a few hours. The 1H and 13C NMR
spectra of the crude product clearly indicated the formation of stable phosphorus ylides 3.
Any products other than 3 could not be detected by NMR spectroscopy. The structures
of compounds 3a–f were deduced from their IR, 1H, 13C, and 31P NMR spectra. Their mass
spectra displayed molecular ion peaks at appropriate m/z values. Any initial fragmentations
involve the missing parts or complete loss of the side chains and scission of the ring system.
The 1H, 13C, and 31P NMR spectra of ylides 3a–f are consistent with the presence of two
isomers. The 1H NMR spectra of 3a showed two sharp lines (δ 3.19 and 3.73) arising from
the methoxy groups in Z-diastereoisomer and two single sharp resonances at 3.73 and 3.82
ppm for methoxy groups in E-diastereoisomer. In this spectra, the characteristic methine
proton appeared at 5.28 and 4.41 ppm for major and minor stereoisomers, respectively.

AZOIC COMPOUNDS AND ANTHRAQUINONE DERIVATIVES
1397
All of the aromatic protons resonated at δ 6.28–8.31 for major and minor isomers. The
1H NMR spectrum of compound 3a exhibited a N–H proton as a doublet at 10.11 ppm
and a doublet at 10.33 ppm for major and minor, respectively. Other partial assignments of
compound 3a have been presented in the Experimental section. The ylide moieties of these
compounds are strongly conjugated with the adjacent carbonyl group, and rotation around
the partial double bond in (E)-3 and (Z)-3 geometrical isomers is slow on the NMR time
scale at ambient temperature (see Scheme 2). Selected 1H-, 13C-, and 31P NMR chemical
shifts and coupling constants are shown in Table I.
Scheme 2
On the basis of the well-established chemistry of trivalent phosphorus nucle-
ophiles,46–51 it is reasonable to assume that phosphorus ylide 3 results from the initial
addition of triphenylphosphine to the acetylenic ester and subsequent protonation of the
1:1 adduct by the NH-compounds to form phosphoranes 3 (see Scheme 3).
Scheme 3
Briefly, we have prepared novel stable phosphorus ylides as a novel dyes, using a
one-pot reaction between triphenylphosphine and dialkyl acetylenedicarboxylates in the
presence of 1-amino-anthraquinone or 1,5-diphenylcarbazone. The present method carries
the advantage that not only is the reaction performed under neutral conditions, but also the
substances can be mixed without any activation or modifications. 1-Amino-anthraquinone
and 1,5-diphenylcarbazone-containing phosphorus ylides 3a–f may be considered as po-
tentially 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.
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

1398
G. MARANDI ET AL.
1
Table I Selected H, 13C, and 31P NMR chemical shifts (δ in ppm) and coupling constants (J in Hz) for H-2,
OR, CO2R, C-2, and C-3 in the major (M) and minor (m) diastereoisomers of compounds 3a–f
1H NMR spectroscopic data
13C NMR data
Compd
Isomer%
H-2 (3JPH
)
OR
CO2R
C-2 (2JPC
)
C-3 (1JPC
)
31P NMR
3a
3a
3b
3b
3c
3c
3d
3d
3e
3e
3f
M (59)
m (41)
M (57)
m (43)
M (63)
m (37)
M (61)
m (39)
M (57)
m (43)
M (79)
m (21)
5.28 (24.0)
4.41 (18.8)
5.26 (24.1)
4.37 (18.9)
5.08 (24.8)
5.08 (24.8)
5.13 (18.5)
5.02 (16.8)
5.12 (18.4)
5.18 (18.6)
5.00 (18.3)
4.87 (18.9)
3.19
3.73
3.74–3.85
4.10–4.23
0.99
1.55
3.07
3.16
4.21–4.44
4.15–4.44
0.88
1.43
3.73
3.82
55.8 (12.0)
55.3 (11.8)
55.8 (13.4)
55.8 (13.4)
56.2 (13.5)
55.3 (12.7)
60.6 (17.6)
61.5 (17.1)
61.7 (17.8)
62.2 (17.7)
61.4 (17.8)
61.4 (17.8)
43.0 (124.9)
44.0 (135.1)
42.6 (127.5)
42.6 (127.5)
42.0 (125.0)
43.3 (124.2)
40.7 (126.2)
40.3 (126.6)
40.0 (126.8)
40.4 (126.0)
39.9 (126.3)
36.9 (126.9)
20.7
22.5
20.7
22.4
19.9
22.4
23.8
23.9
23.8
23.9
23.5
23.6
1.48
1.57
3.82
3.84
1.61
1.55
3f
as a solvent at 500.1, 125.8, and 202.4 MHz, respectively. Elemental analyses for C, H,
and N were performed using a Heraeus CHN-O-Rapid analyzer. In addition, the mass
spectra were recorded on a Shimadzu GC/MS QP 1100 EX mass spectrometer operating
at an ionization potential of 70 eV. Dialkyl acetylenedicarboxylates, triphenylphosphine,
1-amino-anthraquinone, and 1,5-diphenyl carbazone were purchased from Fluka and were
used without further purification.
General Procedures for Preparation of Stable Phosphorus Ylides
To a magnetically stirred solution of triphenylphosphine (0.26 g,1 mmol) and NH
compound (1 mmol) in diethyl ether 10 mL, a mixture of dimethyl acetylenedicarboxylates
(0.14 g,1 mmol) in diethyl ether 3 mL was added dropwise over 10 min at room temperature.
After 24 h stirring at room temperature, the product was filtered off and recrystallized from
ethyl acetate.
Dimethyl-2-(N-1-aminoanthraquinon-1-yl)-3-(triphenylphosphoranylid-
ene)butanedioate (3a). Red powder (0.45 g), yield 95%, mp 176–179◦C. IR (KBr)
(λmax, cm−1): 1620, 1648 (2 C O), 1730 (C Oester), 3400 (N H). MS (m/z,%): 627 (M+,
1), 500 (8), 453 (53), 277 (100), 262 (13), 223 (16), 183 (26), 77 (18). Anal. Calc. for
C38H30NO6P (627.62): C, 72.73; H, 4.78; N, 2.23%; Found: C, 73.08; H, 4.82; N, 2.15%.
Major isomer (Z)-3a (59%): 1H NMR: 3.19 and 3.73 (6H, 2s, 2 OCH3), 5.28 (1H, dd,
3JHH = 5.4 Hz, 3JHP = 24.0 Hz, P = C CH), 6.28–8.31 (22H, m, 3 C6H5 and C14H9NO2),
1
10.11 (1H, d, 3JHH = 6.0 Hz, CH NH). 13C NMR: 43.0 (d, JPC = 124.9 Hz, P C),
2
49.4 and 52.5 (2s, 2 OCH3), 55.8 (d, JPC = 12.0 Hz, P C CH), 113.2, 115.5, 117.0,
1
118.1, 119.9, 123.5 (6C, C14H9NO2), 126.3 (d, JPC = 89.5 Hz, Cipso of 3 C6H5), 128.5
3
(d, JPC = 12.0 Hz, Cmeta of 3 C6H5), 132.1 (Cpara of 3 C6H5), 133.0, 133.2, and 133.4
(3C, C14H9NO2), 133.7 (d, 2JPC = 9.9 Hz, Cortho of 3C6H5), 149.6, 150.2 and 151.4 (3C,
C14H9NO2), 170.2 (d, 3JPC = 12.7, C Oester), 173.6 (d, 2JPC = 17.2, P C C), 184.0 and
185.0 (2 C O, C14H9NO2). 31P NMR: 20.7 (Ph3P+ C).
Minor isomer (E)-3a (41%): 1H NMR: 3.73 and 3.82 (6H, 2s, 2OCH3), 4.41 (1H, dd,
3JHH = 6.8 Hz, 3JHP = 18.8 Hz, P C CH), 6.20–8.31 (22H, m, 3 C6H5 and C14H9NO2),

AZOIC COMPOUNDS AND ANTHRAQUINONE DERIVATIVES
1399
10.33 (1H, d, 3JHH = 7.0 Hz, CH NH). 13C NMR: 44.0 (d, 1JPC = 135.1 Hz, P C), 50.4
and 52.4 (2s, 2 OCH3), 55.3 (d, 2JPC = 11.8 Hz, P C CH), 113.2, 115.5, 117.0, 118.2,
119.9, 123.5 (6C, C14H9NO2), 125.9 (d, 1JPC = 92.3 Hz, Cipso of 3 C6H5), 128.6 (d, 3JPC
=
12.4 Hz, Cmeta of 3 C6H5), 132.0 (Cpara of 3 C6H5), 133.0, 133.2 and 133.4 (3C, C14H9NO2),
133.8 (d, 2JPC = 9.8 Hz, Cortho of 3 C6H5), 149.6, 150.1 and 151.4 (3C, C14H9NO2), 170.2
(d, 3JPC = 12.7, C Oester), 173.6 (d, 2JPC = 17.2, P C C), 183.7 and 184.1 (2 C O,
C14H9NO2). 31P NMR: 22.5 (Ph3P+ C).
Diethyl-2-(N-1-aminoanthraquinon-1-yl)-3-(triphenylphosphoranylidene)
butanedioate (3b). Red powder (0.45 g), yield 90%, mp 126–129◦C. IR (KBr) (λmax
,
cm−1): 1620, 1664 (C O), 1738, 1742 (C Oester), 3422 (N H). MS (m/z,%): 655 (M+,
2), 485 (3), 277 (8), 223 (100), 77 (8). Anal. Calc. for C40H34NO6P (655.67): C, 73.28; H,
5.19; N, 2.14%; Found: C, 73.53; H, 5.25; N, 2.20%.
1
Major isomer (E)-3b (57%): H NMR: 0.46 and 1.28 (6H, 2t, 3JHH = 7.0 Hz,
2OCH2CH3), 3.74–3.85 (4H, m, 2 ABX3 system, 2 OCH2CH3), 5.26 (1H, dd, 3JHH = 5.1
Hz, 3JHP = 24.1 Hz, P C CH), 6.24–8.35 (22H, m, 3 C6H5 and C14H9NO2), 10.14 (1H,
d, 3JHH = 5.7 Hz, CH NH). 13C NMR: 14.1 and 14.2 (2s, 2 OCH2CH3), 42.6 (d, 1JPC
=
2
127.5 Hz, P C), 55.8 (d, JPC = 13.4 Hz, P C CH), 58.0 and 61.3 (2s, 2 OCH2CH3),
113.2, 113.5, 115.3, 117.1, 120.1 and 123.5 (6 C, C14H9NO2), 126.3 (d, 1JPC = 94.1 Hz,
3
Cipso of 3 C6H5), 128.6 (d, JPC = 11.1 Hz, Cmeta of 3 C6H5), 132.0 (Cpara of 3 C6H5),
132.5, 133.0 and 133.2 (3 C, C14H9NO2), 133.8 (d, 2JPC = 9.9 Hz, Cortho of 3 C6H5), 149.7,
150.2 and 151.3 (3 C, C14H9NO2), 165.0 (d, 3JPC = 12.6 Hz, C Oester), 173.0 (d, 2JPC
=
14.6, P C C), 183.6 and 184.2 (2 C O, C14H9NO2). 31P NMR: 20.7 (Ph3P+ C).
1
3
Minor isomer (Z)-3b (43%): H NMR: 1.21 and 1.32 (6H, 2t, JHH = 6.9 Hz, 2
OCH2CH3), 4.10–4.23 (4H, 2m, 2ABX3 system, 2 OCH2CH3), 4.37 (1H, dd, 3JHH = 7.1
Hz, NH-CH, 3JHP = 18.9 Hz, P C CH), 6.24–8.35 (22H, m, 3 C6H5 and C14H9NO2),
10.41 (1H,d, 3JHH = 7.1 Hz, CH NH). 13C NMR: 14.2 and 15.3 (2s, 2 OCH2CH3), 42.6
1
2
(d, JPC = 127.5 Hz, P C), 55.8 (d, JPC = 13.4 Hz, P C CH), 58.7 and 61.4 (2s, 2
OCH2CH3), 113.2, 113.5, 115.3, 117.1, 120.1 and 123.5 (6 C, C14H9NO2), 126.6 (d, 1JCP
3
= 91.6 Hz, Cipso of 3 C6H5), 128.6 (d, JPC = 11.1 Hz, Cmeta of 2 C6H5), 132.0 (Cpara
2
of 3 C6H5), 132.5, 133.0 and 133.2 (3 C, C14H9NO2), 133.7 (d, JPC = 9.9 Hz, Cortho of
3 C6H5), 149.7, 150.2 and 151.3 (3 C, C14H9NO2), 165.0 (d, 3JPC = 12.6 Hz, C Oester),
173.0 (d, 2JPC = 14.6 Hz, P C C), 183.8 and 185.1 (2 C O, C14H9NO2). 31P NMR: 22.4
(Ph3P+ C).
Di-tert-butyl-2-(N-1-aminoanthraquinon-1-yl)-3-(triphenylphosphora-
nylidene)butanedioate (3c). Red powder (0.53 g), yield 92%, mp 162–165◦C. IR
(KBr) (λmax, cm−1): 1598, 1631 (C O), 1730 (C Oester), 3425 (N H). MS (m/z,%): 711
(M+, 1), 684 (25), 402 (17), 277 (100), 262 (7), 223 (15), 183 (24), 77 (18), 57 (47). Anal.
Calc. for C44H42NO6P (711.78): C, 74.26; H, 5.91; N, 1.97%; Found: C, 74.35; H, 6.02;
N, 1.89%.
Major isomer (E)-3c (63%): 1H NMR: 0.99 and 1.48 (18H, 2s, 2 CMe3), 5.08 (1H,
dd, 3JHH = 5.5Hz, 3JHP = 24.8Hz, P C CH), 6.92–8.31(22H, m, 3C6H5 andC14H9NO2),
10.02 (1H, d, 3JHH = 5.5 Hz, CH NH). 13C NMR: 28.0 and 28.4 (2s, 2 CMe3), 42.0 (d,
1JPC = 125.0 Hz, P C), 56.2 (d, 2JPC = 13.5 Hz, P C CH), 78.0 and 81.7 (2s, 2 CMe3),
1
113.0, 113.6, 115.1, 117.2, 120.4 and 123.2 (6C, C14H9NO2), 127.3 (d, JPC = 90.6 Hz,
3
Cipso of 3 C6H5), 128.5 (d, JPC = 10.2 Hz, Cmeta of 2 C6H5), 131.9 (Cpara of 3 C6H5),
133.1, 133.2 and 133.3 (3C, C14H9NO2), 133.9 (Cortho of 3 C6H5), 149.8, 150.2 and 151.2
(3C, C14H9NO2), 169.2 (d, 2JPC = 12.3 Hz, C Oester), 171.9 (d, 2JPC = 14.0 Hz, P C C),
184.3 and185.2 (2C, C14H9NO2). 31P NMR: 19.9 (Ph3P+ C).

1400
G. MARANDI ET AL.
1
Minor isomer (Z)-3c (37%): H NMR: 1.55 and 1.57 (18H, 2s, 2 CMe3), 4.20
3
(1H, dd, 3JHH = 5.3 Hz, JHP = 24.5 Hz, P C CH), 6.97–8.31 (22H, m, 3 C6H5 and
C14H9NO2), 10.54 (1H, d, 3JHH = 5.5 Hz, CH NH). 13C NMR: 28.8 and 29.3 (2s, 2
1
2
CMe3), 43.3 (d, JPC = 124.2 Hz, P C), 55.3 (d, JPC = 12.7 Hz, P C CH), 80.7 and
81.1 (2s, 2 CMe3), 114.8, 117.2, 118.0, 119.6 120.4 and 124.7 (6C, C14H9NO2), 126.4 (d,
1JPC = 92.3 Hz, Cipso of 3 C6H5), 128.2 (d, 3JPC = 9.8 Hz, Cmeta of 2 C6H5), 130.2 (Cpara
of 3 C6H5), 132.4, 133.6 and 132.9 (3C, C14H9NO2), 133.9 (Cortho of 3C6H5), 149.9, 151.3
and 151.0 (3C, C14H9NO2), 170.4 (d, 2JPC = 11.6 Hz, C Oester), 171.7 (d, 2JPC = 13.7 Hz,
P C C), 183.5 and 183.8 (2C, C14H9NO2). 31P NMR: 22.4 (Ph3P+ C).
Dimethyl-2-(1,5-diphenylcarbazone-1-yl)-3-(triphenylphosphoranylidene)
butanedioate (3d). Yellow powder (0.60 g), yield 94%, mp 115–118◦C. IR (KBr) (λmax
,
cm−1): 1588 (N N), 1636, 1735 (C Oester), 3430 (N H). MS (m/z,%): 646 (M++2, 54),
277 (58), 92 (33), 77 (100), 57 (33). Anal. Calc. for C37H33N4O5P (644.66): C, 68.94; H,
5.12; N, 8.70%; Found: C, 69.05; H, 5.18; N, 8.68%.
Major isomer (Z)-3d (59%): 1H NMR: 3.07 and 3.82 (6H, 2s, 2 OCH3), 5.13 (1H, d,
3JHP = 18.5 Hz, P C CH), 1.30 (1H, br, NH), 6.86–7.91 (25H, m, 5 C6H5). 13C NMR: 40.7
(d, 1JPC = 126.2 Hz, P C), 49.3 and 52.5 (2 OCH3), 60.6 (d, 2JPC = 17.6 Hz, P C CH),
113.3, 113.6, 114.2, 117.8, 120.5, 123.1 and 128.7 (7C, (C6H5)2N4HCO), 126.1 (d, 1JPC
=
92.1 Hz, Cipso), 128.7 (d, 3JPC = 12.7 Hz, Cmeta), 132.1 (d, 4JPC = 3.2 Hz Cpara), 133.4 (d,
2JPC = 9.9 Hz, Cortho), 146.1, 149.0, 149.9, 152.2 and 160. 4 (5C, (C6H5)2N4HCO), 167.0
(1C, O C N), 171.4 (d, 3JPC = 12.9 Hz, C Oester), 173.38 (d, 2JPC = 11.32Hz, P C C).
31P NMR: 23.8 (Ph3P+ C).
Minor isomer (E)-3d (41%): 1H NMR: 3.16 and 3.84 (6H, 2s, 2 OCH3), 5.02 (1H, d,
3JHP = 16.8 Hz, P C CH), 1.30 (1H, br, NH), 6.80–7.55 (25H, m, 5C6H5). 13C NMR: 40.3
(d, 1JPC = 126.6 Hz, P C), 52.5 and 52.9 (2 OCH3), 61.5 (d, 2JPC = 17.1 Hz, P C CH),
113.2, 113.4, 114.0, 118.2, 120.1, 124.1 and 129.1 (7C, (C6H5)2N4HCO), 126.0 (d, 1JPC
=
92.1 Hz, Cipso), 128.6 (d, 3JPC = 12.1 Hz, Cmeta), 132.0 (d, 4JPC = 3.2 Hz, Cpara), 133.5 (d,
2JPC = 9.8 Hz, Cortho), 147.3, 148.9, 149.4, 151.5 and 160.3 (5C, (C6H5)2N4HCO), 165.4
(1C, O C N), 171.0 (d, 3JPC = 12.7 Hz, C Oester), 172.3 (d, 2JPC = 10.3 Hz, P C C).
31P NMR: 23.9 (Ph3P+ C).
Diethyl-2-(1,5-diphenylcarbazone-1-yl)-3-(triphenylphosphoranylidene)
butanedioate (3e). Yellow crystal (0.60 g), yield 90%, mp 177–180◦C. IR (KBr) (λmax
,
cm−1): 1620 (N N), 1720, 1732 (C Oester), 3433 (N H). MS (m/z,%): 672 (M++2, 13),
446 (10), 277 (100), 199 (24), 183 (22), 152 (14), 134 (10), 92 (25), 77 (59). Anal. Calc.
for C39H37N4O5P (672.71): C, 69.64; H, 5.51; N, 8.33%; Found: C, 69.71; H, 5.48; N,
8.38%.
1
3
Major isomer (Z)-3e (67%): H NMR: 0.43 and 1.39 (6H, 2t, JHH = 7.1 Hz 2
OCH2CH3), 1.70 (1H, br, NH), 4.21–4.44 (4H, m, 2 ABX3 system, 2 OCH2CH3), 5.12
(1H, d, 3JHP = 18.4 Hz, P C CH), 6.84–7.80 (25H, m, 5 C6H5). 13C NMR: 14.0 and 14.3
1
(2s, 2 OCH2CH3), 40.0 (d, JPC = 126.8 Hz, P C), 58.0 and 61.8 (2 OCH2CH3), 61.7
2
(d, JPC = 17.8 Hz, P C CH), 113.0, 113.3, 113.8, 117.9, 122.5, 123.1 and 124.1 (7C,
(C6H5)2N4HCO), 126.2 (d, 1JPC = 92.1 Hz, Cipso), 128.7 (d, 3JPC = 11.9 Hz, Cmeta), 132.9
(d, 4JPC = 2.6 Hz, Cpara), 133.6 (d, 2JPC = 10.0 Hz, Cortho), 146.0, 148.9, 149.9, 152.2 and
160.9 (5C, (C6H5)2N4HCO), 167.3 (1C, O C N), 170.7 (d, 3JPC = 12.8Hz, C Oester),
172.8 (d, 2JPC = 11.6 Hz, P C C). 31P NMR: 23.8 (Ph3P+ C).
1
3
Minor isomer (E)-3e (33%): H NMR: 1.26 and 1.29 (6H, 2t, JHH = 7.0 Hz,
2OCH2CH3), 1.70 (1H, br, NH), 4.15–4.44 (4H, m, 2 ABX3 system, 2 OCH2CH3), 5.18

AZOIC COMPOUNDS AND ANTHRAQUINONE DERIVATIVES
1401
3
(1H, d, JHP = 18.6 Hz, P C CH), 6.84–7.80 (25H, m, 5 C6H5). 13C NMR: 13.8 and
1
14.1 (2 OCH2CH3), 40.4 (d, JPC = 126.0 Hz, P C), 58.4 and 61.3 (2 OCH2CH3), 62.2
2
(d, JPC = 17.7 Hz, P C CH), 113.2, 113.6, 114.3, 118.1, 121.4, 123.1 and 125.4 (7C,
(C6H5)2N4HCO), 126.3 (d, 1JPC = 92.1 Hz, Cipso), 128.6 (d, 3JPC = 11.8 Hz, Cmeta), 131.9
(d, 4JPC = 2.6 Hz Cpara), 133.5 (d, 2JPC = 10.3 Hz, Cortho), 147.2, 149.1, 150.1, 151.4 and
160.5 (5C, (C6H5)2N4HCO), 165.0 (1C, O C N), 170.7 (d, 3JPC = 12.7 Hz, C Oester),
171.7 (d, 2JPC = 10.4 Hz, P C C). 31P NMR: 23.9 (Ph3P+ C).
Di-tert-buthyl-2-(1,5-diphenylcarbazone-1-yl)-3-(triphenylphosphorany-
lidene)butanedioate (3f). Pale white powder (0.70 g), yield 96%, m.p. 172–175◦C. IR
(KBr) (λmax, cm−1): 1598 (N N), 1688, 1728 (C Oester), 3427 (N H). MS (m/z,%): 728
(M+, 4), 489 (21), 377 (40), 277 (40), 262 (98), 183 (100), 152 (22), 108 (53), 93 (95),
57 (58). Anal. Calc. for C43H45N4O5P (728.81): C, 70.88; H, 6.18; N, 7.69%; Found: C,
70.91; H, 6.09; N, 7.75%.
Major isomer (Z)-3f (79%): 1H NMR: 0.88 and 1.61 (18H, 2s, 2 CMe3), 5.00 (1H,
d, 3JHP = 18.3 Hz, P C CH), 1.28 (1H, br, NH), 6.80–7.92 (25H, m, 5 C6H5).13C NMR:
1
2
28.3 and 28.4 (2 CMe3), 39.9 (d, JPC = 126.3 Hz, P C), 61.4 (d, JPC = 17.8 Hz,
P C CH), 77.5 and 81.2 (2 OCMe3), 113.2, 113.4, 119.9, 120.0, 121.2 and 123.2 (6C,
(C6H5)2N4HCO), 126.7 (d, 1JPC = 92.0 Hz, Cipso), 128.5 (d, 3JPC = 12.0 Hz, Cmeta), 132.0
(Cpara), 133.7 (d, 2JPC = 9.5 Hz, Cortho), 147.2, 149.0, 149.2, 150.0, 159.6 and 160.7 (6C,
(C6H5)2N4HCO), 164.4 (1C, O C N), 170.5 (d, 3JPC = 12.1 Hz, C Oester), 172.0 (d, 2JPC
= 11.9 Hz, P C C). 31P NMR: 23.5 (Ph3P+ C).
Minor isomer (E)-3f (23%): 1H NMR: 1.43 and 1.55 (18H, 2s, 2 CMe3), 4.87 (1H,
d, 3JHP = 18.9 Hz, P C CH), 1.22 (1H, br, NH), 6.80–7.92 (25H, m, 5 C6H5). 13C
1
2
NMR: 28.0 and 28.1 (2 CMe3), 39.6 (d, JPC = 126.9 Hz, P C), 61.4 (d, JPC = 17.8
Hz, P C CH), 81.7 and 82.0 (2 OCMe3), 113.3, 113.8, 120.3, 120.6, 123.7 and 124.1
(6C, (C6H5)2N4HCO), 126.7 (d, 1JPC = 92.0 Hz, Cipso), 128.4 (d, 3JPC = 12.3 Hz, Cmeta),
132.0 (Cpara), 133.6 (d, 2JPC = 9.5 Hz, Cortho), 148.4, 149.0, 151.4, 152.1, 159.6 and 161.1
(6C, (C6H5)2N4HCO), 167.4 (1C, O C N), 170.5 (d, 3JPC = 12.1 Hz, C Oester), 170.6
(d, 2JPC = 10.5 Hz, P C C). 31P NMR: 23.6 (Ph3P+ C).
REFERENCES
1. G. McMullan, C. Meehan, A. Conneely, N. Kirby, T. Robinson, P. Nigam, I. M. Banat, R.
Marchant, and W. F. Smyth, Appl. Microbiol. Biotecnol., 56, 81 (2001).
2. C. I. Pearce, J. R. Lloyd, and J. T. Guthrie, Dyes Pigm., 58, 179 (2003).
3. S.S. Nathan and S. K. Murthy, Organic Chemistry Made Simple (W. H. Allen, London, 1968).
4. M. Matsui, Dyes Pigm., 40, 21 (1998).
5. B. V. Rao, V. Choudhary, and I. K. Varma, J. Soc. Dyers Colour., 106, 388 (1990).
6. W. Herbst, K. Hunger, Industrial Organic Pigments: Production, Properties, Applications, 3rd
ed, (Wiley-VCH, Weinheim, Germany, 2004), chapter 2.
7. V. Buss and L. Eggers, In Encyclopedia of Spectroscopy and Spectrometry, J. C. Lindon, G. E.
Tranter, J. L. Holmes, eds. (Academic Press, New York, 2000), p. 389e96.
8. N. M. Rageh, Spectrochim. Acta, Part A, 60, 103 (2004).
9. A. C. Bratton and J. E. K. Marshall, J. Biol. Chem., 128, (2), 537 (1939).
10. P. Nagaraja, H. S. Yathirajan, C. R. Raju, R. A. Vasantha, M. S. Nagendra, and M. S. Hemantha
Kumar, IL Farmaco, 58, 1295 (2003).
11. H. D. Revanasiddappa and B. Manju, IL Farmaco, 56, 615 (2001).
12. S. M. B. Fraga, M. S. T. Goncalves, J. C. V. P. Moura, and K. Rani, Eur. J. Org. Chem., 8, 1750
(2004).

1402
G. MARANDI ET AL.
13. S. Przeszlakowski and H. Wydra, Chromatographia, 15, 301 (1982).
14. S. H. Ashuto, N. D. Pandey, and J. K. Mehrotra, Colourage, 26, 25 (1979).
15. L. Sommer and V. Koblizko, Collect. Czech. Chem. Commun., 39, 396, (1974).
16. C. Woodward and H. Freiser, Talanta, 20, 417 (1973).
17. M. R. Islami, F. Mollazehi, and Z. Hassani, Russ. Chem. Bull., 56, 532, (2007).
18. P. J. Coelho, L. M. Carvalho, A. M. C. Fonseca, and M. M. M. Raposo, Tetrahedron Lett., 47,
3711 (2006).
19. M. Serwadczak and S. Kucharski, J. Sol-Gel Sci. Technol., 37, 57 (2006).
20. A. D. Towns, Dyes Pigm., 42, 3 (1999).
21. G. Hallas and A. D. Towns, Dyes Pigm., 33, 215 (1997).
22. S. Yin, H. Xu, W. Shi, L. Bao, Y. Gao, Y. Song, and B. Z. Tang, Dyes Pigm., 72, 119 (2007).
23. M. M. M. Raposo, A. M. R. C. Sousa, A. M. C. Fonseca, and G. Kirsch, Tetrahedron, 61, 8249
(2005).
24. A. Carella, R. Centore, A. Sirigu, A. Tuzi, Quatela A, S. Schutzmann, and M. Casalboni,
Macromol. Chem. Phys., 205, 1948 (2004).
25. A. M. Albu, B. Marculescu, and D. Vasilescu, Eur. Polym. J., 35, 2203 (1999).
26. F. Ruyffelaere, V. Nardello, R. Schmidt, and J. M. Aubry, J. Photochem. Photobiol., A, 183, 98
(2006).
27. A. Grafe, K. Haupt, and G. J. Mohr, Anal. Chim. Acta, 565, 42 (2006).
28. D. Zhang, M. Zhang, Z. Liu, M. Yu, F. Li, T. Yi, and C. Huang, Tetrahedron Lett., 47, 7093
(2006).
29. N. Menek and Y. Karaman, Dyes Pigm., 68, 101 (2006).
30. N. Menek and Y. Karaman, Dyes Pigm., 67, 9 (2005).
31. F. S. De Paula, A. G. Cioletti, J. F. Da Silva, and A. E. G. Santana, J. Electroanal. Chem., 544,
25 (2003).
32. R. Jain, M. Bhargava, and N. Sharma, Ind. Eng. Chem. Res., 42, 243 (2003).
33. M. M. Ghoneim, Y. M. Issa, E. M. Mabrouk, and T. Amerah, J. Electrochem. Soc., 133, C133
(1986).
34. H. M. Smith, ed., High Performance Pigments (Wiley-VCH, Weinheim, Germany, 2002), pp.
188–190.
35. S. Patai and Z. Rappaport, ed., The Chemistry of Quinonoid Compounds, vols. 1 and 2, (Wiley-
Interscience, New York, 1988).
36. S. Miki, R. Noda, and K. Fukunishi, J. Chem. Soc., Chem. Commun., 925 (1997).
37. P. Boldt, S. Zippel, and G. Haucke, J. Chem. Res., Synop., 386 (1997).
38. I. Yavari, N. Zabarjad-Shiraz, M. T. Maghsoodlou, and N. Hazeri. Phosphorus, Sulfur, and
Silicon., 177, 759 (2002).
39. M. T. Maghsoodlou, S. M. Habibi-Khorassani, R. Heydari, A. Hassankhani, G. Marandi, M.
Nassiri, and E. Mosaddeg, Mol. Divers., 11, 87 (2007).
40. M. T. Maghsoodlou, N. Hazeri, S. M. Habibi-Khorassani, R. Heydari, M. Nassiri, G. Marandi,
Z. Moeeni, U. Niromand, and Z. E. Torbaghan, Phosphorus, Sulfur, and Silicon, 181, 865
(2006).
41. M. T. Maghsoodlou, S. M. Habibi-Khorassani, N. Hazeri, and M. Nassiri, Phosphorus, Sulfur,
and Silicon, 181, 1363 (2006).
42. I. Yavari and K. Karimi, Phosphorus, Sulfur, and Silicon, 182, 595 (2007).
43. M. T. Maghsoodlou, N. Hazeri, R. Kakaei, and M. Nassiri, Phosphorus, Sulfur, and Silicon, 181,
25 (2006).
44. S. M. Habibi-Khorassani, M. T. Maghsoodlou, N. Hazeri, M. Nassiri, G. Marandi, and A. G.
Shahzadeh, Phosphorus, Sulfur, and Silicon, 181, 567 (2006).
45. S. M. Habibi-Khorassani, M. T. Maghsoodlou, A. Ebrahimi, H. Roohi, M. Zakarianezhad, H. R.
Dasmeh, and M. Moradian, Phosphorus, Sulfur, and Silicon, 181, 1103 (2006).
46. P. J. Murphy, Organophosphorus Reagents, 1st ed. (Oxford University Press: Oxford, UK, 2004),
Chapters 1 and 2.

AZOIC COMPOUNDS AND ANTHRAQUINONE DERIVATIVES
1403
47. O. I. Kolodiazhnyi, Phosphorus Ylides: Chemistry and Application in Organic Synthesis (Wiley-
VCH, Weinheim, Germany, 1999).
48. I. Gosney and A. G. Rowley, Organophosphorus Reagents in Organic Synthesis, J. I. G. Cadogan,
ed. (Academic Press: London, 1979), pp. 17–153.
49. R. Engel and J. I. Cohen, Synthesis of Carbon-Phosphorus Bonds, 2nd ed. (CRC Press, Boca
Raton, FL, 2004), Chapters 1–3.
50. H. R. Hudson, The Chemistry of Organophosphorus Compounds, Vol. 1: Primary, Secondary,
and Tertiary Phosphates and Heterocyclic Organophosphorus (III) Compounds, F. R. Hartley,
ed. (Wiley, New York, 1990), pp. 382–472.
51. D. E. C. Corbridge, In Topics in Phosphorus Chemistry, M. Grayson and J. Griffith, eds. (Inter-
science, New York, 1969), vol. 6, pp. 235–365.