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C‐Vinylation of 1,8‐DihydroxyanthraquinonePromoted by TriphenylphosphineIssa Yavari a b , Ali R. Alborzi b , Bita Mohtat b & FarahnazNourmohammadian ca Chemistry Department , Tarbiat Modares University , Tehran, Iranb Chemistry Department, Science and Research Campus , Islamic AzadUniversity , Tehran, Iranc Department of Organic Colorants , Institute for Colorants, Paint andCoatings , Tehran, IranPublished online: 15 Feb 2008.

To cite this article: Issa Yavari , Ali R. Alborzi , Bita Mohtat & Farahnaz Nourmohammadian (2008)C‐Vinylation of 1,8‐Dihydroxyanthraquinone Promoted by Triphenylphosphine, Synthetic Communications:An International Journal for Rapid Communication of Synthetic Organic Chemistry, 38:5, 703-712, DOI:10.1080/00397910701818669

To link to this article: http://dx.doi.org/10.1080/00397910701818669

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C-Vinylation of 1,8-Dihydroxyanthraquinone Promoted

by Triphenylphosphine

Issa Yavari,1,2 Ali R. Alborzi,2 Bita Mohtat,2

and Farahnaz Nourmohammadian3

1Chemistry Department, Tarbiat Modares University, Tehran, Iran2Chemistry Department, Science and Research Campus, Islamic Azad

University, Tehran, Iran3Department of Organic Colorants, Institute for Colorants, Paint and

Coatings, Tehran, Iran

Abstract: The reaction of dialkyl acetylendicarboxylates with 1,8-dihydroxyanthra-

quinone in the presence of triphenylphosphine (20 mol%) produces dialkyl (E)-2-

(1,8-dihydroxy-9,10-dioxo-9,10-dihydro-2-anthracenyl)-2-butenedioates in good

yields. When the reaction is performed in the presence of 2.2 equivalents of the acet-

ylenic ester, a nearly 2:1 mixture of dialkyl (E)-2-f1,8-dihydroxy-7-[(E)-3-methoxy-1-

(methoxycarbonyl)-3-oxo-1-propenyl]-9,10-dioxo-9,10-dihydro-2-anthracenylg-2-but

enedioates and dialkyl (Z)-2-f1,8-dihydroxy-7-[(E)-3-methoxy-1-(methoxycarbonyl)-

3-oxo-1-propenyl]-9,10-dioxo-9,10-dihydro-2-anthracenylg-2-butenedioates is obtained.

Keywords: acetylenic ester, C-vinylation, 1,8-dihydroxyanthraquinone,

triphenylphosphine

The building blocks in organic pigments are molecules that determine,

directly or indirectly, important performance properties of pigments.[1]

From the earliest days of modern structural theory of organic chemistry,

quinones have been intimately associated with the chemistry of aromatic

compounds.[1 – 3] Their importance in dye industry, in medicinal chemistry,

in biological electron-transport processes, and in other fields has been

Received in Poland August 8, 2007

Address correspondence to Issa Yavari, Chemistry Department, Tarbiat Modares

University, P. O. Box, 14115-175, Tehran, Iran. E-mail: yavarisa@modares.ac.ir

Synthetic Communicationsw, 38: 703–712, 2008

Copyright # Taylor & Francis Group, LLC

ISSN 0039-7911 print/1532-2432 online

DOI: 10.1080/00397910701818669

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documented over the years.[4 – 6] 9,10-Anthraquinone is the parent compound

for a large palette of anthraquinone dyes and so is the most important starting

material in their production.

In continuation of our current interest in the application of triphenylpho-

sphine (Ph3P) and activated acetylenes in organic synthesis,[7 – 10] we report

here a simple one-pot synthesis of functionalized 9,10-anthraquinone deriva-

tives 3–5. Thus, the reaction of 1,8-dihydroxyanthraquinone (1) and dialkyl

acetylenedicarboxylates (2) in the presence of Ph3P (20 mol%) leads to

dialkyl (E)-2-(1,8-dihydroxy-9,10-dioxo-9,10-dihydro-2-anthracenyl)-2-

butenedioates 3a–d in good yields (see Scheme 1).

The reaction of 1 with 1.1 equivalents of dimethyl acetylenedicarboxylate

(2a, DMAD) in the presence of Ph3P proceeded in boiling toluene and was

completed within 24 h. The 1H and 13C NMR spectra of the crude products

clearly indicated the formation of dimethyl (E)-2-(1,8-dihydroxy-9,10-

dioxo-9,10-dihydro-2-anthracenyl)-2-butenedioate (3a) in 88% yield

(Scheme 1). Similarly, compounds 3b–d were prepared in 87–92% yield.

When the reaction was carried out using 2.2 equivalents of the activated acety-

lenes and Ph3P, a nearly 2:1 mixture of dialkyl (E)-2-f1,8-dihydroxy-7-[(E)-3-

methoxy-1-(methoxycarbonyl)-3-oxo-1-propenyl]-9,10-dioxo-9,10-dihydro-

2-anthracenylg-2-butenedioates 4a–d and dialkyl (Z )-2-f1,8-dihydroxy-7-

[(E)-3-methoxy-1-(methoxycarbonyl)-3-oxo-1-propenyl]-9,10-dioxo-9,10-

dihydro-2-anthracenylg-2-butenedioates 5a–d are obtained in excellent

overall yields (see Scheme 2).

The 1H NMR spectrum of 3a exhibited two single sharp resonances due to

the methoxy (d 3.75 and 3.87) protons along with resonances (d 7.38–8.36)

for the aromatic protons. The 13C NMR spectrum of 3a showed 18 distinct res-

onances in agreement with the proposed structure. The 1H and 13C NMR

spectra of 3b and 3c were similar to those of 3a except for the alkoxy

moieties, which exhibited characteristic signals with appropriate chemical

shifts.

Scheme 1. Reaction condition for preparation of dialkyl (E)-2-(1,8-dihydroxy-9,10-

dioxo-9,10-dihydro-2-anthracenyl)-2-butenedioates 3a–d.

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The 1H NMR spectrum of 4a showed two singlets for the methoxy (d 3.99

and 4.08 ppm) protons along with resonances (d 7.50–8.31) for the aromatic

protons. The 13C NMR spectrum of 4a showed 12 distinct resonances. The 1H

and 13C NMR spectra of 4b and 4c were also similar to those of 4a, differing in

the nature of the alkoxy groups.

Although the mechanistic details of the reaction are not clearly known, a

plausible rationalization may be advanced to explain the product formation.

Presumably, the zwitterionic intermediate[11] 6 formed from Ph3P and

dialkyl acetylenedicarboxylate is protonated by 1,8-dihydroxyanthraquinone

to furnish intermediate 7, which then is attacked by the conjugate base 8 to

produce ylide 9. This intermediate undergoes proton transfer to furnish the

1,3-diionic structure 10, which is converted to the final product by loss of

Ph3P (Scheme 3).

Scheme 3. Plausible mechanism for formation of 3.

Scheme 2. Reaction condition for preparation of dialkyl (E)-2-f1,8-dihydroxy-7-

[(E)-3-methoxy-1-(methoxycarbonyl)-3-oxo-1-propenyl]-9,10-dioxo-9,10-dihydro-

2-anthracenylg-2-butenedioates 4a–d and dialkyl (Z )-2-f1,8-dihydroxy-7-[(E)-3-

methoxy-1-(methoxycarbonyl)-3-oxo-1-propenyl]-9,10-dioxo-9,10-dihydro-2-

anthracenylg-2-butenedioates 5a–d.

C-Vinylation of 1,8-Dihydroxyanthraquinone 705

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Thus, the 1H NMR of each of the isolated product 3 and 4 exhibited a

C55CH proton signal at about 7.01–7.18 ppm, which is in agreement with

the (E) configuration for the vinyl moiety in 3 and 4. Compounds 5a–dexhibited a C55CH proton signal at about 6.50–6.69 ppm, which is in

agreement with the (Z ) configuration[12] for one of the double bonds.

Further evidence for the geometry of double bonds in 5 was obtained from

the 13C NMR spectra, which displayed olefinic methine resonances at about

132 and 127 ppm, for the (E) and (Z ) isomers, respectively.

We revealed a novel transformation involving 1,8-dihydroxyanthraqui-

none, dialkyl acetylenedicarboxylates, and Ph3P that results in C-vinylation

of the aromatic ring at the ortho position, affording dialkyl (E)-2-(1,8-

dihydroxy-9,10-dioxo-9,10-dihydro-2-anthracenyl)-2-butenedioates 3a–d.

When the reaction was carried out using 2.2 equivalents of the activated acety-

lenes, a nearly 2:1 mixture of dialkyl (E)-2-f1,8-dihydroxy-7-[(E)-3-methoxy-

1-(methoxycarbonyl)-3-oxo-1-propenyl]-9,10-dioxo-9,10-dihydro-2-

anthracenylg-2-butenedioates 4a–d and dialkyl (Z )-2-f1,8-dihydroxy-7-[(E)-

3-methoxy-1-(methoxycarbonyl)-3-oxo-1-propenyl]-9,10-dioxo-9,10-

dihydro-2-anthracenylg-2-butenedioates 5a–d was obtained. The present

procedure carries the advantage that not only is the reaction performed

under neutral conditions, but also the reactants can be mixed without any

prior activation or modification.

EXPERIMENTAL

General

Melting points were measured on an Electrothermal-9100 apparatus. IR

spectra were measured with a Shimadzu IR-460 spectrometer. 1H and 13C

spectra were determined on a Bruker DRX-300 Avance instrument in

CDCl3 at 300 and 75 MHz, respectively, with d in parts per million and J in

hertz. EI-MS (70 eV) was measured on a Finnigan-MAT-8430 mass spec-

trometer, in m/z. Elemental analyses (C, H, N) were performed with a

Heraeus CHN-O-Rapid analyzer. UV spectra were taken on a Shimadzu

UV-160A spectrometer. 1H and 13CNMR spectra were obtained for

solutions in CDCl3 using TMS as internal standard. All the chemicals used

in this work were purchased from Fluka (Buchs, Switzerland) and were

used without further purification.

General Procedure for the Preparation of Compounds 3

To a stirred solution of Ph3P (0.052 g, 20 mol%) and 1 (0.48 g, 2 mmol) in

toluene (20 mL), a solution of 2 (2 mmol) in toluene (20 mL) was added at

room temperature. The reaction mixture was refluxed for 24 h. The solvent

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was removed under reduced pressure, and the residue was purified by column

chromatography (SiO2; n-hexane/AcOEt 4:1) to afford the pure title

compounds.

Data

Dimethyl 2-(9,10-dihydro-1,8-dihydroxy-9,10-dioxoanthracen-2-

yl)fumarate (3a)

Yellow crystals (EtOH); yield: 0.52 g (88%); mp 202–2058C. IR (KBr)

(ymax/cm21): 1625, 1673, 1719, 1735 (C55O). 1H NMR: d ¼ 3.68, 3.84 (2

s, 2 MeO), 7.18 (s, CH), 7.31 (d, 3J ¼ 7.3, CH), 7.58 (d, 3J ¼ 7.7, CH),

7.70 (dd, 3J ¼ 7.6, 8.3, CH), 7.85 (d, 3J ¼ 7.6, CH), 7.88 (d, 3J ¼ 8.3, CH),

11.99, 12.36 (2 s, 2 OH). 13C NMR: d ¼ 52.5, 53.6 (2 Me); 119.6, 120.5,

125.1, 131.1 (4 CH), 137.8, 138.1, 116.0, 116.2 (4 C), 130.9 (CH), 134.0,

134.0, 140.5 (3 C), 160.2, 163.0 (2 C-OH), 165.2, 166.0, 181.8, 193.1 (4

C55O). MS: m/z (%): 382 (Mþ, 7), 323 (100), 69 (28), 59 (34), 57 (44), 55

(42), 43 (60), 41 (39). Anal. calcd. for C20H14O8 (382.31): C, 62.83; H,

3.69%. Found C, 62.71; H, 3.63%.

The procedure for preparation of other product was similar to that for 3a.

Diethyl 2-(9,10-dihydro-1,8-dihydroxy-9,10-dioxoanthracen-2-

yl)fumarate (3b)

Yellow crystals (EtOH); yield: 0.36 g (92%), mp 139–1408C. IR (KBr)

(ymax/cm21): 1623, 1671, 1723 (C55O). 1H NMR: d ¼ 1.18 (t, 3J ¼ 7.1,

Me), 1.31 (t, 3J ¼ 7.1, Me), 4.13 (q, 3J ¼ 7.1, CH2O), 4.32 (q, 3J ¼ 7.1,

CH2O), 7.17 (s, 1 H, CH), 7.32 (d, 3J ¼ 7.3, 1 H, CH), 7.58 (d, 3J ¼ 7.8,

1 H, CH), 7.71 (dd, 3J ¼ 8.2, 7.8, 1 H, CH), 7.86 (d, 3J ¼ 6.3, 1 H, CH),

7.89 (d, 3J ¼ 7.8, 1 H, CH), 12.02 (s, 1 H, OH), 12.33 (s, 1 H, OH). 13C

NMR: d ¼ 14.3, 14.5 (2 Me); 61.6, 62.6 (2 CH2O); 116.0, 116.2 (2 C);

119.6, 120.5, 125.1, 131.2, 131.3 (5 CH); 133.9, 134.0, 137.8 (3 C), 138.2

(CH), 140.3 (C), 160.3, 163.0, 181.9, 193.6 (4 C55O). MS: m/z (%): 410

(Mþ, 5), 337 (76), 291 (30), 69 (50), 57 (80), 55 (80), 43 (100), 41 (72).

Anal. calcd. for C22H18O8 (410.36): C, 64.39; H, 4.42%. Found C, 64.51;

H, 4.45%.

Di-isopropyl 2-(9,10-dihydro-1,8-dihydroxy-9,10-dioxoanthracen-2-

yl)fumarate (3c)

Yellow crystals (EtOH); 0.37 g (87%), mp 118–1208C. UV (EtOH, 95%)

lmax (nm) ¼ 437, emax (mol21 cm2) ¼ 14353. IR (neat) (ymax/cm21): 1721

(C55O). 1H NMR: d ¼ 1.15 (d, 3J ¼ 6.2, CHMe2), 1.29 (d, 3J ¼ 6.4,

CHMe2), 4.96 (sept, 3J ¼ 6.2, CHMe2), 5.16 (sept, 3J ¼ 6.2, CHMe2), 7.12

C-Vinylation of 1,8-Dihydroxyanthraquinone 707

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(s, CH), 7.32 (d, 3J ¼ 7.4, CH), 7.59 (d, 3J ¼ 7.7, CH), 7.71 (dd, 3J ¼ 7.7, 8.2,

CH), 7.85 (d, 3J ¼ 6.3, CH), 7.88 (d, 3J ¼ 7.7, CH), 12.02, 12.39 (2 s, 2 OH).13C NMR: d ¼ 22.0, 22.1 (2 CHMe2), 69.3, 70.4 (2 CHMe2), 115.8, 116.2 (2

C), 119.6, 120.5, 125.1 (3 CH), 131.5 (C), 131.6 (CH), 133.8, 134.0 (2 C),

137.8, 138.3 (2 CH), 140.2 (C), 160.3, 162.9 (2 C-OH), 164.5, 165.0, 181.9,

193.5 (4 C55O). Anal. calcd. for C24H22O8 (438.42): C, 65.75; H, 5.06%.

Found C, 65.51; H, 5.11%.

Di-tert-butyl 2-(9,10-dihydro-1,8-dihydroxy-9,10-dioxoanthracen-2-

yl)fumarate (3d)

Yellow oil; yield: 0.45 g (91%). IR (KBr) (ymax/cm21): 1623, 1673, 1718

(C55O). 1H NMR: d ¼ 1.32, 1.50 (2 s, 2 CMe3), 7.01 (s, CH), 7.27

(d, 3J ¼ 7.4, CH), 7.56 (d, 3J ¼ 7.7, CH), 7.72 (dd, 3J ¼ 8.2, 7.7, CH), 7.86

(d, 3J ¼ 6.9, CH), 7.89 (d, 3J ¼ 7.7, CH), 12.05, 12.40 (2 s, 2 OH). 13C

NMR: d ¼ 28.2, 28.3 (2 CMe3), 82.4, 83.2 (2 CMe3), 115.8, 116.3 (2 C),

119.6, 120.51, 125.1, 132.2, 132.6 (5 CH), 133.7, 134.1, 137.8 (3 C), 138.2

(CH), 140.0 (C), 160.3, 163.0 (2 C-OH); 164.5, 164.7, 182.0, 193.6 (4

C55O). Anal. calcd. for C26H26O8 (466.47): C, 66.94; H, 5.62%. Found C,

66.75; H, 5.65%.

General Procedure for the Preparation of Compounds 4 and 5

A solution of 2 (2 mmol) in toluene (5 mL) to a stirred solution of Ph3P

(0.104 g, 20 mol%) and 1 (0.48 g, 2 mmol) in toluene (20 mL) was added at

room temperature. The reaction mixture was refluxed for 24 h. The solvent

was removed under reduced pressure, and the residue was purified by

column chromatography (SiO2; hexane/AcOEt 4:1) to afford the pure title

compounds.

Data

Dimethyl (E)-2-f1,8-dihydroxy-7-[(E)-3-methoxy-1-

(methoxycarbonyl)-3-oxo-1-propenyl]-9,10-dioxo-9,10-dihydro-2-

anthracenylg-2-butenedioates (4a)

Red oil; 0.36 g (58%). IR (neat) (ymax/cm21): 1727 (C55O). 1H NMR:

d ¼ 3.62 (s, 6 H, 2 Me), 3.84 (s, 6 H, Me), 7.19 (s, 2 H, CH), 7.59

(d, 3J ¼ 7.7, 2 H, CH), 7.89 (d, 3J ¼ 7.7, 2 H, CH), 12.31 (s, 2 H, OH). 13C

NMR: d ¼ 52.6 (CH3), 53.6 (CH3), 116.0 (C), 119.7 (CH), 131.0 (C), 131.2

(CH), 134.0 (C), 137.6 (CH), 140.4 (C), 160.2 (C-O), 165.2 (C55O), 165.9

(C55O), 181.5 (C55O), 193.6 (C55O). Anal. calcd. for C26H20O12 (524.42):

C, 59.84; H, 3.84%. Found C, 60.01; H, 3.91%.

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Diethyl (E)-2-f1,8-dihydroxy-7-[(E)-3-ethoxy-1-(ethoxycarbonyl)-3-

oxo-1-propenyl]-9,10-dioxo-9,10-dihydro-2-anthracenylg-2-

butenedioate (4b)

Red oil; yield: 0.33 g (64%). IR (neat) (ymax/cm21): 1619, 1671, 1723

(C55O). 1H NMR: d ¼ 1.16 (t, 3J ¼ 4, 6 H, CH3), 1.30 (t, 3J ¼ 7, 6 H,

CH3), 4.10 (q, 3J ¼ 7.1, 4 H, CH2), 4.29 (q, 3J ¼ 7.1, 4 H, CH2), 7.17 (s, 2

H, CH), 7.59 (d, 3J ¼ 7.8, 2 H, CH), 7.85 (d, 3J ¼ 7.8, 2 H, CH), 12.31

(s, 2 H, OH). 13C NMR: d ¼ 14.3 (CH3), 14.4 (CH3), 61.6 (CH2), 62.7

(CH2), 115.9 (C), 119.6 (CH), 131.3 (CH), 131.4 (CH), 133.9 (C), 138.3

(C), 140.2 (C), 161.3 (C-O), 164.8 (C55O), 165.4 (C55O), 181.6 (C55O),

193.6 (C55O). MS: m/z (%): 580 (Mþ., 1), 57 (100), 56 (8), 55 (14), 44 (7),

43 (189), 42 (5), 41 (45). Anal. calcd. for C30H28O12 (580.52): C, 62.07; H,

4.86%. Found C, 61.89; H, 4.85%.

Di-isopropyl (E)-2-f1,8-dihydroxy-7-[(E)-3-isopropoxy-1-

(isopropoxycarbonyl)-3-oxo-1-propenyl]-9,10-dioxo-9,10-dihydro-2-

anthracenylg-2-butenedioate (4c)

Orange crystals (EtOH); 0.31 g (61%), mp 135–1388C. lmax (nm) ¼ 430,

emax (mol21 cm2) ¼ 8305. IR (neat) (ymax/cm21): 1719 (C55O). 1H NMR:

d ¼ 1.14 (d, 3J ¼ 6.2, 12 H, CHMe2), 1.28 (d, 3J ¼ 6.2, 12 H, CHMe2),

4.96 (sept, 3J ¼ 6.2, 2 H, CHMe2), 5.15 (sept, 3J ¼ 6.2, 2 H, CHMe2), 7.12

(s, 2 H, CH), 7.59 (d, 3J ¼ 7.8, 2 H, CH), 7.89 (d, 3J ¼ 7.7, 2 H, CH),

12.64 (s, 2 H, OH). 13C NMR: d ¼ 21.9 (CHMe2), 22.0 (CHMe2), 69.3

(CHMe2), 70.4 (CHMe2), 115.8 (C), 119.6 (CH), 126.0 (C), 131.6 (CH),

133.9 (C), 138.4 (CH), 140.1 (C), 160.3 (C-O), 164.4 (C55O), 165.0

(C55O), 181.6 (C55O), 193.6 (C55O). Anal. calcd. for C34H36O12 (636.63):

C, 64.14; H, 5.70%. Found C, 64.33; H, 5.67%.

Di-tert-butyl (E)-2-f1,8-dihydroxy-7-[(E)-3-tert-butoxy-1-(tert-

butoxycarbonyl)-3-oxo-1-propenyl]-9,10-dioxo-9,10-dihydro-2-

anthracenylg-2-butenedioate (4d)

Orange oil; yield: 0.41 g (60%). IR (KBr) (ymax/cm21): 1616, 1672, 1718

(C55O). 1H NMR: d ¼ 1.31 (s, 18 H, CMe3), 1.50 (s, 18 H, CMe3), 7.01

(s, 2 H, CH), 7.56 (d, 3J ¼ 7.7, 2 H, CH), 7.88 (d, 3J¼ 7.7, 2 H, CH), 12.35

(s, 2 H, OH). 13C NMR: d ¼ 28.2 (CMe3), 28.3 (CMe3), 82.4 (CMe3), 83.2

(CMe3), 115.7 (C), 119.6 (CH), 132.3 (CH), 132.6 (CH), 133.7 (C), 138.3

(C), 140.0 (C), 160.34 (C-O), 164.5 (C55O), 164.7 (C55O), 181.7 (C55O),

193.7 (C55O). Anal. calcd. for C38H44O12 (692.73): C, 65.88; H, 6.40%.

Found C, 65.65; H, 6.25%.

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Dimethyl (Z )-2-f1,8-dihydroxy-7-[(E)-3-methoxy-1-

(methoxycarbonyl)-3-oxo-1-propenyl]-9,10-dioxo-9,10-dihydro-2-

anthracenylg-2-butenedioate (5a)

Red oil; 0.30 g (33%). IR (neat) (ymax/cm21): 1730 (C55O). 1H NMR:

d ¼ 3.81, 3.82, 3.92, 3.93 (4 s, 4 Me), 6.71, 7.17 (2 s, 2 CH), 7.73

(d, 3J ¼ 7.7, 1 H, CH), 7.75 (d, 3J ¼ 8.1, 1 H, CH), 7.88 (d, 3J ¼ 8.1, 1 H,

CH), 7.92 (d, 3J ¼7.7, 1 H, CH), 11.92, 13.0 (2 s, 2 OH). 13C NMR:

d ¼ 52.7, 53.1, 53.3, 54.1 (4 MeO), 116.0, 116.5 (2 C), 120.0 (CH), 120.5

(C), 120.7, 125.1, 125.4 (3 CH), 123.0, 131.1, 133.7, 134.6 (4 C), 137.5

(CH), 137.8 (C), 138.1 (CH), 161.2, 163.1 (2 C-OH), 164.8, 165.2, 165.7,

167.6, 181.5, 193.5 (6 C55O). Anal. calcd. for C26H20O12 (524.42): C,

59.54; H, 3.84%. Found C, 59.31; H, 3.91%.

Diethyl (Z )-2-f1,8-dihydroxy-7-[(E)-3-ethoxy-1-(ethoxycarbonyl)-3-

oxo-1-propenyl]-9,10-dioxo-9,10-dihydro-2-anthracenylg-2-

butenedioate (5b)

Red oil; yield: 0.28 g (29%). IR (neat) (ymax/cm21): 1623, 1672, 1726

(C55O). 1H NMR: d ¼ 1.18, 1.35, 1.38, 1.40 (4 t, 3J ¼ 7.1, 4 Me), 4.13,

4.29, 4.31, 4.40 (4 q, 3J¼ 7.1, 4 CH2O), 6.69, 7.17 (2 s, 2 CH), 7.60

(d, 3J ¼ 7.7, 1 H, CH), 7.77 (d, 3J ¼ 8.0, 1H, CH), 7.87 (d, 3J ¼ 8.0, 1 H,

CH); 7.90 (d, 3J ¼ 7.7, 1 H, CH), 12.22, 12.85 (2s, 2 OH). 13C NMR:

d ¼ 14.2, 14.3, 14.4, 14.5 (4 Me), 61.6, 61.7, 62.4, 62.7 (4 CH2O), 115.8,

116.5 (2 C), 119.8, 120.1, 125.7 (3 CH), 130.4 (C), 131.5, 131.6 (2 CH),

133.7, 134.6, 137.6 (3 C), 138.6 (CH), 140.2, 142.2 (2 C), 160.4, 161.3 (2

C-OH), 164.8, 165.2, 165.3, 167.0, 181.2, 193.6 (6 C55O). Anal. calcd. for

C30H28O12 (580.52): C, 62.07; H, 4.86%. Found C, 61.89; H, 4.85%.

Di-isopropyl (Z)-2-f1,8-dihydroxy-7-[(E)-3-isopropoxy-1-

(isopropoxycarbonyl)-3-oxo-1-propenyl]-9,10-dioxo-9,10-dihydro-2-

anthracenylg-2-butenedioate (5c)

Red oil; 0.23 g (32%). UV (EtOH) lmax (nm) ¼ 443, emax (mol21

cm2) ¼ 12480. IR (neat) (ymax/cm21): 1723 (C55O). 1H NMR: d ¼ 1.15,

1.29, 1.33, 1.36 (4 d, 3J ¼ 6.2, 4 CHMe2), 4.96, 5.13, 6.14, 5.28 (4 sept,3J ¼ 6.2, 4 CHMe2), 6.64 (s, 1 H, CH), 7.12 (s, 1 H, CH), 7.60 (d, 3J ¼ 7.7,

1 H, CH), 7.77 (d, 3J ¼ 8.0, 1 H, CH), 7.87 (d, 3J ¼ 8.0, 1 H, CH), 7.88

(d, 3J ¼ 7.7, 1 H, CH), 12.34, 12.85 (2 s, 2 OH). 13C NMR: d ¼ 21.8, 21.9,

22.0, 22.2 (4 CHMe2), 68.5, 69.3, 70.1, 70.5 (4 CHMe2), 115.7, 116.4 (2

C), 119.8, 120.1, 126.0, 129.2 (4 CH), 130.8 (C), 131.3 (CH), 131.7, 131.8

(2 C), 132.8 (CH), 133.7, 134.5, 137.6, 138.7, 140.1 (5 C), 160.5, 161.6 (2

C-OH), 164.6, 165.3, 165.8, 168.2, 181.3, 193.7 (6 C55O). Anal. calcd. for

C34H36O12 (636.63): C, 64.14; H, 5.70%. Found C, 64.33; H, 5.67%.

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Di-tert-butyl (Z )-2-f1,8-dihydroxy-7-[(E)-3-tert-butoxy-1-(tert-

butoxycarbonyl)-3-oxo-1-propenyl]-9,10-dioxo-9,10-dihydro-2-

anthracenylg-2-butenedioate (5d)

Red oil; yield: 0.27 g (28%). IR (KBr) (ymax/cm21): 1718 (C55O). 1H NMR:

d ¼ 1.32, 1.50, 1.55, 1.58 (4 s, 4 CMe3), 6.50, 7.01 (2 s, 2 CH), 7.57

(d, 3J ¼ 7.8, CH), 7.75 (d, 3J¼ 8.1, CH), 7.85 (d, 3J ¼ 8.1, CH), 7.88

(d, 3J ¼ 7.7, CH); 12.27, 12.78 (2 s, 2 OH). 13C NMR: d ¼ 28.2, 28.3,

28.5, 28.6 (4 CMe3), 82.1, 82.4, 82.5, 83.2 (4 CMe3), 115.7 (CH), 116.3

(C), 119.7, 120.1, 127.3 (3 CH), 132.0 (C), 132.5, 132.7 (2 CH), 133.5,

134.3, 137.7 (3 C), 138.5 (CH), 139.9, 142.0 (3 C), 160.4, 161.2 (2 C-OH),

164.1, 164.4, 164.6, 165.9, 181.4, 193.7 (6 C55O). Anal. calcd. for

C38H44O12 (692.73): C, 65.88; H, 6.40%. Found C, 65.65; H, 6.24%.

ACKNOWLEDGMENTS

We are grateful to the Institute for Colorants, Paint, and Coatings and Tarbiat

Modares University for financial support.

REFERENCES

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8. Yavari, I.; Alborzi, A. R.; Mohtat, B. Synthesis of highly functionalized 9,10-anthraquinones. Dyes Pigments 2006, 68, 85–88.

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