A convenient one-pot completely stereoselective synthesis of trans-4-Hydroxystilbenes and its derivatives and X-ray structure of its precursor

Article abstract of DOI:10.1081/SCC-120021843

The synthesis of E-isomer of 4-Hydroxystilbene and its derivatives 3 by reductive elimination of the carbonyl function in 2-phenyl-1-(4-hydroxyphenyl)ethan-1-one and its derivatives 2 and the X-ray structure of 2a are described.

Full text of DOI:10.1081/SCC-120021843

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A Convenient One-Pot Completely Stereoselective
Synthesis of trans-4-Hydroxystilbenes and Its
Derivatives and X-Ray Structure of Its Precursor
Rakeshwar B. Chhor a , Kunwar A. Singh b , B. Nosse a & Vishnu K. Tandon b
a Institut fur Organische Chemie , Universitat Regensburg , Regensburg, Germany
b Department of Chemistry , Lucknow University , Lucknow, India
Published online: 20 Aug 2006.
To cite this article: Rakeshwar B. Chhor , Kunwar A. Singh , B. Nosse & Vishnu K. Tandon (2003) A Convenient One-Pot
Completely Stereoselective Synthesis of trans-4-Hydroxystilbenes and Its Derivatives and X-Ray Structure of Its Precursor,
Synthetic Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 33:14,
2519-2530, DOI: 10.1081/SCC-120021843
To link to this article: http://dx.doi.org/10.1081/SCC-120021843
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SYNTHETIC COMMUNICATIONSÕ
Vol. 33, No. 14, pp. 2519–2530, 2003
A Convenient One-Pot Completely
Stereoselective Synthesis of
trans-4-Hydroxystilbenes and Its Derivatives
and X-Ray Structure of Its Precursor
Rakeshwar B. Chhor,1 Kunwar A. Singh,2
2,
B. Nosse,1 and VishnuK. Tandon
*
1Institut fur Organische Chemie,
Universitat Regensburg, Regensburg, Germany
2Department of Chemistry,
Lucknow University, Lucknow, India
ABSTRACT
The synthesis of E-isomer of 4-Hydroxystilbene and its derivatives 3
by reductive elimination of the carbonyl function in 2-phenyl-1-
(4-hydroxyphenyl)ethan-1-one and its derivatives 2 and the X-ray
structure of 2a are described.
*Correspondence: VishnuK. Tandon, Department of Chemistry, Lucknow
University, Lucknow 226007, India; Fax: þ91-522-326665; E-mail: tandon_vk@
hotmail.com.
2519
DOI: 10.1081/SCC-120021843
Copyright & 2003 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com

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2520
Chhor et al.
Key Words: Stereoselective; trans-4-Hydroxystilbene; Reductive
elimination; X-ray structure; Fries rearrangement.
In light of synthetic utility and remarkable broad spectrum activity of
trans-4-hydroxystilbene and its derivatives 3 in diversified areas of
organic chemistry demonstrated todate, a short stereoselective synthesis
of 3 was desired. E-4-Hydroxystilbene 3a has been used : in the synthesis
of photocross linkable polymers,[1] in anisotropic phase separation of
polystyrene/polyvinylmethyl-ether (PS/PVME) blends,[2] as an intermedi-
ate in the synthesis of nonsteroidal inhibitors of human prostatic
5a-reductase,[3] and nematocidal compounds,[4] in the development of
LTA-4-Hydrolase inhibitor,[5] in the synthesis of new fluoroescent
whitening agents[6] and in quinone methide chemistry.[7] Compound 3
has also been found to exhibit estrogenic activity[8] and fluorescence exci-
tation under jet cooled conditions.[9] Its acetyl derivative has shown anti-
microbial activity[10] and its trace amount is essential for light induced
isothermal switching of clearing points of the phase equilibrium hexago-
nal isotropic in potassium octanoate water system.[11] On the basis of
QSAR studies, it is found to show a parabolic hydrophobic relationship
for brown-rot activity of wood inhabiting fungi.[12] The polymeric form
of 3 has exhibited liquid crystal properties.[13]
Although several methods for synthesis of 3 are available in
Literature,[14] none of these describes its 100% stereoselective synthesis.
In this article we report first ever single pot synthesis of trans-4-
Hydroxystilbene 3a and its derivatives by use of NaBH4 and conc.HCl
in high yield and 100% stereoselectivity as well as X-ray crystal structure
of precursor 2a.
2-Phenyl-1-(4-hydroxyphenyl)-ethan-1-one 2a containing a 4-hydro-
xyphenyl group was a precursor of choice for the synthesis of trans-4-
hydroxystilbene 3a since not only 2a could be easily prepared from
readily available phenylacetylchloride and phenol (Sch. 1) but
2-phenyl-1-(2-hydroxyphenyl)-ethan-1-one could also be synthesized as
a result of Fries-rearrangement at high temperature. Compound 2a was
obtained in excellent yield from phenolic ester 1a by Fries-rearrangement
at low temperature.[15] It was evident from X-ray crystallographic data
that one of the Fries-rearrangement products 2a is sterically favoured and
this led us to devise a simple, economic and efficient synthetic route to 3a
and its derivatives. The reductive elimination of carbonyl group in 2a was
affected by first reduction with NaBH4 leading to formation of corre-
sponding alcohol 2a and further refluxing in the presence of conc. HCl to
form exclusively trans-4-hydroxystilbene 3a in one-pot in excellent yield.

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trans-4-Hydroxystilbenes
2521
R1
R2
OH
O
R2
R1
R2
Cl
10 % NaOH
O
O
R3
1
1. ∆, AlCl3,
2. H2O-HCl
R2
O
R1
HO
R3
2
(a) R1 = R2 = R3 = H
R2
(b) R1 =Me; R2 = R3 = H
(c) R1 = R3 = H; R3 = Me
(d) R1 = Cl; R2 = R3 = H
(e) R1 = R3 = H; R2 =Cl
R1
1-Naphthyl
=
(j)
R3
R2
R1
(f) R1 = OMe, R2 = R3 = H
(g) R1 = NO2; R2 = R3 = H
(h) R1 = R3 = Me; R2 = H
(i) R1 = H; R2 = R3 = Me
(k)
2-Naphthyl
=
R3
Scheme 1.
R2
O
R2
1. NaBH4 / EtOH
R1
R1
HO
2. HCl / ∆
HO
R3
80-99 %
R3
2 (a-k)
3 (a-k)
E : Z = 100 : 0
Scheme 2.
We then studied the synthesis of a range of substituted trans-4-hydro-
xystilbenes 3b–k (Sch. 2). The yields obtained were excellent in most
cases, being well above those reported in literature.[14]
From X-ray analysis of 2a, it is evident that both phenyl rings are
opposite to each other in the space and geometrically so arranged that the
reductive elimination of the carbonyl function takes place leading to
formation of trans-stereoisomer of 4-hydroxystilbene.

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2522
Chhor et al.
Figure 1. Crystal structure of 2a showing a partial atom labeling.
δ = 8.46 ppm
( bs, 1H)
(D2O shake)
δ = 4.96 ppm
( bs, 1H)
(D2O shake)
OH
OH
H
δ = 7.39 ppm
( d, J = 16.2 Hz )
δ = 7.25 ppm
( d, J = 16.2 Hz )
H δ = 7.12 ppm
( d, J = 16.2 Hz )
H
δ = 6.98 ppm
( d, J = 16.2 Hz )
H
m. p. = 120 °C
m. p. = > 220 °C
3k
3j
Figure 2.
1H NMR spectroscopic studies of 2 and 3 are in accordance with the
structures proposed for these compounds. Benzylic CH2 signal of 2a in
1
1H NMR (250 MHz) appeared at ꢀ 4.27. In H NMR spectra of 3a char-
acteristic doublets for olefinic protons at ꢀ 7.04 and ꢀ 7.18 with geminal
coupling constant of 16.24 Hz appeared and complete disappearance of
1
signal at ꢀ 4.27 was observed. The marked difference in H NMR for
assignment of structures 3j and 3k was observed as depicted in Fig. 2.
In summary, a convenient one-pot completely stereoselective synthe-
sis of trans-4-hydroxystilbene by reductive elimination of carbonyl group
using NaBH4 and conc. HCl as well as X-ray crystal structure of
2-phenyl-1-(4-hydroxyphenyl)-ethan-1-one 2a are described. This proce-
dure provides a very convenient and simple procedure for the stereo-
selective synthesis of substituted and even hindered 4-hydroxystilbenes.
EXPERIMENTAL
CH2Cl2 was freshly distilled over CaCl2 and EtOH over Mg. Melting
points were determined with a Townson Mercker melting point

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trans-4-Hydroxystilbenes
2523
apparatus and are uncorrected. IR spectra were recorded on a Perkin-
1
Elmer 137 spectrometer. H NMR (200 and 250 MHz) and 13C NMR
(62.9 MHz) were recorded on a Perkin-Elmer R-32 spectrometer in
CDCl3/Acetone-d6. EI Mass spectra were obtained on Jeol-JMS-D-300
spectrometer. Elemental microanalysis were carried out by R.S.I.C. of
Central Drug Research Institute, Lucknow.
Arylphenyl Acetates 1(a–k): General Procedure
Phenyl acetyl chloride (3.09 g, 0.02 mol) was added to a stirred solu-
tion of phenol (1.88 g, 0.2 mol) dissolved in 10% aq.NaOH solution
(10 mL) at 0–5ꢀC. Stirring was continuted for additional 2 h at this tem-
perature. The precipitated product was filtered and washed with H2O.
Recrystallization from benzene/hexane affords colorless shining crystals
1a; Yield 1.97 g (93%); m.p. 44ꢀC (Lit.[16] m.p. 42ꢀC). The IR, H and
1
13C NMR spectral data were identical to those reported in the literature.
2-Methylphenyl phenyl acetate (1b). Colorless crystals; benzene–
hexane; m.p. 45ꢀC, (Lit.[16] m.p. 42ꢀC) Yield 88%. IR (KBr): 526, 699,
754, 1136, 1350, 1489, 1596, 1755, 2370. 1H NMR (CDCl3): ꢀ 2.02 (s, 3H,
CH3), 3.87 (s, 2H, CH2), 6.9–7.11 (m, 4H, phenyl-H), 7.13–7.42 (m, 5H,
phenyl-H); Anal. calcd. for C15H14O2 (226): C, 79.64; H, 6.19. Found: C,
79.78; H, 6.24.
3-Methylphenyl phenyl acetate (1c). Pale yellow oil,[17] extracted with
CHCl3; yield 92%. IR (Neat): 514, 705, 749, 943, 1129, 1230, 1454, 1496,
1599, 1756, 2926, 3032;1H NMR (CDCl3): ꢀ 2.32 (s, 3H, CH3), 3.83 (s,
2H, CH2), 6.86–7.02 (m, 3H, phenyl-H), 7.11–7.23 (m, 2H, phenyl-H),
7.28–7.38 (m, 4H, phenyl-H); Anal. calcd. for C15H14O2 (226): C, 79.64;
H, 6.19. Found: C, 79.82; H, 6.22.
2-Chlorophenyl phenyl acetate (1d).[18] Solid, benzene–hexane, m.p.
62–63ꢀC; Yield: 95%. IR (KBr): 564, 692, 748, 868, 940, 1114, 1220,
1
1355, 1469, 1595, 1763, 2829, 3081. H NMR (CDCl3): ꢀ 3.91 (s, 2H,
CH2), 7.10–7.43 (m, 9H, phenyl-H); Anal. calcd. for C14H11ClO2
(246.5): C, 68.15; H, 4.46. Found: C, 68.04; H, 4.52.
3-Chlorophenyl phenyl acetate (1e).[18] Oil extracted with CH2Cl2;
yield 86%. IR (Neat): 519, 673, 759, 878, 936, 1028, 1112, 1215, 1474,
1591, 1760, 2365, 3025. 1H NMR (CDCl3): ꢀ 3.82 (s, 2H, CH2), 6.93–6.98
(m, 1H, phenyl-H), 7.08–7.35 (m, 8H, phenyl-H). Anal. calcd. for
C14H11ClO2 (246.5) : C, 68.15; H, 4.46. Found: C, 68.32; H, 4.40.
2-Methoxyphenyl phenyl acetate (1f ).[19] Oil extracted with CH2Cl2;
yield 98%. IR (Neat): 509, 750, 935, 1031, 1123, 1255, 1458, 1500, 1603,
1
1760, 2841, 2945, 3029. H NMR (CDCl3): ꢀ 3.76 (s, 3H, OCH3), 3.87

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2524
Chhor et al.
(s, 2H, CH2), 6.90–7.00 (m, 3H, phenyl-H), 7.12–7.16 (m, 1H, phenyl-H),
7.27–7.41 (m, 5H, phenyl-H); Anal. calcd. for C15H14O3 (242): C, 74.38;
H, 5.78. Found: C, 74.48; H, 5.86.
2-Nitrophenyl phenyl acetate (1g).[20] Yellow oil, extracted with
CH2Cl2; yield 99%. IR (Neat): 757, 820, 1029, 1080, 1190, 1256, 1474,
1
1595, 1756, 2324. H NMR (CDCl3): ꢀ 3.65 (s, 2H, CH2), 6.97–7.18 (m,
1H, phenyl-H), 7.29–7.33 (m, 5H, phenyl-H), 7.56–8.13 (m, 1H, phenyl-
H); Anal. calcd. for C14H11NO4 (257): C, 65.36; H, 4.28. Found: C, 65.52;
H, 4.36.
2,5-Dimethylphenyl phenyl acetate (1h). Solid; benzene–hexane; m.p.
55ꢀC; Yield 93%. IR (Neat): 562, 701, 811, 1124, 1241, 1348, 1453, 1598,
1754, 2920. 1H NMR (CDCl3): ꢀ 2.27 (s, 6H, 2 ꢁ CH3), 3.80 (s, 2H, CH2),
6.75–7.38 (m, 8H, phenyl-H); Anal. calcd. for C16H16O2 (240): C, 80.00;
H, 6.66. Found: C, 80.18; H, 6.78.
3,5-dimethylphenyl phenylacetate (1i).[21] Oil, extracted with CH2Cl2;
yield 84%. IR (Neat): 521, 694, 725, 1136 1237, 1460, 1596, 1755, 2922,
1
3028. H NMR (CDCl3): ꢀ 2.28 (s, 6H, 2 ꢁ CH3), 3.82 (s, 2H, CH2), 6.66
(s, 2H, phenyl-H), 6,83 (s, 1H, phenyl-H), 7.31–7.37 (m, 5H, phenyl-H);
Anal. calcd. for C16H16O2 (240): C, 80.00; H, 6.66. Found: C, 80.12;
H, 6.80.
1-Naphthyl phenylacetate (1j).[22] Solid, ethylacetate–hexane; m.p.
50–51ꢀC; yield 93%. IR (KBr): 568, 702, 776, 939, 1134, 1225, 1361,
1597, 1751, 2376, 2832. 1H NMR (CDCl3): ꢀ 4.02 (s, 2H, CH2),
7.20–7.25 (m, 2H, phenyl-H), 7.34–7.50 (m, 5H, phenyl-4), 7.58–7.62
(m, 1H, phenyl-H), 7.69–7.73 (m, 1H, phenyl-4), 7.81–7.85 (m, 1H,
phenyl-H); Anal. calcd. for C18H14O2 (262): C, 82.44; H, 5.34. Found:
C, 82.56; H, 5.40.
2-Naphthyl phenyl acetate (1k). Solid, ethylacetate–hexane; m.p.
80ꢀC; (Lit,[23] m.p. 83.5ꢀC)’ Yield 91%. IR (KBr): 606, 757, 1099,
1
1388, 1621, 1743, 2376, 2922. H NMR (Acetone-d6): ꢀ ¼ 3.28 (s, 2H,
CH2), 6.87–7.92 (m, 11H, phenyl-H), 7.95–8.02 (m, 1H, phenyl-H);
Anal. calcd. for C18H14O2 (262): C, 82.44, H, 5.34. Found: C, 82.54;
H, 5.42.
2-Phenyl-1-(4-hydroxyaryl)-ethan-1-one (2a–k)
General Procedure
A mixture of 1a (2.12 g, 0.01 mol) and anhy. AlCl3 (3.99 g, 0.03 mol)
was heated for 1 h at 60–70ꢀC. Resulting mixture was poured onto ice
cold HCl (50 mL), extracted with EtOAc (20 mL ꢁ 3), washed with H2O
(20 mL), brine (20 mL). Ethylacetate, extract was dried (NHSO4) and

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trans-4-Hydroxystilbenes
2525
concentrated in vacuo. Crude product was crystallized with
Benzene/Hexane; colourless solid; 2a; Yield 1.95 g (92%); m.p. 150ꢀC;
(Lit,[24] m.p. 148ꢀC), IR (KBr): 728, 840, 1168, 1206, 1338, 1578, 1601,
1
1667, 2902, 3033, 3370 cmÀ1. H NMR (Acetone-d6): ꢀ ¼ 3.04 (bs, 1H,
phenolic-OH), 4.27 (s, 2H, CH2), 6.85–6.99 (m, 2H, phenyl-H),
7.13–7.55 (m, 5H, phenyl-H), 7.94–8.02 (m, 2H, phenyl-H). 13C NMR
(Acetone-d6): ꢀ 45.38 (–CH2), 116.01 (þ, 2C, phenyl-C), 127.20 (þ,
phenyl C), 129.13 (þ, 2C, phenyl-C), 129.80 (q, phenyl C), 130.37 (þ,
2C, phenyl-C), 131.89 (þ, 2C, phenyl C), 136.70 (q, phenyl-C), 162.67 (q,
C-OH), 196.17 (q, carbonyl-C); MS (EI, 70 eV) m/z (%) : 212.1 (36, Mþ),
121.1 (100%), 93.1 (25.3), 65.1 (25.2).
2-Phenyl-1-(4-hydroxy-3-methylphenyl)-ethan-1-one (2b).[17] Solid,
benzene–hexane; m.p. 143ꢀC; Yield 95%, IR (KBr): 647, 704, 819,
1021, 1051, 1223, 1334, 1508, 1580, 1667, 3339 cmÀ1
.
1H NMR
(CDCl3): ꢀ 2.27 (s, 3H, CH3), 4.22 (s, 2H, CH2), 5.44 (bs, 1H, OH),
6.77–6.79 (d, 1H, J ¼ 2 Hz, phenyl-H), 7.26–7.31 (m, 5H, phenyl-H),
7.77–7.84 (m, 2H, phenyl-H); Anal. calcd. for C15H14O2 (226): C,
79.64; H, 6.19. Found: C, 79.78; H, 6.28.
2-Phenyl-1-(4-hydroxy-2-methylphenyl)-ethan-1-one
(2c).[17]
Oil,
extracted with CH2Cl2; yield 97%. IR (Neat): 669, 756, 869, 935, 1031,
1219, 1346, 1493, 1596, 1637, 1670, 2926, 3377 cmÀ1. 1H NMR (CDCl3): ꢀ
2.21 (s, 3H, CH3), 4.08 (s, 2H, CH2), 6.51–6.89 (m, 2H, phenyl-H),
7.06–7.25 (m, 6H, phenyl-H and phenolic-OH), 7.27–7.63 (m, 1H,
phenyl-H); Anal. calcd. for C15H14O2 (226): C, 79.64; H, 6.19. Found:
C, 79.80; H, 6.28.
2-Phenyl-1-(4-hydroxy-3-chlorophenyl)-ethan-1-one (2d).[25] Solid,
benzene–hexane, m.p. 164ꢀC; yield 90%. IR (KBr): 565, 649, 704, 818,
1053, 1225, 1349, 1593, 1666, 2368, 3341 cmÀ1; 1H NMR (CDCl3): ꢀ 4.21
(s, 2H, CH2), 6.00 (s, 1H, phenolic-OH), 7.05 (d, 1H, J ¼ 7.02 Hz, phenyl-
H), 7.23–7.36 (m, 5H, phenyl-H), 7.86 (dd, 1H, J ¼ 7.02 Hz, phenyl-H),
8.02 (dd, 1H, J ¼ 1Hz, phenyl-H); Anal. calcd. for C14H11ClO2 (246.5):
C, 68.15; H, 4.46. Found: C, 68.24; H, 4.55.
2-Phenyl-1-(4-hydroxy-2-chlorophenyl)-ethan-1-one
(2e).[25]
Oil,
extracted with CH2Cl2; Yield 97%. IR (Neat): 582, 694, 756, 838, 1036,
1217, 1304, 1599, 1664, 2924, 3022, 3402 cmÀ1. 1H NMR (CDCl3): ꢀ 3.60
(s, 2H, CH2), 5.27 (bs, 1H, phenolic OH), 6.44–6.95 (m, 2H, phenyl-H),
7.01–7.27 (m, 1H, phenyl-H), 7.29–7.51 (m, 5H, phenyl-H); Anal. calcd.
for C14H11ClO2 (246.5): C, 68.15; H, 4.46. Found: C, 68.32; H, 4.50.
2-Phenyl-1-(4-hydroxy-3-methoxyphenyl)-ethan-1-one (2f ). Solid,
EtOAc–hexane; m.p. 109ꢀC (Lit,[24] m.p. 108ꢀC); Yield 90%. IR
(Neat): 559, 757, 804, 1024, 1218, 1435, 1508, 1602, 1672, 2364, 2963,
1
3024, 3406 cmÀ1. H NMR (CDCl3): ꢀ 3.88 (s, 3H, OCH3), 4.18 (s, 2H,

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2526
Chhor et al.
CH2), 6.83–6.93 (m, 2H, phenyl-H), 7.23–7.95 (m, 9H, phenyl-H, OH):
Anal. calcd. for C15H14O3 (242): C, 74.38; H, 5.78. Found: C, 74.48; H,
5.82.
2-Phenyl-1-(4-hydroxy-3-nitrophenyl)-ethan-1-one (2g).[26] Solid,
EtOAc–hexane; m.p. 200ꢀC (d); Yield 97%. IR (KBr): 564, 719, 837,
1
1020, 1112, 1278, 1348, 1384, 1592, 1670, 2817, 3386 cmÀ1. H NMR
(CDCl3): ꢀ 3.82 (s, 2H, CH2), 7.11–7.32 (m, 6H, phenyl-H), 7.67–7.71
(m, 1H, phenyl-H), 8.04–8.14 (m, 1H, phenyl-H), 10.47 (bs, 1H, phenolic
OH); Anal. calcd. for C14H11NO4 (257): C, 65.36; H, 4.28. Found: C,
65.48; H, 4.36.
2-Phenyl-1-(4-hydroxy-2,5-dimethylphenyl)-ethan-1-one) (2h). Oil,
extracted with CH2Cl2: yield 95%. IR (KBr): 562, 756, 1122, 1451,
1
1585, 1667, 2929, 3024, 3403 cmÀ1. H NMR (CDCl3): ꢀ 2.25 and 2.27
(2s, 6H, 2 ꢁ CH3), 4.18 (s, 2H, CH2), 6.78–7.38 (m, 7H, phenyl-H), 8.45
(bs, 1H, phenolic OH); Anal. calcd. for C16H16O2 (240): C, 80.00; H,
6.66. Found: C, 80.18; H, 6.72.
2-Phenyl-1-(4-hydroxy-2,6-dimethylphenyl)-ethan-1-one (2i). Oil,
extracted with CH2Cl2; Yield 92%: IR (KBr): 606, 758, 840, 1027,
1
1143, 1219, 1452, 1620, 1670, 1718, 2925, 3022, 3415 cmÀ1. H NMR
(CDCl3): ꢀ 2.24 (s, 3H, CH3), 2.27 (s, 3H, CH3), 6.43–7.63 (m, 7H,
phenyl-H), 11.88 (bs, 1H, phenolic OH); Anal. calcd. for C16H16O2
(240): C, 80.00; H, 6.66. Found: C, 80.14; H, 6.78.
2-Phenyl-1-(4-hydroxy-1-naphthyl)-ethan-1-one (2j). Solid, EtOAc–
hexane, m.p. 125ꢀC (d); yield 88%. IR (KBr): 591, 762, 953, 1100,
1158, 1351, 1469, 1591, 1666, 2373, 3424 cmÀ1 1H NMR (CDCl3); ꢀ
.
4.35 (s, 2H, CH2), 6.04 (bs, 1H, OH), 6.77–6.80 (d, 1H, J ¼ 2 Hz),
7.26–7.36 (m, 5H, phenyl-H), 7.50–7.63 (m, 2H, phenyl-H), 7.98–8.01
(d, 1H, J ¼ 2 Hz), 8.22–8.25 (d, 1H, J ¼ 2 Hz), 8.89–8.92 (d, 1H,
J ¼ 2 Hz); Anal. calcd. for C18H14O2 (262): C, 82.44; H, 5.34. Found:
C, 82.58; H, 5.40.
2-Phenyl-1-(6-hydroxy-1-naphthyl)-ethan-1-one (2k). Solid, EtOAc–
hexane, m.p. 104ꢀC; Yield 99%. IR (KBr): 472, 682, 740, 955, 1168,
.
1214, 1388, 1454, 1509, 1595, 1667, 3351 cmÀ1 1H NMR (CDCl3): ꢀ
4.29 (s, 2H, CH2), 4.87 (s, 1H, phenolic-OH), 6.97–7.80 (m, 11H, aro-
matic-H); Anal. calcd. for C18H14O2 (262): C, 82.44; H, 5.34. Found: C,
82.50; H, 5.44.
E-4-Hydroxystilbenes 3(a–i) General Procedure
To a stirred solution of 2-phenyl-(4-hydroxyphenyl)-ethan-1-one 2a
(1.1 g, 0.05 mol) in 150 mL. Ethanol, NaBH4 (250 mg) was added and

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trans-4-Hydroxystilbenes
2527
stirring continued for 12 h. Few crystals of bromocresol blue were added
as pH indicator and the mixture was allowed to reflux for 1 h. Few drops
of conc. HCl were then added to the solution till colour changes to yellow.
After refluxing for 5 h, the solution was diluted with water (150 mL),
concentrated in vacuo to give 3a as colorless solid, m.p. 188ꢀC (Lit.[27]
;
186ꢀC). IR (KBr): 819, 961, 1258, 1513, 1540, 1593, 1607, 3018, 3416
1
cmÀ1. H NMR (Acetone-d6): ꢀ 3.02 (bs, 1H, phenolic-OH), 6.82–6.91
(m, 2H, phenyl-H), 7.17–7.26 (m, 1H, phenyl-H), 7.29–7.39 (m, 2H,
phenyl-H), 7.42–7.50 (m, 2H, phenyl-H), 7.51–7.59 (m, 2H, phenyl-H).
13C NMR (Acetone-d6): ꢀ 116.37 (þ, 2C, phenyl-C), 126.44 (þ, phenyl-C),
126.95 (þ, 2C, phenyl-C), 127.80 (þ, olefinic-C), 128.73 (þ, 2C, phenyl-
C), 129.33 (þ, olefinic-C), 129.43 (þ, 2C phenyl-C), 129.94 (q, phenyl-C),
138.83 (q, phenyl-C), 158.16 (quart, C-OH); MS (m/z, %): 196.1 (100,
Mþ), 181.1 (20.4), 177.1 (30.7), 165.1 (29.5), 152.1 (19.7).
E-3-Methyl-4-hydroxystilbene (3b). Grey colored solid, EtOAc–
hexane, m.p. 42–44ꢀC; yield 90%. IR (KBr): 760, 1024, 1216, 1261,
1
1381, 1460, 1600, 2856, 2925, 3404 cmÀ1. H NMR (CDCl3): ꢀ 2.26 (s,
3H, CH3), 7.13 (d, J ¼ 16.2 Hz, 1H, olefinic-H), 7.25 (d, J ¼ 16.2 Hz, 1H,
olefinic-H), 5.25 (bs, 1H, phenolic OH), 6.58–7.45 (m, 8H, phenyl-H);
Anal. calcd. for C15H14O (210): C, 85.71; H, 6.66. Found: C, 85.82;
H, 6.72.
E-2-Methyl-4-hydroxystilbene (3c). Green colored oil, extracted with
CH2Cl2, yield 86%. IR (Neat): 757, 860, 1021, 1159, 1218, 1380, 1456,
1
1591, 1601, 2925, 3020, 3365 cmÀ1. H NMR (CDCl3): ꢀ 2.21 (s, 3H,
CH3), 4.84 (bs, 1H, phenolic OH), 7.03 (d, J ¼ 16.2 Hz, 1H, olefinic-H),
7.16 (d, J ¼ 16.2 Hz, 1H, olefinic-H), 6.47–7.42 (m, 8H, phenyl-H); Anal.
calcd. for C15H14O (210): C, 85.71; H, 6.66. Found: C, 85.84; H, 6.78.
E-3-Chloro-4-hydroxystilbene (3d). Colorless solid, benzene–hexane,
m.p. 163ꢀC; yield 86%. IR (KBr): 565, 700, 805, 878, 1022, 1097, 1225,
1354, 1508, 1595, 2961, 3338 cmÀ1
.
1H NMR (CDCl3 þ DMSO-d6): ꢀ
6.99–7.04 (m, 1H, phenyl-H), 7.04–7.34 (m, 5H, phenyl-H), 7.23 (d,
J ¼ 16.2 Hz, 1H, olefinic-H), 7.34 (d, J ¼ 16.2 Hz, 1H, olefinic-H),
7.75–7.80 (m, 1H, phenyl-H), 8.01 (s, 1H, phenyl-H), 9.87 (bs, 1H, phe-
nolic-OH); Anal. calcd. for C14H11ClO (230.5); C, 72.88; H, 4.77. Found:
C, 72.98; H, 4.72.
E-2-Chloro-4-hydroxystilbene (3e). Yellow liquid; extracted with
CH2Cl2; Yield 96%. IR (Neat): 509, 591, 759, 888, 1039, 1087, 1217,
1253, 1417, 1488, 1595, 2364, 2928, 3021, 3365 cmÀ1
.
1H NMR
(CDCl3): ꢀ 5.95 (bs, 1H, phenolic OH), 6.67–7.52 (m, 8H, phenyl-H),
7.11 (d, J ¼ 16.2 Hz, 1H, olefinic-H), 7.24 (d, J ¼ 16.2 Hz, 1H, olefinic-H);
Anal. calcd. for C14H11ClO (230.5) : C, 72.88; H, 4.77; Found, C, 73.02;
H, 4.85.

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2528
Chhor et al.
E-3-Methoxy-4-hydroxystilbene (3f ). Brown Colored solid, EtOAc–
hexane, m.p. 138ꢀC; yield 88%. IR (KBr): 585, 666, 699, 757, 920, 1001,
1089, 1209, 1280, 1359, 1595, 2370, 2790, 3401 cmÀ1. 1H NMR (CDCl3): ꢀ
3.89 (s, 3H, OCH3), 6.65–7.72 (m, 8H, Phenyl-H), 7.17 (d, J ¼ 16.2 Hz,
2H, olefinic-H), 7.30 (d, J ¼ 16.2 Hz, 1H, olefinic-H), 7.60 (s, 1H, pheno-
lic-OH); Anal. calcd. for C15H14O2 (226): C, 79.64; H, 6.19. Found: C,
79.80; H, 6.28.
E-3-Nitro-4-hydroxystilbene (3g). Dark green Colored solid, CH2Cl2–
hexane, m.p. 80ꢀC(d); Yield 78%. IR (KBr): 670, 759, 1020, 1095, 1216,
1
1261, 1380, 1541, 1588, 2402, 2927, 3020, 3401 cmÀ1. H NMR (CDCl3):
ꢀ 5.11 (bs, 1H, phenolic OH), 7.13 (d, J ¼ 16.2 Hz, 1H, olefinic-H),
7.27 (d, J ¼ 16.2 Hz, 1H, olefinic-H), 7.17–8.07 (m, 8H, phenyl-H);
Anal. calcd. for C14H11NO3 (241): C, 69.70; H, 4.56. Found: C, 69.82;
H, 4.66.
E-2,5-Dimethyl-4-hydroxystilbene (3h). Colorless solid, benzene—
hexane, m.p. 107ꢀC; yield 91%. IR (KBr): 507, 669, 758, 1033, 1112,
1
1218, 1271, 1322, 1455, 1582, 2365, 2927, 3021, 3387 cmÀ1. H NMR
(CDCl3): ꢀ 2.23 (s, 3H, CH3), 2.27 (s, 3H, CH3), 5.28 (bs, 1H, phenolic
OH), 6.58–7.63 (m, 7H, Phenyl-H), 7.02 (d, J ¼ 16.2 Hz, 1H, olefinic-H),
7.14 (d, J ¼ 16.2 Hz, 1H, olefinic-H); Anal. calcd. for C16H16O (226): C,
85.71; H, 7.14. Found: C, 85.88; H, 7.23.
E-2,6-Dimethyl-4-hydroxystilbene (3i). Yellow oil, extracted with
CH2Cl2; Yield 99%. IR (Neat): 517, 908, 1123, 1216, 1410, 14377,
1595, 2363, 3023, 3404 cmÀ1
.
1H NMR (CDCl3): ꢀ 2.21 (s, 6H,
2XCH3), 4.25 (bs, 1H, Phenolic-OH), 6.84–8.20 (m, 7H, phenyl-H),
7.09 (d, J ¼ 16.2 Hz, 1H, olefinic-H), 7.22 (d, J ¼ 16.2 Hz, 1H, olefinic-
H); Anal. calcd. for C16H16O (224): C, 85.71; H, 7.14. Found: C, 85.84;
H, 7.25.
4-[(E )-2-Phenylvinyl]-1-naphthol (3j). Black Colored solid, EtOAc—
hexane; m.p. >220ꢀC; yield 93%. IR (Neat): 761, 1033, 1216, 1595, 2926,
3022, 3405 cmÀ1 1H NMR (CDCl3): ꢀ 6.53–6.62 (m, 2H, Phenyl-H),
.
6.76–6.94 (d, 1H, phenyl-H), 6.98 (d, J ¼ 16.2 Hz, 1H, olefinic-H), 7.12
(d, J ¼ 16.2 Hz, 1H, olefinic-H), 7.25–8.31 (m, 8H, phenyl-H), 8.46 (bs,
1H, phenolic-H); Anal. calcd. for C18H14O (246): C, 87.80; H, 5.69.
Found: C, 87.92; H, 5.78.
5-[(E )-2-Phenylvinyl]-1-naphthol (3k). Colorless solid, CH2Cl2—
hexane, m.p. 120ꢀC; yield 80%. IR (Neat): 471, 668, 764, 813, 845,
.
1065, 1219, 1398, 1595, 1626, 2918, 3397 cmÀ1 1H NMR (CDCl3): ꢀ
4.96 (bs, 1H, OH), 6.63–7.14 (m, 3H, Phenyl-H), 7.25 (d, J ¼ 16.2 Hz,
1H, olefinic-H), 7.39 (d, J ¼ 16.2 Hz, 1H, olefinic-H), 7.31–7.46 (m, 4H,
phenyl-H), 7.66–7.77 (m, 4H, phenyl-H); Anal. calcd. for C18H14O (246):
C, 87.80; H, 5.69. Found: C, 87.96; H, 5.74.

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trans-4-Hydroxystilbenes
CRYSTALLOGRAPHIC DATA
2529
Crystallographic data for 2a (translucent, colorless, and prisms,
0.64 ꢁ 0.36 ꢁ 0.24 mm); C14H12O2, M ¼ 212.24, Orthorhombic, a ¼
6.4316 (8) A, b ¼ 8.3094 (11) A, c ¼ 20.813 (2) A, ꢁ ¼ 90ꢀ, ꢂ ¼ 90ꢀ,
g ¼ 90ꢀ, T ¼ 292 (2) K, U ¼ 1112.3 (2) A3, Z ¼ 4, ꢃ (Mo–Ka) ¼
0.674 mmÀ1, 7439 reflections collected, 1895 independent reflections
(Rint ¼ 0.0321), 1854 with 1 ꢂ 2ꢄ (1), R ¼ 0.0313, 0.0318 (all data), WR
(F2) ¼ 0.0851, 0.0858 (all data).
ACKNOWLEDGMENTS
We thank the University Grants commission, New Delhi, India for
financial support of this work. We also gratefully acknowledge RSIC
facilities of CDRI, Lucknow, India and X-ray Crystallographic unit of
the Chemistry Department, University of Regensburg, Germany.
REFERENCES
1. Ivanova, I.G.; Kuckling, D.; Adler, H.J.P.; Wolf, T.; Arndt, K.F.
Des. Monomers Polym. 2000, 3, 447.
2. Miyata, Q.T.C.; Kataoka, K.; Endoh, K. Kobunshi Ronbanshu
1999, 56, 753.
3. Igarashi, S.; Kimura, T.; Naito, R.; Hara, H.; Fujii, M.; Koutoku,
H.; Oritani, H.; Mase, T. Chem. Pharm. Bull. 1999, 47, 1073.
4. Ali, M.A.; Kondo, K.; Tsuda, Y. Chem. Pharm. Bull. 1992, 40, 1130.
5. Chandra Kumar, N.S.; Chen, B.B.; Clare, M.; Desai, B.N.; Djuric,
S.W.; Docter, S.H.; Gasiecki, A.F.; Frank, A.; Haack, R.A.; Chi.
Dean, L. PCT Int. Appl. 1996, 362pp, CODEN: PIXXD2WO
9610999 A2 19960418.
6. Inoue, H.; Asaumi, E.; Hinohara, T.; Sekiguchi, S.; Matsui, K.
Kogyo kagakuZasshi 1970, 73, 187.
7. Guildfored, A.J.; Turner, R.W. Tetrahedron Lett. 1981, 22, 4835.
8. Sugihara, K.; Kitamura, S.; Sanoh, S.; Otha, S.; Fujmoto, N.;
Maruyama, S.; Ito, A. Toxicol. Appl. Pharmacol. 2000, 167, 46.
9. Metzger, B.S.; Spangler, L.H. J. Phys. Chem. A. 1977, 161, 5431.
10. Wyrzykiewicz, E.; Elzbieta, A.; Kedzia, B. Farmaco 2000, 55, 151.
11. Nees, D.; Wolff, T. Colloid. Polym. Sci. 1996, 274, 904.
12. Schultz, T.P.; Fisher, T.H.; Nicholas, D.D. Res. Appl. Chem. Sci.
For; Proc. South. Stn. Chem. Sci. Melt. 4th 1994, 50–60.

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2530
Chhor et al.
13. Malik, S.; Dhal, P.K.; Mashelkar, R.A. Macromolecules 1995, 28,
2159.
14. (a) Wu, P.; Liu, W.; Balasubramanian, S.; Kumar, J.; Samuelson,
L.; Tripathy, S.K. Abstr. Pap. Am. Chem. Soc. 2000, 220th Poy-
269; (b) Dongsoo, K.; Yoongo, L. Han’guk Nonghwa Hakhoechi
1998, 41, 483; (c) Tao, W.; Zhou, X.; Fent, Y.; Zahi, J. Huaixue Shiji
1993, 15, 193; (d) Ganeshpure, P.A.; Satish, S. Tetrahedron Lett.
1988, 29, 6629; (e) Kikumoto, R.; Tobe, A.; Fukami, H.; Ninomiya,
K.; Etawa, M.; J. Med. Chem. 1984, 27, 645; (f ) Bachelor, F.W.;
Loman, A.A.; Snowdon, L.R. Can. J. Chem. 1970, 48, 1554; (g)
Chandra, V.; Srivastava, V.B. J. Ind. Chem. Soc. 1966, 43, 796;
(h) Hargreaves, K.R.; McGookin, A. J. Soc. Chem. Ind. (London)
1950, 69, 186; (1) Massarani, A. Farmaco Ed. Sci. 1957, 12, 380.
15. (a) Saeed, A.; Sharma, A.P.; Durani, N.; Jain, R.; Durani, S.; Kapil,
R.S. J. Med. Chem. 1990, 83, 3210; (b) Coe, P.L.; Seriven, C.E.
J. Chem., Soc. Perkin Trans I 1986, 475–477.
16. Thoi, L.V.; Hoang, N.V. Israel, J. Chem. 1963, 1, 418.
17. Yamamoto, J.; Kisida, M.; Takenaka, Y.; Okamoto, Y. Nippon
KagakuKaishi 1988, 288; Chem. Abs. 1988, 110, 134837.
18. Johnson, M.K. Biochem. Pharmacol. 1975, 24, 797.
19. Herzog, H. Swiss Patent, 1947, 244470; Chem. Abstr. 1947, 43,
P8055b.
20. Barton, H.; Brucice, T.C. J. Am. Chem. Soc. 1969, 91, 2982.
21. Jackman, L.M.; Petrei, M.M.; Smith, B.D. J. Am. Chem. Soc. 1991,
113, 3451.
22. Buzas, A.; Egnell, C.; Freon, P. Compt. Rend. 1963, 256, 1804.
23. Ohasi; T. Ann. Rept. Fac. Pharm. Kanazawa Univ. 1954, 4, 15;
Chem. Abstr. 1954, 50, 11298g.
24. Devi, N.; Jain, N.; Krishnamurty, H.G. Indian J. Chem. 1993,
32B, 874.
25. Pawlek, F.; Kheiri, M.J.; Kammel, R. Metall. 1992, 46, 577. Chem.
Abstr. 1992, 117, 175423b.
26. Hanabusa, K.; Shirai, H.; Hojo, N.; Kondo, K.; Takomoto, K.
Makromol. Chem. 1982, 183, 1101.
27. Gusten, H.; Salzwedel, M. Tetrahedron 1967, 23, 173.
Received in the Netherlands October 30, 2002