Indian Journal of Chemistry

Vol. 44B, September 2005, pp. 1947-1949

Note

A simple conversion of E-3-benzylideneflavanones to 3-benzoylflavones by chromic

acid oxidation

Asok K Mallik & Falguni Chattopadhyay

O

Department of Chemistry, Jadavpur University,

Kolkata 700 032, India

1
a: R = H, b: R = Cl, c: R = OMe

E-mail: mallikak52@yahoo.co.in
Received 2 September 2003; accepted (revised) 4 May 2005
Oxidation of E-3-benzylideneflavanones with CrO3/AcOH
yields 3-benzoylflavones in moderate yield.
Keywords: Benzylideneflavanones,
acid, oxidation

benzoylflavones, chromic

IPC: Int.Cl.7 C 07 D 311/30

In connection with some other problems1 we required

several trans-3-benzylflavanones 1. For preparation
of 1, we chose chromic acid oxidation of 3(S*)benzyl-4(S*)-hydroxy-2(S*)flavans 2 obtainable by
sodium borohydride reduction2 of E-3-benzylideneflavanones 3. Thus, when three 3(S*)-benzyl-4(S*)hydroxy-2-(S*)flavans 2a-c were oxidised in this way,
the first two compounds gave the desired products
while the last one gave trans-3-(p-methoxybenzoyl)flavanone 4 (Scheme I).This observation led us to
suggest that under the reaction condition the initial

CrO3

1a, 1b

H
H

product 1c is readily converted to the radical 5

(having a scope of enjoying extra stability by
resonance) which is then transformed to 4 (ref. 3).
It was envisaged that E-3-benzylideneflavanones 3
on treatment with chromic acid might generate the
radical 6 which would have the scope of enjoying
extra stability like 5 and of transforming to 3-benzoylflavones 7. So, chromic acid oxidation of 3 might be
one method for direct conversion of 3 to 7.
Thus, when the E-3-benzylideneflavanone 3a was
treated with CrO3-HOAc at room temperature, the
reaction was found to be slow and about four days
were required for disappearance of the starting
material. But on refluxing, the reaction was complete
within 6 hr and under both the reaction conditions
only one product was obtained. Analytical and
spectroscopic data confirmed it to be 3-benzoylflavone 7a (Scheme II). The study was then extended
to five other E-3-benzylideneflavanones and the
results are presented in Table I.

R CrO
3

1c

OMe

OH
O

NaBH4

H
H

a: R = H, b: R = Cl, c: R = OMe
Scheme I

OMe

INDIAN J. CHEM., SEC B, SEPTEMBER 2005

1948

R3
R2

R3
R4 CrO , AcOH R2
3

R1

rt / Heat
O

R4

R1

R2

R4

R1
O

R3

a: R1 = R2 = R3 = R4 = H
b: R1 = R2 = R3 = H, R4 = OMe
1
3
4
2
c: R = R = R = H, R = OMe
d: R1 = Cl, R2 = R3 = R4 = H
1
2
3
4
e: R = Me, R = H, R = R = Cl f: R1 = R3 = R4 = Cl, R2 = H
Scheme II
Table I Results of CrO3 oxidation of E-3benzylideneflavanones
Substrate

Product

3a
3b
3c
3d
3e
3f

7a
7b
7c
7d
7e
7f

Yield (%)
At Room Temp.
Under Reflux
(4 days)
(6 hr)
40
38
37
43
35
46

44
42
32
41
38
48

An interesting feature observed in the 1H NMR

spectra of 3-benzoylflavones 7 is that the orthoprotons of their B-ring (H-2',6') are seen to appear at
somewhat higher field as compared to the same
protons of corresponding 3-unsubstituted flavones (
7.80-7.90).
So, this would be a very simple method for direct
conversion of E-3-benzylideneflavanones 3 to 3benzoylflavones 7 and is a good addition to the
methods reported earlier4-6.
Experimental Section
All melting points are uncorrected. IR spectra were
recorded in KBr disc on a Perkin-Elmer 297
spectrophotometer; 1H NMR spectra in CDCl3 on a
Bruker AM-300L (300 MHz) spectrometer.
General procedure for the reaction of CrO3 with
E-3-benzylideneflavanones 3: To a solution of E-3benzylideneflavanone 3 (1 mmole) in glacial acetic
acid (10 mL), a solution of CrO3 (5 mmole) in the
same solvent (5 mL) was added and the resulting
mixture was either kept at room temperature for 4
days or at reflux for 6 hr. It was then poured into
water (100 mL) and aqueous solution of sodium
metabisulphite was added to reduce Cr(VI). The
resulting material was then extracted with chloroform
(3 25 mL), washed with water, dried and con-

centrated. Column chromatography of the material so

obtained furnished the pure products 7.
Analytical and spectral data of the products are as
follows:
7a: m. p. 114-15, IR: 1672 (C=O), 1632
(C=O) cm-1; 1H NMR : 7.33-7.56 (7H, m, Ar-H),
7.60 (1H, br. d, J = 8.4 Hz, H-8), 7.63-7.67 (2H, m,
H-2',6'), 7.77 (1H, ddd, J = 8.4, 7.8 and 1.5 Hz, H-7),
7.91-7.94 (2H, m, H-2",6"), 8.25 (1H, dd, J = 8.1 and
1.5 Hz, H-5); Found: C, 80.78; H, 4.18. C22H14O3
requires C, 80.97; H, 4.32%.
7b: m. p. 168-69, IR: 1655 (C=O), 1615 (C=O)
cm-1; 1H NMR : 3.82 (3H, s, OCH3), 6.87 (2H,
pattern resembles a pair of triplets7, J = 7.2, 2.7 or 2.1
Hz, H-3",5"), 7.33-7.49 (4H, m, Ar-H), 7.59 (1H, br.
d, J = 8.6 Hz, H-8), 7.66-7.69 (2H, m, H-2',6'), 7.76
(1H, ddd, J = 8.1, 7.8 and 1.5 Hz, H-7), 7.89 (2H,
pattern resembles a pair of triplets7, J = 6.9 and 2.1 or
2.7 Hz, H-2",6"), 8.25 (1H, dd, J = 7.8 and 1.5 Hz, H5); EIMS m/z (rel. intensity): 356 (100, M+), 328
(84.6, M+ CO), 314 (10.0), 279 (11.1), 249 (22.3),
208 (8.1), 165 (11.5), 135 (70.7, MeOC6H4CO+),
129(68.2), 107 (13.0), 92 (41.1), 77 (37.4); Found: C,
77.31; H, 4.49. C23H16O4 requires C, 77.52; H, 4.53%.
7c: m. p. 161-62, IR: 1665 (C=O), 1620 (C=O)
cm-1; 1H NMR : 3.95 (3H, s, OCH3) 6.98 (1H, d, J =
2.4 Hz, H-8), 7.03 (1H, dd, J = 8.8 and 2.4 Hz, H-6),
7.35-7.43 (5H,m, Ar-H), 7.52 (1H, t, J = 8.1 Hz, H4"), 7.62-7.65 (2H, m, H-2',6'), 7.90-7.93 (2H, m, H2",6"),8.15 (1H, d, J = 9.0 Hz, H-5); Found: C, 77.39;
H, 4.66. C23H16O4 requires C, 77.52; H, 4.53%.
7d: m. p. 171-72, IR: 1665 (C=O), 1615 (C=O)
cm-1; 1H NMR : 7.32-7.58 (8H, m, Ar-H), 7.63-7.65
(2H, m, H-2',6'), 7.90-7.92 (2H, m, H-2",6"), 8.03
(1H, dd, J = 1.5 and 0.9 Hz, H-5); Found: C, 73.01;
H, 3.77. C22H13O3Cl requires C, 73.23; H, 3.63%.
7e: m. p. 169-70, IR: 1670 (C=O), 1630 (C=O)
cm-1; 1H NMR: 2.49 (3H, s, CH3), 7.34 (2H, pattern
resembles a pair of triplets7, J = 8.7, 2.4 or 1.8 Hz,

NOTES

H-3',5'), 7.39 (2H, pattern resembles a pair of triplets7,

J = 8.4 and 1.5 or 2.4 Hz, H-3",5"), 7.48 (1H, d,
J = 8.4 Hz, H-8), 7.57 (2H, pattern resembles a pair of
triplets7, J = 8.7 and 1.5 or 2.4 Hz, H-2',6'), 7.58 (1H,
dd, J = 8.1 and 2.1 Hz, H-7), 7.85 (2H, pattern
resembles a pair of triplets7, J = 8.7 and 2.4 or 1.5 Hz,
H-2",6"), 8.00 (1H, br. s, H-5); Found: C, 67.55; H,
3.64. C23H14O3Cl2 requires C, 67.49; H, 3.45%.
7f: m.p. 166-67, IR: 1665 (C=O), 1620 (C=O)
cm-1; 1H NMR: 7.32-7.71 (8H, m, Ar-H), 7.90 (2H,
d, J = 7.8 Hz, H-2",6"), 8.19 (1H, d, J = 2.7 Hz, H-5);
Found: C, 61.15; H, 2.54. C22H11O3Cl3 requires C,
61.49; H, 2.58%.
Acknowledgements
The authors are thankful to the authorities of IICB,
Kolkata and RSIC, CDRI, Lucknow for 1H NMR and

1949

mass spectral measurements and to the UGC, New

Delhi for financial assistance.
References
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results).
(b) Chattopadhyay F, Synthesis and Reactions of Some
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University, 2000.
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6 Chawla H M & Sharma S K, Synth Commun, 20, 1990, 301.
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