Introduction

1,3-Dipheylpropan-1,3-diones commonly known as dibenzoylmethanes occupy an

important place in synthetic organic chemistry. These have been used as the
intermediates1 for the synthesis of various heterocyclic compounds such as isoxazoles,
pyrimidines, benzodiazepines etc.

Synthesis of isoxazoles
Simoni et al.2 reported the synthesis of isoxazoles starting from methyl ketones which on
reaction with diethyl oxalate in presence of sodium ethoxide at room temperature gave
ethoxyoxalyl derivatives which were further reacted regiospecifically with an excess of
hydroxylamine hydrochloride in ethanol solution to afford isoxazoles in good yields
(scheme 1).

Scheme 1.

27

Synthesis of pyrimidines
Kuzueva et al.3 reported the synthesis of (2-hydroxy/2-mercapto)-4-trifluoromethyl-6(fluoroalkyl)pyrimidines

by

dehydration

of

4,5-bis(hydroxy)-4-trifluoromethyl-6-

(fluoroalkyl)hexahydropyrimidn-2-ones obtained by reacting ureas (thioureas) with

di(fluoroalkyl) substituted 1,3-diketones (scheme 2).

Scheme 2.
Synthesis of benzodiazepines
Kumar and Joshi4 reported the synthesis of benzodiazepines which are very important
heterocyclic compounds as they have attracted attention in the field of drugs and
pharmaceuticals. Chlorination of 5-(2-ethoxyphenyl)-1-methyl-3-propyl-1,6-dihydro-7Hpyrazolo[4,3-d]pyridin-7-one

(a)

with

phosphorus

oxychloride

afforded

5-(2-

ethoxyphenyl)-1-methyl-7-chloro-1H-pyrazolo[4,3-d]pyridine (b) which was further

condensed with -diketones to obtain -diketones (c). These newly synthesized diketones were condensed with o-phenylenediamine in presence of p-toluene sulphonic
acid to give biologically active 3H-1,5-benzodiazepines (scheme 3).

28

Scheme 3.
-Diketones have been found to exhibit various pharmacological activities which are
briefly described below.
Diana et al.5 reported -diketones (2) to exhibit antiviral activity.

(2)
Acton et al.6 synthesized retinylidene 1,3-diketones (3) and found these compounds to
show good antitumor activity.

29

(3)
Crouse et al.7 synthesized polyfluoro 1,3-diketones (4) and found these compounds to act
as systematic insecticides.

(4)
Andrae et al.8 synthesized substituted dibenzoylmethanes (5) and found these compounds
to protect human lymphoid cells efficiently and hence act as sunscreen agent.

Singletary et al.9 studied the effect of diferuloylmethane (6; curcumin) and

dibenzoylmethane (7) on rat mammary DNA adducts and found these products as breast
cancer chemopreventive agents.

30

(6)

(7)
Bennet et al.10 synthesized -diketone acrylate bioesters of pseudomonic acid (8) and
found these compounds to exhibit antibacterial activity.

Singletary and MacDonald11 found dibenzoylmethane (7) to inhibit benzo[a]pyrene- and

1,6-dinitropyrene-DNA adduct formation in human mammary epithelial cells.
Nishiyama et al.12 synthesized 1,3-indanones (9) and concluded that these compounds
exhibit significant antioxidant activity.

(9)

31

Tchertanov and Mouscadet13 found ketoenols (10, 11) to inhibit HIV-1 integrase.

Importance of 2-hydroxydibenzoylmethanes/ 2-hydroxybenzoylcinnamoylmethanes

Joshi and Wadodkar14 identified 2,2'-dimethoxydibenzoylmethane (12), the only
dibenzoylmethane of natural occurrence, and found it to be a neuroprotective agent
which prevented the production of reactive oxygen species (ROS).

(12)
These compounds have been used for the synthesis of flavones, a sub group of naturally
occurring flavonoids, and other related compounds viz. 3-bromoflavones and 3alkylflavones.
Synthesis of flavones
Flavones are mainly synthesized by cyclodehydration of 2-hydroxydibenzoylmethanes
(Scheme 4).

32

Various reagents have been used under different conditions which include hydroiodic
acid15, conc. sulphuric acid in cold16, hydrobromic acid in acetic acid17, potassium
carbonate in acetone18 under refluxing conditions, p-toulenesulphonic acid in benzene19,
iodine in dimethylsulphoxide20, heteropolyacids in toluene21, potassium hydrogen
sulphate22 and bis-(trichloromehtyl)carbonate23. Also cyclodehydration using mont. K1024 and cupric chloride25 under microwave conditions and using phosphorus pentoxide26
using grinding technique have also been reported.
Synthesis of 3-alkylflavones
3-Alkylflavones have been obtained from -methyl-2-hydroxydibenzoylmethanes which
in turn have been prepared by C-alkylation of 2-hydroxydibenzoylmethanes. C-alkylation
has been reported using dimethylsulphate in potassium carbonate and acetone27,
hexamethylphosphotriamide (HMPT)28 and methyl iodide in presence of fluoride ions29.
But yield in these methods is low due to the formation of ,-dimethyl product alongwith
o-methylation.
A

successful

method

for

selective

mono--methylation

of

2-

hydroxydibenzoylmethanes was reported by Makrandi and Kumari using phase transfer

catalysis30. Reaction of 2-hydroxydibenzoylmethanes with methyl iodide under these
conditions gave -methyl-2-hydroxydibenzoylmethanes which on heating with pyridine
hydrochloride gave 3-methylflavones, dealkylation and cyclodehydration taking place
simultaneously in the same step (Scheme 5).

Scheme 5.
33

Synthesis of 3-bromoflavones
Most common method used for the synthesis of 3-bromoflavones involves bromination of
2-hydroxydibenzoylmethanes to give -bromo-2-hydroxydibenzoylmethanes followed by
cyclization (Scheme 6).

Scheme 6.
Various reagents have been used for bromination which include bromine in sodium
acetate-acetic acid buffer31, bromine in dioxane32, ammonium bromide in hydrogen
peroxide using phase transfer catalysis33 and ammonium bromide with ammonium
persulphate using grinding technique34.
Synthesis of styrylchromones
2-Styrylchromones constitute an important class of naturally occurring flavonoids having
similar structure to that of flavones (2-phenylchromones). These compounds have been
prepared from 2-hydroxybenzoylcinnamoylmethanes following similar methods that are
used for the synthesis of flavones (scheme 7).

34

Scheme 7.
Various

reagents

have

been

used

for

the

cyclodehydration

of

2-

hydroxybenzoylcinnamoylmethanes which include sulphuric acid in acetic acid35, ptoluenesulphonic acid in dinethyl sulphoxide36, iodine in dimethyl sulphoxide under
refluxing37, p-toluenesulphonic acid under microwave irradiations38 and phosphorus
pentoxide26 under grinding conditions.
Synthesis of 2-hydroxydibenzoylmethanes
Various methods have been reported in the literature for the synthesis of 2hydroxydibenzoylmethanes but the base catalyzed Baker-Venkataraman rearrangement
of 2-aroyloxyacetopenones is the most convenient one. A brief description of these
methods is given below:
Kostanecki Method15. This method involves the condensation of various substituted 2alkoxyacetophenones and alkylbenzoates in presence of sodium or sodamide to give 2alkoxydibenzoylmethanes (scheme 8).

Scheme 8.

35

Allan-Robinson Method39. This method involves the heating of appropriately

substituted 2-hydroxyacetophenone with anhydride of aromatic acid in the presence of its
sodium salt at 180oC to give 2-hydroxydibenzoylmethane (scheme 9).

Teoule et al.40 modified Allan-Robinson method by heating phenol with ethyl-3-oxo-3(3,4,5-trimethoxyphenyl)proanoate to get dibenzoylmethanes (scheme 10).

Scheme 10.

36

via Baker Venkataraman rearrangement

Baker and Mahal & Venkataraman developed synthesis of 2-hydroxydibenzoylmethanes
almost simultaneously by base catalyzed rearrangement of 2-aroyloxyacetophenones.
Baker16 synthesized 2-hydroxydibenzoylmethane from 2-hydroxyacetophenone by
refluxing it with benzoyl chloride in presence of potassium carbonate in dry benzene
medium. Benzoylation of 2-hydroxyacetophenone followed by its rearrangement to 2hydroxydibenzoylmethane took place simultaneously in the same pot (scheme 11).

Scheme 11.
Mahal and Venkataraman41 prepared 2-acetyl-1-naphthobenzoate from 2-acetyl-1naphthol and rearranged it to 2-(-benzoylacetyl)-1-naphthol by reacting it with
sodamide in dry ether (scheme 12).

37

After

that

number

of

hydroxydibenzoylmethanes

modifications
by

have

been

Baker-Venkataraman

reported

for

obtaining

rearrangement

of

22-

aroyloxyactetophenone which are briefly described below.

Ullal and Wheeler17 used pulverised sodium in dry ether for rearrangement of 2aroyloxyacetophenones to 2-hydroxydibenzoylmethanes (scheme 13) and later Dunne et
al.42 reported the use of powdered potassium hydroxide in dry pyridine for this
rearrangement. The later conditions were found to be much superior for this reaction and
have been used as a general reaction by various workers (scheme 14).

Scheme 13.

Scheme 14.
Seshadri et al.18 synthesized various flavones from 2-hydroxyacetophenones by heating
them with aroyl chloride or acid anhydride43 in dry acetone in presence of anhydrous
potassium carbonate and resulting 2-hydroxydibenzoymethane intermediates further got
cyclised in the same pot to give flavones but the yields were very low and it took longer
times (48-72 hours) for the reaction (scheme 15).
38

Banerji and Goomer44 reported the synthesis of 2-hydroxydibenzoylmethanes by reaction

of substituted 2-hydroxyacetophenones with lithium diisopropyl amide in tetrahydrofuran
at -25oC and the dianion formed was reacted with aroyl chloride at -78oC. 2Hydroxydibenzoylmethanes were directly obtained in moderate yield on acidification
with conc. HCl (scheme 16).

Scheme 16.
Jain

et

al.19

used

phase

transfer

catalysis

for

the

formation

of

2-

hydroxydibenzoylmethanes. Substituted 2-hydroxyacetophenones were stirred with

substituted aroyl chlorides at 80oC in benzene-aqueous potassium carbonate biphase
medium in the presence of tetra-n-butylammonium hydrogensulphate to yield the
required compounds (scheme 17).

39

Scheme 17.
Hirao

et

al.45

reported

the

conversion

of

2-aroyloxyacetophenones

to

2-

hydroxydibenzoylmethanes by using sodium hydride in dimethylsulphoxide under inert

atmosphere at room temperature (scheme 18).

Bansal et al.46 reported the formation of 2-hydroxydibenzoylmethanes from 2benzoyloxyacetophenone in methanolic sodium hydroxide by irradiating the solution
with ultraviolet radiations in nitrogen atmosphere (scheme 19).

40

Makrandi et al.47 reported the synthesis of 2-hydroxydibezoylmethanes by reacting

appropriately substituted 2-hydroxyacetophenones with anhydride of aromatic acid in the
presence of barium hydroxide in dimethyl sulphoxide medium under thermal as well as
microwave conditions (scheme 20).

Scheme 20.
Krayushkin et al.48 reported the synthesis of 2-hydroxydibenzoylmethanes by reaction of
2-aroyloxyacetophenons with potassium t-butoxide in dimethylformamide at room
temperature (scheme 21).

Scheme 21.
Sharma et al.49 synthesized 2-hydroxydibenzoylmethanes by Baker-Venkataraman
rearrangement of 2-aroyloxyacetophenones in presence of potassium hydroxide using
grinding technique (scheme 22).

41

Some other methods for the synthesis of 2-hydroxydibenzoylmethanes have also been
reported by various workers, but these require tedious experimental conditions and some
of them are listed below.
Nagarathnam and Cushman50 reported the synthesis of 2-hydroxydibenzoylmethanes
from methyl salicylate by reacting it with tert-butyldimethylsilyl chloride. The o-silyl
protected ether obtained on reaction with 2-hydroxyacetophenone in presence of lithium
hexamethyldisilazide (LiHMDS) in THF provided dibenzoylmethane with 2-hydroxyl
protected.

Deprotection

with

tetra

n-butylammonium

fluoride

gave

2-

hydroxydibenzoylmethane (scheme 23).

Scheme 23.
2-Hydroxydibenzoylmethanes were synthesized by the reaction of polyanions generated
from 2-hydroxyacetophenones with O-silyloxylated benzoate in presence of lithium
hexamethyldisilazide (LiHMDS) in THF at -78oC51 (scheme 24).
42

Lee et al.52 synthesized 2-hydroxydibenzoylmethanes by condensation of various

substituted

2-hydroxyacetophenones

with

benzoylating

reagent,

N-methoxy-N-

methylbenzamide, in presence of two equivalent of lithium diisdopropylamide in THF for

24 hours (scheme 25).

Synthesis of 2-hydroxybenzoylcinnamoylmethanes
2-Hydroxybenzoylcinnamoylmthanes (13) are the compounds having the structural
similarity with 2-hydroxydibenzoylmethanes and are used as intermediates for the
synthesis of 2-styrylchromones.

Gaggad et al.35 reported the synthesis of 2-hydroxybenzoylcinnamoylmethanes by base

catalyzed Baker-Venkataraman rearrangement of cinnamoyl esters of substituted 2hydroxyacetophenones using potassium hydroxide in pyridine medium (scheme 26).

43

Scheme 26.
Makrandi and Kumari36 reported the synthesis of 2-hydroxybenzoylcinnamoylmethanes
under phase transfer catalyzed conditions. 2-Hydroxyacetophenones and cinnamic
anhydride were stirred in benzene-aqueous potassium carbonate biphase medium in
presence of tetra-n-butylammonium hydrogensulphate at 70-80oC to give 2hydroxybenzoylcinnamoylmethanes (scheme 27).

Scheme 27.
44

Pinto et al.53 reported the synthesis of 2-hydroxybenzoylcinnamoylmethanes by refluxing

cinnamoyl esters of substituted 2-hydroxyacetophenones with sodium hydride in dry
tetrahydrofuran (scheme 28).

Scheme 28.
Goel et al.38 reported the synthesis of 2-hydroxybenzoylcinnamoylmethanes by reacting
appropriately substituted 2-hydroxyacetophenones with cinnamic anhydride in presence
of barium hydroxide in dimethylsulphoxide medium under microwave irradiations
(scheme 29).

Scheme 29.
Gomes et al.54 reported the synthesis of 2-hydroxybenzoylcinnamoylmethanes by
reaction of substituted 2-cinnamoyloxyacetophenones with potassium hydroxide in dry
dimethylsulphoxide at room temperature (scheme 30).
45

Scheme 30.
Sharma et al.55 reported the synthesis of 2-hydroxybenzoylcinnamoylmethanes by
reaction of 2-cinnamoyloxyacetophenones with potassium hydroxide using grinding
trechnique (scheme 31).

Scheme 31.

46

Present work
2-Hydroxydibenzoylmethanes constitute an important class of compounds which have
been used as intermediates for the synthesis of flavones, 3-alkylflavones, the compounds
of natural occurrence, 3-bromoflavones and also for the synthesis of various heterocyclic
compounds such as isoxazoles, pyrimidines, benzodiazepines, styrylchromones etc.
These -diketones themselves have been found to possess a broad spectrum of
pharmacological activities and 2,2'-dimethoxydibenzoylmethane (4) was found to be a
neuroprotective agent and prevented the production of reactive oxygen species (ROS).
2-Hydroxydibenzoylmethanes are easily obtainable compounds by base catalyzed
Baker-Venkataraman rearrangement of 2-aroyloxyacetophenones. These esters are
normally prepared by the reaction of 2-hydroxyacetophenones with aroyl chlorides or
anhydrides in pyridine under anhydrous conditions. These esters have also been prepared
by direct condensation of 2-hydroxyacetophenones with corresponding acids in presence
of phosphorus oxychloride in pyridine medium35 or DCCI.
As now a days, emphasis is being laid to develop eco-friendly methods for the
synthesis of compounds avoiding the toxic and hazardous chemicals being used during
the reaction. The use of green solvents, i.e. water and ethanol as reaction medium is being
encouraged to achieve the greener procedures for the reaction. But the problem in using
water as reaction medium is that the reactions are quite slow due to non-homogeneity of
the reaction medium. But, the reaction in aqueous medium can be carried out effectively
either by carrying them using microwave radiations in which higher energy is directly
provided to the molecules or by using grinding technique in which collision frequency
increases because of molecules being in direct contact which has been described earlier
(Ch.1, p-4). Therefore, it was thought worth to study the reaction of 2hydroxyacetophenones with aroyl chloride or acid anhydride in aqueous medium using
grinding which could provide a simple eco-friendly procedure for the synthesis of 2aroyloxyacetophenones. But before this, ester formation of simple phenols was taken up
under grinding conditions in order to achieve the optimum conditions for ester formation
and potassium carbonate was chosen as a base due to its moderate basicity.

47

A mixture of phenol (5 mmol), benzoyl chloride (5 mmol) and potassium

carbonate (10 mmol) homogenized with 5 drops of water was ground in a mortar with a
pestle. The progress of the reaction was monitored by TLC when phenol was found to
have reacted completely only after 3 min. The reaction mixture was acidified with conc.
HCl after diluting it with ice cold water and the compound thus obtained was identified
as phenyl benzoate from its IR which showed absorption at 1726 cm-1 due to C=O
stretching and comparison of m.p. with literature56 value (68oC).
The above reaction was repeated omitting water from the reaction, but in this case
the reaction was found to have taken place in a sluggish manner showing tailing on the
TLC and no pure compound could be isolated. Thus, it was concluded that the presence
of water is necessary to homogenize the reaction mixture.

Scheme 32.
The above reaction was also carried out using benzoic anhydride in place of
benzoyl chloride under similar conditions and phenyl benzoate was obtained in 80% yield
(scheme 32). This appears to be a simple and efficient method for the preparation of
esters in aqueous medium at room temperature in very short interval of time.
Following above reaction conditions various other phenols were converted into
corresponding benzoates showing the reaction to be of general nature and these benzoates
are listed below:
(i)

phenyl benzoate

(14)

48

(ii)

p-cresyl benzoate

(15)
(iii)

-naphthyl benzoate

(16)
(iv)

-naphthyl benzoate

(17)
(v)

resorcinol dibenzoate

(18)
(vi)

hydroquinone dibenzoate

(19)

49

(vii)

phloroglucinol tribenzoate

(20)
Using above reaction conditions, 7-hydroxy-4-methylcoumarin55 (21), prepared by
grinding resorcinol with ethylacetoacetate in presence of p-toluenesulphonic acid, was
converted into 7-benzoyloxy-4-methylcoumarin (22) in 92% yield (scheme 33 ).

Scheme 33.
Due to simple nature of the reaction, benzoylation of anilines was next taken up.
A mixture of aniline (5 mmol), benzoyl chloride (5 mmol) and potassium carbonate (10
mmol) moist with few drops of water was ground in mortar with pestle and reaction
mixture on working up as described earlier gave benzanilide in 90% yield.

50

Scheme 34.
Following above procedure, other substituted anilines were also converted into
corresponding N-benzoyl derivatives which are listed below:
(i)

benzanilide

(23)
(ii)

p-toluanilide

(24)
(iii)

p-anisanilide

(25)
N-Tosyl derivatives of aniline are the important compounds that have been used
as the intermediates during the synthesis of various compounds. Therefore, tosylation of
anilines using grinding conditions was next taken up. A mixture of aniline (5 mmol), ptoluenesulphonyl chloride (5 mmol) and potassium carbonate (10 mmol) moist with a few
drops of water was ground under similar conditions and the reaction mixture on working

51

up gave 4-methyl-N-phenyl-benzenesulphonamide (27; m.p. 101-02oC) in 80-90% yield

whose identity was confirmed by its IR spectrum which showed absorption at 3324 cm -1
due to N-H stretching, at 1510 cm-1 due to N-H bending, at 1334 and 1161 cm-1 due to
symmetric and asymmetric S=O stretching and comparison of m.p. with literature60
value (103oC).

Scheme 35.
Following this method other substituted benzene sulphonamides from substituted anilines
were prepared which are listed below:
(i)

4-methyl-N-phenylbenzenesulphonamide

(27)
(ii)

4-methyl-N-p-tolylbenzenesulphonamide

(28)

52

(iii) N-(4-methoxyphenyl)-4-methylbenzenesulphonamide

(29)
After meeting success in benzoylation of phenols, anilines and formation of
sulphonamides from aniline, the synthesis of 2-aroyloxyacetophenones, the key
intermediates

for

the

synthesis

of

2-hydroxydibenzoylmethanes

from

2-

hydroxyacetophenones was next taken up.

A mixture of 2-hydroxyacetophenone (5 mmol), benzoyl chloride (5 mmol) and
potassium carbonate (10 mmol) homogenized with a few drops of water was ground in a
mortar with a pestle and progress of the reaction was monitored by TLC and the reaction
was found to be completed in 3 minutes. The reaction mixture was worked up as
described earlier and 2-benzoyloxyacetophenone (30; m.p. 86-87oC) was obtained in 92%
yield whose identity was confirmed by its IR which showed absorption at 1736 cm -1 and
1682 cm-1 due to C=O stretching. Its 1H NMR showed signal at 2.54 due to three
methyl protons and a multiplet between 7.22-8.22 due to nine aromatic protons. Finally
the identity was confirmed by comparison with authentic sample (Co-TLC) and
comparison of the melting point with literature61 value (87-88oC).
The above reaction was also repeated using benzoic anhydride in place of benzoyl
chloride, the reaction took 8 minutes for the completion and 2-benzoyloxyacetophenone
(30) was obtained in 78% yield.
It was preferred to use acid chloride, which is obtained easily by reaction of acids
with thionyl chloride, over acid anhydride because of preparation of acid anhydrides,
which are generally obtained by the reaction of acids with POCl3 in pyridine or by
reacting them with DCCI in solvent like DMSO. Moreover, after the reaction, half of the
acid from anhydride is used up while other half goes waste.

53

Scheme 36.
Using above reaction conditions various substituted 2-aroyloxyacetophenones
were prepared which are listed below:
(i)

2-benzoyloxyacetophenone

(30)
(ii)

2-benzoyloxy-5-methylacetophenone

(32)

54

(iii)

2-benzoyloxy-4-methoxyacetophenone

(34)
(iv)

2-anisoyloxyacetophenone

(36)
(v)

2-anisoyloxy-5-methylacetophenone

(37)

55

(vi)

2-anisoyloxy-4-methoxyacetophenone

(38)
(vii)

2-(o-anisoyloxy)acetophenone

(40)
(viii)

2-(o-anisoyloxy)-5-methylacetophenone

(41)
2-Hydroxyacetophenones were further reacted with cinnamoyl chloride (42) in
presence of potassium carbonate under grinding conditions as described above to give 256

cinnamoyloxyacetophenones, the required intermediates for the synthesis of 2hydroxybenzoylcinnamoylmethanes which in turn are required for the synthesis of 2styrylchromones.

Differently substituted 2-cinnamoyloxyacetophenones prepared are listed below:

(i)

2-cinnamoyloxyacetophenone

(ii)

2-cinnamoyloxy-5-methylacetophenone

57

(iii)

2-cinnamoyloxy-4-methoxyacetophenone

(45)
This appears to be the efficient procedure for ester formation and excludes the use
of organic solvents and toxic reagents such as pyridine at any stage of the reaction and
thus, is an eco-friendly method.

58

Experimental
Phenyl benzoate (14)
a) Using benzoyl chloride
A mixture of phenol (0.50 g), benzoyl chloride (0.6 ml) and potassium carbonate (1.40 g)
homogenized with 5 drops of water was ground in a mortar with a pestle. The progress of
the reaction was monitored by TLC and it was found to be completed in 3 min. The
reaction mixture was diluted with ice cold water and acidified with conc. HCl and the
colourless solid that separated out was filtered, washed with water and recrystallized
from aqueous ethanol to give the phenyl benzoate (14; 0.90 g), m.p. 66-67oC (lit.56 m.p.
68oC).
IR (KBr): 1726 cm-1 (C=O), 1598, 1477 cm-1 (C=C).
b) Using benzoic anhydride
A mixture of phenol (0.50 g), benzoic anhydride (1.10 g) and potassium carbonate (1.40
g) homogenized with 5 drops of water was ground in a mortar with a pestle. The progress
of the reaction was checked by TLC and was found to be completed in 8 min. The
reaction mixture was diluted with ice cold water and acidified with conc. HCl and the
colourless solid that separated out was filtered, washed with water and recrystallized
from aqueous ethanol to give phenyl benzoate (14; 0.76 g), m.p. 66-67oC (lit.56 m.p.
68oC).
p-Cresyl benzoate (15)
A mixture of p-cresol (0.5 ml), benzoyl chloride (0.6 ml) and potassium carbonate (1.40
g) homogenized with 5 drops of water was ground for 4 min in a mortar with a pestle.
The completion of the reaction was checked by TLC. The reaction mixture was diluted
with ice cold water and acidified with conc. HCl. The colourless solid that separated out
was filtered, washed with water and recrystallized from aqueous ethanol to give p-cresyl
benzoate (15; 1.00 g), m.p. 55-56oC (lit.56 m.p. 56oC).
IR (KBr): 1726 cm-1 (C=O), 1596, 1451 cm-1 (C=C).
59

-Naphthyl benzoate (16)

A mixture of -naphthol (0.72 g), benzoyl chloride (0.6 ml) and potassium carbonate
(1.40 g) homogenized with 5 drops of water was ground for 5 min in a mortar with a
pestle. The completion of the reaction was checked by TLC. The reaction mixture was
diluted with ice cold water and acidified with conc. HCl. The colourless solid that
separated out was filtered, washed with water and recrystallized from aqueous ethanol to
give -naphthyl benzoate (16; 1.14 g), m.p. 54-55oC (lit.56 m.p. 56oC).
IR (KBr): 1735 cm-1 (C=O), 1598, 1450 cm-1 (C=C).
-Naphthyl benzoate (17)
A mixture of -naphthol (0.72 g), benzoyl chloride (0.6 ml) and potassium carbonate
(1.40 g) homogenized with 5 drops of water was ground for 5 min in a mortar with a
pestle. The completion of the reaction was checked by TLC. The reaction mixture was
diluted with ice cold water and acidified with conc. HCl. The colourless solid that
separated out was filtered, washed with water and recrystallized from aqueous ethanol to
give -naphthyl benzoate (17; 1.10 g), m.p. 106-07oC (lit.56 m.p. 107oC).
IR (KBr): 1731 cm-1 (C=O), 1595, 1449 cm-1 (C=C).
Resorcinol dibenzoate (18)
A mixture of resorcinol (0.55 g), benzoyl chloride (1.2 ml) and potassium carbonate (1.40
g) homogenized with 5 drops of water was ground for 5 min in a mortar with a pestle.
The completion of the reaction was checked by TLC. The reaction mixture was diluted
with ice cold water and acidified with conc. HCl. The colourless solid that separated out
was filtered, washed with water and recrystallized from aqueous ethanol to give
resorcinol dibenzoate (18; 1.50 g), m.p. 114-15oC (lit.56 m.p. 117oC).
IR (KBr): 1734 cm-1 (C=O), 1596, 1478 cm-1 (C=C).

60

Hydroquinone dibenzoate (19)

A mixture of hydroquinone (0.55 g), benzoyl chloride (1.2 ml) and potassium carbonate
(1.40 g) homogenized with 5 drops of water was ground for 5 min in a mortar with a
pestle. The completion of the reaction was checked by TLC. The reaction mixture was
diluted with ice cold water and acidified with conc. HCl. The colourless solid that
separated out was filtered, washed with water and recrystallized from aqueous ethanol to
give hydroquinone dibenzoate (19; 1.20 g), m.p. 196-99oC (lit.56 m.p. 199oC).
IR (KBr): 1730 cm-1 (C=O), 1598, 1451 cm-1 (C=C).
Phloroglucinol tribenzoate (20)
A mixture of phloroglucinol (0.63 g), benzoyl chloride (1.8 ml) and potassium carbonate
(1.40 g) homogenized with 5 drops of water was ground for 4 min in a mortar with a
pestle. The completion of the reaction was checked by TLC. The reaction mixture was
diluted with ice cold water and acidified with conc. HCl. The colourless solid that
separated out was filtered, washed with water and recrystallized from aqueous ethanol to
give phloroglucinol tribenzoate (20; 1.60 g), m.p. 182-83oC (lit.57 m.p. 185oC).
IR (KBr): 1738 cm-1 (C=O), 1600, 1451 cm-1 (C=C).
7-Hydroxy-4-methylcoumarin (21)
A mixture of resorcinol (1.10 g) and ethylacetoacetate (1.3 ml) was ground with dry ptoluene sulphonic acid (1.76 g) in a mortar by pestle for 10 min when a colour change of
the mixture took place. The reaction mixture was kept at room temperature for about 20
minutes. The completion of the reaction was checked by TLC and the reaction mixture
was diluted with ice cold water. The solid that separated out was filtered at vacuum,
washed with water and recrystallized from ethanol to give 7-hydroxy-4-methylcoumarin
(21; 1.60 g), m.p. 183-84oC (lit.55 m.p. 184-86oC).
7-Benzoyloxy-4-methylcoumarin (22)
A mixture of 7-hydroxy-4-methylcoumarin (21; 0.80 g), benzoyl chloride (0.6 ml) and
potassium carbonate (1.40 g) homogenized with 5 drops of water was ground for 4 min in
61

a mortar with a pestle. The completion of the reaction was checked by TLC. The reaction
mixture was diluted with ice cold water and acidified with conc. HCl. The colourless
solid that separated out was filtered, washed with water and recrystallized from aqueous
ethanol to give 7-benzoyloxy-4-methylcoumarin (22; 1.28 g), m.p. 122-23oC.
IR (KBr): 1738 cm-1 (ester, C=O), 1728 cm-1 (coumarin, C=O).
1

H NMR (CDCl3): 2.46 (s, 3H, CH3), 6.29 (s, 1H, H-3), 7.20-8.20 (m, 8H, Ar-H).

Benzanilide (23)
A mixture of aniline (0.5 ml), benzoyl chloride (0.6 ml) and potassium carbonate (1.40 g)
homogenized with 5 drops of water was ground for 4 min in a mortar with a pestle. The
completion of the reaction was checked by TLC. The reaction mixture was diluted with
ice cold water and acidified with conc. HCl. The colourless solid that separated out was
filtered, washed with water and recrystallized from aqueous ethanol to give benzanilide
(23; 1.10 g), m.p.112-13oC (lit.58 m.p. 114oC).
IR (KBr): 3325 cm-1 (N-H), 1642 cm-1 (C=O), 1596, 1488 cm-1 (C=C).
p-Toluanilide (24)
A mixture of toluidine (0.54 g), benzoyl chloride (0.6 ml) and potassium carbonate (1.40
g) homogenized with 5 drops of water was ground for 3 min in a mortar with a pestle.
The completion of the reaction was checked by TLC. The reaction mixture was diluted
with ice cold water and acidified with conc. HCl. The colourless solid that separated out
was filtered, washed with water and recrystallized from aqueous ethanol to give ptoluanilde (24; 0.95 g), m.p. 147-48oC (lit.58 m.p. 148oC).
IR (KBr): 3310 cm-1 (N-H), 1647 cm-1 (C=O), 1598, 1490 cm-1 (C=C).
p-Anisanilide (25)
A mixture of p-anisidine (0.63 g), benzoyl chloride (0.6 ml) and potassium carbonate
(1.40 g) homogenized with 5 drops of water was ground for 5 min in a mortar with a
pestle. The completion of the reaction was checked by TLC. The reaction mixture was

62

diluted with ice cold water and acidified with conc. HCl. The colourless solid that
separated out was filtered, washed with water and recrystallized from aqueous ethanol to
give p-anisanilide (25; 1.20 g), m.p. 164-65oC (lit.58 m.p. 169oC).
IR (KBr): 3318 cm-1 (N-H), 1649 cm-1 (C=O), 1590, 1488 cm-1 (C=C).
p-Toluenesulphonyl chloride (26)
A solution of p-toluenesulphonic acid (10.00 g) and thionyl chloride (15 ml) was refluxed
in a round bottom flask fitted with a water condenser carrying a calcium chloride guard
tube on a water bath for one hr until the evolution of SO2 and HCl almost ceased. Excess
of thionyl chloride was distilled off under reduced pressure and the solid residue thus
obtained was p-toluenesulphonyl chloride (26; 10.80 g), m.p. 66-67oC (lit.59 m.p. 69oC).
4-Methyl-N-phenylbenzenesulphonamide (27)
A mixture of aniline (0.5 ml), p-toluenesulphonyl chloride (26; 0.95 g) and potassium
carbonate (1.40 g) homogenized with 5 drops of water was ground in a mortar with a
pestle. The progress of the reaction was monitored by TLC and the reaction was found to
be completed in 5 min. The reaction mixture was diluted with ice cold water and acidified
with conc. HCl and the colourless solid that separated out was filtered, washed with water
and recrystallized from aqueous ethanol to give 4-methyl-N-phenylbenzenesulphonamide
(27; 0.96 g), m.p. 101-02oC (lit.60 m.p. 103oC).
IR (KBr): 3234 cm-1 (N-H), 1596, 1463 cm-1 (C=C), 1510 cm-1 (N-H bend.), 1334, 1161
cm-1 (S=O).
4-Methyl-N-p-tolylbenzenesulphonamide (28)
A mixture of p-toluidine (0.54 g), p-toluenesulphonyl chloride (26; 0.95 g) and potassium
carbonate (1.40 g) homogenized with 5 drops of water was ground for 4 min in a mortar
with a pestle. The completion of the reaction was checked by TLC. The reaction mixture
was diluted with ice cold water and acidified with conc. HCl. The colourless solid that
separated out was filtered, washed with water and recrystallized from aqueous ethanol to
63

give 4-methyl-N-p-tolylbenzenesulphonamide (28; 1.00 g), m.p. 117-18oC (lit.60 m.p.

118oC).
IR (KBr): 3251 cm-1 (N-H), 1598, 1483 cm-1 (C=C), 1510 cm-1 (N-H bend.), 1339, 1158
cm-1 (S=O).
N-(4-Methoxyphenyl)-4-methylbenzenesulphonamide (29)
A mixture of p-anisidine (0.60 g), p-toluenesulphonyl chloride (26; 0.95 g) and potassium
carbonate (1.40 g) homogenized with 5 drops of water was ground for 6 min in a mortar
with a pestle. The completion of the reaction was checked by TLC. The reaction mixture
was diluted with ice cold water and acidified with conc. HCl. The colourless solid that
separated out was filtered, washed with water and recrystallized from aqueous ethanol to
give N-(4-methoxyphenyl)-4-methylbenzenesulphonamide (29; 1.10 g), m.p. 111-12oC
(lit.60 m.p. 114oC).
IR (KBr): 3268 cm-1 (N-H), 1598, 1466 cm-1 (C=C), 1510 cm-1 (N-H bend.), 1332, 1160
cm-1 (S=O).
2-Benzoyloxyacetophenone (30)
Method A: Using benzoyl chloride
A mixture of 2-hydroxyacetophenone (0.6 ml), benzoyl chloride (0.6 ml) and potassium
carbonate (1.40 g) homogenized with 5 drops of water was ground for 3 min in a mortar
by a pestle and completion of the reaction was checked by TLC. The reaction mixture
was diluted with ice cold water and acidified with conc. HCl and the colourless solid that
separated out was filtered, washed with water and recrystallized from aqueous ethanol to
give 2-benzoyloxyacetophenone (30; 1.02 g), m.p. 86-87oC (lit.61 m.p. 87-88oC).
IR (KBr): 1736 cm-1 (C=O, ester), 1682 cm-1 (C=O, ketone).
1

H NMR (CDCl3): 2.54 (s, 3H, CH3), 7.22-8.22 (m, 9H, H-3, H-4, H-5, H-6, H-2', H-3',

H-4', H-5', H-6').

64

Method B: Using benzoic anhydride

A mixture of 2-hydroxyacetophenone (0.6 ml), benzoic anhydride (1.13 g) and potassium
carbonate (1.40 g) homogenized with 5 drops of water was ground for 8 min in a mortar
by a pestle and completion of the reaction was checked by TLC. The reaction mixture
was diluted with ice cold water and acidified with conc. HCl and the colourless solid that
separated out was filtered, washed with water and recrystallized from aqueous ethanol to
give 2-benzoyloxyacetophenone (30; 0.86 g), m.p. 86-87oC (lit.61 m.p. 87-88oC).
IR (KBr): 1736 cm-1 (C=O, ester), 1682 cm-1 (C=O, ketone).
p-Tolylacetate
A mixture of p-cresol (25 ml), acetic anhydride (50 ml) and anhydrous sodium acetate
(40 g) was refluxed in a 250 ml round bottom flask fitted with a calcium chloride guard
tube for 4 hr. The reaction mixture was poured over crushed ice and left overnight,
extracted with ethyl acetate, organic layer was washed with water, dried over calcium
chloride and solvent was removed by distillation. The residue was distilled to give ptolylacetate as colourless liquid (17 ml), b.p. 210-12oC (lit.62 b.p. 212-13oC).
2-Hydroxy-5-methylacetophenone (31)
Powdered aluminium chloride (30 g) was added to p-tolylacetate (9.6 ml) in a 250 ml
round bottom flask fitted with calcium chloride guard tube at 0oC. The temperature was
slowly raised to 120oC in oil bath in 30 min and maintained at 160oC for 2 hr. Aluminium
chloride complex was decomposed with crushed ice (150 g) and hydrochloric acid (15
ml). The solid that separated out was filtered, washed with water, dried and recrystallized
from petroleum ether to give 2-hydroxy-5-methylacetophenone (31; 10 g) as light brown
needles, m.p. 52-53oC (lit.63 m.p. 52oC).
2-Benzoyloxy-5-methylacetophenone (32)
A mixture of 2-hydroxy-5-methylacetophenone (31; 0.75 g), benzoyl chloride (0.6 ml)
and potassium carbonate (1.40 g) homogenized with 5 drops of water was ground for 4
min in a mortar with a pestle and completion of the reaction was checked by TLC. The
reaction mixture was diluted with ice cold water and acidified with conc. HCl and the
65

colourless solid that separated out was filtered, washed with water and recrystallized
from aqueous ethanol to give 2-benzoyloxy-5-methylacetophenone (32; 1.14 g), m.p. 8687oC (lit.64 m.p. 87-88oC).
IR (KBr): 1736 cm-1 (C=O, ester), 1682 cm-1 (C=O, ketone).
1

H NMR (CDCl3): 2.39 (s, 3H, CH3) 2.51 (s, 3H, COCH3), 7.09-8.21 (m, 8H, H-3, H-4,

H-6, H-2', H-3', H-4', H-5', H-6').

2,4-Dihydroxyacetophenone
Anhydrous zinc chloride (33 g) was dissolved in glacial acetic acid (32 ml). To the hot
mixture at 1100C, dry resorcinol (22 g) was added with stirring and the solution was
heated on sand bath at 140-450C for 20 min. Dilute hydrochloric acid (1:1, 100 ml) was
added to the reaction mixture and the resulting solution was cooled, and the solid that
separated out was filtered, washed with water and recrystallized from hot dilute
hydrochloric acid (1:1) to give 2,4-dihydroxyacetophenone as yellow needles (22 g), m.p.
145-47oC (lit.65 m.p. 147oC).
2-Hydroxy-4-methoxyacetophenone (33)
A solution of 2,4-dihydroxyacetophenone (15 g) in acetone (250 ml) in a 500 ml round
bottom flask was refluxed with anhydrous potassium carbonate (40 g) and
dimethylsulphate (10.0 ml) on a water bath using water condenser and calcium chloride
guard tube for 1 hr. The acetone solution was filtered and residue was washed with
acetone. The solvent was removed from combined acetone solution by distillation, water
(400 ml) was added to the residue and solution was cooled in ice bath. The solid that
separated out was filtered, washed with water and dried. The dry solid on crystallization
from diethyl ether-petroleum ether gave 2-hydroxy-4-methoxyacetophenone (33; 13 g) as
long needles, m.p. 50-510C (lit.66 m.p. 52-53oC).
2-Benzoyloxy-4-methoxyacetophenone (34)
A mixture of 2-hydroxy-4-methoxyacetophenone (33; 0.85 g), benzoyl chloride (0.6 ml)
and potassium carbonate (1.40 g) homogenized with 5 drops of water was ground for 5
min in a mortar with a pestle and completion of the reaction was checked by TLC. The
66

reaction mixture was diluted with ice cold water and acidified with conc. HCl and the
colourless solid that separated out was filtered, washed with water and recrystallized
from aqueous ethanol to give 2-benzoyloxy-4-methoxyacetophenone (34; 1.14 g), m.p.
87-88oC (lit.67 m.p. 85-86oC).
IR (KBr): 1734 cm-1 (C=O, ester), 1686 cm-1 (C=O, ketone).
1

H NMR (CDCl3): 2.46 (s, 3H, COCH3), 3.90 (s, 3H, OCH3), 6.71 (s, 1H, H-3), 7.04-

8.12 (m, 7H, H-5, H-6, H-2', H-3', H-4', H-5', H-6').
p-Anisoyl chloride (35; 4-methoxybenzoylchloride)
A mixture of anisic acid (10 g) and thionyl chloride (15 ml) was refluxed in a 100 ml
round bottom flask fitted with a water condenser carrying a calcium chloride guard tube
on a water bath for one hr until the evolution of SO2 and HCl gases almost ceased. Excess
of thionyl chloride was distilled off from the reaction mixture under reduced pressure and
the residue was further distilled under reduced pressure to give p-anisoyl chloride as
colourless liquid (35; 6.0 ml), b.p. 129-31oC/11 mm (lit.68 b.p. 131oC/11 mm).
2-Anisoyloxyacetophenone (36)
A mixture of 2-hydroxyacetophenone (0.6 ml), p-anisoyl chloride (35; 0.7 ml) and
potassium carbonate (1.40 g) homogenized with 5 drops of water was ground for 3 min in
a mortar by a pestle and completion of the reaction was checked by TLC. The reaction
mixture was diluted with ice cold water and acidified with conc. HCl and the colourless
solid that separated out was filtered, washed with water and recrystallized from ethanol to
give 2-anisoyloxyacetophenone (36; 1.60 g), m.p. 114-15oC (lit.69 m.p. 113-14oC).
IR (KBr): 1726 cm-1 (C=O, ester), 1682 cm-1 (C=O, ketone).
1

H NMR (CDCl3): 2.53 (s, 3H, CH3), 3.88 (s, 3H, OCH3), 6.99 (d, 2H, J = 8.04 Hz, H-

3', H-5'), 7.22 (d, 1H, J = 8.04 Hz, H-3), 7.34 (t, 1H, J = 7.00 & 7.08 Hz, H-4), 7.56 (t,
1H, J = 6.92 & 7.20 Hz, H-5), 7.84 (d, 1H, J = 7.24 Hz, H-6), 8.16 (d, 2H, J = 8.04 Hz,
H-2', H-6').

67

2-Anisoyloxy-5-methylacetophenone (37)
A mixture of 2-hydroxy-5-methylacetophenone (31; 0.75 g), p-anisoyl chloride (35; 0.7
ml) and potassium carbonate (1.40 g) homogenized with 5 drops of water was ground for
5 min in a mortar with a pestle and completion of the reaction was checked by TLC. The
reaction mixture was diluted with ice cold water and acidified with conc. HCl and the
colourless solid that separated out was filtered, washed with water and recrystallized
from aqueous ethanol to give 2-anisoyloxy-5-methylacetophenone (37; 1.38 g), m.p. 11415oC (lit.70 m.p. 116oC).
IR (KBr): 1725 cm-1 (C=O, ester), 1682 cm-1 (C=O, ketone).
1

H NMR (CDCl3): 2.4 (s, 3H, CH3), 2.5 (s, 3H, COCH3), 3.89 (s, 3H, OCH3), 6.99 (d,

2H, J = 8.64 Hz, H-3', H-5'), 7.11 (d, 1H, J = 8.16 Hz, H-3), 7.36 (d, 1H, J = 7.80 Hz, H4), 7.64 (s, 1H, H-6), 8.16 (d, 2H, J = 8.64 Hz, H-2', H-6').
2-Anisoyloxy-4-methoxyacetophenone (38)
A mixture of 2-hydroxy-4-methoxyacetophenone (33; 0.83 g), p-anisoyl chloride (35; 0.7
ml) and potassium carbonate (1.40 g) homogenized with 5 drops of water was ground for
5 min in a mortar with a pestle and completion of the reaction was checked by TLC. The
reaction mixture was diluted with ice cold water and acidified with conc. HCl and the
colourless solid that separated out was filtered, washed with water and recrystallized
from aqueous ethanol to give 2-anisoyloxy-4-methoxyacetophenone (38; 1.30 g), m.p.
85-85oC (lit.70 m.p. 84oC).
IR (KBr): 1728 cm-1 (C=O, ester), 1674 cm-1 (C=O, ketone).
1

H NMR (CDCl3): 2.48 (s, 3H, COCH3), 3.88, 3.89 ( each s, 6H, 2OCH3), 6.71 (s, 1H,

H-3), 6.85 (d, 1H, J = 7.64 Hz, H-5), 6.99 (d, 2H, J = 7.48 Hz, H-3', H-5'), 7.88 (d, 1H, J
= 8.20 Hz, H-6), 8.16 (d, 2H, J = 7.48 Hz, H-2', H-6').
o-Anisoyl chloride (39; 2-methoxybenzoyl chloride)
A mixture of 2-methoxybenzoic acid (10 g) and thionyl chloride (15 ml) was refluxed in
a round bottom flask fitted with a water condenser carrying a calcium chloride guard tube
68

on a water bath for one hr until the evolution of SO2 and HCl gases almost ceased. Excess
of thionyl chloride was distilled off from the reaction mixture under reduced pressure and
the residue was further distilled to give o-anisoyl chloride as colourless liquid (39; 6.5
ml), b.p. 252-53oC (lit.68 b.p. 253-54oC).
2-(o-Anisoyloxy)acetophenone (40; 2-(2-mehoxybenzoyloxy)acetophenone))
A mixture of 2-hydroxyacetophenone (0.6 ml), o-anisoyl chloride (39; 0.75 ml) and
potassium carbonate (1.40 g) homogenized with 5 drops of water was ground for 5 min in
a mortar with a pestle and completion of the reaction was checked by TLC. The reaction
mixture was diluted with ice cold water and acidified with conc. HCl and the colourless
solid that separated out was filtered, washed with water and recrystallized from aqueous
ethanol to give 2-(o-anisoyloxy)acetophenone (40; 1.17 g), m.p. 76-77oC (lit.71 m.p.
78oC).
IR (KBr): 1744 cm-1 (C=O, ester), 1666 cm-1 (C=O, ketone).
1

H NMR (CDCl3): 2.55 (s, 3H, COCH3), 3.9 (s, 3H, OCH3), 7.01-7.59 (m, 6H, H-3, H-

4, H-5, H-3', H-4', H-5'), 7.82 (dd, 1H, J = 7.80 & 1.64 Hz, H-6'), 8.10 (dd, 1H, J = 7.72
& 1.76 Hz, H-6).
2-(o-Anisoyloxy)-5-methylacetophenone (41)
A mixture of 2-hydroxy-5-methylacetophenone (31; 0.75 g), o-anisoyl chloride (39; 0.75
ml) and potassium carbonate (1.40 g) homogenized with 5 drops of water was ground for
4 min in a mortar by a pestle and completion of the reaction was checked by TLC. The
reaction mixture was diluted with ice cold water and acidified with conc. HCl and the
colourless solid that separated out was filtered, washed with water and recrystallized
from aqueous ethanol to give 2-(o-anisoyloxy)-5-methylacetophenone (41; 1.20 g), m.p.
111-13oC (lit.72 m.p. 112oC).
IR (KBr): 1744 cm-1 (C=O, ester), 1690 cm-1 (C=O, ketone).
1

H NMR (CDCl3): 2.39 (s, 3H, CH3), 2.54 (s, 3H, COCH3), 3.84 (s, 3H, OCH3), 6.97-

7.62 (m, 5H, H-3, H-4, H-3', H-4', H-5'), 8.00 (dd, 1H, J = 7.80 & 1.80 Hz, H-6), 8.08
(dd, 1H, J = 7.72 & 1.76 Hz, H-6').
69

Cinnamoyl Chloride (42)

A mixture of cinnamic acid (10 g) and thionyl chloride (15 ml) was refluxed in a round
bottom flask fitted with a water condenser carrying a calcium chloride guard tube on a
water bath for one hr until the evolution of SO2 and HCl gases almost ceased. Excess of
thionyl chloride was distilled off from the reaction mixture under reduced pressure and
the residue was further distilled under reduced pressure to give cinnamoyl chloride as
colourless liquid (42; 8.0 ml), b.p.130-31oC/11 mm (lit.68 b.p. 131oC/11 mm).
2-Cinnamoyloxyacetophenone (43)
A mixture of 2-hydroxyacetophenone (0.6 ml), cinnamoyl chloride (42; 0.7 ml) and
potassium carbonate (1.40 g) homogenized with 5 drops of water was ground for 3 min in
a mortar by a pestle and completion of the reaction was checked by TLC. The reaction
mixture was diluted with ice cold water and acidified with conc. HCl and the colourless
solid that separated out was filtered, washed with water and recrystallized from aqueous
ethanol to give 2-cinnamoyloxyacetophenone (43; 1.20 g), m.p. 75-76oC (lit.71 m.p. 7677oC).
IR (KBr): 1720 cm-1 (C=O, ester), 1682 cm-1 (C=O, ketone), 1636 cm-1 (C=C).
1

H NMR (CDCl3): 2.55 (s, 3H, CH3), 6.67 (d, 1H, J = 16.00 Hz, CH=CH- ), 7.18

(dd, 1H, J = 8.08 & 0.96 Hz, H-3), 7.32 (td, 1H, J = 7.64 & 1.60 Hz, H-4), 7.36-7.64 (m,
6H, H-5, H-2', H-3', H-4', H-5', H-6'), 7.82 (dd, 1H, J = 7.76 & 1.60 Hz, H-6), 7.89 (d,
1H, J = 16.00 Hz, -CH=CH-).
2-Cinnamoyloxy-5-methylacetophenone (44)
A mixture of 2-hydroxy-5-methylacetophenone (31; 0.75 g), cinnamoyl chloride (42; 0.7
ml) and potassium carbonate (1.40 g) homogenized with 5 drops of water was ground for
4 min in a mortar by a pestle and completion of the reaction was checked by TLC. The
reaction mixture was diluted with ice cold water and acidified with conc. HCl and the
colourless solid that separated out was filtered, washed with water and recrystallized
from aqueous ethanol to give 2-cinnamoyloxy-5-methylacetophenone (44; 1.26 g), m.p.
72-73oC (lit.73 m.p. 72oC).

70

IR (KBr): 1728 cm-1 (C=O, ester), 1682 cm-1 (C=O, ketone), 1636 cm-1 (C=C).
1

H NMR (CDCl3): 2.36 (s, 3H, CH3), 2.53 (s, 3H, COCH3), 6.66 (d, 1H, J = 16.00 Hz,

-CH=CH- ), 7.06 (d, 1H, J = 8.20 Hz, H-3), 7.32 (dd, 1H, J = 8.20 & 1.96 Hz, H-4), 7.37.57 (m, 5H, H-2', H-3', H-4', H-5', H-6'), 7.60 (d, 1H, J = 1.88 Hz, H-6), 7.87 (d, 1H, J =
16.00 Hz, -CH=CH-).
2-Cinnamoyloxy-4-methoxyacetophenone (45)
A mixture of 2-hydroxy-4-methoxyacetophenone (33; 0.83 g), cinnamoyl chloride (42;
0.7 ml) and potassium carbonate (1.40 g) homogenized with 5 drops of water was ground
for 5 min in a mortar with a pestle and completion of the reaction was checked by TLC.
The reaction mixture was diluted with ice cold water and acidified with conc. HCl and
the colourless solid that separated out was filtered, washed with water and recrystallized
from aqueous ethanol to give 2-cinnamoyloxy-4-methoxyacetophenone (45; 1.40 g), m.p.
87-88oC (lit.72 m.p. 90oC).
IR (KBr): 1728 cm-1 (C=O, ester), 1680 cm-1 (C=O, ketone), 1636 cm-1 (C=C).
1

H NMR (CDCl3): 2.50 (s, 3H, COCH3), 3.82 (s, 3H, OCH3), 6.66 (d, 1H, J = 15.95 Hz,

CH=CH- ), 6.88 (d, 1H, J = 2.44 Hz, H-3), 6.82 (dd, 1H, J = 8.80 & 2.44 Hz, H-5),
7.37-7.58 (m, 5H, H-2', H-3', H-4', H-5', H-6'), 7.85 (d, 1H, J = 8.8 Hz, H-6), 7.89 (d, 1H,
J = 15.95 Hz, -CH=CH-).

71