LAB REPORT

CHM 624
ADVANCED ORGANIC CHEMISTRY
EXPERIMENT 4: SYNTHESIS OF FLAVONE
NAME : NURYASMIN AFINA BT MUHAMAD SHUKERI
STUDENT ID : 2014444792
GROUP : AS 202 5A2
LECTURERS NAME : DR. ROPISAH BT ME.
DATE OF EXPERIMENT : 14TH OCTOBER 2016
GROUP MEMBERS
NURSYAHIRAH SYAHIDAH BT BAHARIM
NOR AZEAN NADHIRAH BT MOHAMED SANI
SHUHAILI BT RASHID
EXPERIMENT 4: Synthesis of flavone

STUDENT
ID
2014851768
2014885566
2014668164

OBJECTIVES:
i.

To synthesis flavones from 2-hydroxyacetophenone.

INTRODUCTION:

Flavone
Flavones (flavus = yellow), are a class of flavonoids based on the
backbone of 2-phenylchromen-4-one Apart from flavones other flavonoids
are

isoflavonoids,

derived

from

3-phenylchromen-4-one

structure

neoflavanoids, derived from 4-phenylcoumarine structure. The three

flavonoid classes are all ketone-containing compounds, and as such, are
anthoxanthins (flavones and flavonols) Flavones are well known for their
various biological activities such as anticancer, anti inflammatory, antiosteoporotic, anti-diabetic, and others. Some of the examples as shown as
under. Synthetic strategies of flavones Traditionally, flavones have been
prepared by Baker Venkatraman rearrangement and Claisen-Schmidt
condensation which involves the conversion of 2hydroxyacetophenones
into

benzoyl

esters,

followed

by

rearrangement

in

base

to1,3-

diphenylpropane1,3-diones which upon cyclization under acidic conditions

furnishes flavones. On the other hand hydroxychalcone synthesized from
2-hydroxyacetophenone

and

benzaldehyde

under

Claisen

Schmidt

conditions can undergo oxidative cyclization to furnish flavones ring.

(Kshatriya, Shaikh, & Nazeruddin, 2013).

EQUIPMENTS AND INSTRUMENTS:

Steam bath
Hot plate with magnetic stirrer
Reflux apparatus
Calcium chloride guard tube
Suction filtration
IR
NMR

MATERIALS:
1. Preparation of 2-benzoyloxyacetophenone
2-Hydroxyacetophenone (FW 136.2) 2.46 mL, 2.72 g (20 mmol)
Benzoyl chloride (FW 140.6) 3.48 mL, 4.22 g (30 mmol)
Pyridine (FW 79.1) 5 mL
Hydrochloric acid (3%)
Methanol
PROCEDURE:
1. Preparation of 2-benzoyloxyacetophenone
The 2-hydroxyacetophenone is dissolved in 5 mL pyridine (dried
over KOH) in a 25 mL round bottomed flask. The benzoyl chloride is
added, the flask is fitted with a calcium chloride guard tube and the
flask is swirled to ensure mixing of the reagents. The temperature of
the reaction mixture rises spontaneously. The reaction mixture is left
for about 20 min or until no further heat is evolved. Then the
mixture is poured into a 250 mL beaker containing 120 mL
hydrochloric acid (3%) and 40 g crushed ice with good stirring. The
product is collected by suction filtration and washed it with 4 mL
cold methanol and then 5 mL water.The product is dried by suction

at the filter pump for 20 min, then recrystallized it from

approximately 5 mL methanol. The yield, mp, and the IR and NMR
(in CDCl3) spectra of the product is recorded after recrystallization.
An IR spectrum of the starting 2-hydroxyacetophenone is recorded
for comparison.
RESULT AND CALCULATION:
(1)
Mass
Mass
Mass

PREPARATION OF 2-BENZOYLOXYACETOPHENONE:
of beaker
: 59.5868g
of beaker + product
: 61.81664g
of 2-benzoyloxyacetophenone obtained : 2.22984g

No. of mol 2-hydroxyacetophenone =

Mass
Molar mass

2.72 g
= 136.15 g/mol
= 0.019978 mol
No. of mol benzoyl chloride

Mass
Molar mass

4.22 g
= 140.6 g /mol
=0.03001 mol
-Since no of mol of 2-hydroxyacetophenone is less than no of mol
benzoyl chloride, therefore 2-hydroxyacetophenone is the limiting
reactant!
Theoretical yield of 2-benzoyloxyacetophenone:
Mass=No of mol Molar mass
= 0.019978 mol 240.258g/mol
= 4.79987 g
Percentage yield =
=

Actual yield
Theoretical yield 100%
2.22984
4.79987 100%

= 46.46%
Melting Point
Observation

: 89C
: Oily yellow liquid was observed

DISCUSSION:
In this experiment, 2-hydroxyacetophenone is synthesised to
get flavone. Unfortunately, the result of flavone is not obtained
might due to some errors. The product at the end of this experiment
is oily yellow liquid which has been used to run in the Fourier
Transform Infrared Spectroscopy (FTIR) in order to get the spectrum
and to identify the functional groups that exist in the product. FTIR
was used to obtain an infrared spectrum of absorption or emission
of a solid, liquid or gas. Even though some cases when some
compound has similar frequencies absorbed, IR can still detect the
compound. Thus, the infrared spectrum can be used for molecules
as much as it can be used as fingerprint for human. (Pavia et al,
2009). The product that obtained in this experiment is 2benzoyloxyacetophenone.

The actual yield that obtained from this experiment is

2.2298g. While the theoretical yield is 4.79987 g. The percentage
yield is 46.46% which the remaining percentage might be due to
some errors. The melting point obtained is 89C.

The first frequency shows in the IR spectrum is 2928.57 cm -1.

This peak indicates alkane group (C-H). This hydrogen atom, H, act
as substituent at benzene ring when carbon atom attached with
hydrogen. This peak is near to 3000 cm-1. C-H absorption which is
sp3 always occur at frequency near 3000 cm -1. Next, the frequency
absorbed is at 1641.54 cm-1. This peak shows that there is alkene
group which is C=C. This peak stretch alkene range which is 16601600 cm-1. This alkene group can make conjugation moves of C=C
stretch to lower frequencies and increase intensity. In addition, there
are two peak indicate alkane group (-CH2) which are 1484.58 cm-1
and 1448.27 cm-1. These peak was present in the alkane group
range which is 1465 cm-1. There are -CH2 structure at 2benzoylacetophenone structure. Methylene group bending peak
have a characteristic to appear approximately 1465 cm-1.
Lastly, there is an ester absorption peak appear that is
completely tally with the structure of 2-benzoylacetophenone which
are 1303.26 cm-1 and 1244.47 cm-1. The ester peak show that the
structure C-O at range 1300 cm-1 - 1000 cm-1.
By comparing the spectrum obtained from FTIR for 2hydroxyacetophenone, which has structure as shown below :-

The peaks that has an absorption at 1640.40 cm -1 and

1487.44 cm-1 indicate an

aromatic ring (C=C). Ring stretch

absorption often occur in pairs at approximately 1600 cm -1 and 1475

cm-1. Aromatic compound show absorption bands in the infrared
spectrum. Next, there is peak indicates C-O which is ether group at
1302.10 cm-1. Simple aliphatic ethers can be identified from alkanes
by the presence of C-O band.
There are some errors that occurred during the experiment
was carried out. Firstly, there are several undefined peak present in
the IR spectrum. The alcohol peak appears at frequency 3393.95
cm-1in the spctrum. It is because, methanol was used to clean the
plate before placed the product. There is also other compound
frequency peak because of contaminated of the plate. The final
product was not successful get because the pyridine is not dried
over KOH as it is prepared by the laboratory assistant. The
apparatus is not carefully rinsed so the mixture poured in the
apparatus might contaminate. Next, during the separation, product
may be extracted together with the unwanted ones. Light petroleum
is used to recrystallize. It is because it has high volatility and
insoluble in water.
Finally , the precaution steps is wear gloves when handling the
chemical because the chemical is dangerous and can cause irritation
while contact with skin. If the chemical is spill on the hand, quickly
wash the hand to avoid any corrosive skin.

CONCLUSION:
The product obtained was 2-benzoyloxyacetophenone which
weighed 4.79987 g, percentage yield of 2-benzoyloxyacetophenone is
46.46% and has the melting point of 89oC.

REFERENCES:
1) Kshatriya, R. B., Shaikh, Y. I., & Nazeruddin, G. M. (2013). Synthesis
of flavone skeleton by different methods. Oriental Journal of
Chemistry, 29(4), 14751487.
2) Solomons, T. W. Graham, and Fryhle, Craig B. (2002). Organic
Chemistry : Friedel-Crafts Acylation (pp. 671-673). (7th ed.), USA:John
Wiley & Sons, Inc.
3) Donald L. Pavia, Gary M. Lampman, George S. Kriz, & James R.
Vyvyan, (2009), Introduction to Spectroscopy (4th Edition), USA:
Department

of

Chemistry

Western

Washington,

University

Bellingham
4) http://www.organic-chemistry.org/namedreactions/bakervenkataraman-rearrangement.shtm. Retrieved on 25 October 2016.

Problems
1. Discuss the mechanism of the Baker-Venkataraman rearrangement.

2. Assign

the

spectroscopic

data

for

the

starting

hydroxyacetophenone, its benzoylated derivative and for flavone.

a) 2-hydroxyacetophenone

FREQUENCY (cm-1)
1640.40
1487.44 & 1447.66

ASSIGNMENT OF THE PEAKS

C=O
Methyl and methylene

2-

1302.10
1023.89
961.77 & 836.65
752.99 & 736.67

Methyl bending
C-O alcohol
=CH bending
-CH3 oop. Bending

b) 2-benzoylaxyacetophenone
FREQUENCY (cm-1)

ASSIGNMENT OF THE

1641.54
1484.58 & 1448.27
1303.6
3393.95
961.23
755.24

PEAKS
C=O
Methyl and methylene
Methyl bending
-OH alcohol
=CH bending
-CH3 oop. Bending