'2.

Chapter 7
ANTHRAQUINONE

PAGE

7. 1 Intr oduction · · · · · · · · · · · · · · · · · · · · · · · · · · · ·· · · · · · · · · · · · ·· · · · · · · · · · · ····· ·············· ·· · · · · · · · · · · · ··· · · ·· 129

7.2 Experimental .......................................................................................... 132
7.3 Ob servations and discussion ....................................................................132
7.4 Chara cterization ...............................................................'...................... 137
7.4. 1 Optical and scanning electron microscopy ..................................: 137
7.4. 2 Infrared analysis ......................................................................... 142
7.4.3 X-ray diffra ction analysis ............................................................ 142
7.4.4 UV-visible spectroscopy ............................................................. 146
7.5 Conclusion ............................................................................................. 146
 1 30

Chapter 7

ANTHRAQUINONE

7.1 Introduction

Derivatives of anthracene, very often, like the parent hydrocarbon

are convertible to other compounds in high yield by direct oxidation.
Anthraquinone come under this class of compounds. It crystallises in the
monoclinic system with space group P2rla with a = 1.581, b = 0.3942 and

c = 0.7865 nm with two molecules per unit cell. Molecules are tightly entangled
across the adjacent (oko) planes. However slip in these planes is forbidden in
the (100) and (001) directions. The weak forbidden reflections were observed
in the zero layer (010) (�urty, 1955, Chaudhury andBhuiya, 1960; Srivastava,
1975; Marwaha and Shah, 1988).

Anthraquinones can be easily produced by oxidation of anthracene. The

mesopositions in anthracene acquire the numbers of 9 and 10 respectively.
Reactivity of high degree is manifested at these positions. The successful
outcome of the reaction can be attributed to both the special reactivity of the
mesopositions and greater stability of anthraquinone. The double bonds in the
 '30 I'

CH I CH
HC�

I
�CH
HC

I
CH CH

· Fig. 7. 1 Anthraquinone
7. Anthraquinone 131

central ring are rendered inert by incorporation of oxygen in the tenninal

benzene rings (Louis and Mary, 1960). Considerable work has been reported
on the synthesis of anthraquinone by catalytic oxidation of anthracene (Ivan
and William, 1949; James and shoen, 1950; Corliss and Irving, 1951; Owens,
1958; Rusyavona and Kharlam, 1962; Morgan and Simon, 1969; Noboru .e.t
al., 1969; Grozev � al., 1976; Shmel' ov and Anastov, 1976; Traxler, 1977;
Chung, 1978; Das and Nikhilendu, 1982; Malik and Dohnal, 1988; Malik and
Dohnal, 1990; Pielichiouski and Polazzek, 1992).

Optical properties of mixed anthraquinone crystals were investigated by

Yao (1962). It undergoes auto oxidation exhibiting' chemiluminescence
(Kazakov, � al., 1976; Sergeev � al., 1985). William and Adam (1969)
have reported the relationship between dislocation and molecular structure.
Photosemiconducting properties were studied by Grozev .e.tal. (1976). Studies
were also made on the diamagnetic susceptibilities of anthraquinone (Hideo and
Yoshio, 1953). Electrochemical study of complexes formed by alkali metal
ions was performed by Bezuglyi .e.t al. (1984). Another interesting property
observed was the third harmonic generation (Mizoguchi .e.t al., 1991).
Lumina � al. (1993) have noticed electron accepter centres on the surface of
. a high temperature modification of adsorbed anthraquinone. Infrared and
ultraviolet spectra were studied by Karobeinnicheva .e.t al. (1993). Photo
reduction of anthraquinone was investigated using ESR technique (Kausche,
1996). In present study anthraquinone crystals were grown by
the
photoreaction of anthracene solution with the aid of gel which has not been
reported so far.
 7. Anthraquinone 132

7.2 Experimental

The chemicals used in this study were of BDH/AR grade. Sodiwn

metasilicate of gel density 1.05 glee was prepared, treated with glacial acetic
acid in the pH range 5 to 7.5 and mixed with acetone for different gel acetone
ratios (2: 1, 3: 1, 4: 1). The mixture was allowed to set. The mixtures with
higher pH ( > 6.5) were set within forty eight hours whereas those with lower
pH (5) took nearly one week to set. Over the set gels, 0.5% (w/v) solution of
anthracene in acetone was incorporated as top solution. The samples were kept
open to diffuse sunlight. Few samples were kept in a dark room. The
experiment was repeated using gel without mixing with acetone also.

7.3 Observations and discussion

In the first set of experiment using acetone mixed gel, over a period of
one week, the level of top solution decreased slightly due to slow evaporation
and diffusion into the gel. Tiny transparent crystals were observed floating on
the surface of the top solution. These crystals acted as substrate for the growth
of yellow needles of anthraquinone. Within two weeks yellow needles were
observed growing. In the second approach with pure gel, large number of
transparent crystals of anthracene were formed in the solution over the pure
gel. Here formation of anthraquinone was delayed by two months and only
few yellow needles of poor quality were obtained. Formation of anthraquinone
is found to depend on several factors. An important parameter which determine
the yield of anthraquinone was the concentration of anthracene solution kept
over the gel. Higher concentration (1 % ) of anthracene solution produces a
 1.6

,. 4

f .2

- 1.0
f� '�

....-,:
·--:r
&i.

- o.s
�.
�;;,,-
�� i
�
�

�-�' g
·�

(,s·, : ?,f
,,_,-.,.. ,;,.�

.....
0-6 (rtf
"'J. ., ....,
:-_s

0-4

0.2

o..__�.,__�--�...,_�_.._�__,_�__._���-'-�-'-���--"�---'----J
0 40 80 120 160 320 360 400 440 480 520
200 240 280
Time (hours)
w
w
Fig. 7.2 Growth kinetics of anthraquinone crystal
7. Anthraquinone 134

large number of anthracene crystals on the gel surface and tiny needles of
anthraquinone were formed after a long period (- two months). A better
yield of anthraquinone was achieved in a solution of concentration 0.5% (w/v)
within two weeks.

A typical sample of gel adjusted for pH 5 over which few yellow needles
of anthraquinone were formed is shown in Fig. 7.4(A). In this case, tiny
crystals were formed on the surface of top solution moved down to gel surface
and yellow needles of anthraquinone were grown from them. In certain other
samples when the illumination was high, large number of yellow needles were
obtained.

Eventhough, pH of gel medium has no major role in the crystallization

of organic non-polar molecules, crystals were formed only in a top solution of
particular pH ( -6) irrespective of the gel pH. Hence pH of top solution and
in tum pH of the gel should have some effect on the nucleation of anthraquinone.
Crystals of anthraquinone were found in all pH value tried (5-7.5). But better
yield was obtained in 5-6 range. Another notable observation is made for pH
5.5 in which yellow needles were formed to grow into the gel medium in
addition to that in the top solution. The rate of growth of these needles were
studied. A uniform increase in the growth rate of needles into the gel medium
was observed upto six days. After one week, the crystals attained maximum
size, with a lower growth rate. This was followed by dissolution of crystals
and the size of crystals fluctuates as represented in Fig. 7 .2.
7. Anthraquinone 135

The samples kept in darkness did not yield yellow crystals of

anthraquinone but only platy crystals of anthracene. This confirms that the
yellow needles of anthraquinone were produced by the photoreaction of
anthracene as reported earlier (Corey and Taylor, 1964). By the irradiation of
anthracene in acetone, anthraquinone is obtained as a final product as repre­
sented by the following conversion (Fig. 7.3).

cco coo --
Anthracene Anthracene peroxide Anthraquinone

Fig. 7.3 Photoreaction of anthracene

Investigation on the solvent (acetone) incorporated over the gel in this

experiment revealed that there was a gradual increase in the density, surface
tension and conductance of the solvent (figures 3.6, 3.8 and 3.10). Hence it
can be presumed that such changes might have modified the anthracene solution
favourably for being converted into anthraquinone by photoreaction. Density
measurement of solvent and solution (Table. 7.1) showed that the supernatant
solution of anthracene undergoes a change similar to the behaviour of acetone­
water mixture as represented in Fig. 3.7. Thus the supernatant solution might
have been tuned for the growth of yellow needles. The differences in growth
of anthraquinone in pure gel and acetone mixed gel is also noted. When the
7. Anthraquinone 136

solution was kept over pure gel, the changes in supernatant solution was fast
and resulted in the nucleation and growth of large nwnber of anthracene
crystals. Solution over the acetone -mixed gel was found to undergo a slow
change in parameters and few anthracene crystals were formed. Within this
time the solution is tuned for easy photoreaction and growth of anthraquinone.

Table 7.1 Density of solvent/solution at 30°C

Solvent/Solution Density Kg!m3

Pure acetone 753

Acetone kept over the gel for one week 895

Saturated solution of anthracene in acetone 764

Top solution in which anthraquinone is formed 847

In order to have better understanding of the role played by water-acetone

system, water was mixed with acetone in different proportions. This mixture was
used to prepare anthracene solution so as to grow crystals by slow evaporation
without the aid of gel. A notable observation was that yellow needles of
anthraquinone were formed in acetone - water system only if a seed was added.
Good yield (Fig. 7.4(E)) was obtained when the mixture containing 5 to 30 % of
water was kept in an illuminated room.

The crystals were separated, washed, dried and characterised with X-ray
powder diffraction, IR, UV-visible spectroscopy, optical and scanning electron
7. Anthraquinone 137

rrucroscopy. Tiny transparent crystals that formed on the top solution as a

substrate for yellow needles were also separated and characterised. Studies
confirmed that they are anthracene crystals. After removing the transparent
crystals and yellow needles from the top solution of the gel, the solution is
decanted, filtered and allowed to crystallise. An yellow powder is obtained
after slow evaporation. This yellow powder was also analysed using IR
spectroscopy.

7.4 Characterization

7.4.1 · Optical and scanning electron microscopy

Optical micrographs of the single crystals of anthraquinone were taken

using "LEITZ ORTHLUX II POL BK" petrological microscope attached
camera. Fig. 7.4(B) shows a needle of anthraquinone nucleated from anthra­
cene crystal substrate. Hollow cavity of the anthraquinone is also seen in the
crystal. Fig. 7.4(C) gives the micrograph of certain needles of anthraquinone
obtained under crossed Nicol position. A single crystal of anthraquinone

photographed in straight extinction position with Nicol in 45° for maximum

illumination is given in Fig. 7.4(D). Yellow needles of anthraquinone crystals
grown in the supernatant solution kept over the gel is shown in Fig. 7.4(A).
Fig. 7.4(E) shows the growth of large number of yellow needles in acetone -
water solution of anthracene. The transparent tiny crystals at the bottom of the
test tube are anthracene. Fig. 7.4(F) gives the SEM picture of the anthraquinone
needle.
 FIGURE CAPTIONS

7.4.(A) Needles of anthraquinone seen growing in the supernatant solution

kept over the gel

7.4.(B) A needle of anthrqquinone nucleated from a cluster of anthracene

crystals ·

7.4.(C) Micrograph of needles obtained under crossed nicol prism

7.4.(D) A single crystal ofanthraquinone photographed in straight extinction

position with nicol in 45°

7.4(E) Micrograph showing the growth of a large number of yellow needles

of anthraquinone in acetone-water solution of anthracene

7.4(F) SEM photograph of a needle of anthraquinone

 •

-
a,
0
C
0

E
V)

,_e
C

40)() �200 2400 1700 1100 500

Wavenumber. ( crn 1 )

Fig. 7.5 Infrared spectrum of anthracene crystals

 (0)

........
�

-
Q)
0
C
0
(b)
E
UJ

e
C

J-

2400 1600 600

4000 3200
1
Wavenumber (cm )

uinone needles grown

Fig_ 7_6 lnfrbred spedrum of antluaq muxed gel
efone solution inc oirpo mted over oceffone
)
{a in ac
n
(b) in acelone-watef'" soi1U1lio
 I�)

40

Q)
30
C
0
+-
.._
E
V)
C
0 20

10

0 � � -'-�����-1������_J �-----�-'--��-1-�
20 CXJ 1500 1000 - 500 400
1
Wavenumber ( crn )

owder p recipitated from th e

Fig. 7.7 Infra red spectrum of th e yellow p
top solution
7. Anthraquinone 142

7.4.2 Infrared analysis

The infrared spectra of the crystals were recorded in the range 4000
-400 cm- l by K.Br pellet method. Preliminary analysis of the transparent
crystals formed on the top solution by IR spectroscopy has confirmed that the
crystals are anthracene. Fig. 7.5 shows the IR spectrum of these crystals. The
IR spectrum of yellow needles grown in acetone solution and those grown in
acetone - water mixture are given in Fig. 7.6(A) and 7.6(B), respectively. The
IR spectrum of the yellow powder precipitated from top solution is also
reproduced in Fig. 7.7. Certain additional bands in the spectrum of yellow
powder may be due to the presence of the intermediate product, anthracene
peroxide. The vibrational frequencies and their assignments are given in

Table. 7.2. The intense bands at 1676 and 1653 cm-1

carbonyl grouping not present in anthracene but seen in the case of anthraqui-
none (Singh and Singh, 1968). The intense band at 694 cm-1 is identical to
the ring breathing frequency reported for anthraquinone (Singh, 1991).

7.4.3 X-ray diffraction analysis

The XRD scan of the crystals with Cu.Ka. radiation in the 2 9 range

0 to 50° is shown in Fig. 7.8. The calculated 'd' values (0.360, 0.762 and
0.314 nm) are found to be in close agreement with the ASTM 'd' values (0.352,
0.769 and 0.314 nm) of anthraquinone.
-
N
0

-
�
0
� 0
en
C:
<l)
-
C:

IC')
Q
Q=

50 45 40 35 30
20 (degree)
25 20 15 10 5
-
. Fig. 7.8 XRD pattern of anthraquinone crystals
 5 a

t 4
\LJ
o>
0 3

200 225 250 275 300 325 350 375

...r
A nm �
...r

7.9 UV-visible spectra of anthraquinone crystals

{a} grown in acetone-water mixture
(b) grown by solution-gel technique -F
 145
7. Anthraquinone

Table 7.2 IR spectral data of anthraquinone

Yellqw needles Yellow powder Assignments

Yellow needles
grown in acetone grown in acetone- obtained by slow
solutionkept over water mixture by evaporation of
the acetone solution growth supernatant
mixed gel solution
1
cm - 1 c m -1 cm-

950
937 935 880 CH out of plane bending
810 810 720

900
920 Skeletal deform
621 470

690 690 Ring breathing

694

990
1160 1140 CH in plane bending
1170 1160
1284 1280
1280

1310
1304 1330 1340
1332 1470 1440 Ring stretching
1473 1560 1550
1522 1620 1615
1635

1585 Aromatic vibrations of quinones

1591 1580
.
1600 C=O stretch of quinones
16 53 1678 1700
1676
 7. Anthraquinone 146

7.4.4 Ultraviolet and visible spectroscopy

UV-visible speqtra of the anthraquinone crystals grown in this study were

recorded using a SHIMADZU UV-2100S, UV-visible recording spectrometer.
The UV-spectrum of the anthraquinone crystals dissolved in chloroform is
displayed in Fig. 7.9. Very strong band at 253 nm and the medium intense
band at 273 nm are in agreement with reported values (Mortan and Elans,
1941).

7.5 Conclusion

Formation of anthraquinone crystals was observed during the growth

studies of anthracene. Better crystals of anthraquinone were obtained in 0.5%
(w/v) solution of anthracene kept over acetone-mixed gel of pH (5-6). At
higher concentration, nucleation and growth of anthracene occurred hindering
photoreactive conversion to anthraquinone. For all the pH values (5-7.5) tried,
crystals of anthraquinone were obtained with varying nucleation time and
quality. Growth of needles into the gel medium was observed for pH 5.5.
Acetone mixed gel was found to be a better medium in aiding the growth of
anthraquinone rather than pure gel. Solution studies revealed that acetone­
water mixture can also be used as a solvent for growing anthraquinone crystals
by photo reaction.

In this series of experiments anthraquinone were grown as needle shaped

crystals, in addition to microscopic anthracene crystals. Careful separation
and characterisation of needles revealed that the crystals are of pure an­
thraquinone. This method of photoreactive oxidation can be tried for similar
materials which cannot be easily grown by other methods.