81 (1962) RECUEIL 679

547.672.1 542.951
ACETYLATION OF ANTHRACENE BY THE FRIEDEL-CRAFTS
REACTION USING CHLOROFORM AS THE SOLVENT
BY
H. F. BASSILIOS, M. SHAWKY AND A. Y. SALEM
(Faculty of Engineering, Alexandria University, Egypt, U.A.R.)

Acetylation of anthracene by the Friedel-Crafts Reaction using chloroform

as the solvent leads to a high yield of 9-acetyl or 1,5-diacetylanthracene.

Introduction
Techniques for the preparation of acetyl and some propionyl anthracenes
are the subject of some German, British and French patents l, which
describe the acylation of anthracene under a variety of conditions, using
benzene, carbon disulphide or nitrobenzene as the solvent and report
obtaining 9-ace;yl-, 1-acetyl-, a mixture of 1- and 2-acetyl-anthracene, or a
mixture of two diacetylanthracenes but no yields are indicated. The striking
feature of this reaction as described by these patents, and as found on
repeating the examples given, is that the products differ geatly in nature
and quantity according to the conditions. Waldman repeated part of this
work and confirmed some results, although neither did he report yields.
The procedure for the preparation of 9-acetylanthracene using benzene as
the solvent was checked by Merritt and Braun 3 , a yield of 57-60 % being
reported.
The object of this publication is to give some useful information about
the acetylation of anthracene in one of the solvents which were found
suitable for FI-iedel-Crafts acvlations 4 : chloroformi This solvent having the
property of dissolving aluminium chloride in presence of an equivalent
amount of acetyl chloride, and of being a good solvent for anthracene, leads
to a homogenous reaction. It is also known to have a special orienting
effect 4.
During the course of experiments it has been found that:
1. Acetylation of anthracene in this solvent gives rise mainly to the
- ___~__
G . Pat. 492, 247 (1926), 493, 688 (1926), 499, 051 (1926), French Pat. 663, 071 (1928),
Brit. Pat. 289,585 (1928), U.S. Pat. I , 730,081 (1929), I , 766,443 (1930).
Waldman and Murmorstein, Ber. 70, 106 (1937).
Merritf and Braun, Org. Synth. 30, 1 (1950).
Salem, “Friedel-Crafts Acetylation of Naphthalene”, M. Sc. Thesis, Alexandria Univ.
(1953); Bussilios, Makar and Salem, Bull. SOC. chim. France 21, 72 (1954).
680 H.F. Ba.wilios, M . Shawky und A. Y. Sakm
- . -
_.___

9-acetyl-isomer, accompanied by a small proportion of the I-isomer. The

9-isomer can be completely separated from the I-isomer, as the aluminium
chloride complex of the latter is almost completely insoluble in chloroform
while that of the former is completely soluble, allowing their separation by
filtration of the anhydrous reaction mixture.
2. N o 2-acetylanthracene could be obtained under a wide variety of
conditions.
3. If excess acetyl chloride-aluminium chloride complex is used, the
rate of formation of I-acetylanthracene increases; however, there is a
tendency for the formation of 1$diacetylanthracene. On the other hand,
increasing the ratio of acetyl chloride with respect to aluminium chloride
inhibits the formation of 1-acetyl anthracene. It also inhibits diacetylation.
4. Under properly chosen conditions excellent yields of 9-acetyl and
1 ,5-diacetyl anthracene are obtained.
Acetylation of anthracene using other solvents in order to obtain 2-acetyl-
anthracene, 1 ,%diacetylanthracene or a better yield of I -acetylanthracene
is the object of further investigation.

Experirnen tal
Preparation of 9-acetylanthracene
In a 500 ml reaction vessel equipped with a mechanical stirrer were introduced 50 nil
of 10 % v./v. solution of acetyl chloride ( I .2 mol.) in carefully dried and distilled chloro-
form, and coarsely ground anhydrous aluminium chloride (9 g; 1.2 mol.), and the mixture
stirred at 30 to 35" to complete dissolution of the aluminium chloride (about 30 min).
Separately, finely powdered anthracene (10 g, 1 mol.) was suspended in chloroform
(200 ml) and shaken for 5 min, when most of it dissolved, and the mixture was then
added slowly (during 10 min) with stirring to the aluminium chloride-acetyl chloride
complex solution keeping the temperature below 40". The solution turned blood red and
evolution of hydrogen chloride occurred. The whole mixture was left with stirring for a
further 50 min; the blood red solution which was at first clear began to deposit a red
precipitate. The anhydrous mixture was filtered, and the precipitate washed twice with
a small quantity of dry chloroform and both precipitate and filtrate decomposed sepa-
rately with cold dilute hydrochloric acid.
The precipitate provided a dirty yellow product, m.p. 100-102" (1.5 g), which on
crystallisation from alcohol gave 1.4 g of 1-acetylanthracene, m.p. 109",not depressed
on admixture with I -acetylanthracene, m.p. 109" obtained by acetylation of anthracene
as described in the patents mentioned above.
The filtrate, after decomposition with dilute hydrochloric acid, gave a brownish emul-
sion. The organic layer was separated, washed until acid-free and the solvent distilled off
on a steam bath from a weighed flask, the last traces of the solvent being removed by
applying reduced pressure. The residue (10.5 g) was treated with boiling alcohol (50 ml)
and the clear solution decanted and cooled quickly. Unchanged anthracene (0.7 g) was
deposited and filtered off. To the clear filtrate distilled water was added drop by drop
until turbidity occurred. The emulsion was shaken vigorously when droplets of brown
oil coagulated leaving a clear yellow solution. The solution was tested by adding a few
drops of distilled water to see if any more'liquid separated. Crystals began to deposit.
The mixture was then reheated until homogeneous and then left overnight in an ice box
giving 9-acetylanthracene, m.p. 72", which was recrystallised from dilute alcohol by a
Acetybtion of onthracene by the Friedel-Crafts, etc. 81 (1962) RECUEIL 681
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similar technique giving pure 9-acetylanthracene, m.p. 78", identical with the product,
obtained by acetylation of anthracene following the directions of Merritt and Braun 3.
The oil, together with any material not dissolved in the first 50 ml portion of alcohol,
was treated with a further 20 ml of boiling alcohol and worked u p in a similar way
giving a further quantity of 9-acetylanthracene. The combined yield of 9-acetylanthracene
was 9 g (73 % of theory). The total yield of acetylanthracenes based on anthracene actually
used in the reaction is about 90%.

Preparation of 1,Miacetylanthracene
In a 500 ml reaction vessel were introduced 120 ml of a 10 % solution v./v. of acetyl
chloride in dry chloroform (3 mol. acetyl chloride), and coarsely ground anhydrous
aluminium chloride (22.5 g, 3 mol.) and the mixture stirred at 30 to 35" until complete
dissolution of the aluminium chloride (about 30 min) occurred. Separately, anthracene
(10 g, 1 mol.) suspended in 180 ml of anhydrous chloroform, was added slowly during a
period of 10 min, after which the whole mixture was left with stirring for a total period
of 2 hours. The blood red solution which was at first clear quickly deposited a red pre-
cipitate which progressively increased in quantity and its colour changed gradually from
deep red to brick red. The mixture was filtered, washed twice with dry chloroform and
both residue and filtrate decomposed separately with cold dilute hydrochloric acid. The
precipitate provided a dirty yellow product (12 g) which was sparingly soluble in alcohol
but could be crystallised from glacial acetic acid (100 ml) yielding 1 g of an unidentified
insoluble material and 10.5 g of dark yellow needles, m.p. 213", depressed on admixture
with anthracene. This product gave a violet colour with concentrated sulphuric acid and
a positive iodoform test. It was identified as 1 ,Sdiacetylanthracene (see later). The filtrate,
after decomposition with hydrochloric acid, gave a brownish solution, from which, after
washing, dehydration and driving off the solvent, 1.5 g more of 1,5-diacetylanthracene
could be isolated by crystallisation from acetic acid. The total yield was 12 g (81.5 '%,of
the theoretical amount calculated on anthracene).

Oxidation of 1,S-diacetylanthracene to 1,Sdiacetylanthraquinone

I .5-Diacetylanthracene (5 g, m.p. 21 3") was added with stirring to a mixture of chromic
acid (6 g) and glacial acetic acid (50 ml); a slightly exothermic reaction occurred. The
reaction mixture was boiled gently for 5 min, when a white solid separated from the
green reaction mixture; it was filtered after cooling to 60", then washed with water.
dilute hydrochloric acid, water again, dilute ammonia, and finally with water several
times. The crude product (5.2 g, m.p. 315-318") was crystallised from nitrobenzene giving
fine needles of 1,5-diacetylanthraquinone,m.p. 320" (block) (Coulson records 317").
This compound gave positive anthraquinone test (red vat with alkaline hydrosulphite),
positive iodoforni test, and no reaction with sodium bicarbonate, indicating an acetyl-
anthraquinone.

Oxidation of 1,s-diacetylanthraquinone to anthraquinone-1,Sdicrboxylic acid

1,5-Diacetylanthraquinone prepared as described above (5 g) was ground to a tine
paste with 10 ml of concentrated sulphuric acid, and the paste was poured with stirring
on to about 2: g of crushed ice when a fine suspension was obtained. It was diluted to
100 ml with water containing sodium hydroxide (8 g) and heated to 70". Sodium hypo-
chlorite solution (400 ml, 39.8 g available chlorine per litre) was added, keeping the
temperature of the reaction at 7 0 . The mixture was stirred with an efficient mechanical
stirrer. On addition of the hypochlorite solution the mixture remained yellow at first,

Coulson, J. Chem. SOC.1930, 193I .

682 H . F. Bassilios and co.'s, Acetylation of anthracene by the Friedel-Crafrs, etc.

but soon turned red; the red colour was destroyed whenever it developed by the addition
of a fresh portion of hypochlorite until complete dissolution and no red colour developed
on standing. Excess hypochlorite was then destroyed by the addition of a slight excess of
sodium bisulphite solution. The solution was filtered from any insoluble impurity, and
the anthraquinone-l,5-dicarboxylicacid was precipitated by the addition of 50 % sul-
phuric acid till acid to congo red paper. The yield was 4.9 g, m.p. 399" (block) identical
with anthraquinone-1,s-dicarboxylicacid, m.p. 399" prepared as described by Scholl 6 .
It gave a positive anthraquinone test, negative iodoform test, and dissolved with effer-
vescence in dilute sodium bicarbonate solution.

(Received June 17th. 1961).

Scholl, Ham and Meyer, Ber. 62B,107 (1929).