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Addison Ault,
Rachel Kooet..
and Arthur Serianz


Cornell College
Vernon, Iowa 52314

Two Thermorhrotnir Compounds

Preparations for the introductory
organic laboratory

zinc duat


2 xanthone
dixanthylene (I)
Believing that students enjoy preparing
compounds with interesting or unusual properties, we
Dianthraquinone may be prepared by bromination of
have develo~edore~arationsof two com~oundswhich
to give 9-bromoanthrone, followed by treatexhibit a pronounced thermoohromism. ~ i x a n t h ~ l e n e
product with diethylamine in chloroform

. '



is a pale yellow-green solid a t room temperature, but

becomes dark blue when melted or heated in solution;
at liquid nitrogen temperature, it is completely colorless.
Dianthraquinone (11)

is a bright canary yellow a t room temperature, but
becomes a brilliant parrot green when heated in solution. The thermochromism of both compounds can
be observed very nicely during recrystallization from
boiling mesitylene.
The preparation of dixanthylene (I) may be carried
out by the light-catalyzed addition of xanthene to
xanthone to give 9-hydroxydixanthyl, followed by
elimination of water




Shydmxydixanthyl AcO

2 Shrornoanthrone E&NH

dianthraquinme (11)

8-Hydrozydizanthyl from X a n t h a e and X a n t h a e (1). Place
3.23 g. (16.5 mmole) xanthone and 3.00 g (16.6 mmole) xanthene
in a 125-ml Pyrex erlenmeyer flask. Add 75 ml of benzene and
bring the solids into solution with swirling and gentle heating.
Stopper the flask and allow it to stand in bright sunlight until it
appears that the formation of the coarse granular crystalline
materid has ceased.' At this time, collect the crystalline 9-hydroxydixanthyl by suction filtration and wash it with a little benzene. Yield: about 5.3 g. (85%); mp, 193.5-194.5"C (lit.z,
--- ,.
Dizanthylae ( I ) from 9-Hydrozydizanthyl. Place 1.0 g (2.65
mmole) of 9-hydroxydixanthyl in a. 25-ml erlenmeyer flask. A d d
14 ml of acetic anhydride and boil the mixture under reflux
until dl the solid has dissolved. Add 7.0 g (3.7 mmole) of p-toluenesulfonic acid monohydrate down the condenser and continue
to boil the mixture until no more solid appears to form and no further color change occurs; about 3 min will be required; the color
ohanges from red to dark brown to dark green. Allow themixture
to cool to room temperature for one hour and then collect the
dixanthylene by suction filtration, washing it with a little Zcetic
acid. Itecrystdise the dixanthylene by heating it under reflux
with about 10 ml of mesitylene (adding mare down the condenser, if necessary, to bring d l the solid into solution) and
allowing the blue solution to cool to room temperature. Yield:
about 400 mg (about 40%) of yellowish crystals; (lit.3 mp: 315").
Dizanthylne from X ~ n t h o n e .Place
2.5 g (12.7 mmole) of
xanthone in a 250-ml boiling flask, add 100 ml of glacial acetic
acid and swirl until most of the solid has dissolved. Add 0.8 g
(12 mmole) of zinc dust, 2 drops of conc. hydrochloric acid, and
boil the mixture under reflux for about 90 mi". Every 5 minor
so, add 2 drops of conc. hydrochloric acid dawn the condenser,


Alternatively, dixanthylene may be prepared by the

reductive dimerization of xanthone by means of zinc
and acid

H Br

Journal o f Chemical Education

This work was supported in part by funds from the National

Science Foundation (COSIP) and from the Sloan Foundation.
1 Three to fourteen days in the sunlight will be required; overexposure does apparent harm'
A,, J. Chen. Soc., 67 (1944).
S., Ber., 28, 2310


taking carenot to add the acidso often that the solution takes on a
red color. Add three more 0.8 g portions of zinc dust, one a t a
time at intervals of about 20 min, adding the first about 20 min
after the mixture has been brought to a boil. At the end of the
period of boiling under reflw, allow the solution to cool completely
to room temperature, collect the solid by suction filtration,
and wash it thoroonhlv
.. . with water. S e ~ a r a t eanv zinc from the
prodllrr hy I h , i l ~ nir ~with mwi~).lmr. di-3rlve therlirnnthyle~w
nl,out 2: ml wll he required , filtering rhe hot, blue d t ~ t i o nby
gravity, reheating the filtrate if necessary to redissolve any material which may have crystallized, and allowing the filtrate to cool
to room temperature. Collect the very pale yellow-green cryatdls by suction filtration and wash them with s. little benzene.
Yield: about 0.8 g (35%).
The thermochromism of dixmthylene (I) may be observed by
heating a. sample in a. melting point capillary over a. small burner
flame, or, better, by recrystallization from boiling mesitylene,
nsingabout 19 ml/g (recovery: about 90%).
g-Bromaanthraefrom Anthrone.' Suspend 5.0 g (26 mmole) of
anthrone in 15 ml of carbon disulfide and add bromine dropwise
with stirring over a period of about 15 minutes until the bromine
color persists; about 4.1 g (1.4 ml; 1 equivalent) will be required.*
Collect the tan crystalline product by suction filtration and wash
it with a little benzene. Yield: 6.0 g (85%).
Dianthrquinone jvom 9-Bromoanth~onc.~Dissolve 2.0 g (7.3

mmole) of 9-bromoanthronel in 30 ml of chloroform.' Add 2.0 ml

(1.4 g; 19 mmole) of diethylamine, swirl to mix, and allow the resulting warm solution to stand for two hours. During this time,
the color of the solution will change from yellow to a dark redbrown. At this time, add 75 ml of ether slowly with swirling.
After 5 min, collect the yellow precipitate by suction filtration and
wash it thoroughly with ether. Suspend the precipitate in about
10 ml of 95% ethanol and then collect the canary yellow dianthraquinone by suction filtration, washing it with a little ethanol.
Yield: about 0.8 g (55%).
The thermochromism of dianthraquinone (11) can be observed
very nicely upon recrystallization from boiling mesitylene using
about 50 ml/g.

E.. COOK.J. W..

M. A.. J . Chen.
.\tr.vFn, K. H., ,Inn., 379.02 1191 I .
Sinre hydrogru bmwide gas is evdveJ i u tlri* rcnvtiun, it must
be iwrriwl out i n the hood or sowe pruvisim n ~ i ltw made 10nb-

.Tor., 123,l!l!i4 ,iw3

sorb the gasproduced.

H. H.,
J. Chem.
Soc., 121,2059 (1922).
'The 9-bromoantbrone m w t be prepared just before use;
otherwise the vield of dianthraauinone is ereatlv reduced.
Any insol;ble material shoild be removedMatthis point by
gravity filtration.

Volume 48, Number 6, June 1971

41 1