Org. Synth. 1962, 42, 66
DOI: 10.15227/orgsyn.042.0066
HEXAHYDROXYBENZENE
[Benzenehexol]
Submitted by A. J. Fatiadi and W. F. Sager
1.
Checked by B. C. McKusick and J. K. Williams.
1. Procedure
One hundred grams (0.44 mole) of stannous chloride dihydrate is added to a boiling solution of
10 g. (0.058 mole) of tetrahydroxyquinone2 in
200 ml. of 2.4N hydrochloric acid contained in a
1.5-l. beaker. The initial deep-red color disappears, and grayish crystals of
hexahydroxybenzene precipitate.
Two hundred fifty milliliters of 12N hydrochloric acid is added, and the mixture is heated to boiling with constant stirring. The beaker is removed from the hot plate, an additional
600 ml. of 12N hydrochloric acid is added, and the solution is cooled in a refrigerator. The
hexahydroxybenzene is collected on a
Büchner funnel fitted with a
sintered-glass disk (Note 1) and sucked dry.
The crude hexahydroxybenzene is dissolved in 450 ml. of hot 2.4N hydrochloric acid containing 3 g. of hydrated stannous chloride and 1 g. of decolorizing carbon. The solution is filtered while hot, and the carbon is rinsed with 75 ml. of boiling water that is combined with the filtrate. One liter of 12N hydrochloric acid is added, and the mixture is cooled in a refrigerator. The snow-white crystals of hexahydroxybenzene that separate are collected under carbon dioxide or nitrogen (Note 2) on a Büchner funnel fitted with a sintered-glass disk. The hexahydroxybenzene is washed with 100 ml. of a cold 1:1 mixture of ethanol and 12N hydrochloric acid and dried in a vacuum desiccator over sodium hydroxide pellets; yield 7.1–7.8 g. (70–77%). It fails to melt on a hot plate at 310° (Note 3).
2. Notes
1.
Filter paper cannot be used because it is attacked by strong
hydrochloric acid.
2.
By rapid manipulation it is possible to obtain a product of fair quality. The moist product is susceptible to air oxidation, as is shown by a development of pink coloration on the crystals. The filtration is best carried out under a blanket of
carbon dioxide or
nitrogen obtained by inverting a funnel attached to a source of
carbon dioxide or
nitrogen over the Büchner funnel.
3.
The decomposition point of
hexahydroxybenzene is not a good criterion of purity. If the product is light in color, there can be no significant amount of oxidized material in it, for even traces of
tetrahydroxyquinone cause intense coloration. Decomposition of a sample with
nitric acid followed by evaporation and ignition of the residue should give a negligible amount of
tin oxide. The product can be characterized as the hexaacetate, m.p.
202–203°, by treating it with
acetic anhydride and
sodium acetate.
3
3. Discussion
The present procedure is a modification of the procedure of Anderson and Wallis.
4 Hexahydroxybenzene can also be prepared by acidic hydrolysis of
potassium carbonyl3 or by nitration and oxidation of
diacetyl hydroquinone.
54. Merits of the Procedure
This is the most convenient synthesis of
hexahydroxybenzene, and the present procedure gives better yields than reported by Anderson and Wallis.
4 Hexahydroxybenzene is of interest as the most highly hydroxylated member of the polyhydroxybenzene family.
It has been used as a source of the biologically important
myo-inositol6,7 (1235/46 isomer) by hydrogenation over
palladium and of
cis-inositol (123456 isomer) by hydrogenation over palladium-on-carbon.
This preparation is referenced from:
Appendix
Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)
ethanol (64-17-5)
hydrochloric acid (7647-01-0)
acetic anhydride (108-24-7)
sodium acetate (127-09-3)
sodium hydroxide pellets (1310-73-2)
nitric acid (7697-37-2)
nitrogen (7727-37-9)
stannous chloride
carbon dioxide (124-38-9)
decolorizing carbon,
carbon (7782-42-5)
palladium (7440-05-3)
stannous chloride dihydrate (10025-69-1)
Hexahydroxybenzene,
Benzenehexol (608-80-0)
Tetrahydroxyquinone (319-89-1)
tin oxide
potassium carbonyl
diacetyl hydroquinone
myo-inositol (87-89-8)
cis-inositol
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