Benzoquinone 1
Benzoquinone
K. Thomas Finley, State University of New York, Brockport, New York, United States
1. Introduction . . . . . . . . . . . . . . .
2. Physical Properties . . . . . . . . . .
3. Chemical Properties . . . . . . . . . .
4. Production of 1,4-Benzoquinone . .
1. Introduction
In 1838 the parent compound 1,4-benzoqui-
none (1) [106-51-4] was prepared by oxida-
tion of quinic acid [36413-60-2] with maga-
nese dioxide [1]. More than half a century later
its much less stable isomer, 1,2-benzoquinone
(2) [583-63-1] was obtained by silver ion ox-
idation of catechol [120-80-9] [2]. Since then
these colorful and reactive compounds have oc-
cupied a central place in practical and theoret-
ical studies, which are the subject of two ex-
tensive reviews [3, 4]. Other, more specialized
reviews are given in [5 – 8]. The chemistry of
the quinones includes a vast array of specific re-
actions and has been explored in great detail,
including addition and cycloaddition reactions,
photochemistry, biochemistry, oxidative chem-
istry, and electrochemistry [9 – 19].
1 2 3 principal entry for 2-isopropyl-5-methyl-1,4-
While there are many different quinonoid
structures by far the most common are 1 and
2. This article will be restricted to the physical,
chemical, industrial, and toxicological charac-
teristics of these compounds and their simple
derivatives. The general references provide cov-
erage of many other structural types.
1,4-Benzoquinones can be substituted by a
wide variety of alkyl, aryl, halo, oxygen, nitro-
gen, and sulfur groups. They are usually named
as derivatives of 1, e.g., 2-methyl-1,4-benzoqui-

c 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
10.1002/14356007.a03 571.pub2
. 1 5. Uses . . . . . . . . . . . . . . . . . . . . . 3
. 2 6. Toxicology . . . . . . . . . . . . . . . . . 4
. 2
. 3 7. References . . . . . . . . . . . . . . . . . 4
none (3) [553-97-9]. The CAS nomenclature
of the quinones, e.g., 2,5-cyclohexadiene-1,4-
dione for 1, is seldom used. Trivial names like
p-benzoquinone and p-tolyquinone (3) exist and
are used occasionally. Two very useful oxidiz-
ing agents are universally known by a trivial
name and an acronym: p-chloranil [118-75-2]
(4) (2,3,5,6-tetrachloro-1,4- benzoquinone) and
DDQ [84-58-2] (5) (2,3-dichloro-5,6-dicyano-
1,4-benzoquinone).
4 5
This lack of widespread concensus con-
cerning nomenclature for the quinones is
well illustrated by the latest Aldrich Cata-
log Handbook of Fine Chemicals [20] where
one finds: “DDQ, see 2,3-dichloro-5,6-dicyano-
1,4-benzoquinone”, but “2,5-dichloro-3,6-dihy-
droxy-1,4-benzoquinone, see chloranilic acid”
(6), [87-88-7]. Thymoquinone (7) is still the
benzoquinone [490-91-5].
6 7
A few compounds with no apparent re-
lationship to quinones continue to be mis-
named, e.g., camphorquinone [10373-78-1]
(2,3-camphandione).
2 Benzoquinone
2. Physical Properties
1,4-Benzoquinone (1), C6 H4 O2 , M r 108.10, mp
113 ◦ C, d20 20
4 1.318, pv 12 Pa, is soluble in most
oxygenated organic solvents (ether, alcohol, ace-
tone), and hot ligroin, slightly soluble in pentane,
and insoluble in water. Crystallization from al-
cohol or sublimation produces yellow monoclin-
ic prisms.
1,2-Benzoquinone (2), C6 H4 O2 , M r 108.10,
mp 60 – 70 ◦ C (decomp.), crystallizes in red
plates or prisms. It is much less stable than 1,
e.g., it decomposes in water. Compound 2 is sol-
uble in ether, acetone, and benzene, but insoluble
in pentane.
2,3,5,6-Tetrachloro-1,4-benzoquinone (4), p-
chloranil, C6 Cl4 O2 , M r 245.88, mp 290 ◦ C
(sealed tube); and 2,3-dichloro-5,6-dicyano-1,4-
benzoquinone (5), DDQ, M r 227.01, mp 213 –
216 ◦ C are yellow to bright yellow in color and
crystallize as monoclinic prisms and plates.
These and most other low molecular mass
benzoquinones have high vapor pressures and
pungent, irritating odors.
3. Chemical Properties
Many of the quinones found in nature are im-
portant as oxidants, and this property is well
illustrated in metabolic processes [14, 15] and
has found widespread synthetic applications [16,
17]. The cross-conjugated system of two α,β-
unsaturated carbonyl groups creates versatile re-
activity.
Michael addition has a long and productive
history; similar radical and electrophilic reac-
tions offer important alternative and often com-
plementary synthetic routes [9 – 11]. The syn-
thesis of natural products [21] and polycyclic
aromatic compounds [22] shows quinones to be
important dienophiles for Diels – Alder chem-
istry. When additions fail to achieve the desired
result, substitution reactions are often the route
of choice [9 – 11]. There is also a growing liter-
ature on the role of quinones in photochemical
processes [12].
The addition of arylsulfinic acids to 1,4-
benzoquinones has been studied in detail as a
model for the more complicated cases of thiol
and sulfite anion addition [23]. These other oxi-
dation states of sulfur are interesting in biochem-
istry [24] and photography [25]. The protonated
quinone is the reactive species, a fact that is sup-
ported by the product distribution observed with
2-methyl-1,4-benzoquinone (Eq. 1). While 2,5-
addition (8) is favored by both resonance and
molecular orbital arguments, the 2,6-product (9)
is obtained in a 3:1 ratio.
It has also been shown that the product distri-
bution in this reaction can be strongly influenced
by changes in acidity and solvent mixture [26].
Furthermore, the use of ionic liquids shows great
promise as “green” solvents [27] in this chem-
istry. When the acidity or solvent is varied, the
relative yields of 8 and 9 can change dramati-
cally [26]. Over the pH range 1 to 4.5 in aqueous
buffers one observes the 9/8 ratio changing from
4:1 to 2:3. In a similar fashion this same ratio is
9:1 with absolute ethanol as the solvent and 2:3
when carried out in 50% aqueous acetic acid.
This same reaction (Eq. 1) has been studied in
ionic liquids [27]. The 9/8 ratio almost exactly
reverses to 1:8.5. These interesting media are
being promoted as much more environmentally
friendly green solvents.
a:
(8); b: (9)(Eq. 1)
With a single electron-withdrawing sub-
stituent 2,3-addition provides the major product
[28]. This observation has been exploited as an
important route to heterocyclic molecules as il-
lustrated in Equation 2.
(Eq. 2)

The tripeptide glutathione (10) adds to 1,4-
benzoquinone to form the thioether 11. Subse-
quent cross-oxidation and further addition (Eq.
3) give a mixture of the three possible isomeric
products [29]. This situation has only been re-
ported once before, and then it also involved
the formation of a bisthioether addition product
[30].
a: (10); b: (11)(Eq. 3)
A widely used example of electrophilic
quinone chemistry may be described as a tandem
reaction of acetic anhydride [31]. The result is
the reductive addition of acetate together with
esterification. This Thiele – Winter acetoxyla-
tion has been used productively, for example,
in the synthesis of the antitumor, antibiotic fred-
ericamycin A (Eq. 4) [32].
(Eq. 4)
The Meerwein arylation reaction has been re-
viewed [33] and support obtained for the impor-
tance of the semiquinone radical ion as an inter-
mediate [34]. The synthesis of natural products
has involved such radical arylations (Eq. 5) [35].
Benzoquinone 3
(Eq. 5)
4. Production of 1,4-Benzoquinone
A variety of quinones are available as fine or-
ganic chemicals and most of these are prepared
by standard oxidative procedures. Quinones of
higher oxidation potential such as chororanil
(4) (742 mV) or 2,3-dichloro-5,6-dicyano-1,4-
benzoquinone (5) (ca. 1000 mV) are often the
reagents of choice. There are many proposed
syntheses of 1,4-benzoquinone, but the oxida-
tion of aniline or phenol remains the practical
route. Steam distillation produces a high yield
and excellent purity [36]. Glucose is a possible
raw material for the preparation of quinones (Eq.
6) [37].
(Eq. 6)
The original preparation of the simplest
quinones by oxidation continues to be the prin-
cipal method for the commercial and labora-
tory synthesis of quinones [16, 17, 38]. The
use of ceric ammonium nitrate for the oxidation
of 1,4-dimethoxybenzene derivatives has been
used frequently and with great success in the
preparation of sensitive quinones. The synthesis
of blattellaquinone (gentisyl quinone isovaler-
ate) [849762-24-9], the sex pheromone of the
German cockroach is an important example [39].
5. Uses
Important uses of 1,4-benzoquinone include ap-
plications in the inhibition of polymerization,
determination of amino acids, and an additive
in adhesive mixtures. Additional uses include
4 Benzoquinone
research laboratory applications, especially ox-
idative syntheses, analytical methods, and bacte-
ricidal substances. Hydroquinone is important in
the photographic, dye, and leather industries and
is often prepared from 1,4-benzoquinone. Naph-
thoquinones are important as vitamin K substi-
tutes, fungicides, and antihemorragic agents.
6. Toxicology
Benzoquinone and many of its low molecular
mass derivatives have a high vapor pressure, a
penetrating odor, and present a health hazard
[40 – 42]. Quinone vapor and the quinone result-
ing from hydroquinone dust in moist air produce
eye injuries that can lead to appreciable loss of
vision. The odor of 1,4-benzoquinone is defi-
nite at concentrations of 0.1 – 0.15 ppm, and at
0.5 ppm it becomes irritating. Both the MAK
and TLV (TWA) are 0.1 ppm and 0.4 mg/m3 ; the
STEL is 0.3 ppm and 7 mg/m3 [43, 44]. How-
ever, Russia has fixed the threshold limit in air at
0.01 ppm [45]. Both solid quinones and their so-
lutions must be handled with care because they
can cause severe local damage to the skin and
mucous membranes [46, 47].
The limited carcinogenicity studies on 1,4-
benzoquinone conducted with mice and rats do
not permit definite classification, and it is listed
as a questionable carcinogen. Results for p-
chloranil are suggestive but inconclusive [48,
49].
7. References
Specific References
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Benzoquinone 5
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