Benzoquinone 1

Benzoquinone
K. Thomas Finley, State University of New York, Brockport, New York, United States

1. Introduction . . . . . . . . . . . . . . . . 1 5. Uses . . . . . . . . . . . . . . . . . . . . . 3
2. Physical Properties . . . . . . . . . . . 2 6. Toxicology . . . . . . . . . . . . . . . . . 4
3. Chemical Properties . . . . . . . . . . . 2
4. Production of 1,4-Benzoquinone . . . 3 7. References . . . . . . . . . . . . . . . . . 4

1. Introduction none (3) [553-97-9]. The CAS nomenclature

of the quinones, e.g., 2,5-cyclohexadiene-1,4-
In 1838 the parent compound 1,4-benzoqui- dione for 1, is seldom used. Trivial names like
none (1) [106-51-4] was prepared by oxida- p-benzoquinone and p-tolyquinone (3) exist and
tion of quinic acid [36413-60-2] with maga- are used occasionally. Two very useful oxidiz-
nese dioxide [1]. More than half a century later ing agents are universally known by a trivial
its much less stable isomer, 1,2-benzoquinone name and an acronym: p-chloranil [118-75-2]
(2) [583-63-1] was obtained by silver ion ox- (4) (2,3,5,6-tetrachloro-1,4- benzoquinone) and
idation of catechol [120-80-9] [2]. Since then DDQ [84-58-2] (5) (2,3-dichloro-5,6-dicyano-
these colorful and reactive compounds have oc- 1,4-benzoquinone).
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, 4 5
including addition and cycloaddition reactions,
photochemistry, biochemistry, oxidative chem- This lack of widespread concensus con-
istry, and electrochemistry [9 – 19]. 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
1 2 3 principal entry for 2-isopropyl-5-methyl-1,4-
benzoquinone [490-91-5].
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-
6 7
erage of many other structural types.
1,4-Benzoquinones can be substituted by a A few compounds with no apparent re-
wide variety of alkyl, aryl, halo, oxygen, nitro- lationship to quinones continue to be mis-
gen, and sulfur groups. They are usually named named, e.g., camphorquinone [10373-78-1]
as derivatives of 1, e.g., 2-methyl-1,4-benzoqui- (2,3-camphandione).

c 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a03 571.pub2
2 Benzoquinone

2. Physical Properties dation states of sulfur are interesting in biochem-

istry [24] and photography [25]. The protonated
1,4-Benzoquinone (1), C6 H4 O2 , M r 108.10, mp quinone is the reactive species, a fact that is sup-
113 ◦ C, d20 20
4 1.318, pv 12 Pa, is soluble in most ported by the product distribution observed with
oxygenated organic solvents (ether, alcohol, ace- 2-methyl-1,4-benzoquinone (Eq. 1). While 2,5-
tone), and hot ligroin, slightly soluble in pentane, addition (8) is favored by both resonance and
and insoluble in water. Crystallization from al- molecular orbital arguments, the 2,6-product (9)
cohol or sublimation produces yellow monoclin- is obtained in a 3:1 ratio.
ic prisms. It has also been shown that the product distri-
1,2-Benzoquinone (2), C6 H4 O2 , M r 108.10, bution in this reaction can be strongly influenced
mp 60 – 70 ◦ C (decomp.), crystallizes in red by changes in acidity and solvent mixture [26].
plates or prisms. It is much less stable than 1, Furthermore, the use of ionic liquids shows great
e.g., it decomposes in water. Compound 2 is sol- promise as “green” solvents [27] in this chem-
uble in ether, acetone, and benzene, but insoluble istry. When the acidity or solvent is varied, the
in pentane. relative yields of 8 and 9 can change dramati-
2,3,5,6-Tetrachloro-1,4-benzoquinone (4), p- cally [26]. Over the pH range 1 to 4.5 in aqueous
chloranil, C6 Cl4 O2 , M r 245.88, mp 290 ◦ C buffers one observes the 9/8 ratio changing from
(sealed tube); and 2,3-dichloro-5,6-dicyano-1,4- 4:1 to 2:3. In a similar fashion this same ratio is
benzoquinone (5), DDQ, M r 227.01, mp 213 – 9:1 with absolute ethanol as the solvent and 2:3
216 ◦ C are yellow to bright yellow in color and when carried out in 50% aqueous acetic acid.
crystallize as monoclinic prisms and plates. This same reaction (Eq. 1) has been studied in
These and most other low molecular mass ionic liquids [27]. The 9/8 ratio almost exactly
benzoquinones have high vapor pressures and reverses to 1:8.5. These interesting media are
pungent, irritating odors. being promoted as much more environmentally
friendly green solvents.

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
a:
history; similar radical and electrophilic reac-
tions offer important alternative and often com- (8); b: (9)(Eq. 1)
plementary synthetic routes [9 – 11]. The syn-
thesis of natural products [21] and polycyclic With a single electron-withdrawing sub-
aromatic compounds [22] shows quinones to be stituent 2,3-addition provides the major product
important dienophiles for Diels – Alder chem- [28]. This observation has been exploited as an
istry. When additions fail to achieve the desired important route to heterocyclic molecules as il-
result, substitution reactions are often the route lustrated in Equation 2.
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 (Eq. 2)
and sulfite anion addition [23]. These other oxi-
 Benzoquinone 3

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 (Eq. 5)
[30].

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
a: (10); b: (11)(Eq. 3) route. Steam distillation produces a high yield
and excellent purity [36]. Glucose is a possible
raw material for the preparation of quinones (Eq.
A widely used example of electrophilic 6) [37].
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- (Eq. 6)
ericamycin A (Eq. 4) [32].
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-
(Eq. 4) ate) [849762-24-9], the sex pheromone of the
German cockroach is an important example [39].

The Meerwein arylation reaction has been re-

viewed [33] and support obtained for the impor- 5. Uses
tance of the semiquinone radical ion as an inter-
mediate [34]. The synthesis of natural products Important uses of 1,4-benzoquinone include ap-
has involved such radical arylations (Eq. 5) [35]. 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- 6. T. Laird: “Quinones,” in J. F. Stoddart (ed.):

idative syntheses, analytical methods, and bacte- Comprehensive Organic Chemistry, the
ricidal substances. Hydroquinone is important in Synthesis and Reactions of Organic
the photographic, dye, and leather industries and Compounds, vol. 1, Chap. 5.5, Pergamon
is often prepared from 1,4-benzoquinone. Naph- Press, Oxford 1979.
thoquinones are important as vitamin K substi- 7. R. H. Thomson: Naturally Occurring
tutes, fungicides, and antihemorragic agents. Quinones, 3rd ed., Chapman & Hall, London
1987.
8. R. H. Thomson, in J. ApSimon (ed): The Total
Synthesis of Natural Products, Vol. 8, John
6. Toxicology Wiley & Sons, Inc., New York 1992.
9. K. T. Finley: “The Addition and Substitution
Benzoquinone and many of its low molecular Chemistry of Quinones,” Chap. 17, in [3].
mass derivatives have a high vapor pressure, a 10. K. T. Finley: “Quinones as Synthones”, Chap.
penetrating odor, and present a health hazard 11, in [4].
[40 – 42]. Quinone vapor and the quinone result- 11. K. T. Finley, in S. Patai (ed.): Supplement E:
ing from hydroquinone dust in moist air produce The Chemistry of Hydroxyl, Ether and
eye injuries that can lead to appreciable loss of Peroxide Groups, vol. 2, John Wiley & Sons,
vision. The odor of 1,4-benzoquinone is defi- Inc., New York 1993, pp. 1027 – 1134.
nite at concentrations of 0.1 – 0.15 ppm, and at 12. J. M. Bruce: “Photochemistry of Quinones,”
0.5 ppm it becomes irritating. Both the MAK Chap. 9, in [3].
and TLV (TWA) are 0.1 ppm and 0.4 mg/m3 ; the 13. K. Maruyama, A. Osuka, “Recent Advances of
STEL is 0.3 ppm and 7 mg/m3 [43, 44]. How- the Photochemistry of Quinones,” Chap. 13, in
ever, Russia has fixed the threshold limit in air at [4].
0.01 ppm [45]. Both solid quinones and their so- 14. R. Bentley, I. M. Campbell: “Biological
Reactions of Quinones,” Chap. 13, in [3].
lutions must be handled with care because they
15. H. Inouye, E. Leistner: “Biochemistry of
can cause severe local damage to the skin and
Quinones,” Chap. 22, in [4].
mucous membranes [46, 47]. 16. H.-D. Becker: “Quinones as Oxidants and
The limited carcinogenicity studies on 1,4- Dehydrogenating Agents,” Chap. 7, in [3].
benzoquinone conducted with mice and rats do 17. H.-D. Becker, A. B. Turner: “Quinones as
not permit definite classification, and it is listed Oxidants and Dehydrogenating Agents,”
as a questionable carcinogen. Results for p- Chap. 23, in [4].
chloranil are suggestive but inconclusive [48, 18. J. Q. Chambers: “Electrochemistry of
49]. Quinones,” Chap. 14, in [3].
19. J. Q. Chambers: “Electrochemistry of
Quinones,” Chap. 12, in [4].
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