Benzoquinone and Naphthoquinone Dyes 1

Benzoquinone and Naphthoquinone Dyes

John Griffiths, Department of Colour Chemistry, The University, Leeds LS2 9JT, United Kingdom

1. Introduction . . . . . . . . . . . . . . . . . 1 3.2. Heteroannelated 1,4-Naphthoquinones

2. Benzoquinone Dyes . . . . . . . . . . . . 1 3
3. 1,4-Naphthoquinone Dyes . . . . . . . . 2 4. 1,5-Naphthoquinones . . . . . . . . . . . 5
3.1. Simple 1,4-Naphthoquinones . . . . . . 2 5. References . . . . . . . . . . . . . . . . . . 6

1. Introduction est in these chromogens remains unabated, even

though they have failed to make any major im-
A large number of naphthoquinone and ben- pact as textile dyes.
zoquinone dyes occur naturally as plant con- Details of naphthoquinone and benzoquinone
stituents, and in the past many of these have dyes that have been marketed at one time or an-
found use as colorants. The chemistry of syn- other may be found in the Colour Index [2], and
thetic analogues began with the discovery of natural coloring matters of this type have been
naphthazarin (1) [475-38-7] by Roussin in discussed by Thomson [3]. Several reviews of
1861, which was followed ten years later by naphthoquinone and benzoquinone chemistry
the synthesis of naphthoxidine (the “naphthaz- have appeared [4 – 8].
arin intermediate”) (2) [27823-83-2] by De
Aguir and Bayer. Naphthazarin and its deriva-
tives first found use as black chrome mor-
dant dyes for wool and silk. In contrast to
the naphthoquinones, synthetic benzoquinone
dyes are few in number and are generally
of the 2,5-diarylamino-1,4-benzoquinone type,
suitable for application as vat dyes, e.g., Helin- 1 2
don Yellow CG (3) [4370-55-2], C.I. 56 005.
From about 1930 onwards, developments in
the field of naphthoquinone dyes concentrated
on the use of naphthazarin and naphthoxidine
as intermediates for the preparation of violet,
3
blue, and green acid and disperse dyes. Perhaps
the most successful of these was Artisil Blue
GFL (4), a blue dye for acetate fibers, introduced
by Sandoz in 1946. The many developments in
this area were reviewed by Merian in 1959 [1].
More recently there has been interest in the syn-
thesis and color and constitution properties of
4
simple colored naphthoquinones, stimulated by
the fact that such dyes have similar tinctorial
properties to the anthraquinones but a smaller
molecular size. The naphthoquinones provide a
useful alternative to the anthraquinones for cer- 2. Benzoquinone Dyes
tain specialized applications, e.g., as pleochroic
dyes with improved solubility for liquid crys- From the commercial point of view, only the 2,5-
tal display devices. As a result, research inter- diarylamino-1,4-benzoquinones have been of

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

10.1002/14356007.a03 575.pub2
2 Benzoquinone and Naphthoquinone Dyes

any significance, e.g., Helindon Yellow CG (3). rings. The spectroscopic effects of such substitu-
These were used as vat dyes for wool and cot- tions have been investigated in detail [13 – 16].
ton, but are no longer in commercial production. 2-Amino-1,4-naphthoquinones are generally
Other examples of early dyes of this type are yellow to red, with εmax values of ca. 2000 –
listed in the Colour Index under numbers 56 000 5000 L mol−1 cm−1 , depending on the nature
– 56 050. The inadequate color properties of of the substituents attached to the amino group
the amino-substituted benzoquinone chromogen and to the 3-position of the ring. In general, sub-
are exemplified by 2,5-bis(dimethylamino)-1,4- stituents in the 3-position cause a decrease in
benzoquinone [1521-02-4], which absorbs at intensity due to steric crowding, whereas N-aryl
530 nm in ethanol with an absorption coefficient groups induce a higher intensity. Typically, 2-
of only ca. 500 L mol−1 cm−1 . This low inten- phenylamino-1,4-naphthoquinone [6628-97-3]
sity is characteristic of the 2,5-disubstitution pat- has λmax 472 nm, εmax 4800 L mol−1 cm−1 . A
tern. Although other substitution patterns have now obsolete vat dye of this type is Helindon Red
higher intensities (e.g., the 2-amino derivatives CR (5) [3144-89-6], C.I. 56 050. Fluoro- and tri-
have εmax ca. 5000 L mol−1 cm−1 ), dyes based fluoromethylphenylamino analogues have been
on these have not been exploited. described for coloring wool and polyester [17].
More recently the 2,5-diamino-1,4-ben-
zoquinone dyes have found applications
other than as colorants. For example,
they form stable complexes with trans-bis-
(triphenylphosphine)phenylnickel(II) chloride,
and these have proved to be useful catalysts
for the polymerization of ethylene [9]. If 1,4-
benzoquinone is condensed with a diamine 5
under oxidizing conditions, polymeric 2,5-
diaminobenzoquinones are formed, and these
afford excellent anticorrosive coatings for steel
[10].
One or both of the carbonyl groups of the 1,4-
benzoquinone system have the potential to be re-
placed by imino groups, but the corresponding
dyes have received little attention until recently.
1,4-Benzoquinone monoimines with electron-
donating groups (e.g., alkylamino, alkoxy) in
the 2- or 2,5-positions provide useful red per-
manent hair dyes [11]. The color properties
of the 2,5-dialkylamino-1,4-benzoquinone di-
imines are more complex, and show an interest-
ing dependence of color on pH [12]. Thus, the
neutral species is yellow, the monoprotonated
form red, and the diprotonated form blue.
The 2-pyrrolyl derivatives A and B, formed
respectively by condensation of 1,4-naphtho-
quinone with N-methylpyrrole [18, 19] and 2,5-
3. 1,4-Naphthoquinone Dyes dimethylpyrrole [20], can be regarded as viny-
logues of the 2-amino-1,4-naphthoquinones.
3.1. Simple 1,4-Naphthoquinones Such compounds have proved useful as direct
Color can be produced in the 1,4-naphtho- dyes for hair [19, 20].
quinone chromogen by introduction of amino The more intensely colored 1,4-naphtho-
and hydroxyl groups into the quinonoid ring quinones with amino and/or hydroxyl groups
(i.e., positions 2 and 3), into the benzenoid ring in the 5- and 8-positions are analogous to
(more particularly positions 5 and 8), or into both the commercial anthraquinone dyes, but are
 Benzoquinone and Naphthoquinone Dyes
generally more bathochromic [14]. For ex-
ample, 5-methylamino-1,4-naphthoquinone has
λmax 529 nm in cyclohexane, whereas 1-
methylaminoanthraquinone has λmax 495 nm.
This is also true for the 5,8-disubstituted naph-
thoquinones, but this potential advantage has
not proved of commercial significance and few
such compounds have been considered as textile
dyes. An exception is 5-amino-2,3-dichloro-8-
hydroxy-1,4-naphthoquinone (6) [68217-33-4],
which has been claimed as a violet disperse dye
for acetate fibers [21]. Naphthazarin (1) is an
example of a 5,8-disubstituted naphthoquinone
of greater value as an intermediate than as a
dyestuff.
6 been reviewed extensively [6 – 8]. If X consists
When auxochromes such as −NHR or −OH
are present in both rings of the naphthoquinone
system, the absorption spectrum consists of two
overlapping bands, and this can result in dull
colors, typically blue-greys. A 3-cyano group
appears to counteract the dulling effect, and 7
[79469-30-0] has been described as a blue dye
for polyester [22].
7 then be produced in the usual way by attach-
There is considerable interest in 1,4-naphtho-
quinones that absorb in the near-infrared, partic-
ularly for application in optical recording ma-
terials and related high-technology areas. The
first simple near-infrared 1,4-naphthoquinone to
be described was the 5-amino-2,3-dicyano-8-
phenylaminoderivative (8, X = H) [68217-41-
4], which despite its relatively small molecu-
lar size has λmax at 770 nm in dichloromethane
[14]. The derivative 8 (X = C12 H25 ) has been
produced as Langmuir – Blodgett films which
can be written on with 830 nm laser light with
high sensitivity [23]. Other derivatives related
3
to 8 have been patented extensively for optical
recording discs [24] and have found commercial
use.
8
3.2. Heteroannelated
1,4-Naphthoquinones
A very large number of quinones of the gen-
eral structure 9 are known, where X corre-
sponds to a heterocyclic residue containing one
or more rings, and the chemistry of these has
of a benzenoid or azabenzenoid ring system,
then such compounds are best regarded as an-
thraquinone analogues. In the case of other het-
erocyclic residues, they may be considered as
1,4-naphthoquinone derivatives.
9
The simplest members of this group are those
where X is a monocyclic residue, such as furan,
thiophene, and pyrrole ring systems. Color may
ing auxochromes to the 5- and/or 8-positions.
Few dyes of this type have been suggested for
textile applications, presumably because their
chemistry is generally more complex than that of
comparable anthraquinones. It appears that the
color properties of such dyes differ only slightly
from those of related anthraquinone structures,
as exemplified by studies of imidazole dyes of
general structure 10 [25]. However, triazole dyes
of formula 11, where R1 to R3 are auxochromes,
have been patented as disperse dyes for polyester
[26].
4 Benzoquinone and Naphthoquinone Dyes
10
11
Of greater potential are dyes of general struc-
ture 9 in which X corresponds to a polycyclic
heterocyclic system, and a large number of these
have been examined as possible dyes and pig-
ments. Perhaps the most closely investigated
are the brazanquinones (12), which have been
known for more than eighty years. They can
be prepared readily by condensing 2,3-dichloro-
1,4-naphthoquinone [117-80-6] with substituted
phenols and naphthols. For example, arylamides
of 2-hydroxy-3-naphthoic acid, which are com-
mercially available as coupling components for
azoic dye combinations, condense to give yellow
and orange vat dyes (13) with good substantivity
for cotton [27].
12
13
The brazanquinone system has also been
used to provide disperse dyes by attaching aux-
ochromes to the benzene ring of the naphtho-
quinone moiety. Thiophene equivalents of the
brazanquinones have received much less atten-
tion. Disperse dyes of the type 14 proved to be
rather more bathochromic than corresponding
anthraquinones, but of lower intensity [28]. Pyr-
role analogues have also been neglected, but it is
interesting to note that the old dye Helindon Yel-
low R (15) [6451-05-4], C.I. 56 070, a vat dye
for cotton, is the parent compound of this type.
14
15
A different class of polycyclic naphtho-
quinone dyes is that based on the naphth[2,3-
b]indolizine-6,11-dione system (16), which
may be accessed readily by condensation
of 2,3-dichloro-1,4-naphthoquinone with ac-
tive methylene compounds in the presence of
pyridine [29], or by reaction of 2-methoxy-
3-pyridinio-1,4-naphthoquinone with an active
methylene compound [30]. In 16 the bridge-
head nitrogen atom acts as an effective aux-
ochrome and thus orange to red colors are ob-
served without further substitution. Derivatives
16 (R = amide group) are of particular value as
vat dyes and pigments. Related isomeric hetero-
cyclic structures have also attracted interest, e.g.,
17, a yellow disperse dye for polyester [31].
16
17
 Benzoquinone and Naphthoquinone Dyes
As with the simple 1,4-naphthoquinones,
research activity in the heteroannelated com-
pounds has been directed towards the de-
velopment of dyes that absorb in the near-
infrared. Noteworthy is the dithiadinaphtho-
1,4-naphthoquinone system 18 (X = S), which
can be prepared by condensing 2,3-dichloro-
5,8-dihydroxy-1,4-naphthoquinone with 2-
aminothiophenol [32]. The parent compound
18 (X = S) [96692-25-0] shows multiple ab-
sorption bands between 400 and 800 nm, with
the most intense peak at 725 nm in chloroform
(εmax 15 200 L mol−1 cm−1 ) [32]. Oxidation
of the sulfur atoms to SO groups produces a large
bathochromic shift, and 18 (X = SO) shows a
peak at 827 nm (εmax 17 600 L mol−1 cm−1 )
in chloroform [32].
18
4. 1,5-Naphthoquinones
Dyes of this class have the general formula
19, in which R1 and R2 may be hydrogen,
alkyl, or aryl groups. Historically and struc-
turally, naphthoxidine (2) may be regarded as
the parent compound; it is a violet-blue com-
pound possessing strong intramolecular hydro-
gen bonding and exhibiting solubility in organic
solvents and in water. This substance and its
N-substituted derivatives have been represented
variously as 1,5-naphthoquinones (19) and as
the tautomeric 1,4-naphthoquinone imines (20).
Naphthoxidine itself, for example, is listed un-
der two CAS registry numbers, i.e., [27823-
83-2] and [6259-68-3], for the 1,5-quinone and
the 1,4-quinone imine forms, respectively. Al-
though definitive structural evidence has yet to
be provided, the generally preferred formula-
tion is the former, and the exceptionally low
IR carbonyl frequencies of these compounds
(i.e., below 1600 cm−1 ) support this sugges-
5
tion. Such a low frequency would be charac-
teristic of a 1,5-naphthoquinone [33], particu-
larly if intramolecular hydrogen bonding were
present. Hydrogen bonding in a 1,4-quinone
structure such as 20 would not account for
such low frequencies, because, for example, 5-
amino-1,4-naphthoquinones show absorptions
for hydrogen-bonded carbonyl groups near 1630
cm−1 . In the following account, the 1,5-quinone
structure (19) will be assumed.
19
20
Naphthoxidine is a very useful intermediate
for dyes of this group, and it can be prepared
conveniently by reacting 1,5-dinitronaphthalene
with sulfur in oleum.
Procedure [34, 35]. A solution of sulfur (1.25 g)
in 20 % oleum (15 cm3 ) was added slowly over
35 min to a slurry of 1,6-dinitronaphthalene (2.5
g) in concentrated sulfuric acid (10 cm3 ), main-
taining the temperature at 50 – 55 ◦ C. The dark
brown mixture was stirred for a further 10 min
at this temperature and then for 30 min at 20
◦
C. The mixture was then poured onto ice (200
g) and the suspension filtered. The blue filtrate
was made alkaline with sodium hydroxide so-
lution, employing efficient external cooling in
order to keep the temperature below 40 ◦ C. The
resultant blue precipitate of the sodium salt of
naphthoxidine was filtered off and washed with
a little water. The solid was extracted with boil-
ing acetic acid, and concentration of the extracts
gave lustrous red needles of naphthoxidine (1.44
g, 68 %).
6 Benzoquinone and Naphthoquinone Dyes

The most successful naphthoxidine-derived

dye was Artisil Blue GFL (4) [26846-51-5],
which is prepared by bromination of naphthox-
idine in acetic acid in the presence of a catalytic
amount of iodine or iron. The commercial dye
is in fact a mixture of various brominated prod-
ucts, of which 4 is the predominant component.
The product is a clear blue disperse dye suitable
for acetate and polyester fibers.
22
Condensation of naphthoxidine with ary-
lamines results in replacement of one or both It is possible by modification of reaction con-
primary amino groups by the amine, and the re- ditions to effect the introduction of amino groups
sultant N-aryl derivatives are greener than 2 and into the 2-position of naphthoxidine, but this
can be used as disperse dyes. An example is Se- generally produces dyes with reduced purity of
tacyl Blue Green BS (19; R1 = 4-ethoxyphenyl, shade and of lower light fastness [1].
R2 = H) [1]. Arylamines react directly with 2 As in the case of the 1,4-naphthoquinones,
in acetic acid, but the reaction is unsuccessful there has been considerable interest in devel-
with alkylamines. The latter can be introduced oping near-infrared dyes of this class. The dye
by first reducing 2 to a stable leuco compound 23 [100012-51-9] is essentially the 1,5-quinone
with hydrosulfite and then condensing this with analogue of dye 18 (X = S) and shows a long-
the alkylamine. The product is then oxidized to wavelength peak at 750 nm in trichloromethane
give the quinone dye. It appears that monocon- (εmax 32 000 L mol−1 cm−1 ) [37]. Thus al-
densed dyes have greater affinity for cellulose though 23 has the same molecular mass as 18
acetate fibers than the bis-condensation prod- (X = S), it is both more bathochromic and more
ucts. Interest in the latter has been stimulated by intensely absorbing.
the discovery that such compounds can provide
useful dyes for liquid crystal display devices and
exhibit high-order parameters (i.e., contrast ra-
tios). For example, the compound 19 with R1 =
R2 = 4-methoxyphenyl is a blue-green dye pro-
viding an excellent contrast ratio in liquid crystal
media [36].
Brominated condensation products can be
obtained by using appropriately halogenated
naphthoxidine intermediates, e.g., 4. For ex-
23
ample, 4 may be condensed with aniline in
acetic acid at 90 ◦ C to give 21 [1]. Naphthox-
idine and its brominated derivatives may also
be condensed with aminoazo compounds, giv-
5. References
ing mixed azo – quinone chromogens, e.g., 22. General References
These are of interest as homogeneous green dyes
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3. R. H. Thomson: Naturally Occurring
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4. Houben-Weyl, 7 (3 a).
5. S. Patai (ed.): The Chemistry of the Quinoid
21 Compounds, parts 1 and 2, J. Wiley & Sons,
London–New York 1974.
 Benzoquinone and Naphthoquinone Dyes
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7
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