Methods for dyeing hair with anthraquinone hair dyes having a quaternary ammonium side chain

Anthraquinone compounds of formula I ##STR1## wherein R.sub.1 and R.sub.2 are methyl and R.sub.3 is propyl, or R.sub.1 and R.sub.2 are ethyl and R.sub.3 is methyl and A.sup.- is a cosmetically acceptable anion, are useful for the dyeing of hair. Compounds of formula I may advantageously be employed with direct dyes. Compositions and a method of use employing same are disclosed.

DISCUSSION OF THE PRIOR ART 
Anthraquinone compounds having a quaternary ammonium side chain and their 
use as hair dyes are known in the art. The prior art appreciates that 
there would be problems in formulating a hair dye product with dyes that 
have different rates of dye uptake and that positively charged dyes (i.e. 
basic dyes) have qualitatively different rates of dye uptakes than typical 
neutral semipermanent dyes (i.e. direct dyes). However, it is totally 
unappreciated that minor variations in the side chain containing the 
quaternary ammonium group can vary the dye uptake rate (as indicated by 
the color change on hair) sufficiently so that dyes with certain groups 
will dye at rates similar to an uncharged semipermanent dye. In point of 
fact in the hair conditioning art, wherein cationic materials are 
employed, there is a teaching that would lead one skilled in the art to 
conclude that modifications in the side chain of the cationic material 
will have no effect on the rate of adsorption onto the hair. 
U.S. Pat. No. 4,964,874 describes some of the problems associated with 
formulating a product with both basic dyes and neutral dyes. Patentees 
teach that when using certain basic dyes, color uptake by the hair is 
rapid in that only a short treatment time of a few minutes is needed to 
achieve a moderate darkening of the hair. Unacceptable hand staining can, 
however, occur when the concentration of the basic dye is sufficiently 
high to achieve adequate dyeing. 
Patentees also teach that when using certain neutral dyes, uniform dye 
coverage can be obtained, but the color uptake by the hair is slower than 
with basic dyes, in that a longer treatment time is needed to achieve a 
moderate darkening of the hair. Patentees state that little or no hand 
staining is experienced with neutral dyes at concentrations sufficient to 
give adequate dyeing which is usually higher than that of the basic dye. 
Differences in rates of dye uptake can lead to another problem. Many 
hairdye formulations are made by a combination of yellow, red and blue 
dyes, in different amounts and ratios. In order to incorporate a new dye 
into an existing product, its rate of dyeing must be comparable to the 
other dyes in that particular formulation. If a hair dye product 
containing individual dyes which are picked up by hair at significantly 
different rates, is applied to the hair, the shade (i.e. the color as 
opposed to the intensity) will change through several stages with the 
passing of time. For example, if the product contains blue, yellow and red 
dyes with the blue dye dyeing the fastest, the yellow dye dyeing at an 
intermediate rate and the red dye dyeing the slowest, initially, the hair 
will be bluish. After a certain period of time, the hair will turn 
greenish (blue plus yellow) and, finally, when the red dye imparts its 
color, the hair might exhibit a brown coloration. Although this is an 
exaggerated case even smaller variations would be totally unacceptable 
(i.e. from a bluish brown to a greenish brown). Clearly, from a consumer's 
point of view, a product which dyes hair in such a manner is undesirable 
because the consumer would never be sure of obtaining the hair color that 
he or she wants or even the same color from the same formulation. 
Obtaining the exact color is a crucial factor for a hairdye product and 
this is why most products offer between 25 and 50 different shades. 
In a recent paper, C. R. Robbins et al (J. Soc. Cosmet. Chem. 45(2), 85-94, 
(1994)), report the results of a study of the adsorption onto hair of the 
following cationic surfactants. 
##STR2## 
They report that at a pH higher than hair's isoelectric point, all of 
these hair conditioners had the same adsorption in 10 minutes. This 
teaching demonstrates that modification of the alkyl groups of the 
quaternary ammonium conditioners has no effect on the rate of their 
adsorption of such conditioners onto hair. As a consequence of this 
teaching, one skilled in the art would expect that modification of the 
alkyl groups on basic anthraquinone dyes would, like the conditioning 
agents of this reference, have little or no effect on dye uptake. 
British patent 909,700 discloses a method of dyeing human hair. A wide 
range of dyes having cationic charges is disclosed. Among such dyes are 
the compounds of Examples 17 and 2. Their respective structures are as 
follows: 
##STR3## 
Hair was only dyed with mixtures of compounds containing quaternary 
ammonium groups. These dyes were never tested with standard nitro dyes. 
U.S. Pat. No. 3,817,698 discloses a dye formed by a covalent bond between 
two dye compounds. In Example 10, patentees disclose the compound: 
##STR4## 
Patentee state, at column 7, lines 11-24, that "It is known that the 
technique for dyeing different natural and synthetic fibers is based on 
the use of a greater or smaller number of individual dyes used 
collectively. The action of such mixtures during the dyeing often poses 
serious problems, particularly as concerns the harmonization of the 
different affinities of dyes used simultaneously and harmonization of the 
speed with which they act on the fibers and of their fastness to washing. 
Consequently, users frequently discover significant difficulties as much 
from the point of view of the formulation of these mixtures as from the 
point of view of their application. Use of dyes according to the invention 
partly solves the problem since a single dye has the tinctorial properties 
of the two dyes from which it was formed." 
British patent 1,053,535 discloses a dyestuff of the formula: 
##STR5## 
in which n is an integer from 2 to 6 and R, R' and R" are the same or 
different and each represents an alkyl of 1 to 3 carbon atoms, such as, 
for example, methyl or ethyl. Alternatively, R, and R', together with the 
adjacent nitrogen atom, can represent a saturated monocyclic heterocyclic 
radical, especially a morpholino or piperidino radical. All of the 
examples describe hair dyeing with compositions containing only the dye 
described above and the problem of different rates of uptake is not 
mentioned. 
British patent 1,053,536 is closely related to British patent 1,053,535, 
except that the dyestuffs of the '536 patent contain no hydroxyl 
substituent on the ring and the substituted amino alkyl amino group is at 
the 2' rather than the 1' position on the ring. 
(2-Anthraquinonylaminoethyl)-diethylmethylammonium methylsulfate and 
(2-anthraquinonylaminopropyl)-diethylmethylammonium methylsulfate are 
examples of the dyestuffs disclosed. Like British Patent 1,053,535, 
British Patent 1,053,536 does not refer to the problem of different rates 
of dye uptake. 
U.S. Pat. No. 3,531,502 discloses 
1-hydroxy-2,4-bis-(p-dimethylaminophenyl)aminoanthraquinone and a 
quaternary salt having the formula 
##STR6## 
in which R.sub.1 is C.sub.1-4 lower alkyl and A.sup.- is an anion. Such 
compounds are disclosed to have utility as hair dyes. 
U.S. Pat. No. 3,692,461 is related to U.S. Pat. No. 3,531,502 and directed 
to hair dye composition comprising a solvent and the quaternary ammonium 
salt of U.S. Pat. No. 3,531,502. In both the '461 patent and the '502 
patent, there is only one example (#7) in which these dyes are mixed with 
an uncharged dye and since this solution was dyed for one length of time, 
the problem of different rates of dye uptake would not be apparent. 
British patent 1,205,365 claims anthraquinone derivatives of the formula 
##STR7## 
in which one X is hydrogen and the other X is --NH(CH.sub.2).sub.n Y 
wherein n is 2 to 6 and Y is --NR.sup.1 R.sup.2, where R.sup.1 and R.sup.2 
are alkyl groups having from 1 to 4 carbon atoms or, together with the 
nitrogen atom to which they are attached, form a saturated heterocyclic 
ring which may contain an additional heteroatom, or Y is an aromatic 
heterocyclic ring attached to the alkylene chain --(CH.sub.2).sub.n -- 
though a carbon atom. Also, encompassed are the acid addition and 
quaternary ammonium salts of such compounds. The compounds are disclosed 
to be useful for dyeing keratinaceous fibers. Included among such 
anthraquinone derivatives are 1-amino-5-(.gamma.-piperidinopropylamino) 
anthraquinone, 1-amino-5-.gamma.-trimethylaminopropylamino) anthraquinone 
methylsulfate and 
1-amino-8-(.gamma.-trimethylaminopropylamino)anthraquinone methylsulfate. 
All of the examples describe hair dyeing with only one dye at a time. The 
dyes which were employed are the subject of the patent. 
Ger. Offen. 2,026,096 discloses anthraquinone hair dyes having the 
structure 
##STR8## 
wherein R or R.sup.1 is amino and X.sup.+ is N.sup.+ (CH.sub.3).sub.3, 
1-methylpiperidinio or 1-methylpyridinium-2-yl and n is 2 or 3. The 
compounds dye human hair dark red to reddish violet shades. The dyes of 
this patent were tested individually and there is no appreciation that 
that the rate of dye uptake for such dyes differ from typical 
semipermanent dyes. 
U.S. Pat. No. 4,226,784 discloses 2- and 5- aminoalkylamino anthraquinone 
dyes useful as basic dyes in coloring hair. The compounds conform to the 
formula A--NR--(CH.sub.2).sub.n --NHR', wherein R and R' are hydrogen, n 
is 2 to 6 and A is anthraquinonyl (in which case the NR--(CH.sub.2).sub.n 
--NHR' chain is in position 2 of the anthraquinonyl) or A is an 
anthraquinonyl of the formula 
##STR9## 
wherein R.sub.1 and R.sub.2 are selected from the group consisting of 
hydrogen and lower alkyl and NR--(CH.sub.2).sub.n --NHR' occupies position 
5 of the anthraquinonyl. 2-.beta.-Aminoethylamino anthraquinone and 
1,4-diamino-5-.gamma.-aminopropylamino anthraquinone are specifically 
disclosed. Different rates of dye uptake are not mentioned in this patent 
but of the ten hair dyeing examples cited, five contain only one dye, four 
are mixed with other dyes that have the same side chain and in only one 
case (Example #10) are these dyes mixed with a typical semipermanent dye 
(1-amino-2-nitro-4-methylamino benzene). Therefore, the problem of 
different rates of dye uptake would not have been apparent. 
U.S. Pat. No. 3,806,525 discloses a basic anthraquinone dye for keratinic 
fibers. The dye conforms to the formula 
##STR10## 
in which n is 2 to 6. The problem of dye uptake at different rates is not 
mentioned. Only two examples of hair dyeing are described. One example 
uses only a one dye composition and the other uses two dyes with similar 
side chains. 
British patent 1,159,557 is related to U.S. Pat. No. 4,226,784. Patentees 
disclose in the '557 patent a composition suitable for dyeing keratinic 
fibers, particularly human hair. The composition comprises a solution of 
at least one compound of the formula A--NR--(CH.sub.2).sub.n --NHR' in 
which each of R and R' is independently hydrogen, lower alkyl or lower 
hydroxy alkyl; n is 2 to 6; and A is either an anthraquinone radical of 
the formula 
##STR11## 
in which case R represents a hydrogen atom, and Z' is hydrogen or 
--NHR.sub.1 wherein R.sub.1 is hydrogen or lower alkyl; and Z is hydrogen 
or --NRR" wherein R is as previously defined and R" is hydrogen, lower 
alkyl or --(CH.sub.2).sub.n --NHR' in which R' and n are as previously 
defined, the chain NR(CH.sub.2).sub.n --NHR' occupying on the 
anthraquinone nucleus either the 1- position, in which case the radical Z' 
is a hydrogen atom and the radical Z, unless it is hydrogen, may occupy 
only the 4-, 5- or 8- position; or the NR(CH.sub.2).sub.n --NHR' chain 
occupies on the anthraquinone nucleus the 2-position, in which case the 
radical R' and the radicals Z and Z' are all hydrogen; or the 
NR(CH.sub.2).sub.n NHR' chain occupies the 5- position on the 
anthraquinone nucleus, in which case the radical R' is hydrogen, and the 
radical Z' is NHR.sub.1 in the 4- position, R.sub.1 being as previously 
defined, and Z is --NHR.sub. 2 in the 1- position, R.sub.2 being hydrogen 
or lower alkyl. As with the '784 patent, the problem of dye uptake at 
different rates is not mentioned. 
U.S. Pat. No. 3,661,500 discloses hair dyeing compositions containing as 
the hair coloring agent 
##STR12## 
in which R is hydrogen, methyl or ethyl. The examples (e.g. Example #9-12) 
of this patent vividly illustrate the problems that can occur because of 
different rates of dye uptake. In these examples, the dyes, their 
concentrations and the hair are all the same but the above positively 
charged dye was mixed with typical semipermanent dyes 
(2-nitro-p-phenylenediamine and 4-nitro-m-phenylenediamine). The only 
differences between these examples are minor differences in the thickener 
of the base. Yet, four different colors were obtained: (Example #9) dark 
greyish brown; (Example #10) medium brown; (Example #11) dark grey; 
(Example #12) dark ash brown. The dyeing times were not cited and it may 
be that there were differences and these may account for the color 
changes. 
In French patent of addition 1,422,016, compounds of the formula 
##STR13## 
where one of X or Y is H and the other is --HN--p--C.sub.6 H.sub.4 
--N(CH.sub.3).sub.2 or an aminoalkylene-N-morpholino are treated with 
dimethyl sulfate to give bis-quaternary ammonium salts which dye hair 
violet red to green shades. Bis-quaternary ammonium salts having the 
following structures are disclosed: 
##STR14## 
There is no indication that the rate of dye uptake was appreciated and 
each example uses only one dye. 
U.S. Pat. No. 5,314,505 discloses aminoanthraquinone hair dyes having a 
quaternary center with a long aliphatic chain. Such dyes conform to the 
general formula Q--NR.sub.6 (CH.sub.2).sub.n N.sup.+ R.sub.1 R.sub.2 
R.sub.3 X.sup.- wherein Q can be 
##STR15## 
wherein R is hydrogen, C.sub.1-6 alkyl, C.sub.1-6 hydroxyalkyl, C.sub.1-6 
polyhydroxyalkyl, halogen, C.sub.1-6 alkoxy, halogenated C.sub.1-3 alkyl, 
polyhalogenated C.sub.1-3 alkyl, CN, CONH.sub.2, SO.sub.3 H or COOH; R is 
C.sub.1-6 alkyl, C.sub.1-6 hydroxyalkyl or C.sub.1-6 polyhydroxyalkyl; 
R.sub.2 is C.sub.1-6 alkyl, C.sub.1-6 hydroxyalkyl or C.sub.1-6 
polyhydroxyalkyl; R.sub.3 is C.sub.8-22 aliphatic chain; R.sub.4 and 
R.sub.5 are independently, hydrogen, C.sub.1-6 alkyl, C.sub.1-6 
hydroxyalkyl or C.sub.1-6 polyhydroxyalkyl or together with N, a 5 or 6 
member heterocyclic ring; R.sub.6 is hydrogen, C.sub.1-6 alkyl, C.sub.1-6 
hydroxyalkyl or C.sub.1-6 polyhydroxyalkyl; n is 2 to 12; and p, q, x and 
y are independently 0, 1 or 2. Again, each example uses only one dye and 
the problem of different rates of dye uptake is unappreciated by 
patentees. 
As is evident from U.S. Pat. Nos. 5,314,505, 5,298,029, 5,256,823, 
5,198,584, 5,169,403, 5,139,532 and 5,135,543 there is continued interest 
in hairdyes with side chains containing quaternary ammonium salts. As 
noted above, the prior art does appreciate that incorporating in a single 
formulation dyes having different rates of dye uptake can present a 
serious problem to product performance. Considering the paucity of 
information on the rate of dye uptake, it is not hard to understand that 
there has been no appreciation prior to the present disclosure that minor 
changes in the quaternary ammonium side chain of a basic dye can 
significantly effect the rate of dye uptake. The teaching of the Robbins 
et al paper discussed earlier indicates that it would not. 
The present invention provides novel anthraquinones having a quaternary 
ammonium side chain. The compounds of the invention are useful as hair 
dyes and, more particularly, as semipermanent blue hair dyes in 
formulations containing neutral semipermanent dyes. 
The novel compounds of the instant invention have the structures: 
##STR16## 
Formula I emcompasses the novel compounds Ia and Ib as follows: 
##STR17## 
The anthraquinones of formula I surprisingly dye hair at a rate such that 
they can be used in formulations containing typical neutral semipermanent 
dyes. 
It should be noted that as used throughout this specification and claims 
A.sup.- connotes a cosmetically acceptable anion such as a halide e.g. 
iodide, chloride, bromide, fluoride, an alkylsulfate e.g. methylsulfate, 
or an alkylcarboxylate e.g. acetate. Iodide is the most preferred. 
The compounds of Tables 1 and 2 (including compounds I and II of the 
present invention) were synthesized by the following general procedure. 
##STR18## 
1-Bromo-1-methylaminoanthraquinone was prepared by bromination of 
1-methylaminoanthraquinone with N-bromosuccinimide in DMF at 4.degree. C. 
An Ullman type substitution on 1-bromo-1-methylamino-anthraquinone was 
performed with 20 wt % copper powder and 3-dimethylaminopropylamine (or 
3-diethylaminopropylamine) in DMSO at 80.degree. C. to produce compound C 
(wherein R.sub.1 and R.sub.2 are methyl when 3-dimethylaminopropylamine is 
employed or R.sub.1 and R.sub.2 are ethyl when 3-diethylaminopropylamino 
is employed). The reaction mixture was hot filtered through Celite to 
remove the insoluble copper. Quaternization of compound C (wherein R.sub.1 
and R.sub.2 are methyl or R.sub.1 and R.sub.2 are ethyl) was performed in 
DMF with various iodoalkanes (see Tables I and II) to afford compound D.

EXAMPLE 1 
##STR19## 
The resultant compound so produced had a melting point of 
192.5.degree.-193.6.degree. C. and the following H.sup.1 NMR: 
(300 MHz, DMSO-d6) .delta. 2.99 (d, 3H, J=4.8 Hz), 7.11 (d, 1H, J=9 Hz), 
7.79-7.89 (m, 3H), 8.06-8.13 (m, 2H), 9.87 (bs, 1H, exchange with D.sub.2 
O). 
EXAMPLE 2 
##STR20## 
The resultant compound so produced had a melting point of 
111.0.degree.-112.5.degree. C. and the following H.sup.1 NMR: 
(300 MHz, DMSO-d6) .delta. 1.76 (m, 2H), 2.13 (s, 6H), 2.31 (m, 2H), 3.05 
(t, 3H, J=5.0 Hz), 3.44 (t, 2H, J=2.4 Hz), 7.41-7.53 (m, 2H), 7.74-7.78 
(m, 2H), 8.20-8.23 (m, 2H), 10.65 (bs, 1H, exchange with D.sub.2 O), 10.84 
(bs, 1H, exchange with D.sub.2 O). 
EXAMPLE 3 
##STR21## 
The resultant compound so produced had a melting point of 
227.0.degree.-228.3.degree. C. and the following H.sup.1 NMR: 
(300 MHz, DMSO-d6) .delta. 0.87 (t, 3H, J=7 Hz), 1.63-1.71 (m, 2H), 
2.06-2.09 (m, 2H), 3.01 (s, 6H), 3.07 (d, 3H, J=5 Hz), 3.23 (m, 2H), 3.36 
(m, 2H) 3.53 (m, 2H), 7.44-7.56 (m, 2H), 7.77-7.80 (m, 2H), 8.21-8.24 (m, 
2H), 10.60 (m, 1H, exchange with D.sub.2 O), 10.78 (m, 1H exchange with 
D.sub.2 O). 
EXAMPLE 4 
##STR22## 
The resultant compound so produced had a melting point of 
160.2.degree.-161.7.degree. C. and the following H.sup.1 NMR: 
(300 MHz, DMSO-d6) .delta. 0.80 (s, 3H), 1.19 (s, 8H), 1.59-1.60 (s, 2H), 
2.04-2.05 (s, 2H), 3.01(s, 6H), 3.07-3.08 (d, 4H), 3.24-3.26 (m, 3H), 
3.52-3.53 (m, 2H), 7.44-7.56 (m, 2H), 7.78-7.80 (m, 2H), 8.22-8.23 (m, 
2H), 10.61 (d, 1H, exchange with D.sub.2 O), 10.79 (s, 1H, exchange with 
D.sub.2 O). 
EXAMPLE 5 
##STR23## 
The resultant compound so produced had a melting point of 
70.0.degree.-71.7.degree. C. and the following H.sup.1 NMR: 
(300 MHz, DMSO-d6) .delta. 0.91-0.96 (t, 6H), 1.68-1.78 (m, 2H), 2.41-2.48 
(m, 6H), 3.05-3.07 (d, 3H), 3.42-3.48 (m, 2H), 7.42-7.52 (m, 2H), 
7.75-7.78 (m, 2H), 8.20-8.23 (m, 2H) , 10.64-10.66 (d, 1H, exchange with 
D.sub.2 O), 10.83-10.87 (t, 1H, exchange with D.sub.2 O). 
EXAMPLE 6 
##STR24## 
The resultant compound so produced had a melting point of 
176.0.degree.-177.7.degree. C. and the following H.sup.1 NMR: 
(300 MHz, DMSO-d6) .delta. 1.20 (t, 6H, J=7 Hz), 2.03 (m, 2H), 2.92 (s, 
3H), 3.07 (d, 3H, J=5 Hz), 3.31 (m, 6H), 3.54 (m, 2H), 7.45-7.57 (m, 2H), 
7.77-7.80 (m, 2H), 8.21-8.23 (m, 2H) , 10.60 (bs, 1H, exchange with 
D.sub.2 O) , 10.78 (bs, 1H, exchange with D.sub.2 O). 
EXAMPLE 7 
##STR25## 
The resultant compound so produced had a melting point of 
180.0.degree.-183.8.degree. C. and the following H.sup.1 NMR: 
(300 MHz, DMSO-d6) .delta. 1.14-1.18 (t, 8H), 1.96-2.01 (m, 2H), 3.07-3.09 
(d, 3H), 3.21-3.28 (m, 9H), 3.53-3.55 (m, 2H), 7.45-7.57 (m, 2H), 
7.77-7.81 (m, 2H), 8.21-8.23 (m, 2H), 10.61-10.62 (d, 1H, exchange with 
D.sub.2 O), 10.78-10.82 (t, 1H, exchange with D.sub.2 O). 
All compounds (except for the heptyl compounds) were purified by 
recrystallization from isopropyl alcohol and water or methanol. The heptyl 
compound was used without recrystallization. After recrystallization, they 
were then dried under vacuum over P.sub.2 O.sub.5 at 65.degree. C. 
overnight and analyzed by HPLC. That analysis showed the purity to be at 
least 90%. Tresses of Piedmont hair weighing 1.25 g were dyed for time 
specified at room temperature with 10 g of 0.5% solutions of 
4-(N,N,N-trialkyl-3'-ammonium-n-propylamino)-1-methylamino-anthraquinone 
iodide in a commercially available hair dye base. It should be noted that 
as used herein, unless otherwise indicated, percent means percent by 
weight and is based on the total weight. The dyed tresses were rinsed 
under tap water for 1-2 minutes and dried. The tristimulus reflectance 
values of the dyed swatches were determined by means of a Hunterlab 
LabScan 6000 0.degree./45.degree. Spectrocolorimeter. Untreated swatches 
were used as a control. The results are reported in Table 1 which follows. 
It should be noted that "L" represents the intensity of the color and "a 
and b" represent the relative purity of the color with "a" being the 
relative greenness or redness of the color and "b" being the relative 
yellowness or blueness of the color. .DELTA.E, shown in Table 2, is the 
total color difference and is defined by the equation: 
##EQU1## 
.DELTA.'s (e.g. .DELTA.L, .DELTA.a, .DELTA.b) refer to the change in that 
parameter for some operation. For example, .DELTA.L for 0.fwdarw.15 
minutes is the change in L on dyeing from 0 minutes to 15 minutes. It 
should be further noted that in Table 1, the Piedmont hair had the 
following Hunter Reflectance Values prior to being dyed with the test 
compounds: L=69.4, a=-0.7, b=21.8 
From the Hunter reflectance values in Table 1 and the .DELTA.E's in Table 
2, it can be seen that almost all of the dye uptake of the trimethyl 
compound occurs in the first 15 minutes. At 30 minutes, the color of hair 
dyed with the trimethyl compound stops changing. In comparison (by 
examining principally .DELTA.E's in Table 2), HC Blue 2 initially does not 
dye as rapidly but then keeps on dyeing even at 60 minutes. At first 
glance, it may appear from Table 1 that the trimethyl compound and HC Blue 
2 are more similar than the other compounds to HC Blue 2. This is due to 
the similarity of the L values. However, this is misleading because these 
anthraquinones are bright blue while HC Blue 2 is actually violet. 
.DELTA.E is a much better indicator when different colors are involved. 
The data of Table 2 shows how much more rapid the dye uptake is for the 
trimethyl compound (.DELTA.E.sub.0.fwdarw.15 =44.7) in comparison to HC 
Blue 2 (.DELTA.E.sub.0.fwdarw.15 =37.2). The other three compounds in 
Table 2 are much closer to HC Blue 2 in their initial color changes. 
Between 15 and 30 minutes, the color changes of hair dyed with the 
trimethyl compound and HC Blue 2 are similar but after 30 minutes hair 
dyed with the trimethyl compound essentially stops changing color. These 
qualitative differences (faster initial color change and the color change 
ending after 30 minutes for the trimethyl compound) between the trimethyl 
compound and HC Blue 2 demonstrate that the trimethyl compound is 
unacceptable for use with typical semipermanent dyes. 
The triethyl and the heptyl, dimethyl compounds demonstrate other 
unacceptable attributes. The heptyl compound (and most higher alkyl 
derivatives) has a very low dye uptake; for example, as shown by Table 1, 
after 60 minutes of dyeing the Hunter values are only L=50.7, a=-8.8, 
b=1.4. Obviously, a dye which does not impart much color is of little 
value. The triethyl compound, according to .DELTA.E.sub.0.fwdarw.15, is 
similar to HC Blue 2 initially but after 15 minutes, its dye uptake is 
much lower than HC Blue 2. If this compound were used in combination with 
a neutral 
TABLE 1 
__________________________________________________________________________ 
The Hunter Reflectance Readings (L,a,b) for Piedmont Hair Dyed with 
4-(N,N,N- 
Trialkyl-3'-Ammonium-n-Propylamino)-1-Methylaminoanthraquinones Iodide, 
I, in a 
Commercial Hairdye Base 
Hunter Reflectance Readings (L,a,b) 
Substitutents on 
the Quaternary 
Dyeing Time 
Ammonium Group 
15 minutes 
30 minutes 
60 minutes 
__________________________________________________________________________ 
Trimethyl 39.1, -5.6, -11.3 
35.9, -5.2, -15.0 
34.2, -4.7, -15.6 
(Basic Blue 22) 
39.4, -5.7, -10.4.sup.1 
34.7, -4.8, -13.6.sup.1 
35.7, -5.1, -14.6.sup.1 
average 39.2, -5.6, -10.8.sup.2 
35.3, -5.0, -14.3.sup.2 
35.0, -4.9, -15.1.sup.2 
Propyl, Dimethyl (Ia) 
44.6, -7.3, -6.8 
43.4, -6.1, -10.4 
39.9, -7.0, -11.6 
43.3, -7.6, -7.3.sup.1 
42.5, -7.4, -9.3.sup.1 
39.8, -6.8, -12.1.sup.1 
average 44.0, -7.4, -7.0.sup.2 
43.0, -6.8, -9.8.sup.2 
39.8, -6.9, -11.8.sup.2 
Heptyl, Dimethyl 
55.7, -8.0, 6.3 50.7, -8.8, 1.4 
Diethyl, Methyl (Ib) 
43.0, -7.3, -6.5 
42.3, -6.6, -9.5 
40.2, -6.8, -10.4 
Triethyl 45.1, - 7.4, -5.9 
43.8, -7.3, -6.9 
43.0, -7.4, -9.2 
HC Blue 2.sup.3 
41.1, 4.7, -1.7 
36.0, 5.9, -4.7 
34.2, 6.5, -6.8 
__________________________________________________________________________ 
.sup.1 Entire dyeing experiment repeated. 
.sup.2 The average of these two experiments will be used in subsequent 
calculations. 
.sup.3 A direct dye (i.e. semipermanent dye) evaluated for comparative 
purposes 
TABLE 2 
______________________________________ 
The Total Color Change (.DELTA.E) of Piedmont Hair Dyed 
with 4-(N,N,N-Trialkyl-3'-Ammonium-n-Propylamino)-1-Methyl- 
aminoanthraquinones Iodide, I, for Different Lengths of Time 
Substituents 
on the Qua- 
ternary 
Ammonium .DELTA.E 
Group 0.fwdarw.15 min. 
15.fwdarw.30 min. 
30.fwdarw.60 min. 
15.fwdarw.60 min. 
______________________________________ 
Trimethyl 
44.7 5.3 0.9 6.0 
(Basic Blue 
22) 
Propyl, 39.0 3.0 3.8 6.4 
Dimethyl (Ia) 
Heptyl, 21.9 7.0 
Dimethyl 
Diethyl, 39.3 3.2 2.3 4.8 
Methyl (Ib) 
Triethyl 37.4 1.6 2.4 3.9 
HC Blue 2.sup.1 
37.2 6.0 2.8 8.8 
______________________________________ 
.sup.1 A direct dye (i.e. semipermanent dye) evaluated for comparative 
purposes 
semipermanent dye, the color (i.e. shade and intensity as opposed to only 
the intensity) would vary after 15 minutes. Thus, this compound is 
unacceptable. 
While the propyl, dimethyl (Ia) and the diethyl, methyl (Ib) are not 
perfect matches for HC Blue 2, they are the closest fit and give the 
overall best combination of properties. During the first 15 minutes of 
dyeing, the rate of color change on hair with both of these compounds is 
just slightly faster than that of HC Blue 2. Thereafter, their rate of 
color change is slightly less than that of HC Blue 2, as evident by their 
.DELTA.E's in Table 2. It is surprising and unexpected that: (1) hair dyed 
with the trimethyl compound would stop changing color after a particular 
period of time; (2) the rate of color change on hair with the trimethyl 
could be modified by minor changes in the alkyl groups on the quaternary 
ammonium center, and; (3) this minor change in the alkyl groups modifies 
the rate of color change so that the so modified compound can be used with 
neutral semipermanent dyes. 
The present invention includes the novel compounds of Formulae Ia and Ib, 
compositions containing a tinctorially effective amount of either compound 
with neutral semipermanent dyes in a cosmetically acceptable vehicle and a 
method for dyeing a keratin fiber by contacting such fiber with either 
compound Ia or Ib. 
Dye compositions employing the anthraquinone dyes of the present invention 
may be formulated as a solution, a liquid shampoo (which can be a solution 
or an emulsion), a cream, a gel, a powder, or an aerosol. 
Examples of the semipermanent dyes with which these compounds can be used 
can be found in any of the numerous reviews on hair dyes such as the one 
by J. F. Corbett in the Review of the Progress of Coloration, Volume 15, 
pages 52-65, (1985). Examples of these dyes are: 
N-(2'-Hydroxyethyl)-o-nitroaniline, 4-Nitro-o-phenylenediamine, 
N1-(2-Hydroxyethyl)-4-nitro-o-phenylenediamine, 
N1-Tris(hydroxymethyl)methyl-4-nitro-o-phenylenediamine, 
2-Amino-3-nitrophenol, 2-Amino-4-nitrophenol, 4-Amino-2-nitrophenol, 
2-Amino-5-nitrophenol, O,N-Bis(2'-hydroxyethyl)-2-amino-5-nitrophenol, 
N-(2'-Hydroxyethyl)-2-amino-5-nitroanisole, 4-Amino-3-nitrophenol, 
N-(2'-Hydroxyethyl)-4-amino-3-nitrophenol, 
N-(2'-Hydroxyethyl)-4-amino-3-nitroanisole, 
1-(3-Methylamino-4-nitrophenoxy)propane-2,3-diol, 
3-Methylamino-4-nitrophenoxyethanol, 2-Nitro-p-phenylenediamine, 
N1-(2'-Hydroxyethyl)-2-nitro-p-phenylenediamine, 
N4-(2'-Hydroxyethyl)-2-nitro-p-phenylenediamine, 
N1-Methyl-2-nitro-p-phenylenediamine, 
N1,N4,N4-Tris-(2'-hydroxyethyl)-2-nitro-p-phenylenediamine, 
N4-(2'-Hydroxyethyl)-N1,N4-dimethyl-2-nitro-p-phenylenediamine, 
N4-(2',3'-Di-hydroxypropyl)-N1,N4-dimethyl-2-nitro-p-phenylenediamine, 
4-Nitro-m-phenylenediamine, Picramic Acid, N-Methyl-isopicramic acid, 
4-Amino-2-nitrodiphenylamine, 4-Hydroxy-2'-nitrodiphenylamine, 
4-(p-Aminophenylazo)-N,N-bis(2'-hydroxyethyl)aniline, 
1,4,5,8-Tetraaminoanthraquinone, 1,4-Diaminoanthraquinone, 
1-Amino-4-methylaminoanthraquinone, 
1-(2'-Hydroxyethylamino)-4-methylaminoanthraquinone, 
2,4-Diamino-2'-hydroxy-5'-nitroazobenzene-5-sulphonic acid (Na salt). 
These dyes may be incorporated with the anthraquinones of the present 
invention provided such agents do not interfere with the dyeing ability of 
these dyes or react with them. 
Materials typically included in hair dye compositions and/or developers 
include for example, organic solvents and solubilizing agents, surface 
active agents, thickening agents, buffers, chelating agents, perfumes, 
sunscreens, conditioners, dyeing assistants or penetrating agents, 
preservatives, emulsifiers and fragrances. A particular material may 
perform several functions. For example, a surfactant may also act as a 
thickener. The dye compounds of formulas I are cationic. The dye uptake of 
cationic dyes is inhibited by an excess certain anionic materials with 
which the cationic dyes would complex, precipitate or similarly react. 
Consequently, care should be exercised in formulating with such materials. 
It is often advantageous to include in the dye compositions of the present 
invention an organic solvent or solvent system which helps solubilize the 
dyes and adjuvants contained in the compositions. A number of organic 
solvents are known for such purpose. These include: alcohols, particularly 
alkyl alcohols of 1-6 carbons, especially ethanol and propanol; glycols of 
up to about 10 carbons, preferably less than 6 carbons, especially 
propylene glycol and butylene glycol; glycol ethers of up to about 10 
carbons, especially diethyleneglycol monobutyl ether; carbitols; and 
benzyl alcohol. When present, the solvents will constitute from about 1% 
to about 60%, preferably from about 10 to about 30%, by weight of the 
dyeing composition. 
Typical surfactant types useful in the compositions of the invention 
include: alkyl sulfates, alkyl ether sulfates, amide ether sulfates, 
soaps, alkyl ether carboxylates, acylsarcosinates, protein/fatty acid 
condensates, sulfosuccinic acid esters, alkane sulfonates, alkylbenzene 
sulfonates, a-olefin sulfonates, acylisethionates, acyltaurines, 
ethoxylates, sorbitan esters, alkanolamides, amine oxides, quaternary 
ammonium salts, alkyl betaines, amidopropyl betaines, sulfobetaines, 
glycinates/aminopropionates and carboxyglycinates/aminodipropionates. A 
combination of different surfactants can be used to impart particular 
viscosity and foaming properties. 
Illustrative of specific surfactants that may be employed are: lauryl 
sulfate; polyoxyethylene lauryl ester; myristyl sulfate; glyceryl 
monostearate; sodium salt of palmitic acid, methyl taurine; cetyl 
pyridinium chloride; lauryl sulfonate; myristyl sulfonate; lauric 
diethanolamide; polyoxyethylene stearate; stearyl dimethyl benzyl ammonium 
chloride: dodecyl benzene sodium sulfonate; nonyl naphthalene sodium 
sulfonate; dioctyl sodium sulfosuccinate; sodium N-methyl-N-oleyl taurate; 
oleic acid ester of sodium isethionate; sodium dodecyl sulfate, and the 
like. The quantity of water soluble surface active agent employed can vary 
widely up to about 15%. Preferably, the surface active agent is employed 
in an amount of from about 0.10% to about 10%, based on the weight of the 
composition. Note however that when an anionic surfactant is employed the 
amount must be restricted so as to avoid possible incompatibility with the 
dye compounds of the present invention. 
The thickening agent, when employed, may be one or a mixture of those 
commonly used in hair dyeing compositions or in hair developers. Such 
thickening agents include: sodium alginate; gum arabic; cellulose 
derivatives, such as methylcellulose or the sodium salt of 
carboxymethylcellulose; acrylic polymers, such as polyacrylic acid sodium 
salt; and inorganic thickeners, e.g., bentonite and fumed silica. 
Electrolytes, alkanolamides, cellulose ethers and highly ethoxylated 
compounds (such as ethers, esters and diesters) may also be used to 
thicken the composition. The quantity of thickening agent can vary over a 
wide range. Typicaily the thickening agent(s) is employed in an amount of 
up to about 20%, more preferably, from about 0.1% to 5%, based on the 
weight of the composition. 
The pH of the dye composition can vary from about 2.5 to about 11. Any 
compatible water-dispersible or water soluble alkalizing agent can be 
incorporated in the composition in an amount suitable to give the desired 
pH. Typically, the amount of alkalizing agent employed is less than about 
10%, preferably, from about 0.1 % to about 5%, based on the weight of the 
composition. 
Compatible alkalizing agents are those which under the conditions of use do 
not interact chemically with the dye(s) employed, that do not precipitate 
the dye(s), and are non-toxic and non-injurious to the scalp. Preferred 
alkalizing agents include: mono-, di- and trialkanolamines, such as 
triethanolamine and 2-amino-2-methyl-1,3-propanediol; alkyl amines, such 
as monoethylamine, diethylamine and dipropylamine; and heterocyclic 
amines, such as morpholine, piperidine, 2-pipecoline and piperazine. 
Any inorganic or organic acid or acid salt, that is compatible with the dye 
composition and does not introduce toxicity under its conditions of use, 
can also be employed to adjust the pH of the dye composition. Illustrative 
of such acids and acid salts are sulfuric acid, formic acid, acetic acid, 
lactic acid, citric acid, tartaric acid, ammonium sulfate, sodium 
dihydrogen phosphate, and potassium bisulfate. 
Common chelating agents that can be employed in the compositions of the 
invention include the salts of ethylenediaminetetraacetic acid (EDTA), 
nitrilotriacetic acid, phosphates, pyrophosphates and zeolites. 
Conditioners that can be incorporated in the present compositions include: 
encapsulated silicones; silicones, such as amino functional and carboxy 
silicones; volatile silicones; combinations of a cationic polymer, a 
decomposition derivative of keratin and a salt; quaternary ammonium 
compounds such as cocos--(C.sub.12-18)-alkyl poly (6) oxyethyl 
di-(2-lauroyloxyethyl)-methyl ammonium chloride; combinations of a plant 
extract and a polypeptide; a dimethyl diallyl ammonium chloride 
(DMDAAC)/acrylic acid type polymer; and a dialkyl quaternary ammonium 
compound where the alkyl groups are C.sub.12 -C.sub.16. Other well known 
conditioners, such as lanolin, glycerol, oleyl alcohol, cetyl alcohol, 
mineral oil and petrolatum, can also be incorporated. 
It is a common practice to add solvents or swelling agents to enhance the 
penetration of hair dyes. Materials useful for swelling hair include 
acetic acid, formic acid, formamide, urea, ethyl amine and certain alkali 
halides (potassium iodide, sodium bromide, lithium bromide and lithium 
chloride, but not sodium chloride). N-Alkyl pyrrolidones and epoxy 
pyrrolidone may be employed to potentially increase the penetration of dye 
into hair. Imidazolines such as disclosed in U.S. Pat. No. 5,030,629 may 
be employed in the compositions to enhance the penetration of hair dyes. 
Emulsifiers may be used when the final form of the hair dye is an emulsion. 
Many emulsifiers are by their nature also surfactants. There are five 
general categories: anionic, cationic, nonionic, fatty acid esters and 
sorbitan fatty acid esters. Examples include: mono-, dialkyl and trialkyl 
ether phosphates, long-chain fatty acids with hydrophilic compounds such 
as glycerin, polyglycerin or sorbitol and long chain alkyl primary and 
secondary amines, quaternary ammonium and quaternary pyridinium compounds. 
Materials which may render the product aesthetically more appealing, such 
as fragrances, proteins hydrolysates, vitamins and plant extracts, may be 
added. Examples include chamomile, aloe vera, ginseng, and pro-vitamin B.