Quaternized monoalkylenediamine nitrobenzene compounds and their use as dyes for keratinaceous fibers

Quaternized monoalkylenediamine nitrobenzene compounds of general formula ##STR1## wherein one of Z or Y is the quaternized group ##STR2## the other of Y or Z being H, alkyl hydroxyalkyl or hydroxyalkoxy when it is not said quaternized group, and the use of said compounds in the dyeing of keratinaceous fibers.

FIELD OF INVENTION 
This invention relates to quaternized monoalkylenediamine nitrobenzene 
compounds and to their use in dyeing keratinaceous fibers, particularly 
human hair. More particularly, it concerns compounds of the following 
formula and their use in dyeing human hair on the head. 
##STR3## 
wherein (a) Z is selected from the group consisting of hydrogen, alkyl, 
hydroxyalkyl, hydroxyalkoxy and the group 
##STR4## 
(b) Y is selected from the group consisting of H, 
##STR5## 
alkyl and hydroxyalkoxy; wherein 
(1) only one of Y or Z is the group 
##STR6## 
(2) R is a divalent alkylene radical; (3) R.sub.1, R.sub.2 and R.sub.3 are 
alkyl or hydroxyalkyl groups and 
(4) X.sup.- is an anion. 
BACKGROUND OF INVENTION 
In dyeing keratinaceous fibers, particularly human hair, it is desirable 
that the dyed fibers have a natural appearance. This often requires 
blending dyes that are primarily red, blue or yellow in color in the 
proper portions to provide the natural looking shade. A major problem is 
the general lack of yellow dyes having light-fast qualities comparable to 
such qualities in the red and blue dyes in the shade. As a result, blended 
dyes containing yellow are prone to shifts in hue with normal sunlight 
exposure. 
It has been found, unexpectedly, that the presence of the quaternary group 
in the compounds of formula I above shifts the light absorbancy of these 
compounds to the shorter wavelength when compared with the corresponding 
unquaternized compounds. This shift provides useful dyes having a yellower 
color when dyed out on keratinaceous fibers, e.g., hair or wool. It has 
also been found, unexpectedly, that these quaternized compounds provide 
dyes that have an improved lightfastness when compared with the 
corresponding unquaternized compounds. 
PRIOR ART 
U.S. Pat. Nos. 3,560,136; 3,904,690; 4,018,556 and 4,115,934 to Kalopissis 
et al are each directed to nitrophenylenediamine compounds said to be 
useful as hair dyes. The most pertinent among these is perhaps U.S. Pat. 
No. 4,155,934 which discloses compounds of the formula: 
##STR7## 
which compounds may also be quaternized. 
However, the Kalopissis et al compounds of the '934 patent are structurally 
significantly different from the compounds of this invention. In all 
instances, the Kalopissis et al compounds are nitrophenylene diamines. 
That is, two amino groups (or substituted amino groups) are bound to the 
ring carbon atoms (the aromatic nucleus) of the Kalopissis et al 
compounds. In the compounds of the present invention only one of the amino 
groups is bound to a ring carbon atom These are different classes of 
compounds in the hair dye art and are not expected to function in the same 
manner, inasmuch as both amino groups present on the nucleus of the 
Kalopissis et al compounds contribute to the chromophoric value of the 
compounds. This appears quite clear from the Kalopissis et al disclosure 
in that both nuclear-substituted amino groups are always present and are 
always deemed essential. Furthermore, there is nothing in Kalopissis et al 
to suggest that its quaternized compounds have better lightfastness than 
their unquaternized compounds, as in the case with the compounds of the 
present invention. 
U.S. Pat. No. 4,417,896 to Bugaut et al disclose compounds of general 
formula 
##STR8## 
wherein Z represents a substituted lower alkyl radical and each R.sub.1 
and R.sub.2 is hydrogen or a lower alkyl identical with or different from 
Z, the functional groups --NO.sub.2 and --NR.sub.1 R.sub.2 occupying any 
of the ring positions, with the stipulation that if Z is 
.beta.-hydroxyethyl, --NO.sub.2 is in the 4 position and the group 
--NR.sub.1 R.sub.2 is in the 2 position, then either R.sub.1 or R.sub.2 is 
other than hydrogen. In this case the structure of the compound is given 
by the formula 
##STR9## 
where R is not H. The compound of Example 12 in Buguat et al, which has 
the structure 
##STR10## 
is clearly outside of the scope of the compounds of the present invention. 
In the case of the compounds corresponding to the unquaternized compounds 
of this invention, when the groups --NHCH.sub.2 CH.sub.2 
N(CH.sub.3)CH.sub.3 and --NO.sub.2 are para to each other, the position 
ortho to the group --NHCH.sub.2 CH.sub.2 N(CH.sub.3)CH.sub.3 is occupied 
by a hydrogen atom and not --OCH.sub.2 CH.sub.2 OH. Moreover Bugaut et al 
does not teach quaternizing compounds of the type shown in Example 12. The 
only type of quaternary compound suggested by Bugaut et al are those in 
which the radical carrying the quaternized group is bound to a nuclear 
carbon atom through an oxygen bridge, i.e., 
##STR11## 
Furthermore, no precedent in the literature indicates that a quaternary 
ammonium center can cause a hypsochromic shift of a nitro dye molecule. 
The present finding that the quaternary center induces a more useful 
yellow color by eliminating the red hue is unexpected. 
U.S. Pat. No. 3,897,496 to Crounse et al teaches quaternary ammonium 
compounds of the formula 
##STR12## 
These compounds are said to be useful as germicides, fungicides and 
algicides. These are clearly far removed from the compounds of this 
invention. 
West German Patent 34 25 151 discloses a direct hair dye of formula: 
##STR13## 
in which A is --SO.sub.3 H or --COOH; R.sub.1 and R.sub.2 are, among other 
things, hydrogen or (CH.sub.2).sub.n X in which n is a number from 2-4, 
and X is --OH or --NR.sub.3 R.sub.4, wherein R.sub.3 and R.sub.4 are H, 
alkyls of 1 to 4 carbons, hydroxyalkyls of 2 to 4 carbons or aminoalkyls 
having 2-4 carbons. There is no suggestion of the compounds of the present 
invention. 
DETAILED DESCRIPTION OF INVENTION AND PREFERRED EMBODIMENT 
It is a primary object of the present invention to provide a novel class of 
quaternary amine compounds defined by formula I above that are useful in 
dyeing keratinaceous fibers and particularly human hair on the head. The 
compounds can also be viewed as encompassing two groups of compounds 
defined by having the formulas: 
##STR14## 
wherein R is a divalent alkylene radical typically having from 1 to about 
8 carbons, which may be a straight or branched chain group, and preferably 
contains 2 to about 5 carbons such as ethylene, propylene, isopropylene, 
butylene; R.sub.1, R.sub.2 and R.sub.3 are straight or branched chain 
alkyl and hydroxyalkyl radicals having up to about 6 carbons, preferably 
from 1 to 5 carbons, e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, 
t-butyl, n-pentyl, and A is H, alkyl, hydroxyalkyl and hydroxyalkoxy, the 
alkyl moiety, which may be straight or branch chained, having up to about 
8 carbons, preferably from 1 to 5 carbons. The hydroxyalkoxy group, which 
usually takes the form --O--R--OH wherein R is a divalent alkylene radical 
as described above, may be one that contains more than one hydroxy group, 
e.g., --O--CH.sub.2 --CH(OH)--CH.sub.2 OH. The hydroxyalkyl radical 
typically will be a monovalent radical that takes the form --ROH in which 
R is a divalent radical as described above. This radical will also usually 
have up to about 5 carbon atoms in its chain. 
Typical radicals of this character include --CH.sub.2 --CH.sub.2 --OH, 
--CH.sub.2 --CH(OH)--CH.sub.3, --CH.sub.2 --CH.sub.2 --CH.sub.2 --OH, 
--CH.sub.2 --CH.sub.2 --CH(CH.sub.3)--OH, etc. Moreover, in addition to 
the substituent groups designated for the aromatic nucleus in structure II 
and III and defined herein, the Compounds II and III may also include as 
ring substituents any group that does not substantially affect the 
chromophoric nature of the molecules. 
As also indicated above, X.sup.- in formula I, II or III above is an anion. 
Although this is designated as a monovalent anion, it may also be a 
polyvalent anion such as SO.sub.4.sup.-. However, in the usual cases it 
will be a monovalent anion and preferably a halide. This can be 
illustrated by such halide ions as Cl.sup.-, Br.sup.- and I.sup.-. 
OH.sup.- is also a suitable anion. 
The quaternary amine compounds of this invention may be made by reacting a 
compound of formula 
##STR15## 
with a quaternizing agent which will ordinarily take the form of a halide 
of the formula R.sub.3 X. In this reaction A, R, R.sub.1, R.sub.2, R.sub.3 
and X have the meaning ascribed to above. More particularly, 
quaternization is conducted by heating an essentially equimolar mixture of 
amine and alkyl halide in dimethylformamide, the progress of the reaction 
being monitored by TLC. The desired quaternized product precipitates out 
after cooling to room temperature. 
The quaternary ammonium compounds of this invention have special utility in 
dyeing keratinaceous fibers and particularly human hair. This may be used 
as a direct dye, i.e., as a dye that does not require an oxidizing agent 
in order to produce a color in the hair. However, as described in more 
detail below, it may also be used as a sunscreen to protect other dyes in 
the dye composition from fading under direct sunlight. Generally, the 
utilities occur concurrently so that both effects are exploited together. 
When used as a direct dye it may, for example, be applied to the human 
head, from any of a variety of direct hair dye vehicles well known to 
those skilled in the art. The concentration of the dyes of this invention 
which will be contained in said direct hair dye vehicle may vary somewhat 
depending on the nature of vehicle, the presence of other hair dyes, the 
results desired, and the like. All that is required is that a tinctorially 
effective amount of the subject dyes be employed. Generally, however, the 
dyes herein disclosed will be present in said vehicles at a concentration 
in the range of from about 0.01% to about 10%, preferably from about 0.1% 
to about 5%, most preferably from 0.1% to 2% by weight based on total 
weight of the dye composition. As used herein, the term "dyeing 
composition" means the total dyeing composition including the dyes of this 
invention, other dyes if present, vehicles and adjuvants. 
The vehicles employed in dyeing hair with the dyes of this invention may 
vary in complexity from simple solutions or dispersions that employ 
aqueous or aqueous alcoholic solvents to very complex systems including 
thickened shampoo compositions as the vehicle. Water will ordinarily 
constitute the major component of the dyeing compositions of this 
invention, but can vary widely depending on the types and quantity of 
adjuvants or additives contained in the composition. Thus, water may 
constitute as little as 10% by weight of the dyeing composition based on 
the total weight of the dyeing composition but more usually constitutes 
from about 70% to about 90% by weight on the same weight basis. 
It is often advantageous to include in the dyeing compositions of the 
present invention an organic solvent or solvent system which helps 
solubilize the dyes and adjuvants contained therein. A number of organic 
solvents are known in the prior art that are useful for the present 
purposes. 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, 
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. 
The dyeing compositions of this invention may also contain other 
conventional adjuvants or additives commonly found in direct hair dye 
compositions. There include such items as surface active agents, 
thickening agents, alkalizing agents, chelating agents, perfumes, and the 
like. 
The surface active agents are typically water soluble, less preferably 
water dispersible, and include anionic, nonionic or cationic surface 
active agents. Illustrative of the various types of water soluble surface 
active agents are: higher alkyl benzene sulfonates; alkyl naphthalene 
sulfonates; sulfonated esters of alcohols and polybasic acids; taurates; 
fatty alcohol sulfates; sulfates of branched chain or secondary alcohols; 
alkyl dimethylbenzyl ammonium chlorides, and the like. 
Illustrative of specific surfactants 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-oleoyl 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 from about 0.10% to 10% by weight of the composition. 
The thickening agent when employed may be one or several of those commonly 
used in hair dyeing, such as 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. The quantity of 
thickening agent can vary over a wide range, typically up to about 20%, 
preferably from about 0.1% to 5% by weight of the composition. 
The pH of the composition can vary from about 2.5 to about 11, but it is 
preferred that the compositions be in the alkaline range and particularly 
at a pH of about 7.5 to 10. Any compatible water-dispersible alkalizing 
agent can be incorporated in an amount suitable to give the desired pH. 
Illustratively, the alkalizing agent is less than about 10%, preferably 
from about 0.1% to about 5% by weight of the composition. 
Compatible alkalizing agents are those that do not interact chemically with 
the dye(s) employed, will not precipitate the dye(s), and are non-toxic 
and non-injurious to the scalp, under the conditions of use. Preferred 
alkalizing agents are 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, which is compatible with the 
composition and will not introduce toxicity under its conditions of use, 
can also be employed for adjusting the pH of the dye composition. 
Illustrative of acids or acid salts are sulfuric, formic, acetic, lactic, 
citric or tartaric acid; ammonium sulfate, sodium dihydrogen phosphate, or 
potassium bisulfate. 
The dyeing compositions of this invention can be prepared by the 
conventional methods used in the hair dyeing art. Thus, they can be 
prepared by dissolving or dispersing the dye in water of the desired 
concentration. Water miscible organic solvents can be employed to 
facilitate solution of the dye; in this event, the dye can be dissolved 
first in the solvent and then diluted with water. The dispersion of the 
various ingredients can also be facilitated by heating the composition. 
The dyeing compositions can be applied to living human hair on the head by 
the conventional techniques known in the art. Illustratively they can be 
poured over the hair or applied with a brush, sponge, or other means of 
contact until the hair is properly impregnated. The time of contact of the 
dyeing composition with the hair is not critical and can vary over the 
wide range used in the hair dyeing art, such as periods of about 5 minutes 
to 2 hours or more, preferably from about 10 to 60 minutes. As mentioned 
hereinabove, the dyeing on live hair is preferably effected at 
temperatures below 40.degree. C. such as those from 15.degree. C. to 
40.degree. C., preferably at ambient room temperatures such as those of 
about 20.degree. C. to 35.degree. C. 
Dyes of the present invention can also be used in combination with 
conventional oxidation dyes, e.g., p-phenylenediamine, .alpha.-naphthol, 
p-aminophenol, m-aminophenol, resorcinol and m-phenylenediamine, and their 
derivatives, in the presence of a conventional oxidizer such as hydrogen 
peroxide, to provide a range of shades on the hair. When the oxidation dye 
so used exhibits a degree of lightfastness lower than desired, the 
quaternized dyes of the present invention also function as stabilizers 
against shade change. 
Similarly, the dyes herein disclosed can be used in combination with other 
conventional semipermanent dyes to produce different shades. The 
conventional semipermanent dyes include, e.g., o- and p-nitroanilines, 
nitro-p-phenylenediamines, aminoanthraquinones, aminoazobenzenes, and 
their derivatives.

The following examples are illustrative of a preferred form of the 
invention: 
EXAMPLE 1 
N,N,N-Trimethyl-2-(2-nitroanilino1ethanaminium Iodide 
##STR16## 
Compound (1) was prepared as indicated below: 
(a) Preparation of N-(2-Dimethylamino)ethyl-2-nitroaniline. 
To a stirred solution of 1-fluoro-2-nitrobenzene (7 g, 50 mmol), 
N,N-dimethylethylenediamine (5.2 g, 60 mmol), and potassium carbonate (7 
g, 50 mmol) in 50 ml of diemethyl sulfoxide was added 0.2 g 
tris-(2-(2-methoxyethoxy)ethyl)amine (TDA-1). The heterogeneous mixture 
was heated at 90.degree. for 2 hours. After cooling to room temperature, 
100 g of crushed ice was added, the desired product was isolated by 
filtration in 90% yield (9.2 g, 4.5 mmol). 
(b) Preparation of N,N,N-Trimethyl-2-(2-nitroanilino)ethanaminium iodide. 
A solution of N-(2-dimethylamino)ethyl-2-nitroaniline (1.0 g, 5 mmol) and 
methyl iodide (0.9 g, 6 mmol) in 10 ml of dimethylformamide was heated at 
90.degree.. The progress of reaction was monitored by tlc until the 
disappearance of starting material. After cooling to room temperature, the 
quaternary ammonium salt was isolated in 95% yield (1.7 g, 4.5 mmol). Its 
melting point was 191.degree.-3.degree. C. 
EXAMPLE 2 
N,N-Dimethyl-N-(2-hydroxyethyl)-2-(2-nitroanilino)ethanaminium Bromide 
##STR17## 
Compound (2) was prepared as indicated below: 
N-(2-Dimethylamino)ethyl-2-nitroaniline 1.25 q, 10 mmol) was heated at 
100.degree. with 2-bromoethanol (6 g, 50 mmol) until the disappearance of 
starting material (monitored by tlc). Excess of 2-bromoethanol was removed 
in vacuo to give the quaternized salt in quantitative yield. Its melting 
point was 105.degree.-8.degree. C. 
EXAMPLE 3 
N,N,N-Trimethyl-2-(5-.beta.-hydroxyethoxy-2-nitroanilino)ethanaminium 
Iodide 
##STR18## 
Compound (3) was prepared as follows: 
To a stirred solution of 2,4-difluoronitrobenzene (3.2 g, 20 mmol), 
N,N-dimethylethylenediamine (1.76 g, 20 mmol), and potassium carbonate 
(2.8 g, 20 mmol) was heated at 80.degree. for 2 hours in dimethyl 
sulfoxide with catalytic amount of TDA-1. Another equivalent of potassium 
carbonate and 5 eq of ethylene glycol was added and heating was continue 
for another hour. After aqueous workup, an orange oil was obtained which 
was quaternized in dimethylformamide to give the desired product in 70% 
yield (5.8 g, 14 mmol). Its melting point was 238.degree.-40.degree. C. 
EXAMPLE 4 
N,N,N-Trimethyl-2-(5-methyl-2-nitroanilino)ethanaminium Iodide 
##STR19## 
Compound (4) was prepared as follows: 
To a stirred solution of 3,4-dinitrotoluene (3.64 g, 20 mmol) and 
N,N-dimethylethylenediamine (1.76 g, 20 mmol) was heated at 80.degree. C. 
in dimethyl sulfoxide and catalytic amount of TDA-1 for 2 hours. 
N,N-Dimethyl-2-(5-methyl-2-nitroanilino)ethanamine was isolated in 80% 
yield (3.6 g, 16 mmol) after aqueous work-up. Quaternization was achieved 
in quantitative yield with methyl iodide and dimethylformamide. Its 
melting point was 225.degree.-7.degree. C. 
EXAMPLE 5 
N,N,N-Trimethyl-4-(2-nitroanilino)ethanaminium Iodide 
##STR20## 
Compound (5) was prepared as set forth below: 
The synthesis of the compound (5) was the same as in Example 1, except 
1-fluoro-4-nitrobenzene (7 g, 50 mmol) was employed. Its melting point was 
119.degree.-203.degree. C. (decomposed). 
Dyeing compositions of the present invention are illustrated in the 
following examples: 
EXAMPLE 6 
The following dyeing composition containing the Compound (1) of Example 1 
was made by admixing the various constituents: 
______________________________________ 
Constituents Concentration (wt %) 
______________________________________ 
Compound (1) 0.3 
Aminomethyl propanol 
1.0 
Hydroxymethyl cellulose 
1.4 
PEG-50 Tallow amide 
1.5 
Lauramide DEA 1.5 
Oleic acid 2.0 
Diethyleneglycol monoethyl ether 
5.0 
Water q.s. 100% 
______________________________________ 
This mixture was applied to blended gray hair for about 30 minutes at room 
temperature, rinsed and washed by shampooing. A bright orange-yellow color 
was obtained on hair. 
EXAMPLE 7 
The Compound (3) of Example 3 was used in the following composition: 
______________________________________ 
Constituents Concentration (wt %) 
______________________________________ 
Compound (3) 0.3 
Ethanol (95% aq. sol'n) 
33.0 
Diethanolamine to pH 9.5 
Water q.s. 100% 
______________________________________ 
This composition was used to treat bleached hair by applying it to the hair 
for 30 minutes at room temperature. An intense yellow color was obtained. 
EXAMPLE 8 
This example illustrates the ability of the quaternized dyes of the present 
invention to protect conventional dyes from the effect of sunlight. 
Solution A below is a conventional oxidative dye lotion to be used in an 
oxidative dyeing procedure. Solution B further contains 0.3% Compound (3). 
______________________________________ 
Concentration (wt %) 
Constituents A B 
______________________________________ 
p-phenylenediamine HCl 
0.23 0.23 
.alpha.-Naphthol 0.18 0.18 
Compound (3) -- 0.30 
Ethanol (95% aq. sol'n) 
37 37 
Water q.s. 100% 
q.s. 100% 
______________________________________ 
8 ml Solution A was mixed with 5 ml of a 6% hydrogen peroxide solution, pH 
being adjusted to 9.6 with concentrated ammonium hydroxide. The resulting 
solution was applied to dye blended gray hair for 30 minutes. A violet 
color was obtained. The hair was then rinsed and shampooed. Solution B was 
similarly applied to blended gray hair to obtain a golden brown shade. 
Both tresses were subjected to a test for lightfastness using an Atlas 
color Fad-ometer instrument, Type FDA-RC. The before and after color 
values were measured and recorded as changes in the Hunter Tristimulus 
values L, a and b. The test was conducted for 5 hours. The total shade 
change, designated as x, is calculated from the expression 
x=[(.DELTA.a).sup.2 +(.DELTA.b).sup.2 ].sup.1/2. In this case, when x=0 
there is no change in the shade, i.e., the lower the number, the less the 
change in shade. The swatch treated with Solution A displayed a total 
change of 3 units, while the swatch treated with Solution B exhibited a 
change of only 1.2 units. 
EXAMPLE 9 
This example illustrates the utility of the quaternized dyes of the present 
invention when used in combination with conventional semipermanent dyes. 
As shown below, the use of the subject quaternized dyes not only provides 
the ability to modify the shades normally obtained, but also protects the 
semipermanent dyes from conventional fading occasioned by light. 
______________________________________ 
Concentration (wt. %) 
Constituent A B C D 
______________________________________ 
Semipermanent Dye #1.sup.(2) 
1.47 2.94 0.87 1.0 
Semipermanent Dye #2.sup.(2) 
-- -- 1.47 -- 
Compound (1).sup.(3) 
-- -- -- 1.47 
Monoethanolamine .rarw.q.s. to pH 10.fwdarw. 
Ethanol (95% Aq. Sol'n) 
33.0 33.0 33.0 33.0 
Water .rarw.q.s. 100%.fwdarw. 
______________________________________ 
(1) N2-hydroxyethyl-o-2-hydroxyethoxy-p-nitroaniline 
.sup.(2) N2-dimethylaminoethyl-o-nitroaniline 
.sup.(3) N,N,Ntrimethyl-2-(2-nitroanilino)ethanaminium iodide 
Solution D is within the scope of the present invention, while Solutions 
A-C are not. Four gray hair tresses were prepared by treating each of the 
swatches with one of the Solutions A-D for 30 minutes at room temperature. 
Solution D dyed the gray hair bright yellow, while Solution C provided a 
weaker yellow color. Both Solutions A and B produced a greenish-yellow 
color on the gray hair, but the intensity was stronger in the tress 
treated with Solution B due to a higher concentration of semipermanent dye 
#1. 
All of the tresses were exposed to direct sunlight for about 25 hours, the 
tress treated with Solution D undergoing the least shade change, as 
indicated below. 
______________________________________ 
Solution Total Unit Change in Shade (x)* 
______________________________________ 
A 4.9 
B 5.0 
C 4.1 
D 1.0 
______________________________________ 
*See text at Example 8 for discussion of Total Unit Shade Change value, x 
 
To demonstrate that the quaternization of compounds of formulas IV and V 
above shifts the light absorbance of the dye to a shorter wavelength than 
that recorded for the corresponding nonquaternized compounds, the 
following experiments were carried out: 
EXPERIMENT A 
A series of dye compositions were prepared each containing a different dye 
recited in Table I. With reference to Compound I, the structures of the 
dyes contained in respect of compositions of the series mentioned above 
are given in Table I below. As will be noted compound 1', 3', 4' and 5' 
are nonquaternized versions of compounds 1, 2, 3, 4 and 5. 
TABLE 1 
______________________________________ 
Com- 
pound Y Z 
______________________________________ 
1 H NH(CH.sub.2).sub.2 N.sup.+ (CH.sub.3).sub.3 
I.sup.- 
1' H NH(CH.sub.2).sub.2 N(CH.sub.3).sub.2 
2 H NH(CH.sub.2).sub.2 N.sup.+ (CH.sub.3).sub.2 
CH.sub.2 CH.sub.2 
OH Br.sup.- 
3 OCH.sub.2 CH.sub.2 OH 
NH(CH.sub.2).sub.2 N.sup.+ (CH.sub.3).sub.3 
I.sup.- 
3' OCH.sub.2 CH.sub.2 OH 
NH(CH.sub.2).sub.2 N(CH.sub.3).sub.2 
4 CH.sub.3 NH(CH.sub.2).sub.2 N.sup.+ (CH.sub.3).sub.3 
I.sup.- 
4' CH.sub.3 NH(CH.sub.2).sub.2 N(CH.sub.3).sub.2 
5 NH(CH.sub.2).sub.2 N.sup.+ (CH.sub.3).sub.3 I.sup.- 
H 
5' NH(CH.sub.2).sub.2 N(CH.sub.3).sub.2 
H 
______________________________________ 
The compositions were as follows: 
______________________________________ 
Compositions 
For For Dye 2 For 
Dye Pairs and Dye Dye Pair 
Ingredient 1,1' and 3,3' 
Pairs 4,4' 
5,5' 
______________________________________ 
Dye of Table I 30 mg 30 mg 40 mg 
Ethanol (95% Aq. Soln.) 
4 ml 3.5 ml 4 ml 
Water 6 ml 6.5 ml 6 ml 
Monoethanolamine 
.rarw.q.s. to pH 9.5.fwdarw. 
______________________________________ 
Each of said dye compositions containing each of the nine dyes identified 
in Table I was used to dye wool fibers samples. The composition was 
applied to the wool fibers for about 30 minutes at room temperature, 
followed by a water rinse. 
The maximum absorption wavelength of the respective nitro dyes mentioned 
above in isopropyl alcohol was measured as well as the color values (i.e., 
the Hunter Tristimulus L, a and b values) on wool cloth obtained from said 
dye compositions containing the respective nitro dyes. The results of 
these tests are summarized in Table II below: 
TABLE II 
______________________________________ 
Maximum Absorption Wavelength of the Nitro Compounds in 
Isopropyl alcohol and the Color on Wool Cloth 
i-PrOH Initial Values 
Compound* .lambda.max (nm) 
L a b 
______________________________________ 
1 405 68.4 -6.5 42.9 
1' 423 60.7 7.3 40.0 
2 408 66.2 -6.8 40.0 
3 396 70.0 -14.4 37.2 
3' 410 68.9 -13.1 41.0 
4 405 67.9 -9.7 38.6 
4' 414 61.0 8.5 40.3 
5 367 72.4 -15.9 36.3 
5' 380 70.1 -15.3 43.2 
______________________________________ 
*1', 3', 4' and 5' are the nonquaternized analogues of 1, 2, 3, 4 and 5. 
An examination of the wavelength data (column 2) shows that the presence of 
the quaternary center in the nitro dye molecule shifts the light 
absorbance maximum (.lambda.max) of the dye to a shorter wavelength. 
Compare 1 and 2 with 1', 3 with 3', 4 with 4' and 5 with 5'. No shift was 
found in the absorption spectrum if a foreign quaternary ammonium salt was 
added to the solution of one of the nitro dyes, i.e., 1'-5'. This 
demonstrates a significant interaction between the quaternary centers and 
the dye chromophore since the .lambda.max's of this class of dyes has 
shifted from blue to yellow approximately 15 nm when compared with the 
nonquaternized analogues. 
An examination of the Hunter Tristimulus values indicates that on wool, the 
color is more yellow when the quaternized form of the dye is employed and 
the red hue is suppressed. Compare particularly the "a" values for 
compounds with and without the quaternary center. In the case of the 
Hunter Tristimulus "a" values, the lower the number, the greener the color 
and, conversely, the higher the Hunter Tristimulus "a" value, the redder 
the color. Hence, when the red hue in the dye out is suppressed, the 
yellow becomes more dominant. 
EXPERIMENT B 
The photostability of the dyes of Table I, i.e., the lightfastness of 
dyeings on wool and bleached hair, was measured. The stability was 
represented by the changes in final Hunter Tristimulus values of the fiber 
after it wa exposed to light from its initial tristimulus values. The 
dyeing procedure employed was described above with respect to Experiment 
A, and the lightfastness test was performed in an Atlas Color Fad-ometer 
equipped with a carbon arc lamp. A piece of wool cloth (2.5 cm.times.10 
cm) or a swatch of bleached hair (about 2 g) was treated with the solution 
for 30 minutes. The treated sample was then rinsed, and subjected to 
illumination after it was dry. 
The color changes resulting from these tests were measured and recorded as 
changes in the tristimulus values L, a and b. The total shade change, 
designated as x, is calculated from the expression x=[(.DELTA.a).sup.2 
+(.DELTA.b).sup.2 ].sup.1/2. In this case, when x=0 there is no change in 
the shade, i.e., the lower the number, the less the change in shade. 
The results of these tests are summarized in Table III. 
TABLE III 
______________________________________ 
Comparison of Photostability of Nitro-dyes with and 
without a quaternary Ammonium Center 
Compound* .DELTA.L 
.DELTA.a .DELTA.b 
x** 
______________________________________ 
1 -0.5 -1.1 1.9 2.2 
1' -0.4 -2.2 -2.7 3.3 
3 -3.6 6.4 -7.4 9.8 
3' -6.7 8.0 -7.4 10.9 
4 -2.1 -0.2 -1.6 1.6 
4' -2.2 -2.5 -2.1 3.3 
5 -2.9 3.6 2.3 4.3 
5' -4.7 7.1 -1.2 7.2 
______________________________________ 
*The study was done on wool for 1, 1', 3, 3', 5 and 5'; and on bleached 
hair for 4 and 4'. 
**x = [(.DELTA.a).sup.2 + (.DELTA.b).sup.2 ].sup. 
An examination of the last column of Table III shows that in each case the 
quaternized compound designated by the number without the prime showed 
less change in shade when exposed to light in accordance with the protocol 
than the analogous nonquaternized compound.