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(en)A dye composition for keratinous fibers comprising a specific type of trifluoromethylated aniline derivative, as a developer, and a coupling substance is disclosed. The composition provides high degree of saturation and vividness of colors as well as good fastness. Dyeing with the use of the dye composition ensures a variety of developer-coupling agent combinations, which can provide a wide variety of colors with a high degree of color saturation and vividness. The color produced possesses excellent light resistance, washing resistance, and wear resistance. Amoung the trifluoromethylated aniline derivative, used as a developer, a p-phenylenediamine-type trifluoromethylated aniline derivative of the following formula is a novel compound. ##STR1## in which X represents a specific type of mono- or polyhydroxyalkyl group, alkyl group, or other organic group.
1.ApplicationNumber: US-36650290-A
1.PublishNumber: US-5041608-A
2.Date Publish: 19910820
3.Inventor: MANO; TSUTOMU
KAWASE; JIRO
MISU; DAISUKE
OBAYASHI; MICHIO
4.Inventor Harmonized: MANO TSUTOMU(JP)
KAWASE JIRO(JP)
MISU DAISUKE(JP)
OBAYASHI MICHIO(JP)
5.Country: US
6.Claims:
(en)A dye composition for keratinous fibers comprising a specific type of trifluoromethylated aniline derivative, as a developer, and a coupling substance is disclosed. The composition provides high degree of saturation and vividness of colors as well as good fastness. Dyeing with the use of the dye composition ensures a variety of developer-coupling agent combinations, which can provide a wide variety of colors with a high degree of color saturation and vividness. The color produced possesses excellent light resistance, washing resistance, and wear resistance. Amoung the trifluoromethylated aniline derivative, used as a developer, a p-phenylenediamine-type trifluoromethylated aniline derivative of the following formula is a novel compound. ##STR1## in which X represents a specific type of mono- or polyhydroxyalkyl group, alkyl group, or other organic group.
7.Description:
(en)This is a division of application Ser. No. 07/217,776, filed on July 12, 1988, now U.S. Pat. No. 4,871,372.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a dye composition for keratinous fibers, and, more particularly, to a dye composition for keratinous fibers which is capable of dyeing keratinous fibers such as hairs and the like at a high degree of saturation and vividness, and to a p-phenylenediamine derivative useful as a developer when formulated into such a dye composition. The invention also is directed to a process for preparing the p-phenylenediamine derivatives.
2. Description of the Background
Oxidizing dyes, in which a developer and a coupling agent are employed in combination, have widely been used for dyeing keratinous fibers such as hairs or the like. These oxidizing dyes make use of the strong dyeing capability of oxidizing coloring substances which are produced by the oxidizing-coupling reaction of a developer and a coupling agent. Para-phenylenediamine derivatives, diaminopyridine derivatives, 4-aminopyrazolone derivatives, hetero-cyclic hydrazone, and the like are used as the developer.
These conventional oxidizing dyes have defects in their performance which are yet to be satisfied in terms of saturation or vividness of colors, dyeing capability, and fastness. Development of a dye which is free from these defects has, therefore, been desired.
Performance of an oxidizing dye such as saturation or vividness of colors, dyeing capability, fastness, and the like is greatly dependent upon the characteristics of the developer used. It is, therefore, very important in eliminating the above defects of oxidizing dyes to find a developer possessing an excellent characteristics.
The present inventors have undertaken extensive studies in order to overcome the above problems in oxidizing dyes, and as a result found that use of a trifluoromethylated aniline derivative for dyeing keratinous fibers provides a high degree of saturation and vividness of colors as well as good fastness. This finding has led to the completion of this invention.
SUMMARY OF THE INVENTION
Accordingly an object of this invention is to provide a dye composition for keratinous fibers comprising a developer and a coupling substance, wherein said developer is a trifluoromethylated aniline derivative represented by the following formula (I) or a salt thereof: ##STR2## in which R represents a hydroxyl group or a group represented by --NHR', wherein R, represents a C 2-6 mono- or polyhydroxyalkyl group, a C 1-20 alkyl group, or a group represented by --(CH 2 ) n --O--R", [wherein R" stands for a C 1-4 alkyl group, a C 1-4 mono- or polyhydroxyalkyl group and n denotes an integer of 1 to 4], a group represented by --(CH 2 ) n --NR 3 R 4 (wherein R 3 and R 4 may be same or different and denote hydrogen atoms, C 1-20 alkyl groups, or C 2-6 mono- or polyhydroxyalkyl groups, and n denotes an integer of 1 to 4), or --(CH 2 ) n --COOR 5 (wherein R 5 is a hydrogen atom, a C 2-6 alkyl group, or a C 2-6 mono- or polyhydroxyalkyl group, and n denotes an integer of 1 to 4).
Another object of this invention is to provide a novel p-phenylenediamine derivative represented by the following formula (Ia) or a salt thereof: ##STR3## in which X represents a C 2-6 mono- or polyhydroxyalkyl group, a C 1-20 alkyl group, or a group represented by --(CH 2 ) n --O--R", [wherein R" stands for a C 1-4 alkyl group, a C 1-4 mono- or polyhydroxyalkyl group and n denotes an integer of 1 to 4], a group represented by --(CH 2 ) n --NR 3 R 4 (wherein R 3 and R 4 may be same or different and denote hydrogen atoms, C 1-20 alkyl groups, or C 2-6 mono- or polyhydroxyalkyl groups, and n denotes an integer of 1 to 4), or --(CH 2 ) n --COOR 5 (wherein R 5 is a hydrogen atom, a C 1-6 alkyl group, or a C 2-6 mono- or polyhydroxyalkyl group, and n denotes an integer of 1 to 4).
Still another object of this invention is to provide a process for preparing the above novel p-phenylenediamine derivative the formula (Ia) or a salt thereof, which comprises reducing a compound represented by the following formula (II): ##STR4## in which X has the same meaning as defined for the formula (Ia).
Other objects, features and advantages of the invention will hereinafter become more readily apparent from the following description.
DETAILED DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS
Among trifluoromethylated aniline derivatives, p-phenylenediamine derivatives represented by the following formula (Ia) or the salts thereof are novel compounds. ##STR5## in which X represents a C 2-6 mono- or polyhydroxyalkyl group, a C 1-20 alkyl group, or a group represented by --(CH 2 ) n --O--R", [wherein R" stands for a C 1-4 alkyl group, a C 1-4 mono- or polyhydroxyalkyl group, and n denotes an integer of 1 to 4] a group represented by --(CH 2 ) n --NR 3 R 4 (wherein R 3 and R 4 may be same or different and denote hydrogen atoms, C 1-20 alkyl groups, or C 2-66 mono- or polyhydroxyalkyl groups, and n denotes an integer of 1 to 4), or --(CH 2 ) n --COOR 5 (wherein R 5 is a hydrogen atom, a C 1-6 alkyl group, or a C 2-6 mono- or polyhydroxyalkyl group.
The p-phenylenediamine derivative of formula (Ia) can be prepared, for example, by reducing the compound (II) according to the following reaction scheme: ##STR6##
The compound (II) can be prepared, for example, by the reaction of the chlorinated compound of the formula (III) and mono- or polyhydroxyalkylamine of the formula (IV). ##STR7##
This reaction may be carried out according to the method described in Arzneim. Forsch., 25, 681 (1975).
The reduction of the compound of formula (II) may be carried out according to the conventional reduction of a nitro group. A simple and effective method, however, is a catalytic hydrogenation or reduction in the presence of zinc under alkaline conditions
Palladium, platinum, copper, nickel, or the like are used for the catalytic hydrogenation. A solvent such as methanol, ethanol, ethyl acetate, dimethylformamide, or the like is desirably used in the reaction. The reaction temperature is in the range between room temperature and the boiling point of the solvent used, and the pressure may be 1 to 250 kg/cm 2 . Upon completion of the reaction, the catalyst is removed by filtration. After condensation of the filtrate, purification can be performed very easily by evaporating the solvent or recrystallizing the target compound.
Reduction using zinc is carried out by heating the raw materials under reflux in an aqueous solution of alkali such as sodium hydroxide, potassium hydroxide, or the like in the presence of an excess amount of zinc, and adding to the reaction system, as required, a solvent dissolvable in water such as methanol, ethanol, acetone, N,N-dimethylformamide, dimethylsulfoxide, or the like. Upon completion, solid substances are removed by filtration, and the filtrate is extracted with a suitable solvent and condensed. The condensate thus obtained can be easily purified by evaporating the solvent or recrystallizing the target compound.
The compound of this invention of formula (Ia) thus prepared can be converted according to a conventional method into a salt by reaction of this compound with an organic or inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, propionic acid, lactic acid, citric acid, or the like.
Compounds of formula (I), other than those of formula (Ia) which is novel in the art, can be prepared by reducing p-nitrophenol or p-nitroaniline trifluoromethylated according to the process which was discussed just above in connection with the process for preparing the compound of formula (Ia). More specifically, trifluoromethylated p-aminophenol is prepared by the method described in J. Org. Chem., 27, 4460 (1962), and trifluoromethylated p-phenylenediamine is prepared by the method described in J. Ind. Chem.,
69, 2229, (1966), for example.
Given as particularly preferable examples of trifluoromethylated aniline derivatives of formula (I) are 4-(2'-hydroxyethyl)amino-3-trifluoromethylaniline, 4-(2'-hydroxyethyl)amino-2-trifluoromethylaniline, 4-(2',3'-dihydroxypropyl)amino-3-trifluoromethylaniline, 1,4-diamino-2-trifluoromethylbenzene, 4-hydroxy-2-trifluoromethylaniline, 4-hydroxy-3-trifluoromethylaniline, 4-(3'-hydroxypropyl)amino-3-trifluoromethylaniline, 4-(2'-hydroxypropyl)amino-3-trifluoromethylaniline, 4-n-butylamino-3-trifluoromethylaniline, 4-sec-butylamino-3-trifluoromethylaniline, 4-n-dodecylamino-3-trifluoromethylaniline, 4-(2'-methoxyethyl)amino-3-trifluoromethylaniline, 4-[2'-(2"-hydroxyethoxy)ethyl]amino-3-trifluoromethylaniline 1-N-(2'-aminoethyl)amino-2-trifluoromethyl-4-aminobenzene, 1-N-(2'-dimethylaminoethyl)amino -2-trifluoromethyl-4-aminobenzene, and 1-N-(2'-carboxyethyl)amino-2-trifluoromethyl-4-aminobenzene. Preferable salts of these trifluoromethylated aniline derivatives are salts of these derivatives of an organic or inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, propionic acid, lactic acid, citric acid, and the like.
There is no specific restriction as to the coupling agent to be used in the dye composition of this invention. Any conventionally used coupling agent can be used for the purpose of this invention. Examples are 5-amino-o-cresol, α-naphthol, o-cresol, m-cresol, 2,6-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, benzcatechin, pyrogallol, 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, hydroquinone, 2,4-diaminoanisole, m-toluylenediamine, 4-aminophenol, resorcin, resorcinmonomethylether, m-phenylenediamine, 1-phenyl-3-methyl-5-pyrazolone, 1-phenyl-3-amino-5-pyrazolone, 1-phenyl-3,5-diketopyrazolidine, 1-methyl-7-dimethyl-amino-4-hydroxy-2-quinolone, 1-amino-3-acetyl-acetamino-4-nitrobenzole, 1-amino-3-cyanacetyl-amino-4-nitrobenzole, m-aminophenol, 4-chlororesorcin, 2-methylresorcin, 2,4-diaminophenoxyethanol, 2,6-diaminopyridine, 2,4-diaminofluorobenzene, 3,5-diamino-fluorobenzene, 3,5-diaminotrifluoromethylbenzene, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-triamino-pyrimidine, 2-amino-4,6-dihydroxypyrimidine, 4-amino-2,6-dihydroxypyrimidine, 4,6-diamino-2-hydroxypyrimidine, p-nitro-o-phenylenediamine, p-nitro-m-phenylenediamine, 2-amino-5-nitrophenol, o-nitro-p-phenylenediamine, 2-amino-4-nitrophenol, and the like. Among these, 5-amino-o-cresol and α-naphthol are desirable for producing a vivid red color, and m-phenylenediamine is effective in obtaining a blue color with a high degree of saturation.
The proportion of the developer and the coupling agent to be formulated into the dye composition of this invention is approximately in the range of 1:0.5 to 1:2 in molar ratio. Excessive use of one component to the other is allowable in this range. One type of developer and coupling agent can be employed either independently or in combination with one or more other types of developers or coupling agents.
In addition to the above-mentioned developers or coupling agents, any known developers, conventional direct dyes, or the like compounds can be formulated to the composition of this invention, if necessary for producing a desired color.
Hairs or other objects are colored by the dye composition of this invention through an oxidizing coupling reaction of the components with the aid of oxygen in the air, when the dye composition is applied to the object to be dyed. Effecting the oxidizing coupling reaction with the aid of a chemical oxidizing agent, however, is more desirable. Especially preferable oxidizing agents are hydrogen peroxide, hydrogen peroxide-adduct of urea, melamine, or sodium borate, or a mixture of one of these hydrogen peroxide-adducts and potassium peroxide-disulfate, and the like.
It is usually desirable to provide the dye composition of this invention in the form of either a cream, emulsion, gel, solution, or the like. Preparing the composition in such forms can be performed according to the conventional method. In this instance, in addition to the developers and coupling agents, various ingredients which are commonly used in cosmetics are formulated into the composition. Such ingredients include wetting agents (emulsifiers), solubilizing agents, viscosity increasing agents, stabilizers, tactile sence improvers, hair conditioning base components, perfumes, and the like. Wetting agents (emulsifiers) used in the composition include, for example, alkylbenzenesulfonates, fatty alcohol sulfates, alkylsulfonates, fatty acid alkanolamides, ethylene oxide adducts of fatty alcohol, and the like. Given as examples of viscosity increasing agents are methyl cellulose, starch, higher fatty alcohols, paraffin oils, fatty acids, and the like. Examples of stabilizers include reducing agents such as sulfites, hydroquinone derivatives, chelating agents, and the like. Tactile sence improvers and hair conditioning base components are typified by silicones, higher alcohols, various kinds of nonionic surface active agents and cationic polymers, and the like.
The amounts of the developers plus coupling agents to be formulated into the abovementioned form of the invented composition are 0.2 to 5% by weight, and preferably 1 to 3% by weight. The desirable amount of the wetting agents (emulsifiers) and viscosity increasing agents in the composition is usually 0.5 to 30% by weight and 0.1 to 25% by weight, respectively.
It is desirable that the overall pH of the composition be adjusted to the range of 8 to 10.
A typical procedure for dyeing keratinous fibers using the dye composition of this invention is now illustrated. A dye fluid is first prepared by adding an oxidizing agent to the dye composition to effect oxidizing coupling of the mixture. This dye fluid is applied to the subject keratinous fibers, which are then allowed to stand for about 10 to 50 minutes, preferably 25 to 35 minutes to effect action of the dye onto the fibers. The keratinous fibers thus sufficiently dyed are finally washed and dried. It is desirable that the temperature of the dye fluid be maintained between 15° to 45° C.
Dyeing with the use of the dye composition according to the present invention ensures a variety of developer - coupling agent combinations, which can provide a wide variety of colors ranging from yellow, red, blue through gray or charcoal with a high degree of color saturation and vividness. In addition, the color produced possesses excellent light resistance, washing resistance, and wear resistance.
Other features of the invention will become apparent in the course of the following description of the exemplary embodiments which are given for illustration of the invention and are not intended to be limiting thereof.
EXAMPLES
Reference Example 1
Synthesis of 1-N-(2'-hydroxyethyl)amino-2-trifluoromethyl-4-nitrobenzene
A mixture of 13.53 g (0.06 mol) of 1-chloro-2-trifluoromethyl-4-nitrobenzene and 8.06 g (0.132 mol) of ethanolamine was stirred under heating at 100°-120° C. for 5 hours. A yellow solid substance deposited in the reaction mixture by the addition of water thereinto was collected by filtration, washed with water, and dried. This substance was recrystallized from chloroform to produce 10.16 g of 1-N-(2'-hydroxyethyl)amino-2-trifluoromethyl-4-nitrobenzene at a yield of 69%.
Melting Point: 86°-87° C. [88° C. in literature (Arzneim. Forsch., 25, 681 (1975)]
Reference Examples 2-17
The compounds listed in Table 1 were prepared in the same manner as in Reference Example 1.
TABLE 1__________________________________________________________________________ ##STR8## (II) Melting Pt.Reference Position Yield or Elemental AnalysisExample X of CF.sub.3 (%) Boiling Pt. C H N__________________________________________________________________________2 CH.sub.2 CH(CH.sub.3)OH 3 91 62-63° C. Found 45.71 4.50 10.81 (m.p.) Calculated 45.46 4.20 10.603 CH.sub.2 CH.sub.2 CH.sub.2 OH 3 97 79-82° C. Found 45.22 4.28 10.32 (m.p.) Calculated 45.46 4.20 10.604 CH.sub.2 CH(OH)CH.sub.2 OH 3 76 99-102° C. Found 42.91 3.81 9.92 (m.p.) Calculated 42.87 3.96 10.005 CH.sub.2 CH.sub.2 OH 2 48 106-109° C. Found 43.33 3.81 11.21 (m.p.) Calculated 43.21 3.63 11.206 CH.sub.2 CH(CH.sub.3)OH 2 47 104-106° C. Found 45.31 4.29 10.48 (m.p.) Calculated 45.46 4.20 10.607 CH.sub.2 CH.sub.2 CH.sub.2 OH 2 53 106-109° C. Found 45.58 4.26 10.87 (m.p.) Calculated 45.46 4.20 10.608 CH.sub.2 CH(OH)CH.sub.2 OH 2 42 96-99° C. Found 42.52 3.99 9.89 (m.p.) Calculated 42.87 3.96 10.009 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 3 85 110° C./0.15 mmHg Found 50.42 5.03 10.91 (b.p.) Calculated 50.38 5.00 10.6810 ##STR9## 3 87 105° C./0.20 mmHg (b.p.) Found Calculated 50.61 50.38 5.01 5.00 10.43 10.6811 (CH.sub.2).sub.5 CH.sub.3 3 80 130° C./0.15 mmHg Found 54.01 5.99 9.72 (b.p.) Calculated 53.79 5.90 9.6512 (CH.sub.2).sub.11 CH.sub.3 3 67 180° C./0.10 mmHg Found 60.22 7.48 7.16 (b.p.) Calculated 60.95 7.81 7.4813 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH 3 86 49-51° C. Found 44.99 4.48 9.53 (m.p.) Calculated 44.90 4.45 9.5214 CH.sub.2 CH.sub.2 OCH.sub.3 3 88 77-79° C. Found 45.52 4.25 10.81 (m.p.) Calculated 45.46 4.19 10.6015 CH.sub.2 CH.sub.2 COOH 3 81 118.5-120.5° C. Found 43.31 3.42 10.55 (m.p.) Calculated 43.17 3.26 10.0716 CH.sub.2 CH.sub.2 NH.sub.2 3 86 89.2-91.6° C. Found 43.31 4.61 16.53 (m.p.) Calculated 43.38 4.33 16.8617 CH.sub.2 CH.sub.2 NMe.sub.2 3 84 83.3-85.0° C. Found 47.22 5.31 20.00 (m.p.) Calculated 47.65 5.09 15.16__________________________________________________________________________
Example 1
Synthesis of 4-(2'-hydroxyethyl)amino-3-trifluoromethylaniline
(1) Synthesis via catalytic reduction
Into 150 ml of ethanol was dissolved 10 g (0.04 mol) of 1-N-(2'-hydroxyethyl)amino-2-trifluoromethyl-4-nitrobenzene. To the mixture 1 g of palladium on charcoal was added, and theoretically equivalent amount of hydrogen was charged at normal temperature and pressure. Catalyst was removed from the reaction mixture by filtration and the filtrate was condensed to produce a solid material. Through recrystallization from carbon tetrachloride 7.48 g of 4-(2'-hydroxyethyl)amino-3-trifluoromethylaniline was obtained at a yield of 85%.
(1) Synthesis via reduction using zinc
To 9.48 g (0.038 mol) of 1-N-(2,-hydroxyethyl)amino-2-trifluoromethyl-4-nitrobenzene were added 11 g of zinc powder, 5 ml of 20% sodium hydroxide and 20 ml of ethanol and the mixture was heated under reflux for 2 hours. After the zink powder was removed from the reaction mixture by filtration, water was added to the filtrate followed by extraction with ethyl acetate. The organic phase obtained was dried over salt cake and codensed to produce a solid material, which was then recrystallized from carbon tetrachloride to obtain 7.16 g of 4-(2'-hydroxyethyl)amino-3-trifluoromethylaniline at a yield of 86%.
Melting point: 74°-75° C.
Elemental analysis:
Found C: 49.29 , H: 5.21 , N: 12.97.
Calculated C: 49.09 , H: 5.04 , N: 12.72.
Examples 2-17
The compounds listed in Table 2 were prepared in the same manner as in Example 1.
TABLE 2__________________________________________________________________________ ##STR10## (Ia) Melting Pt.Reference Position Yield* or Elemental AnalysisExample X of CF.sub.3 (%) Boiling Pt. C H N__________________________________________________________________________2 CH.sub.2 CH(CH.sub.3)OH 3 82 91-93° C. Found 51.36 5.71 11.81 (m.p.) Calculated 51.24 5.59 11.963 CH.sub.2 CH.sub.2 CH.sub.2 OH 3 85 88-90° C. Found 51.22 5.57 11.90 (m.p.) Calculated 51.24 5.59 11.964 CH.sub.2 CH(OH)CH.sub.2 OH 3 94 114-115° C. Found 47.92 5.01 11.03 (m.p.) Calculated 48.00 5.24 11.205 CH.sub.2 CH.sub.2 OH 2 75 47-48° C. Found 49.31 5.21 12.99 (m.p.) Calculated 49.09 5.04 12.726 CH.sub.2 CH(CH.sub.3)OH 2 87 53-55° C. Found 51.33 5.80 12.09 (m.p.) Calculated 51.24 5.59 11.967 CH.sub.2 CH.sub.2 CH.sub.2 OH 2 86 oil** Found 51.31 5.50 11.91 Calculated 51.24 5.59 11.968 CH.sub.2 CH(OH)CH.sub.2 OH 2 75 89-92° C. Found 47.81 5.22 11.48 (m.p.) Calculated 48.00 5.24 11.209 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 3 63 88° C./0.15 mmHg Found 56.88 6.52 12.38 (b.p.) Calculated 56.89 6.51 12.0510 ##STR11## 3 77 75° C./0.1 mmHg (b.p.) Found Calculated 56.66 56.89 6.38 6.51 12.17 12.0611 (CH.sub.2).sub.5 CH.sub.3 3 72 103° C./0.15 mmHg Found 59.76 7.32 10.21 (b.p.) Calculated 59.99 7.36 10.7612 (CH.sub.2).sub.11 CH.sub.3 3 89 140° C./0.10 mmHg Found 65.98 9.21 8.44 (b.p.) Calculated 66.25 9.07 8.1313 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH 3 73 oil** Found 51.12 5.86 10.41 Calculated 50.00 5.72 10.6014 CH.sub.2 CH.sub.2 OCH.sub.3 3 75 90° C./0.15 mmHg Found 51.62 5.82 11.68 (b.p.) Calculated 51.28 5.59 11.9615 CH.sub.2 CH.sub.2 COOH 3 85*** 129.2-130.6° C. Found 48.16 4.40 11.38 (m.p.) Calculated 48.39 4.47 11.2916 CH.sub.2 CH.sub.2 NH.sub.2 3 82 105° C. (0.15 mmHg) Found 49.35 5.58 20.00 (b.p.) Calculated 49.30 5.51 19.1717 CH.sub.2 CH.sub.2 NMe.sub.2 3 84 102° C. (0.1 mmHg) Found 53.51 6.82 17.02 (b.p.) Calculated 53.42 6.52 16.99__________________________________________________________________________ *yield when zinc was used as a reducing catalyst **purified by silica gel column chromatography after reduction ***the reducing yield by PdC
Example
Preparation and Evaluation of the Inventive Compositions
______________________________________Base components:______________________________________oleic acid 10%diethanolamide oleate 8%oleyl alcohol 2%polyoxyethyleneoctyl- 10%dodecylether(Average EO mols: 20)ethanol 15%propylene glycol 10%ammonium chloride 3%25% aqueous ammonium 7%water 35%______________________________________
Into 100 g of the above base components 0.01 mol of the developer Table 3 and 0.01 mol of the coupling agent listed in Table 4 were mixed. The mixture was then adjusted to pH 9.5 with ammonia to produce the dye composition of this invention.
To 100 g of the dye composition of this invention an equivalent weight of 6% aqueous hydroperoxide solution was added to prepare a dye solution. This dye solution was applied to a gray human hair, which was left at 30° C. for 30 minutes. The hair was subsequently washed with a normal shampoo and dried. Table 5 shows the observed color tone of the dyed hair.
TABLE 3______________________________________Developers______________________________________P1: 4-(2'-hydroxyethyl)amino-3-trifluoromethylanilineP2: 4-(2'-hydroxyethyl)amino-2-trifluoromethylanilineP3: 4-(2',3'-dihydroxypropyl)amino-3-trifluoromethylanilineP4: 1,4-diamino-2-trifluoromethylbenzeneP5: 4-hydroxy-2-trifluoromethylanilineP6: 4-hydroxy-3-trifluoromethyl-anilineP7: 4-sec-butylamino-3-trifluoromethylanilineP8: 4-n-butylamino-3-trifluoromethylanilineP9: 4-n-dodecylamino-3-trifluoromethylanilineP10: 4-(2'-methoxyethyl)amino-3-trifluoromethylaniline______________________________________
TABLE 4______________________________________Coupling Agents______________________________________C1: m-phenylenediamineC2: resorcinC3: m-aminophenolC4: p-amino-o-cresolC5: α-naphtholC6: m-phenylenediamineC7: resorcinC8: m-aminophenolC9: 5-amino-o-cresol______________________________________
TABLE 5______________________________________Composition CouplingNos. Developers agents Color tone______________________________________ 1 P1 C1 blue 2 P1 C2 brown 3 P1 C3 brown-black 4 P1 C4 red 5 P1 C5 purplish red 6 P2 C1 grayish green 7 P2 C2 pale yellow 8 P2 C3 red 9 P2 C4 purplish red10 P2 C5 blue11 P3 C1 blue12 P3 C2 brown13 P3 C3 brown-black14 P3 C4 red15 P3 C5 purplish red16 P4 C6 blue17 P4 C7 green18 P4 C8 liver color19 P4 C9 red20 P5 C6 brown21 P5 C7 ivory22 P5 C8 yellowish orange23 P5 C9 orange24 P6 C6 light brown25 P6 C7 ivory26 P6 C8 light brown27 P6 C9 orange28 P7 C1 green29 P7 C2 cream30 P7 C4 orange31 P7 C5 purplish red32 P8 C4 orange33 P8 C5 violet34 P9 C4 cream35 P9 C5 light purple36 P10 C4 orange37 P10 C5 violet______________________________________
Obviously, numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.
1.PublishNumber: US-5041608-A
2.Date Publish: 19910820
3.Inventor: MANO; TSUTOMU
KAWASE; JIRO
MISU; DAISUKE
OBAYASHI; MICHIO
4.Inventor Harmonized: MANO TSUTOMU(JP)
KAWASE JIRO(JP)
MISU DAISUKE(JP)
OBAYASHI MICHIO(JP)
5.Country: US
6.Claims:
(en)A dye composition for keratinous fibers comprising a specific type of trifluoromethylated aniline derivative, as a developer, and a coupling substance is disclosed. The composition provides high degree of saturation and vividness of colors as well as good fastness. Dyeing with the use of the dye composition ensures a variety of developer-coupling agent combinations, which can provide a wide variety of colors with a high degree of color saturation and vividness. The color produced possesses excellent light resistance, washing resistance, and wear resistance. Amoung the trifluoromethylated aniline derivative, used as a developer, a p-phenylenediamine-type trifluoromethylated aniline derivative of the following formula is a novel compound. ##STR1## in which X represents a specific type of mono- or polyhydroxyalkyl group, alkyl group, or other organic group.
7.Description:
(en)This is a division of application Ser. No. 07/217,776, filed on July 12, 1988, now U.S. Pat. No. 4,871,372.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a dye composition for keratinous fibers, and, more particularly, to a dye composition for keratinous fibers which is capable of dyeing keratinous fibers such as hairs and the like at a high degree of saturation and vividness, and to a p-phenylenediamine derivative useful as a developer when formulated into such a dye composition. The invention also is directed to a process for preparing the p-phenylenediamine derivatives.
2. Description of the Background
Oxidizing dyes, in which a developer and a coupling agent are employed in combination, have widely been used for dyeing keratinous fibers such as hairs or the like. These oxidizing dyes make use of the strong dyeing capability of oxidizing coloring substances which are produced by the oxidizing-coupling reaction of a developer and a coupling agent. Para-phenylenediamine derivatives, diaminopyridine derivatives, 4-aminopyrazolone derivatives, hetero-cyclic hydrazone, and the like are used as the developer.
These conventional oxidizing dyes have defects in their performance which are yet to be satisfied in terms of saturation or vividness of colors, dyeing capability, and fastness. Development of a dye which is free from these defects has, therefore, been desired.
Performance of an oxidizing dye such as saturation or vividness of colors, dyeing capability, fastness, and the like is greatly dependent upon the characteristics of the developer used. It is, therefore, very important in eliminating the above defects of oxidizing dyes to find a developer possessing an excellent characteristics.
The present inventors have undertaken extensive studies in order to overcome the above problems in oxidizing dyes, and as a result found that use of a trifluoromethylated aniline derivative for dyeing keratinous fibers provides a high degree of saturation and vividness of colors as well as good fastness. This finding has led to the completion of this invention.
SUMMARY OF THE INVENTION
Accordingly an object of this invention is to provide a dye composition for keratinous fibers comprising a developer and a coupling substance, wherein said developer is a trifluoromethylated aniline derivative represented by the following formula (I) or a salt thereof: ##STR2## in which R represents a hydroxyl group or a group represented by --NHR', wherein R, represents a C 2-6 mono- or polyhydroxyalkyl group, a C 1-20 alkyl group, or a group represented by --(CH 2 ) n --O--R", [wherein R" stands for a C 1-4 alkyl group, a C 1-4 mono- or polyhydroxyalkyl group and n denotes an integer of 1 to 4], a group represented by --(CH 2 ) n --NR 3 R 4 (wherein R 3 and R 4 may be same or different and denote hydrogen atoms, C 1-20 alkyl groups, or C 2-6 mono- or polyhydroxyalkyl groups, and n denotes an integer of 1 to 4), or --(CH 2 ) n --COOR 5 (wherein R 5 is a hydrogen atom, a C 2-6 alkyl group, or a C 2-6 mono- or polyhydroxyalkyl group, and n denotes an integer of 1 to 4).
Another object of this invention is to provide a novel p-phenylenediamine derivative represented by the following formula (Ia) or a salt thereof: ##STR3## in which X represents a C 2-6 mono- or polyhydroxyalkyl group, a C 1-20 alkyl group, or a group represented by --(CH 2 ) n --O--R", [wherein R" stands for a C 1-4 alkyl group, a C 1-4 mono- or polyhydroxyalkyl group and n denotes an integer of 1 to 4], a group represented by --(CH 2 ) n --NR 3 R 4 (wherein R 3 and R 4 may be same or different and denote hydrogen atoms, C 1-20 alkyl groups, or C 2-6 mono- or polyhydroxyalkyl groups, and n denotes an integer of 1 to 4), or --(CH 2 ) n --COOR 5 (wherein R 5 is a hydrogen atom, a C 1-6 alkyl group, or a C 2-6 mono- or polyhydroxyalkyl group, and n denotes an integer of 1 to 4).
Still another object of this invention is to provide a process for preparing the above novel p-phenylenediamine derivative the formula (Ia) or a salt thereof, which comprises reducing a compound represented by the following formula (II): ##STR4## in which X has the same meaning as defined for the formula (Ia).
Other objects, features and advantages of the invention will hereinafter become more readily apparent from the following description.
DETAILED DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS
Among trifluoromethylated aniline derivatives, p-phenylenediamine derivatives represented by the following formula (Ia) or the salts thereof are novel compounds. ##STR5## in which X represents a C 2-6 mono- or polyhydroxyalkyl group, a C 1-20 alkyl group, or a group represented by --(CH 2 ) n --O--R", [wherein R" stands for a C 1-4 alkyl group, a C 1-4 mono- or polyhydroxyalkyl group, and n denotes an integer of 1 to 4] a group represented by --(CH 2 ) n --NR 3 R 4 (wherein R 3 and R 4 may be same or different and denote hydrogen atoms, C 1-20 alkyl groups, or C 2-66 mono- or polyhydroxyalkyl groups, and n denotes an integer of 1 to 4), or --(CH 2 ) n --COOR 5 (wherein R 5 is a hydrogen atom, a C 1-6 alkyl group, or a C 2-6 mono- or polyhydroxyalkyl group.
The p-phenylenediamine derivative of formula (Ia) can be prepared, for example, by reducing the compound (II) according to the following reaction scheme: ##STR6##
The compound (II) can be prepared, for example, by the reaction of the chlorinated compound of the formula (III) and mono- or polyhydroxyalkylamine of the formula (IV). ##STR7##
This reaction may be carried out according to the method described in Arzneim. Forsch., 25, 681 (1975).
The reduction of the compound of formula (II) may be carried out according to the conventional reduction of a nitro group. A simple and effective method, however, is a catalytic hydrogenation or reduction in the presence of zinc under alkaline conditions
Palladium, platinum, copper, nickel, or the like are used for the catalytic hydrogenation. A solvent such as methanol, ethanol, ethyl acetate, dimethylformamide, or the like is desirably used in the reaction. The reaction temperature is in the range between room temperature and the boiling point of the solvent used, and the pressure may be 1 to 250 kg/cm 2 . Upon completion of the reaction, the catalyst is removed by filtration. After condensation of the filtrate, purification can be performed very easily by evaporating the solvent or recrystallizing the target compound.
Reduction using zinc is carried out by heating the raw materials under reflux in an aqueous solution of alkali such as sodium hydroxide, potassium hydroxide, or the like in the presence of an excess amount of zinc, and adding to the reaction system, as required, a solvent dissolvable in water such as methanol, ethanol, acetone, N,N-dimethylformamide, dimethylsulfoxide, or the like. Upon completion, solid substances are removed by filtration, and the filtrate is extracted with a suitable solvent and condensed. The condensate thus obtained can be easily purified by evaporating the solvent or recrystallizing the target compound.
The compound of this invention of formula (Ia) thus prepared can be converted according to a conventional method into a salt by reaction of this compound with an organic or inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, propionic acid, lactic acid, citric acid, or the like.
Compounds of formula (I), other than those of formula (Ia) which is novel in the art, can be prepared by reducing p-nitrophenol or p-nitroaniline trifluoromethylated according to the process which was discussed just above in connection with the process for preparing the compound of formula (Ia). More specifically, trifluoromethylated p-aminophenol is prepared by the method described in J. Org. Chem., 27, 4460 (1962), and trifluoromethylated p-phenylenediamine is prepared by the method described in J. Ind. Chem.,
69, 2229, (1966), for example.
Given as particularly preferable examples of trifluoromethylated aniline derivatives of formula (I) are 4-(2'-hydroxyethyl)amino-3-trifluoromethylaniline, 4-(2'-hydroxyethyl)amino-2-trifluoromethylaniline, 4-(2',3'-dihydroxypropyl)amino-3-trifluoromethylaniline, 1,4-diamino-2-trifluoromethylbenzene, 4-hydroxy-2-trifluoromethylaniline, 4-hydroxy-3-trifluoromethylaniline, 4-(3'-hydroxypropyl)amino-3-trifluoromethylaniline, 4-(2'-hydroxypropyl)amino-3-trifluoromethylaniline, 4-n-butylamino-3-trifluoromethylaniline, 4-sec-butylamino-3-trifluoromethylaniline, 4-n-dodecylamino-3-trifluoromethylaniline, 4-(2'-methoxyethyl)amino-3-trifluoromethylaniline, 4-[2'-(2"-hydroxyethoxy)ethyl]amino-3-trifluoromethylaniline 1-N-(2'-aminoethyl)amino-2-trifluoromethyl-4-aminobenzene, 1-N-(2'-dimethylaminoethyl)amino -2-trifluoromethyl-4-aminobenzene, and 1-N-(2'-carboxyethyl)amino-2-trifluoromethyl-4-aminobenzene. Preferable salts of these trifluoromethylated aniline derivatives are salts of these derivatives of an organic or inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, propionic acid, lactic acid, citric acid, and the like.
There is no specific restriction as to the coupling agent to be used in the dye composition of this invention. Any conventionally used coupling agent can be used for the purpose of this invention. Examples are 5-amino-o-cresol, α-naphthol, o-cresol, m-cresol, 2,6-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, benzcatechin, pyrogallol, 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, hydroquinone, 2,4-diaminoanisole, m-toluylenediamine, 4-aminophenol, resorcin, resorcinmonomethylether, m-phenylenediamine, 1-phenyl-3-methyl-5-pyrazolone, 1-phenyl-3-amino-5-pyrazolone, 1-phenyl-3,5-diketopyrazolidine, 1-methyl-7-dimethyl-amino-4-hydroxy-2-quinolone, 1-amino-3-acetyl-acetamino-4-nitrobenzole, 1-amino-3-cyanacetyl-amino-4-nitrobenzole, m-aminophenol, 4-chlororesorcin, 2-methylresorcin, 2,4-diaminophenoxyethanol, 2,6-diaminopyridine, 2,4-diaminofluorobenzene, 3,5-diamino-fluorobenzene, 3,5-diaminotrifluoromethylbenzene, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-triamino-pyrimidine, 2-amino-4,6-dihydroxypyrimidine, 4-amino-2,6-dihydroxypyrimidine, 4,6-diamino-2-hydroxypyrimidine, p-nitro-o-phenylenediamine, p-nitro-m-phenylenediamine, 2-amino-5-nitrophenol, o-nitro-p-phenylenediamine, 2-amino-4-nitrophenol, and the like. Among these, 5-amino-o-cresol and α-naphthol are desirable for producing a vivid red color, and m-phenylenediamine is effective in obtaining a blue color with a high degree of saturation.
The proportion of the developer and the coupling agent to be formulated into the dye composition of this invention is approximately in the range of 1:0.5 to 1:2 in molar ratio. Excessive use of one component to the other is allowable in this range. One type of developer and coupling agent can be employed either independently or in combination with one or more other types of developers or coupling agents.
In addition to the above-mentioned developers or coupling agents, any known developers, conventional direct dyes, or the like compounds can be formulated to the composition of this invention, if necessary for producing a desired color.
Hairs or other objects are colored by the dye composition of this invention through an oxidizing coupling reaction of the components with the aid of oxygen in the air, when the dye composition is applied to the object to be dyed. Effecting the oxidizing coupling reaction with the aid of a chemical oxidizing agent, however, is more desirable. Especially preferable oxidizing agents are hydrogen peroxide, hydrogen peroxide-adduct of urea, melamine, or sodium borate, or a mixture of one of these hydrogen peroxide-adducts and potassium peroxide-disulfate, and the like.
It is usually desirable to provide the dye composition of this invention in the form of either a cream, emulsion, gel, solution, or the like. Preparing the composition in such forms can be performed according to the conventional method. In this instance, in addition to the developers and coupling agents, various ingredients which are commonly used in cosmetics are formulated into the composition. Such ingredients include wetting agents (emulsifiers), solubilizing agents, viscosity increasing agents, stabilizers, tactile sence improvers, hair conditioning base components, perfumes, and the like. Wetting agents (emulsifiers) used in the composition include, for example, alkylbenzenesulfonates, fatty alcohol sulfates, alkylsulfonates, fatty acid alkanolamides, ethylene oxide adducts of fatty alcohol, and the like. Given as examples of viscosity increasing agents are methyl cellulose, starch, higher fatty alcohols, paraffin oils, fatty acids, and the like. Examples of stabilizers include reducing agents such as sulfites, hydroquinone derivatives, chelating agents, and the like. Tactile sence improvers and hair conditioning base components are typified by silicones, higher alcohols, various kinds of nonionic surface active agents and cationic polymers, and the like.
The amounts of the developers plus coupling agents to be formulated into the abovementioned form of the invented composition are 0.2 to 5% by weight, and preferably 1 to 3% by weight. The desirable amount of the wetting agents (emulsifiers) and viscosity increasing agents in the composition is usually 0.5 to 30% by weight and 0.1 to 25% by weight, respectively.
It is desirable that the overall pH of the composition be adjusted to the range of 8 to 10.
A typical procedure for dyeing keratinous fibers using the dye composition of this invention is now illustrated. A dye fluid is first prepared by adding an oxidizing agent to the dye composition to effect oxidizing coupling of the mixture. This dye fluid is applied to the subject keratinous fibers, which are then allowed to stand for about 10 to 50 minutes, preferably 25 to 35 minutes to effect action of the dye onto the fibers. The keratinous fibers thus sufficiently dyed are finally washed and dried. It is desirable that the temperature of the dye fluid be maintained between 15° to 45° C.
Dyeing with the use of the dye composition according to the present invention ensures a variety of developer - coupling agent combinations, which can provide a wide variety of colors ranging from yellow, red, blue through gray or charcoal with a high degree of color saturation and vividness. In addition, the color produced possesses excellent light resistance, washing resistance, and wear resistance.
Other features of the invention will become apparent in the course of the following description of the exemplary embodiments which are given for illustration of the invention and are not intended to be limiting thereof.
EXAMPLES
Reference Example 1
Synthesis of 1-N-(2'-hydroxyethyl)amino-2-trifluoromethyl-4-nitrobenzene
A mixture of 13.53 g (0.06 mol) of 1-chloro-2-trifluoromethyl-4-nitrobenzene and 8.06 g (0.132 mol) of ethanolamine was stirred under heating at 100°-120° C. for 5 hours. A yellow solid substance deposited in the reaction mixture by the addition of water thereinto was collected by filtration, washed with water, and dried. This substance was recrystallized from chloroform to produce 10.16 g of 1-N-(2'-hydroxyethyl)amino-2-trifluoromethyl-4-nitrobenzene at a yield of 69%.
Melting Point: 86°-87° C. [88° C. in literature (Arzneim. Forsch., 25, 681 (1975)]
Reference Examples 2-17
The compounds listed in Table 1 were prepared in the same manner as in Reference Example 1.
TABLE 1__________________________________________________________________________ ##STR8## (II) Melting Pt.Reference Position Yield or Elemental AnalysisExample X of CF.sub.3 (%) Boiling Pt. C H N__________________________________________________________________________2 CH.sub.2 CH(CH.sub.3)OH 3 91 62-63° C. Found 45.71 4.50 10.81 (m.p.) Calculated 45.46 4.20 10.603 CH.sub.2 CH.sub.2 CH.sub.2 OH 3 97 79-82° C. Found 45.22 4.28 10.32 (m.p.) Calculated 45.46 4.20 10.604 CH.sub.2 CH(OH)CH.sub.2 OH 3 76 99-102° C. Found 42.91 3.81 9.92 (m.p.) Calculated 42.87 3.96 10.005 CH.sub.2 CH.sub.2 OH 2 48 106-109° C. Found 43.33 3.81 11.21 (m.p.) Calculated 43.21 3.63 11.206 CH.sub.2 CH(CH.sub.3)OH 2 47 104-106° C. Found 45.31 4.29 10.48 (m.p.) Calculated 45.46 4.20 10.607 CH.sub.2 CH.sub.2 CH.sub.2 OH 2 53 106-109° C. Found 45.58 4.26 10.87 (m.p.) Calculated 45.46 4.20 10.608 CH.sub.2 CH(OH)CH.sub.2 OH 2 42 96-99° C. Found 42.52 3.99 9.89 (m.p.) Calculated 42.87 3.96 10.009 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 3 85 110° C./0.15 mmHg Found 50.42 5.03 10.91 (b.p.) Calculated 50.38 5.00 10.6810 ##STR9## 3 87 105° C./0.20 mmHg (b.p.) Found Calculated 50.61 50.38 5.01 5.00 10.43 10.6811 (CH.sub.2).sub.5 CH.sub.3 3 80 130° C./0.15 mmHg Found 54.01 5.99 9.72 (b.p.) Calculated 53.79 5.90 9.6512 (CH.sub.2).sub.11 CH.sub.3 3 67 180° C./0.10 mmHg Found 60.22 7.48 7.16 (b.p.) Calculated 60.95 7.81 7.4813 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH 3 86 49-51° C. Found 44.99 4.48 9.53 (m.p.) Calculated 44.90 4.45 9.5214 CH.sub.2 CH.sub.2 OCH.sub.3 3 88 77-79° C. Found 45.52 4.25 10.81 (m.p.) Calculated 45.46 4.19 10.6015 CH.sub.2 CH.sub.2 COOH 3 81 118.5-120.5° C. Found 43.31 3.42 10.55 (m.p.) Calculated 43.17 3.26 10.0716 CH.sub.2 CH.sub.2 NH.sub.2 3 86 89.2-91.6° C. Found 43.31 4.61 16.53 (m.p.) Calculated 43.38 4.33 16.8617 CH.sub.2 CH.sub.2 NMe.sub.2 3 84 83.3-85.0° C. Found 47.22 5.31 20.00 (m.p.) Calculated 47.65 5.09 15.16__________________________________________________________________________
Example 1
Synthesis of 4-(2'-hydroxyethyl)amino-3-trifluoromethylaniline
(1) Synthesis via catalytic reduction
Into 150 ml of ethanol was dissolved 10 g (0.04 mol) of 1-N-(2'-hydroxyethyl)amino-2-trifluoromethyl-4-nitrobenzene. To the mixture 1 g of palladium on charcoal was added, and theoretically equivalent amount of hydrogen was charged at normal temperature and pressure. Catalyst was removed from the reaction mixture by filtration and the filtrate was condensed to produce a solid material. Through recrystallization from carbon tetrachloride 7.48 g of 4-(2'-hydroxyethyl)amino-3-trifluoromethylaniline was obtained at a yield of 85%.
(1) Synthesis via reduction using zinc
To 9.48 g (0.038 mol) of 1-N-(2,-hydroxyethyl)amino-2-trifluoromethyl-4-nitrobenzene were added 11 g of zinc powder, 5 ml of 20% sodium hydroxide and 20 ml of ethanol and the mixture was heated under reflux for 2 hours. After the zink powder was removed from the reaction mixture by filtration, water was added to the filtrate followed by extraction with ethyl acetate. The organic phase obtained was dried over salt cake and codensed to produce a solid material, which was then recrystallized from carbon tetrachloride to obtain 7.16 g of 4-(2'-hydroxyethyl)amino-3-trifluoromethylaniline at a yield of 86%.
Melting point: 74°-75° C.
Elemental analysis:
Found C: 49.29 , H: 5.21 , N: 12.97.
Calculated C: 49.09 , H: 5.04 , N: 12.72.
Examples 2-17
The compounds listed in Table 2 were prepared in the same manner as in Example 1.
TABLE 2__________________________________________________________________________ ##STR10## (Ia) Melting Pt.Reference Position Yield* or Elemental AnalysisExample X of CF.sub.3 (%) Boiling Pt. C H N__________________________________________________________________________2 CH.sub.2 CH(CH.sub.3)OH 3 82 91-93° C. Found 51.36 5.71 11.81 (m.p.) Calculated 51.24 5.59 11.963 CH.sub.2 CH.sub.2 CH.sub.2 OH 3 85 88-90° C. Found 51.22 5.57 11.90 (m.p.) Calculated 51.24 5.59 11.964 CH.sub.2 CH(OH)CH.sub.2 OH 3 94 114-115° C. Found 47.92 5.01 11.03 (m.p.) Calculated 48.00 5.24 11.205 CH.sub.2 CH.sub.2 OH 2 75 47-48° C. Found 49.31 5.21 12.99 (m.p.) Calculated 49.09 5.04 12.726 CH.sub.2 CH(CH.sub.3)OH 2 87 53-55° C. Found 51.33 5.80 12.09 (m.p.) Calculated 51.24 5.59 11.967 CH.sub.2 CH.sub.2 CH.sub.2 OH 2 86 oil** Found 51.31 5.50 11.91 Calculated 51.24 5.59 11.968 CH.sub.2 CH(OH)CH.sub.2 OH 2 75 89-92° C. Found 47.81 5.22 11.48 (m.p.) Calculated 48.00 5.24 11.209 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 3 63 88° C./0.15 mmHg Found 56.88 6.52 12.38 (b.p.) Calculated 56.89 6.51 12.0510 ##STR11## 3 77 75° C./0.1 mmHg (b.p.) Found Calculated 56.66 56.89 6.38 6.51 12.17 12.0611 (CH.sub.2).sub.5 CH.sub.3 3 72 103° C./0.15 mmHg Found 59.76 7.32 10.21 (b.p.) Calculated 59.99 7.36 10.7612 (CH.sub.2).sub.11 CH.sub.3 3 89 140° C./0.10 mmHg Found 65.98 9.21 8.44 (b.p.) Calculated 66.25 9.07 8.1313 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH 3 73 oil** Found 51.12 5.86 10.41 Calculated 50.00 5.72 10.6014 CH.sub.2 CH.sub.2 OCH.sub.3 3 75 90° C./0.15 mmHg Found 51.62 5.82 11.68 (b.p.) Calculated 51.28 5.59 11.9615 CH.sub.2 CH.sub.2 COOH 3 85*** 129.2-130.6° C. Found 48.16 4.40 11.38 (m.p.) Calculated 48.39 4.47 11.2916 CH.sub.2 CH.sub.2 NH.sub.2 3 82 105° C. (0.15 mmHg) Found 49.35 5.58 20.00 (b.p.) Calculated 49.30 5.51 19.1717 CH.sub.2 CH.sub.2 NMe.sub.2 3 84 102° C. (0.1 mmHg) Found 53.51 6.82 17.02 (b.p.) Calculated 53.42 6.52 16.99__________________________________________________________________________ *yield when zinc was used as a reducing catalyst **purified by silica gel column chromatography after reduction ***the reducing yield by PdC
Example
Preparation and Evaluation of the Inventive Compositions
______________________________________Base components:______________________________________oleic acid 10%diethanolamide oleate 8%oleyl alcohol 2%polyoxyethyleneoctyl- 10%dodecylether(Average EO mols: 20)ethanol 15%propylene glycol 10%ammonium chloride 3%25% aqueous ammonium 7%water 35%______________________________________
Into 100 g of the above base components 0.01 mol of the developer Table 3 and 0.01 mol of the coupling agent listed in Table 4 were mixed. The mixture was then adjusted to pH 9.5 with ammonia to produce the dye composition of this invention.
To 100 g of the dye composition of this invention an equivalent weight of 6% aqueous hydroperoxide solution was added to prepare a dye solution. This dye solution was applied to a gray human hair, which was left at 30° C. for 30 minutes. The hair was subsequently washed with a normal shampoo and dried. Table 5 shows the observed color tone of the dyed hair.
TABLE 3______________________________________Developers______________________________________P1: 4-(2'-hydroxyethyl)amino-3-trifluoromethylanilineP2: 4-(2'-hydroxyethyl)amino-2-trifluoromethylanilineP3: 4-(2',3'-dihydroxypropyl)amino-3-trifluoromethylanilineP4: 1,4-diamino-2-trifluoromethylbenzeneP5: 4-hydroxy-2-trifluoromethylanilineP6: 4-hydroxy-3-trifluoromethyl-anilineP7: 4-sec-butylamino-3-trifluoromethylanilineP8: 4-n-butylamino-3-trifluoromethylanilineP9: 4-n-dodecylamino-3-trifluoromethylanilineP10: 4-(2'-methoxyethyl)amino-3-trifluoromethylaniline______________________________________
TABLE 4______________________________________Coupling Agents______________________________________C1: m-phenylenediamineC2: resorcinC3: m-aminophenolC4: p-amino-o-cresolC5: α-naphtholC6: m-phenylenediamineC7: resorcinC8: m-aminophenolC9: 5-amino-o-cresol______________________________________
TABLE 5______________________________________Composition CouplingNos. Developers agents Color tone______________________________________ 1 P1 C1 blue 2 P1 C2 brown 3 P1 C3 brown-black 4 P1 C4 red 5 P1 C5 purplish red 6 P2 C1 grayish green 7 P2 C2 pale yellow 8 P2 C3 red 9 P2 C4 purplish red10 P2 C5 blue11 P3 C1 blue12 P3 C2 brown13 P3 C3 brown-black14 P3 C4 red15 P3 C5 purplish red16 P4 C6 blue17 P4 C7 green18 P4 C8 liver color19 P4 C9 red20 P5 C6 brown21 P5 C7 ivory22 P5 C8 yellowish orange23 P5 C9 orange24 P6 C6 light brown25 P6 C7 ivory26 P6 C8 light brown27 P6 C9 orange28 P7 C1 green29 P7 C2 cream30 P7 C4 orange31 P7 C5 purplish red32 P8 C4 orange33 P8 C5 violet34 P9 C4 cream35 P9 C5 light purple36 P10 C4 orange37 P10 C5 violet______________________________________
Obviously, numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.
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