N-Monosubstituted indoanilines

The present invention relates to indoanilines in which the amino group in the 4'-position is monosubstituted.
It is known to dye keratin fibers, more particularly living human hair, by applying to the hair, in the presence of an oxidizing agent such as hydrogen peroxide, added at the time of use, a dyeing composition comprising a mixture, in a suitable cosmetic carrier, of compounds belonging to each of two categories. The first category of compounds, generally called "oxidation bases", comprises mainly para-phenylene-diamines or para-amino-phenols which lead, on oxidation, to para-benzoquinonediimines or to para-benzoquinone-monoimines. The second category of compounds, generally called "coupling agents", comprises meta-amino-phenols, meta-acetylamino-phenols, meta-diamines and meta-diphenols. They are compounds with which the benzoquinonemono or di-imines will react to give rise to dyestuffs called, depending on their structure, indophenols, indoanilines or indamines.
These dyestuffs, from which a range of exceptionally rich shades can be obtained, are primarily noted for the luminous nature and for the rich sheen attainable therewith. However, when a complex dyeing composition is used, that is to say a composition which comprises several bases and several coupling agents, it is often very difficult to predict the contribution which each possible combination of oxidation base and coupling agent will make to the final shade. In other words, firstly, it is very difficult at the start to make an exact prediction as to the final shade, and, secondly, for a given dyeing composition, it is not often easy to be certain of perfect reproducibility. These difficulties are increased by the fact that various side reactions change the final shade. Examples of such side reactions are the formation of compounds of the Bandrowsky base type from the oxidation bases, the recondensation of a molecule of oxidation base with certain indophenols or with certain indoanilines or indamines and the formation of quinones.
An object of the present invention is to provide a process for dyeing keratin fibers, and particularly living human hair, which does not require the addition of an oxidizing agent at the time of use. The present invention also relates to the dyes and dye compositions for use in said process.
The objects of the present invention can be achieved by using certain novel indoanilines which possess the advantage of being able to give a very particularly rich range of extremely luminous shades of excellent aesthetic quality.
It has been found that by varying the nature of the substituent in the 4'-position it is possible to change various characteristics of such dyes, in particular their solubility, affinity and compatibility. Thus, increased solubility can be achieved by introducing a hydroxyalkyl or sulphoalkyl substituent, while the solubility of the dye in an alkaline medium can be improved by introducing a mesylaminoalkyl substituent. The affinity of the dye for keratin fibers can be increased by introducing an aminoalkyl substituent.
The present invention provides a N-monoalkylamino-indoaniline of the formula (I) ##STR2## wherein
each of R.sub.1 and R.sub.4, which may be identical or different, represents hydrogen, halogen, lower alkyl, lower alkoxy, acylamino or ureido;
each of R.sub.2 and R.sub.3, which may be identical or different, represents hydrogen, halogen, lower alkyl, lower alkoxy, amino, N-(lower alkyl)-amino, N-[hydroxy-(lower alkyl)]-amino, N-[carbamyl-(lower alkyl)]-amino, acylamino or ureido;
each of R.sub.5 or R.sub.6, which may be identical or different, represents hydrogen, halogen, lower alkyl or lower alkoxy, with the proviso that R.sub.5 and R.sub.6 can occupy any two free positions but when they are both other than a hydrogen, at least one of the two occupies a meta-position relative to the --NHR.sub.7 group; and
R.sub.7 represents unsubstituted lower alkyl or substituted lower alkyl, and in particular hydroxy-(lower alkyl), acylamino-(lower alkyl), mesylamino-(lower alkyl), carbamyl(lower alkyl), amino-(lower alkyl), piperidino-(lower alkyl) or morpholino(lower alkyl).
By "lower" alkyl or "lower" alkoxy is meant alkyl or alkoxy containing 1 to 6, preferably 1 to 4, carbon atoms.
The invention also relates to the tautomeric form of the compounds of formula (I), especially those of the formula ##STR3## or in the case where R.sub.3 denotes an optionally monosubstituted amino group, those of the formula ##STR4## wherein R represents hydrogen, lower alkyl, hydroxy-(lower alkyl) or carbamyl-(lower alkyl).
The compounds of this invention can be prepared by condensing a compound of the formula: ##STR5## or an addition salt thereof, on a phenolic compound of the formula ##STR6## or an addition salt thereof.
In formula (IV), Z represents --NH.sub.2 or --NO. When Z denotes --NH.sub.2, R.sub.1 to R.sub.7 are as defined above for formula (I). When Z denotes --NO, R.sub.1 to R.sub.6 are as defined above for formula (I) and R.sub.7 represents unsubstituted lower alkyl.
When Z denotes --NH.sub.2, the condensation is suitably carried out in an aqueous, aqueous-alcoholic or aqueous-acetone medium, at an alkaline pH generally greater than 8 and in the presence of an oxidizing agent, for example, ammonium persulphate, potassium ferricyanide or hydrogen peroxide. Generally the alkaline pH is obtained with ammonia or with an alkaline carbonate preferably sodium carbonate and the reaction is carried out at a temperature from 0.degree. to 25.degree. C.
When Z denotes --NO, the condensation is generally carried out at a temperature of about 50.degree. C., in an aqueousethanolic medium which is neutral or has been rendered alkaline by adding a dilute solution of a base preferably sodium hydroxide.
The present invention also provides a dyeing composition for keratin fibers, and particularly for living human hair, which contains in a compatible vehicle, usually an aqueous or aqueous-alcoholic solution, at least one compound of the present invention.
These dyeing compositions generally contain 0.001 to 2% of compound of formula (I), relative to the total weight of the composition.
The dyeing composition according to this invention can contain the indoanilines of formula (I) as the only dyestuff. It is, however, possible to mix the dyestuffs of this invention with other dyestuffs usually employed for dyeing hair, for example nitrobenzene, azo, anthraquinone, indamine, indophenol and/or other indoaniline dyestuffs. Generally when a dye other than the dye of the present invention is employed, the said other dye or dyes is present in amounts of about 0.001 to 1 percent by weight of said composition.
The compositions according to the present invention are generally in the form of an aqueous or aqueous-alcoholic solution containing one or more compounds of formula (I), which may or may not be mixed with other dyestuffs. They can however also contain, for example, thickeners and be in the form of creams or gels. Suitable thickeners which can be used include cellulosic derivatives such as methyl-cellulose, hydroxyethyl-cellulose and carboxymethyl-cellulose; acrylic polymers such as the sodium salt of polyacrylic acid and ethanolamides of fatty acids, preferably mono- or diethanolamide of fatty acids of copra, carboxyvinyl polymers. The thickener can be present, for instance, in amounts of about 0.5 to 7 percent by weight of said composition.
The dyeing composition can contain, as solvents, water, lower alkanols, for example ethanol or isopropanol, and polyhydric alcohols such as glycols, for example ethylene glycol, propylene glycol, butyl glycol, diethylene glycol and the monomethyl ether of diethylene glycol. The solvent is generally present in amounts of about 1 to 60 percent by weight of said composition.
The compositions can also contain various adjuvants usually employed in cosmetics for the hair, such as wetting agents, for example oxyethylenated alkylphenols and oxyalkylenated fatty alcohol sulphates and sulphonates, dispersing agents, swelling agents, penetrating agents, softeners or perfumes. They can, moreover, be packaged in aerosol containers in the presence of a propellant gas. Suitable propellant gases include nitrogen, nitrous oxide, volatile hydrocarbons such as butane, isobutane or propane, or, preferably, fluorinated hydrocarbons (sold under the name of "Freon") such as dichloridifluoromethane, 1,1-difluoro-methane, 1,2,-dichloro-1,1,2,2-tetrafluoro-ethane or 1-chloro-1,1-difluoro-methane; mixtures of two or more hydrocarbons or fluorinated hydrocarbons can also be used.
The pH of the compositions, which can vary within wide limits, is generally from about 5 to 11 and preferably from 7 to 9. The pH can be adjusted by means of an alkali, for example ammonia, mono-, di- or tri-ethanolamine, di- or tri- sodium phosphate, or sodium or potassium carbonate, or by means of an acid, for example acetic acid, lactic acid, phosphoric acid or citric acid.
The dyeing of keratin fibers, particularly living human hair, by means of the dyeing compositions according to the present invention can be carried out in the usual way by applying the composition to the fibers to be dyed, leaving it in contact therewith for about 5 to 30 minutes, and then rinsing the fibers and optionally washing them and drying them.
Depending on the nature of the substituents, the indoanilines of the present invention make it possible to obtain a very wide range of colors ranging from greens to violets via blues; only yellows and oranges are not represented. The dyeings obtained are notable for their luminous nature and their rich sheen, especially a pearly or metallic sheen.
When the compositions according to the invention are in the form of aqueous-alcoholic solutions, they can also contain a cosmetic resin, in which case they form what are commonly called colored wavesetting lotions, which can be applied to wet hair before setting it in waves. These compositions generally contain about 0.001 to 0.5% of a compound of formula (I).
Representative cosmetic resins which can be used in such wavesetting lotions according to this invention include such film-forming polymers as polyvinylpyrrolidone, copolymers of vinylpyrrolidone and vinyl acetate, copolymers of vinyl acetate and an unsaturated carboxylic acid such as crotonic acid, copolymers resulting from the copolymerization of vinyl acetate, crotonic acid and an acrylic or methacrylic ester, copolymers resulting from the copolymerization of vinyl acetate and an alkyl vinyl ether, copolymers resulting from the copolymerization of vinyl acetate, crotonic acid and a vinyl ester of an acid with a long carbon chain (i.e. more than 8 carbon atoms) or an allyl or methallyl ester of an acid with a long carbon chain, copolymers resulting from the copolymerization of an ester derived from an unsaturated alcohol and from an acid with a short carbon chain (i.e. not more than 8 carbon atoms), an unsaturated acid with a short chain and at least one ester derived from a saturated alcohol with a short chain and from an unsaturated acid, and copolymers resulting from the copolymerization of at least one unsaturated ester and at least one unsaturated acid.
Representative preferred resins include polyvinylpyrrolidone having a molecular weight of 10,000 to 360,000; copolymers comprising 10% of crotonic acid and 90% of vinyl acetate having a molecular weight of 10,000 to 70,000; copolymers of vinylpyrrolidone (VP) and vinyl acetate (VA) with a molecular weight of 30,000 to 200,000, the VP/VA ratio being from 30/70 to 70/30; copolymers of maleic anhydride and methyl vinyl ether, the specific viscosity of which, measured at 25.degree. C. as 1 g/100 ml solution in methyl ethyl ketone, is from 0.1 to 3.5 centipoises, the ethyl, isopropyl and butyl monoesters of copolymers of maleic anhydride and methyl vinyl ether; copolymers of maleic anhydride and butyl vinyl ether; terpolymers of methyl methacrylate (15-25%), stearyl methacrylate (25-35%) and dimethylaminoethyl methacrylate (52-62%), preferably quaternized, for example by means of dimethyl-sulphate, the viscosity of which, measured at the boiling point of the ether as 5% solution in dimethylformamide, is from 8 to 12 centipoises; and terpolymers of vinyl acetate (75-85%), allyl stearate (10-20%) and allyloxy-acetic acid (3-10%), the viscosity of which, measured at the boiling point of the ether as a 5% solution in dimethylformamide, is from 4.4 to 5 centipoises.
These resins are generally used in an amount from 1 to 3% by weight of the total weight of the composition.
The alcohols which are suitable for producing wavesetting lotions according to the invention are alcohols of low molecular weight, preferably ethanol or isopropanol. These alcohols are suitably employed in an amount from 20 to 70% by weight.
The wavesetting lotions according to the present invention can be employed in the usual way, by applying them to wet hair which has been washed and rinsed beforehand, constraining in a deformed state, for example by winding up on curlers and drying the hair.
The dye composition of the present invention can include a surface active agent as a carrier or as a thickening agent. Representative surface active agents that can usefully be employed include oxyethylenated alcohols, particularly oxyethylenated lauryl alcohol; partially sulfated oxyethylenated lauryl alcohol and preferably a mixture consisting of 19% lauryl alcohol oxyethylenated with 2 moles of ethylene oxide and 81% of the sodium sulfate salt of this same oxyethylenated alcohol; the alkaline or ammonium sulfate salts of long chain fatty alcohols, for example, ammonium lauryl sulfate; and oxyethylenated alkylphenols and preferably nonylphenol oxyethylenate with 4 or 9 moles of ethylene oxide per mole of alkylphenol. The surface active agent is generally employed in amounts of about 2 to 30 percent by weight of said composition.
The invention is illustrated by the following examples which are tabulated in Tables I, II, III and IV.

Examples pertaining to the preparation of the dyes of the present invention appear in Tables I and II. Table I which provides data concerning the characteristics of the prepared benzoquinoneimine dyes of this invention has columns numbered 1 through 9 inclusive. Column 1 indicates the number of the Example; Column 2 identifies the benzoquinoneimine prepared; Column 3 gives the melting point of the prepared benzoquinoneimine; Column 4 provides the empirical formula for the prepared benzoquinoneimine; and Columns 5 through 9 tabulate respectively the percentages of C, H, N, Cl and S in said dye. For each compound prepared, columns 5 through 9 carry two or three lines. The first line indicates the theoretical percentage of the indicated element corresponding to the empirical formula of column 4; line 2, and when provided, line 3 indicate the percentages found by analysis.
Table II which synopsizes the process by which the benzoquinones appearing in Table I are prepared, has eight columns numbered 1 and 10-16. Column 1 indicates, as in Table I, the number of the Example of preparation; Column 10 indicates the substituted aniline initial reactant; Column 11 identifies the substituted phenol initial reactant; Column 12 gives the molar ratio of the substituted phenol of Column 11 to the substituted aniline of Column 10; Column 13 identifies the reaction medium employed; Column 14 lists when appropriate the particular oxidizing agent used; Column 15 indicates, also when appropriate, the molar ratio of the oxidizing agent of Column 14 to phenol of Column 11; and Column 16 identifies the reaction temperature employed in degrees centigrade.
The benzoquinoneimines of Examples 1 to 8 are prepared by the reaction of a substituted nitroso aniline of the formula ##STR7## on a substituted phenol of formula (V), in ethanol or a 1:1 ethanol-water mixture made alkaline by sodium hydroxide and in the absence of an oxidizing agent.
The benzoquinoneimines of Example 9 and following are prepared by the reaction of a substituted p-phenylenediamine (substituted aniline) of the formula (VII) ##STR8## on a substituted phenol of formula (V). The molar ratio of substituted phenol:substituted aniline can be between 1:0.5 and 1:1.2 and preferably between 1:0.65 and 1:1. The molar ratio of oxidizing agent:phenol is between 1:1 and 4:1 when there is employed, as the oxidizing agent, ammonium persulfate or potassium ferricyanide. This molar ratio however is from 8:1 when there is used, as the oxidizing agent, hydrogen peroxide. The latter is generally employed in the form of a 6 weight percent solution. The reaction medium comprises water, a lower alkanol, preferably ethanol, propanol or isopropanol, an acetone-water mixture or a lower alkanol-water mixture, both generally in a 1:1 volume ratio. The pH of the reaction medium is alkalinized to a pH of at least 8, preferably by the addition thereto of an alkalizing agent such as ammonia or an alkaline carbonate.
The Examples of use include not only examples of simple dye compositions which are tabulated in Table IV, but also of dye compositions containing a cosmetic film forming resin. The latter compositions are often referred to as hair setting lotions and are tabulated in Table III.
Table III contains 12 columns numbered from 11 to 22. Column 11 indicates the number of the Example of the hair setting lotion. The column carries a number preceded by the letter M. Column 12 indicates the number of the Example of preparation according to which is prepared the benzoquinoneimine used as the dye or the letter C followed by a number which represents another dye used in admixture with the benzoquinoneimine. The name of this additional dye appears at the bottom of the table. Column 13 indicates the amount of dye expressed in weight percent of the total weight of the composition. Columns 14-17 concern the cosmetic resin used. Column 14 indicates the name of the resin and column 15 its average molecular weight. Column 16 reports the viscosity of the resin in centipoises while Column 17 indicates the weight percent of the resin relative to the total weight of the composition. Columns 18 and 19 reveal, respectively, the name and the weight percent (relative to the total weight of the composition), of the alcohol used. Column 20 indicates the pH of the composition while Column 22 indicates the color obtained on the bleached hair (D) or 95% naturally white hair (B 95). This latter indication of the type of hair to which the composition is applied appears in column 21. In Column 14, the name of the resin, polymer or copolymer, is indicated by abbreviations. These abbreviations and their meaning are as follows: PVP=polyvinylpyrrolidone; VA/CA=copolymer of vinyl acetate and crotonic acid; VP/VA=copolymer of vinylpyrrolidone and vinyl acetate; and MM/StM/DEM=copolymer of methyl methacrylate (15-25%)/stearyl methacrylate (25-35%)/dimethylaminoethyl methacrylate (52-62%) quaternized with dimethyl sulfate.
The viscosity of the VP/VA copolymer is measured at 25.degree. C. in a 5% solution in ethanol. The viscosity of the terpolymer MM/StM/DEM is measured at the boiling point of ether (35.degree. C.) and at a concentration of 5% in dimethylformamide.
Table IV carries 12 columns numbered from 31 to 42. Column 31 indicates the number of the Example of the dye composition. This column carries a number preceded by the letter T. Column 32 indicates the number of the Example of preparation according to which is prepared the benzoquinoneimine used as the dye or the letter C followed by a number which represents another dye used in admixture with the benzoquinoneimine and for which the name appears at the bottom of the Table. Columns 34 and 35 indicate respectively the nature and the weight percent of the surface active agent used. Column 33 indicates the amount of dye employed, expressed in weight percent. Columns 36 and 37 indicate, respectively, the name and weight percent of the solvent used while Columns 38 and 39 indicate the name and weight percent of the adjuvant used. Column 40 indicates the pH of the composition and Column 42 indicates the color obtained on bleached hair (D) or on 95% naturally white hair (B 95). This latter indication of the type of hair to which the composition is applied appears in Column 41. All percents indicated are by weight of the total weight of the composition.
In Columns 34 and 38, the name of the surface active agent and various adjuvants are indicated by abbreviations, the meanings of which appear at the bottom of the Table.
TABLE I ANALYSIS Example Melting C H N Cl S N.degree. BENZOQUINONEIMINE Point Empirical Formula % % % % % (1) (2) (.degree.C.)(3) (4) (5) (6) (7) (8) (9) 1 N--[(4'-ethylamino)phenyl]-2-methyl-5- 225 C.sub.17 H.sub.20 N.sub.4 O.sub.2 65.36 6.45 17.94 carbamylmethylamino benzoquinoneimine 65.06 6.59 18.16 65.08 6.64 18.04 2 N--[(4'-ethylamino- 2'-methyl)phenyl]-2,6- 128 C.sub.17 H.sub.21 N.sub.3 O 72.05 7.47 14.83 dimethyl-3-amino benzoquinoneimine 72.38 7.62 15.12 72.45 7.51 15.09 3 N--[(4'-ethylamino-2'-methyl)phenyl]-2- 182 C.sub.16 H.sub.19 N.sub.3 O 71.34 7.11 15.60 methyl-5-amino benzoquinoneimine 71.41 7.21 15.76 71.32 7.32 15.82 4 N--[(4'-ethylamino)phenyl]-2-chl oro-5-amino 184 C.sub.14 H.sub.14 N.sub.3 OCl 60.98 5.09 15.25 12.87 benzoquinoneimine 61.07 5.17 15.24 12.92 60.94 5.14 15.34 13.90 5 N--[(4'-ethylamino-3'-methyl)phenyl]-2,6- 147 C.sub.17 H.sub.21 N.sub.3 O 72.05 7.47 14.83 dimethyl-3-amino benzoquinoneimine 71.78 7.42 15.04 71.67 7.53 14.65 6 N--[4'-ethylamino)phenyl]-2,6-dimethyl-3- 162 C.sub.16 H.sub.19 N.sub.3 O 71.34 7.11 15.60 amino benzoquinoneimine 71.12 7.11 15.79 71.28 6.90 15.76 7 N--[(4'-methylamino-2',5'-dimeth yl)phenyl]- 210 C.sub.17 H.sub.21 N.sub.3 O 72.05 7.47 14.83 2,6-dimethyl-3-amino benzoquinoneimine 71.94 7.77 14.81 8 N--[(4'-methylamino)phenyl]-2-methyl-5-amino 162 C.sub.14 H.sub.15 N.sub.3 O 69.69 6.27 17.42 benzoquinoneimine 68.52 6.33 17.62 68.57 6.39 17.55 9 N--[(4'-methylamino-3'-methoxy)p henyl]-2,6- 156 C.sub.16 H.sub.18 N.sub.2 O.sub.2 71.09 6.71 10.36 dimethyl benzoquinoneimine 70.86 6.83 10.42 70.79 6.76 10.49 10 N--[(4'-methylamino)phenyl]-2,6-dimethyl-3- 166 C.sub.15 H.sub.17 N.sub.3 O 70.56 6.71 16.46 amino benzoquinoneimine 70.75 6.67 16.49 MW = 255 (1) 70.41 6.68 16.52 251 (2) 11 N--[(4'-ethylamino-2'-methyl)phenyl]-3-chloro 222 C.sub.16 H.sub.17 N.sub.4 O.sub.2 Cl 57.74 5.11 16.87 10.67 6-ureido benzoquinoneimine 57.26 5.04 16.61 10.41 57.30 5.21 16.71 10.47 12 N--[(4'-butylamino-3'-chloro)phenyl]-2-methyl 87 C.sub.19 H.sub.22 N.sub.3 O.sub.2 Cl 63.42 6.16 11.67 9.85 5-acetylamino benzoquinoneimine 63.06 6.16 11.87 9.69 63.14 6.23 11.73 9.66 13 N--[(4'-eth ylamino-2'-methyl)phenyl]-3-ureido 212 C.sub.16 H.sub.18 N.sub.4 O.sub.2 64.41 6.08 18.78 benzoquinoneimine 64.29 6.25 18.47 64.58 6.09 18.62 14 N--[(4'-methylamino)phenyl]-2,6-dimethyl 158 C.sub.17 H.sub.19 N.sub.3 O.sub.2 68.66 6.44 14.13 3-acetylamino benzoquinoneimine 68.29 6.57 14.25 68.32 6.58 14.34 15 N--[(4'-ethylamino-2'-methyl)phenyl]-3-chloro 162 C.sub.17 H.sub.18 N.sub.3 O.sub.2 Cl 61.54 5.43 12.67 10.71 6-acetylamino benzoquinoneimine 60.98 5.26 12.97 10.39 61.22 5.25 12.86 10.45 16 N--[(4'-e thylamino)phenyl]-2-methyl-5-acetyl- 100 C.sub.17 H.sub.19 N.sub.3 O.sub.2 68.66 6.44 14.13 amino benzoquinoneimine 68.12 6.44 13.98 68.41 6.66 13.94 (1) Molecular weight calculated (2) Molecular weight determined by potentiometric titration in acetic aci using perchloric acid17 N--[(4'-butylamino-3'-chloro)phenyl] 124 C.sub.18 H.sub.20 N.sub.3 O.sub.2 Cl 62.52 5.80 12.15 10.25 3-acetylamino benzoquinoneimine 62.35 6.03 12.21 10.40 62.29 6.04 12.09 10.17 18 N--[(4'-ethylamino)phenyl]-2-chloro-5-acetyl- 198 C.sub.16 H.sub.16 N.sub.3 O.sub.2 Cl 60.47 5.04 13.22 amino benzoquinoneimine 59.98 4.97 13.21 59.85 5.06 13.17 19 N-[(4'-ethylamino-3'chlor o)phenyl] 144 C.sub.17 H.sub.18 N.sub.3 O.sub.2 Cl 61.53 5.46 12.66 10.68 2-methyl-5-acetylamino benzoquinoneimine 61.57 5.61 12.53 10.79 61.28 5.51 12.86 10.65 20 N--[4'-(.beta.-acetyla mino-ethyl)amino phenyl] 126 C.sub.17 H.sub.18 N.sub.3 O.sub.2 Cl 61.54 5.46 12.64 10.70 3-methyl-6-chloro benzoquinoneimine 61.24 5.60 12.55 10.59 61.32 5.54 12.47 10.48 21 N--[(4'-(.beta. -hydroxyethyl)amino phenyl] 206 C.sub.14 H.sub.14 N.sub.3 O.sub.2 50.00 4.16 12.50 23.84 2-bromo-5-amino benzoquinoneimine 50.12 4.35 12.60 23.62 50.24 4.28 12.36 23.65 22 N--[(4'-.beta.-h ydroxyethylamino-3'-methyl)phenyl] 242 C.sub.18 H.sub.21 N.sub.3 O.sub.3 66.03 6.47 12.84 2-methyl-5-acetylamino benzoquinoneimine 65.85 6.65 12.93 65.87 6.44 13.06 23 N--[(4'-.beta.-morpholino ethylamino)phenyl]-2-chloro 180 C.sub.20 H.sub.23 N.sub.4 O.sub.3 Cl 59.62 5.71 13.91 8.81 5-acetylamino benzoquinoneimine 59.03 5.61 14.06 8.72 58.98 5.87 14.18 8.74 24 N--[(4'-.beta.-mo rpholinoethylamino)phenyl]-3-ureido 178 C.sub.19 H.sub.23 N.sub.5 O.sub.3 61.77 6.28 18.96 benzoquinoneimine 61.05 6.26 18.82 61.28 6.22 18.75 25 N--[(4'-.beta.-mesylamino-ethylamino)phenyl ]-2- 126 C.sub.18 H.sub.22 N.sub.4 O.sub.4 S 55.38 5.68 14.35 methyl-5-acetylamino benzoquinoneimine 55.02 5.97 14.35 55.17 5.82 14.43 26 N--[(4'-.beta.-acetylaminoethylamino)phenyl]-3- 230 C.sub.17 H.sub.18 N.sub.5 O.sub.3 Cl 54.33 4.80 18.64 chloro-6-ureido benzoquinoneimine 54.22 5.11 18.67 54.48 5.08 18.55 27 N--[(4'-.beta.-hydroxyethylamin o-3'-methoxy)phenyl] 150 C.sub.16 H.sub.19 N.sub.3 O.sub.3 63.77 6.36 13.95 2-methyl-5-amino benzoquinoneimine 63.81 6.53 14.02 64.02 6.65 14.19 28 N--[(4'-.beta.-mesylaminoethylamino-3'-methyl) 148 C.sub.20 H.sub.26 N.sub.4 O.sub.4 S 57.40 6.26 13.39 7.64 phenyl]-2,6-dimethyl-5-acetylamino benzoqui- 57.52 6.24 13.53 7.66 noneimine 57.23 6.27 13.45 7.44 29 N--[(4'-.be ta.-acetylaminoethylamino-3'-methoxy) 183 C.sub.19 H.sub.24 N.sub.4 O.sub.3 64.02 6.79 15.72 phenyl]-2,6-dimethyl-5-amino benzoquinonei- 63.87 6.58 15.51 mine 63.74 6.70 15.20 30 N--[(4'-.beta .-mesylamino ethylamino-3'-chloro) 244 C.sub.18 H.sub.21 N.sub.4 O.sub.4 S Cl 50.88 4.98 13.18 7.54 phenyl]-2-methyl-5-acetylamino benzoquin onei- 50.71 5.20 13.36 7.26 mine 50.77 5.20 13.42 7.38 31 N--[(4'-.beta.-acetylamino-3'-chloro)phenyl]2,6- 161 C.sub.18 H.sub.20 N.sub.3 O.sub.2 Cl 62.51 5.79 12.15 10.27 dimethyl benzoquinoneimine 62.29 5.80 12.21 10.23 62.36 5.94 12.10 10.38 32 N--[(4'-.beta.-hydroxyethylamino-3'-methoxy)phenyl] - 165 C.sub.17 H.sub.21 O.sub.3 N.sub.3 64.74 6.71 13.33 2,6-dimethyl-5-amino benzoquinoneimine 64.66 6.78 13.17 64.50 6.78 13.15 33 N--[(4'-.beta.-hyd roxyethylamino-3'-methoxy)phenyl]- 110 C.sub.19 H.sub.23 O.sub.4 N.sub.3.H.sub.2 O 60.79 6.71 11.19 2,6-dimethyl-5-acetylamino benzoquinoneimine 60.53 6.58 11.31 60.45 6.61 11.36 34 N--[(4'-.beta.-hydroxyethylamino-3'-chloro)phenyl]- 144 C.sub.16 H.sub.15 N.sub.3 O.sub.3 Cl.sub.2 52.19 4.10 11.41 19.26 3-chloro-6-acetylamino benzoquinonei mine 52.05 4.42 11.52 19.16 51.93 4.38 11.36 19.23 35 N--[(4'-.beta.-aminoethylamino-3'-methyl-6'-methoxy) 168 C.sub.18 H.sub.24 N.sub.4 O.sub.2 65.83 7.37 17.06 phenyl]-2,6-dimethyl-3-amino benzoquinoneimi ne 65.12 7.03 16.98 65.24 7.17 16.84 36 N--[(4'-.beta .-mesylaminoethylamino-3'-methyl) 242 C.sub.19 H.sub.24 N.sub.4 O.sub.4 S 56.43 5.98 13.86 7.91 phenyl]-2-methyl-5-acetylamino benzoquinone i- 56.41 6.04 14.07 7.74 mine 56.58 6.21 14.12 7.84 37 N--[(4'-.beta.-acetylaminoethylamino-3'-methyl) 222 C.sub.18 H.sub.21 N.sub.5 O.sub.3 60.83 5.96 19.71 phenyl]-3-ureido benzoquinoneimine 60.66 6.16 19.61 60.57 5.97 19.70 38 N--[(4'-.beta.-carbamylme thylamino-3'-methyl) 240 C.sub.19 H.sub.22 N.sub.4 O.sub.3 64.39 6.26 15.81 phenyl]-2,6-dimethyl-3-acetylamino benzo- 64.98 6.47 15.45 quinoneimine 64.87 6.53 15.78 39 N--[(4'-.gamma.-morpholino propylamino-3'-chloro) 214 C.sub.21 H.sub.24 N.sub.4 O.sub.3 Cl.sub.2 55.87 5.36 12.41 15.74 phenyl]-3-chloro-6-acetylamino benzoquinonei- 55.58 5.56 12.56 15.78 mine MW 451 (1) 448 (2) 40 N--[ (4'-methylamino)phenyl]-2,6-dimethyl benzo- 132 C.sub.15 H.sub.16 N.sub.2 O 74.97 6.71 11.66 quinoneimine 74.68 6.91 11.44 MW 240 (1) 239 (2) 41 N--[(4'-methylamino-3'-methyl)phenyl]-2,6-di- 160 C.sub.18 H.sub.21 N.sub.3 O.sub.2 69.43 6.80 13.50 methyl-3-acetylamino benzoquinoneimine 69.36 6.73 13.28 42 N--[(4'-methylamino-2'-methyl)phenyl]-2,6-di- 218 C.sub.18 H.sub.21 N.sub.3 O.sub.2 69.43 6.80 13.50 methyl-3-acetylamino benzoquinoneimine 69.60 6.68 13.27 43 N--[(4'-methylamino-3'-methyl)phenyl]-2,6-di- 138 C.sub.16 H.sub.18 N.sub.2 O 75.56 7.13 11.02 methyl benzoquinoneimine 75.69 7.12 11.11 44 N--[(4'-methylamino-2'-methyl)phenyl]-2,6- 129.5 C.sub.16 H.sub.18 N.sub.2 O 75.56 7.13 11.02 dimethyl benzoquinoneimine 75.61 7.01 11.32 MW 254 (1) 260 (2) 45 N--[(4'-.beta.-hydroxyethylamino-2'-methoxy)phe nyl]- 163 C.sub.18 H.sub.21 N.sub.3 O.sub.4 62.96 6.16 12.24 2-methyl-5-acetylamino benzoquinoneimine 62.76 6.31 12.24 46 N--[(4'-.beta.-acetylaminoethylamino-3'-chloro) 156 C.sub.17 H.sub.18 N.sub.3 O.sub.3 Cl 58.70 5.18 12.08 phenyl]-3-methoxy benzoquinoneimine 58.41 4.97 12.20 58.56 5.04 12.17 47 N--[(4'-.beta.-mesylamino ethylamino)phenyl]-2,6-di- 157 C.sub.19 H.sub.24 N.sub.4 O.sub.4 S 56.43 5.98 13.86 8.07 methyl-3-acetylamino benzoquinoneimine 56.30 6.00 13.98 7.91 48 N--[(4'-.beta.-hydroxyethylamino)phenyl]-2-methyl- 5- 162 C.sub.17 H.sub.19 N.sub.3 O.sub.3 65.16 6.11 13.41 acetylamino benzoquinoneimine 65.16 6.25 13.63 49 N--[(4'-.beta.-hydroxyethylamin o-3'-methoxy)phenyl]- 166 C.sub.17 H.sub.20 N.sub.2 O.sub.3 67.98 6.71 9.33 2,6-dimethyl benzoquinoneimine 67.90 6.72 9.30 50 N--[(4'-.gamm a.-morpholinopropylamino-3'-chloro) 212 C.sub.19 H.sub.22 N.sub.4 Br.sub.2 ClO.sub.2 50.17 4.85 12.35 phenyl]-2-bromo-5-amino benzoquinoneimine 50.10 5.06 12.65 51 N--[ (4'-methylamino-2'-methoxy)phenyl]-2,6-di- 249 C.sub.18 H.sub.21 N.sub.3 O.sub.3 66.03 6.47 12.84 methyl-5-acetylamino benzoquinoneimine 65.84 6.52 12.79 52 N--[(4'-methylamino-2'-methoxy)phenyl]-2-methyl 204 C.sub.17 H.sub.19 N.sub.3 O.sub.3 65.16 6.11 13.41 5-acetylamino benzoquinoneimine 64.92 6.19 13.34 53 N--[(4'-methylamino-3'-methoxy) phenyl]-2,6-di- 195 C.sub.16 H.sub.19 N.sub.3 O.sub.2 67.34 6.71 14.73 methyl-5-amino benzoquinoneimine 67.20 6.71 14.99 54 N--[(4'-methyla mino-2'-methoxy)phenyl]-2- 178 C.sub.15 H.sub.17 N.sub.3 O.sub.2.0.5H.sub.2 O 64.28 6.42 15.00 methyl-5-amino benzoquinoneimine 64.26 6.61 14.87 55 N--[(4'-methylamino-3'-chloro)phenyl]-2-methyl- 206 C.sub.16 H.sub.16 Cl N.sub.3 O.sub.2 60.45 5.07 13.22 5-acetylamino benzoquinoneimine 60.35 5.23 13.31 56 N--[(4'-methylamino-3'-chloro)phenyl]-2,6- 166 C.sub.17 H.sub.18 Cl N.sub.3 O.sub.2 61.53 5.47 12.66 10.68 dimethyl-5-acetylamino benzoquinoneim ine 61.61 5.62 12.51 10.53 57 N--[(4'-methylamino-3'-chloro)phenyl]- 2,6-di- 127 C.sub.15 H.sub.15 Cl N.sub.2 O 65.58 5.50 10.19 12.90 methyl benzoquinoneimine 65.41 5.60 10.24 12.90 58 N--[(4'-methylami no-3'-chloro)phenyl]-2,6- 165 C.sub.15 H.sub.16 Cl N.sub.3 O.0.5H.sub.2 O 60.30 5.70 14.01 11.91 dimethyl-5-amino benzoquinoneimine 60.64 5.70 14.07 11.98 59 N--[(4'-methylamino-3'-chloro)phenyl]-2-methyl- 174 C.sub.14 H.sub.14 Cl N.sub.3 O 60.98 5.11 15.24 12.86 5-amino benzoquinoneimine 61.17 5.32 15.10 12.67 60 N--[(4'-methylamino-2'-c hloro)phenyl]-2,6- 235 C.sub.17 H.sub.18 Cl N.sub.3 O.sub.2 61.53 5.47 12.66 10.68 dimethyl-5-acetylamino benzoquinoneimine 61.26 5.56 12.90 10.47 61 N--[(4'-methylamino-2'-chloro)phenyl]-2,6-di- 182 C.sub.15 H.sub.16 N.sub.3 OCl 62.16 5.56 14.50 12.23 methyl-5-amino benzoquinoneimine 61.92 5.71 14.30 12.05 62 N--[(4'-methylamino-2'-c hloro)phenyl]-2-methyl- 180 C.sub.14 H.sub.14 N.sub.3 O Cl 60.98 5.11 15.24 12.86 5-amino benzoquinoneimine 60.83 4.99 15.10 12.74 63 N--[(4'-methylamino-2'-chloro)phenyl]-2- 234 C.sub.16 H.sub.16 N.sub.3 O.sub.2 Cl 60.47 5.07 13.22 methyl-5-acetylamino benzoquinoneimine 60.42 5.29 13.18 64 N--[(4'-methylamino-3'-methoxy)phenyl]-2,6- 120 C.sub.18 H.sub.21 N.sub.3 O.0.5H.sub.2 O 64.28 6.54 12.50 dimethyl-5-acetylamino benzoquinoneimine 158(1) 64.52 6.78 12.69 65 N--[(4'-methylamino-2'-chloro)phenyl]-2-methyl- 190 C.sub.16 H.sub.18 N.sub.3 O.sub.2 Cl 60.09 5.67 13.14 11.11 5-.beta.-hydroxyethylamino benzoquinoneimine 60.15 5.86 13.31 11.19 66 N--[(4'-methylamino-2'-methoxy)phenyl]-2,6-di- 152 C.sub.16 H.sub.18 N.sub.2 O.sub.2 71.09 6.71 10.36 methyl benzoquinoneimine 71.40 6.91 10.15 67 N--[(4'-methylamino-2'-methoxy)phenyl]-2,6-di- 200 C.sub.16 H.sub.19 N.sub.3 O.sub.2 67.34 6.71 14.73 methyl-5-amino benzoquinoneimine 67.25 6.57 14.77 68 N--[(4'-methylamino-2'-methyl)p henyl]2-methyl- 140 C.sub.15 H.sub.17 N.sub.3 O.0.5H.sub.2 O 68.16 6.86 15.90 5-amino benzoquinoneimine 68.35 6.99 16.11 69 N-- [(4'-methyl amino-2'-methyl)phenyl]-2,6-di- 149 C.sub.16 H.sub.19 N.sub.3 O 71.34 7.11 15.60 methyl-5-amino benzoquinoneimine 71.30 7.03 15.59 70 N--[(4'-methylamino-2'-chloro)phenyl]-2,6-di- 138 C.sub.15 H.sub.15 N.sub.2 O Cl 65.57 5.50 10.20 12.91 methyl benzoquinoneimine 65.56 5.74 10.35 12.76 71 N--[(4'-methylamino-2'-methyl)phenyl]-2-methyl- 175 C.sub.17 H.sub.19 N.sub.3 O.sub.2 68.66 6.44 14.13 5-acetylamino benzoquinoneimine 68.66 6.63 14.35 72 N--[(4'-methylamino-3'-methyl)p henyl]-2,6-di- 152 C.sub.16 H.sub.19 N.sub.3 O 71.34 7.11 15.60 methyl-5-amino benzoquinoneimine 71.20 7.01 15.73 73 N--[(4'-methylam ino-3'-methyl)phenyl]-2-methyl- 210 C.sub.17 H.sub.19 N.sub.3 O.sub.2 68.66 6.44 14.13 5-acetylamino benzoquinoneimine 68.64 6.49 14.28 74 N--[(4'-methylamino-3'-methyl)phenyl]-2-methyl- 166 C.sub.15 H.sub.17 N.sub.3 O 70.56 6.71 16.46 5-amino benzoquinoneimine 70.33 6.72 16.34 75 N--[(4'-methylamino)phenyl]-2-methyl-5-acetyl- 161 C.sub.16 H.sub.17 N.sub.3 O.sub.2 67.82 6.05 14.83 amino benzoquinoneimine 67.72 6.18 14.92 76 N--[(4'-methylamino-3'-methoxy)phenyl]-2- 179 C.sub.18 H.sub.21 N.sub.3 O.sub.4 62.96 6.16 12.24 methyl-5-carbethoxyamino benzoquinoneimine 63.02 6.28 12.06 77 N--[(4'-methylamino-3'-chloro)phenyl]-2-methyl- 228 C.sub.15 H.sub.15 N.sub.4 O.sub.2 Cl 56.51 4.71 17.58 11.14 5-ureido benzoquinoneimine 56.61 4.90 17.63 10.93 78 N--[(4'-.beta.- hydroxyethylamino-3'-chloro)phenyl]- 195 C.sub.17 H.sub.19 N.sub.4 O.sub.3 Cl 56.30 5.24 15.42 9.79 2,6-dimethyl-3-ureido benzoquinoneimine 56.41 5.34 15.33 9.81 79 N--[(4'-.beta.-hydroxyethylamino-3'-chloro)ph enyl]- 280 C.sub.15 H.sub.15 N.sub.4 O.sub.3 Cl 53.81 4.48 16.74 10.61 3-ureido benzoquinoneimine 53.86 4.71 16.62 10.36 80 N--[(4'-.beta.-hydroxyethylamino-3'-chloro)phenyl]- 178 C.sub.16 H.sub.16 N.sub.3 O.sub.3 Cl 57.57 4.79 12.59 10.64 3-acetylamino benzoquinoneimine 57.39 4.79 12.71 10.48 81 N--[(4'-.beta.-hydroxyet hylamino-3'-chloro)phenyl]- 176 C.sub.17 H.sub.18 N.sub.3 O.sub.3 Cl 58.70 5.18 12.08 10.21 2-methyl-5-acetylamino benzoquinoneimine 58.83 5.19 12.17 10.36 82 N--[(4'-.beta.-hydroxyethylamino-3'-chloro)p henyl]- 240 C.sub.16 H.sub.17 N.sub.4 O.sub.3 Cl 55.09 4.88 16.07 10.18 2-methyl-5-ureido benzoquinoneimine 54.84 4.97 16.03 10.18 54.83 4.91 16.00 10.30 83 N--[(4'-methylamino)phenyl]-2- methyl-5- 228 C.sub.16 H.sub.18 N.sub.4 O.sub.2 --H.sub.2 O 17.71 carbamylmethylamino benzoquinoneimine 17.40 MW 298 (1) 304 (2) 84 N--[(4'-methylamino-2'-methyl)phenyl]- 200 C.sub.17 H.sub.20 N.sub.4 O.sub.2 17.94 2-methyl-5-carbamylmethylamino benzoquinonei- 17.58 mine 17.68 85 N--[(4'-methylamino-3'-m ethyl)phenyl] -2-methyl- 240 C.sub.17 H.sub.20 N.sub.4 O.sub.2 65.36 6.45 17.94 5-carbamylmethylamino benzoquinoneimine 65.18 6.60 18.10 86 N--[(4'-.beta.-acetylaminoethylamino-3'chloro) 230 with C.sub.19 H.sub.22 N.sub.5 O.sub.3 Cl 56.50 5.45 17.35 phenyl]-2-methyl-5-carbamylmethylamino benzo- decomposi- 56.20 5.53 17.45 quinoneimine tion 87 N--[(4'-.beta.-mesyl aminoethylamino-3'-chloro) 203 with C.sub.18 H.sub.22 N.sub.5 O.sub.4 SCl.H.sub.2 O 47.21 5.28 15.30 7.74 6.99 phenyl]-2-methyl-5-carbamylmethylamino - decomposi- 47.34 5.15 14.98 7.78 7.03 benzoquinoneimine tion 88 N--[(4'-.beta.-hydroxyethylamino)phenyl]-2-methyl 235 with C.sub.17 H.sub.20 N.sub.4 O.sub.3.H.sub.2 O 58.94 6.40 16.18 5-carbamylmethylamino benzoquinoneimine decomposi- 59.15 6.26 16.33 tion 89 N--[(4'-.beta.-mesylaminoethylamino-3'-met hyl) 215 with C.sub.19 H.sub.25 N.sub.5 O.sub.4 S 54.40 6.01 16.70 phenyl]-2-methyl-5-carbamylmethylamino decomposi- 54.26 5.90 16.57 benzoquinoneimine tion 90 N--[(4'-methylamino-3'chloro)phenyl]-2-methyl- 120 C.sub.16 H.sub.17 N.sub.4 O.sub.2 Cl.H.sub.2 O 54.78 5.46 16.26 10.11 5-carbamylmethylamino benzoquinoneimine 212(3) 54.67 5.16 16.53 10.13 91 N--[(4'-.beta.-mesylaminoethylamino-3'-chloro) 228 C.sub.17 H.sub.20 N.sub.5 O.sub.4 SCl 47.94 4.70 16.45 8.34 7.50 phenyl]-2-methyl-5-ureido benzoquino neimine 47.78 4.74 16.63 8.54 7.52 8.47 7.56 92 N--[(4'-.beta.-mesylaminoethylamino-3'-chloro) 253 C.sub.16 H.sub.18 N.sub.5 O.sub.4 SCl 8.62 7.72 phenyl]-3-ureido benzoquinoneimine 8.70 7.94 8.79 93 N--[(4'-methylamino-3'-chloro)phenyl] -3-acetyl-198 C.sub.15 H.sub.14 N.sub.3 O.sub.2 Cl 59.31 4.61 13.84 amino benzoquinoneimine 59.21 4.81 13.93 94 N--[4'-ethylamino-3'-meth yl)phenyl]-2-methyl- 185 C.sub.18 H.sub.21 N.sub.3 O.sub.2 69.45 6.75 13.50 5-acetylamino benzoquinoneimine 69.20 7.00 13.74 95 N--[(4'-.b eta.-hydroxyethylamino-3'-chloro)phenyl]- 98 C.sub.18 H.sub.20 N.sub.3 O.sub.3 Cl 59.75 5.53 11.61 2,6-dimethyl-3-acetylamino benzoquinoneimine 59.44 5.77 11.61 96 N--[(4'-methylamino-3'-chloro)phenyl]-2,6- 218 C.sub.16 H.sub.17 N.sub.4 O.sub.2 Cl 57.74 5.11 16.84 dimethyl-3-ureido benzoquinoneimine 57.77 5.45 16.90 97 N--[(4'-.beta.-hydroxyethylamino-3'-chloro)phenyl] 170 C.sub.17 H.sub.19 N.sub.4 O.sub.3 Cl.H.sub.2 O 53.63 5.51 14.71 2-methyl-5-carbamylmethylamino benzoquinonei- 53.65 5.38 14.94 mine 98 N--[(4'-mesylaminoethylamino-3'-chloro)phenyl]- 230 C.sub.17 H.sub.19 N.sub.4 O.sub.4 S Cl 49.69 4.63 13.64 7.80 3-acetylamino benzoquinoneimine 49.95 4.82 13.54 7.76 99 N--[(4'-methylamino-3'-chloro)phenyl]-3-ure ido 258 C.sub.14 H.sub.13 N.sub.4 O.sub.2 Cl 55.17 4.27 18.39 11.66 benzoquinoneimine 55.14 4.56 18.64 11.57 (1) molecular weight calculated (2) molecular weight determined by potentiometric titration in acetic aci using perchloric acid (3) double melting point
TABLE II__________________________________________________________________________Ex- Reaction Reactionam- Molar Medium Molar Temp-ple Ratio (13) Oxidizing Ratio eratureNo ANILINE (Substituted) PHENOL (11):(10) 1:1 Agent (14):(11) (C..degree.)(1) (10) (11) (12) vol ratio (14) (15) (16)__________________________________________________________________________ 1 4-nitroso-N--ethylaniline hydrochloride 2-methyl-5- 1:1 Ethanol-water 50.degree. carbamyl- methylamino phenol 2 3-methyl-4-nitroso-N--ethylaniline 2,6-dimeth- 1:1 " 45.degree. yl-3-amino phenol hy- drochloride 3 " 2-methyl-5- 1:1 " 50.degree. amino phenol 4 4-nitroso-N--ethylaniline hydrochloride 2-chloro-5- 1:1 " 40.degree. amino phenol 5 2-methyl-4-nitroso-N--ethylaniline 2,6-dimeth- 1:1 " 40.degree. yl-3-amino phenol hy- drochloride 6 4-nitroso N--ethylaniline hydrochloride 2,6-dimeth- 1:1 " 40.degree. yl-3-amino phenol hy- drochloride 7 2,5-dimethyl-4-nitroso-N--methylaniline 2,6-dimeth- 1:1 " 50-60.degree. hydrochloride yl-3-amino phenol hy- drochloride 8 4-nitroso-N--methylaniline 2-methyl-5- 1:1 " 45.degree. amino phenol 9 2-methoxy-4-amino-N--methylaniline sulfate 2,6-dimeth- 1:1 Acetone-water Ammonium 2:1 0 yl phenol persulfate10 N--methyl paraphenylenediamine dihydro- 2,6-dimeth- 1:1 " Ammonium 1:1 0 chloride yl-3-amino sulfate phenol hy- drochloride11 3-methyl-4-amino-N--ethylaniline dihydro- 3-chloro-6- 1:1 Isopropanol- Ammonium 1:1 0 chloride ureido water persulfate phenol12 2-chloro-4-amino-N--butylaniline sulfate 2-methyl-5- 1:1 acetone-water Ammonium 1:1 3 acetylamino persulfate phenol13 3-methyl-4-amino-N--ethylaniline dihydro- 3-ureido 1:1 " Ammonium 1:1 0 chloride phenol persulfate14 N--methyl paraphenylenediamine dihydro- 2,6-dimeth- 1:1 " Ammonium 1:1 0 chloride yl-3-ace- persulfate tylamino phenol15 3-methyl-4-amino-N--ethylaniline dihydro- 3-chloro-6- 1:1 " Ammonium 2:1 0 chloride acetylamino persulfate phenol16 N--ethyl paraphenylenediamine dihydro- 2-methyl-5- 1:1 " Ammonium 1:1 0 chloride acetylamino persulfate phenol17 2-chloro-4-amino-N--butylaniline sulfate 3-acetyl- 1:1 " Ammonium 1:1 0 amino phenol persulfate18 N--ethyl paraphenylenediamine dihydro- 2-chloro-5- 1:1 water Ammonium 2:1 0 chloride acetylamino persulfate phenol19 2-chloro-4-amino-N--ethylaniline sulfate 2-methyl-5- 1:1 acetone-water Ammonium 1:1 0 acetylamino persulfate phenol20 4-amino-N--(.beta.-acetylamino) ethylaniline 3-methyl-6- 1:1 Isopropanol- Ammonium 2:1 0 sulfate chloro phenol water persulfate21 4-amino-N--(.beta.-hydroxyethyl) aniline 2-bromo-5- 1:1 Isopropanol- Ammonium 2:1 0 sulfate amino phenol water persulfate22 2-methyl-4-amino-N--(.beta.-hydroxyethyl) 2-methyl-5- 1:1 Acetone-water Ammonium 2:1 0 aniline sulfate acetylamino persulfate phenol23 4-amino-N--(.beta.-morpholinoethyl) aniline 2-chloro-5- 1:1 " Ammonium 2:1 0 acetylamino persulfate phenol24 4-amino-N--(.beta.-morpholinoethyl) aniline 3-ureido 1:1 Isopropanol- Potassium 4:1 0 phenol water ferricyanide25 4-amino-N--(.beta.-mesylaminoethyl) aniline 2-methyl-5- 1:1 Isopropanol- Ammonium 2:1 0 sulfate acetylamino water persulfate phenol26 4-amino-N--(.beta.-acetylaminoethyl) aniline 3-chloro-6- 1:1 Isopropanol- Ammonium 2:1 0 sulfate ureido phenol water persulfate27 2-methoxy-4-amino-N--(.beta.-hydroxyethyl) 2-methyl-5- 1:1 Isopropanol- Ammonium 1:1 +5 aniline sulfate amino phenol water persulfate28 2-methyl-4-amino-N-- (.beta.-mesylaminoethyl) 2,6-dimetnyl- 1:1 Acetone-water Ammonium 1:1 0 aniline sulfate 5-acetylamino persulfate phenol29 2-methoxy-4-amino-N--(.beta.-acetylaminoethyl) 2,6-dimethyl 1:1 Water Ammonium 1:1 0 aniline sulfate 5-amino persulfate phenol hydrochloride30 2-chloro-4-amino-N--(.beta.-mesylaminoethyl) 2-methyl-5- 1:1 Acetone-water Ammonium 2:1 0 aniline sulfate acetylamino persulfate phenol31 2-chloro-4-amino-N--(.beta.-acetylaminoethyl) 2,6-dimeth- 1:1 " Ammonium 2:1 0 aniline sulfate yl phenol persulfate32 2-methoxy-4-amino-N--(.beta.-hydroxyethyl) 2,6-dimeth- 1:1 Water Ammonium 2:1 0 aniline sulfate yl-5-amino persulfate phenol hy- drochloride33 2-methoxy-4-amino-N--(.beta.-hydroxyethyl) 2,6-dimeth- 1:1 Acetone-water Ammonium 1.1:1 0 aniline sulfate yl-5-acetyl- persulfate amino phenol34 2-chloro-4-amino-N--(.beta.-hydroxyethyl) 3-chloro-6- 1:1 " Ammonium 1:1 0 aniline sulfate acetylamino persulfate phenol35 2-methyl-4-amino-5-methoxy-N--(.beta.-amino- 2,6-dimeth- 1:1 Ethanol-water Ammonium 2:1 0 ethyl) aniline trihydrochloride yl-3-amino persulfate phenol hy- drochloride36 2-methyl-4-amino-N--(.beta.-mesylaminoethyl) 2-methyl-5- 1:1 Acetone-water Ammonium 2:1 0 aniline sulfate acetylamino persulfate phenol37 2-methyl-4-amino-N--(acetylaminoethyl) 3-ureido 1:1 " Ammonium 2:1 0 aniline sulfate phenol persulfate38 2-methyl-4-amino-N--carbamylmethyl 2,6-dimethyl- 1:1 Water Ammonium 2:1 0 aniline hydrobromide 3-acetyl- persulfate amino phenol39 2-chloro-4-amino-N--(.gamma.-morpholinopropyl) 3-chloro-6- 1:1 Acetone-water Ammonium 2:1 20 aniline trihydrochloride acetylamino persulfate phenol40 N--methyl paraphenylenediamine dihydro- 2,6-dimeth- 1:1 " Ammonium 2:1 15 chloride yl phenol persulfate41 2-methyl-4-amino-N--methyl aniline sulfate 2,6-dimeth- 1:1 " Ammonium 2:1 10 yl-3-acetyl- persulfate amino phenol42 3-methyl-4-amino-N--methylaniline dihydro- 2,6-dimeth- 1:1 Isopropanol- Ammonium 1:1 5 chloride yl-5-acetyl- water persulfate amino phenol43 2-methyl-4-amino-N--methylaniline sulfate 2,6-dimethyl 1:1 acetone-water Ammonium 2:1 15 phenol persulfate44 Monohydrate of 3-methyl-4-amino- 2,6-dimethyl 1:1 " Ammonium 2:1 5 N--methylaniline dihydrochloride phenol persulfate45 3-methoxy-4-amino-N--(.beta.-hydroxyethyl) 2-methyl-5- 1:1 " Ammonium 2:1 15 aniline sulfate acetylamino phenol46 2-chloro-4-amino-N--(.beta.-acetylaminoethyl) 3-methoxy 1:1 " Ammonium 2:1 0 aniline sulfate phenol persulfate47 N--(.beta.-mesylaminoethyl)paraphenylenediamine 2,6-dimeth- 1:1 " Ammonium 1:1 5 sulfate yl-3-acetyl- persulfate amino phenol48 N--(.beta.-hydroxyethyl)paraphenylenediamine 2-methyl-5- 1:1 " Ammonium 2:1 5 sulfate acetylamino persulfate phenol49 2-methoxy-4-amino-N--(.beta.-hydroxyethyl) 2,6-dimethyl 1:1 Isopropanol- Ammonium 2:1 10 aniline sulfate phenol water persulfate50 2-chloro-4-amino-N--(.gamma.-morpholino propyl) 2-bromo-5- 1:1 Acetone-water Ammonium 2:1 20 aniline trihydrochloride amino phenol persulfate51 3-methoxy-4-amino N--methylaniline dihy- 2,6-dimeth- 1:0.85 " Ammonium 2:1 0 drochloride yl-5-acetyl- persulfate amino phenol52 3-methoxy-4-amino-N--methylaniline dihy- 2-methyl-5- 1:0.85 Isopropanol- Potassium 2:1 0 drochloride acetylamino water ferricyanide phenol53 Dihydrate of 2-methoxy-4-amino-N--methyl- 2,6-dimeth- 1:1 Water Ammonium 2:1 0 aniline sulfate yl-5-amino persulfate phenol54 3-methoxy-4-amino-N--methylaniline dihy- 2-methyl-5- 1:0.85 Water- Potassium 2:1 0 drochloride amino phenol isopropanol ferricyanide55 2-chloro-4-amino-N--methylaniline sulfate 2-methyl-5- 1:1 Acetone-water Ammonium 2:1 10 acetylamino persulfate phenol56 2-chloro-4-amino-N--methylaniline sulfate 2,6-dimeth- 1:1 " Ammonium 2:1 5 yl-5-acetyl- persulfate phenol57 2-chloro-4-amino-N--methylaniline sulfate 2,6-dimethyl 1:1 " Ammonium 2:1 10 phenol persulfate58 2-chloro-4-amino-N--methylaniline sulfate 2,6-dimeth- 1:1.10 " H.sub.2 O.sub.2 8:1 20 yl-5-amino phenol hydro- chloride59 2-chloro-4-amino-N--methylaniline sulfate 2-methyl-5- 1:1.10 " " 8:1 20 amino phenol60 Monohydrate of 3-chloro-4-amino-N--methyl- 2,6-dimeth- 1:1 " Ammonium 2:1 5 aniline dihydrochloride yl-5- persulfate acetylamino phenol61 Monohydrate of 3-chloro-4-amino-N--methyl- 2,6-dimeth- 1:1 " Ammonium 1:1 5 aniline dihydrochloride yl-5-amino persulfate phenol hydrochlor- ide62 Monohydrate of 3-chloro-4-amino-N--methyl- 2-methyl-6- 1:1 " Ammonium 1:1 5 aniline dihydrochloride amino phenol persulfate63 Monohydrate of 3-chloro-4-amino-N--methyl- 2-methyl-5- 1:0.65 " Ammonium 2:1 5 aniline dihydrochloride acetylamino persulfate phenol64 Dihydrate of 2-methoxy-4-amino-N--methyl- 2,6-dimethyl- 1:1 " Ammonium 1:1 0 aniline sulfate 5-acetyl- persulfate amino phenol65 3-chloro-4-amino-N--methylaniline dihydro- 2-methyl-5- 1:1 Ethanol-water Ammonium 1:1 0 chloride N--.beta.-hydroxy- persulfate ethylamino phenol66 3-methoxy-4-amino-N--methylaniline dihy- 2,6-dimethyl 1:1 Acetone-water Ammonium 2:1 0 drochloride phenol persulfate67 3-methoxy-4-amino-N--methylaniline dihy- 2,6-dimeth- 1:0.85 " Ammonium 1.75:1 0 drochloride yl-5-amino- persulfate phenol hy- drochloride68 Monohydrate of 3-methyl-4-amino- 2-methyl- 1:1 " Ammonium 2:1 0 N--methylaniline dihydrochloride 5-amino persulfate phenol69 Monohydrate of 3-methyl-4-amino-N--methyl- 2,6-di- 1:1 " Ammonium 2:1 5 aniline dihydrochloride methyl-5- persulfate amino phenol hydro- chloride70 3-chloro-4-amino-N--methylaniline dihydro- 2,6-di- 1:1 " Ammonium 2:1 5 chloride methyl persulfate phenol71 Monohydrate of 3-methyl-4-amino-N--methyl- 2-methyl- 1:1 " Ammonium 1:1 5 aniline dihydrochloride 5-acetyl- persulfate amino phenol72 2-methyl-4-amino-N--methylaniline sulfate 2,6-di- 1:1 " Ammonium 1:1 5 methyl-5- persulfate amino phenol hydro- chloride73 " 2-methyl-5- 1:1 " Ammonium 2:1 10 acetylamino persulfate phenol74 " 2-methyl-5- 1:1 " Ammonium 2:1 10 amino phenol persulfate75 4-amino-N--methylaniline dihydrochloride 2-methyl-5- 1:1 " Ammonium 1:1 0 acetylamino persulfate phenol76 2-methoxy-4-amino-N--methylaniline sulfate 2-methyl-5- 1:1 " Ammonium 2:1 0 carbethoxy- persulfate amino phenol77 2-chloro-4-amino-N--methylaniline sulfate 2-methyl-5- 1:1 Propanol-water Ammonium 2:1 0 ureido persulfate phenol78 2-chloro-4-amino-N--.beta.-hydroxyethylaniline 2,6-dimethyl 1:1 Acetone-water Ammonium 2:1 0 sulfate 3-ureido persulfate phenol79 2-chloro-4-amino-N--.beta.-hydroxyethylaniline 3-ureido 1:1 " Ammonium 2:1 0 sulfate phenol persulfate80 2-chloro-4-amino-N--.beta.-hydroxyethylaniline 3-acetyl- 1:1 Isopropanol- Ammonium 2:1 0 sulfate amino phenol water persulfate81 2-chloro-4-amino-N--.beta.-hydroxyethylaniline 2-methyl-5- 1:1 Isopropanol- Ammonium 2:1 0 sulfate acetylamino water persulfate phenol82 2-chloro-4-amino-N--.beta.-hydroxyethylaniline 2-methyl-5- 1:1 Isopropanol- Ammonium 2:1 0-5 sulfate ureido water persulfate phenol83 4-amino N--methylaniline dihydrochloride 2-methyl 5- 1:1 Acetone-water Ammonium 2:1 0 carbamylme- persulfate thylamino phenol84 3-methyl-4-amino-N--methylaniline dihy- 2-methyl 5- 1:1 " Ammonium 2:1 0 drochloride carbamylme- persulfate thylamino phenol85 2-methyl-4-amino-N--methylaniline dihy- 2-methyl 5- 1:1 " Ammonium 2:1 0 drochloride carbamylme- persulfate thylamino phenol86 2-chloro-4-amino-N--(acetylaminoethyl) 2-methyl-5- 1:1 " Ammonium 2:1 0-5 aniline sulfate carbamylme- persulfate thylamino phenol87 2-chloro-4-amino-N--mesylaminoethyl- 2-methyl-5- 1:1 " Ammonium 2:1 5 aniline sulfate carbamylme- persulfate thylamino phenol88 4-amino-N--.beta.-hydroxyethylaniline sulfate 2-methyl-5- 1:1 " Ammonium 2:1 0 carbamylme- persulfate thylamino phenol89 2-methyl-4-amino-N--mesylaminoethylaniline 2-methyl-5- 1:1 " Ammonium 2:1 5 sulfate carbamylme- persulfate thylamino phenol90 2-chloro-4-amino-N--methylaniline sulfate 2-methyl-5- 1:1 " Ammonium 2:1 0 carbamylme- persulfate thylamino phenol91 2-chloro-4-amino-N--(mesylaminoethyl) 2-methyl-5- 1:1 " Ammonium 2:1 0 aniline sulfate ureido persulfate phenol92 2-chloro-4-amino-N--(mesylaminoethyl) 3-ureido 1:1 " Ammonium 2:1 5 aniline sulfate phenol persulfate93 2-chloro-4-amino-N--(methylaniline sulfate) 3-acetyl- 1:1 " Ammonium 2:1 5 amino phenol persulfate94 2-methyl-4-amino N--ethylaniline sulfate 2-methyl-5- 1:1 " Ammonium 2:1 5 acetylamino persulfate phenol95 2-chloro-4-amino-N--.beta.-hydroxy-ethylaniline 2,6-dimeth- 1:1 " Ammonium 1:1 0 sulfate yl-3-acetyl- persulfate amino phenol96 2-chloro-4-amino-N--methylaniline sulfate 2,6-dimeth- 1:1 " Ammonium 2:1 5 yl-3-ureido persulfate phenol97 2-chloro-4-amino-N--.beta.-hydroxyethylaniline 2-methyl-5- 1:1 " Ammonium 2:1 0 sulfate N--carbamyl- persulfate methylamino phenol98 2-chloro-4-amino-N--mesylaminoethylaniline 3-acetyl- 1:1 " Ammonium 2:1 5 sulfate amino phenol persulfate99 2-chloro-4-amino-N--methylaniline sulfate 3-ureido 1:1 " Ammonium 5 phenol persulfate__________________________________________________________________________
TABLE III__________________________________________________________________________(11) (12) (13) (14) (15) (16) (17) (18) (19)EX. DYE POLYMER ALCOHOL (20) (21) (22)No Ex. No Wt. % Type M.W. (cps) % Type % pH Hair Color__________________________________________________________________________ AchievedM 1 10 0.5 VA/CA 90/10 10,000 2 Ethanol 50 7.8 B 95 (1) violineM 2 4 0.1 " 10,000 1 " 36 8.1 D (2) silvery glycineM 3 5 0.05 PVP 40,000 2 Isopropanol 25 9 D parmeM 4 12 0.008 VA/CA 90/10 10,000 2 Ethanol 50 8.1 D pale pearly rose mauveM 5 15 0.025 VP/VA 30/70 160,000 2 " 40 8.8 D emerald greenM 6 19 0.004 VA/CA 90/10 25,000 1 " 36 8.4 D light pink blondeM 7 2 0.05 PVP 160,000 2 Isopropanol 25 9 D pearly mauveM 8 17 0.01 VP/VA 60/40 4 2 " 35 9.6 D very light silverM 9 1 0.05 VA/CA 90/10 25,000 1 Ethanol 20 9.5 D pale silvery mauveM 10 18 0.1 VP/CA 30/70 160,000 2 " 40 10.2 D pearly turquoise blueM 11 5 0.002 " " 2 " 40 5.7 D light pink blondM 12 18 0.1 " " 2 " 40 10.2 B 95 silvery eucalyptus greenM 13 14 0.1 VA/CA 90/10 25,000 1 " 36 8.5 D very luminous gentianM 14 10 0.2 " 25,000 2 " 50 7.4 D purpleM 15 3 0.1 VP/VA 60/40 3.3 2 Isopropanol 35 9.8 B 95 beige grey with violet glintsM 16 16 0.02 VP/VA 70/30 40,000 3 Ethanol 25 8.7 D ice-blueM 17 10 0.002 " " 3 " 25 10.1 " pearly pale pinkM 18 9 0.015 VP/VA 30/70 160,000 2 " 40 9.3 " pearly light blueM 19 13 0.013 VP/VA 60/40 3.7 2 Isopropanol 35 9.3 " light turquoise blueM 20 6 0.05 MM/StM/DEM 8 2.5 Ethanol 30 8 " deep violet pink 20/23/57M 21 18 0.1 VP/VA 30/70 160,000 2 " 40 10.2 " deep chestnut with bronze glints 14 0.05M 22 10 0.1 VA/CA 90/10 50,000 2 " 50 6.7 D deep violet C.sub.1 (3) 0.08 14 0.05M 23 10 0.002 VA/CA 90/10 70,000 2 " 50 7.5 D golden light chestnut C.sub.1 (3) 0.15 with violet glints C.sub.2 (4) 0.12M 24 7 0.2 MM/StM/DEM 12 2.5 " 30 10.5 B 95 tin grey with light violet glintsM 25 28 0.09 VA/CA 90/10 25,000 2 " 50 6.3 D silvery glycineM 26 30 0.09 VP/VA 60/40 4 2 Isopropanol 35 8.1 D silvery blue greyM 27 20 0.009 VP/VA 70/30 40,000 3 Ethanol 25 8.5 D pearly light greenM 28 34 0.02 VP/VA 60/40 4 2 Isopropanol 35 9.4 D pearly light blueM 29 32 0.02 " 3.3 2 " 35 5.5 D light parmeM 30 31 0.05 " 3.7 2 " 35 9 D silvery grey with mauve glintsM 31 23 0.015 PVP 360,000 2 " 25 8.9 D light green with golden glintsM 32 33 0.025 VA/CA 90/10 50,000 1 Ethanol 36 5.5 D pearly light blueM 33 25 0.5 " 50,000 2 " 50 10.1 B 95 metallic greyM 34 35 0.05 " 70,000 1 " 36 9.2 D silvery pale mauveM 35 21 0.05 " 50,000 2 " 50 7 D silvery blue greyM 36 36 0.06 " " 2 " 50 8.8 D pearly greyM 37 37 0.065 VP/CA 60/40 3.3 2 Isopropanol 35 9.3 B 95 dark blue greyM 38 27 0.05 MM/StM/DEM (5) 2.5 2.5 Ethanol 30 10.3 D pink beige greyM 39 24 0.1 VA/CA 90/10 50,000 2 " 50 6.4 D very luminous deep violetM 40 26 0.033 VP/CA 70/30 40,000 3 " 25 6.7 D pearly light blueM 41 22 0.09 VP/CA 30/70 160,000 2 " 40 9.7 B 95 metallic greyM 42 21 0.002 PVP 360,000 2 Isopropanol 25 10.3 D very light silver with blue glintsM 43 29 0.045 MM/StM/DEM (5) 8 2.5 Ethanol 30 9 D tamarisk pinkM 44 39 0.3 PVP 40,000 2 Isopropanol 25 5.5 D deep royal blueM 45 38 0.1 VA/CA 90/10 70,000 1 Ethanol 36 9 B 95 silvery grey with mauve glints 36 0.1M 46 22 0.2 VA/CA 90/10 " 2 " 50 7 B 95 steel grey C.sub.3 (5a) 0.02 C.sub.4 (6) 0.03M 47 57 0.25 VP/VA 60/40 3.7 2 Isopropanol 35 8.5 D silvery pale violetM 48 60 0.1 " 4 2 " 35 5.5 D silvery grey with light mauve glintsM 49 69 0.3 VA/CA 90/10 45,000 2 Ethanol 50 5 D violineM 50 99 0.35 " " 2 " 50 7 B 95 metallic greyM 51 94 0.1 " " 2 " 50 6.5 D very light pearly blueM 52 66 0.35 " " 2 " 50 7 D royal blueM 53 92 0.15 VP/VA 70/30 40,000 3 " 25 8 D pearly pink beigeM 54 91 0.15 VA/CA 90/10 50,000 1 " 36 7 D lilacM 55 65 0.3 " " 2 " 50 9.5 D violet beigeM 56 75 0.1 VP/VA 60/40 4 2 Isopropanol 35 5 D silvery blueM 57 63 0.05 " 4 2 " 35 10.5 D cyclamen pinkM 58 59 0.035 " 3.5 2 " 35 6 D salmon pinkM 59 53 0.05 VP/VA 30/70 160,000 2 Ethanol 40 6 D beige shaded mauveM 60 67 0.09 " " 2 " 40 8.5 D pearly glycineM 61 61 0.07 VP/VA 60/40 3.7 2 Isopropanol 35 9.5 D pearly pale pinkM 62 71 0.03 VP/VA 30/70 160,000 2 Ethanol 40 8.5 D pearly myosotis blueM 63 76 0.05 " " 2 " 40 10 D light blue greyM 64 72 0.2 " " 2 " 40 4.5 D purpleM 65 73 0.1 " " 2 " 40 5 D silvery lavender blueM 66 88 0.2 VP/VA 70/30 40,000 3 " 20 8.5 D silvery grey violet 26 0.15M 67 62 0.025 VA/CA 90/10 70,000 1 " 35 7 D pink beigeM 68 64 0.15 " 10,000 2 " 50 7 D myosotis blueM 69 68 0.13 " 50,000 1 " 36 4.5 D violet pinkM 70 58 0.05 " " 2 " 50 8.5 D very luminous salmon pinkM 71 51 0.1 " " 1 " 36 7 D silvery grey blueM 72 89 0.1 VP/VA 60/40 3.7 2 Isopropanol 35 4 D silvery glycineM 73 88 0.1 PVP 40,000 2 " 25 9 B 95 metallic grey with mauve glintsM 74 87 0.05 VP/VA 30/70 160,000 2 Ethanol 40 8.5 D golden pale pinkM 75 86 0.075 VP/VA 70/30 40,000 3 " 25 6.5 D eglatineM 76 85 0.05 VP/VA 60/40 4 2 Isopropanol 35 4 D glycineM 77 98 0.1 VP/VA 30/70 160,000 2 Ethanol 40 7 D light silverM 78 56 0.2 VA/CA 90/10 70,000 1 " 36 9 D mauveM 79 50 0.2 " 50,000 1 " 36 5.5 D violetM 80 81 0.2 VP/VA 30/70 160,000 2 " 40 4 D light grey with mauve glintsM 81 79 0.075 VA/CA 90/10 50,000 1 " 50 7 D light silvery grey shaded mauveM 82 54 0.1 " 50,000 1 " 50 7 D violet blueM 83 45 0.1 " 70,000 1 " 36 8 D silvery myosotis blueM 84 46 0.1 " 70,000 1 " 36 9 D pearly mauveM 85 8 0.2 VP/VA 30/70 160,000 2 " 40 8 D tamarisk pinkM 86 42 0.1 VA/CA 90/10 70,000 2 " 50 6.5 D silvery blue greyM 87 44 0.3 " 70,000 2 " 50 6 D lavender__________________________________________________________________________ blue (1) B 95 = 95% natural white hair (2) D = bleached hair (3) C.sub.1 = N[(4hydroxy)-phenyl2,6-dimethyl benzoquinoneimine (4) C.sub.2 = 4nitro-N,N--dihydroxyethylaniline (5) Terpolymer of methyl methacrylate (20%)stearyl methacrylate (23%) dimethylaminoethyl methacrylate (57%) quaternized with dimethyl sulfate and having a viscosity of 8-12 cps, at 5% in dimethylformamide and at the boiling temperature of ether. (5a) C.sub.3 = Nitroortho pphenylenediamine (6) C.sub.4 = lamino propylamino anthraquinone
TABLE IV__________________________________________________________________________(31) (32) (33) (34) (35) (36) (37) (38) (39) (40) (41) (42) Surface active agent SOLVENT OTHER ADJUVANTSEX. DYE wt. wt. wt.No EX. No Wt. % Type % Type % Type % pH Hair Color__________________________________________________________________________ achievedT 1 1 0.53 Isopropanol 40 11 D (10) silver with mauve glintsT 2 2 0.04 MEDG (1) 5 9 D silvery mauve grey Ethanol 25T 3 15 0.077 Ethanol 23 CMC (2) 3.9 10.4 D emerald greenT 4 5 AL 10.5OE (3) 5 Butylglycol 5 6 D light pink blondT 5 16 0.6 2 0.5 C1 (4) 0.05 " 20 8.5 D pink beige C2 (5) 0.07T 6 3 0.30 LSS 19 (6) 20 EDTA (7) 2 10.6 D silvery grey with blue glintsT 7 9 0.06 Ethanol 20 CMC 4 8 D pearly light turquoise blueT 8 18 0.2 NP 4OE (8) 10 NP 9OE (9) 10 5.6 B 95 (11) vervainT 9 10 0.1 ALS (12) 10 9.7 D pearly light mauve pinkT 10 16 0.1 " 10 10.5 D pearly light greenT 11 6 0.33 Ethanol 30 CMC 3 10.5 B 95 silvery violetT 12 4 0.4 AL 10.5OE 20 10 " eucalyptus greenT 13 15 0.1 LSS 19 20 EDTA 2 10.5 D mahogany C3 (14) 0.08 C4 (15) 0.10 C5 (16) 0.04T 14 11 0.025 Isopropanol 50 "Carbopol 2.38 6 D light green 934" (17)T 15 27 0.07 LSS 19 20 EDTA 0.2 10.7 D light beige greyT 16 23 1 NP 9OE 10 " 15 5.5 B 95 petroleum blueT 17 20 0.7 DFAC (13) 7.5 Ethanol 25 7 " eucalyptus greenT 18 32 0.1 " 20 10.5 D pearly pink beige MEDG 10T 19 23 0.30 NP 4OE 8.5 9 B 95 light chestnut with 20 0.35 NP 9OE 8.5 Ethanol 15 copper glints C6 (18) 0.03 C7 (19) 0.1T 20 24 0.4 Ethanol 40 9 D deep violet blueT 21 37 1.1 " 45 9.5 D myosotis blueT 22 33 0.8 " 20 CMC 4 5.5 D silvery light blueT 23 37 0.3 24 0.2 " 40 10.5 B 95 silvery mauve gray C2 (5) 0.09 C8 (20) 0.05T 24 26 0.65 " 33 "Carbopol 3 10 D light emerald green 934" (17)T 25 25 0.22 NP 9OE 10 Butylglycol 5 5.5 D platinum with light blue glintsT 26 34 2 DFAC (13) 6.5 Ethanol 35 10.5 D pearly light turquoise blueT 27 43 0.4 AL 10.5OE 5 Butylglycol 5 7 D very silvery pale (3) blueT 28 40 0.25 DFAC (13) 10 9.5 D pearly pastel blueT 29 48 0.2 ALS (12) 10 9 D ice blueT 30 49 0.4 "Carbopol 4.76 9.5 D pearly pastel blue 934" (17)T 31 47 0.4 LSS 19 (6) 20 EDTA 0.2 12 D light bluish silverT 32 41 0.05 CMC (2) 5 10 D very light pearly blueT 33 90 0.5 AL 10.5OE (3) 5 9 D eglantine pinkT 34 95 0.35 LSS 19 (6) 20 EDTA (7) 0.2 10 D light silver greyT 35 93 0.3 CMC (2) 5 9 D light blue greyT 36 96 0.3 MEDG (1) 10 5 D silvery mauveT 37 97 0.4 DFAC (13) 10 9 D very light pink blondT 38 78 0.5 LSS 19 (6) 20 EDTA (7) 0.2 10 D mauveT 39 52 0.15 Ethanol 25 9 D light turquoise blueT 40 70 0.6 " 20 " 0.2 11 D pearly light beige greyT 41 84 0.35 " 20 "Carbopol 3.6 10 D silvery pale 934" (17) mauveT 42 83 0.35 ALS (12) 5 9.2 D light silver gray with mauve glintsT 43 74 0.6 DFAC (6) 2 " 30 10.5 B 95 metallic grey with mauve glintsT 44 55 0.8 NP 4OE (8) 8 " 2 11 D light silver grey NP 9OE (9) 8 with mauve glintsT 45 80 0.4 AL 10.5OE (3) 5 Butylgly- 5 9 D silvery light blue col greyT 46 77 0.5 AL 10.5OE (3) 20 4 D pearly light parmeT 47 82 0.2 Propylene 5 CMC (2) 4 8 D light pink ash glycol beigeT 48 93 0.2 Ethanol 50 " 2.5 10 B 95 metallic grey 87 0.5 shaded violet 35 0.1__________________________________________________________________________ (1) MEDG = monomethyl ether of diethyleneglycol (2) CMC = Carboxymethylcellulose (3) AL 10.5OE = laurylalcohol oxyethylenated with 10.5 moles of ethylene oxide (4) C1 = 2methoxy-4-nitro-hydroxyethylaniline (5) C2 = 1aminopropylamino anthraquinone (6) LSS 19 = mixture consisting of 19% laurylalcohol oxyethylenated with moles of ethylene oxide and 81% of sodium sulfate salt of the same oxyethylenated alcohol (7) EDTA = ethylene diamine tetraacetic acid (8) NP 4OE = Nonylphenol oxyethylenated with 4 moles of ethylene oxide (9) NP 9OE = Nonylphenol oxyethylenated with 9 moles of ethylene oxide (10) D = bleached hair (11) B 95 = 95% naturally white hair (12) ALS = ammonium laurylsulfate (13) DFAC = diethanolamides of fatty acids of copra (14) C3 = N--[(4hydroxy)-phenyl2,6-dimethyl benzoquinoneimine (15) C4 = N[(4amino)phenyl2-methyl-5-amino benzoquinoneimine (16) C4 = Nitroorthophenylenediamine (17) "Carbopol 934" = Polymer of acrylic acid having a molecular weight between 2-3 million (18) C6 = N[(4ethylamino)-phenyl2-methyl-5-acetylamino benzoquinoneimine (19) C7 = nitroparaphenylenediamine (20) C8 = 3nitro-4(hydroxyethyl) amino anisole

N-Monosubstituted indoanilines

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Chem Abstracts: 75,75576z (1971).
Vittum et al., J.A.C.S., vol. 68, 1946, pp.2235-2237.
Figueras, J. A. Chem. Soc., 93:13, Jun. 30, 1971, pp. 3255-3262.
Conet et al., Arg. Magnetic Resonance, 1971, vol. 3, pp. 313-323.
Kuroki et al., Chemical Abstracts, 49:4298(d), 1955.