the following examples are intended to illustrate but not to limit the scope of the invention . preparation of 4 - methylthio - 3 - aminophenol hydrochloride , denominated in accordance with iupac nomenclature as 3 - amino - 4 - methlsulfanylphenol hydrochloride . 65 . 9 g ( 0 . 25 mole ) of 1 - chloro - 2 - nitro - 4 -( benzyloxy ) benzene was added portionwise to a suspension of sodium thiomethylate ( 0 . 35 mole ) in 100 ml dimethoxyethane at room temperature . the reaction was exothermic . the mixture was cooled to maintain the temperature between 25 ° and 30 ° c . the reaction mixture was poured into a litre of iced water . the crystalline precipitate was dried then taken up in water . after recrystallization from 96 ° ethanol then isopropyl acetate , 34 . 4 g of orange crystals were obtained which melted at 78 ° c . elemental analysis calculated for c 14 h 13 no 3 s was as follows : ______________________________________ % c h n o s______________________________________calculated 61 . 07 4 . 76 5 . 09 17 . 43 11 . 65found 61 . 30 4 . 81 4 . 90 17 . 34 11 . 57______________________________________ a mixture of 2 . 2 g ammonium chloride , 15 ml water , 140 ml 96 ° alcohol and 70 g finely powdered zinc was heated under reflux . the [ 2 - nitro - 4 -( benzyloxy ) phenyl ] methylsulfane obtained from step 1 was added portionwise ( 33 . 8 g , 0 . 123 mole ) so as to maintain the reflux without heating . the reduction was exothermic . following addition , heating under reflux was continued for 15 minutes . the decolorized reaction medium was boil filtered . on cooling the filtrate , pale yellow crystals precipitated which were dried ( 28 . 2 g ). following recrystallization from cyclohexane , this compound melted at 64 ° c . elemental analysis calculated for c 14 h 15 nos was as follows : ______________________________________ % c h n o s______________________________________calculated 68 . 54 6 . 16 5 . 71 6 . 52 13 . 07found 68 . 40 6 . 11 5 . 61 6 . 72 13 . 11______________________________________ the 28 . 2 g ( 0 . 115 mole ) of 2 - methylsulfanyl - 5 -( benzyloxy ) phenylamine obtained from step 2 was heated at 90 °- 95 ° c . in a mixture of 50 ml of 36 % hydrochloric acid and 5 ml water for one hour . after vacuum drying over potash and recrystallization from absolute ethanol , 8 . 3 g of white crystals of 3 - amino - 4 - methylsulfanylphenol hydrochloride were obtained which melted with decomposition at 210 °- 214 ° c . elemental analysis calculated for c 7 h 10 clnos was as follows : ______________________________________ % c h n s cl______________________________________calculated 43 . 86 5 . 26 7 . 31 16 . 73 18 . 50found 43 . 36 5 . 42 7 . 08 16 . 46 18 . 26______________________________________ preparation of 2 - methoxy - 4 - methylthio - 5 - aminophenol hydrochloride , denominated in accordance with iupac nomenclature as 5 - amino - 2 - methoxy - 4 - methylsulfanylphenol hydrochloride . a suspension of 50 . 5 g ( 0 . 237 mole ) methyl -( 6 - nitrobenzo [ 1 , 3 ] dioxol - 5 - yl )- sulfane in 230 ml methanol was heated under reflux . 105 ml of a solution of 30 % sodium methylate in methanol was added dropwise . the mixture was cooled in an ice bath and the sodium phenate of the expected compound was dried . following dissolution of the phenate in 2 liters of water and acidification with a concentrated hydrochloric acid solution , the crystalline precipitate was dried , taken up again in water and dried again . after recrystallization from isopropanol , 44 . 5 g of yellow crystals were obtained which melted at 158 ° c . elemental analysis calculated for c 8 h 9 no 4 s was as follows : ______________________________________ % c h n o s______________________________________calculated 44 . 65 4 . 21 6 . 51 29 . 73 14 . 90found 44 . 62 4 . 21 6 . 42 29 . 95 14 . 72______________________________________ the compound obtained from step 1 ( 18 . 8 g - 0 . 0873 mole ) was reduced using the method described for example 1 step 3 , the reaction mixture being boil filtered into hydrochloric acid in absolute ethanol . 9 . 6 g of white crystals of 5 - amino - 2 - methoxy - 4 - methylsulfanylphenol hydrochloride were obtained which melted with decomposition at 235 °- 240 ° c . elemental analysis calculated for c 8 h 12 clno 2 s was as follows : ______________________________________ % c h n o s cl______________________________________calculated 43 . 34 5 . 46 6 . 32 14 . 43 14 . 46 15 . 99found 43 . 55 5 . 52 6 . 20 14 . 67 14 . 22 15 . 80______________________________________ ______________________________________4 - methylthio 3 - aminophenol hydrochloride 0 . 383 gparaphenylenediamine 0 . 216 goctyldodecanol sold under the trade name 8 geutanol d by henkeloleic alcohol 20 gmonoethanolamiine laurylethersulfate sold under 3 gthe trade name sipon lm 35 by henkelethyl alcohol 10 gbenzyl alcohol 10 gcetylstearyl alcohol oxyethylenated to 33 moles 2 . 4 gethylene oxide sold under the trade name simulsolgs by seppicethylenediamine tetracetic acid 0 . 2 gcationic polymer solution containing the following : 3 . 7 g ## str17 ## to 60 % m . a . monoethanolamine 7 . 5 gdiethanolamide of linoleic acid sold under the 8 gtrade name comperlan f by henkelammonia solution , 20 % nh . sub . 3 10 . 2 gsodium metabisulfite , 35 % aqueous solution 1 . 3 ghydroquinone 0 . 15 g1 - phenyl 3 - methyl 5 - pyrazolone 0 . 2 gdemineralized water q . s . p . 100 g______________________________________ this composition was mixed just before use with an equal weight of 20 vol hydrogen peroxide with a ph of 3 . the ph of the mixture was - equal to 9 . 5 . the mixture was applied to permed gray hair and left for 30 minutes at room temperature . the hair was then rinsed , shampooed and dried . it was dyed a dark beige blond . ______________________________________2 - methoxy 4 - methylthio 5 - aminophenol hydro - 0 . 665 gchloride2 , 6 - dimethyl paraphenylenediamine dihydro - 0 . 627 gchlorideoleic alcohol polyglycerolated to 2 moles glycerol 4 goleic alcohol polyglycerolated to 4 moles glycerol 5 . 7 goleic acid 3 goleic amine oxyethylenated to 2 moles ethylene 7 goxide sold under the trade name ethomeen012 by akzosodium salt of diethylaminopropyl laurylamino 3 gsuccinamateoleic alcohol 5 goleic acid diethanolamide 12 gpropylene glycol 3 . 5 gethyl alcohol 7 gdipropylene glycol 0 . 5 gpropylene glycol monomethyl ether 9 gsodium metabisulfite , 35 % aqueous solution 0 . 45 g maammonium acetate 0 . 8 gantioxidant , sequestrum producer qsperfume , preservative qsmonoethanolamine ph : 9 . 8 qsdemineralized water qsp 100 g______________________________________ the above composition was mixed just before use with an equal weight of 20 vol hydrogen peroxide whose ph had been adjusted to between 1 and 1 . 5 by addition of orthophosphoric acid ( 2 . 5 g orthophosphoric acid per 100 g of 20 vol hydrogen peroxide ). the ph of the mixture was equal to 6 . 5 . the mixture was applied to gray hair with 90 % white and left for 30 minutes at room temperature . the hair was rinsed , shampooed , rinsed again then dried . it had been dyed a light blue ash blond .
sulfated metaaminophenols are disclosed and have the formula ## str1 ## where : z is alkyl , aralkyl , monohydroxyalkyl , polyhydroxyalkyl , aryl , aminoalkyl ; r 1 is hydrogen , alkyl , monohydroxyalkyl , polyhydroxyalkyl , monocarbamylalkyl , dicarbamylalkyl , aminoalkyl , acylaminoalkyl , carbalkoxyalkyl , carbamyl , or monoalkylcarbamyl ; r 2 is hydrogen , alkyl , monohydroxyalkyl , alkoxy ; and their acid salts . intermediate products used for their preparation are also disclosed . these sulfated metaaminophenols are used to dye keratinous fibers .