US3344031A - N, n-disubstituted isopicramic acid salts for dyeing human hair - Google Patents

N, n-disubstituted isopicramic acid salts for dyeing human hair Download PDF

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Publication number
US3344031A
US3344031A US329868A US32986863A US3344031A US 3344031 A US3344031 A US 3344031A US 329868 A US329868 A US 329868A US 32986863 A US32986863 A US 32986863A US 3344031 A US3344031 A US 3344031A
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Prior art keywords
acid
isopicramic
carbon atoms
ammonium
hydroxyethyl
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Expired - Lifetime
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US329868A
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English (en)
Inventor
Bartoszewicz Jerzy Josef
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Lever Brothers Co
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Lever Brothers Co
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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41—Amines
    • A61K8/418—Amines containing nitro groups
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A61Q5/065—Preparations for temporary colouring the hair, e.g. direct dyes

Definitions

  • a process of dyeing keratinous fibres which comprises applying thereto an aqueous solution having a pH of from 2 to 9 of a compound of the general formula:
  • M is a hydrogen, an alkali or alkaline-earth metal, or
  • R is an alkyl group or a hydroxylalkyl group having up to 4 carbon atoms
  • R is a hydroxyalkyl group having up to 4 carbon atoms.
  • substitutedammonium radicals for the group M are ammonium radicals in which one or more of the hydrogen atoms is substituted by an alkyl group having up to 6 carbon atoms or by a hydroxyalkyl or aminoalkyl group having up to 4 carbon atoms.
  • Suitable hydroxyalkyl groups for R and R are the groups -CH CH OH, 'CH CH CH OH, CH CH(OH)CH and -CH CH(OH)CH OH. Of these groups, the preferred one is the Z-hydroxyethyl group.
  • metals for the group M in the above formula are mentioned sodium, potassium, and calcium, and as examples of substituted-ammonium radicals for M are mentioned those derived from mono-, di-, and tri-ethanolamine or isopropanolamine, and those derived from mono-, di-, and tri-methylamine, ethylamine and isobutylamine.
  • the dyes employed in the process of the invention produce on keratinous fibres deep blue-violet to violet dull shades free or substantially free of a red tone which is rare for a nitro dye.
  • the invention also provides a composition for the direct dyeing of keratinous fibres, especially living hair, containing a dye of the above-mentioned general formula in aqueous solution having a pH of from 2 to 9, preferably having a pH of from 3.5 to 8; best results are obtained with solution having a pH of from 6.5 to 7.5.
  • Dyes of the above-mentioned general formula may be used with other suitable nitro dyes to produce blonde, brown and grey shades.
  • the yellow dye is preferably 2-nitro-N-methyl-N-acetyl-p-amino-phenol or N- methyl-N-acetyl-isopicramic acid or an alkali metal, alkaline-earth metal, ammonium or substituted-ammonium salt thereof; in the case of a substituted-ammonium salt, the substituted-ammonium radical may be one as given above for the group M in the above general formula. Since these yellow dyes have a similar chemical structure to that of the blue-violet to violet dyes of the above general formula, the combination possesses useful properties. For instance, selectivity on certain hairs is minimised and also the fastness of the colour of the dyed fibre is very good. The combination also has good stability on storage of the composition.
  • the invention further provides new direct dyes, for use in the above process and composition, having the general formula OzN NO:
  • R1 I N where M is an alkali or alkaline-earth metal, an ammonium or substituted-ammonium radical; and R and R have the above meanings.
  • Example 1 Preparation of N,N-di-(2-hydr0vcyethyl)- isopicramic acid potassium salt
  • 132 g. of the ammonium salt of isopicramic acid were added to 400 ml. of methyl alcohol, 96 ml. of water and 540 ml. of 2-chloro-ethanol.
  • the temperature of the water-bath was raised to C. 92 g. of potassium hydroxide dissolved in 360 ml. of water were added over a period of one hour.
  • the temperature of the water-bath was then gradually increased over a period of half an hour and the reaction mixture was kept refluxing for 2 /2 hours at 86 C.
  • 144 ml. of 2- chloro-ethanol were added followed by 72 g. of potassium hydroxide in 144 ml. of water during 20 minutes.
  • the reaction mixture was refluxed for a further 1% hours. It was then cooled for 40 minutes and filtered.
  • the deep violet filtrate was then poured into 3 litres of water and made acid to Congo Red paper with 90 ml. of concen trated hydrochloric acid. It was left overnight for the N,N-di-(2-hydroxyethy1)-isopicramic acid to crystallise out and on filtration 112 g. of moist dyestuif cake were produced.
  • the potassium salt of N,N-di-(2-hydroxyethyl)-isopicramic acid was then produced as follows.
  • the welldrained dyestuff cake previously produced was mixed to a smooth paste with ml. of isopropyl alcohol and with a solution of g. of potassium carbonate in 20 g. of water. Evolution of carbon dioxide took place.
  • the dyestuff was then dried at 50-60 C. in a vacuum oven under a reduced pressure (60-70 cm. Hg). The yield was 93 g. of soft bronzy lumps which were easy to grind.
  • N,N-di-(2-hydroxyethyl)-isopicramic acid obtained (such as N-methyl-isopicramic acid) instead of from a salt of isopicramic acid.
  • the alkaline-earth metal salts of, for instance, N,N-di- (Z-hydroxyethyl)-isopieramic acid can be prepared by reacting this acid with a suitable alkaline-earth metal compound, such as calcium carbonate.
  • a suitable alkaline-earth metal compound such as calcium carbonate.
  • the alkanolammonium and aminoalkyl-ammonium salts of N,N-di- (Z-hydroxyethyl)-isopicramic acid may be prepared by neutralising this acid with an alkanolamine, such as mono-, dior tri-ethanolamine or isopropanolamine, or an alkylene diamine, for example diethylene diamine.
  • the invention is further illustrated by the following Examples 4 to 7 of compositions for the direct dyeing of hair.
  • the percentages are percentages by Weight.
  • Example 2 Preparation of N,N-di-(2-hydroxyethyl)- picramic acid ammonium salt The preparation of N,N-di-(2-hydroxyethyl) -isopicramic acid was first carried out as described in Example 1.
  • the dyestufif cake obtained was mixed to a smooth paste with a solution of 1 volume of ammonia (specific gravity 0.88) in 4 volumes of methyl alcohol.
  • the dyestuif paste was then dried at -60 C. in a vacuum oven at reduced pressure (60-70 cm. Hg) and ground in a mortar.
  • the yield was similar to that obtained in Example 1.
  • On recrystallisation from boiling water the pure dyestuff was obtained in the form of blackish bronzy prisms which melted at 165-167 C. With decomposition.
  • Example 3 Preparation of N,N-a'i-(Z-hydroswethyl)- isopicramic acid di-iso-butylamine salt The preparation of N,N-di-(2-hydroxyethyl)-isopicramic acid was first carried out as described in Example 1.
  • the dyestuif produced in this way had lower solubility in water but had more afiinity for hair and other keratinous fibres and when dyed from aqueous shampoo base produced darker shades of blue-violet than the potassium and ammonium salts.
  • Compounds having an alkyl group attached to the amino nitrogen atom can be prepared in a similar manner to that described in Example 1 by starting from a salt, for example the ammonium salt, of N-alkyl-isopicramic acid
  • a salt for example the ammonium salt
  • the following procedure was adopted in preparing the above compositions.
  • the dyestuffs, glycerol or formamide, lauryl polyethylene glycol and water were mixed and heated to 70-75 C.
  • a 2% w./w. aqueous dispersion of Carbopol 934 was partly neutralised with ammonium hydroxide (specific gravity 0.88) to a pH of 7.0 to 7.5 and perfume mixed in.
  • the mixture containing the dyestuifs was then stirred slowly into the Carbopol 934 paste and stirring continued until a homogeneous paste was obtained.
  • the pH of the paste was adjusted to 6.5-7.0 by the addition of 10% lactic acid or 10% monoethanolamine.
  • Example 4 gave a light grey shade; Example 5 a blonde shade; Example 6 a light brown shade; and Example 7 a medium brown shade.
  • compositions can be applied with a sponge or a brush or from an applicator to either dry or previously shampooed and towel-dried hair.
  • the dyestuffs used in the process of this invention have a number of important advantages over those dyestuffs in 'Which in the above formula R or R or both of these groups are hydrogen atoms. Apart from being considerably bluer, which makes the dyestuffs better for the formulation of colourants for producing blonde and brown shades, the dyestuffs used in this invention give shades having superior fastness to acids (and therefore to perspiration), and to light and permanent waving.
  • Isopicramic acid changed from bluish-red to orange-yellow
  • N-methyl-isopicramic acid changed from purple to pinkish-yellow
  • N,N-di-(2-hydroxyethyl)-isopicramic acid changed from claret to reddish-brown.
  • a process of dyeing human hair which comprises applying to the hair an aqueous solution having a pH of from 2 to 9 of at least one direct dye of the formula:
  • M is selected from the class consisting of hydrogen, alkali and alkaline earth metals and ammonium and alkylammonium, hydroxyalkylammonium and aminoalkylammonium;
  • R is selected from the class consisting of alkyl having up to 6 carbon atoms and hydroxyalkyl having up to 4 carbon atoms;
  • R is hydroxyalkyl having up to 4 carbon atoms.
  • M is selected from the group consisting of alkylammonium wherein the alkyl contains 1-6 carbon atoms and hydroxyalkylammonium and aminoalkylammonium wherein the alkyl contains 1-4 carbon atoms.
  • a composition for the direct dyeing of keratinous fibres comprising an aqueous solution having a pH of from 2 to 9 of a compound of the formula:
  • M is selected from the class consisting of hydrogen
  • R is selected from the class consisting of alkyl having up to 6 carbon atoms and hydroxyalkyl having up to 4 carbon atoms;
  • R is hydroxyalkyl having up to 4 carbon atoms.
  • M is selected from the class consisting of alkali and alkaline-earth metals and ammonium and alkylammonium, hydroxyalkylammonium and aminoalkylammonium groups;
  • R is selected from the class consisting of alkyl having up to 6 carbon atoms and hydroxyalkyl having up to 4 carbon atoms;
  • R is hydroxyalkyl having up to 4 carbon atoms.
  • M is selected from the group consisting of alkylammonium wherein the alkyl contains 1-6 carbon atoms and bydroxyalkylammonium and aminoalkylammonium wherein the alkyl contains 1-4 carbon atoms.
  • a yellow dye selected from the class consisting of 2-nitro-N-methyl-N-acetyl-p-aminophenol and N-methyl-N-acetyl-isopicramic acid and alkali metal, alkaline-earth metal, ammonium and substituted-ammonium salts thereof.
  • a yellow dye selected from the class consisting of 2-nitro-N-methyl-N-acetyl-pamino-phenol and N-methyl-N-acetyl-isopicramic acid and alkali metal, alkaline-earth metal, ammonium and substituted-ammonium salts thereof.

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Cosmetics (AREA)
  • Coloring (AREA)
US329868A 1962-12-21 1963-12-11 N, n-disubstituted isopicramic acid salts for dyeing human hair Expired - Lifetime US3344031A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3630654A (en) * 1968-05-15 1971-12-28 Bristol Myers Co Aqueous alcoholic acid dye-carboxylated polymer compositions for dyeing and grooming hair
US4125601A (en) * 1976-04-21 1978-11-14 L'oreal Substituted nitroaminophenols, process for their preparation and dyeing compositions in which they are present
WO1985003222A1 (en) * 1984-01-18 1985-08-01 Wella Aktiengesellschaft Hair colorant with picramic acid derivatives, new picramic acid derivatives and production process thereof
EP0352489A3 (en) * 1988-07-23 1990-06-27 Wella Aktiengesellschaft Use of 2,6-dinitrophenol derivatives in hair dyeing compuse of 2,6-dinitrophenol derivatives in hair dyeing compositions ositions

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB889327A (en) * 1958-04-10 1962-02-14 Gillette Industries Ltd Improvements in or relating to shampoo compositions

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB889327A (en) * 1958-04-10 1962-02-14 Gillette Industries Ltd Improvements in or relating to shampoo compositions

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3630654A (en) * 1968-05-15 1971-12-28 Bristol Myers Co Aqueous alcoholic acid dye-carboxylated polymer compositions for dyeing and grooming hair
US4125601A (en) * 1976-04-21 1978-11-14 L'oreal Substituted nitroaminophenols, process for their preparation and dyeing compositions in which they are present
WO1985003222A1 (en) * 1984-01-18 1985-08-01 Wella Aktiengesellschaft Hair colorant with picramic acid derivatives, new picramic acid derivatives and production process thereof
EP0151400A3 (en) * 1984-01-18 1985-09-18 Wella Aktiengesellschaft Hair dyeing compositions with picramic acid derivatives, new picramic acid derivatives and process for preparing same
EP0352489A3 (en) * 1988-07-23 1990-06-27 Wella Aktiengesellschaft Use of 2,6-dinitrophenol derivatives in hair dyeing compuse of 2,6-dinitrophenol derivatives in hair dyeing compositions ositions

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