Classifications

• • 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
  • A61Q5/08—Preparations for bleaching the hair
• • 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
  • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
  • A61K8/22—Peroxides; Oxygen; Ozone
• • 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
  • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
  • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
  • C11D3/3905—Bleach activators or bleach catalysts
  • C11D3/3907—Organic compounds
  • C11D3/3917—Nitrogen-containing compounds
  • C11D3/392—Heterocyclic compounds, e.g. cyclic imides or lactames
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S424/00—Drug, bio-affecting and body treating compositions
  • Y10S424/03—Hair bleach

Definitions

• acylated glycolurils of the formula in which at least two of the residues R to R represent acyl residues having two to eight carbon atoms, while the other residues represent hydrogen atoms and/or alkylor arylresidues with one to eight carbon atoms and/or acyl residues with two to eight carbon atoms.
• the acyl residues present in the molecule may be the same or different; tetraacylglycolurils with the same C acyl residues, especially tetraacetylglycoluril, are preferably used.
• An object of the present invention is the development of materials which will activate per-compounds, particularly at temperatures below 45C.
• Another object of the invention is the development of a method of oxidative treatment of human hair which consistsessentially of contacting human hair, at a temperature of from 20C to 45C, with an aqueous liquid containing an oxidizer selected from the group consisting of water-soluble peroxyhydrates and hydrogen peroxide in an amount sufficient to supply from gm to 200 gm per liter of H 0 equivalent and from gm to 500 gm per liter of an activator diacylated 2,5- diketopiperazine having the formula wherein R and R are acyls of organic carboxylic acids having from two.
• R and R are members selected from the group consisting of hydrogen, alkyl having from one to three carbon atoms, hyclroxyalkyl having one to three carbon atoms, haloalkyl having one to three carbon atoms, nitroalkyl having one to three carbon atoms, nitriloalltyl having two to four carbon atoms and alkoxyalkyl having two to five carbon atoms.
• the invention relates to the use of certain organic substances as activators for per-compounds, which enable the minimum temperature needed for a practically effective bleaching and oxidative treatment of human hair to be reduced and/or the oxidation process to be accelerated.
• the substances to be used as activators for the percompounds according to the invention are diacylated 2,5-diketopiperazines of the following formula I in which R, and R each represent acyl residues of organic carboxylic acids with two to nine carbon atoms, and R and R each represent hydrogen and/or an optionally substituted hydrocarbon residue with one to three carbon atoms.
• the acyl residues present in the molecule may be the same or different.
• the said compounds are therefore used as activators for H 0 or per-compounds (peroxycompounds) yielding H 0 in water.
• Diacyl-diketopiperazines with the same R, and R residues are easier to prepare than those with different acyl residues; therefore the former have greater practical importance.
• the residues R, and R are aliphatic, they preferably contain two to four carbon atoms, and when they represent aromatic residues, they may contain up to nine carbon atoms. Consequently, the following are preferably used as the residues R and R acetyl, propionyl, nor isobutyryl, benzoyl, toluoyl or xyloyl.
• Suitable substituents are C alkoxy groups, halogen atoms, and nitro or nitrile groups; chloroand- /or nitro-substituted aromatic residues which are of especially practical interest are m-chloroor mor pnitro substituted residues;
• the residues R and R are preferably the same, for example, methyl or ethyl resigen atoms, or nitro, nitrile, methoxy or ethoxy groups.
• R and R are acyls of organic carboxylic acids having from two to nine carbon atoms selected from the group consisting of alkanoic acids, nitriloacetic acid, haloalkanoic acids, benzoic acid, nitrobenzoic acid, halobenzoic acid, alkylbenzoic acid, nitroalkylbenzoic acid, haloalkylbenzoic acid, alkoxybenzoic acid and nitrilobenzoic acid, and R and R are members selected from the group consisting of hydrogen, alkyl having from one to three carbon atoms, hydroxyalkyl having one to three carbon atoms, haloalkyl having one to three carbon atoms, nitroalkyl having one to three carbon atoms, nitriloalkyl having two to four carbon atoms and alkoxyalkyl having two to five carbon atoms.
• R, and R are the same and are acyls of alkanoic acids having two to four carbon atoms, nitriloalkanoic acids having three to four carbon atoms, haloalkanoic acids having two to four carbon atoms, benzoic acid, halobenzoic acids, nitrobenzoic acids, nitrilobenzoic acids and methoxybenzoic acids; and R and R are the same and are hydrogen or alkyl having one to three carbon atoms.
• Suitable acyl residues of organic carboxylic acids having from two to nine carbon atoms are, for example, alkanoyls, such as acetyl, propionyl, butyryl, etc; haloalkanoyls, such as monobromoacetyl and preferably chloroalkanoyls such as monochloroacetyl, dichloroacetyl, trichloroacetyl, etc.; nitriloacetyl, benzoyl and toluyl which may be substituted with nitro groups or halogen atoms such as chlorobenzyl, nitrobenzoyl, chlorotoluyl and nitrotoluyl; methoxybenzoyls; and nitrilobenzoyls.
• alkanoyls such as acetyl, propionyl, butyryl, etc
• haloalkanoyls such as monobromoacetyl and
• the diketopiperazines alkylated in the 3- and/or 6-position can be acylated.
• the alkylated piperazines to be used as starting materials are oba a b e assq s iwg Balkan is. a.s z t,h i m de France, 1942, pp. 487-494, by condensation of the corresponding amino acids.
• the 3,6-dimethyl-2,5- diketo-piperazine can be acetylated according to Recueil des Travaux Chimiques des Pays-Bas, 1908, 27, p. 205.
• Dipropionyl-diketopiperazine is obtained, for example, by the following method: A suspension of 22.8 g. (0.2 mol) of 2,5-diketopiperazine in 350 ml. (2.7 mol) of propionic anhydride is stirred for 3 hours at 140C. After cooling, undissolved material is filtered off and the clear filtrate is evaporated in vacuo. The crude 1,4- dipropionyl-2,5-diketopiperazine thus obtained is already utilizable in this state as an activator for percompounds. However it can be purified by washing with water and isopropanol and then recrystallizing from isopropanol, a yield of 23.5 g (52.7 percent of theory) being then obtained. The melting point is 1l3-114.5C.
• 1,4-dipropionyl-3,6-dimethyl- 2,5-diketopiperazine a suspension of 28.4 g (0.2 mol) of 3,6-dimethy1-2,5-diketopiperazine in 130 g (1 mol) of propionic acid anhydride is treated with 0.5 ml of percent perchloric acid and the mixture is heated for 8 hours at C to C.
• the clear solution obtained is concentrated and the crude dipropionyl-dimethyldiketopiperazine obtained as residue is digested with petrol (b.p. 80100C), filtered by suction and the residue is again washed with petrol.
• the crude product is obtained in a yield of 14.8 g (29.3 percent of theory).
• the melting point lies at 106C to l 14C. 1t can be used in this state as an activator. However, after recrystallizing from isopropanol, the pure product used for analysis melts at l 13C to l 14C.
• the per-compounds to be activated can be any type of inorganic or organic per-compound which will release active oxygen in an aqueous solution.
• the per-compounds preferably utilized are inorganic peroxides, inorganic per-acids, inorganic peroxyhydrates and products of the addition of hydrogen peroxide with inorganic and organic compounds.
• hydrogen peroxide is of the greatest practical importance. It may be used as such, but may also be used in the form of its mostly solid peroxyhydrates or products of addition with inorganic and organic compounds.
• the latter include, for example, the products of addition of hydrogen peroxide to urea or melamine, and examples of the peroxyhydrates and the perborates, perortho-, perpyro-, and perpoly-phosphates, percarbonates and persilicates.
• These peroxyhydrates are preferably soluble in water and are ordinarily utilized in the form of their alkali metal salts, such astheir sodium salts.
• the activators according to the invention may also be used together with true per-acids, such as for example, Caros acid (peroxymonosulfuric acid, H 50 or peroxydisulfuric acid (H S O or their salts.
• Each acyl residue present in the activator is able to activate an active oxygen atom of the per-compound used.
• one molecule of a diacylated 2,5diketopiperazine is in a position to activate 2 oxygen atoms.
• the activator may also be used in relatively large excess. in general, the amount of activator used is chosen so that 0.5 to 6,-preferably 0.75 to 3 acyl residues are present per active oxygen atom.
• the acceleration of the bleaching and oxidizing processes on human hair is shown at low temperatures in the range from 20C to 45C, and preferably from 20C to 37C and more, particularly from 20C to 30C.
• the technician when using the activators according to the invention, either'to reduce the temperature of treatment and/or to shorten the time of treatment, the temperature remaining the same.
• the conditions to be maintained during operation with the activators according to the invention depend substantially on the color of the hair to be oxidized and/or bleached and the brightness of the desired color tone if an oxidative dyestuff is employed.
• the usually aqueous oxidizing or bleaching liquids may contain gm to 200 gm, preferably gm to 100 gm, per liter of H 0 equivalent and have a pH value from 7 to l l, and especially from 8 to l0.5.
• aqueous solutions of percompounds and diacylated 2,5-diketopiperazine activators may be utilized.
• These aqueous solutions preferably contain sufficient per-compounds to give a concentration of from 20 mg to 500 mg, preferably 50 mg to 250 mg per liter of active oxygen and sufficient diacylated 2,5-diketopiperazine activators to provide from 0.5 to 6, preferably 0.75 to 3 acyl residues of the diacylated 2,5-diketopiperazine per active oxygen atoms and preferably from 20 gm to 500 gm per liter of the diacylated 2,5-diketopiperazine.
• the activators may be used wherever per-compounds, especially hydrogen peroxide or perborates, have previously been used as oxidizing and/or bleaching agents for the oxidative treatment of human hair, preferably living human hair.
• the desired pl-l-value is adjusted by addition of neutralor alkaline-reacting substances, possibly by buffer mixtures, and particularly by additives which have also been co-employed in a corresponding, formerly customary, treatment.
• alkaline substances which serve to decrease the surface tension of the aqueous oxidizing or bleaching liquid, such as for example, soap or known synthetic detergents of anionic, non-ionic or amphoteric nature.
• soap or known synthetic detergents of anionic, non-ionic or amphoteric nature When working in the alkaline range, alkaline substances may be added as well as inorganic or organic complex-forming compounds, especially complex-forming compounds suitable for binding the so-called hardness-producing substances in water or heavy metals which may possibly be present.
• the maximum degree of activation is already reached after a period of one minute, and this is maintained over a certain length of time, irrespective of the temperature.
• the subsequent falling off of the values is due to the spontaneous decomposition of the first formed peracetic acid or perpropionic acid.
• the amount of activated oxygen slowly rises in the course of the experiment. The products therefore difi'er in the period of activation per unit of time and it is possible to choose an activator, the action of which is optimal to the bleaching or oxidizing process in question.
• EXAMPLE 4 For the bleaching of human hair, the dyeing of hair by means of oxidation dyestuffs, and the oxidative treatment of hair after setting by the action of reducing thio-compounds (cold wave process), aqueous solutions containing 10 gm to 200 gm of H per liter are normally used. When this treatment was carried out after addition of 20 gm to 500 gm per liter of diacetylor dipropionyl-diketopiperzine, a considerable intensifying of the oxidizing action of the H 0 was observed, so that, if desired, smaller concentration of H 0 could also be used.
• EXAMPLE 6 For the bleaching of living human hair, for the dyeing of hair with the aid of oxidation dyes and for the oxidative treatment of hair after setting by the action of reducing thio-compounds, an aqueous solution is used which is prepared in the following way:
• the bleaching activation is less at the start of the treatment. It is thus easier to attain only a partial lightening of the color tone up to a definite, desired color tone.
• a method of oxidative treatment of human hair which consists essentially of contacting human hair, at a temperature of from 20C to 45C, with an aqueous liquid containing an oxidizer selected from the group consisting of water-soluble peroxyhydrates and hydrogen peroxide in an amount sufficient to supply from 10 gm to 200 gm per liter of H 0 equivalent and from 20 gm to 500 gm per liter of an activator diacylated 2,5- diketopiperazine having the formula acid, haloalkanoic acids, benzoic acid, nitrobenzoic acid, halobenzoic acid, alkylbenzoic acid, nitroalkylbenzoic acid, halolkylbenzoic acid, alkoxybenzoic acid and nitrilobenzoic acid, and R and R are members selected from the group consisting of hydrogen, alkyl having from one to three carbon atoms, hydroxyalky] having one to three carbon atoms, haloalkyl having one to three
• activator diacylated '2,5-diketopiperazine is l,4-diacetyl-2,5-
• activator diacylated 2,5-diketopiperazine is l,4-dipropionyl2,5- diketopiperazine.
• activator diacylated 2,5-diketopiperazine is l,4-diacetyl-3,6- dimethyl-2,5-diketopiperazine.
• Priority number shouldread l "aceylated should read -acy1ated-- "Berichte” should read -Ber i c hter I “found;” shou d read '-found "2.5piperazine” should read --2.5-diketo-piperazine-.
• alkanoic acids should read 3 Cla im l) (12) --alkano1c acid-- 9 14 I y 3 "haloalkanoic acids” should read Claim 1) (l3) --haloalkanoic acid- 9 7 members should be deleted. Claim 1) (16) claim 8 2 v A "is added” should read --*is ,presentclaim 8 2 I “to said aqueous liquid” should be deleted Claim 8 5 1 "solution” should read --lig uid Signed and sealed this 3rd day of June 1975.

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• Life Sciences & Earth Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical & Material Sciences (AREA)
• Veterinary Medicine (AREA)
• Public Health (AREA)
• General Health & Medical Sciences (AREA)
• Animal Behavior & Ethology (AREA)
• Birds (AREA)
• Epidemiology (AREA)
• Inorganic Chemistry (AREA)
• Organic Chemistry (AREA)
• Wood Science & Technology (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Emergency Medicine (AREA)
• Detergent Compositions (AREA)
• Cosmetics (AREA)

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Publications (1)

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Cited By (6)

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• 1970
  • 1970-07-31 DE DE19702038106 patent/DE2038106A1/de active Pending
  • 1970-10-21 DE DE19702051554 patent/DE2051554A1/de active Pending
• 1971
  • 1971-06-29 NL NL7108986A patent/NL7108986A/xx unknown
  • 1971-06-29 NL NL7108972A patent/NL7108972A/xx unknown
  • 1971-07-28 BE BE770595A patent/BE770595A/xx unknown
  • 1971-07-29 FR FR7127796A patent/FR2112195B1/fr not_active Expired
  • 1971-07-30 GB GB3505671A patent/GB1339257A/en not_active Expired
  • 1971-07-30 CH CH1130571A patent/CH577936A5/xx not_active IP Right Cessation
  • 1971-07-30 AT AT669871A patent/AT317142B/de not_active IP Right Cessation
  • 1971-07-30 GB GB3585371A patent/GB1339256A/en not_active Expired
  • 1971-08-02 US US00168404A patent/US3812247A/en not_active Expired - Lifetime
  • 1971-08-02 US US00168374A patent/US3775332A/en not_active Expired - Lifetime
  • 1971-10-18 BE BE774073A patent/BE774073A/xx unknown
  • 1971-10-20 CH CH1525771A patent/CH574495A5/xx not_active IP Right Cessation
  • 1971-10-21 FR FR7137822A patent/FR2110038A5/fr not_active Expired
  • 1971-10-21 AT AT911871A patent/AT326610B/de not_active IP Right Cessation

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