US3549303A - Nitro-paraphenylenediamine derivative and dyeing keratinic fibers therewith - Google Patents

Nitro-paraphenylenediamine derivative and dyeing keratinic fibers therewith Download PDF

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US3549303A
US3549303A US544094A US3549303DA US3549303A US 3549303 A US3549303 A US 3549303A US 544094 A US544094 A US 544094A US 3549303D A US3549303D A US 3549303DA US 3549303 A US3549303 A US 3549303A
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nitro
hydroxyethyl
methylaminobenzene
amino
keratinic fibers
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Gregoire Kalopissis
Andree Bugaut
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LOreal SA
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LOreal SA
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    • 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
    • A61Q5/10—Preparations for permanently dyeing 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
    • A61K8/30—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

Definitions

  • Substituted nitro-paraphenylenediamine products are well known as active ingredients in solutions for dyeing keratinic fibers and in particular for dyeing living hair.
  • the alkyl and hydroxyalkyl groups are especially well known as substituents for modifying the shades which may be obtained with nitro-paraphenylenediamine itself.
  • the object of the present invention is to provide a new dye which is a di-substituted derivative of nitro-paraphenylenediamine.
  • This new dye is 1-amino-2-nitro-4-(2- hydroxyethyl)-methylaminobenzene, which has the formula:
  • the invention also comprises two new methods of preparing the compound according to the above formula.
  • the first of these methods of preparation is essentially characterized by the fact that 1-amino-2-nitro-4-methylaminobenzene is hydroxyalkylated by means of a halohydrin, for example. Hydroxyalkylation in the meta position of the nitro group can be effectuated in commercial quantities, without impurities, especially when using a bromohydrin.
  • the second method of preparation according to the invention which makes it possible to obtain the compound according to Formula I is essentially characterized by the fact that 1-acetamino-4-(2-hydroXyethyl)-methylaminobenzene is nitrated with a sulfonitric mixture and that the resulting product is deacetylated by means of "ice broad limits, but falls preferably between 10 and 30 minutes.
  • the temperature at which these dyes are applied may also be varied, but in most cases they are preferably applied at room temperature.
  • the pH of these solutions is in general between 7 and 10 and preferably between 8 and 9.5.
  • An alkali such as plain ammonia, or an organic base such as an alkylamine, an alkanolamine, or a heterocyclic amine may be used to adjust this pH.
  • concentration of the dyes according to the invention may be varied, but this concentration is preferably between 0.1% and 3%.
  • the new dye may be mixed with other nitro, azo or anthraquinone dyes, or any other dyes conventionally used for dyeing hair.
  • a further object of the present invention is to provide a new method of dyeing keratinic fibers and especially human hair, which method is essentially characterized by the steps of applying to the hair a dyeing composition comprising in solution at least one compound according to Formula I and leaving this composition in contact with the hair for from 10 to 30 minutes.
  • the compound according to Formula I may also be used as a base product in the organic synthesis of tri-substituted derivatives of nitroparaphenylenediamine.
  • the present invention therefore envisages as a particular method of using the compounds according to the invention, a process of synthesizing 1- methylamino-2-nitro-4-(2' hydroxyethyl)-methylamino benzene by using the compound of Formula I.
  • This process is essentially characterized by the fact that benzenesulfochloride is reacted with the compound of Formula I so that the former becomes attached to the unsubstituted nitrogen atom.
  • the resulting product is treated with methyl sulfate in an alkaline medium, and the sulfonylbenzene radical fixed in the first step of the process is removed by hydrolysis in a hydrochloric acid medium.
  • the present invention also envisages, as a particular use for the compound according to the invention, a process of preparation which makes it possible to synthesize 1-(2- hydroxyethyl)-amino 2 nitro-4-(2' hydroxyethyl)- methylaminobenzene.
  • This process is essentially characterized by the fact that chloroethyl-chloroformate is reacted with the compound according to Formula I to yield the fi-chloroethylic ester of [2-nitro-4-(2'-hydroxyethyl)- methylamino]-phenylcarbamic acid and this ester is then hydrolyzed with caustic potash purified by solution in alcohol.
  • EXAMPLE 1 First method of preparing l-amino-2-nitro-4-(2'- hydroxyethyl) -methylamino'benzene
  • One mol (167 g.) of 1-amino-2-nitro-4-methylaminobenzene' is mixed with 1000 cm. of water and 60 g. of calcium carbonate.
  • the mixture is boiled under reflux and 1.2 mols (150 g.) of glycol bromohydrin is added drop by drop, while stirring.
  • 1500 cm. of boiling water is added, and after having continued the reflux for several minutes, the mixture is filtered through a funnel for hot filtration. After cooling, the filtrate yields 161 g. of the crude product, which, after two recrystallizations in methylisobutylketone, melts at C.
  • Second step deacetylation and purificati0n.
  • the acetylated derivative obtained in the first step is introduced into a mixture of 30 cm. of concentrated hydrochloric acid and 60 cm. of water. This is kept for /2 hour in a boiling water bath. A little animal black is added, the product is filtered, and after drying and cooling yields 16 g. of crystallized hydrochloride. This is dissolved in boiling water, which is rendered alkaline by adding ammonia, cooled, and on drying yields 13 g. of 1-amino-2-nitro-4-(2 hydroxyethyl) methylaminobenzene, whichafter recrystallization in chloroform, melts at 115 C.
  • tosylatiom-A solution is prepared comprising 0.15 mol (31.65 g.) of 1-amino-2-nitro-4-(2'- hydroxyethyl)-methylaminobenzene in 110 cm. of pyridine. 0.15 mol (19.2 cm. of benzene-sulfochloride is added little by little, while stirring, at between 45 and 50 C. The reaction mixture is kept at 45 C.
  • a composition for dyeing keratinic fibers comprising dyeing amounts of the compound of claim 1 in an aqueous solution having a pH between 7 to 10.
  • composition as claimed in claim 2 in which the concentration of said compound lies between 0.1% and 3% inclusive.

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Cosmetics (AREA)
  • Coloring (AREA)

Description

United States Patent 48,4 8 Int. (:1. A61k 7/12 US. Cl. 8-101 Claims ABSTRACT OF THE DISCLOSURE l-ainino 2 nitro-4-(2'-hydroxyethyl)-methylaminobenzene, a new compound, is used to dye keratinic fibers, especially living human hair.
Substituted nitro-paraphenylenediamine products are well known as active ingredients in solutions for dyeing keratinic fibers and in particular for dyeing living hair. The alkyl and hydroxyalkyl groups are especially well known as substituents for modifying the shades which may be obtained with nitro-paraphenylenediamine itself.
The object of the present invention is to provide a new dye which is a di-substituted derivative of nitro-paraphenylenediamine. This new dye is 1-amino-2-nitro-4-(2- hydroxyethyl)-methylaminobenzene, which has the formula:
CH; 7K /\CH2OH2OH The invention also comprises two new methods of preparing the compound according to the above formula.
The first of these methods of preparation is essentially characterized by the fact that 1-amino-2-nitro-4-methylaminobenzene is hydroxyalkylated by means of a halohydrin, for example. Hydroxyalkylation in the meta position of the nitro group can be effectuated in commercial quantities, without impurities, especially when using a bromohydrin.
The second method of preparation according to the invention which makes it possible to obtain the compound according to Formula I is essentially characterized by the fact that 1-acetamino-4-(2-hydroXyethyl)-methylaminobenzene is nitrated with a sulfonitric mixture and that the resulting product is deacetylated by means of "ice broad limits, but falls preferably between 10 and 30 minutes. The temperature at which these dyes are applied may also be varied, but in most cases they are preferably applied at room temperature. The pH of these solutions is in general between 7 and 10 and preferably between 8 and 9.5. An alkali such as plain ammonia, or an organic base such as an alkylamine, an alkanolamine, or a heterocyclic amine may be used to adjust this pH. The concentration of the dyes according to the invention may be varied, but this concentration is preferably between 0.1% and 3%. It should be noted that the new dye may be mixed with other nitro, azo or anthraquinone dyes, or any other dyes conventionally used for dyeing hair. A further object of the present invention is to provide a new method of dyeing keratinic fibers and especially human hair, which method is essentially characterized by the steps of applying to the hair a dyeing composition comprising in solution at least one compound according to Formula I and leaving this composition in contact with the hair for from 10 to 30 minutes. It should be emphasized that the compound according to Formula I may also be used as a base product in the organic synthesis of tri-substituted derivatives of nitroparaphenylenediamine. The present invention therefore envisages as a particular method of using the compounds according to the invention, a process of synthesizing 1- methylamino-2-nitro-4-(2' hydroxyethyl)-methylamino benzene by using the compound of Formula I. This process is essentially characterized by the fact that benzenesulfochloride is reacted with the compound of Formula I so that the former becomes attached to the unsubstituted nitrogen atom. The resulting product is treated with methyl sulfate in an alkaline medium, and the sulfonylbenzene radical fixed in the first step of the process is removed by hydrolysis in a hydrochloric acid medium.
The present invention also envisages, as a particular use for the compound according to the invention, a process of preparation which makes it possible to synthesize 1-(2- hydroxyethyl)-amino 2 nitro-4-(2' hydroxyethyl)- methylaminobenzene. This process is essentially characterized by the fact that chloroethyl-chloroformate is reacted with the compound according to Formula I to yield the fi-chloroethylic ester of [2-nitro-4-(2'-hydroxyethyl)- methylamino]-phenylcarbamic acid and this ester is then hydrolyzed with caustic potash purified by solution in alcohol.
Two methods of preparing the compound according to the invention, and its method of use in hair dyes and as a starting material for the synthesis of 1-methylamno-2- nitro-4-(2'-hydroxyethyl)-methylaminobenzene and 1-(2'- hydroxyethyl)-amino-2-nitro 4 (2 hydroxyethyl)- methylaminobenzene will now be described, purely by way of example.
EXAMPLE 1 'First method of preparing l-amino-2-nitro-4-(2'- hydroxyethyl) -methylamino'benzene One mol (167 g.) of 1-amino-2-nitro-4-methylaminobenzene'is mixed with 1000 cm. of water and 60 g. of calcium carbonate. The mixture is boiled under reflux and 1.2 mols (150 g.) of glycol bromohydrin is added drop by drop, while stirring. After boiling under reflux for two hours, 1500 cm. of boiling water is added, and after having continued the reflux for several minutes, the mixture is filtered through a funnel for hot filtration. After cooling, the filtrate yields 161 g. of the crude product, which, after two recrystallizations in methylisobutylketone, melts at C.
Analysis of end product: Calculated for C H O N (percent): C, 51.18; H, 6.16; N, 19.90. Found (percent): C, 50.8950.98; H, 6.l66.43; N, 20.21-20.23.
3 EXAMPLE 2 (a) First step: nitratin.-0.1 mol (21 g.) of l-acetamino-4-(2-hydroxyethyl)-methylarninobenzene is dissolved in 75 cm. of concentrated sulfuric acid, while keeping the temperature between 0 and 2 C. A sulfonitric mixture formed by adding 6.6 g. of concentrated sulfuric acid to 6.6 g. of nitric acid having a density of 1.52 is then added immediately, little by little, while stirring and keeping the temperature between 0 and 2 C. The reaction mixture is then poured over ice, and neutralized with ammonia to extract the isopropyl alcohol. After having eliminated this alcohol under vacuum 23.5 g. of crude 1-acetamino-2-nitro-4-(2'-hydroxyethyl) aminobenzene is obtained. (b) Second step: deacetylation and purificati0n.The acetylated derivative obtained in the first step is introduced into a mixture of 30 cm. of concentrated hydrochloric acid and 60 cm. of water. This is kept for /2 hour in a boiling water bath. A little animal black is added, the product is filtered, and after drying and cooling yields 16 g. of crystallized hydrochloride. This is dissolved in boiling water, which is rendered alkaline by adding ammonia, cooled, and on drying yields 13 g. of 1-amino-2-nitro-4-(2 hydroxyethyl) methylaminobenzene, whichafter recrystallization in chloroform, melts at 115 C.
Analysis of end product: Calculated for C H O N (percent): C, 51.18; H, 6.16; N, 19.90. Found (percent): C, 51.16-51.22; H, 6.12-6.42; N, 20.03-20.03.
EXAMPLE 3 The following composition is prepared:
1-amino-2-nitro-4-(2 hydroxyethyl) methylaminobenzene-0.75 g.
Polyoxyether of fatty alcohol (Remcopal 21.411 sold by Paix) g.
20% ammonia q.s.p.pH=8
Water, q.s.p.-100 g.
This solution is applied to white hair and left in contact therewith for minutes. The hair is then rinsed, shampooed and dried. The result is a very slightly mauve rose blond shade.
EXAMPLE 4 The following composition is prepared:
1-amino-2-nitro-4-(2 hydroxyethyl) methylaminobenzene0.75 g.
1-methylamino-2-nitro-4-(fl-hydroxyethyl)-methylaminobenzene0.5 g.
Polyoxyether of fatty alcohol (Remc'opal 21.411 sold I by Paix)5 g.
20% ammonia q.s.p.pH=8
Water, q.s.p.lOO g.
This solution is applied to light chestnut hair and left in contact therewith for 10 minutes. The air is then rinsed, shampooed and dried. A light chestnut with glints of violine results.
EXAMPLE 5 The following composition is prepared:
1-amino-2-nitro-4-(2 -hydroxyethyl) methylaminobenzene0.75 g.
1-( -diethyl-aminopropyl) -amino-2-zimino-4-nitro benzene-0.01 g.
Polyoxyether of fatty alcohol (Remcopal 21.411 sold by Paix)-5 g.
20% ammonia q.s.p.pH=8
Water, q.s.p.100 g.
This solution is applied to 100% white hair and left in contact therewith for 20 minutes. The hair is then rinsed, shampooed, and dried. A warm, slightly pearlescent blond shade results.
. EXAMPLE 6 Use of 1-amino-2-nitro-4(2-hydroxyethyl)-methylaminobenzene to synthesize 1-methylamino-2-nitro-4-(2- hydroxyethyl) -methylaminobenzene (a) First step: tosylatiom-A solution is prepared comprising 0.15 mol (31.65 g.) of 1-amino-2-nitro-4-(2'- hydroxyethyl)-methylaminobenzene in 110 cm. of pyridine. 0.15 mol (19.2 cm. of benzene-sulfochloride is added little by little, while stirring, at between 45 and 50 C. The reaction mixture is kept at 45 C. for 2 hours and then poured into a liter of ice water which contains cm. of concentrated hydrochloric acid, thus precipitating a brown resinous product which is then redissolved in methylisobutyl-ketone. The methylisobutyl-ketone solution is then extracted, using a normal sodium hydroxide solution, and the residual solution is neutralized with hydrochloric acid. On drying, this yields 36 g. of l-benzene sulfonylamino-2-nitro-4-(2-hydroxyethyl) methylaminobenzene, which, after recrystallization in alcohol, melts at 112 C.
Analysis of end product.Calculated for C15H17N3O5S (percent): C, 51.28; H, 4.84; N, 11.96. Found (percent): C, 51.56-51.39; H, 4.69-4.94; N, 12.05-12.01.
(b) Second step: alkylation.-A solution containing 0.0142 mol (5 g.) of the product. obtained in the first step in 65 cm. of 0.5 N sodium hydroxide is prepared. To this solution, 0.032 mol (3 cm?) of methyl sulfate is added, while keeping the temperature between 25 and 30 C. The reaction mixture is left for two hours at this temperature, and after cooling and drying, yields 4 g. of 1- (benzene sulfonyl)-methylamino 2-nitro-4-(2-hydroxyethyl)-methylaminobenzene. 50 cm. of 0.5 N sodium hydroxide is added to this product, while stirring, to eliminate any of the starting product which has not reacted. The product is then dried, washed with water, and recyrstallized in a mixture of 75% ethyl acetate and 25% petroleum ether, yielding 3.6 g of the pure product, which melts at 116 C.
Analysis of end product.Calculated for C H N O S (percent): C, 52.60; H, 5.20; N, 11.50. Found (percent): C, 52.87-52.70; H, 5.44-5.26; N, 11.43-11.63.
(c) Third step: hydrolysis.A solution of 0.028 mol (10.22 g.) of the product obtained in the first step in 25 cm. of concentratedhydrochloric acid mixed with 5 cm. of water is heated for an hour in a boiling water bath. After cooling and dilution, the solution is neutralized with sodium hydroxide and on drying yields 5.1 g. of l-methylamino-2-nitro-4-(2'-hydroxyethyl) methylaminobenzene,
which is practically pure, and melts at 94 C.
Analysis of end product-Calculated for C H O N (percent): C, 53.33;H, 6.67; N. Found (percent): C, 53.71-53.74; H, 6.46-6.93.
EXAMPLE 7 Use of 1-amino-2-nitro-4-(2-hydroxyethyl) -methylamino benzene to synthesize l-(2'hydroxyethyl)-amino-2-nitro- 4- (2'-hydroxyethyl)-methylaminobenzene (a) First step: producing an ester.0.1 mol 21.1 g.) I
cooled an dried, yielding 12.2 g. of the starting product in the form of the hydrochloride. The filtrate is evaporated under vacuum and yields 16.5 g. of the chloroethylic ester of [2 nitro-4-(2(hydroxyethyl)-methylamino] -phenylcarbamic acid.
(b) Second step: hydrolysis.-The ester obtained in the first step is dissolved in 135 cm. of a solution of caustic potash in alcohol containing 110 g. of potash per liter. This solution is heated to reflux for two hours, and then cooled and poured into 600 cm. of ice water. This is then extracted with methyl-isobutyl-ketone and the solvent evaporated under vacuum. The yield is 11 g. of 1-(2- hydroxyethyD-amino-Z nitro-4-(2'-hydroxyethyl)-methylaminobenzene, which, after recrystallization in benzene, melts at 99 C.
Analysis of end product.Calculated for C H N O (percent): C, 51.76; H, 6.66; N, 16.47. Found (percent): C, 51.26-51.61; H, 6.66-6.68; N, 16.27-16.53.
It will of course be appreciated that the methods of producing and using the products which have just been described have been given purely by way of example, and may be modified as to detail without thereby departing from the basic principles of the invention.
What is claimed is:
1. 1 amino-2-nitro-4-(2'-hydroxyethyl)-methylaminobenzene.
2. A composition for dyeing keratinic fibers comprising dyeing amounts of the compound of claim 1 in an aqueous solution having a pH between 7 to 10.
3. A composition as claimed in claim 2 in which the concentration of said compound lies between 0.1% and 3% inclusive.
4. The method of dyeing keratinic fibers which comprises the steps of applying the composition claimed in claim 2 thereto, and leaving said composition in contact with said fibers for between 10 and minutes, inclusive.
5. The method of claim 4, wherein said keratinic fibers are live human hair.
References Cited UNITED STATES PATENTS 2,687,431 8/1954 Marschall 260573X 2,750,326 6/ 1956 Eckardt I 167-88 2,750,327 6/ 1956 Eckardt II 16788 3,088,878 5/1963 Brunner et al. I l6788 3,168,442 2/1965 Brunner et al. II 167-88 3,194,838 7/1965 Ross 260-573 OTHER REFERENCES ALBERT T. MEYERS, Primary Examiner V. C. CLARKE, Assistant Examiner U.S. Cl. X.R.
US544094A 1965-04-26 1966-04-21 Nitro-paraphenylenediamine derivative and dyeing keratinic fibers therewith Expired - Lifetime US3549303A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3764625A (en) * 1969-04-01 1973-10-09 United States Borax Chem Trifluoromethyl-1,3-phenylenediamine compounds
US3973900A (en) * 1971-03-29 1976-08-10 Wella Ag Hair dye
US11129782B2 (en) 2017-11-15 2021-09-28 National University Of Singapore Derivatives of PPD useful for coloring hair and skin

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU547270B2 (en) * 1980-08-08 1985-10-10 L'oreal Direct nitro hair dyeing compositions
GB2086408B (en) * 1980-10-16 1985-10-09 Oreal New nitro-derivatives of the benzene series the process for their preparation and their use in the dyeing of keratin fibres
DE3543020A1 (en) * 1985-12-05 1987-06-11 Wella Ag Process for preparing 4-[ethyl-(2'-hydroxyethyl)amino]-1-[(2'-hydroxyethyl)amino]-2-nitroben zene

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2687431A (en) * 1950-12-20 1954-08-24 Gen Aniline & Film Corp Process of preparing nitro phenylenediamines
US2750327A (en) * 1953-06-01 1956-06-12 Lever Brothers Ltd Process of dyeing animal fibers and dyes and dyeing compositions therefor
US2750326A (en) * 1951-02-07 1956-06-12 Lever Brothers Ltd Process and composition for dyeing hair
US3088878A (en) * 1960-11-22 1963-05-07 Walter H Brunner Method of dyeing keratinaceous materials with nitro-substituted para-phenylene diamine compositions
US3168442A (en) * 1964-06-12 1965-02-02 Clairol Inc Compositions and methods of dyeing human hair with nitro-p-phenylenediamines
US3194838A (en) * 1962-02-19 1965-07-13 Polaroid Corp Process for preparation of alpha-hydroxy-beta-alkyl-aminonaphthalene

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2687431A (en) * 1950-12-20 1954-08-24 Gen Aniline & Film Corp Process of preparing nitro phenylenediamines
US2750326A (en) * 1951-02-07 1956-06-12 Lever Brothers Ltd Process and composition for dyeing hair
US2750327A (en) * 1953-06-01 1956-06-12 Lever Brothers Ltd Process of dyeing animal fibers and dyes and dyeing compositions therefor
US3088878A (en) * 1960-11-22 1963-05-07 Walter H Brunner Method of dyeing keratinaceous materials with nitro-substituted para-phenylene diamine compositions
US3194838A (en) * 1962-02-19 1965-07-13 Polaroid Corp Process for preparation of alpha-hydroxy-beta-alkyl-aminonaphthalene
US3168442A (en) * 1964-06-12 1965-02-02 Clairol Inc Compositions and methods of dyeing human hair with nitro-p-phenylenediamines

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3764625A (en) * 1969-04-01 1973-10-09 United States Borax Chem Trifluoromethyl-1,3-phenylenediamine compounds
US3973900A (en) * 1971-03-29 1976-08-10 Wella Ag Hair dye
US11129782B2 (en) 2017-11-15 2021-09-28 National University Of Singapore Derivatives of PPD useful for coloring hair and skin

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DE1569812B2 (en) 1974-12-12
DE1569812C3 (en) 1975-08-07
DE1569815B2 (en) 1975-03-06
DE1569815A1 (en) 1970-10-22
LU48468A1 (en) 1966-10-26
DE1569812A1 (en) 1969-11-27
NL6605558A (en) 1966-10-27
DE1569814A1 (en) 1969-08-14
DE1569813A1 (en) 1970-07-09
GB1138171A (en) 1968-12-27
DE1569814B2 (en) 1975-12-18
DE1619613A1 (en) 1970-11-12
AT273070B (en) 1969-07-25
AT276636B (en) 1969-11-25
DE1569813B2 (en) 1976-04-22
DE1569815C3 (en) 1975-10-23
AT274782B (en) 1969-09-25

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