Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B51/00—Nitro or nitroso dyes
• • 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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
  • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
  • C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
  • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
  • C07D295/12—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
  • C07D295/125—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
  • C07D295/13—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain

Definitions

• R, and R are H, alkyl or hydroxyalkyl and may form a heterocyclic ring with the N atom, R is H, alkyl or hydroxyalkyl, R is H or CH and n is 2-6.
• the present invention relates to new intermediate compounds which can be used to form dye compounds which can be used to dye keratin fibers, such as live human hair and animal fibers.
• the object of the present invention is to provide improved nitroparaphenylenediamine dye compounds selected from the croup consisting of R1 R-I I(CHz)nN in which R, R and R are selected from the group consisting of H, lower alkyl having one to six carbon atoms and lower hydroxyalkyl having one to six carbon atoms, and R and R are selected from the group consisting of H, lower alkyl having one to six carbon atoms and lower hydroxyalkyl having one to six carbon atoms, and together with the N a group piperidino, morpholino or phtalimido, n is a number from 2 to 6, and the N group is in the 2 or 3 position on the benzene ring, wherein R and R cannot both be H, and the amino group on the benzene ring situated in the ortho position to the nitro group is never tertiary, and when the N0 group is in the 2 position either R or R" must be H, and when R and R are H, R
• Dyes having formula (I) have the advantage of having, when cold, a great affinity for keratinic fibers. Hair dyes made from these dyes can form very strong shades and the strength of the coloration and the affinity of the dye compound for keratinic fibers, permit the dyes to be used, even in very small quantities, in tinctorial solutions at room temperature. This peculiarity is very valuable because it makes the use of dyes having a relatively poor solubility possible and satisfactory.
• dye colorations of the dyes of the present invention have a particularly good resistance to fading caused by light and washing.
• they may be used in a pH range which is much wider than the presentlyknown range of usage for analogous types of dyes. They may in fact be used in compositions having a pH of 4 to 10. The preferable range is 6-10.
• Dyes of the present invention also have the peculiarity of having as a substituent on one of the amino groups fixed on the benzene ring, a chain which has a terminal amino group which is quatemizable when said terminal amino group is tertiary.
• the quaternary compounds thus obtained may also be used as hair dyes in the same way as the corresponding tertiary compounds, and the chloro compounds of formula ll.
• tinctorial compositions of this invention do not require the addition of peroxides such as hydrogen peroxide as other hair dyes do in order to develop the color.
• peroxides such as hydrogen peroxide
• other ingredients commonly used in hair-dyeing treatments may be added to these tinctorial compositions, such as organic solvents, thickeners, detergents, lacs, etc.
• dyes of the type conforming to the invention it is possible to notably vary the dye compound concentration in the tinctorial solutions, but the preferable concentration is between 0.1 and 3.5 percent.
• the time during which the aforementioned tinctorial solutions are in contact with the hair may vary within wide limits, but preferably it should be between 5 and 30 minutes.
• the temperature at which the tinctorial solutions are applied may also be varied, but in most cases they may be advantageously used at ordinary room temperature.
• any of the dyes of this invention may be mixed with other dyes of the invention or with any other nitrated dyes, such as, nitroorthophenylenediamine, nitroparaphenylenediamine and alkyl or hydroxyalkyl derivatives of these compounds.
• the new dyes of the invention may also be mixed with azo or anthraquinone dyes or other types of dyes usually used for hair-dyeing.
• the intermediate dye forming compounds of this invention are compounds which have the formula:
• R and R are selected from the group consisting of hydrogen, lower alkyl and lower hydroxyalkyl, and may form a heterocyclic ring with the nitrogen atom to which they are attached, R is selected from the group consisting of hydrogen, lower alkyl and lower hydroxyalkyl, R is selected from the group consisting of hydrogen, and methyl, and n is an integer between 2 and 6 inclusive, and a compound having the formu- SOQ-Rr N/ (CH1) n N in which R,, R R R and n have the meaning defined above, in which said lower alkyl and hydroxyalkyl groups have one to six carbon atoms.
• Second step Preparation of l-N-methylamino-2-nitro-4-[N- (B-diethylamino)ethyl]amino benzene dihydrochloride.
• the base is then isolated from this dihydrochloride in a conventional manner.
• reaction mixture is kept at 60 C for 3 hours. After chilling, it is extracted with ethyl acetate and the ethyl acetate solution is washed first with normal sodium hydroxide, and then with water to eliminate the initial product in the form of its tosylate. The product is then extracted using iced normal hydrochloric acid, in the form of its hydrochloride.
• Third step 0.0133 mol(6 g) of l-[N-benzenesulfonyl-N-,B- diethyl-aminoethyl ]amino-2-nitro-4-( N '-methyl-N-acetyl amino benzene in 50 cm of concentrated hydrochloric acid is heated to reflux for 2 hours. After dilution, it is chilled while adding 5 N sodium hydroxide. Drying yields 3.2 g of l-N-B- diethyl-aminoethylamino-Z-nitro-4-methylamino benzene which after recrystallization in a mixture of benzene and hexane, melts at 74 C.
• nitro-4-amino benzene First step: Preparation of 1-N-p-toluene-sulfonylamino-2- nitro-4-acetylarnino benzene This product is prepared in the usual manner, by reacting ptoluene sulfochloride with 1-amino-2-nitro-4-acetyl-amino benzene in solution in pyridine.
• Second step Preparation of 1-N-p-toluenesulfonyl-N-fldiethyl-aminoethyl-amino-2-nitro-4-acety1amino benzene 0.086 mols (14.8 g) of B-diethylarnino-ethylchloride hydrochloride in solution in 50 cm of water, and 60 cm of 2 N sodium hydroxide, are simultaneously added little by little, at about 60 C, to a solution of 0.0286 mols g) of l-N-ptoluene-sulfonyl-amino-2-nitro-4-acetylamino benzene in 40 cm of normal sodium hydroxide.
• reaction mixture is kept for three hours at 60 C. After cooling, it is extracted with ethyl acetate, and the resulting ethyl acetate solution washed first with sodium hydroxide and then with water in order to eliminate the starting product in the form of the tosylate. The product is then extracted in the form of its hydrochloride, using iced normal hydrochloric acid. The resulting solution is alkalized with sodium hydroxide and 7 g of 1-(N-p-toluenesulfonyl-N-B- diethylaminoethyl)-amino-2-nitro-4-acetylamino benzene is precipitated. When dried under vacuum and recrystallized in a toluene-hexane mixture, this melts at 166 C.
• hydrazine hydrate 0.04 mol of hydrazine hydrate is added to a solution of 0.02 mol (10.16 g) of substituted phthalimide in 80 cm of propanol, and then heated for 30 minutes in a boiling waterbath. Most of the resultant phthalhydrazide is eliminated by filtration of the hot reaction mixture. After cooling, an orange oil is isolated by decantation and dissolved in ethyl acetate. This ethyl acetate solution is extracted with a /2 N hydrochloric solution.
• the aqueous hydrochloric phase is alkalized, and drying yields 4.5 g of 1-N-methylamino-2-nitro-4-(N'- benzenesulfonyl-N'w-aminobutyl)-amino benzene which, after recrystallization in ethyl acetate, melts at 135 C.
• the analysis of this product is:
• Second step Preparation of the dihydrochloride of l-N- methylamino-2-nitro-4-( N -'y-[ N B-hydroxyethyl-methyl 'y-aminopropyl )-amino benzene.
• Second step Preparation of l-N-methylamino2-nitro-4-(N'- benzenesulfonyl-N-w-phthalimidohexyl)amino benzene.
• 0.0268 rnol (12.6 g) of 1-N-methylamino-2-nitro-4-(N- benzenesulfonyl-N'-w-bromohexyl)-amino benzene is dissolved in 50 cm of dimethylformamidc. 0.0322 rnol (5.96 g) of potassium phthalimide is added and the reaction mixture is heated for an hour in a boiling water-bath. It is poured into 400 cm of water and drying yields 13.8 g of a crude product which, after recrystallization in ethyl acetate, melts at 149 C.
• the propanolic mother liquor after saturation with dry hydrochloric acid, yields another 2 g of the desired product, isolated in the form of the hydrochloride.
• reaction mixture After chilling, the reaction mixture is poured into a liter of water and drying yields a gummy product which, after three crystallizations in toluene, yields 12 g of l-N- methylamino-2-nitro-4-(N-benzenesulfonyl-N'-B- phthalimidoethyl)-amino benzene, which melts at 218 C.
• the yield is poorer than that obtained by the preceding method.
• Second step Preparation of l-N-methylamino-2-nitro-4-(N- benzenesulfonyl-N'-/3-aminoethyl )-amino benzene.
• the propanolic solution is then concentrated to about 80 cm After chilling, 30 g of the desired product are obtained in the form of an oil which crystallizes slowly. After recrystallization in a mixture of ethanol and water, the product melts at 1 C. Analysis yields the following results:
• the sodium salt of l-N-benzene-sulfonyl-amino-2-nitro-4- acetamido benzene is used as raw material.
• This salt may be prepared in the manner indicated in Luxembourg Pat. application No. 49,213 filed 30 July 1965. It should be noted, however, that in this Luxembourg patent it is indicated that the reaction may be carried out in water. It has since been found that the yield is much higher if dimethyl-formamide is used as the solvent, and dimethyl-formamide has accordingly been used in the first step of the present example, which will now be described.
• Second step Preparation of the dihydrobromide of l-N- B- (diethylamino)-ethylamino2-nitro4-amino benzene.
• 0.1 mols (34 g) of l-N-'y-(diethylamino)-propylamino-2- nitro-4 amino benzene is heated for 2 hours in a boiling waterbath, with 50 g (0.4 mols) of 99.5% glycol bromohydrin added to 10 cm of water and 20 g of calcium carbonate. 200 cm of water is then added, and the solution filtered. After alkalization with sodium hydroxide, the solution is extracted with butyl-alcohol. The solvent is eliminated under vacuum and the oily residue dissolved in methanol. The methanolic solution is saturated with dry gaseous hydrochloric acid and drying yields 30.12 g of the dihydrochloride, which melts and decomposes at C.
• diethylaminoethyl lamino-benzene 0.152 g 4-nitro-l,3-phenylenediamine 0.030 g
• Dihydrochloride of l-N-B-(diethylamino)- ethylamino-2-nitro-4-N'-di-fi- This composition is applied to 90% white hair and left for 10 minutes, followed by rinsing and shampooing. The result is a light golden blond.
• This composition is applied to 90% white hair. It is left to act for 10 minutes. The hair is then rinsed and shampooed. An ash blond shade results.
• All of the compounds of this invention may be made by reacting substituted amino chloride or halide with an alkaline, such as Na, K, etc. or alkaline earth such as Ca, Mg, etc. metal salt of an aromatic or phenyl N-aryl or phenyl sulfonyl amine in the manner illustrated by Example 2.
• an alkaline such as Na, K, etc. or alkaline earth such as Ca, Mg, etc.
• metal salt of an aromatic or phenyl N-aryl or phenyl sulfonyl amine in the manner illustrated by Example 2.
• R and R are selected from the group consisting of hydrogen, lower alkyl and lower hydroxyalkyl, R is selected from the group consisting of hydrogen, lower alkyl and lower hydroxyalkyl, R is selected from the group consisting of hydrogen and methyl, and n is an integer between 2 an 6 inclusive, and a compound having the formula:

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• Organic Chemistry (AREA)
• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Veterinary Medicine (AREA)
• Animal Behavior & Ethology (AREA)
• General Health & Medical Sciences (AREA)
• Public Health (AREA)
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• Cosmetics (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Applications Claiming Priority (4)

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Cited By (20)

Families Citing this family (14)

• 0
  • NL NL130871D patent/NL130871C/xx active
• 1965
  • 1965-07-30 LU LU49214D patent/LU49214A1/xx unknown
  • 1965-07-30 LU LU49213D patent/LU49213A1/xx unknown
• 1966
  • 1966-01-27 LU LU50348D patent/LU50348A1/xx unknown
  • 1966-07-04 LU LU51474A patent/LU51474A1/xx unknown
  • 1966-07-26 CH CH1082066A patent/CH457491A/fr unknown
  • 1966-07-27 AT AT00342/68A patent/AT281222B/de not_active IP Right Cessation
  • 1966-07-27 AT AT00340/68A patent/AT277414B/de not_active IP Right Cessation
  • 1966-07-27 AT AT718366A patent/AT279053B/de not_active IP Right Cessation
  • 1966-07-27 AT AT00341/68A patent/AT278988B/de active
  • 1966-07-28 CH CH924568A patent/CH519465A/fr not_active IP Right Cessation
  • 1966-07-28 CH CH1617971A patent/CH524370A/fr not_active IP Right Cessation
  • 1966-07-28 CH CH924768A patent/CH510624A/fr not_active IP Right Cessation
  • 1966-07-28 CH CH1096866A patent/CH518096A/fr not_active IP Right Cessation
  • 1966-07-28 CH CH924668A patent/CH516507A/fr not_active IP Right Cessation
  • 1966-07-28 CH CH924868A patent/CH519466A/fr not_active IP Right Cessation
  • 1966-07-28 CH CH924468A patent/CH518902A/fr not_active IP Right Cessation
  • 1966-07-29 DE DE19661569816 patent/DE1569816A1/de not_active Ceased
  • 1966-07-29 GB GB34259/66A patent/GB1164824A/en not_active Expired
  • 1966-07-29 FR FR71525A patent/FR1506350A/fr not_active Expired
  • 1966-07-29 GB GB25277/68A patent/GB1164825A/en not_active Expired
  • 1966-07-29 BE BE684863D patent/BE684863A/xx not_active IP Right Cessation
  • 1966-07-29 BE BE684859D patent/BE684859A/xx unknown
  • 1966-07-29 FR FR71524A patent/FR1491617A/fr not_active Expired
  • 1966-07-29 NL NL6610759A patent/NL6610759A/xx unknown
  • 1966-07-29 DE DE1617699A patent/DE1617699B2/de active Granted
  • 1966-07-29 IT IT18156/66A patent/IT1048380B/it active
  • 1966-07-29 NL NL6610757A patent/NL6610757A/xx unknown
• 1967
  • 1967-07-29 DE DE1967O0011844 patent/DE1543810A1/de active Granted
• 1970
  • 1970-02-09 US US10040A patent/US3665036A/en not_active Expired - Lifetime
  • 1970-04-27 NL NL7006131A patent/NL7006131A/xx unknown

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