Derivatives of 2-amino-6-chloro-4-nitrophenol and containing means for coloring hair

 

(57) Abstract:

Use: in the production of substituted phenols dyes for dyeing hair. The inventive product is a compound of the formula (2-Cl-4-NO2-6-OTHER)C6H2OH, where R is a C1-C5-alkyl. Reagent 1: 2-amino-6-chloro-4-NITROPHENOL. Reagent 2: the anhydride or the acid chloride of the corresponding R-acid. Reaction conditions: the process is conducted under stirring, followed by reduction of the resulting amide with NaBH4in the presence of air nortryptaline. Means for color-treated hair contains a dye - 2-amino-6-chloro-4-nitrophenolate and water in certain amounts, as well as the developer, a color-forming component, the base or additionally contains a wetting agent, thickener, substantive dyes in certain quantities. 2 S. and 2 C.p. f-crystals, 1 table.

The invention relates to derivatives of 2-amino-6-chloro-4-NITROPHENOL of the formula I

(I) where R is a linear or branched alkyl with 1-5 carbon atoms, and a means for coloring hair on the basis of these derivatives.

The dyes used for dyeing human hair, presented a number of requirements. They are due the Los requires good light fastness, the acid resistance and resistance to abrasion. Their use in the oxidation dyes for hair further assumes that ntracranial are resistant to hydrogen peroxide in ammonia solution and antioxidants. The tool according to the invention satisfies these requirements.

Examples relevant to the invention compounds of formula (I) are 2-chloro-6-methylamino-4-NITROPHENOL, 2-chloro-6-ethylamino-4-NITROPHENOL, 2-chloro-4-nitro-6-Propylamine, 2-chloro-6-//2-methylpropyl/amino/-4-NITROPHENOL and 2-chloro-6// 2 2-dimethylpropyl/amino/-4-NITROPHENOL.

New microcrystal General formula I can, for example, to obtain the following ways:

According to the first method, first made by the reaction of 2-amino-6-chloro-4-NITROPHENOL with an acid chloride of the carboxylic acid of formula R1C/O/CL or with a carboxylic acid anhydride of the formula O/C/O/R1/2moreover, R1represents hydrogen, a linear or branched alkyl radical with carbon atoms of 1 to 4, and then restore the received R1substituted N-(3-chloro-2-hydroxy-5-nitrophenyl)amide carboxylic acid with sodium borohydride in the presence of air nortryptaline to the compounds of formula (I).

The stage was way first dissolve 2-amino-6-chloro-4-NITROPHENOL in the carboxylic acid of formula R1C/O/OH, in which R1means hydrogen or a linear or branched alkyl radical with carbon atoms of 1 to 4, then mix the resulting solution with sodium borohydride and then the reaction mixture is heated to 60-70aboutC.

The end product of the alkylation can easily be separated by diluting the reaction mixture with water.

Under the third method is first made by the reaction of 2-amino-6-chloro-4-NITROPHENOL with ether carboxylic ortability formula R1C/OP2/3in which R1represents hydrogen or linear or branched alkilany radical with carbon atoms of 1 to 4, and R2means methyl or ethyl, and then restore the thus obtained benzoxazol-derivative with sodium borohydride in an alcohol solution.

The proposed tool may not contain an oxidizer, but can contain it.

In the case of the dye to the hair without the addition of an oxidant, it is a means that can contain, along with the coloring substances of the formula (I) other known substance for direct dyeing.

Of these known dyes for instance, one should mention the following: aromatic microcredit is Nilin, 1-meilani - but-2-nitro-4-di-(2'-hydroxyethyl)amino - benzene, 1-(2', 3'-dihydroxypropyl)-amino)-2-nitro-4-N-ethyl,N-(2"-hydroxyethyl/AMI - no/-benzene, 1-(2", 3"-dihydroxy-propyl/amino-2-nitro-4-dimethylaminobenzoyl, 1-(2', 3'-dihydroxypropyl/amino-2-nitro-4-pyrrolidinone, 1-/3'-dihydroxypropyl /amino-2-nitro-4-di-/2'-hydroxy - ethyl/aminobenzoyl 2,5-bis/2'-hydroxyethyl/aminonitriles, triphenylmethane dyes, such as basic violet 1 (C. 1. 42 535), azo dyes such as acid brown 4 (C. 1. 14 805), dispersed purple 4 (C. 1. 61 105), antrahinonovye dyes, for example, 1,4,5,8-tetraaminoanthraquinone or 1,4-diaminoanthraquinone, and the dyes of these classes can have depending on the type of their substituents acid, nonionic or main character.

Suitable for direct application to the hair dyes described, for example, in the book Johnson, I. C. Dyes for the hair. Noyes data Corp., Park ridge (USA) (1973), page 3-91 and 113-139.

Preparative form dyes described here on the basis of presocratic substances can be, for example, a solution, in particular a water-spirit.

The preferred forms are ready in the future, cream, gel or emulsion.

Described to the synthetic, natural or modified natural polymers, thanks simultaneously with the coloration is achieved by strengthening the hair. Such dyes are usually referred to as the fixers tone or color.

Known for this purpose in cosmetics synthetic polymers, mention should be made, for example, polyvinylpyrrolidon, polyvinyl acetate, polyvinyl alcohol or polyacrylic-compounds such as polyacrylic acid or polymethacrylic acid, basic polymerizate esters of polyacrylic acid, polymethacrylic acids and aminoalcohols and their salts or quaternization products, polyacrylonitrile, polyvinyl acetate, and copolymerizate of such compounds, as polyvinylpyrrolidones and the like.

Natural polymers or modified natural polymers such as chitosan (entityliving chitin) or chicozapote can also be used for that purpose.

Described hair dye without the addition of oxidizing agent may optionally contain other conventional for hair dye additives, for example, substances for the care, wetting, thickening agents, emollients, preservative substances and perfume oils and other usual oxidizable dye additives.

To photiou. The dye contains, in addition to the dyestuffs of the formula (I) and, if necessary, known directly onto your hair done dyes, additional well-known oxidative dyes, which require oxidative manifestation.

Under these oxidation dyes it comes to aromatic n-diamines and n-aminophenols, for example, n-toluylenediamine, n-phenylenediamine, n-aminophenol and similar compounds, which for the nuances of color combined with the so-called modifiers, for example, m-phenylenediamine, resorcinol, m-aminophenol or with others.

P R I m e R 1. Getting 2-chloro-6-ethylamino-4-NITROPHENOL

+ H

of 3.77 g (20 mmole) of 2-amino-6-chloro-4-NITROPHENOL are dissolved in 100 ml of acetic acid. Then add in 10aboutWith 3.03 g (80 mmole) of sodium borohydride. Within an hour, stir the mixture at room temperature and then for 3 h and heated to 60aboutC. For readiness mixture is diluted with 200 ml of water and 30% caustic soda solution was adjusted pH to a value of 5. Precipitated precipitated product is extracted, washed with water and dried in a desiccator over calcium chloride. Obtain 2.0 g (estimated 47 percent) orange-brown crystals, which melt IU the second acid. So get applying somaclonal acid product, which is identical with the product in example 5, stage 2, and the application pavlinovoi acid in example 6, stage 2.

P R I m m e R 2. Getting 2-chloro-6-ethylamino-4-NITROPHENOL 1 stage:

N-/3-chloro-2-hydroxy-5-nitro-phenyl/ndimethylacetamide

+

In a sulphonation flask 500 ml of acetic acid are placed (0.37 mmole) of 2-amino-chloro-4-NITROPHENOL. While stirring precapitalist at 25aboutWith 100 ml of 1.06 mol) of acetic anhydride. The mixture is stirred for 5 h at room temperature. The mixture is then poured into 2.5 kg of ice water and stirred for another hour. Precipitated precipitated product is extracted, washed with water, precrystallization of 2 parts of ethanol and one part water. Get to 59.9 g (69,9% of theory) ecru powder, which has a melting point of more than 200aboutC. stage 2: 2-chloro-6-ethylamino-4-NITROPHENOL

Under nitrogen atmosphere was placed 50 g (0,22 mole) N-/3-chloro-2-hydroxy-5-nitro-phenyl/ACET - amide from stage 1 and 600 ml of dry tetrahydrofuran. Then add upon cooling of 18.9 g (0.5 mole) sodium borohydride. When hydrogen gas will subside, was added dropwise while cooling 85 ml of 0.68 mole) of ateleta of nortryptaline. The reaction I have is 2 h to 60aboutC. the mixture is Then hydrolyzed at 0aboutWith 185 ml of a mixture of tetrahydrofuran-water (ratio 1:1), acidified 110 ml policecontributing hydrochloric acid and stirred at room temperature for one hour. The product is separated by extraction 3x250 ml diethyl ether, then with sodium hydroxide solution set pH 5. The ether phase is washed with a saturated solution of sodium chloride and dried over magnesium sulfate. The crude product precrystallization from ethanol/water (2:1). Get 40.6 g (86.5% of theory) of brown to dark-brown needles, which have a melting point of 136 to 138aboutC. CHN analysis:CHN8H9ClN2O3Calculated: 44,36 4,19 12,93 Found: 44,33 4,25 12,93

This product, obtained in this way is identical to the product that was described in example 1.

P R I m e R 3. Getting 2-chloro-6-//2 - hydroxyethyl/amino/-4-NITROPHENOL

< / BR>
1.88 g (10 mmole) of 2-amino-6-chloro-4-NITROPHENOL, 40 ml of 2-bromoethanol and 1.0 g (10 mmole) of calcium carbonate is heated for one hour to 120aboutC. Then the mixture is diluted with 300 ml of water and caustic soda solution is set to pH 12. The aqueous phase is extracted with CH ml of diethyl ether. The extract contains by-products gross ether. The ether phase is dried over magnesium sulfate. Obtained after removal of the solvent the residue is recrystallized twice from water. Gain of 0.68 g (29% of theory) of orange-coloured powder with a melting point of between 142 and 144aboutC. HN analysis:CHN C8H9ClN2O4x 1/2 H2O Calculated: 39,78 4,14 11,59 Found: 40,15 4,16 to 11.61

P R I m e R 4. Getting 2-chloro-4-nitro-6-propylenediene stage 1: Amide N-/3-chloro-2-hydroxy-5-nitro-phenyl/propionic acid

+ HCH3_____< / BR>
In a three-neck flask with reflux condenser, thermometer and drip funnel was dissolved under stirring 9,43 g (50 mmole) of 2-amino-6-chloro-4-NITROPHENOL in 200 ml of dioxane. Then added dropwise at room temperature 6.20 g (5,85 ml, 67 mmole) of the acid chloride propionic acid. The mixture is stirred at room temperature for 2 h and then 1 h, heated to 90aboutC. the mixture is Then poured onto 500 g of ice. Loose beige precipitate is sucked off and recrystallized from ethanolamides mixture (1:1). Get of 9.21 g (75% of theory) of brown-beige product, which melts at 167aboutWith decomposition. HN analysis: CHN C9H9ClH2O4Calculated: 44,19 3,71 of 11.45 Found: of 44.24 of 3.77 11,30

stage 2: 2-chloro-4-nitro-6-profilemanager

Under nitrogen atmosphere in the room is rufuran. Then add upon cooling of 2.27 g (60 mmole) of sodium borohydride. When hydrogen gas is quieter, precapitalist when cooled to 11.3 ml (9 mmole) of diethyl ether nortryptaline. The reaction is exothermic and is supported by cooling to 30aboutC. Then the reaction mixture is heated for 2 hours to 60aboutC. Following this, the mixture is cooled to 0aboutWith and hydrolyzed with 15 ml of a mixture of tetrahydrofuran-water (ratio 1:1), acidified with 10 ml policecontributing hydrochloric acid and stirred at room temperature for one hour. The product is separated by extraction with diethyl ether h ml after sodium hydroxide solution set pH 5. The ether phase is washed with a saturated solution of sodium chloride and dried over magnesium sulfate. The crude product is recrystallized from 200 ml of cyclohexane. Get 4,00 g (58,5% of theory) of a yellow-orange powder, which melts between 81 and 82.5aboutC. CHN analysis:CHN C9H11ClN2O3Calculated: 46,87 4,81 12,15 Found: 46,52 4,93 11,85

P R I m e R 5. Getting 2-chloro-6-//2-methylpropyl/amino/-4-NITROPHENOL. stage 1 Amide N-/3-chloro-2-hydroxy-5-nitrophenyl/somaclonal acid

The composition of the initial mixture: 9,43 g (50 mmole) of 2-amino-6-chloro-4-NITROPHENOL in 100 ml of Tetra is about in example 4, stage 1. Get the 10.1 g (75% of theory) of a beige product, which melts with decomposition at 158aboutC. CHN analysis:CHN10H11ClN2O4Calculated: 46,44 4,29 of 10.93 Found: 46,46 of 4.38 10,59 stage 2: 2-chloro-6-//2-methylpropyl/amino/-4-nitro - phenol

The composition of the initial mixture:

7,76 g (30 mmole) of amide N-/3-chloro-2-hydroxy-5-nitro-phenyl/somaclonal acid from stage 1 100 ml of tetrahydrofuran, and 2.27 g (60 mmole) sodium borohydride

11.3 ml (90 mmole) of diethyl ether nortryptaline.Connection receive in the same way as described in example 4, stage 2. Obtain 6.0 g (82% of theory) of an orange product, which melts between 115 and 116aboutC. CHN analysis: CHN C10H13ClN2O3Calculated: 49,09 are 5.36 of 11.45 Found: 48,90 of 5.45 11,27

P R I m e R 6. Getting 2-chloro-6-//2',2'-dimethylpropyl/amino/-4-NITROPHENOL stage 1: Amide N-/3-chloro-2-hydroxy-5-nitro-phenyl/pavlinovoi acid

The composition of the initial mixture: 9,43 g (50 mmole) of 2-amino-6-chloro-4-NITROPHENOL 150 ml of tetrahydrofuran

6,63 g (6,77 ml) (55 mmole) of the acid chloride pavlinovoi acid.The compound is obtained in the same way as described in example 4, stage 1. Obtain 10.7 g (78% of theory) of a beige powder which melts with decomposition at 140aboutC. stage 2. 2-chloro-6-//2'2'-dimethylpropyleneurea acid from stage 1 to 7.99 g (211 mmole) sodium borohydride 260 ml of tetrahydrofuran

40,68 g (36 ml) (286 mmole) of diethyl ether nortryptaline. The compound is obtained in the same way as described in example 4, stage 2. After recrystallization from ethanol-water (1: 1) obtain 19.3 g (81% of theory) of a reddish-brown powder with a melting point of between 110 and 111aboutC. CHN analysis:CHN C11H15ClN2O3Calculated: 51,07 of 5.84 10,83

Found: 51,10 of 5.89 of 10.73

P R I m e R 7. Getting 2-chloro-6-methylamino-4-nitrophenyl stage 1: 7-chloro-5-nitro-benzooxazol

HC(OCH

of 3.77 g (20 mmole) of 2-amino-6-chloro-4-nitro-phenol and of 41.0 g (46 ml, 277 mmole) teeterboro ether orthomorphisms acid is heated for three hours under reflux (temperature of the oil bath of 120 to 130aboutC). Then unreacted ether of orthomorphisms acid is distilled at 149aboutWith, and the residue is absorbed in 50 ml of warm ethanol. Upon cooling to 0aboutThe product is recrystallized. It is sucked off, washed with a small amount of cold ethanol and dried. Obtain 2.7 g (68% of theory) of yellow-white crystals that melt between 121 and 122,5aboutC. HN analysis:CHN C7H3ClN2O3Calculated: 42,34 1,52 14,11 Found: 42,19 1,66 14,02 2 stage 2-chloro-6-methylamino-4-NITROPHENOL

< / BR>
2.0 g (10 mmole) obtained in stage 1 ro heats up and becomes red. It is stirred for 30 min at room temperature. The mixture is then filtered and the ethanol Argonauts. The residue is mixed with 200 g of water. The red solution set of 2N-hydrochloric acid to pH 4. Usageprice beige product is extracted and precrystallization out of the water. Obtain 2.0 g (50% of theory) of yellow crystalline substance, which melts between 147 and 149aboutC. HN analysis:CHNCl C7H7ClN2O3Calculated: 41,50 3,48 13,83 17,50 Found: 41,36 3,67 13,78 17,43

Examples of dyes hair.

P R I m e R 8-13: dyes hair.

As part of the solution, coloring hair: 0.3 g of the dye; 2.0 g of sodium salt of solitaire lauric alcohol and diglycol (28% aqueous solution); 2.0 g of ammonia (25% aqueous solution); 95,7 water 100.0 g was used as the dye 2-amino-6-chloro-4-NITROPHENOL, 6-chloro-2-//2'-hydroxyethyl/amino/-4-NITROPHENOL or dyes of formula (1), where R is CH3C2H5CH2CH(CH3)2or CH2-C(CH3)3. Bleached hair treated 20 min at room temperature with a solution of example 13. Then the hair opolaskivaetsya water and dried. Hair be colored as shown in the table:

P R I m e R 14. Coloring RAS g of isopropanol; of 58.8 g water 100.0 g

White human hair fit using color-fixing solution and dried. Hair dyed red and fixed.

P R I m e R 15. Oxidative hair dye: 0.40 g of 2,5-diaminotoluene; 0.26 g of resorcinol, and 0.40 g of 4-aminophenol; of 0.13 g of 2,4-diaminoanisole; 0.50 g of the dye of example 2; 0,30 g ethylendiaminetetraacetic disodium salt; 0,30 g ascorbic acid; 15,00 g of cetyl alcohol; 3.50 g of sodium salt of sulfate lauric alcohol (28% aqueous solution); 6,00 g of ammonia (25% aqueous solution); 73,21 g water, completely desalinated to 100.00 g

50 ml of the above hair dye are mixed shortly before use with 50 ml hydrogen peroxide solution (6%). The mixture was then applied to gray human hair and left for 30 min at 40aboutC. After rinsing the hair with water and then drying the hair, take the rosewood color. Hair is colored evenly from root to ends.

1. Derivatives of 2-amino-6-chloro-4-NITROPHENOL General formula

< / BR>
where R is a linear or branched C1C6-alkyl,

as the dyes for dyeing the hair.

2. Means for dyeing hair containing the dye and water

< / BR>
where R is a linear or branched C1C5-alkyl,

in the following, wt.

The dye is 0.01 to 4.0

Water the Rest

3. Means under item 2, characterized in that it further comprises a developer, a color-forming component, the basis in the following ratio, wt.

The developer of 0.01 to 4.0

Color-forming component of 0.01 to 4.0

The basis of 0.1 to 5.0

4. Tool for PP. 2 and 3, characterized in that it additionally contains a wetting agent, a thickener and optionally substantive dyes at the ratios, wt.

Wetting agent-30.0

The thickener To 25.0

Substantive dyes To 3.0

 

Same patents:

The invention relates to methods for complex alilovic esters of 3-chlorantraniliprole acid formula

where R is an alkyl group with unbranched or branched chain, with a number of carbon atoms from 1 to 4, characterized in that it comprises the reaction of complex Olkiluoto of Anthranilic acid formula

where R has the above significance, with 1,3-dichloro-5,5-dimethylhydantoin in an inert solvent at 0-150aboutAnd the selection alkyl-3-chlorastrolite from the mixture obtained

The invention relates to the medical industry, in particular, to the manufacture of drugs used in the treatment of headache, neuralgia and colds

The invention relates to medicine, in particular to pediatric neuropathology and can be used in the treatment of hyperkinesis in children

The invention relates to dentistry and can be used in prosthetic dentistry and orthodontics with increased pharyngeal reflex in a patient

The invention relates to agriculture, in particular animal is used to treat the affected endo - and ectoparasites of animals, in particular against Estrosi sheep larvae nasopharyngeal (abdominal) gadfly

The invention relates to agriculture, in particular animal is used to treat the affected endo - and ectoparasites of animals, in particular against Estrosi sheep larvae nasopharyngeal (abdominal) gadfly

The invention relates to medicine and relates to a treatment for BPH and prostate cancer

The invention relates to organic chemistry, specifically to the derivatives of nitroglycerin, namely alkoxycyanobiphenyl General formula

-H2O-CHH2OR having cardiotonic activity that involves their use in medical practice

The invention relates to medicine and can be used to enhance antibacterial activity and expansion of the spectrum of antibacterial action

The invention relates to medicine, in particular to the surgery and the result they have proved
The invention relates to medicine, namely to traumatology

FIELD: medicine, in particular ophthalmology.

SUBSTANCE: treatment of ophthalmology diseases by administration in conjunctival sac of patient eye as well as injection of medicine, in particular alkali salt of 5-amino-2,3-dihydro-1,4-phtalasindione is disclosed. Eye drops, eye ointment contain alkali salts of 5-amino-2,3-dihydro-1,4-phtalasindione or mixture thereof, wherein lithium or sodium, or potassium, or calcium salt of 5-amino-2,3-dihydro-1,4-phtalasindione is selected as alkali salt, and mixture of above mentioned salt in equal ratio is used as mixture salts of 5-amino-2,3-dihydro-1,4-phtalasindione.

EFFECT: treatment method with improved effectiveness and reduced treatment duration.

16 cl, 6 ex

FIELD: medicine, ophthalmology.

SUBSTANCE: the present innovation deals with decreasing intraocular pressure during carrying out operative interferences in case of cataract and glaucoma. One should introduce 5%-pentamine solution together with anesthetic solution into sub-Tenon's space at the quantity of 0.1-0.4 ml and 1.0-1.5 ml, correspondingly. The method enables to achieve considerable decrease of intraocular pressure and, thus, provide decreased quantity of such complications, as prolapse of vitreous body, iris and corneal endothelium traumatization.

EFFECT: higher efficiency.

4 ex

FIELD: medicine; pharmaceutical engineering.

SUBSTANCE: pharmaceutical composition COMPRISES 5-(2-pyrazinyl)-4-methyl-1,2-dithyol -3-thion (oltipraze) and dimethyl-4,4'-dimetoxi-5,6,5',6'-dimethylene-dioxybiphenyl-2,2' dicarboxilate (DDB) as the main components. Oltipraze: DDB proportion is preferentially equal to 50-1:1-50, the most preferential being 5:1.

EFFECT: enhanced effectiveness of treatment.

6 cl, 6 dwg, 9 tbl

FIELD: medicine.

SUBSTANCE: the present innovation deals with antiviral preparations that contain aliphatic alcohol C21-C28 in combination with either nucleoside or nucleotide analog or phosphoformic acid in pharmaceutically acceptable carrier. It is necessary to mention that n-docosanol is considered to be a preferable aliphatic alcohol. Concentration of aliphatic alcohol C21-C28 corresponds to 0.05% to 40% by weight. Concentration of either nucleoside or nucleotide analog or phosphoformic acid corresponds to 0.1% to 10% by weight. The innovation, also, deals with the ways to treat viral infections due to applying such compositions. Aliphatic alcohols C21-C28 synergistically intensify antiviral activity of nucleoside analogs directed against replication of several herpetic viruses and that of cow's pox.

EFFECT: higher efficiency of inhibition.

28 cl, 13 dwg, 21 ex, 6 tbl

FIELD: medicine, obstetrics, gynecology, mammology.

SUBSTANCE: method involves administration of alcohol-air mixture into cyst cavity wherein the amount of air and alcohol is similar and represents 40-60% of the content volume evacuated from the cyst cavity. Invention promotes to prophylaxis of diseases relapses and prevention of iatrogenic complications associated with carrying out this procedure. Invention can be used for treatment of patients with cystic mactopathy.

EFFECT: improved method for treatment.

2 tbl

Up!