DE19534214C1 - New 4-(2,5-di:amino-phenoxymethyl)-1,3-dioxolane derivs. - Google Patents

Abstract

New (un)substd. 4-(2,5-diaminophenoxymethyl)-1,3- dioxolanes of formula (I) and their salts with (in)organic acids, are claimed. R1-R4 = H, formyl, acetyl, 1-4C alkyl, 2-3C hydroxyalkyl, alkoxy(2-3C)alkyl, amino-(2-3C)alkyl, or 2,3-dihydroxypropyl; R5, R6 = H or 1-4C alkyl. Pref. the hair dye is a cream, soln., foam or gel, contg. (I) and opt. a coupler, with oxidn. dyeing occurring by addn. of an oxidising agent or an oxidising agent and a catalyst for air oxidn. dyeing, esp. a salt or complex of a transition metal, partic. CuSO4, CuCl2, or Cu acetate, alone or as adduct with NH3, ethylene diamine, phenanthroline, Ph3P, 1,2- or 1,2-diphenylphosphino-ethane, 1,3-diphenylphosphino-propane or an aminoacid. Esp., the hair dye contains (I) as developer, a coupler and 0.05-0.5 wt.% of Cu(II)-1,2-diaminoethane chloride, Cu(II)-1,10-phenanthroline chloride, Cu(II)-tetramine sulphate and/or Cu(II) glycinate as catalyst.

Description

The present invention relates to substituted and unsubstituted 4- (2,5-diaminophenoxymethyl) -1,3-dioxolanes general formula (I), and their salts with inorganic and organic acids. Procedure to their Production and hair dyes containing these compounds

So-called oxidation colors are used for dyeing keratin fibers, because these deliver intense colors of high color fastness in the coloring result. Among the users boundary conditions (low dyeing temperature and short dyeing time) use intense colors with good fastness properties. The dyes are used during the Dyeing process through the oxidative coupling of a developer component and one Coupler component formed. Such coupler and developer components for education different shades, hereinafter referred to as the hair dye intermediate, are in the literature (K. Venkataraman, The Chemistry of Synthetic Dyes, Vol. V, Aca demic press, 1971; F. Brody and M. S. Burns, J. Soc. Cosmet. Chem. 19, 361-379, 1968; H. Husemeyer, J. Soc. Cosmet. Chem. 25, 131-138, 1974).

Although the oxidative coupling, i.e. H. the development of coloring, in principle, too can be caused by atmospheric oxygen, but this is usually too slow and / or To produce uneven staining results, chemical oxidizing agents are usually used set. Oxidizing agents based on hydrogen peroxide are preferred, in addition to hydrogen peroxide itself also addition compounds with urea, melamine or alkali perborate.

Usually, ortho- or para-phenylenediamines and ortho- or para-aminophenols which are substituted both on the nitrogen atom and on the nucleus can be used. Meta-phenylenediamines, Naph thole, resorcinol and its derivatives as well as meta-aminophenols use.

A developer component can be combined with a variety of couplers bindings produce a large number of very different shades and shades. Nevertheless, it is generally not enough to form a single developer compound the multitude of natural hair color nuanches. So in practice you put one Combination of different developer and coupler components to make one natural  to get effective hair coloring. Therefore, there is a constant need for new developers ler connections.

In the literature, the use of para-phenylenediamine and 1-alkoxy substituted 2,5-diaminobenzene derivatives as hair dye precursors, especially as developer substances zen, known for a long time. However, many of these compounds are toxicologically conceivably, since z. B. can trigger allergic reactions. So there is still before a great interest in new hair dye precursors that are toxicological and dermatologically harmless, but at the same time intense colors with ho provide authenticity.

So in the literature is the use of 1-alkoxy-substituted 2,5-diaminobenzolderi vaten already described as developer compounds. In the design specification DE 27 37 291 N- (2-alkoxyalkyl) -p-phenylenediamines are listed, where alkoxy is either methoxy or ethoxy and alkyl mean either ethyl or propyl, the developer compo found in oxidation hair dyes.

In the patent US 38 84 627 hair dye precursors with substituted para-Phenyldiaminen described, in addition to unsubstituted prara-Pheny Lendiamines with tertiary amino group also with para-phenylenediamines which are substituted on the nucleus include secondary amino function. Unfortunately, these connections have very detrimental effects toxicological properties or are not suitable to produce deeper hair colors.

Surprisingly, it has now been found that the be in the present invention Compounds of the general formula (I) wrote these requirements particularly well fulfill.

The present invention relates to new substituted and unsubstituted 4- (2,5-diaminophenoxymethyl) -1,3-dioxolanes general formula (I), and their salts with inorganic and organic acids, process for their Production and hair dyes containing these compounds

wherein R¹, R², R³ and R⁴ independently represent a hydrogen atom, a formyl group, an acetyl group, a (C₁ to C₄) alkyl group, a hydroxy (C₂ or C₃) alkyl group, an alkoxy (C₂ or C₃) alkyl group, an amino (C₂ or C₃) alkyl group, a 2,3-dihydroxypropyl group, and R⁵ and R⁶ independently of one another water can represent material or a (C₁ to C₄) alkyl group.

The developer substances of the general formula (I) according to the invention are obtained represents by 2-nitrohalobenzenes of the general formula (II), wherein R³ and R⁴ the  have the meanings given and where X is fluorine, chlorine, bromine or iodine, with 4- Hydroxymethyl-1,3-dioxolanes of the general formula (III), wherein R⁵ and R⁶ the have the meanings given, in an alkaline reaction medium, if appropriate under Zu set of phase transfer catalysts to 5-substituted 4- (2-nitrophenoxymethyl) -1,3- implemented dioxolanes of the general formula (IV) and these to the compounds of general formula (V) can be reduced. These can, if appropriate after hydrolysis a protective group when R³ is NHCOH, NHCOCH₃, and optionally after one Alkylation or oxalkylation, converted in connection with the general formula (I) will.

The compounds of general formula (III) are already known and can by Reaction of glycerol with carbonyl compounds are produced (see example wise E. Fischer, Ber. German Chem. Ges. 28, 1169 (1895); H. S. Hill, E. C. Hill, and H. Hibbert, J. Am. Chem. Soc. 50, 2246 (1928); M. S. Newman and M. Renoll, ibid 67, 1621 (1945)).

For the oxyalkylation, the compounds of the general formula (V) are inert Solvent with 2-chloroethyl chloroformate or 3-chloro chloroformate propyl ester converted into compounds of general formula (VI), wherein R⁷ CH₂CH₂Cl or CH₂CH₂CH₂Cl means.

The intermediates of the general formula (VI) are then with strong bases, for. B. Sodium or potassium hydroxide, vice versa to compounds of general formula (VII) sets, wherein R⁸ CH₂CH₂OH or CH₂CH₂CH₂OH means that with known alkyl reacting or oxalkylating agents to give products of the general formula (I), wherein R¹ to R⁴ have the meanings already given, and these optionally with a transferred inorganic or organic acid into their salt.

The compounds of general formula (II) can be obtained by using 5-amino-2- halonitrobenzene with formic acid or acetic anhydride or acetic acid [R³ = NHCOH, NHCOCH₃] or with known alkylating or oxalkylating agents.

For practical use as a hair dye, the hair dye is intermediate products incorporated into a suitable cosmetic base, depending on the type of The final product can be a solution, a cream, a foam or a gel. These Preparation is mixed with the oxidizing agent immediately before application to the hair mixes.

To form blue shades, 1,3-diaminobenzene derivatives are predominantly used as Couplers and 1,4-diaminobenzene derivatives are used as developer substances. It was now found that 4- (2,5-diaminophenoxymethyl) -1,3-dioxolanes of the general formula (I) in combination with known coupler substances blue to blue-black color Exercises of surprisingly high color strength and excellent fastness properties surrender. These colors are by means of an oxidizing agent or by the addition of a Catalyst into the dye and subsequent air oxidation (i.e. by omission  the otherwise usual aqueous oxidizing agents based on hydrogen peroxide) receive.

For the hair colorants according to the invention, known coupler and ent winder combinations are used. Preferred couplers and developers are fol combinations:

• 1. p-toluenediamine, resorcinol, meta-aminoaniline, 4-chlororesorcinol,
• 2. p-toluenediamine, 2-methylresorcinol, 4-chlororesorcinol, 2-amino-3-hydroxypyridine,
• 3. p-toluenediamine, resorcinol, meta-aminoaniline, para-aminoaniline, 2-hydroxy-4-ami notoluene,
• 4. 3-methyl-4-aminoaniline, meta-aminoaniline, 2-hydroxy-4-aminotoluene, 2-amino-3- hydroxypyridine,
• 5. 3-methyl-4-aminoaniline, 2-methylresorcinol, meta-aminoaniline, para-toluenediamine, 2-hydroxy-4-aminotoluene, 2-amino-3-hydroxypyridine.

A special preferred embodiment of the invention is therefore a hair dye based on oxidation colors, characterized by

• 1. a content of at least one new substituted 4- (2,5-diaminophenoxyme thyl) -1,3-dioxolane derivatives or its salt,
• 2. avoiding pretreatment of the hair with catalysts,
• 3. the addition of a catalyst to the coloring composition,
• 4. dispensing with hydrogen peroxide as an oxidizing agent,
• 5. Transition metal salts and transition metal complexes, especially copper (II) - chloride, sulfate, acetate, alone or as an adduct with ammonia, 1,2-ethylenediamine, Phenanthroline, triphenylphosphine, 1,2-diphenylphosphinoethane, 1,3-diphenyl phosphinopropane or amino acids; e.g. B. be ge named: glycine, leucine, methionine, alanine, phenylalanine or proline as a catalyst for addition to the coloring material.

The basic composition of the hair dye according to the invention is, depending on the type the desired end product, for example a gel, a cream, a foam or a surfactant solution. The basic mass consists of the prior art knew and components suitable for use on the hair in for this Purposes usual quantities. The components of such foundations are e.g. B.

• 1. wetting and emulsifying agents,
• 2. thickener,  
• 3. reducing agent,
• 4. perfume oils,
• 5. hair care additives and
• 6. Solvents, e.g. B. water or lower alcohols.

The dyeing of hair with the hair dye according to the invention is carried out by the Component, diluted or undiluted with water, applied to the hair and distributed becomes. The required amount of hair dye is, as is known to those skilled in the art depending on the length of the hair to be dyed. The application temperatures are available preferably in a range of 15 to 40 ° C and the exposure time preferably between 5 and 45 minutes, especially 10 to 35 minutes. The hair dye will then removed by rinsing, if necessary, wash the hair with a shampoo and rinsed again and then dried.

The hair dye according to the invention is in the special preferred embodiment compared to previously known hair dyes easier to use, milder and more tolerable by the air oxidation color development in the presence of the in the Coloring agent as an additive contained catalyst, the waiving of hydrogen peroxide, without sacrificing the coloring result.

The reaction of the compound of general formula (II) or (V) with a chlorine 2-chloroethyl formate or 3-chloropropyl chloroformate is carried out in An based on the known selective hydroxyalkylation of an amine with chloroformic acid chloroalkyl esters with subsequent basic treatment of the chloroalkyl carbamates (cf. Otto, J. Prakt. Chem. 44, 15, (1890); R. Adams and J. B. Segur, J. Am. Chem. Soc. 45, 785, (1923). J. S. Pierce and R. Adams, J. Am. Chem. Soc. 45, 790. (1923) detailed the implementation of the chloroformic acid chloroalkyl ester with primary aromati amines. To form the compounds of general formula (VIII) Compound of general formula (V) in an inert organic solvent, e.g. B. Dioxane, C₁ to C₄ alcohols, dimethylformamide, tetrahydrofuran, toluene, chlorobenzene, Methyl ethyl ketone, 1,2-dimethoxyethane, methyl tert-butyl ether or diethylgenglycol di methyl ether, submitted and to a temperature between room temperature and reflux temperature, preferably between 30 ° C and reflux temperature, heated. Subsequently is one of the chloroformic acid chloroalkyl esters mentioned in an equimolar amount or in little excess metered. If necessary, the solvents can be mixed with water be combined. An acid-binding agent can either be initially charged or be added in parallel to the chloroalkyl chloroformate already mentioned. As Acid-binding agents come from bases, such as alkali metal hydroxides, bicarbonates, and carbo nates, alkaline earth oxides, hydroxides, bicarbonates and carbonates as well as tertiary orga African amines. The reaction time is between 1 and 12 hours.  

After the reaction is complete, the carbamates are isolated by a) water or ice or a mixture of ice and water is added to the mixture with stirring, or b) the inorganic salts are filtered off and the solvent partially or completely is distilled, if necessary with cooling, for. B. by adding ice, thereby the formed carbamates of the general formula (VI) in solid form almost quantitatively fall.

By treating with strong bases - this is where alkali or alkaline earth hydroxides come in traditional, preferably 10 to 50% sodium or potassium hydroxide solution is used - the Carbamates of the general formula (VI) in the hydroxyalkyl compounds of the general converted formula (VII). There are two ways to do this:

• a) The carbamate of the general formula (VI) is in water or an organic Solvents, e.g. B. a C₁ to C₄ alcohol, a water-miscible ether or Mixtures of these are submitted, at room temperature is then approximately the calculated Amount of lye, that is 4 moles of lye per mole of carbamate, is metered in and it is up to complete reaction stirred, optionally heated to reflux or lye can be adjusted.
• b) the alkali, which can be diluted with the solvents mentioned, is initially introduced, doses the carbamate with the general formula (VI) in pure form or dissolved in one the organic solvents mentioned at a temperature between space temperature and approx. 70 ° C and then stir until the reaction is complete.

In both variants, the reaction solution, which has a pH of approx. 12 to 14 has to work up by adding an organic or inorganic acid to one pH of about 5 to 10 can be blunted. Then the salts are separated from, optionally adding water and isolating the product of the general formula (VII) after removing the organic solvent.

In the above two procedures, adding about 25 to 30 Ge % by weight of one of the above-mentioned organic solvents in the aqueous Re Action approach significantly reduced the reaction time, with the inorganic salts still remain dissolved in the reaction medium. The implementation will take about 1 to 12 hours needed.

The compounds of the general formula (I) can be prepared by reducing the Compounds of the general formula (IV), optionally after alkylation or oxal kylation, with base metals or by catalytic reduction.

In the catalytic reduction, conventional catalysts, e.g. B. Raney-Nickel, Palla dium on activated carbon or platinum on activated carbon. The reaction temperature is  between room temperature and 120 ° C, preferably between 35 and 100 ° C, the pressure is between normal pressure and 100 bar, preferably between 20 and 70 bar. As Lö Solvents find common solvents such as water, toluene, glacial acetic acid, lower alcohols or ether use. After reduction and separation of the catalyst the product of the general formula (I), optionally after alkylation or oxalkyly tion, isolated by removing the solvent under a protective gas in free form will. The known compounds dimethyl and Diethyl sulfate and the known compounds ethylene oxide and Proven propylene oxide. The product according to general formula (I) is preferred under a protective gas by adding an approximately equivalent amount of an acid in transferred a salt that either precipitated directly or obtained after removal of the solvent will.

As inorganic acids such. B. hydrochloric acid, sulfuric acid, phosphoric acid and as orga African acids acetic acid, propionic acid, lactic acid or citric acid for salt formation suitable.

The following examples are intended to describe and explain the invention.

A. Preparation of the catalysts Example A.1 Preparation of copper (II) glycinate

1.8 g (9.8 mmol) of copper (II) acetate are dissolved in 100 ml of hot methanol and one Solution of 1.5 g (20 mmol) of glycine in 50 ml of methanol was added with stirring. The Lö solution becomes cloudy due to unusual product. Stir for two more hours as the water falls Temperature, the precipitated product is filtered off and dried.

Yield: 2.49 g (96% of theory),
Mp: <210 ° C.

Example A.2 Preparation of copper (II) -1,2-diaminoethane chloride

26.9 g (160 mmol) of copper (II) chloride dihydrate are dissolved in 300 ml of hot methanol and a solution of 9.6 g (160 mmol) of 1,2-diaminoethane in 100 ml of methanol with stirring admitted. The solution becomes cloudy due to the unusual product. You stir another one Hour after reflux. The mixture is allowed to cool with stirring, the is filtered precipitated product and dries it.

Yield: 12.5 g (40% of theory),
Mp: <210 ° C.

B. Creating new developers

All compounds produced are by IR or IR (KBr compact) and 1 H-NMR Spectra (in D₆-DMSO) have been characterized. In the IR spectra, only those are very strong and strong gangs listed. In the information on the 1 H-NMR spectra be interpret Φ phenyl, s singlet, d doublet, dd doublet from doublet, t triplet, m multiplet, ³J or ⁴J the couplings over three or four bonds, as well as H³, H⁴ and H⁶ the water atoms in positions 3, 4 and 6 of the benzene ring.

Example B.1 Preparation of 4- (2,5-diaminophenoxymethyl) -2,2-dimethyl-1,3-dioxolane Stage a) Preparation of 4- (4-amino-2-nitro-phenoxymethyl) -2,2-dimethyl-1,3-dioxolane

In a mixture of 65 ml 1,2-dimethoxyethane, 66.1 g (0.5 mol) isopropylidene glycerol and 0.7 g of methyl-tri (C₆-C₈) alkylammonium chloride are 17.3 g (0.1 mol) of 4-amino-2- chloronitrobenzene dissolved. 18.5 g (0.16 mol) of 50% potassium hydroxide solution are added dropwise with stirring and then heated to reflux until the exchange is complete. Then distilled the 1,2-dimethoxyethane is removed, 140 ml of water are added and the product is stirred out. The precipitated product is filtered off, washed twice with about 25 ml of water and out 75 ml of ethanol recrystallized.

Yield: 246.7 g (86.8% of theory),
Melting point: 138-140 ° C,
IR: 3458, 3364, 3245 cm ^-1 (ν CH, NH), 1644 cm ^-1 (ν C = C), 1604 cm ^-1 (ν _as NO₂), 1299 cm ^-1 (ν _s NO₂),
1 H-NMR: 7.80 ppm (H⁶, d, 3 J _{H, H} = 9.02 Hz); 6.54 ppm (NH₂, s); 6.28 ppm (H³, d, ⁴J _{H, H} = 2.12 Hz); 6.20 ppm (H⁴, dd, ³J _{H, H} = 9.11 Hz, ⁴J _{H, H} = 2.14 Hz); 4.40 ppm (1H, m, ³J _{H, H} = 11.40 Hz, anti-C H CH₂OC (CH₃) ₂, ³J _{H, H} = 6.26 Hz, syn-C H CH₂OC (CH₃) ₂, ³J _{H, H} = 5.12 Hz , ΦOCH₂C H ); 4:09 ppm (1H, dd, ²J _{H, H} = -8.38 Hz, ³J _{H, H} = 6.43 Hz, syn-C H ₂OC (CH₃) ₂); 4.04 ppm (2H, d, ³J _{H, H} = 5.01 Hz, ΦOC H ₂CH); 3.97 ppm (1H, dd, ²J _{H, H} = -8.38 Hz, ³J _{H, H} = 6.42 Hz, C H ₂OC anti-(CH₃) ₂); 1.36 ppm (3H, s, syn-C (CH₃) ₂); 1.31 ppm (3H, s, anti-C (CH₃) ₂).

Stage b) Preparation of 4- (2,5-diaminophenoxymethyl) -2,2-dimethyl-1,3-dioxolane

150 ml of methanol are placed in a 0.3 l autoclave, 25.4 g (0.1 mol) of 4- (4- Amino-2-nitro-phenoxymethyl) -2,2-dimethyl-1,3-dioxolane (stage a) dissolved and 0.6 g pal Ladium on activated carbon 10% (Degussa) added. After sealing and inerting with nitrogen at a pressure of 4 bar and a temperature of 35-40 ° C hy third until no more hydrogen is absorbed. Add to the warm solution 1.3 g of activated carbon under nitrogen and the catalyst is filtered off. The solution is below Ice cooling at 5 ° C with 14 g of 70% sulfuric acid added dropwise. That unusual The product is filtered off, washed with methanol and dried.

Yield: 68.9 g (68.3% of theory),
Mp: <250 ° C,
IR: 3427, 2878 cm ^-1 (ν OH / NH₃⁺), 1614 cm ^-1 (ν C = C), 1514 cm ^-1 (ν SO₄),
1 H NMR: 8.3-7 ppm (NH); 6.87 ppm (H⁶, d, ³J _{H, H} = 8.39 Hz); 6.56 ppm (H³, d, ⁴J _{H, H} = 1.89 Hz); 6.40 ppm (H⁵, dd, ³J _{H, H} = 8.35 Hz, ⁴J _{H, H} = 1.73 Hz); 4.43 ppm (1H, m, ³J _{H, H} = 11.69 Hz, anti-C H CH₂OC (CH₃) ₂, ³J _{H, H} = 5.81 Hz, syn-C H CH₂OC (CH₃) ₂, ³J _{H, H} = 5.72 Hz , ΦOCH₂C H ,); 4.12 ppm (1H, dd, ²J _{H, H} = -8.52 Hz, ³J _{H, H} = 6.53 Hz, syn-C H ₂OC (CH₃) ₂); 3.97 ppm (2H, d, ³J _{H, H} = 5.71 Hz, ΦOC H ₂CH); 3.85 ppm (1H, dd, ²J _{H, H} = -8.62 Hz, ³J _{H, H} = 5.93, anti- C H ₂OC (CH₃) ₂); 1,374 ppm (3H, s, syn-C (CH₃) ₂); 1,319 ppm (3H, s, anti-C (CH₃) ₂).

C. Staining examples

The hair colorants according to the invention are aqueous agents. Below are all of them Understood means that contain water in some way, such as. B. Creams, Emulsio nen, gels or simple solutions. The compositions of the hair dye make a mixture of the dye components with those for such cosmetic preparations The usual additives in solutions, creams, emulsions or Gels are e.g. B. solvents such as water, lower aliphatic alcohols, for example Ethanol, propanol and isopropanol, or glycols such as glycerin and glycol ethers such as Pro pylene glycol, further wetting agents or emulsifiers from the classes of anionic, ka ionic, amphoteric or non-ionic surface-active substances such as fatty alcohol holsulfates, alkylsulfonates, alkylbenzenesulfonates, alkyltrimethylammonium salts, alkyl betaine, ethoxylated fatty alcohols, ethoxylated nonylfluorobenzenes, fatty acid alkanolamides,  ethoxylated fatty acid esters, also thickeners such as higher fatty alcohols, starch, cellulose de derivatives, petroleum jelly, paraffin oil and fatty acids. The examples mentioned are in the for amounts used for such purposes, for example the wetting agents and emulsifiers ren in concentrations of about 0.5 to 30 wt .-%, while the thickener in one Amounts of about 0.1 to 25 wt .-% can be contained in the preparations.

Depending on the composition, the hair colorants according to the invention can be weak react acidic, neutral or alkaline. In particular, they have a pH in alkali range between 7.5 and 11.5, the setting preferably using Am moniak takes place. Organic amines, e.g. B. monoethanolamine and Triethanolamine, or inorganic bases such as sodium hydroxide and potassium hydroxide, find use.

In processes for the oxidative coloring of hair, the hair dye of this Er invention, which is a combination of developer substances known in hair coloring zen with at least one compound of the general formula (I) as developer substance, as well as optionally known coupler substances and direct absorbing substances Dyes and optionally contain the catalysts already mentioned, or the Hair dye according to claims 8 to 10, which before or during use no oxidizing agents are added to the hair. Optionally, the Coloring agent according to claims 4 to 7 also with an oxidizing agent before application be mixed. As an oxidant to develop hair color come at all Hydrogen peroxide (for example as a 6% aqueous solution) and its addi tion compounds on urea, melamine or sodium borate, and mixtures of such against hydrogen peroxide addition compounds with potassium peroxodisulfate.

The application temperatures range from 15 to 40 ° C. After a Development time of about 10-30 minutes is the hair dye from the dye Hair removed by rinsing. After that, the hair can be replenished with a mild shampoo wash and dry.

The following examples are intended to explain the subject of the invention in more detail.

example 1 Hair dye in cream form

3.16 g HC blue AC [4- (2-hydroxyethylamino) -2-aminoanisole sulfate]
3.36 g of 4- (2,5-diaminophenoxymethyl) -2,2-dimethyl-1,3-dioxolane sulfate
1.20 g oleic acid
0.50 g sodium dithionite
6.20 g lauryl alcohol diglycol ether sulfate, sodium salt (28% solution)
18.0 g cetyl stearyl alcohol
7.50 g ammonia, 25%
Water to 100 g

50 g of the hair dye mentioned above are in proportion shortly before use 1: 1 mixed with 50 g H₂O₂ solution (6%) and on 100% gray hair using a Brush applied. After an exposure time of 30 minutes at room temperature, it will Colorant rinsed off and the hair dried. The hair has an even deep preserved blue hue.

Example 2 Hair dye in gel form

1.10 g resorcinol
3.36 g of 4- (2,5-diaminophenoxymethyl) -2,2-dimethyl-1,3-dioxolane sulfate
12.0 g oleic acid
12.0 g isopropanol
5.00 g nonoxynol-4
10.0 g ammonia, 25%
0.5 g sodium sulfite, anhydrous
Water to 100 g

50 g of the above-mentioned colorant are mixed with 50 g of Was mixed peroxide solution (6%). The mixture is left in the room for 30 minutes act on 100% gray hair. Then the color mass is rinsed out, shampooed and the hair dried. The hair is ashy in a medium blonde Hue colored.

Example 3 Hair dye in cream form

1.09 g m-aminophenol
3.36 g of 4- (2,5-diaminophenoxymethyl) -2,2-dimethyl-1,3-dioxolane sulfate
2.50 g lauryl sulfate sodium salt (70% paste)
1.00 g oleic acid
0.60 g sodium sulfite, anhydrous
12.0 g cetyl stearyl alcohol
6.00 g myristyl alcohol
1.00 g propylene glycol
10.0 g ammonia, 25%
Water to 100 g

60 g of the above colorant are mixed with 60 g of water shortly before use mixed peroxide solution (6%). The mixture is left at room temperature for 30 minutes act on 100% gray hair. The dye is then removed rinses, the hair is shampooed and dried. The hair has a blue-violet color volume.

Example 4 Hair dye in gel form

3.16 g HC blue AC [4- (2-hydroxyethylamino) -2-aminoanisole sulfate]
3.36 g of 4- (2,5-diaminophenoxymethyl) -2,2-dimethyl-1,3-dioxolane sulfate
0.80 g of 4- (3-hydroxypropylamino) -3-nitrophenol
2.00 g oleic acid
0.10 g polyacrylic acid
0.50 g sodium sulfite, anhydrous
4.0 g lauryl alcohol glycol ether sulfate, sodium salt (28% solution)
8.0 g ammonia, 25%
Water to 100 g

50 g of the above-mentioned colorant are mixed with 50 g of water shortly before use mixed peroxide solution (6%). The mixture is left at room temperature for 30 minutes act on 100% gray hair. The dye is then removed rinses, the hair is shampooed and dried. The hair has a red-violet shade receive.

Example 5 Hair dye in gel form

2.10 g HC Violet AS [2,6-di- (2-hydroxyethylamino) toluene]
3.36 g of 4- (2,5-diaminophenoxymethyl) -2,2-dimethyl-1,3-dioxolane sulfate
14.00 g oleic acid
10.0 g isopropanol
2.0 g PEG-3 cocamine
0.5 g ascorbic acid
8.0 g ammonia, 25%
Water to 100 g

50 g of the above-mentioned colorant are mixed with 50 g of water shortly before use mixed peroxide solution (6%). The mixture is left at room temperature for 30 minutes act on 100% gray hair. The dye is then removed rinses, the hair is shampooed and dried. The hair has an intense purple-red Hue preserved.

Example 6 Hair dye in cream form

1.60 g of 1,7-dihydroxynaphthalene
3.36 g of 4- (2,5-diaminophenoxymethyl) -2,2-dimethyl-1,3-dioxolane sulfate
1.20 g oleic acid
0.50 g sodium dithionite
6.20 g lauryl alcohol diglycol ether sulfate, sodium salt (28% solution)
18.0 g cetyl stearyl alcohol
0.3 g copper (II) phenanthroline chloride
7.50 g ammonia, 25%
Water to 100 g

50 g of the hair dye mentioned above are mixed with 50 g of water shortly before use mixed and applied to 100% gray hair using a brush. After egg After 10 minutes at room temperature, the colorant is rinsed off and the hair dried. The hair has a uniform bluish silver-gray color receive. The depth of the color obtained builds up according to the exposure time.

The following Table 1 shows further developers of the general For mel (I) can be found, the columns R³, R⁴, R⁵ and R⁶ in columns 2 to 5 (R¹ and R² is always hydrogen in the cases listed) and in column 6 the analog Example 1 with hue obtained with para-toluenediamine is listed.

Table 1

Coloring of further compounds analogous to example 1 on keratin fibers

Claims (10)

1. Substituted and unsubstituted 4- (2,5-diaminophenoxymethly) -1,3-dioxolanes of the general formula (I) and their salts with inorganic and organic acids, wherein R¹, R², R³ and R⁴ independently of one another a hydrogen atom, a formyl group, an acetyl group, a (C₁ to C₄) alkyl group, a hydroxy (C₂ or C₃) alkyl group, an alkoxy (C₂- or C₃ ) alkyl group, an amino (C₂ or C₃) alkyl group, a 2,3-dihydroxypropyl group, and R⁵ and R⁶ can independently represent hydrogen or a (C₁ to C₄) alkyl group. 2. A process for the preparation of compounds of the general formula (I), characterized in that 4-substituted 2-halonitrobenzenes of the general formula (II), in which R³ and R⁴ have the meanings mentioned and in which XF, Cl, Br or iodine , with 4-hydroxymethyl-1,3-dioxolanes of the general formula (III), in which R⁵ and R⁶ have the meanings given, in an alkaline reaction medium to give 4- (2-nitrophenoxymethyl) -1,3-dioxolanes of the general formula ( IV) implemented which, after reduction to give compounds of the general formula (V) and optionally by alkylation or oxyalkylation, reacted to the developer substances of the general formula (I) according to the invention and, if appropriate, converted to their salt form with inorganic or organic acids. 3. A process for the preparation of the compounds of general formula (I) and their salts with inorganic and organic acids, in which R¹, R², R³, R⁴, R⁵ and R⁶ have the meanings mentioned, characterized in that a compound of the general formula ( V), reacted in an inert solvent with 2-chloroethyl chloroformate or 3-chloropropyl chloroformate to give the compounds of the general formula (VI) in which R⁷ is CH₂CH₂Cl or CH₂CH₂CH₂Cl, which are reacted in a solvent with bases to give the compounds of the general formula (VII), in which R⁸ is CH₂CH₂OH or CH₂CH₂CH₂OH, with known alkylating agents or oxalkylating agents to give the compounds of general formula (I), wherein R² to R⁵ have the meanings given, are reacted and, if appropriate, converted into their salt with an inorganic or organic acid. 4. Hair dye based on the compounds of general formula (I) in the form a cream, solution, foam or gel that contains at least one compound of the general contain my formula (I) alone or with at least one coupler. 5. Hair dye based on the compounds of general formula (I) in the form a cream, solution, foam or gel that contains at least one compound of the general my formula (I) alone or with at least one coupler in which the Oxidation coloring is effected by adding an oxidizing agent. 6. Hair dye based on the compounds of the general formula (I) in the form a cream, solution, foam or gel that contains at least one compound of the general my formula (I) alone or with at least one coupler in which the Oxidation coloring by adding an oxidizing agent and an oxidation kata lysators is effected. 7. Hair dye based on the compounds of general formula (I) in the form a cream, solution, foam or gel that contains at least one compound of the general my formula (I) included in the absence of a coupler. 8. Hair dye based on the compounds of the general formula (I) in the form a cream, solution, foam or gel that contains at least one compound of the general my formula (I) alone or with at least one coupler, and one Oxidation catalyst for the formation of an oxidation color due to atmospheric oxygen have, wherein the oxidation catalyst from a transition metal salt or Transition metal complex, especially copper (II) chloride, sulfate, acetate, alone or as an adduct with ammonia, ethylenediamine, phenanthroline, triphenylphosphine,  1,2-diphenylphosphinoethane, 1,3-diphenylphosphinopropane or amino acids individual or in a mixture. 9. hair colorants which produce a hair oxidation coloration by air oxidation, a cream, solution, foam or gel that has at least one developer of the general formula (I) and contain at least one coupler and as oxidati Catalyst for air oxidation, copper (II) -1,2-diaminoethane chloride, copper (II) - 1,10-phenanthroline chloride, copper (II) tetramine sulfate, copper (II) glycinate individually or contained in the mixture. 10. A hair dye as claimed in claim 9, in which the catalyst content is 0.05 to 0.5 Weight percent based on the weight of the hair dye is.