JPS582204B2 - Senshiyokuso Saibutsu - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION It is known to use nitroparaphenylenediamines and their substitution products as additives to hair dyeing solution compositions.

The present invention aims to provide a new product within this scope, which provides improved results as a hair dye.

The object of the present invention is to provide a new hair dyeing composition, which has the formula [wherein R is hydrogen or a lower alkyl group; " is the formula (wherein n represents an integer of 2 to 6, R1 and R2
are selected from the same or different lower alkyl groups, hydrogen or lower hydroxyalkyl groups, or form a heterocycle together with the nitrogen atom, and when the amine group is tertiary, the amine group may optionally be quaternized. ), but when the nitro group is in the meta position with respect to the amine group to which R''' is attached, the amine group in the ortho position to the nitro group is not tertiary, R' and R'' do not represent hydrogen at the same time, and the nitro group is in the meta position with respect to the amino group to which R''' is attached, n is 2, R' is hydrogen,
When R'' is methyl, and R is hydrogen or a methyl group, neither R1 nor R2 represents a lower alkyl group]. This is a characteristic feature.

The dye having the formula (■) is characterized in that it has a great affinity for keratinous fibers even when it is cold.

Very deep shades can be obtained with the hair dyes obtained from such dyes and have two characteristics: deep dyeing and affinity for keratinous fibers, in this way even very small amounts of the dye solution can be obtained. It can be used as a dye.

Such a feature is advantageous since it allows even dyes with relatively low solubility to be used satisfactorily.

It is also noted that the dyes according to the invention have particularly advantageous resistance to light and washing.

Furthermore, it may be used over a much wider range of pH than is known and used in practice for dyes of the same family type known to date.

Thus, a range of pH 4 to pH 10 can be used.

A preferred range of use is from pH 6 to pH 10.

The dye according to the invention is furthermore characterized in that the substituent on one of the amine groups bonded to the benzene nucleus is a chain whose terminal end is an amino group, this amino group being tertiary.
It has characteristics that can be categorized.

Thus, the quaternized products, like the corresponding tertiary compounds, are used as dyes for hair.

The dye composition according to the present invention does not require the addition of peroxides, such as aqueous hydrogen peroxide, as is required with other dyes used on hair to produce color.

Furthermore, various ingredients such as those currently used in hair dyeing, such as organic solvents, thickeners, detergents and lacquers, can be added to such dye compositions.

The contact time of the dye solution with the hair can vary within a wide range.

However, as much as possible, it should be between 5 and 30 minutes.

The application temperature of the stain solution can vary.

However, in most cases normal temperature is advantageous.

Furthermore, the concentration of dyes of the type according to the invention can be varied considerably.

However, concentrations of 0.1% to 3.5% are advantageous.

Adding to one of the dyes of formula (I) other dyes according to the invention and further nitrated dyes, such as nitroorthophenylenediamine, nitroparaphenylenediamine, and alkyl or hydroxyalky derivatives of these compounds. can do.

Furthermore, depending on the desired purpose, the new dyes according to the invention can be used to replace azo dyes or anthraquinone dyes or other types of dyes commonly used for hair dyeing.

Next, non-limiting examples of how to make and use the dyes of the invention are presented.

Example 1 1-N-methylamino-2-nitro-4-N'-β-(
1st step of production of methyl, hydroxyethyl)-aminoethylamine benzene: 1-N-methylamino-2-nitro-4-N
'-β-Chloroethylamine Preparation of benzene 0.118 mol (25 g) of 1-N-methylamino-2
-300c of a solution containing nitro-4-N'-β-hydroxyethylaminobenzene in 1,2-dichloroethane
While cooling and stirring, 20 cc of thionyl chloride is added in portions to c.

Once the addition was complete, the reaction mixture was brought to room temperature for 2 hours at 60°C.
Keep at ℃ for 1 hour.

Upon cooling, 28 g of 11N-methylamino-2-nitro-4-N-β-chloroethylaminebenzene in the form of the hydrochloride are separated.

To purify this crude product, it is dissolved in IN hydrochloric acid under reflux, refluxed for several minutes in the presence of animal charcoal and filtered hot.

Cool the liquid and saturate it with hydrochloric acid gas.

The filtrate is cooled on ice overnight and 23 g of substantially pure 1-N-methylamino-2-nitro-4-N'-β-chloroethylaminobenzene hydrochloride is separated.

The base is liberated from the hydrochloride by making it alkaline using a conventional method.

Recrystallize from benzene-hexane.

Melting point: 93°C. The analytical values of the product are as follows: Analytical Values The chlorinated compounds obtained and similar chlorinated compounds described elsewhere herein can be used as dyes to dye hair.

Second stage: action of amine on the product of the first stage 0.0349 mol (8 g) of 1-N-methylamino-2
-Nitro-4-N'-β-chloroethylamine A mixture of benzene and 0.2792 mol (20.9 g) of methyl-β-hydroxyethylamine was heated at 120 to 130°C.
Heat for 8 hours.

Excess methyl-β-hydroxyethylamine is distilled off under reduced pressure.

The oily residue is dissolved in benzene and the benzene solution is washed with water, dried over sodium sulfate and filtered.

The benzene is distilled off under reduced pressure to obtain 7fI of substantially pure l-N-methylamino-2-nitro-4-N'-β-(methylhydroxyethyl)amino-ethylaminobenzene.

This oil was dissolved in 100 cc of Gropanol, cooled on ice, and saturated with dry hydrochloric acid gas.

8.1 g of product in the form of the dihydrochloride are obtained. Melting point 137-142°C (decomposition).

An oily base is obtained from the dihydrochloride by making alkaline and using a conventional method.

The analytical values of the product are shown below.

Analysis value example 2 Production of 1-methylamino-2-nitro-4-(N'-β-hydroxyethyl, N'-β-diethylaminoethyl)-aminobenzene 0.237 mol (50 g) of 1-N-methyl Amino-2
-Nitro-4-N'-β-hydroxyethylamine A mixture of benzene, 200 cc of water and 20 g of calcium carbonate is refluxed.

0.355 mol (61 g) of β-diethylamino-ethyl chloride hydrochloride is dissolved in 120 cc of water and added in portions.

After refluxing for 3 hours, it is filtered while hot, and the filtrate is cooled and made alkaline with sodium hydroxide.

The product is extracted with ethyl acetate, the ethyl acetate solution is washed with water, dried over sodium sulfate and filtered.

This solution was then cooled and saturated with dry hydrochloric acid gas to give 1-
N-methylamino-2-nitro-4-(N'-β-hydroxyethyl-N'-β-diethylaminoethyl)aminebenzene dihydrochloride is obtained.

Recrystallize from propanol hydrochloride.

Melting point 110-115°C. The base isolated from the dihydrochloride by a conventional method is in the form of an oil and shows the following Q analysis value.

Analysis value example 3 First manufacturing method of 1-methylamino-2-nitro-4-(N'-methyl, N'-β-aminoethyl)benzene 0.2 mol (36.2 g) of 1-methylamino -2-Nitro-4-N'-methylamine A mixture of benzene, 15 g of calcium carbonate and 200 cc of water is refluxed.

0.3 mol (61.5 g) of β-bromoethylamine hydrobromide is dissolved in 100 cc of water and added little by little with stirring.

Cool and collect 5 g of unreacted starting material.

The filtrate containing the product in the form of the hydrochloride salt is extracted with ethyl acetate to remove any traces present from said product.

The aqueous phase is made alkaline to pH=11 with 5N sodium hydroxide.

Oily 1-N-methylamino-2-nitro-4 (N/
-methyl, N'-β-aminoethyl)benzene is liberated.

Extract this oil with ethyl acetate and dilute the ethyl acetate solution with approx.
Concentrate to 0 cc, add 20 cc of acetic anhydride little by little, reflux for 4 hours, cool and 1-N-methylamino-2-
37 g of nitro-4-N'-methyl, N'-β-acetylaminoethylbenzene are separated.

Recrystallize from alcohol.

Melting point: 127°C. 34g of acetyl derivative (melting point 127°C
) in 150 cc of concentrated hydrochloric acid for 30 minutes.

Cool, dilute and add 5N sodium hydroxide.
Set it to H5.

Substantially pure l-methylamino-2-nitro-4-
34.25 g of (N'-methyl, N'-aminoethyl)-aminobenzene is obtained.

The base is liberated from the monohydrochloride in a conventional manner.

It is in oil form and the analytical values are as follows.

Example 4 Second manufacturing method for 1-methylamino-2-nitro-4-(N'-methyl, N/β-aminoethyl)aminobenzene First step: 1-methylamino-2-nitro-4(N'
-Production of β-chloroethyl)aminebenzene 0.33 mol (74 g) of 1-methylamino-2-nitro-4-(N'-methyl, N'-β-hydroxyethyl)aminebenzene was dissolved in 750 cc of dichloroethane. dissolve in

Add 0.37 mol (26 cc) of thionyl chloride while stirring at room temperature.

Reflux and cool for 1 hour to obtain 75 g of 1-methylamino-2-nitro-4-(N'-methyl, N'-β-chloroethyl)niaminebenzene hydrochloride.

Dissolved in 1N hydrochloric acid, boiled with a small amount of animal charcoal, filtered, cooled, and made alkaline with IN sodium hydroxide solution to reduce 58% of chloride.
get g.

Recrystallize from benzene-hexane.

Melting point: 90°C. The analytical value of the product is as follows: Analytical value 2nd step: 0.02 mol (4.87 g) of 1-methylamino-2-nitro-4-(N'-methyl, N'-β-chloroethyl)aminobenzene. 0.022 mol (4.0
7 mol) potassium phthalimide and carefully ground and mixed.

Heat to 130-140°C for 1 hour.

The reaction mixture is cooled, ground and washed with water to remove the potassium chloride formed and also to remove any unreacted potassium phthalimide that may be present.

Recrystallization of the water-insoluble fraction (i.e. 6.53 g) from benzene yields substantially pure 1-methylamino-2-nitro-4-N'-methyl, N'-(β
-phthalimidoethyl)aminobenzene 5.5 g was obtained.

The analysis results are as follows.

Analysis Values 0.014 mol (5 g) of the substituted phthalimide obtained in the first step is combined with a large excess of hydrazine hydrate and refluxed in a propanol solution for 2 hours.

After cooling, the phthalhydrazide formed is separated.

Insoluble in propanol. Next, pass dry hydrochloric acid gas through 1
-methylamino-2-nitro-4-(N'-methyl, N
'-β-aminoethyl)benzene dihydrochloride (2.3g)
precipitate.

The dihydrochloride salt is recrystallized from a propanol-hydrochloric acid mixture having a specific gravity of 1.19 to obtain a substantially pure oily base.

The analytical values are as follows. Example 5 Preparation of 1-N-methylamino-2-nitro-4-N'-methyl, N'-β-piperidino-ethylaminobenzene 0.041 mol (10 g) of 1-methylamino-2-nitro-4 -(N'-methyl, N'-β-chloroethyl)
Dissolve aminobenzene in 733 cc of piperidine.

The solution is heated to 115-120° C. for 8 hours, cooled, the piperidine hydrochloride formed is filtered off, and excess piperidine is removed under reduced pressure.

12 g of crystalline product are obtained.

Wash with water, dry and recrystallize from hexane.

Pure 1-methylamino-2-nitro-4-(N'-methyl, N'-β-piperidinoethyl)aminebenzene 102
get.

Melting point 74℃ The analysis results of the product are as follows.

Example 6 Preparation of quaternized β-[N-methylN-(3-nitro-4-N'-methylamino)-phenyl]aminoethylmethylpiperidinium iodide of the dye prepared in Example 5. l-methylamino-2-nitro-4-(
0.0274 mol (8 g) of N'-methyl, N'-β-piperidinoethyl)amine benzene is dissolved in 80 cc of benzene.

0. 0 2 7 4 mol (1.7 cc) of methyl iodide are added in portions and the reaction mixture is left at room temperature for 2 days.

10 g of quaternary product are obtained. Melting point 178 to 180℃ (
Disassembly).

Example 7 Preparation of 1-N-methylamino-2-nitro-4-(N'-methyl, N'-β-(methyl, hydroxyethyl)aminoethylbenzene 0.0985 mol (24 g) of 1-methylamino-2 −
Nitro-4 (N'-methyl, N'-β-chloroethyl)
Amine benzene and 0. 7 8 8 mol (59.2g)
of methylethanolamine at 120 to 1
Heat to 30°C for 8 hours.

Excess methylethanolamine is removed under reduced pressure and the oily residue is dissolved in benzene.

This benzene solution is washed with water, dried over sodium sulfate, and filtered.

Benzene was removed under reduced pressure to obtain 1-methylamino-2-nitro-4-(N'-methyl, N'-β-(methyl, hydroxyethyl)aminoethyl)aminebenzene as a purple oil.

This oil is dissolved in 100 cc of propyl alcohol and passed through hydrochloric acid gas to obtain a substantially pure dihydrochloride salt.

Melting point 115-120°C (decomposition).

The base separated from pure dihydrochloride by a conventional method shows the following analysis results.

Example 8 Production of 1-N-β-(hydroxyethyl, methyl)aminoethylamino-2-nitro-4-N'-methylaminebenzene First step: 1-N-β-chloroethylamino-2-nitro-4 -Preparation of N'-methylaminebenzene 0.071 mol (15F) of 1-N-β-hydroxyethylamino-2-nitro-4-N'-methylaminebenzene is dissolved in 150 cc of 1,2-dichloro-ethane. Add 0.0% to the containing solution while stirring well. A solution of 0 7 6 mol (5.5 cc) of thionyl chloride in 50 cc of 1,2-dichloro-ethane is added in portions.

Reflux for 2 hours and cool to obtain crude product 17F in the form of the hydrochloride salt.

This product must be purified, which requires 2
00cc and adjust the pH to 3 with sodium carbonate to 1-
N-β-chloroethylamino-2-nitro-4-N'-
Methylaminobenzene 122 is obtained.

Contains a small amount of thionylamine as an impurity.

12 g of the separated product was dissolved in 5N hydrochloric acid and refluxed for 0.5 hours to hydrolyze the thionylamine contained.

Upon cooling, 10 g of substantially pure 1-N-β-chloroethylamino-2-nitro-4-N'-methylaminebenzene hydrochloride are obtained.

9 g of product, redissolved in water and adjusted to pH 3 with sodium carbonate.
get.

Recrystallize from a benzene-hexane mixture.

Melting point: 98°C. The analysis of the product is as follows: Second stage: 0.0366 mol (8.4 g) of 1-N-β
-Chloroethylamino-2-nitro4-N'-methylaminebenzene to methylethanolamine 0.292
Dissolve in 8 mol (22 g).

Heat to 120-130°C for 8 hours, cool and remove excess methylethanolamine under reduced pressure.

The residue is taken up in water and the methanolamine hydrochloride is redissolved to obtain 8.8 y of 1-N-β-(hydroxymethyl-methylamine)-1ethylamino-2-nitro-4-N'-methylamine benzene.

Recrystallize from benzene.

Melting point: 85°C. Analytical values of the product Example 9 1-N-β-hyheridinoethylamino-2-nitro-4
0.0166 mol (3.El) of 1-N-β- produced in the first step of Production Example 8 of -N'-methylaminebenzene
Dissolve chloroethylamino-2-nitro-4-N'-methylaminobenzene in 18 cc of pyherizine.

The mixture is refluxed for 8 hours, cooled, the formed piperidine hydrochloride is filtered off, and excess piperidine is removed under reduced pressure.

5 g of the crystalline product are washed with water, dried and recrystallized from a hexane-benzene mixture.

1-N-β-piperidinoethylamino- with a melting point of 103°C
2-nitro-4-N'-methylaminebenzene 4.45
get g.

The analytical values of the product are as follows: Example 10 The quaternized β-[N-(2-nitro, 4-N′-methylamino)-
Preparation of phenyl]-amino-ethyl-methyl-piperidinium iodide 0.02 mol (5.56 g) of 1-N-β-piveridinoethylamino-2-nitro-4-N'-methylamine benzene was added to benzene s. Dissolve in occ.

10 cc of a benzene solution containing 0.02 mol (1-25 cc) of methyl iodide is added in portions.

The reaction mixture is left at room temperature for 2 days.

Eight pieces of the above quaternary salt are obtained.

Melting point: 130°C (decomposition). Example 11 Preparation of 1-N-β-diethylamineethyl-2-nito0-4-N'-methylaminebenzene 1st step: t
- N-Hensensulfonylamino-2-nitro-4-
(N'-methyl, N'-acetyl) monoaminobenzene is produced by a known method in which a solution of 1-amino-2-nitro-4-methylacetaminobenzene dissolved in pyridine is reacted with benzenesulfonic acid chloride. .

Recrystallize from alcohol.

Melting point: 144°C. The analytical values are as follows.

N-β-diethylamine ethyl)2-nitro-4(N
Production of '-methyl, N'-acetyl)aminebenzene0. To a solution containing 0.5 moles (17.4 g) of 1-N-benzenesulfonylamino-2-nitro-4-(N'-methyl, N'-acetyl)benzene in 60 cc of 1N sodium hydroxide, 60 C. and at the same time a solution containing 0.152 mol (26 g) of diethylamino-ethyl chloride hydrochloride in 100 cc of water and 100 cc of 2N sodium hydroxide are added.

Once the addition is complete, the reaction mixture is left at 60° C. for 3 hours, cooled and extracted with ethyl acetate, the ethyl acetate solution is washed with IN sodium hydroxide and then with water to remove the tosylate form. Remove starting product.

The product is then extracted in the form of the hydrochloride salt with water-cooled IN hydrochloric acid.

When this hydrochloric acid solution is made alkaline with 1N sodium hydroxide, 1-(N-benzenesulfonyl-N-β-diethylamineethyl)-amino-2-nitro4-(N
'-methyl, N'-7cetyl)amine benzene 92 precipitates.

Recrystallize from toluene-hexane mixture.

Melting point: 128°C.

Third step: 0.0133 mol (6 g) l-N-benzenesulfonyl, N-β-diethylamineethylamino-2-nitro 4-(N'-methyl, N'-acetyl)
Aminobenzene is heated to reflux in 50 cc of concentrated hydrochloric acid.

Dilute and add 5N sodium hydroxide while cooling.

3.21 of 1-N-β-diethylamineethylamino-2-nitro-4-methylaminebenzene are obtained.

Recrystallize from a benzene-hexane mixture.

Melting point: 74°C. Example 12 First method for producing 1-N-β-(diethylamino)ethylamino-2-nitro-4-aminebenzene First step: Production of 1-N-β-chloroethylamino-2-nitro-4-aminebenzene 0.0570 mol (11.2 r) of 1-N-β-hydroxyethylamino-2-nitro-4-aminebenzene are dissolved in 150 cc of 1,2-dichloroethane.

To this solution, while stirring under reflux, a solution of 50 cc of 1,2-dichloroethane containing 0.114 mol (8.3 cc) of thionyl chloride is added little by little, and the solution is refluxed for 2 hours.

About 100 cc of solvent was distilled off under reduced pressure, cooled, and a small amount of hexane was added to give 1-N-β-chloroethylamino-2
9.2 g of -nitro-4-thionylaminobenzene are separated.

Recrystallize from benzene.

Melting point: 116°C. The analytical values are as follows.

The filtrate is 1-N-β-chloroethylamino-2-nitro-
Note that it contains 4-amine benzene.

After separating thionylamine as described above, the filtrate was saturated with dry hydrochloric acid gas to separate 4 g of 1-N-β-chloroethylamino-2-nitro-4-amine benzene hydrochloride.

Dissolve this hydrochloride in ice water and adjust the pH to 4 with ammonia to 1
3 g of -N-β-chloroethylamino-2-nitro-4-aminebenzene are obtained.

Recrystallize from benzene. Melting point: 115°C.

The analytical values are as follows.

1-N-β-
Chloroethylamino-2-nitro-4-thionylaminobenzene9. 2g to 1. Heat in 300 cc of 5N hydrochloric acid on a boiling water bath for 2 hours.

Cool and add ammonia to adjust pH to 4.

In this way, 1-N-β-chloroethylamino-2-
7.5 g of nitro-4-aminobenzene are obtained.

It has a melting point of 115°C and is substantially pure.

Second step: 0.0139 mol (3 g) of 1-N-β-chloroethylamino-2-nitro-4-aminobenzene and 0.167 mol (12.25 g) of diethylamine in a sealed tube at 120°C. Heat for 20 hours.

After cooling, diethylamine hydrochloride is removed by filtration and excess diethylamine is removed under reduced pressure.

The oily residue is dissolved in benzene, the benzene solution is washed with water, dried over sodium sulfate and filtered.

Benzene was distilled off under reduced pressure to obtain 3.34 g of crystalline product.

Recrystallize once from benzene-hexane.

Melting point: 65°C. The analytical values of the product are as follows.

Example 13 Second process for producing 1-N-β-(diethylamino)ethylamino-2-nitro-4-aminebenzene First step: 1-N-p-}ruene-sulfonylamino-2-nitro-4- Method for producing acetylaminobenzene This product is produced by the conventional method of reacting 1-amino-2-nitro-4-acetylaminobenzene Kp-toluenesulfonic acid chloride dissolved in pyridine.

Reconstitutes from alcohol.

Melting point: 161.5°C. gives the following result.

Second step: 1-N-p-toluenesulfonyl-
Preparation of N-β-diethylaminoethyl 1-amino-2-nitro-4-acetylaminobenzene 0. 0 2 8
To a solution containing 6 moles (10 g) of 1-N-p-toluene-sulfonylamino-2-nitro-4-acetylaminobenzene in 40 cc of 1N sodium hydroxide, 6
at 0°C and at the same time on the one hand 0. 0 86
A solution containing mol (14.8 g) of β-diethylamino-ethyl chloride hydrochloride in 50 cc of water and on the other hand 60 cc of 2N sodium hydroxide are added.

Once the addition is complete, the reaction mixture is left at 60° C. for 3 hours.

After cooling, the mixture is extracted with ethyl acetate and the ethyl acetate solution is washed with sodium hydroxide and then with water to remove the starting product in the form of tosylate.

The product is extracted as the hydrochloride salt with 1N ice-cold hydrochloric acid.

When this hydrochloric acid solution is made alkaline with IN sodium hydroxide, 1-(N-p-toluenesulfonyl-N-β-diethylaminoethyl)-1-amino-2-nitro-4-
7 g of acetylaminobenzene precipitates.

Dry under reduced pressure and recrystallize from a toluene-hexane mixture.

Melting point: 166°C. 3rd step = 1-N-β-(dimethylamino)ethylamino-2-nitro-4-acetylaminobenzene production method 0.02 mol (8.96f) of 1-
Add (N-p-toluenesulfonyl-N-β-diethylamino)-ethylamino-2-nitro-4-acetylaminobenzene little by little with stirring.

After the addition is complete, the reaction mixture is left at 15° C. for 3 hours.

Place on ice, make alkaline with sodium hydroxide, and add 1-N-
β-(diethylamino)-ethylamino-2-nitro-
5.8 g of 4-acetylaminobenzene are obtained.

Recrystallize from alcohol and dry under reduced pressure over phosphoric anhydride.

Melting point: 96°C. Fourth stage: 0.02 mol (5.9 g) l
-N-β-(diethylamino)ethylamino-2-nitro-4-acetylaminobenzene in 5N hydrochloric acid 30
cc and reflux for 1 hour.

Cool and alkaline to give 5 g of 1-N-β-(diethylamino)-ethylamino-2-nitro-4-aminebenzene.

Recrystallize from a benzene-hexane mixture. Melting point 65-66°C (mixed with that prepared in Example 12, no melting point depression).

Example 14 Preparation of 1-N-β-(methyl, hydroxyethyl)aminoethyl-amino-2-nitro-4-aminobenzene 0.02 mol (4.315') of 1-N-β-chloroethylamino- 12g of 2-nitro-4-aminobenzene
of N-N-methyl, β-hydroxyethylamine and the solution is heated to 120-130°C for 9 hours.

Excess methylethanolamine is distilled off under reduced pressure and the oily residue is redissolved in ethyl acetate.

The ethyl acetate solution is washed with water, dried over sodium sulfate and filtered.

The solvent was distilled off under reduced pressure to obtain 5 g of crystalline product.

Recrystallize from benzene.

Melting point: 89°C. Example 15 l-N-β-piperidinoethylamino-2-nitro-4
-1-N-β-chloroethylamino-2-nitro-4-aminebenzene produced in the first step of Example 12 of aminebenzene 0.0695
Mol (15 g) is dissolved in 75 cc of piperidine and refluxed for 8 hours.

After cooling, piperidine hydrochloride was removed, excess piperidine was distilled off under reduced pressure, and the oily residue was dissolved in 100 cc of benzene.

The benzene solution is washed with water, dried with sodium sulfate, and filtered.

Benzene was distilled off under reduced pressure to obtain 18.1 g of 1-N-β-piperidinoethylamino-2-nitro-4-aminobenzene.
get.

Recrystallize from benzene-hexane.

Melting point: 91°C. Example 16 Quaternization of the product of Example 15 β-[N-(2-nitro-4-amine)phenyl]-aminoethyl, methyl, 1- Dissolve N-β-piperidinoethylamino-2-nitro-4-aminobenzene in 50 cc of toluene.

10 cc of a benzene solution containing 0.02 mol (125 cc) of methyl iodide is added in portions.

The reaction mixture was left at room temperature for 3 days to obtain 8.2 g of quaternized compound.

Corresponds to the above formula.

The melting point of this compound is 125°C (decomposition).

Example 17 1-N-β-aminoethylamino-2-nitro-4-N
Preparation of '-bis-β-hydroxyethylaminobenzene First step: In the first step, 1-N-β-chloroethylamino-2
-Produce nitro-4-aminobenzene.

Second step: Preparation of 1-N-β-chloroethylamino-2-nitro-4-N'-bis-β-hydroxyethylaminobenzene 0.05 moles (10.752) of 1-N-β-chloro Ethylamino-2-nitro-4-aminobenzene in 10 parts water
Dissolve at 95°C in 120cc of alcohol to which cc has been added.

The solution was saturated with ethylene oxide at room temperature, and by paper chromatography, the starting product was also 1-N-β-
The reaction is allowed to proceed until chloroethylamino-2-nitro-4-N'-β-hydroxyethylaminobenzene is no longer detected.

The alcohol is distilled off under reduced pressure. 15.1 g of oil are obtained.

Substantially pure 1-N-β-chloroethylamino-2-
Nitro-4-N'-bis-β-hydroxyethylaminobenzene is obtained.

Third step: 1-N-β-7thalimidoethylamino-2
-Preparation of nitro-4-N'-bis-β-hydroxyethylaminobenzene 0.070 mol (21.2 g) of 1-N-β-chloroethylamino-2-nitro-4-N'-bis-β -Hydroxyethylaminobenzene with dimethylformamide 67
Dissolve in cc.

0.104 mol (19.5 g) of potassium phthalimide is added and the reaction mixture is heated on a boiling water bath for 1 hour.

Filter while hot, add water to the filtrate, and obtain 1-N-β-phthalimidoethylamino-2-nitro-4-N′-bis-β.
-21 g of hydroxyethylaminobenzene are precipitated.

Recrystallize from n-propyl alcohol.

Melting point: 140°C. Fourth step: Preparation of 1-N-β-aminoethylamino-2-nitro-4-N'-bis-β-hydroxyethylaminobenzene 0.0282 mol (11.67 g) of 1-N-β-diph A solution containing tarimidoethylamino-2-nitro-4N'-bis-β-hydroxyethylaminobenzene in 200 cc of n-propyl alcohol was mixed with 0. 4 2
Reflux with 3 mol (1.8 CC) of 98% hydrazine hydrate for 2 hours.

After filtration while hot, a portion of the propyl alcohol is evaporated under reduced pressure and cooled to obtain 11.5 g of the desired product in the form of a salt.

The primary amine functionality is salted with phthal hydrazide.

This product is dissolved in water, made strongly alkaline with sodium hydroxide, and the desired product is extracted with butanol.

The phthalhydrazide is removed as the sodium salt into the aqueous phase.

Butanol was removed under reduced pressure to obtain 7 g of oil.

Substantially pure 1-N-β-aminoethylamino-2-
Nitro-4-N'-bis-β-hydroxyethylaminobenzene is obtained.

The oil is dissolved in n-propyl alcohol and the solution is saturated with dry hydrochloric acid.

1-N-β-aminoethylamino-2-nitro-4-N
'-bis-β-hydroxyethylaminobenzene is obtained.

Melting point: 158-163°C (decomposed).

The analytical values are as follows.

Example 18 1-N-β-hydroxyethylamino-2-nitro-
Production of 4-N'-methyl-N'-β-diethylaminoethylaminobenzene This production method can be diagrammed as follows.

A mixture of 0.237 mol (50 g) of 1-N-β-hydroxyethylamino-2-nitro-4-N'-methylaminebenzene, 200 cc of water and 20 g of calcium carbonate is refluxed.

Gradually and while stirring, add 0.355 mol (61
The β-diethylamino-ethyl chloride hydrochloride from g) is dissolved in 120 cc of water and introduced.

Reflux for 3 hours, then filter hot.

The filtrate is cooled, made alkaline with sodium hydroxide, and the product is extracted with ethyl acetate.

The ethyl acetate solution was washed with water, dried over sodium sulfate, and the solvent was distilled off under reduced pressure.

The remaining oil (65 g) is dissolved in 500 cc of propanol.

The glopanol solution is cooled and saturated with dry hydrochloric acid gas.

1-N-β-hydroxyethylamino-2-nitro-4
- (N'-methyl, N'-β-diethylamine ethyl)-aminobenzene is obtained.

Melting point 118-123°C (decomposition).

The analysis results of the oily substance isolated from the dihydrochloride by a conventional method are as follows.

Example 19 Production of 1-N-methylamino-2-nitro-4-N'-aminobutylaminobenzene dihydrochloride The reaction for production can be schematically illustrated as follows.

First step: l-N-methylamino-2-nitro-4-
(N'-benzenesulfonyl, N'-promobutyl)
Aminebenzene 1-N-methylamino-2-nitro-4-N'-benzenesulfonylaminebenzene 0. 4 moles (138g)
Dissolve in 350 cc of dimethylformamide.

0.8 mol (95.5 CC) of 1,4-dibromobutane is added and the reaction mixture is kept at 90°C for 30 minutes.

Cool and pour into 2.5 l of water to obtain 190 g of crude product.

Fractional crystallization from benzene. On the one hand, 1-N-
145 g of methylamino-2-nitro-4-(N'-benzenesulfonyl-N'-ω-butimoethyl)-aminobenzene are obtained.

Melting point: 140°C. On the other hand, the analytical value is bis-[N'
30 g of -(4-methylamino-3-nitro)-phenyl]benzenesulfamidobutane are obtained.

Melting point: 245°C. The analysis results are as follows.

Second step: 1-N-methylamino-2-nitro-4-(
Preparation of 0.25 mol (110.5 g) of 1-N-methylamino-2-nitro-4-(N'-benzenesulfonyl, N'-benzenesulfonyl, N'-phthalimidobutyl)amine
'-ω-promobutyl) in dimethylformamide 500
Dissolve in cc.

0.3 mol (55.5 g) of potassium phthalimide is added and the reaction mixture is heated on a boiling bath for 1 hour.

Pour into 4 l of water to obtain 126 g of crude product.

Recrystallize from benzene-hexane.

Melting point: 141°C. The analysis results are shown below.

Third step: 1-N-methylamino-2-nitro-4-(
Preparation of N'-benzenesulfonyl, N'-ω-aminobutylbenzene A solution containing 0.02 moles (10.16 g) of substituted phthalimide in 80 cc of propanol was prepared by adding 0.04 moles of substituted phthalimide to 80 cc of propanol.
Add 30 moles of hydrazine hydrate on a boiling bath.
Heat for a minute.

The reaction mixture is filtered hot to remove most of the phthal hydrazide formed.

Cool and decant to obtain an orange oil.

Dissolve in ethyl acetate.

This ethyl acetate solution is extracted with 0.5N hydrochloric acid.

When the hydrochloric acid aqueous phase is made alkaline, 1-N-methylamino-2-nitro-4-(N'-benzenesulfonyl, N'
45 g of -ω-aminobutyl)aminebenzene are obtained.

Recrystallize from ethyl acetate.

Melting point: 135°C. The analysis results of this product are as follows.

The propanol mother liquor is cooled, saturated with hydrochloric acid gas, and separated to obtain 2 g of hydrochloride.

Fourth step: 1-N-methylamino-2-nitro4-N'
-Production of ω-aminobutylaminobenzene 0.013 mol (5 g) of 1-N-methylamino-2-
Nitro-4-(N'-benzenesulfonyl, N'-ω-
(aminobutyl)amine benzene in 15 cc of concentrated hydrochloric acid.
Reflux for an hour.

An equal volume of alcohol is added to the cooled hydrochloric acid solution to obtain 3.2 g of 1-N-methylamino-2-nitro-4-N'-ω-aminobutyl-aminobenzene dihydrochloride.

It was recrystallized from concentrated hydrochloric acid, and the analytical values are as follows.

Example 20 l-N-methylamino-2-nitro-4-N'-γ-[
The reaction formula for producing N''-(β-hydroxyethyl, methyl)]-γ-aminopropylbenzene is as follows.

First step: 1-N-methylamino-2-nitro-4
- (N'-benzenesulfonyl, N'- γ- [
Preparation of 0.0466 mol (20 g) of 1-N-methylamino-
2-nitro-4-(N'-benzenesulfonylN'-γ
-bromopropyl)aminobenzene in 0.373 mol (28 g) of methyl β-hydroxyethylamine.
Heat to 120°C for an hour.

Excess methyl, β-hydroxyethylamine is removed under reduced pressure.

The residue is taken up in water-cooled 2N hydrochloric acid. The product is obtained in the form of the hydrochloride.

This hydrochloride is dissolved in hot water and made alkaline with sodium hydroxide.

Cool, 1-N-methylamino-2-nitro-4-
(N'-benzenesulfonyl, N'-γ-[N'-(β
-Hydroxyethyl, methyl)]-γ-aminopropyl)amine 16 g of benzene are obtained.

Recrystallize from methanol.

Melting point: 85°C. Second step: Preparation of 1-N-methylamino-2-nitro-4-(N′-γ[N″-(β-hydroxyethyl, methyl)]-γ-aminopropyl)aminebenzene 0.048 mol ( 2.04 g) of 1-N-methylamino-2-nitro-4-N'-benzenesulfonyl, (N
′-γ-[N″-(β-hydroxyethyl, methyl)]
- γ-Aminopropyl-aminobenzene is refluxed in 6 CC of concentrated hydrochloric acid for 2 hours.

Dilute and make alkaline with sodium hydroxide and extract the sodium hydroxide solution with methyl isobutyl ketone.

Methyl isobutyl ketone is distilled off under reduced pressure and the remaining oil is
- Redissolve in propyl alcohol, cool the solution sufficiently and saturate it with dry hydrochloric acid gas.

1-N-methylamino-2-nitro-4-( N'-γ
1.4 g of -[N-(β-hydroxyethyl-methyl)]γ-aminopropyl)aminebenzene are obtained.

Melts (with decomposition) at 160°C. Example 21 The reaction for producing 1-N-β-ethylamino-2-nitro-4-amine benzene dihydrochloride is as shown in the following formula.

First step: 1-(N-p-toluenesulfonyl-N-β
-phthalimidoethyl)-amino-2-nitro-4-
Preparation of N'-acetylaminobenzene 0.01 mol (4.565') of 1-(N-p-toluenesulfonyl-N-β-bromoethyl)2-nitro-4
-N'-acetylaminobenzene is dissolved in 16 cc of dimethylformamide.

0.012 mol of potassium phthalimide is added and the reaction mixture is heated on a boiling water bath for 1 hour.

Filter while hot and pour into 200 cc of water to obtain 5 g of crude product.

Recrystallize from an acetone-water mixture.

Melting point: 205°C. Second step: Preparation of 1-(N-p-toluenesulfonyl-N-β-aminoethyl)-amino-2-nitro-4-N'-acetylaminobenzene 0.215
0.43 mole (112.2 g) of 1-(N-p-toluenesulfonyl N-β-phthalimidoethyl)-amino-2-nitro-4N'-acetylaminobenzene dissolved in 500 cc of propanol.
Add Mol (22 g) and heat on a boiling water bath for 20 minutes.

The reaction mixture is filtered hot to separate 34 g of phthal hydrazide.

The propanol mother liquor is cooled to -5°C. A red oil separates.

The kerosene is removed and the alcoholic solution is saturated with dry hydrochloric acid gas.

The product is obtained in the form of the hydrochloride.

The base is liberated in a conventional manner. 66 g of 1-(N-p-}luenesulfonyl, N-β-amino-ethyl)amino-2-nitro-4-N'-acetylaminobenzene are obtained by recrystallization from pyridine.

Melting point: 223°C. Analysis of the product shows that the oil removed during production easily crystallizes in methanol.

The second product (melting point 175°C) is 1-[N-β-(p-
toluenesulfonyl)aminoethyl-2-nitro-4-
N'-acetylaminobenzene.

Third step: Preparation of dihydrochloride of l-N-β-aminoethylamino-2-nitro-4-aminebenzene 0.102 mol (40 g) of 1-(N-p-toluenesulfonyl-N-β- (aminoethyl)-amino-2-nitro-4-N'-acetylaminobenzene was dissolved in 7N hydrochloric acid 2
Heat on a boiling water bath for 1 hour in 0 0 cc.

Cooled and 1-N-β-aminoethylamino-2-nitro-
26.7 g of 4-aminebenzene are obtained.

Recrystallize from concentrated hydrochloric acid. The analytical values are as follows.

Example 22 1-N-β-hydroxyethylamino-2-nitro-4
The reaction process for producing -N'-β-diethylaminoethylaminobenzene is as follows.

0.17 mol (33 g) of 1-N-β-hydroxyethylamino-2-nitro-4-aminobenzene and 250
A mixture of CC water and 12 g of calcium carbonate is brought to reflux.

While stirring little by little, add 0.19 mol (32.7 g) of diethylaminoethyl chloride hydrochloride to 100 cc of water.
Dissolve and add.

After the addition is complete, the mixture is refluxed for a further 1 hour, filtered hot, and the filtrate is cooled and extracted with methyl isobutyl ketone to remove any unreacted starting product present.

The aqueous phase is made alkaline with sodium hydroxide and the desired product, contained as the monohydrochloride, is extracted with methyl isobutyl ketone.

The solvent was distilled off under reduced pressure to obtain 46 g of a purple oil.

Crystallizes very quickly. Recrystallize from a cyclohexane-benzene mixture.

Melting point: 73°C.

Example 23 Production of 1-N-methylamino-2-nitro-4-N'-ω-aminehexylaminobenzene The production process is shown as follows.

First step: l-N-methylamino-2-nitro-4-
Preparation of (N'-benzenesulfonyl, N'-ω-bromohexyl)-aminobenzene 0.05 mol (17.25 g) of 1-N-methyl-amino-2-nitro-4-N'-benzenesulfonylamino Dissolve the potassium salt of benzene in 40 cc of dimethylformamide.

0.1 mol (24.4 g) of 1,6-dibromohexane is added and the reaction mixture is kept at 80 DEG C. for 30 minutes.

Cool and pour into 300 cc of water to obtain 23.35' of crude product.
get.

The product is obtained by fractional crystallization from absolute alcohol.

On the one hand, l-N-methylamino-2-nitro-
17 g of 4-(N'-benzenesulfonyl, N'-ω-promohexyl)-aminobenzene are obtained.

Melting point: 101°C. On the other hand, 4 g of bis-N'-[4-N-methylamino-3-nitrophenyl]-benzenesulfamidohexane are obtained.

Melting point: 200°C. Second step: 1-N-methylamino-2-
Nitro-4-(N'-benzenesulfonyl, N'-ω-
Production of (phthalimidohexyl)-aminobenzene 0.0
268 moles (12.6 g) of 1-N-methylamino-2
-nitro-4- (N'-benzenesulfonyl N'
-ω-bromohexyl)-aminobenzene at 50 c
Dissolve c in dimethylformamide.

0.0322 mol (5.96 g) of potassium phthalimide is added and the reaction mixture is heated on a boiling water bath for 1 hour.

Pour into 400 cc of water to obtain crude product 13. Separate 8 g.

Recrystallize from ethyl acetate. Melting point: 149°C.

The analytical value of the product is determined in the third step: 1-N-methylamino-
2-nitro-4-(N'-benzenesulfonyl, N'-
Preparation of ω-aminehexyl)-aminobenzene 2 g of hydrazine hydrate are added to a solution containing 0.0193 mol (10.37 g) of substituted phthalimide in 80 cc of propanol and heated on a boiling water bath for 30 minutes.

The reaction mixture is filtered hot to remove most of the phthal hydrazide formed.

Cool and obtain the coconut oil, which has an orange color.

Dissolve in ethyl acetate and extract with 0.5N hydrochloric acid.

Make the hydrochloric acid phase alkaline with sodium hydroxide and add 3.5 g of 1
-N-methylamino-2-nitro-4-(N'-benzenesulfonyl, N'-ω-aminoalkyl)-aminobenzene is obtained.

Melting point: 130°C. The propanol mother liquor is saturated with dry hydrochloric acid to obtain 2 g of the desired product in the form of the hydrochloride salt.

Fourth step: 1-N-methylamino-2-nitro-4
- Preparation of (N'-ω-aminohexyl)-aminobenzene dihydrochloride 0. 0 0 8 mol (3.2 g) of 1-N-methylamino-2-nitro-4-(N'-ω-aminohexyl)
- Aminobenzene in 10 cc of concentrated hydrochloric acid on a boiling water bath
Heat for 0 minutes.

After cooling, 10 cc of absolute alcohol was added to obtain 2 g of 1-H-methylamino-2-nitro-4-(N'-ω-aminohexyl)-aminobenzene.

The analytical values of the product obtained by adding an equal volume of alcohol to concentrated hydrochloric acid and reconsolidating it are as follows: Example 24 First step of production of 1-N-methylamino-2-nitro-4-N'-β-aminoethylaminobenzene: l-N-methylamino-2-nitro-4-(
N'-benzenesulfonyl, N'-β-phthalimidoethyl)-aminobenzene Process (a): 0.122 mol (50.5 g) of 1-N
-Methylamino-2-nitro-4-(N'-benzenesulfonyl, N'-β-bromoethyl)-aminobenzene is dissolved in 150 cc of dimethylformamide.

0.162 mol (30 g) of potassium phthalimide is added and the reaction mixture is heated on a boiling bath for 1 hour.

Pour 57.5 g of 1-N-methylamino-2 into 2 liters of water.
-nitro-4-(N'-benzenesulfonyl, N'
-β-phthalimidoethyl)-aminobenzene is obtained.

Recrystallize from toluene. Melting point: 218°C.

Method (b): 0.05 mol (17.25 g) of 1-N-
Methylamino-2-nitro-4-N'-benzenesulfonyl-aminobenzene is dissolved in 5 o cc of dimethylformamide.

Add 13.97 g of β-bromoethylphthalimide and heat to 140° C. for 1 hour.

After cooling, the reaction mixture was poured into 1 liter of water to obtain a rubbery product.
Recrystallization three times from toluene yields 12 g of 1-N-methylamino-2-nitro-4-(N'-benzenesulfonyl, N'-β-phthalimidoethyl)-aminobenzene having a melting point of 218°C.

The yield is inferior to the previous method.

Second stage: 1-N-methylamino-2-nitro-4
- Preparation of (N'-benzenesulfonyl, N'-β-aminoethyl)-aminobenzene 0.119 mol (57 g) of 1-N-methylamino-2
-nitro-4- (N'-benzenesulfonyl-N
'-β-phthalimidoethyl)-aminobenzene 3
Dissolve in 50 cc of propanol.

Add 0.0% hydrazine hydrate to this solution. 2 Add 38 moles (11.9 g).

Heat on boiling bath for 1 hour.

The reaction mixture is cooled to room temperature and the formed phthal hydrazide is removed.

Concentrate the propanol solution to approximately 30 cc.

Cooling yields approximately 30 g of oily product.

Crystallizes slowly.

Recrystallize from an ethanol-water mixture. Melting point: 110°C.

I get the following result: Third step: l-N-methylamino-2
-Nitro-4-N'-β-aminoethylaminobenzene production method 0.0074 mol (2.6 P) of 1-N-methylamino-2-nitro-4-(N'-benzenesulfonyl N'- 15cc of β-aminoethyl)benzene
Soluble in sulfuric acid.

The reaction mixture was left at 15°C for 4 hours, then soaked in ice water for 15 hours.
Open at 0CC.

Make alkaline with sodium hydroxide.

Leave in the refrigerator overnight, and 1.5% of 1-N-methylamino-2-nitro-4-N'-β-aminoethylaminobenzene
Get 1.

Recrystallize from cyclohexane-benzene.

Melting point: 120°C.

Example 25 1-N'-methylamino-2-nitro-4-N'-β-
Second method for producing aminoethylaminobenzene The reaction for production is shown as follows.

0.30 mol (505') of 1-N-methylamino-2
- A mixture of nitro-4-aminobenzene, 250 cc of water and 171 cc of calcium carbonate is refluxed.

β-bromoethylamine hydrobromide 0. 3 3 0
A solution containing mol (67.6 g) in 150 cc of water is added little by little with stirring.

After the addition is complete, the mixture is refluxed for an additional hour and filtered while hot.

The filtrate was cooled to 0°C to produce 60% of the product in the form of monohydrobromide.
get g.

The monohydrobromide salt is dissolved in sufficient water and extracted with methyl isobutyl ketone to remove a small amount of unreacted starting product.

The aqueous phase was made alkaline with sodium hydroxide, and the melting point was 120.
1-N-methylamino-2-nitro-4-N'-β at °C
-40 g of aminoethylaminobenzene are obtained.

Example 2 6(a) 1-N-β-(diethylamino)-ethylamino-2-
The reaction for producing nitro-4-N'-di-β-hydroxyethylaminobenzene dihydrochloride can be shown as follows.

First step: Preparation of 1-N-benzenesulfonyl, N-β-(diethylamino)-ethylamino-2-nitro-4-acetaminobenzene 1-N-benzenesulfonyl-amino-2-nitro-
The sodium salt of 4-acetaminobenzene is used as the starting material.

This salt can be prepared by the method described in L'Oreal Luxembourg Patent No. 49213.

In the first step of this example, the above-mentioned Luxembourg patent no.
The derivative production method described in No. 213 is used.

In this method, dimethylformamide is used as a solvent, and the above salt is reacted with a dialkylaminoalkyl halide.

To date, and in the Luxembourg patent mentioned above, it has been shown that the reaction can be carried out in water.

However, it has been found that the yield of the reaction can be clearly improved when using dimethylformamide as solvent.

Such improvements are used in the manufacturing method of this example.

In the first stage of the production described in this example, 0.2 mol (71.4
g) 1-N-Benzene-sulfonylamino-2-nitro-4-acetaminobenzene is dissolved in 280 CC of dimethylformamide at 80°C.

0.2 mol (27.1 g) of diethylamine ethyl chloride is added quickly enough and the reaction mixture is boiled on a boiling bath for 2 hours.
Heat for 0 minutes.

Cool and pour into 1 liter of water to obtain 70 g of crude product.

This is treated with 2N sodium hydroxide solution to remove the starting product, washed with water and recrystallized from alcohol.

Melting point: 132°C.

Second step: Preparation of 1-N-β-(diethylamino)-ethylamino-2-nitro-4-amine benzene dihydrobromide 0.217 mol of 1-N-benzenesulfonyl, N-β
-(diethylamino)-ethylamino-2-nitro-4
- Acetaminobenzene with hydrobromic acid 2 with a specific gravity of 1.78
00 cc and 150 cc of water were added to the solution and heated on a boiling bath for 4 hours.

Cool to obtain 72 g of dihydrobromide.

The base obtained from dihydrobromide has a melting point of 65°C.

Third step: Preparation of 1-N-β-(diethylamino)-ethylamino-2-nitro-4-N'-cy-β-hydroxyethylaminebenzene 0.05 mol (20.7 t) of 1- N-β
-(jethylamino)-ethyl 2-nitro-4-aminobenzene is heated with 25 cc (0.2 mol) of 99.5% glycol bromohydrin (added to 5 cc of water and 102 calcium carbonate) on a boiling bath for 2 hours.

200 cc of water is added, the mixture is sifted, made alkaline with sodium hydroxide, and the sodium hydroxide solution is extracted with methyl isobutyl ketone.

The solvent was removed under reduced pressure and the oily residue was dissolved in 100% absolute alcohol.
The alcoholic solution is thoroughly cooled and saturated with dry gaseous hydrochloric acid.

Recrystallized from 20 cc of anhydrous alcohol to which 3 cc of concentrated hydrochloric acid was added to give 17 g of 1-N-β-(diethylamino)-ethylamino-2-nitro-4-N'-di-β-hydroxyethylaminebenzene dihydrochloride. get.

Melting point 140-145°C (decomposition).

Example 26 (b) 1-N-γ-(diethylamino)-propylamino-2
The reaction for producing -nitro-4-N'-di-β-hydroxyethylaminobenzene is shown as follows.

In the presence of calcium carbonate, glycol bromohydrin and 1-N-γ-(diethylamino)propylamino-2-
and nitro-4-aminobenzene dihydrochloride.

In order to obtain this dihydrochloride, diethylaminopropyl chloride and 1-N-benzenesulfonylamino-2-nitro-4-acetaminobenzene sodium salt were dissolved in dimethylformamide by the method described in Luxembourg Patent No. 49213. 1-N-benzene-sulfonyl, N-γ-(diethylamino)propylamino-2 obtained by condensing diethylaminopropyl chlorite
- Hydrolyzing nitro-4-acetaminobenzene with acid.

First step: Preparation of l-N-benzenesulfonyl N-γ-(diethylamino)-propylamino-2-nitro-4-acetaminobenzene. 0.6 mol (215 g) of the sodium salt are dissolved in 860 cc of dimethylformamide at 80°C.

Diethylaminopropyl chloride 0.62 mol (93
g) is added fast enough and the reaction mixture is heated on a boiling water bath for 1 hour.
Heat for an hour.

Cool and pour into 4 liters of ice-cold water to separate the crude product.

The crude product is treated with IN sodium hydroxide solution to remove small amounts of starting product, washed with water, dried and recrystallized from methanol.

163 g of recrystallized product are obtained.

Melting point: 98°C. 2nd step: Preparation of 1-N-γ-(diethylamino)-propylamino-2-nitro-4-aminobenzene. Heat to 80° C. for 4 hours in concentrated sulfuric acid.

The reaction mixture is poured into ice, made alkaline with sodium hydroxide, and the hydrolyzed product is extracted with ethyl acetate.

Ethyl acetate was distilled off under reduced pressure at °C, and the remaining oil was dissolved in methanol 1
Take it in 00cc.

This methanol solution was kept ice-cooled and saturated with dry hydrochloric acid gas.
38.2 g of 2-nitro-4-aminobenzene are obtained.

Melting point: 190°C (decomposition). Third step: 1-N-γ-(diethylamino)-propylamino-2-nitro-4-N'
-Production of β-hydroxyethylaminobenzene 0.1 mol (34f) of 1-N-γ-(diethylamino)-propylamino-2-nitro-4-aminobenzene and 10 cc of water were added.99.5 % glycol promhydrin 50 g (0.4 mol) and calcium carbonate 2
0g on a boiling bath for 2 hours.

Add 200 cc of water, make the solution alkaline with sodium hydroxide, and extract the alkaline solution with butyl alcohol.

The solvent was removed under reduced pressure, the oily residue was taken up in methanol, and the methanol solution was saturated with dry hydrochloric acid gas to prepare the dihydrochloride 3.
Obtain 0.12 g.

Melting point: 140°C (decomposition).

Example 27 Prepare a solution with the following composition.

β-[N-methyl-N(3-nitro-0.4g4-N'
- Methylaminophenyl] aminoethyl, methylpiperidinium iodide 10.5 molecules of ethylene oxide 5 g oxyethylene lauryl alcohol sodium carbonate pn 9 Add water to make 100 cc This solution will give you a dark blonde color. Treat hair.

Leave for 15 minutes.

Rinse shampoo - deep AUBURN
get.

Example 28 Prepare a solution with the following composition.

1-N-methylamino-2-nitro- 0.17g4-
N'-Methyl, N'-β-(methyl, hydroxyethylamine)ethylaminobenzene 1-N-γ-(diethylaminopropyl 0.5 g)-
Amino-2-amino-4-nitrobenzene Oxyethylated lauryl alcohol sodium carbonate with 10.5 molecules of ethylene oxide Amount to bring the pH to 9. Add water to make 100.

Treat 100% gray hair with this solution.

Rinse shampoo and apply BLONDD
ORE ROUX).

Example 29 Prepare the following solution.

1-N-methylamino-2-nitro- 0.015'4
-N/-Methyl, N'-β-piperidino-ethylaminobenzene 10.6 molecules of ethylene oxide-containing oxy 5 g ethylenic lauryl alcohol monoethanolamine Amount to adjust to pH 9 Add water to make 100 cc.

Use this solution on brown hair.

Rinse shampoo and use Bois De R
OSE) colors.

Example 30 Prepare the following solution.

1-N-β-piperidinoethylamine 0.084g
2-Nitro-4-N'-methylaminobenzene 1-N-r-(diethylaminopro 0.035 g pyl)amino-2-amino-4-nitrobenzene 10.5 molecules Containing ethylene oxide 51 oxyethylenated lauryl alcohol water Add to make 100cc.

Treat 100% white hair with this solution for 15 minutes.

BLONDROUX
).

Example 31 Prepare the following solution.

1-N-methylamino-2-nitro 0.152g-
4-(N'-β-hydroxyethyl, N'-β-diethylaminoethyl)aminobenzene 4-nitro-1,3-phenylenedi 0.030 g Amine 10.5 molecules Ethylene oxide containing oxy 5 g Ethylated lauryl alcohol 2N Sodium carbonate Add enough water to adjust pH to 9 to make 100 CC.

Treat ioo% gray hair with this solution for 15 minutes.

Rinse with shampoo and dye to beige (7) tone.

Example 32 Prepare the following solution.

1-N-β-piperidinoethylamine 0.235g
Add 10.5 molecules of 2-nitro-4-aminobenzene and 5 g of ethylene oxide-containing oxyethylene oxide to make 100 cc.

Treat light chestnut hair with this solution for 10 minutes.

Rinse shampoo and apply Acaju Violaine Pouisant (AC
AJOU VIOLINE PUISSANT).

Example 33 Prepare the following solution.

1-N-methylamino-2-nitro 0.514-N
'-(β-diethylamine)ethylaminobenzene dihydrochloride 1-N-methylamino-2-nitro 0. 2 fI
4-N'-β-piperidinoethylamine 10 molecules of benzene Ethylene oxide-containing oxide 51-ethylenated lauryl alcohol monoethanolamine Amount to adjust to pH 9 Water 100 cc
Treat light chestnut hair with the desired amount of this solution for 10 to 15 minutes.

Rinse shampoo and CHATAIN CLAIRA REFLE
TS MOIRE ROSE).

Example 34 Prepare the following solution.

β-[N-methyl, N-(3-nitro 0.4g-4-
N'-Methylaminophenyl]aminoethyl, methylpiperidinium iodide 1-N-methylamino-2-nitro- 0.2g4-N
'-(β-diethylamino)ethylaminobenzene dihydrochloride 1-N-methylamino-2-nitro-0.15g4-N
'-Methyl, N'-β-(methyl, hydroxyethylamino)ethylaminobenzene dihydrochloride 10.5 molecules ethylene oxide-containing oxygen 5g tyrenated lauryl alcohol 2N sodium carbonate Amount to adjust pH to 8.5 Add water to make 100cc do.

Treat dark chestnut hair with this solution for 20 minutes, rinse and shampoo to create a dark chestnut hair color.
IOLINE) staining is obtained.

Example 35 1-N-β-piperidinoethylamine 0.5g-2-
Nitro-4-aminobenzene l-N-methylamino-2-nitro- 0.1g4-N
'-β-diethylamine ethyl, N'-β-hydroxyethylaminobenzene 1-N-β-piperidinoethylamino 0.1g-2-
Nitro-4-N'-methylaminobenzene 10.5 molecules Oxygen oxide containing ethylene oxide 5g Thyrenated lauryl alcohol 2N Sodium carbonate Amount to make pH 7.5 Water Amount to make 100cc Wash dark chestnut hair with this solution for 20 to 25 minutes. Process.

Rinse and shampoo and stain with CHATAIN, which has a deep purple reflected light.

Example 36 1-N-methylamino-2-nitro-0.0314-
(N'-Methyl N'-β-aminoethyl)-aminobenzene 4-nitro-1,3-phenylenedia 0.05 fmin 10.5 molecules ethylene oxide-containing oxygen 7 g tyrenated lauryl alcohol Sodium carbonate Amount to bring the pH to 7 Add water Add 100 cc of this solution to 100% white hair for 15 minutes.

Rinse and shampoo to obtain a beige tone. Example 37 1-N-β-(methyl, hydroxye) 0.1 4g
methyl)aminoethyl-2-nitro-4-■-methylaminobenzene 1-N-γ-(diethylaminopropyl 0.05g)
Amino-2-amino-4-nitrobenzene 10 molecules of ethylene oxide-containing acid 5 g oxyethylated lauryl alcohol Sodium carbonate Amount to adjust pH to 9 Add water to make 100 cc.

Treat 100% gray hair with this solution for 15 minutes.

Rinse and shampoo. Dyed with blonde roux.

Example 38 Prepare the following solution.

β(N-(2-nitro-4-N'-methy 0.21gruamino)phenyl]aminoethyl, methylpiperidinium iodide 1-N-γ-diethylaminopropyl) 0.05F amino-2-amino-4 - Nitrobenzene 10.5 molecules Oxygenate containing ethylene oxide 5 g Thyrenated lauryl alcohol monoethanolamine Amount to make pH 7 Water Amount to make 100 cc Treat 100% white hair with this solution for 15 minutes.

Rinse and shampoo. Akaju Quibble (copper color)
Colored with Claire (ACAJOU CUIVRECLAIR).

Example 39 Prepare the following solution.

β(N-(2-nitro-4-amine) 0.28g-
phenyl]aminoethyl, methylpiperidinium iodide 10.5 molecules Oxygenate containing ethylene oxide 2g Thyrenated lauryl alcohol Sodium carbonate Amount to adjust to pH 9 Add water to make 100cc.

Treat light chestnut hair with this solution for 10 minutes.

Rinse and shampoo to dye your hair a deep shade.

Example 40 Simmer the following solution.

1-N-methylamino-2-nitro- 0.09g4-
(N'-methyl, N-β-aminoethyl)-aminobenzene dihydrochloride l-N-β-(methyl, hydroxyethyl)amine ethyl amino-2-nitro-4-N'-methyl Amine benzene β [N-(2-nitro-4-N'-methylamino)-phenyl 0.13g aminoethyl, methylpiperazinium iodide containing 10.5 molecules of ethylene oxide 2g oxyethylated alcohol monoethanolamine Add enough water to adjust pH to 9 to make 100 cc.

Treat light chestnut hair with this solution for 10 minutes.

It is dyed a deep acaju violet.

Example 41 Prepare the following solution.

1-N-β-Aminoethylamino-2 0.36 g-Nitro-4-N'-bis-β-hydroxyethylamine benzene dihydrochloride 10.5 molecules of ethylene oxide containing oxy 5 g Ethylated lauryl alcohol Sodium carbonate pH 7 Amount to make 100 cc of water Treat 100% gray hair with this solution for 15 minutes.

Rinse and shampoo. Blue Biolage (BLE
U VIOLAGE).

Example 42 Prepare the following solution.

[l-N-methylamino-2-nitro 0.73g-4
-N'-β-aminoethylaminobenzene] monohydrobromide 10.5 molecules Oxygen oxide containing ethylene oxide 5g Thyrenated lauryl alcohol 2N, Na2CO3 Water to pH 8 Amount to make 100g Natural light chestnut colored hair with this composition Process for 10 minutes.

Rinse and shampoo.

dyed deep purple.

Example 43 [1-N-β-hydroxyethyla 0. 2 96
g Mino-2-nitro-4-N'-β-diethylaminoethylaminobenzene dihydrochloride 1-N-β-aminoethylamino-0.042g2-
Nitro-4-methyl 5-aminobenzene 10.5 molecules Oxygen oxide 2g Ethylated lauryl alcohol 2N, Na2CO3 solution Amount to make pH 9 Water Amount to make 100g Treat 100% gray natural hair and leave for 10 minutes .

Rinse, shampoo and wash. Dyed with blonde roux.

Example 44 Prepare the following stain composition.

[l-β-hydroxyethylamine 0. 3 0 4
f-2-Nitro-4-(N'-methyl, N-β-diethylaminoethyl)aminobenzene dihydrochloride 1-β-aminoethylamino-2- 0.042g Nitro-4-methyl-5-aminobenzene Oxygen containing 10.5 molecules of ethylene oxide 2 g Ethylated lauryl alcohol 2 N, Na2CO3 solution Amount to pH 7 Water Amount to 100 g Strongly brown hair is treated with this composition.

Leave it on for 10 minutes, then rinse and shampoo.

Strong ACAJOU CUIVRE
).

Example 45 Prepare the following stain composition.

(1-N-Methylamino-2-nito 0.233g rho-4-N'-ω-aminobutylaminobenzene) dihydrochloride 1-β-aminoethylamino-2- 0.052g nitro-4-methyl- 5-Aminobenzene 10.5 molecules Ethylene oxide containing 2 g Ethylated lauryl alcohol 2N, Na2CO3 solution Amount to make pH 9 Water Amount to make 100 g Treat 100% gray hair with this solution for 10 minutes.

Rinse, shampoo and wash. Blonde Honsenakure (
BLONDE FONCE NCRE).

Example 46 Prepare the following stain composition.

(l-N-β-aminoethylamino- 1.2g2-
Nitro-4-aminobenzene] dihydrochloride Containing 10.5 moles of ethylene oxide 2 g of ethylene oxide Amount to pH 8 with tyrenated lauryl alcohol 2N, Na2CO3 solution Amount to make 100 g of water 100% white natural hair treated with this composition do.

Leave it on for 10 minutes, rinse and shampoo. It is dyed a deep red with a slight purple hue.

Example 47 (1-N-methylamino-2-nitro 1.5g-4-
Amine hexylaminobenzene] dihydrochloride 10.5 mol ethylene oxide-containing acid 5.0 g oxyethylated lauryl alcohol 2N, Na2CO3 solution to pH 8 water Quantity to 100 g 100% gray natural hair is treated with this composition.

Wait 10 minutes, then rinse and shampoo. Colors very deep purple.

Example 48 (1-N-methylamino-2-nitro 0.5 0g
-4-N'-γ-(methyl, β-hydroxyethyl)-aminopropylaminobenzene] dihydrochloride Oxygenate containing 10.5 moles of ethylene oxide 5.00 g Thyrenated lauryl alcohol 2N, Na2CO3 Amount to pH 9 Water 100 g Treat chestnut-colored hair with this solution for 20 minutes.

Rinse, shampoo and wash.

dyed deep purple. Example 49 Prepare the following stain composition.

1-N-β-(diethylamino)-ethylamino-2-nitro-4-N'-di-β-hydroxyethylaminobenzene dihydrochloride l0.5 mole ethylene oxide-containing oxy 5 g ethylenic lauryl alcohol 2N, Na2C03 Amount to pH 7 Quantity to 100 g Water Treat golden-brown hair with this composition for 10 minutes.

Rinse, shampoo and wash. It is dyed a maroon color with pearlescent reflections.

Example 50 Prepare the following stain composition.

1-N-β-(diethylamino)-0.369gethylamino-2-nitro-4-N'-di-β-hydroxyethylaminebenzene dihydrochloride 1-N-β-aminoethylamino-0.021g2-
Nitro-4-methyl-5-aminobenzene 10.5 moles Oxygen containing ethylene oxide 4.51 Ethylated lauryl alcohol 2N, Na2CO3 solution Amount to make pH 9 Water Amount to make 100 g Treat 90% gray hair with this solution for 10 minutes do.

Rinse, shampoo and wash.

It is dyed a light blonde with a golden hue.

outside the scope of the invention. All desired modifications may be made to the methods of manufacture and use in the examples described above.

Example 51 Prepare the following stain composition.

1-N-γ-(diethylamino)-p 0. 4 3
g Lobylamino-2-nitro-4-N'-di-β-hydroxyethylaminobenzene dihydrochloride 10.5 moles Oxygenate containing ethylene oxide 1.5 g Thyrenated lauryl alcohol 2N, Na2CO3 solution Adjusted to pH 9 Water 100 g 90% gray hair is treated with this composition for 15 minutes.

Rinse, shampoo and wash. It is dyed a deep purple-gray color.

Example 52 Prepare the following stain composition.

4-Nitro-3-β-aminoethyla 0.02g Mino-N,N-dimethylaniline 1-N-γ-(diethylamino)-p 0.38g Ropylamino-2-nitro-4-N'-di-β-hydroxy 10.5 moles of ethylaminobenzene Oxygen containing ethylene oxide 1 g Thyrenated lauryl alcohol Na2CO3 2N solution Adjusted to pH 8.5 Water 100 g Amount 90% Gray hair was treated with this composition for 10 minutes. Rinse and shampoo. Wash.

It turns grayish blonde.

Claims (1)

[Scope of Claims] 1 General formula [wherein R is hydrogen or a lower alkyl group; R' and R'' are hydrogen, lower alkyl, or lower hydroxyalkyl; R''' is a formula (in the formula, n is 2 represents an integer of ~6, R1 and R2 are selected from the same or different lower alkyl groups, hydrogen or lower hydroxyalkyl groups, or form a heterocycle together with the nitrogen atom, and when the amine group is tertiary, In some cases, the amino group may be quaternized); however, when the nitro group is in the meta position with respect to the amino group to which R''' is attached, the amino group is in the ortho position with respect to the nitro group. Some amino groups are not tertiary, R' and R'' do not represent hydrogen at the same time, and the nitro group is in the meta position with respect to the amino group to which R''' is attached, n is 2, R' is hydrogen, When R'' is methyl, and R is hydrogen or a methyl group, neither R1 nor R2 represents a lower alkyl group]. Hair dyeing composition.