JPH023634A - Production of n4-substituted 1-methoxy-2, 4-diaminobenzole, n4-substituted 1-methoxy-2, 4-diaminobenzole intermediate product and aqueous colorant for keratine fiber - Google Patents

Abstract

PURPOSE: To obtain the subject substance by a method in which 4-methoxy-3- nitroacetoanilide is treated with an inorganic strong acid to be converted into an aniline derivative, which is reacted with alkyl chloroformate, and the obtained carbamate is made basic and further reduced.

CONSTITUTION: A compound of formula I is deacylated by heating with inorganic strong acid in an aqueous solvent at 60-95°C for 3-8 hr into an aniline derivative, which is reacted with a compound of formula II (X¹ is H; Y¹ is C or CH₂Cl, or X¹ is CH₃; Y¹ is Cl) at 70°C-reflus temperature in the presence of an acid binder, and the product is made basic to obtain a compound (new material) of formula III (A is H; B is OH or CH₂OH, or A is CH₃; B is OH). Next, the product is reduced using base metal or reduced catalytically to obtain a compound of formula IV [R is -CH₂-CH(A)-B]. The compound of the formula IV is useful as a coupler for an aqueous colorant for keratin fibers and is novel excepting the combination in which A is H and B is OH.

COPYRIGHT: (C)1990,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a compound of the general formula I: [wherein R is a compound of the general formula Ia 0H2-CH(A)-B (Ia
), provided that in the above formula Ia, when a hydrogen atom is represented by a hydrogen atom, B represents a hydrophosyl group or HO-
CH2 group; When A represents a methyl group, B is a hydrosyl group] 7
-2.4-Diaminopenzole production method N4-substitution 1
- Methomuk 2.4-Diaminopenzole, intermediate products and aqueous colorants for keratin fibers.

[Conventional technology]

For hair dyeing, color developing components (e.g. p-)unilene diamine, p-aminophenol, T)-diamino t-lysine, etc.) and coupling components (tatoeba phenol, resorcin, m-aminophenol, m-7 Of particular importance are the so-called oxidative dyes which are produced by oxidative coupling with 22-diamines, naphthols, pyrazoles, etc.).

This is because these dyes are produced already under the limit conditions of practical technology (for example low dyeing temperatures and short dyeing times) in strong shades and with very good fastness properties.

Similarly, these oxidative dyes are important in the dyeing of fur.

Good oxidative dye pre-products must first of all fulfill the following technical prerequisites: These pre-products must be able to form the desired oxidative coupling with the respective coupling or developer component. The dyes must be produced in sufficient strength, and it is desirable that these dyes have sufficient dyeing and leveling power on hair or fur.

The dyes formed must generally be stable, in particular washfast, sunfast, sweatfast and heat stable.

In particular, these dyes should not have a tendency to shift in initial shade under the conditions after dyeing.

Moreover, these dyes must be toxicologically and dermatologically safe.

These requirements cannot always be reconciled. This is especially true for so-called blue couplers (B
laukupler). In this case, with respect to 2,4-diamino-anisole, according to the state of the art, it is almost completely satisfactory from a practical technical standpoint in terms of -, but there are compounds that are toxicologically controversial in other respects. do.

The compound 2-amino-4-(β-human e1atdiethylamino)anisole is often described as a color coupler in the prior art, for example in German published patent application No. 3,132,885;
Specification No. 51377, Specification No. 3625916 (1st paragraph, line 55: 4th paragraph, line m10), No. 354
5! Specification No. 171 (page 2, lines 24/25; se
schretbung page 5, line 62), $344
Specification No. 1148 (page 1, line 24 and Example 2)
and Specification No. 3609504 (Page 5, No. 20)
row and Example 6).

After a thorough search of the literature, we were unable to find a method for preparing cudiethylaminoanisole in 2-amino-4-(β-hydro).

[Problem to be solved by the invention]

Therefore, the objects of the present invention are a) to fully satisfy the staining problem, and b
) technologically inventive in producing known and novel compounds such as blue cassilla, which are toxicologically free and c) can be produced economically, such as 2°4-diaminoanisole and its derivatives; The purpose is to provide a method.

[Means to solve the problem]

Dell couplers that meet the above requirements are standard size! It was not previously known that these compounds and their salts could be economically produced with high purity from commercially available raw materials.

and -C1 The subject of the present invention is a method described at the beginning, in which a) a group represented by the formula (Ia); where, when A represents a hydrogen atom, B is a hydroxyl group or) 10-CH2 group;
When A represents a methyl group, B is a hydroxyl group.
1
7 is converted into 4-methoxy6-nitroaniline of formula I by treatment with a strong inorganic acid in an aqueous medium, in which xl and 71 are as defined above;
The carbamate represented by the general b) obtained under basic conditions is converted into the compound of the formula ■; the formula ■c1-Coo-CH (
Xl)-CH2-Yl (ff) [wherein X
i is a hydrogen atom and yl is a chlorine atom or (J-CH
2 groups, and when xl represents a methyl group, Yl is a chlorine atom] Equimolar amount of glue C: 1c! 1
c) the resulting general compound V; in which A and B represent the same as described for formula Ia; d) - up to ■ and optionally e) converting the obtained compound of maximum ■ into a salt using an inorganic or organic acid in a manner known per se.
A process for the preparation of N4-substituted 1-methoxy-2,4-diaminopenzoles and their salts with inorganic or organic acids.

Next, details of the method according to the present invention will be explained.

In step a, 4-methomal7-3-nitroacedoe=
Inorganic strong fR in an aqueous medium by a method known per se.
(e.g. hydrochloric, sulfuric or phosphoric acid) for about 6 to 8 hours to about 60-95°C ("Ba1lsltsinaHandbuah a
er organiachen Chemie”,
Publisher s'pr1ng Varlag, Volume 13, Er
(see page 1201). In this case, surprisingly, a water-dilutable inert organic solvent, such as methanol, dimethoxyethane, ethanol, about 10 to 15 hydroxides, is added to the reaction mixture, which was previously assumed to be present in a pure aqueous medium. It could then be confirmed that additional purification of the alternative deacylated product could be carried out without incurring more expense or yield loss.

The completely reacted batch is neutralized with an inorganic base, such as aqueous sodium hydroxide solution, and after cooling to about 5-10° C., the reaction product of formula I is separated, and this product is filtered or centrifuged. It can be isolated by the minute corner. Usually with water
Washed and dried.

Reacting the substituted compound with the general chloroalkyl ester of chloroalic acid leads to the known selective hydroxylation of amines with the chloroalkyl ester of chloroalic acid and subsequent basic treatment of the chloroalkyl carbamate. (written by Otto, '''J
, Prakt.

Chew, , m 2nd edition, Volume 44, Page 15 (18
1990); J, S, Pierce and R0A
aams, “, 7. Am, Chsm, 8oc,
, Vol. 45, p. 790 (1923): 1IJ describes in detail the reaction of chloroalic acid chloroaltyl ester with a primary aromatic amine]. -Maximum V
In order to form the compounds, inert organic solvents, such as dioxin, dimethoxyethane, C1<4-alcohol, dimethylformamide, tetrahtomifuran, doluol, chloropenzole, methyl ethyl ketone, ethylene glycol dimethyl ether or The compound of Part I in diethylene glycol dimethyl ether is charged and heated to a temperature between room temperature and reflux temperature, in particular 70 DEG C. to reflux temperature. Subsequently, the chlorozaic acid roloalyl ester of up to 1 is fed in equimolar amounts or in slight excess. Optionally the solvent can be combined with water.

In this case, the acid binder can be co-introduced or the acid binder can be added in parallel to the ester in the loroloza acid loroloal as described above.

Acid binders include bases, such as alkali metal hydroxides, alkali metal hydrogen carbonates, alkali metal carbonates, alkaline earth metal oxides, alkaline earth metal hydroxides, alkaline earth metal hydrogen carbonates and alkaline earth metals. Mention may be made of metal carbonates and tertiary organic amines. Reaction time is about 4-12 hours.

The carbamate is isolated after complete reaction, in which case a) water is added and the patch is stirred cold or t-fi
b) Separation of the inorganic salt and partial or total distillation of the solvent, optionally cooling, for example by the addition of ice, whereby the carbamate of general formula V formed is Precipitates almost quantitatively in solid form.

Strong bases (in this case alkali metal or alkaline earth metal hydroxides are mentioned, preferably 10 to 50% aqueous soda solution or caustic potash solution are used)
By treatment with -maximum V carbamate can be obtained by formula ■
The hydrochloride compound can be converted into a compound.

Two processes are advantageous: a) The carbamate of formula V is introduced into a water bath in an organic solvent, such as (01-C4)-alcohol, a water-miscible ether or a mixture thereof, and then allowed to cool at room temperature to approximately A calculated strength soda or potassium solution, i.e. 6 mol per mol of carbamate, is fed and stirred until complete reaction, optionally with heating until reflux occurs. can.

b) Charge a strong soda solution or a strong potassium solution, which may be diluted with said solvent, and - carbamate of up to V in pure form or in one of said organic solvents at room temperature to approx. It is fed at a temperature of 70° C. and then stirred until complete reaction. For both methods, approximately 12 to 1
A reaction solution having a value of 4 can be neutralized to a PIL value of from about 7 to about 10 by addition of an organic or inorganic acid for work-up. After subsequent separation of the inorganic salts, addition of distilled water if necessary and removal of the organic solvent, the general product is isolated.

In the case of the two methods mentioned above, the reaction time is clearly shortened by adding about 25-30% by weight of the organic solvent into the aqueous reaction patch, while the inorganic salts still remain dissolved in the reaction medium. .

Approximately 4-12 hours are required for this reaction.

Compounds of general size 1 can be prepared by reducing compounds of general size 1 with base metals or by catalytic reduction.

For catalytic reduction, conventional catalysts are used, such as Raney nickel, palladium on activated carbon, platinum on activated carbon. The reaction temperature is room temperature to 1200C1, especially 40 to 1.00C.
'O, the pressure is normal pressure ~ 100 par, especially 20~
It is a 7o pearl.

As solvents used are the customary solvents, such as water, doluol, glacial acetic acid, lower alcohols and niter compounds. After reduction and separation of the catalyst, the general product can be isolated in free form by solvent t-distillation in a cloudy gas, but preferably (also ) is converted into a salt by adding an equivalent amount of acid kfA, the salt being either precipitated directly or obtained after distillation of the solvent.

For salt formation, inorganic acids include, for example, hydrochloric acid, sulfuric acid,
Phosphoric acid is preferred; however, suitable organic acids include, for example, acetic acid, protonic acid, lactic acid or citric acid.

[Example] Backing method C) The following example details the production method. Preparation A of 1-methoxy-2-2) Preparation of 0-4-aminopenzole: 1-methoxy-2-2 -Nitro 4-acetyl-aminopenzole 650.51! (5 moles), 1500 - of water,
A mixture consisting of ethanol/l15001j was heated to 80°C.
and add 1062 g of concentrated hydrochloric acid. Furthermore, 88
Stir for an additional 372 hours at °C, then cool to 75 °C,
- Adjust the value to 7.0 using aqueous soda solution. After cooling the batch to about 10° C., the product is filtered with suction, washed with water and dried.

Yield: 475.5,! il (94th coefficient of theoretical value) -
Points: 54-559C B, Preparation of β-chloroethyl-N-(3-nitro-4-methoxyphenyl)-carbamate: 1-methoxy-2-nitro-4-aminopenzole 4 prepared as above
20.59 (2.5 soles) to calcium carbonate 135.
li' and 1275 ml of monoethylene glycol dimethyl ether and 1 soy of water and heated to 78°C.

Chlorochloric acid-.beta.-chloroethyl ester is added dropwise to this mixture over a period of 3 hours, and the reaction mixture undergoes a slight reflux due to the evolution of carbon dioxide.

Stir under reflux for another 1 to 2 hours until complete reaction,
Cool to 5° C. and add water and ice. The precipitated product was filtered off with suction, washed with water and dried.

Yield: 663g (theoretical 96.5g) Melting point 283-8
4°C IR-spectrum: see Figure 1 IH-NMR-spectrum: (CDσ3)δ=3.
6-3.8(t s 2HN CH2-0); δ=3
．． 9(a,3)i10-CH5): δ=4.
! l −4,5(t, 2H.

CH2-CJ); δ=6.9-7.5 (
m%3H%Ar-H)ppm c, 1-Metho17-2-nitro-4-(β-hydroxyethylamino)-penzole production: β-chloroethyl-N-(6- Nitro-4-methoxyphenyl)-carbamate 618,9 (2,25 mol) in water 2025! A and ethanol 67 S WLt
Insert it inside. The reaction mixture was heated to 60 °C and 1!2
7661111: Add drops. After stirring for 21!2 hours at 60° C., the batch value is adjusted to 8.0 with acetic acid and the reaction mixture is slowly cooled. The precipitated product is filtered with suction, washed with water and dried at 50° C. in a vacuum box.

Yield: 439.59 (92 coefficient of theoretical value) [Phase] point near 9°G IR spectrum: See Figure 2 1! (-NMR-spectrum: (CD(J3)δ=
3-3.2 (t% 2H% CH2-N): δ=
5.6-3.8(2HXCH2-0); δ=3
．． 8 (11,3H.

0-CH5) : δ= 6.75-7.25 (
m, 3H.

Ar-H)ppm.

D. Production of 1-methoxy-2-amino-4-(β-hydroxyethylamino)-penzole sulfate: 1-methoxy-2-nitro-4-(β-
Hydroxyethylamino)-Pen 1 Nor 159P(0
,75+=L) together with 3 Q Q mA of methanol into a special steel autoclave and about 2
．． 9t-[ and catalytic reduction at 70° C. using 20 bar hydrogen pressure for 5 hours. 1 After removing the solvent, d adds 73.5.9 parts of sulfuric acid to the solution. After the batch has cooled, the precipitated product is filtered off with suction, the residue is washed with a little methanol and dried at about 50° C. in a vacuum box.

Yield: 197. ! i' (94th coefficient of theoretical value) Melting point: -1
48-149°C IR spectrum: See Figure 3 1H-1flJR-spectrum: (r)MSO-as
) δ= 3.15-3.4 (t, -2H,, ca2
-N): δ=3.3-3.75 (2H, CH
2-0; δ= 3.9 (a, 3H, 0-CH5)
; δ= 7.2-7.9 (m 13H, Ar-H
)ppm・Example 2 A, r-riaopropyl-N-(3-nitro-4-
Preparation of methoxyphenyl)-carbamate: 168.2 g (1 mol) of 1-methoxy-2-nitro-4-aminopenzole (prepared according to Example 1A) and 549 g of calcium carbonate were dissolved in monoethylene glycol dimethyl ether/water. mixture (9:1) at 570 mA,
Condition F described in Example 1B was followed by chloroalic acid-γ-C! React with loderovir ester 164I and work up accordingly.

Yield: 280 g (97th coefficient of theoretical value) - point = 74°O IR spectrum: See Figure 4 "H-NMR-spectrum) v: (CDCl2) δ =
1.9-2.15 (2H, C-CHa-C); δ=
3.5-3.7(t s 2H% CH2-0aδ=
3.8 (a, 3H.

0-CH5) ; δ= 4.2-4.4 (t, 2)!
.

-CH2-CJ); δ=6.9-7.6 (m,
3H.

Ar-H) ppm.

B. Preparation of 1-methoxy-2-nitro-4-(γ-hydroxyzolobylamino)-penzole: γ-chloropropyl-N-C5-nitro-4-methoxyphenyl)-carbamate 216.
9 (0.75 mol) in water 675 mol under the conditions described in Example 1C.
The mixture is reacted with 250 g of a 50% strength potash solution in 225 g of ethanol and 225 g of ethanol. After section PI-111, the product is extracted with acetic acid ester.

Yield: 16ON oil (theoretical value 94) IR spectrum: see Figure 5 1H-NMR-spectrum): (CDCl2) δ = 1
．． 7-2.0 (2H, C-CH, -C): δ
= 3.1 -3.3('', 2H% CH2-N)
s δ = 3.6-3.8 (2H, 0H2-0;
δ=3.9 (s, 3H, o-CH3): δ=
6.7-7.3 (m, 3H%Ar-H) ppm.

c, Preparation of 1-methoxy-2-amino-4-(r-hydroxy-7-derogylamino)-penzole sulfate 1-methoxy-2-amino-4-(γ-hydro-siderogylamino)- Pe/sol (produced in Example 2B) 11
5 g (0.5 mol) t-hydrogenated under the conditions described in Example 1D and III! Separate from lI medium and sulfuric acid 49! i and isolate the product.

Yield: 140 g (95% of theory) Melting point: 166-168°C (decomposed) IR spectrum: See Figure 6 IH-NMR spectrum: (DMSO-(16)δ
= 1. +5-1.9 (2H, C-CH, -8);
δ=3.1-3.3(t121'l, CH2-
N): δ = 3.4-5.6 (3% 2H, CH2-
0); δ=3.8(1,3H.

0CH3); δ=6.5-7.0 (mt3a
.

Ar-H)ppm・Example 3 Salt production A, (2-ri no-1-methyl)-ethyl A/ -N-(
Preparation of 3-nitro-4-methoxy-phele)-carbamate: 16.8 g (0.1 mol) of 1-methoxy-2-2) o-4-aminopenzole (prepared in Example 1A) and carbamyl Calcium salt 5.4, li' t-monoethylene glycol dimethyl ether/water mixture (9:
1) Chlorozacic acid in 55-M under the conditions described in Example 1B.
(2-chloro-1-methyl)-ethyl ester 16.5
g and worked up accordingly.

Revenue! : 28.5.9 (I[099%) melting point near 2°C 8, Preparation of 1-methoxy2-nitro-4-(β-hydroxyzolobylamino)-penzole: Preparation in Example 3A (2-ioa-1-methyl)-ethyl-N-(3-di)l:l-diphenyl in 4-meth)-
Carbamate 27.4.9 (0,095 mol) in water 85
504 with a strong potash solution 32.5.9 under the conditions described in Example 1C in mj and ethanol 3oWLt. After pH adjustment, the product is extracted with acetic acid ester.

Yield: 20g red oil (93% of theory) Preparation of C,i-methoxy-2-amino-4-(β-hydroxyzolobylamino)-penzole II salt: Produced in Supplementary Note B 2-nitro-4-(
18. I
II (0,08 mo #) t-1 Hydrogenated using 0.31 nickel in 180 mJ of methanol under the conditions described in Example ID, separated from the catalyst, yielding 11 g of sulfur! 7.89
The product is isolated after t-coagulation and evaporation of the solvent.

Yield: 16 g (681 theoretical).

General formula 1 as a coupling component: [In the formula, R is a general
represents a group represented by a), provided that in the above formula Ia, A represents a methyl group and B represents a hydrodP-ful group;
or, when A is a hydrogen atom, B represents 1 (represents 0-CH2 group), the compound according to claim 2, a color developing component generally used for oxidative hair dyeing, and hair according to the present invention containing gold. Colorants for hair dyes, i.e. hair dyes, are distinguished by good storage violet stability and, when in use, provide very strong shades ranging from reddish-brown to blue-black, as well as good fastness of the resulting dyes. .

When used in hair dyes, the coupling component is generally used in approximately equimolar amounts to the color developer component used.

However, it is not disadvantageous to use a certain excess or deficiency of the coupling component, even if equal dosages prove advantageous.

The compounds according to claim 2 to be used as coupling components in the present invention can be used as such or in the form of salts with inorganic or organic acids. It can be used as a salt, prot-ionate, lactate, citrate.

The novel compound as a coupling component according to claim 2 is present in the hair dye according to the invention in an amount of about 0.001 to 5.0% by weight;
In particular, it is desirable that it be contained in a concentration of 0.2 to 3.0% by weight.

Furthermore, it is not necessary to use only one type of color developer component; on the contrary, it is also possible to use a mixture of various color developer compounds.

Examples of color developing components to be used are primary aromatic or heteroaromatic amines having another functional group in the p-position;
For example, p-phenylene diamine, p-tolylene diamine, p-aminophenol, N,N-dimethyl-p
-phenylene-diamine, chloro-p-7-22-diamine, 7-p-p-phenylene-diamine, 2,5-diaminopyridine and derivatives thereof, additionally containing one or several functional groups, nine For example, OH- group, NF2- group, N
Mention may be made of further compounds of the abovementioned type, such as those having an HR group or a NRR group, in which R represents an optionally substituted alkyl group having 1 to 4 carbon atoms.

Moreover, it is not necessary to use only the coupling component according to the invention; on the contrary, in order to obtain a specific sex sensation, other coupling components already known and used, such as α-naphthol, 3. 4-Diaminobenzoic I! !
! nsorcin, 4-chlororesorcin, m-aminophenol, m-phenylenediamine, m-tolylenecyamine, 2,4-zoaminoanilin, birocatemus,
Girogallol, 1,5- or 1,7-dihydro-naphthalene, 5-amino-2-methylphenol, 6-
It is also possible to use derivatives of amino-2-methylphenol or the abbreviated compounds, such as 2,4-diaminophenyltetrahydrofurfuryl ether according to DE 35 16 906.

Additionally, the hair dye can contain conventional direct dyes if necessary to obtain a particular shade. Oxidative coupling, ie color development, can in principle be carried out with atmospheric oxygen as with other oxidative dyes. However, it is advantageous to use chemical oxidizing agents.

The hair dye according to the invention is an aqueous hair dye. Aqueous hair dyes mean all hair dyes that contain water in some way, such as creams, emulsions, dels or simple solutions. Common additives in hair dye compositions, creams, emulsions or gels are solvents, such as water, lower fatty auxiliary alcohols such as ethanol, propatool and isopropanol, or glycols,
For example, glycerin and glycol etherification, eg propylene glycol, as well as anions, cations,
Wetting agents or emulsifiers consisting of the class of amphoteric or nonionic surfactants, such as fatty alcohol sulfates, alkyl sulfonates, alkylpenzole sulfonates, trimethylammonium salts in alcohol, lupetaine in alcohol, diethyl fatty alcohols, diethylated fatty alcohols. Nonylphenols, fatty acid alkanolamides, diethyl fatty acid esters, and also thickening agents such as higher fatty alcohols, starches, cellulose derivatives, petrolatum, paraffin oil and fatty acids.

The listed ingredients are used in amounts customary for such purposes, such as wetting agents and emulsifiers in concentrations of about 0.5 to 30% by weight, thickeners in amounts of about 0.1 to 25% by weight. It may be included in these cosmetics.

Depending on the composition, the hair dyes according to the invention can be weakly acidic, neutral or alkaline reactive.

In particular, the hair dye according to the invention has a value in the alkaline range between 7.5 and 11.5, in which case the adjustment is preferably carried out with ammonia.

However, it is also possible to use organic acids, such as monoethanolamine and triethanolamine, or inorganic bases, such as sodium hydroxide and potassium hydroxide.

In the case of the method of dyeing hair 1e, a combination of a color developing component known in hair dyeing and at least one compound according to claim 2 as a coupling component, and in some cases additionally known methods Immediately before use, the hair dye according to the invention containing a coupling component and a substantive dye is mixed with an oxidizing agent and this mixture is applied to the hair. Oxidizing agents for color development include, for example, hydrogen peroxide as an aqueous solution and its addition compounds to urea, melamine or sodium borate, and hydrogen peroxide addition compounds of this type, as well as potassium peroxonisulfate and rum. A mixture of: In this case, the stool temperature is 15-4
Move within the range of 0°C. After a development time of approximately 60 minutes, the hair dye is removed from the electrical equipment to be dyed by washing. Thereafter, the hair is washed with a mild yande and dried.

The following example illustrates the object of the invention in detail: Example A Hair dye in cream form 1-Method 2-Amino-4-Cr-Hydro dipropylamino) Penzole sulphate 3.209p -Phenylenediamine/t'AfR salt 1.951m-Aminophenol 0.10g oil 1! ! !
2.009 polyacrylic acid
0.10. ? Sodium sulfite (no water) 0.50g
5 IJ alcohol-cylicol ether sulfate, sodium salt (28% aqueous solution) 5.50 I cetyl alcohol 15.0 (), li'
water 73
．． 65.9100.00.9 The above hair dye sogt - Hydrogen peroxide solution 5 immediately before use
0. Mix with li+. This mixture was applied to light brown natural hair for 30 minutes at 40'C. The dye is then washed off, the hair washed with 7 yen and dried. A saturated, intense blue-black tone was obtained.

Everyday Cream-type hair dye 1-methoxy 2-amino-4-(β-human c2J?cupaviramino)-penzole.
Sulfate 0.4091-Methyl-2-hydroquine-4-aminobenzole 2-chloro-p-phenylenecyamine oil Sodium sulfite polyacrylate (water free) Lauryl alcohol-diglycol ether sulfate, o, os g O, 32g 2.00,! i' 0.10g 0.509 Sodium salt (28% aqueous solution) 3.50,9 Cetyl alcohol 15.009 Water
78.139
100.009 One coat of hair dye 509 i! Mix with 50 g of 6L4 hydrogen peroxide solution. This mixture t 40 '0 at 60
Act on natural hair for minutes and half a day. The dye is then washed out, the hair is jump washed and dried. A powerful lavender with saturated colors (Lavand・1b)
1au)-tone was obtained.

[Brief explanation of the drawing]

Figure 1 shows β-chloroethyl-N- in Production Example 1-B.
Infrared absorption spectrum diagram of (3-nitro-4-methodiphenyl)-carbamate, Figure 2 shows the infrared absorption spectrum of 1-methoxy-2-nitro-4-(β-hydroxyethylamino)-penzole in Production Example 1-c. Infrared absorption spectrum diagram, Figure 3 shows 1-methquine-2 in Production Example 1-D.
-amino-4-(β-hydroxyethylamino)-pe/
The infrared absorption spectrum diagram of Sol.1 competitive salt, Figure 4 is γ-chlorobu cIV in IA Preparation Example 2-A! Lou N
-(3-nitro-4-methodiphenyl)-carbamate infrared absorption spectrum diagram, Figure 5 is Production Example 2-B
1-methI? Figure 6 is an infrared absorption spectrum diagram of v-2-nitro-4-(γ-hydromodipropylamino)-penzole, and Figure 6 shows the 1-methoxy-2-amino-4-(r-hydroxy FIG. 2 is an infrared absorption spectrum diagram of progylamino)-penzole sulfate.

Claims (1)

[Claims] 1. General formula I: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R is the general formula Ia: -CH_2-CH(A)-B(Ia) represents a group shown in the formula Ia above, provided that when A represents a hydrogen atom, B represents a hydroxyl group or a HO-C
H_2 group; when A represents a methyl group, B is a hydroxyl group] and their salts with inorganic and organic acids. a) formula I
I: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) By treating 4-methoxy-3-nitroacetanilide shown in an aqueous medium with a strong inorganic acid, formula III: ▲There are mathematical formulas, chemical formulas, tables, etc. ▼(III) b) The resulting compound of formula III is converted into 4-methoxy-3-nitroaniline represented by general formula IV: Cl-COO-CH(X^1)-CH_2-Y^1(I
V) [In the formula, X^1 is a hydrogen atom, Y^1 is a chlorine atom or a Cl-CH_2 group, and when X^1 represents a methyl group, Y^1 is a chlorine atom] c) The resulting general formula V: ▲There are numerical formulas, chemical formulas, tables, etc.▼(V) [In the formula, X^1 and Y^1 are the above-mentioned Under basic conditions, the carbamate represented by formula VI: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (VI) [In the formula, A and B represent the same thing as described for formula I a. ], d) reduction to the compound of general formula VI, and optionally e) converting the obtained compound of general formula I into a salt using an inorganic or organic acid in a manner known per se. characterized by changing
Process for the preparation of N^4-substituted 1-methoxy-2,4-diaminobenzoles and their salts with inorganic or organic acids. 2. General formula I: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [In the formula, R represents a group represented by the general formula Ia: -CH_2CH(A)-B(Ia), but the above N^4-substituted 1-methoxy- represented by formula Ia, A represents a methyl group, B represents a hydroxyl group, or when A is a hydrogen atom, B represents a HO-CH_2 group] 2,4-
Diaminobenzole. 3. General formula VI: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (VI) [In the formula, when A represents a hydrogen atom, B is a hydroxyl group or HO-CH_2 group; When A represents a methyl group , B is a hydroxyl group]. 4. Aqueous colorants for keratinous fibers such as fur and human hair, containing at least one compound according to claim 2 as a coupler and at least one developer component and customary additives and auxiliaries. 5. The compound according to claim 2 is added in an amount of 0.001 to 5 of the total coloring agent.
5. Aqueous coloring agent according to claim 4, containing in an amount of % by weight. 6. The aqueous coloring agent according to claim 4 or 5, which contains a dye for direct dyeing. 7. The aqueous colorant according to any one of claims 4 to 6, which has a pH value within the range of 6.0 to 12.5.