JPS609062B2 - Novel 2-substituted amino-5-γ-picolines or salts thereof, methods for producing them, and dyes for horny fibers containing them - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel two-layer fusuma amino-5-amino-y-hyurins or salts thereof, methods for producing them, and oxidative dyes for keratinous fibers (especially hair and fur) containing them. be.

In order to dye horny fibers beautifully and robustly by a simple and economical method, dye intermediates that develop color through oxidation are usually used.

That is, if a neutral or slightly alkaline aqueous solution of this pigment intermediate mixed with an oxidizing agent is applied or impregnated on the horny fibers immediately before dyeing, this will be oxidized on the horny fibers.
It becomes a water-insoluble pigment, and this pigment dyes the horny fibers.

Such an intermediate is called a color developing intermediate, and aromatic para or ortho diamines or para or ortho aminophenols are usually used.

When dyeing keratinous fibers with a color-developing intermediate, a modifying intermediate is added together with the color-developing intermediate in order to change the dyeing. Although this modifying intermediate does not have the ability to develop color even when oxidized alone, it undergoes a condensation reaction with the color-developing intermediate in the oxidation field, resulting in a color tone or solidity that cannot be created by the color-developing intermediate alone. This term refers to the pigment intermediate that generates the pigment, and aromatic compounds that are easily attacked by electrophilic reagents, such as meta-diamino compounds, meta-di/hydroxy compounds, and meta-aminophenols, are generally used. It will be done. Now, in order to dye horny fiber substances with oxidation dyes in a fast manner, oxidation dyes containing vararaphenylenediamine, varatolylenediamine, or para-aminophenol as color-developing intermediates are generally commercially available. This substance is a powerful drug that is highly irritating to the skin, and if used as a hair dye, especially for people with allergies, it has the drawback of causing severe hair dye dermatitis, nephritis, blurred vision, and other disorders.

Therefore, in the hair dyeing industry, which requires safe and durable dyeing of hair, which is a type of keratinous fiber substance, there is a demand for an oxidative dye that is non-inflammatory to the human body. Prior art techniques for safely dyeing hair with oxidative dyes without using these inflammatory benzene-based intermediates as color-developing intermediates include technologies that use pyridine-based color-developing intermediates and pyridine-based color-developing intermediates. exist.

However, the oxidation dyes obtained by these techniques tend to be expensive. In addition, inexpensive y-picoline derivatives, namely 2,5-diamino-y
- Attempts have already been made to use picoline as a mauve intermediate for non-inflammatory oxidative dyes, but this y-picoline derivative has weak color developing power and is difficult to use as a color developing intermediate for oxidative dyes. But Seifen Ele Fetsetebax (Seifen 戊leFet to Wachse
), Vol. 91, p. 594 (1965). In view of the above circumstances, the inventors of the present invention have conducted extensive research and have unexpectedly discovered that novel 2-mono-substituted amino-5-amino-y-picolines or salts thereof, which are derivatives of 2,5-diamin-picoline, or their salts are beautiful. We discovered that this compound has a bright color tone, is non-inflammatory, fast, and is useful as a color-developing intermediate for inexpensive oxidation dyes. The novel 2-substituted amino-5-amino-y-picolines or salts thereof of the present invention can be synthesized by the general formula (wherein R is a hydrogen atom or an alkyl group having 1 or no carbon atoms, 1 is none, and the alkyl group in 4 represents an alkanol group.

) or their salts (hereinafter referred to as "compounds of the present invention"). Specific examples of compounds targeted by the present invention include 2-methylamino-5-amino-y-picoline, 2-dimethylamino-5-amino-y-picoline, 2-ethylami/-5-amino-y-picoline, and 2-methylamino-5-amino-y-picoline. diethylamide/-5-amino-y-picoline, 2-propylamino-5-amino-y-picoline,
2-butylamino-5-amino-2-picoline, 2-[
N-ethyl-N-(8-hydroxyethyl)]amino-
Examples include 5-amino-y-picoline. More specifically, when these compounds are used as color-developing intermediates for oxidative dyes, oxidative dyes having warm color tone and good fastness can be obtained.

Among them, 2-methylamino-5-amino-picoline and 2-ethylamino-5-amino-y-picoline produce a vivid red color that was impossible to see with conventional non-inflammatory oxidation dyes. 5
-Amino-y-picoline, 2-diethylamino-5-amino-y-picoline, 2-[N-ethyl-N-(8-hydroxyethyl)]amino-5-amino-y-picoline is impossible to see with conventional non-flame oxidation dyes. It can be an excellent head color intermediate for oxidation dyes that can develop an intense black color, and furthermore, it is generally possible to use 2. It has been discovered that 5-diamino-y-picoline can be used as an excellent color-developing intermediate for oxidation dyes. Although the bright red color of hair oxidation dyes is a necessary tone to dye the fringe color, which is common among Western people, to the golden yellow most preferred by Westerners, it is non-inflammatory and vivid. No red oxidation dye currently exists. A mixture of Q-naphthol and P-toluylene diamine is used as a red oxidation dye, but this is inflammatory to allergic people, and its color is a bluish red, making it difficult to understand if it is a true red oxidation dye. In addition to not being a red color, Q naphthol has a lacquer-like property and has a large molecular weight, so it has poor dyeing properties and cannot be called a valuable dye.

In addition, 2,5-diaminopyridine or 2-(B-hydroxyethyl)amino-5-aminopyridine is known as a relatively inexpensive color-developing intermediate for non-inflammatory red hair oxidation dyes. However, the former is a head color intermediate that produces a brown-red color, and the latter a bluish-red color, and cannot produce a true red color.

Furthermore, a mixture of 2,3-diamino-4-propylpyridine or 2,5-diamino-4-propylpyridine and zorcin can also dye horny fibers in a light pink color, but these mixture dyes have the disadvantage of low dyeing power; Moreover, it has the disadvantage that when dyeing it, the color tone shifts to brown if the dye concentration is increased. On the contrary, 2-methylamino-5-amino-y-picoline and 2-ethylamino-5-amino-y-picoline proposed in this application are color-developing intermediates of non-inflammatory oxidative dyes with a bright red color. Not only can these dyes dye the fringe-colored hair color commonly seen in Westerners to the golden yellow most preferred by Westerners, but these dyes can also dye fur a rich red color that was previously considered impossible. .

Furthermore, among the 0-oxidation dyes for black hair that are most preferred by people of color, attempts have already been made to use pyridine-based dye intermediates as color-developing intermediates for oxidation dyes, as they are relatively inexpensive and non-inflammatory dyes. , the document is British patent 1025414
No. 51-12681 and Japanese Patent Publication No. 48-148
No. 80, etc., but all of the dyes shown in these 5 documents have insufficient fastness and are not satisfactory.

However, the 2-dimethylamino-5-amino-y-picoline and 2-diethylamino-5-amino-y proposed in this application
-picoline or 2-[N-(8o-hydroxyethyl)]amino-5-amino-y-picoline as a color developing intermediate, and 2,6-bis-ditylamino-y-picoline 2
When we conducted a sunlight fading test (JIS-L-084-1974 method) on non-inflammatory black oxidation dyes using hydrochloride as a modifying intermediate, we found that these black oxidation dyes had a high fastness level of grade 4. , and its fastness is better than the above-mentioned known black oxidation dye (its fastness to sunlight is grade 1 to 2),
Ultimately, the present invention was completed by discovering that the compound of the present invention is an excellent intermediate for oxidation dyes.

The compound of the present invention is an inexpensive substance that is industrially produced in large quantities and can be easily produced as a raw material for y-picoline, which is cheaper than pyridine.

Now, the compound of the present invention is shown in the following formula Q}, '2}☆
It is synthesized by reduction of a nitro compound represented by the general formula (wherein R and R. have the same meanings as above).

The method {1} synthesizes 2-substituted amino-5-amino-y-picoline by reducing 2-substituted amino-5-nitro-y-picoline with a metal and an acid. Zinc*, etc., and as the acid, hydrochloric acid, L-sulfuric acid, formic acid, harsh acid, etc. are used.

In the following examples, reactions are carried out according to a chemical formula such as formula [1'] as an example of formula m.

In this case, zinc is 3.5 to 7. Powder forms are often used, and hydrochloric acid is often used at a concentration of 20% to 38%, and the reaction usually takes place at a molar ratio of 5% to 38%.
It is done from 0 to 10000. {2} method is 2
It is characterized by reducing -substituted amino-5-nitro-picoline with hydrogen and a metal catalyst, and nickel, copper, platinum, palladium, etc. are generally used as the metal catalyst. In the following examples, the reaction is carried out according to the chemical formula (2) as an example of the '2} formula, but in this case, dimethylformamide or methanol is used as the reaction solvent, and the temperature is 50°C. None/9000
range is used for a long time. The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples unless it departs from the gist thereof.

For example, in the hair dyeing examples below, only a method using a mixture of a Z emulsion type dye and an oxidizing agent aqueous solution is described, but when the compound of the present invention is used as a hair dye intermediate, this intermediate Adhesives known in the hair dyeing industry (starch, seaweed powder, synthetic thickeners, higher alcohols, Arabica Zum, etc.), foaming agents and wetting agents (surfactants), stabilizers (urea, phenacetin, acetanilide,
(ethylenediaminetetraacetic acid, sodium sulfite, etc.) swelling agents (triethanolamine, etc.), hair nourishing agents (lanolin, cholesterin, pantothenic acid, etc.), fragrances (di2yasmin, etc.)
, a propellant (1,1-difluoroethane, etc.), etc., and can be used for hair dyeing in various forms such as solid, aqueous solution, suspension, and aerosol.

In addition, in the following examples, all the compounds of the present invention are used in the form of basic compounds, but these are difficult to react with minerals such as hydrochloric acid and sulfuric acid, or organic acids such as acetic acid and formic acid. It is therefore also possible to use the resulting salt form.

The nitro compounds represented by the general formula [B] used as starting materials for the compounds of the present invention are all compounds that have not been described in the literature, but the synthesis techniques for these are disclosed by the present inventors. The invention is described in detail in the specification of ``Novel 2-substituted amino-5-nitro-y-picoline, method for producing the same, and straight tricycle dye for hair containing the same'' which was previously filed by .

Example 12 - Synthesis of [N-ethyl-N-(8-hydroxyethyl)]amino-5-amino-5-amino-y-picoline In a 4300 customer flask, 2-N-ethyl-N-(8-hydroxyethyl)amino-5- Nitro-Picoline 8.5 and 3
After adding 95% of 0% hydrochloric acid and stirring to dissolve the former into the latter, 11.8% of zinc powder was gradually added to it under the heat, and then the temperature was raised to about 8,000℃ and heated to 8,000℃ for one and a half hours. The reaction solution was further cooled to room temperature, and 150 g of 25% aqueous ammonia was added thereto to neutralize it.

After that, an extraction solvent loo consisting of an equal volume ratio of ethyl ether and n-butanol was added to the reaction solution, and after shaking, an oily fraction was separated by liquid separation, and this oily fraction was distilled under reduced pressure to a boiling point of 183. A fraction of Hg on the ~185q014 side (synthesis yield 54.0%) is taken.

The physical properties of this fraction are as shown below, confirming that this fraction is the title compound. Elemental analysis results; (C
, Nagi, 7N30) C day N Experimental value (%) 60.54 8.92 21.18 Theoretical value (%) 61.51 8.77 21.51 Nuclear magnetic resonance characteristics; measurement conditions are nuclide (IH) measurement frequency (60MH
z) Equipment used (Hitachi R-24) Standard material (TMS) Extraction speed (2Hz/sec) Measurement temperature (35℃) Solvent (CD
C13) Measured concentration (20%).

The results of measuring the relationship between the proton position on the material structure and its assigned position on the spectrum are shown in the table below. Note that this spectrum diagram is shown in FIG.

Example 2 Synthesis of 2-methylamino-5-amino-y-picoline 3
[Put 10 parts of 2-methylamino-5-nitro-y-picoline, 100 parts of methanol, and 5 parts of Raney Nickel into an autoclave, and autoclave hydrogen gas under a pestle at 60 to 90 °C for 2 and a half hours. After the reaction is completed, the reaction liquid is cooled, filtered in a furnace, 35% hydrochloric acid is added to the furnace liquid, and evaporated to dryness to give 11.5 days of crude crystals (yield/theoretical value = 922.0%). When this is recrystallized from 20% hydrochloric acid water, the dihydrochloride salt of the title compound having the following physical properties is obtained.

Melting point: 259-26000 Elemental analysis result: (C7 days, 3N3CI2) C days N Experimental value (%) 40.09 6.28 19.51 Theoretical value (%) 40.01 6.23 19.99 Also, this hydrochloric acid After dissolving the salt in methanol, this was neutralized with caustic soda, and the oil extracted from this neutralized solution using benzene as an extractant was distilled under reduced pressure.
When the fraction on the ~13500/2 side is distilled under reduced pressure, the physical properties of this fraction are as follows, confirming that this fraction is the title compound.

Elemental analysis results; (C?day, .N3) Cday N Experimental value (%) 61.21 8.01 30.61 Theoretical value (%) 61.29 8.08 30.63 Nuclear magnetic resonance characteristics; Measurement conditions is the same as in Example 1.

However, the measured concentration is 1% by volume. The results of measuring the relationship between the proton position on the material structure and its assigned position on the spectrum are shown in the table below.

Note that this spectrum diagram is shown in FIG.

Example 3 Synthesis of 2-dimethylamino-5-amino-y-picoline
Nitro-y-picoline 159, methanol 150'
If 7 units of Raney nickel were added and the nitro compound was catalytically reduced according to the method of Example 2, a crude crystal of 18.0 kg (yield/theoretical value = 95.0%) was obtained. The dihydrochloride salt of the title compound having the following physical properties is obtained by recrystallization according to the following procedure.

Melting point: 250-25500 Elemental analysis result: (C8 days.5
CI2) C day N Experimental value (%) 42.24 6.84 18.43 Theoretical value (%) 42.87 6.75 18.75 In addition, this hydrochloride was neutralized and depressurized according to the method of Example 2. When distilled to obtain a fraction of 130-135°C/8 skin Hg, this fraction exhibits the following physical property values and is confirmed to be the title compound.

Melting point: 69-7〆○ Elemental analysis results: (C8 days, 3N3) C days N Experimental value (%) 63.59 8.61 27.71 Theoretical value (%) 63.55 8.67 27.79 Nuclear magnetism Resonance characteristics; measurement conditions are the same as in Example 1.

However, the measured concentration is 1% by volume. The results of measuring the relationship between the proton position on the material structure and its assigned position on the spectrum are shown in the table below. Note that this spectrum diagram is shown in FIG. 3.

Example 4 Synthesis of 2-ethylamino-5-amino-y-picoline 3
00 [2-ethylamino-5-nitro-picoline in the customer's autoclave 20 minutes, dimethylformamide 10 minutes]
Add 50% of Raney Nickel and blow hydrogen gas into the autoclave at 60 to 80qo for about 1 hour. After the reaction is complete, cool the reaction liquid, filter it through the furnace, and distill the furnace liquid under reduced pressure. Possibly boiling point 129.5-130.5 pm
If a fraction of /2 side Hg (synthesis yield = 85.0%) is taken, this fraction exhibits the following physical property values and is confirmed to be the title compound.

Melting point: 65-6700 Elemental analysis result: (C8 days, 3N3) C days N Experimental value (%) 63.51 8.61 27.71 Theoretical value (%) 63.55 8.67 27.79 Nuclear magnetic resonance characteristics ;The measurement conditions are the same as those shown in Example 1.

However, the measured concentration is 1% cough volume. The results of measuring the relationship between the proton position on the material structure and its assigned position on the spectrum are shown in the table below. Note that this spectrum diagram is shown in FIG.

Example 5 Synthesis of 2-diethylamino-5-amino-y-picoline 2-diethylamino-5
- Add 35% of -nitro-y-picoline, 100% of dimethylformamide, and 5% of Raney nickel, catalytically reduce the nitro compound according to the method of Example 4, and distill the reduction product under reduced pressure to 124.6~125.5o /2.5 Willow Hg fraction (synthesis yield = 85.0%) is taken, and this fraction exhibits the following physical property values, confirming that it is the title compound.

Melting point: 46-4800 Elemental analysis result: (C, 2 days, 7N3) C day N Experimental value (%) 65.36 9.58 24.18 Theoretical value (%) 67.00 9.65 23.43 Nuclear magnetism Resonance characteristics; measurement conditions are the same as those shown in Example 1.

The results of measuring the relationship between the proton position on the material structure and its assigned position on the spectrum are shown in the table below.

Note that this spectrum diagram is shown in FIG.

Example 6 Synthesis of 2-ethylamino-5-amino-y-picoline dihydrochloride After dissolving 2-ethylamino-5-amino-y-picoline in 35% purity hydrochloric acid, the hydrochloric acid solution was evaporated to dryness and the resulting solid was mixed with methanol. When recrystallized with a mixed solvent of ether, crystals of the desired product (pale pink) having the following physical properties are obtained.

Melting point: 165-16800 Elemental analysis result: (C6 days, 5N3CI2) C days N Experimental value (%) 42.82 6.71 18.79 Theoretical value (%) 42,87 6.75 18.75 Example 72- Synthesis of ethylamino-5-amino-y-picoline dihydrochloride After dissolving 2-diethylamino-5-amino-y-picoline in hydrochloric acid with a purity of 35%, the hydrochloric acid solution was evaporated to dryness and the resulting solid was dissolved in methanol. - When recrystallized with a mixed solvent of tel, the desired crystals (pale red color) with the following physical properties are obtained.

Melting point: 195-19700 Elemental analysis result: (C, phantom, 9N3CI2) C day N Experimental value (%) 47.69 7.50 17.03 Theoretical value (%) 47.63 7.59 16.06 Example 82 -[N-ethyl-N-(8-hydroxyethyl)
]Synthesis of amino-5-amino-y-picoline dihydrochloride 2
After dissolving 1[N-ethyl-N-(8-hydroxyethyl)]amino-5-amino-y-picoline in 35% purity hydrochloric acid, the hydrochloric acid solution was evaporated to dryness and the resulting solid was mixed with methanol and ether. When recrystallized from a solvent, crystals of the desired substance (light yellow) are obtained having the following physical properties.

Melting point: 173-17500 Elemental analysis result: (C, Rainbow, Bu30CI2) C day N Experimental value (%) 47.85 7.09 15.58 Theoretical value (%) 47.79 7.14 15.67 Example
92-ethylamino-5-amino-y-picoline 1.3
12 isopropanol 12 oleyl alcohol
Add 13 parts of polyoxyethylene lauryl ether, 4 parts of coconut oil fatty acid jetanolamide, 27 parts of polyoxyethylene nonyl phenyl ether to 16 parts of distilled water,
Shake to make a complete solution.

Next, 28% aqueous ammonia solution was added to this solution for 5 minutes, and the solution was shaken until it became homogeneous.The resulting dye solution 60% was removed, and 60% hydrogen peroxide solution was added thereto and mixed well. This is applied to gray hair, left at room temperature or human body temperature for 20 minutes, and then washed with water. Gray hair is dyed red with high temperature fastness, sunlight fastness, and brightness. Example 10 Dye intermediate 2-ethylamino-5- used in Example 9
When gray hair is dyed by the method shown in Example 9 using the following dye intermediate instead of amino-y-picoline 1.3, gray hair is dyed to the following color tone with high wet fastness and sunlight fastness.

Example 25 Dissolve 25 parts of 2-ethylamino-5-picoline in 50 parts of water, add about 30% ammonia water until the pH becomes 8.0, make the liquid temperature about 30 qo, and add the water to this solution in advance by the supplementary field method (
Add 25k9 (dry product equivalent) of alum-tanned white rabbit fur using dyes and chemicals, Vol. 8, p. 109, p. 196
If you throw it for a minute, then add 30% of 30% hydrogen peroxide solution and let it fly for 3 hours and 30 minutes, then take out the fur, wash it thoroughly with water, and dry it at room temperature, the fur will have high moisture and sunlight fastness. dyed red.

Examples 26 to 27 The following dye intermediates were used in place of the dye intermediate 2-ethylamino-5-amino-y-picoline used in Example 9, and the edge flavor was obtained by the method shown in Example 9. When Western hair is dyed, it can be dyed to the following colors with high wet fastness and sunlight fastness.

[Brief explanation of the drawing]

Figure 1 shows 2-[N-ethyl-N-(P-hydroxyethyl)]amino-5-amino-y-picoline, Figure 2 shows 2
-Methylamino-5-amino-y-picoline, Figure 3 is 2-dimethylamino-5-amino-y-picoline, Figure 4 is
The figure shows nuclear magnetic resonance spectra of 2-ethylamino-5-amino-y-picoline, and FIG. 5 shows the nuclear magnetic resonance spectra of jethylamino-5-amino-y-picoline. Mi-style・f・ゞ・ゞigi

Claims (1)

[Claims] 1 General formula▲ Numerical formula, chemical formula, table, etc.▼ (In the formula, R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R_1 is an alkyl group having 1 to 4 carbon atoms, or Indicates an alkanol group.) Compounds or salts thereof. 2. The compound or salt thereof according to claim 1, wherein R is a hydrogen atom and R_1 is a methyl group. 3. The compound or salt thereof according to claim 1, wherein R is a hydrogen atom and R_1 is an ethyl group. 4. The compound or salt thereof according to claim 1, wherein both R and R_1 are methyl groups. 5. The compound or salt thereof according to claim 1, wherein both R and R_1 are ethyl groups. 6. The compound or salt thereof according to claim 1, wherein R is an ethyl group and R_1 is a β-hydroxyethyl group. 7 General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R_1 represents an alkyl group or an alkanol group having 1 to 4 carbon atoms.) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R and R_1 have the same meanings as above. ) A method for producing a compound represented by 8. The manufacturing method according to claim 7, wherein the metal is zinc and the acid is hydrochloric acid. 9 Claim 7 in which the reduction catalyst is a nickel catalyst
Manufacturing method described in section. 10 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R_1 represents an alkyl group or an alkanol group having 1 to 4 carbon atoms.) An oxidation dye for horny fibers containing the compound represented by or a salt thereof. 11. The oxidative dye for horny fibers according to claim 10, wherein R is a hydrogen atom and R_1 is a methyl group. 12. The oxidative dye for horny fibers according to claim 10, wherein R is a hydrogen atom and R_1 is an ethyl group. 13. The keratin oxidation dye according to claim 10, wherein R and R_1 are both methyl groups. 14. The oxidative dye for keratin according to claim 10, wherein both R and R_1 are ethyl groups. 15. The oxidative dye for horny fibers according to claim 10, wherein R is an ethyl group and R_1 is a β-hydroxyethyl group.