DE1492069C3 - N-Substituted-m-aminophenols and their uses - Google Patents

Description

in which R is hydrogen and R 'is the radical -CH ₂ CON (C ₂ H,), -COCH ₂ N (C ₂ H ₅ J ₂

or

or in which R is the methyl group and R 'is one of the radicals

or

-CH ₂ CONH ₂ -CH ₂ CON (C ₂ H ₅ ) ₂

-COCH ₂ N (C ₂ H _{5 I 2}

means.

2. Use of the compounds according to claim 1 as a coupling component in hair dyes.

- different combinations the most diverse color nuances.

The claimed N-Substituierlen-m-aminophenols result in more weather-resistant and lightfast hair colorations than that according to the prior art used m-aminophenol hydrochloride.

The compounds according to the invention are prepared according to the following examples.

B is ρ ie I 1
3 - [(N'-Diethyl) carbamyl methyl] aminophenol

In a ki-ben equipped with stirring devices equimolar amounts of 3-aminophenol and diethylchloracctamide are mixed, each dissolved in 2 parts Ethanol at 20 "C. Then, with continuous stirring, the mixture is heated under reflux and added in the course of the process from 4 to 5 hours per mole of chloracctamide 1 mole of potassium carbonate in the form of an aqueous solution with a concentration of 50Og per liter of water; then it is heated for a further K hours.

The alcohol is then drawn off as vapor. The aqueous solution is cooled and then extracted three times with chloroform in a ratio of 2 parts of chloroform per part of aminophenol. The chloroform solution is evaporated to dryness and the residue is five times Amount of its weight in ammonia solution (density 0.9) resumed. The dispersion is ice-cooled and nitrided. The 3 - [(N'-diethyl) carbamylmethyl] aminophenol is obtained in a yield of about 55 percent by weight, which essentially corresponds to the weight of aminophenol used, with a melting point of 91 "C.

The lirlimlung affects N-Substiluierle-m-aminophenols the general formula

HO

in which R is hydrogen and R 'is the remainder

means or in
one of the leftovers

CH ₂ CONH ₂ CH ₂ CON (C ₂ II ₅ ),

COCII ₂ N (C ₂ II ₅ ),

40

50

- CH ₂ CON (C ₂ H ₅ ), COCH ₂ N (C ₂ H ₅ J ₂ of R the methyl group and R '

60 Example 2
6-methyl-3- (N-earbamylmethyl) aminophenoI

According to the procedure described in Example 1, 3-amino-6-methylphenol is made with chloracelamide condensed, the reaction time being about Κ hours. After completion of the heating is evaporated at reduced pressure until a thick broth is obtained, then added per part Aminocresol 5 parts water to complete the precipitation. It is filtered while warm. Cooling gives a dark beige precipitate in a yield of about 92% a melting point of 140 "C.

This precipitate is umkrislallisierl in water (3 parts of water per part of precipitate), after which one pale yellow crystals with a melting point of 140 C in a total yield of about 80% receives.

Example 3

f) -Melhyl-3- | (N'-diethyl) -carba my! methyl j-aminopheiiol

means, as well as the use of these compounds. The one described in Example 1 is repeated

as coupling components in hair dyes. Working method using 3-amino

The compounds according to the invention are suitable (15 6-methylphenol to) NN-Diälhylchloracelamid as

excellent as coupling components for the starting materials and maintains the above

Manufacture of llaarfarbsloffen. You will be product with a melting point of 126 C in one

combined with a base and the yield of about 50 "ή.

3 4

Example 4 Example5

3- [a- (N'-diethyl) -amino] -acetamidophenol 6-methyl-3 - [«- (N'-diethyl) -amino] -

_ ", Acetamidophenol

Level 1 ^r

υ * ii -w /-U.1 \.-JU ι 5 The above product is manufactured according to the labor

Production of 3- («- chlorine) -acetamidophenol was _{produced by Volume 4; w} J _{at in stage} , _that

In 0.5 l of absolute alcohol, 3-aminophenol is dissolved with stirring by 3-amino-6-methylphenol, 55 g of 3-aminophenol and then 84 g of molten material are replaced. The pro-sodium acetate obtained in step 1. The mixture is cooled to a temperature between 6 - methyl - 3 - (a - chloro) - acetamidophenol at 3 and 5 ° C. and 60 g of chloroacetyl chloride with a melting point of 129 ° C. are then added, whereby one is added The temperature rises above the reaction according to stage 2 of example 4, which avoids ^{ge-5 ° C.} wished 6-methyl-3- [rHN'-diethyl) -amino] -acet-

After one hour, the mixture is allowed to cool to umamidophenol with a melting point of 162.5 ° C. ambient temperature and removed by filtration. The use of the compounds of the invention precipitated sodium chloride, which with a little 15 'fertilizers as coupling components in hair color water-free Alcohol is washed. Averaging the filtrate is offset from the following five uses then with 200 g of water, subsequently explained by way of example, most of the alcohol is reduced. ,,. . , < Pressure and about 40 ° C evaporated. Application example 1

It is allowed to cool, 600 g of water are added and 20 white hairs are left to stand for a few hours with the following solution. Then the educated acts:
The precipitate is nitrided off, washed with 200 g of water, 3 - ["- (N'-diethyl) -amino] -suctioned off and 300 g of boiling water close- \ -ah \ 1 11 ο

installed. Precipitation begins at 92 to _{u /} ^a _R * ^P Vr-

95 ° C to form. After cooling down to ambient 25 aqueous ammonia solution

temperature, the precipitate is filtered off with 50 g _M if water fill up to '.'. Υ. '.'. '.'. 100 cm ^{3 of} ice water washed, filtered off with suction and in a vacuum

100 ° C dried. After 20 minutes the hair is rinsed and with

In this way, 68 g of 3- (a-chloro) -acet- treated with a solution of the following composition are obtained:

amidophenol with a melting point of 134 ° C, 30 + .AminoO-methyl-N-ethyl-

the yield is 73%. N-carbamylmethylaniline sulfate .. 1.28 g

Aqueous ammonia solution

_{Ot f} - 22 ° Be 6 cm ³

^Stage _{2 35} H 2 O ₂ 6g

Preparation of 3- [a- (N'-diethyl) amino] - ^{With water at 10} ° ^{aufmilen Cm}

acetamidophenols The color obtained after 20 minutes is gray

. green.

In a flask provided with stirring device AnwendunasbeisDiel 2 are 50 cm ³ of acetone, 19 g of 3- (a-chloro) -acetamido- 40 Anwendungsoeispiel ι phenol and introduced 18 g of diethylamine. Then the dyeing process is the same as in the application, the mixture is heated under reflux for 1 hour and example 1 is added, only the first solution is then subsequently added 50 g of water. Then destil- is replaced:

liert, adding a little water if necessary,. ,. . _ _r , _XT,, ...., _n

continues until the distillate becomes neutral. The not distilled 45 6-Meth _y l-3 - [«- (N -diethyl) -

On cooling, the lated residue forms a lower amino] acetam.dophenol 1.18 g

blow. This precipitate is filtered off and two- ^W g _o ⁿ | ^e ammonia solution ^

washed times with 25 g of water. Then.,. ", ^E ~ .j. ή _inn ° ^m 3

the precipitate in 100 cm ³ 1 η-sodium hydroxide solution again ^{fill up with water to 10} ° ^cm

dissolved and it is filtered. The filtrate becomes through 50. The color obtained is gray-green.

Addition of concentrated hydrochloric acid. .

pH 8.5. After standing, application example 3 is filtered off

and washed twice with 25 g of water. The man prepares a solution for the following

Melting point is 93 ° C. The product obtained is:

is a hydrate whose water of crystallization 55. . . _rxT ...., _xr , _XT ,, · ..., _u

to boiling with dry benzene (about 10 parts) 4-Am, no- [N-ath _y lN- (Nd.athyl) -

can be removed. Then from a mixture of carbamylmethyl] -anhn-

of 1 part benzene and 3 parts heptane recrystalline, 5.57, SV '"Ü'" V \ Ü ü ""' ^g

sated. Cooling gives white crystals 6-Methyi-3- (N-carbamylmethyl) -

with a melting point of 91 ° C in a yield of 60 ",» i? ¹ - ^110P _A V j V- ' ^g

of about 55%. Aqueous ammonia solution

When the mother liquors evaporate to dryness., ". ,,» ':'^;,"crr \

a further 8% of the same amount of ^{water is obtained to 50 cm}

table product. The pH of this solution is 10.5. This

1 f r u η μ Lösun ⁶ 5 'is the same when they are used with the

Analysis for C ₁₂ H ₁₈ U ₂ N ₂ : volume of H ₂ O ₂ (20 vol.) Added and 20 minutes

■ Calculated ... C 64.90, H 8.2, N 12.62%; left to act on the hair at room temperature

found C 64.27, H 8.17, N 12.73%. sen. it gives a deep blue color.

5 6

Application example 4 Application example 5

Prepare a solution of the following - Prepare a solution of the following composition: Settlement:

..., χ, ·· ι. ι χι ι ι ^ Amino-iN-ethyl-N-carbamyl-

^ Amino-iN-ethyl-N-carbamyl-methyl) -aniline-chloroh _y drat .... I, l5g

methyl) aniline chlorohydrate l _; l5g i

(H

g 6-Methvl-3-r (N-diethyi) -

^ (N'-DiethylI-carbamylmethyl] - 'SSSopW 2.36 g

«/ Τ · ^ΠΟΡ ^ ^enO ■■ U- · - ^{'22 g} Aqueous ArrimohiaTclösung

Aqueous ammonia solution at 22 ° Re 6 cm ³

_Λ . ² } ° yy ^€ ■ :. j. ·, J? ^cm l Fill up with water to ........ 100 cm ³

Fill up with water to 100 cm

The pH of this solution is 10.6. Will

The pH of this solution is 10.6. This solution under the same conditions as in

Solution under the same conditions as in application example 3 with hydrogen peroxide

Application example 3 applied with hydrogen peroxide, a dark carmine-red-gray color is obtained

worn gives a carmine-red-gray color. Color.

Claims (1)

Patent claims: I. N-Substiluted-m-aminopheiiole der my formula lue- HO H N-R '