BE801158A - 2,5-diamino-1,4-benzoquinones - useful for tinting hair - Google Patents

Abstract

Diaminobenzoquinones (I): where R1, R2, R3 and R4 = H, halogen, low alkyl or low alkoxy, R5 = H, low alkyl (opt. substd. by >=1 OH gps.) or -(CH2)n-N(R8)(R9) where n = integer 2-6 (pref. 2) and R8 and R9 = H, alkyl (opt. substd. by >=1 OH or acylamino residuese and R8 and R9 together with the N atom may form a heterocyclic 6-ring in which O may also be present, scuh as a morpholine or piperidine ring; Z may be (a) OH or (b) a gp. -N(R6)(R7) where R6 and R7 = H, lower alkyl (opt. substd. by OH, carbamyl, acylamino, mesylamino, or benzoylamino residues) or a gp. -(CH2)n-N(R10(R11) where n = integer 2-6 (pref. 2) and R10 and R11 = lower alkyl (opt. substd. by >=1 OH or acylamino residues) or R10 and R11 together with the N atom may form a heterocyclic 6-ring such as a piperidine or morpholine ring, in cyclic 6-ring such as a piperidine or morpholine ring, in which 'lower alkyl' indicates 1-4C alkyl and 'acyl groups' are 2-5C aliphatic acyl residues. The products are useful in aq. or aq/alcoholic soln. for dyeing and tinting hair in green shades.

Description

       

   <EMI ID = 1.1>

  
of obtaining and dyeing compositions - the containing ,, <EMI ID = 2.1>

  

 <EMI ID = 3.1>


  
 <EMI ID = 4.1>

  

 <EMI ID = 5.1>


  
preferably the number Z,

  
 <EMI ID = 6.1>

  
 <EMI ID = 7.1>

  
attached, a six-membered heterocycle likely to contain an atom

  
 <EMI ID = 8.1>

  

 <EMI ID = 9.1>


  
 <EMI ID = 10.1>

  
alkyl of formula:

  

 <EMI ID = 11.1>


  
 <EMI ID = 12.1> <EMI ID = 13.1>

  

 <EMI ID = 14.1>


  
 <EMI ID = 15.1>

  
laid, or on one of its strong salts with mineral or organic acids: <EMI ID = 16.1>

  

 <EMI ID = 17.1>


  
 <EMI ID = 18.1>

  
of such a compound, the molar ratio of compounds III / II preferably being

  
 <EMI ID = 19.1>

  
 <EMI ID = 20.1>
- either a benzoquinone-monoimine or -diimine of formula:

  

 <EMI ID = 21.1>
 

  
 <EMI ID = 22.1>

  
 <EMI ID = 23.1>

  
on a nitrose derivative of formula:

  

 <EMI ID = 24.1>


  
 <EMI ID = 25.1>

  
quées, or a salt of such a compound, the condensation taking place of

  
 <EMI ID = 26.1>

  
between 1 and 1.5.

  
Condensation of compounds (III) or (IV) on the compound

  
 <EMI ID = 27.1>

  
at pH made alkaline by adding for example ammonia and in the presence of a large excess of hydrogen peroxide (10 to 75% of hydrogen peroxide at

  
20 volumes in addition to the theoretical amount required, the compounds being used generally in equimolecular amounts.

  
The condensation of the compound (V) on the compound (II) takes

  
 <EMI ID = 28.1>

  
 <EMI ID = 29.1>

  
absolute cool, in particular when compound (I) is isolated as a salt. The compounds (V) and (II) are preferably used in equimolecular amounts and the pH of the reaction medium can either be made alkaline by addition of ammonia or be made slightly acidic by addition of acid. acetic. It should be noted that this reaction medium is in itself acidic when the compound used is a hydrochloride, a hydrobromide or a sulfate of a

  
 <EMI ID = 30.1>

  
superfluous.

  
The condensation of compound (V) on compound (II) is most often carried out in the presence of hydrogen peroxide. However, the presence of hydrogen peroxide is not necessary in certain cases, in <EMI ID = 31.1>

  
When the compound of formula (I) contains a quaternary tertiary amine function, it is possible to prepare a quaternary salt of this compound by reacting it with an alkylating agent such as methyl or ethyl sulfate, iodide or methyl or ethyl bromide, benzyl chloride. This quaternization reaction is carried out at room temperature in a suitable solvent such as dioxane or a mixture of dioxane and ethanol.

  
The new compounds according to the invention constitute dyes which have a good affinity for keratin fibers, in particular for human hair.

  
It is known that many dyes used to dye the hair impart to the latter a reddish reflection which is not always appreciated. -

  
We therefore sought a means of

  
 <EMI ID = 32.1>

  
 <EMI ID = 33.1>

  
greens which attenuate or suppress the red reflection of the traditional shades and in particular the red hair.

  
 <EMI ID = 34.1>

  
formula :

  

 <EMI ID = 35.1>


  
 <EMI ID = 36.1>

  
each other, denote H, alkyl or aryl.

  
These compounds are dyes which dye wool in yellow, brown and red-brown shades, so they are not suitable for the intended purpose.

  
 <EMI ID = 37.1>

  
 <EMI ID = 38.1>

  
yellow and brown. These compounds are also unsuitable for the intended purpose.

  
 <EMI ID = 39.1>

  
rubbers and plastics.

  
A subject of the present invention is also: the new industrial product which constitutes a dyeing composition for kera fibers

  
 <EMI ID = 40.1>

  
contains in solution at least one compound of formula 1 or a salt or a quaternary ammonium derivative of such a compound,. The compositions according to the invention are aqueous solutions capable of containing one or more alcohols of low molecular weight. EMI ID = 41.1>

  
weight while the proportion of glycol generally varies from 2 to 5% by weight.

  
 <EMI ID = 42.1>

  
their salts in the dyeing compositions according to the invention can vary from

  
 <EMI ID = 43.1>

  
in weight.

  
The pH of the compositions according to the invention can vary between

  
 <EMI ID = 44.1>

  
 <EMI ID = 45.1>

  
 <EMI ID = 46.1>

  
or acetic acid or a base such as ammonia or triethanolamine.

  
The compositions according to the invention may contain conne

  
 <EMI ID = 47.1>

  
In this case, they make it possible to obtain a whole range of very luminous green shades rich in metallic reflections, ranging from silvery almond green to very dark green, passing through light bronzes, ash blondes and linden shades with golden reflections.

  
The compositions according to the invention may however also contain other direct dyes, for example nitrogen dyes, anthraquinone dyes, nitro dyes of the series

  
 <EMI ID = 48.1>

  
The compositions according to the invention can also contain various ingredients usually used in cosmetics, such as

  
wetting agents, dispersing agents, blowing agents, penetrating agents, emollients or perfumes. They can also be packaged in aerosol bottles.

  
The compositions according to the invention can be used

  
for the purpose of lasting dyeing of the hair: in this case they are applied to the hair for a time varying from 10 to 30 minutes, after which they are rinsed <EMI ID = 49.1>

  
thyle; vinyl acetate-allyl stearate-allyloxy acetic acid terpolymers.

  
 <EMI ID = 50.1>

  
of the total weight of the composition.

  
The alcohols suitable for making hair styling lotions according to the invention are low molecular weight alcohols, and

  
 <EMI ID = 51.1>

  
 <EMI ID = 52.1>

  
 <EMI ID = 53.1> <EMI ID = 54.1>

  

 <EMI ID = 55.1>


  
 <EMI ID = 56.1>

  

 <EMI ID = 57.1>

Example 2

  
 <EMI ID = 58.1>

  

 <EMI ID = 59.1>


  
 <EMI ID = 60.1>

  
 <EMI ID = 61.1>

  

 <EMI ID = 62.1>


  
Excels 3

  
 <EMI ID = 63.1>

  

 <EMI ID = 64.1>


  
 <EMI ID = 65.1>

  

 <EMI ID = 66.1>

Example 4

  
 <EMI ID = 67.1>

  

 <EMI ID = 68.1>
 

  
 <EMI ID = 69.1>

  

 <EMI ID = 70.1>


  

 <EMI ID = 71.1>


  

 <EMI ID = 72.1>

Example 5

  
 <EMI ID = 73.1>

  

 <EMI ID = 74.1>


  
0.01 mole (1.39 g) of 3-amino 4-methoxy phenol is dissolved in

  
 <EMI ID = 75.1>

  
melts at 199 "

  

 <EMI ID = 76.1>

Example 6

  
 <EMI ID = 77.1>

  

 <EMI ID = 78.1>


  

 <EMI ID = 79.1>

Example 7

  
 <EMI ID = 80.1>

  
 <EMI ID = 81.1>
 <EMI ID = 82.1>
  <EMI ID = 83.1>

  

 <EMI ID = 84.1>


  
Molecular mass found by potentiometric assay

  

 <EMI ID = 85.1>


  

 <EMI ID = 86.1>

Example 8

  
 <EMI ID = 87.1>

  

 <EMI ID = 88.1>


  
0.0027 mol (1 g) of the compound of Example 7 is dissolved in 7 cm of absolute alcohol and 20 cm of dioxane. This solution is added dropwise.

  
 <EMI ID = 89.1>

  

 <EMI ID = 90.1>

Example 9

  
 <EMI ID = 91.1>

  
aniline) 1,4-benzoquinone of the formula:

  

 <EMI ID = 92.1>


  
Has a solution of 0.01 mol '(1.83 g) of 3-N- &#65533; -hydroxyethylamino 4-methoxy phenol in 25 this water to the addition of 10 cm <3> ammonia at 22 [deg.] Bé and

  
 <EMI ID = 93.1>

  
 <EMI ID = 94.1>

  
 <EMI ID = 95.1>

  

 <EMI ID = 96.1>

Example 10

  
 <EMI ID = 97.1>

  

 <EMI ID = 98.1>


  
 <EMI ID = 99.1>

  

 <EMI ID = 100.1>


  
 <EMI ID = 101.1>

  

 <EMI ID = 102.1>


  
 <EMI ID = 103.1> <EMI ID = 104.1>

  

 <EMI ID = 105.1>


  
 <EMI ID = 106.1>

  

 <EMI ID = 107.1>


  

 <EMI ID = 108.1>

Example 12

  
 <EMI ID = 109.1>

  

 <EMI ID = 110.1>


  
0.02 mole (2.78 g) of 3-amino 4-methoxy phenol is dissolved in 200 cm of water

  
 <EMI ID = 111.1>

  
first 100 cm of hydrogen peroxide at 20 volumes then, immediately afterwards and with stirring

  
 <EMI ID = 112.1>

  
room before filtering off the expected 2-amino 5- (3-chloro 4-hydroxy anilino) 1,4-benzoquinone. The crude product is washed with water, recrystallized in a

  
 <EMI ID = 113.1>

  

 <EMI ID = 114.1>
 

  
 <EMI ID = 115.1>

  

 <EMI ID = 116.1>


  
 <EMI ID = 117.1>

  

 <EMI ID = 118.1>

Example 14

  
 <EMI ID = 119.1>

  

 <EMI ID = 120.1>


  
 <EMI ID = 121.1>

  
of hydrogen peroxide at 20 volumes. As soon as this solution is prepared, we add

  
 <EMI ID = 122.1>

  
 <EMI ID = 123.1> <EMI ID = 124.1>

  

 <EMI ID = 125.1>

Example 15

  
 <EMI ID = 126.1>

  

 <EMI ID = 127.1>


  
 <EMI ID = 128.1>

  

 <EMI ID = 129.1>

Example 16

  
 <EMI ID = 130.1>

  

 <EMI ID = 131.1>


  
 <EMI ID = 132.1>

  
stirring for 8 hours then filtered, washed with a little dioxin then sulfuric ether 1.18 g of the expected quaternary salt which melts at 243 [deg.].

  

 <EMI ID = 133.1>

Example 17

  
 <EMI ID = 134.1>

  
anilino) 1,4-benzoquinone of the formula

  

 <EMI ID = 135.1>


  
 <EMI ID = 136.1>

  

 <EMI ID = 137.1>
 

  
 <EMI ID = 138.1>

  

 <EMI ID = 139.1>


  
 <EMI ID = 140.1>

  
paratoluylenediamine in 20 cm <3> of water. Stirring is maintained for one hour. The precipitate formed is filtered off, washed with water and then recrystallized twice from a dimethylformamide-water mixture. After vacuum drying &#65533; 80 [deg.] On

  
 <EMI ID = 141.1>

  

 <EMI ID = 142.1>

Example 19

  
 <EMI ID = 143.1>

  

 <EMI ID = 144.1>


  
 <EMI ID = 145.1> <EMI ID = 146.1>

  
 <EMI ID = 147.1>

  
nel in the ice. Stirring is maintained for two hours and then filtered off and washed with water: The precipitate formed. After two recrystallizations at

  
 <EMI ID = 148.1>

  

 <EMI ID = 149.1>

Example 20

  
 <EMI ID = 150.1>

  

 <EMI ID = 151.1>


  
 <EMI ID = 152.1>

  
solution of 0.02 mole (4.24 g) of 3-chloro 4-nitroso N, N-diethylaniline in

  
 <EMI ID = 153.1>

  
and washing the precipitate formed thoroughly with hot water. After a recrystalli-

  
 <EMI ID = 154.1>

  

 <EMI ID = 155.1>


  
 <EMI ID = 156.1>

  

 <EMI ID = 157.1>

Example 21

  
 <EMI ID = 158.1>

  
amino aniline 1,4-benzoquinone of the formula:

  

 <EMI ID = 159.1>


  
 <EMI ID = 160.1>

  
at 174 [deg.] C.

  

 <EMI ID = 161.1>

Example 22

  
 <EMI ID = 162.1>

  

 <EMI ID = 163.1>


  
 <EMI ID = 164.1> <EMI ID = 165.1>
 <EMI ID = 166.1>
 <EMI ID = 167.1>

  

 <EMI ID = 168.1>


  
 <EMI ID = 169.1>

  
water and vacuum drying melts at 265 [deg.] C.

  

 <EMI ID = 170.1>
 

  
 <EMI ID = 171.1>

  

 <EMI ID = 172.1>


  
 <EMI ID = 173.1>

  

 <EMI ID = 174.1>


  
 <EMI ID = 175.1>

  
 <EMI ID = 176.1>

  

 <EMI ID = 177.1>


  
 <EMI ID = 178.1>

  
 <EMI ID = 179.1>

  
oxygenated at 20 volumes.

  
 <EMI ID = 180.1>

  
 <EMI ID = 181.1> <EMI ID = 182.1>

  

 <EMI ID = 183.1>


  
 <EMI ID = 184.1>

  

 <EMI ID = 185.1>


  
 <EMI ID = 186.1>

  
After drying under vacuum the product melts at 227 ° C.

  

 <EMI ID = 187.1>
 

  
 <EMI ID = 188.1>

  

 <EMI ID = 189.1>


  
 <EMI ID = 190.1>

  

 <EMI ID = 191.1>

Example 28

  
 <EMI ID = 192.1>

  

 <EMI ID = 193.1>


  
 <EMI ID = 194.1>

  
22 [deg.] Bé and 100 ml of hydrogen peroxide at 30 volumes.

  
 <EMI ID = 195.1>

  

 <EMI ID = 196.1>

Example 29

  
 <EMI ID = 197.1>

  

 <EMI ID = 198.1>


  
 <EMI ID = 199.1>

  

 <EMI ID = 200.1>
 

  
 <EMI ID = 201.1>

  

 <EMI ID = 202.1>


  
 <EMI ID = 203.1>

  
of 4-nitroso dibutylaniline hydrochloride. The mixture is left with stirring for one hour at room temperature. The expected product is filtered off

  
 <EMI ID = 204.1>

  
 <EMI ID = 205.1>

  
of ammonia at 22 [deg.] Bé to precipitate the expected 1,4-benzoquinone, in the form

  
 <EMI ID = 206.1>

  

 <EMI ID = 207.1>

Example 31

  
 <EMI ID = 208.1>

  

 <EMI ID = 209.1>


  
 <EMI ID = 210.1> <EMI ID = 211.1>

  

 <EMI ID = 212.1>

Example 32

  
 <EMI ID = 213.1>

  

 <EMI ID = 214.1>


  
 <EMI ID = 215.1>

  
 <EMI ID = 216.1>

  
the expected product which precipitates. After recrystallization from dimethyl

  
 <EMI ID = 217.1>

  

 <EMI ID = 218.1>
 

  
 <EMI ID = 219.1>

  
: EXAMPLE 33

  
We prepare the following solution:

  

 <EMI ID = 220.1>


  
This solution is applied to bleached hair for 20

  
 <EMI ID = 221.1>

  
very silvery almond.

  
EXAMPLE 34

  
We prepare the following solution:

  

 <EMI ID = 222.1>


  
(vinyl acetate 90%, crotonic acid 10% -

  
molecular weight 45,000 to 50,000)

  

 <EMI ID = 223.1>


  
This solution, applied as a styling lotion to bleached hair, gives it a pearly appearance with green reflections.

EXAMPLE 35

  
We prepare the following solution:
 <EMI ID = 224.1>
 <EMI ID = 225.1>

  
This solution is applied to bleached hair for 15 minutes at 30 [deg.]. After rinsing and shampooing, a very green shade is obtained.

  
 <EMI ID = 226.1>

  
EXAMPLE 36

  
We prepare the following solution:

  

 <EMI ID = 227.1>


  
This solution is applied to naturally white hair at

  
 <EMI ID = 228.1>

  
a silvery gray-green shade is obtained.

  
 <EMI ID = 229.1>

  

 <EMI ID = 230.1>


  
 <EMI ID = 231.1>

  

 <EMI ID = 232.1>


  
 <EMI ID = 233.1>

  
We prepare the following solution:

  

 <EMI ID = 234.1>


  
This solution is applied to bleached hair for 20 minutes at room temperature. After rinsing and shampooing, the following is obtained: a pale silvery green shade.

  
 <EMI ID = 235.1>

  
 <EMI ID = 236.1>

  

 <EMI ID = 237.1>


  
 <EMI ID = 238.1>

  
 <EMI ID = 239.1>

  
very silvery dark green shade.

  
 <EMI ID = 240.1>

  
We prepare the following solution:

  

 <EMI ID = 241.1>


  
 <EMI ID = 242.1>

  

 <EMI ID = 243.1>


  
This solution, applied as a styling lotion on the hair

  
 <EMI ID = 244.1>

  

 <EMI ID = 245.1>


  
 <EMI ID = 246.1>

  
This solution is applied to bleached hair for 20

  
 <EMI ID = 247.1>

  
with golden reflections,

  
 <EMI ID = 248.1>

  
We prepare the following solution:

  

 <EMI ID = 249.1>


  
 <EMI ID = 250.1>

  
minutes room temperature. After rinsing and shampooing, a pearly almond green shade is obtained.

  
 <EMI ID = 251.1>

  
We prepare the following solution:
 <EMI ID = 252.1>
 <EMI ID = 253.1>

  
1

  
 <EMI ID = 254.1> <EMI ID = 255.1> metallic green shade.

  
EXAMPLE 4-5

  
We prepare the following solution:

  

 <EMI ID = 256.1>
 

  
 <EMI ID = 257.1>

  
 <EMI ID = 258.1>

  

 <EMI ID = 259.1>


  
 <EMI ID = 260.1>

  

 <EMI ID = 261.1>


  
This solution, applied as a styling lotion on the hair

  
 <EMI ID = 262.1>

  
EXAMPLE 47

  
We prepare the following solution:

  

 <EMI ID = 263.1>


  
 <EMI ID = 264.1>
 <EMI ID = 265.1>
- This solution, applied as a comfortable lotion in folds on bleached hair, gives it a light bronze shade.

  
 <EMI ID = 266.1>

  
We prepare the following solution:

  

 <EMI ID = 267.1>


  
This solution is applied to bleached hair for

  
20 minutes at 40 [deg.]. After rinsing and shampooing, a linden shade is obtained.

  
 <EMI ID = 268.1>

  
We prepare the following solution: <EMI ID = 269.1> <EMI ID = 270.1>

  
 <EMI ID = 271.1>
 <EMI ID = 272.1>
 This solution, applied as a styling lotion on discolored hair ... gives it a silvery almond green shade,

  
 <EMI ID = 273.1>

  
We prepare the following solution:
 <EMI ID = 274.1>
- Ammonia at 22 [deg.] B q.s.p. pH 8

  
This solution, applied as a styling lotion to bleached hair, gives it a linden shade with a pearly appearance.

  
 <EMI ID = 275.1>

  
We prepare the following solution:
 <EMI ID = 276.1>
 <EMI ID = 277.1>

  
This solution, applied as a styling lotion to bleached hair, gives it a very luminous kentia green shade.

  
 <EMI ID = 278.1>

  
 <EMI ID = 279.1>

  

 <EMI ID = 280.1>


  
Cr, apply this solution to bleached hair for 20

  
 <EMI ID = 281.1>

  
pearly.

  
EXAMPLE 53

  
We prepare the following solution:

  

 <EMI ID = 282.1>
 

  

 <EMI ID = 283.1>


  
 <EMI ID = 284.1>

  
nutes at room temperature. After rinsing and shampooing the hair has a pearly appearance with silvery green reflections.

EXAMPLE 5'4.

  
We prepare the following solution:

  

 <EMI ID = 285.1>


  
 <EMI ID = 286.1>

  
molecular weight 45,000 to 50,000)

  

 <EMI ID = 287.1>


  
 <EMI ID = 288.1>

  
discolored, gives them a light bronze green shade with golden reflections.

EXAMPLE 55

  
We prepare the following solution:
- Colorant of example 3 0.15 g <EMI ID = 289.1> <EMI ID = 290.1>

  
molecular weight 45,000 to 50,000)

  

 <EMI ID = 291.1>


  
This solution, applied as a styling lotion to bleached hair, gives it a verbena shade.

  
 <EMI ID = 292.1>

  
We prepare the following solution:

  

 <EMI ID = 293.1>


  
 <EMI ID = 294.1>

  
molecular weight 45,000 to 50,000)

  

 <EMI ID = 295.1>


  
This solution, applied as a styling lotion on

  
 <EMI ID = 296.1>

  
 <EMI ID = 297.1>
 <EMI ID = 298.1>
 <EMI ID = 299.1>

  

 <EMI ID = 300.1>


  
This solution, applied as a styling lotion on hair? discolored, gives them a pearly light beige shade with green-golden reflections.

  
 <EMI ID = 301.1> <EMI ID = 302.1>

  

 <EMI ID = 303.1>


  
 <EMI ID = 304.1>

  
molecular weight 45,000 to 50,000)

  

 <EMI ID = 305.1>


  
 <EMI ID = 306.1>

  
discolored hair, gives them a lime shade.

  
 <EMI ID = 307.1>

  
We prepare the following solution:
 <EMI ID = 308.1>
 <EMI ID = 309.1>

  
This solution is applied to bleached hair for 20

  
 <EMI ID = 310.1>

  
 <EMI ID = 311.1>

  
 <EMI ID = 312.1>

  
 <EMI ID = 313.1>

  
We prepare the following solution:

  

 <EMI ID = 314.1>
 

  
 <EMI ID = 315.1>

  
 <EMI ID = 316.1>
 <EMI ID = 317.1>
 <EMI ID = 318.1>

  
 <EMI ID = 319.1>

  
 <EMI ID = 320.1>

  
a steel gray-blue shade.

  
 <EMI ID = 321.1>
 <EMI ID = 322.1>
 <EMI ID = 323.1>

  
We apply this solution to hair naturally

  
 <EMI ID = 324.1>

  
we obtain an icy brown shade with purple reflections.

  
 <EMI ID = 325.1>

  

 <EMI ID = 326.1>


  
 <EMI ID = 327.1>. Molecular weight 45,000 to 50,000)
 <EMI ID = 328.1>
 <EMI ID = 329.1>

  
bleached hair, gives them a pinkish beige shade with golden highlights.

  
 <EMI ID = 330.1>

  
We prepare the following solution:
 <EMI ID = 331.1>
 <EMI ID = 332.1>

  
This solution, applied for 20 minutes at room temperature to bleached hair, gives them after rinsing and shampooing a golden bronze shade.

EXAMPLE 65

  
We prepare the following solution:
 <EMI ID = 333.1>
 <EMI ID = 334.1> <EMI ID = 335.1>

  
molecular weight 45,000 to 50,000)

  

 <EMI ID = 336.1>


  
This solution, applied as a styling lotion to bleached hair, gives it a tin gray shade.

  
 <EMI ID = 337.1>
 <EMI ID = 338.1>
 <EMI ID = 339.1>

  

 <EMI ID = 340.1>


  
 <EMI ID = 341.1>

  
 <EMI ID = 342.1>

  
 <EMI ID = 343.1>

  
Oa prepares the following solution:

  

 <EMI ID = 344.1>


  
 <EMI ID = 345.1>

  

 <EMI ID = 346.1>


  
This solution applied as a lotion of = [pound] wrinkles on

  
 <EMI ID = 347.1>

  
We prepare the following solution:

  

 <EMI ID = 348.1>


  
This solution, applied as a styling lotion on discolored horses, gives them a light golden bronze shade.

  
 <EMI ID = 349.1>

  

 <EMI ID = 350.1>


  
This solution is applied to bleached hair for

  
 <EMI ID = 351.1>

  
shampoo, a METALLIC GREEN shade is obtained.

  
EXAMPLE 70

  
We prepare the following solution:

  

 <EMI ID = 352.1>


  
This solution applied as a styling lotion on

  
bleached hair gives them a LIGHT GREEN PEARL shade.

  
EXAMPLE 71

  
We prepare the following solution:

  

 <EMI ID = 353.1>


  
This solution applied as a styling lotion to bleached hair, gives it a SILVER ALMOND GREEN shade.

  
 <EMI ID = 354.1>

  

 <EMI ID = 355.1>


  
This solution applied as a lotion of ease in folds, sire

  
 <EMI ID = 356.1>

  
 <EMI ID = 357.1>

  
We prepare the following solution:

  

 <EMI ID = 358.1>


  
This solution applied as a styling lotion on

  
bleached hair, gives it a GREEN TILLEUL shade.

  
---

  
EXAMPLE 74

  
We prepare the following solution:

  

 <EMI ID = 359.1>


  
This solution is applied to naturally white hair

  
 <EMI ID = 360.1>

  
 <EMI ID = 361.1>

  
 <EMI ID = 362.1>

  
We prepare the following solution:

  

 <EMI ID = 363.1>


  
This solution applied as a styling lotion on

  
bleached hair, gives it a LIGHT BRONZE GREEN shade.

  
 <EMI ID = 364.1>

  
We prepare the following solution:

  

 <EMI ID = 365.1>


  
Or .. apply this solution to naturally white hair

  
 <EMI ID = 366.1>

EXAMPLE 77

  
We prepare the following solution:

  

 <EMI ID = 367.1>


  
This styling lotion is applied to previously bleached hair. After drying, a

  
 <EMI ID = 368.1>

EXAMPLE 78

  
We prepare the following solution:

  

 <EMI ID = 369.1>


  
 <EMI ID = 370.1>

  
on white hair, gives them a GREEN BRONZE shade after drying.

  
EXAMPLE 79

  
We prepare the following solution:

  

 <EMI ID = 371.1>


  
This solution applied as a styling lotion,

  
on gray hair, gives them a PHOQUE shade after drying. [pound] - <EMI ID = 372.1>

  

 <EMI ID = 373.1>


  
This solution, applied as a styling lotion, on bleached hair, gives them a shade after drying.

  
 <EMI ID = 374.1>

  
 <EMI ID = 375.1>

  

 <EMI ID = 376.1>


  
 <EMI ID = 377.1>

  
on white hair, gives them a TILLEUL shade after drying. -.

  
 <EMI ID = 378.1>

  
 <EMI ID = 379.1>

  

 <EMI ID = 380.1>


  
This solution, applied to gray hair, gives it a GREEN YELLOW shade after drying.

  
 <EMI ID = 381.1>

  
We prepare the following solution:

  

 <EMI ID = 382.1>


  
This crèue is applied for 15 minutes to previously bleached hair. After rinsing, shampooing,

  
rinsing and drying, a BLOND GREEN color is observed

WITH GOLDEN REFLECTIONS.

  
EXAMPLE 84

  
 <EMI ID = 383.1>

  

 <EMI ID = 384.1>


  

 <EMI ID = 385.1>


  

 <EMI ID = 386.1>


  
This solution applied to white hair, with an exposure time of 25 minutes, gives them after rinsing, shampooing, rinsing and drying a BOTTLE GREEN shade.

  
This same solution, applied to gray hair, gives them a PINK GREEN shade.


    

Claims (1)

<EMI ID = 387.1> <EMI ID = 388.1> where: <EMI ID = 389.1> hydrogen or halogen or a lower alkyl / or alkoxy radical; <EMI ID = 390.1> lower alkyl substituted by one or more hydroxyl groups, a radical <EMI ID = 391.1> <EMI ID = 392.1> <EMI ID = 393.1> <EMI ID = 394.1> a hydrogen atom, a lower alkyl, lower hydroxyalkyl, acyl- <EMI ID = 395.1> nitrogen to which they are attached, a six-membered heterocycle capable of containing an oxygen atom, such as a piperidine or morpholine ring; - z represents (a) a hydroxyl residue or (b) a group: <EMI ID = 396.1> where: <EMI ID = 397.1> a lower alkyl, lower hydroxyalkyl or lower carbamylalkyl radical, <EMI ID = 398.1> lower, or an aminoalkyl residue of formula: <EMI ID = 399.1> <EMI ID = 400.1> <EMI ID = 401.1> <EMI ID = 402.1> <EMI ID = 403.1> <EMI ID = 404.1> <EMI ID = 405.1> <EMI ID = 406.1> <EMI ID = 407.1> 3 - Process for preparing the compounds defined in claim 1, characterized in that the condensation of a 3-aaino 4-methoxy phenol of general formula is carried out: <EMI ID = 408.1> <EMI ID = 409.1> <EMI ID = 410.1> <EMI ID = 411.1> <EMI ID = 412.1> <EMI ID = 413.1> nitrose derivative of formula: <EMI ID = 414.1> <EMI ID = 415.1> <EMI ID = 416.1> 5 - Method according to claims 2, 3 and 4, characterized <EMI ID = 417.1> hydroalcoholic at alkaline pH, the compounds being used in equimolecular proportions, 6 - Method according to claims 2, 3 and 4, characterized in that the condensation takes place in the presence of a large excess of hydrogen peroxide. <EMI ID = 418.1> <EMI ID = 419.1> <EMI ID = 420.1> 16 - Composition according to claim 15, characterized in that the glycol is butyl glycol or propylene glycol. 17 - Composition according to any one of claims <EMI ID = 421.1> lower aliphatic alcohol having 1 to 4 carbon atoms. 18 - Composition according to claim 17, characterized in that the alcohol is ethanol or isopropanol. 19 - Composition according to any one of claims 17 and 18 constituting a hair styling lotion, characterized by <EMI ID = 422.1> in weight. 20 - Composition according to claim 1 ?, characterized <EMI ID = 423.1> vinyl, maleic anhydride-butylvinyl ether copolymer, methyl methacrylate-stearyl methacrylate-dimethyl methacrylate terpolymer, vinyl acetate-alkyl stearate-allyloxy acetic acid terpolymer. <EMI ID = 424.1> 22 - Process for dyeing human hair, characterized <EMI ID = 425.1> <EMI ID = 426.1> <EMI ID = 427.1> <EMI ID = 428.1> <EMI ID = 429.1> 23 - Process for styling human hair, characterized in that a composition as defined in any one of claims 19 to 21 is applied to the hair previously washed and rinsed, <EMI ID = 430.1>