DE1935234C - Disazo compounds and their uses - Google Patents

Description

the two B each - CO - or - SO ₂ -

-CH- -CH-

CH ₂ C ₆ H ₅ cyclohexyl

-CH- -CH-

CH ₂ CH ₂ S - CH ₃ • naphthyl

-CH-phenyl

where the phenyl nucleus is unsubstituted or chlorine atoms, Carry bromine, nitro, methyl, methoxy or acetoxy groups as substituents can means.

2. Process for dyeing or printing fibers or threads or made therefrom Materials made from fully or semi-synthetic, hydrophobic, high-molecular organic substances, characterized in that dyes of the formula (I) according to Claim 1 are used.

The invention relates to fully or semi-synthetic, hydrosoluble material heavy in water Disazo compounds, which are excellent phobic, high molecular weight, organic substances, for dyeing or printing fibers or fiber The new dyes correspond to the formula

R ₄

N-X-B-N-A-N-B-X-N

N = N-D

R, ^{1X5 IV7 1} ^ ⁸ "* R ₂

wherein the two D are unsubstituted or by chlorine or bromine atoms, cyano, nitro, methylsulfonyl,

Benzylsulfonyl, methylaminosulfonyl, dimethylaminosulfonyl, Benzoyl or acetylamino groups or a group of the formula

- CH = N - OH

substituted phenyl radicals, unsubstituted or substituted by methyl or nitro groups, thiazolyl radicals, substituted by methylsulfonyl or rhodane groups, benzthiazolyl-3 radicals, the 1-phenyl-3-methylpyrazole radical or the methylsulfonylnaphthyl radical, R ₁ and R ₂ independently of one another hydrogen, chlorine or Bromine atoms, methyl, methoxy, acetylamino, propionylamino, ChloφΓopionylamino- or methoxycarbonylammo groups, R ₃ and R ₄ independently of one another hydrogen, chlorine or bromine atoms, methyl, methoxy or ethoxy groups, R ₅ and R ₆ independently of one another hydrogen atoms or alkyl groups with 1 to 3 carbon atoms, which are unsubstituted or as substituents chlorine or bromine atoms, hydroxy, methoxy, ethoxy, cyano, phenyl, formyloxy, acetoxy, propionyloxy, benzoyloxy, methoxycarbonyl, methoxycarbonyloxy, Ä wear thoxycarbonyloxy or aminocarbonyl groups, R ₇ and R ₈ each have a hydrogen atom or a methyl or cyanoethyl group or together an Ät ethylene bridge, the two X are each a group of the formula

- CH ₂ - - CH ₂ CH ₂ - - CH -

A is a bridge link of the formulas

- CH ₂ - - C ₂ H ₄ - C ₃ H ₆

Cl

Cl.

- CH- -CH-

CH ₂ C ₆ H ₅

Cyclohexyl

20th

or

CH,

CH- -CH-

I I

CH ₂ CH ₂ S - CH ₃ naphthyl

- CH-phenyl

-CH ₂

the two B in each case —CO— or —SO ₂ - and where the phenyl nucleus can be unsubstituted or can carry chlorine atoms, bromine atoms, nitro, methyl, methoxy or acetoxy groups as substituents.

The azo compounds of the formula R are particularly preferred.

D ₁ -N =

R ₁ ,

Rl2 ¹ N 2

N-CH ₂ -CO-NH-CH-NH-CO-CH ₂ -N- <> -N = N-D ₁

R "

I ^ f

13th

wherein the two D ₁ each have a phenyl radical substituted by chlorine or bromine atoms, cyano, nitro or methylsulfonyl groups, the two R ₁₀ independently of one another a hydrogen atom or an ethyl radical which is unsubstituted or chlorine atoms, cyano, acetoxy, propionyloxy or Carries methoxycarbonyl groups as substituents, the two R _n independently of one another a hydrogen, chlorine or bromine atom or a methyl, methoxy, acetylamino or propionylamino group, the two R ₁₂ independently of one another a hydrogen atom or a methoxy or ethoxy group and R ₁₃ a Means hydrogen atom, a methyl, ethyl or phenyl group.

The new compounds of the formula (I) are prepared by diazotizing two moles of one Amine or a mixture of amines of the formula

D-NH ₂ (III)

and coupling the obtained diazonium compounds

with 1 mole of a compound of the formula

N-X-B-N-A-N-B-X-N

R ₅ R ₇ Rg

In general, the coupling takes place in an acidic, optionally buffered medium with cooling, e.g. B. at temperatures between -1O and +30 ⁰ C, preferably between 0 and 5 ° C, instead. A preferred buffer substance is e.g. B. sodium acetate.

The coupling components of the formula (IV) can, depending on the meaning of the radicals X, B, A, R ₇ and R ₈ , be prepared by one of the following methods.

a) 1 mole of a compound of the formula

Halogen-XBNANBX-Halogen
R ₇ R ₈

wherein halogen is a chlorine or bromine atom, with 1 mole of a compound of formula

and with 1 mol of a compound of the formula

in water or an inert organic solvent, preferably in the presence of an acid-binding agent, at temperatures between 50 and 200 ^° C., if necessary under pressure. As inert organic solvents, for. B. toluene, dioxane, xylene, nitrobenzene or chlorobenzenes into consideration. Preferred acid-binding agents include alkali metal carbonates, bicarbonates or acetates or magnesium oxide.

b) 1 mole of a compound of the formula

Γ ■

- X - B - NH

R ₇

and 1 mole of a compound of the formula

Ν — Χ —Β —NH
'R ₆ R ₈

are diluted with 1 mole of an aliphatic or aromatic aldehyde, in the presence of a Mineral acid, preferably sulfuric acid or one containing 2 to 4 carbon atoms Alkanoic acid, e.g. B. glacial acetic acid, in the presence of a little sulfuric acid (see: E. S c h r a u Γ-s t ä 11 e r et al., Z. f. Naturforschung, 17 b [1962], P. 505 to 516), optionally at elevated temperature, implemented.

<> - N — χ — β -:

c) 1 mole of a compound of the formula

R ₃

/ ~ VNX - B - halogen

Ri

ίο and 1 mole of a compound of the formula

- X - B - halogen

where halogen is again chlorine or bromine, preferably in the presence of an acid-binding agent Means, with 1 mole of a compound of the formula

HN-A -NH

I.
R ₇

R ₈

d)

as described under a), but reacted ^{at temperatures between 0 and 10O 0 C.}

1 mole of a compound of the formula

= ch-co-nan-co-ch = ch ₂

is, optionally in the presence of a catalyst, with 1 mol of a compound of the formula

R ₅

and 1 mole of a compound of the formula
R4

55 at temperatures between 50 and 200 ⁰ C, optionally under pressure, implemented.

Suitable catalysts are, for. B. low molecular weight Alkanoic acids (containing 1 to 4 carbon atoms), especially glacial acetic acid.

Azo compounds of the formula (I) can also be prepared if 1 mole of an aldehyde is the formula

A = O (V)

with a mixture of 1 mole of an azo compound

the formula r
R. -N - X i - B - N (VI) D-N = N R ₇ - H

and 1 mole of an azo compound of the formula

(VII)

D - N = N - \ / ~ N - X - B - N

D-N = N

R,

NR ₅

-X -B -Shark

and I moles of an azo compound of the formula

D-N = N

35

40

where in the formulas (IX) and (X) Hai denotes a chlorine or bromine atom, condensation takes place.

Azo compounds of the formula (1) are also obtained if 1 mol of a compound of the formula 45

Shark - X - B - N - A - N - B - X - Shark

7 ^K 8 (Λ-1)

wherein Hai is a chlorine or bromine atom, with a mixture of 1 mole of an azo compound of formula

^R 3

D-N = N

NH

R ₁

55

60

and 1 mole of an azo compound of the formula

NH P (III) ⁶ 5

condensed.

Finally, azo compounds of the formula (I) are also obtained if 1 mole of a compound is used the formula

CH ₂ = CH-BNANB-CH =

R ₇

(XIV)

ίο with a mixture of 1 mol of an azo compound the formula

R ₃

D-N =

is condensed.

Further, azo compounds of the formula (I) can be prepared when 1 mole of a diamine of formula

HN-A-NH ²⁰

I I (viii)

R ₇ R ₈

with a mixture of 1 mole of an azo compound of formula ²⁵

R ₃ (IX)

NH

PCV)

R ₁

and 1 mole of an azo compound of the formula

NH (XVI)

in a fatty acid containing 1 to 4 carbon atoms dissolved, at temperatures between 70 and 15 (T C implements. The preferred fatty acid is acetic acid (glacial acetic acid).

The reaction of an aldehyde of the formula (V) with the compounds of the formulas (VI) and (VII) preferably takes place in the presence of a dilute mineral acid, preferably sulfuric acid or a 2 to 4 carbon atoms containing alkanoic acid, e.g. B. glacial acetic acid, in the presence of a little sulfuric acid.

The diamine of the formula (VIII) is reacted with the compounds of the formulas (IX) and (X) generally at temperatures between 0 and 100 ° C in water or an inert organic Solvent, preferably in the presence of an acid-binding agent, if necessary under pressure.

As inert organic solvents, for. B. toluene, dioxane, xylene, nitrobenzene or chlorobenzenes into consideration. Preferred acid-binding agents include alkali metal carbonates and bicarbonates or acetates or magnesium oxide.

It is particularly advantageous to use the new To convert dyes into dye preparations before they are used. Processing to dye preparations takes place in well known manner, e.g. B. by grinding in the presence of dispersants and / or fillers. With the preparations, optionally dried in a vacuum or by atomization, can after adding more or less water, dyeing in so-called long or short liquor, padding or print.

The dyes are extremely well absorbed from aqueous suspension on textile material made of fully synthetic or semi-synthetic, hydrophobic, high molecular weight organic substances. Especially suitable are acetate for dyeing or printing textile material composed of linear aromatic polyesters, and cellulose ^ _^1/2 cellulose triacetate and synthetic polyamides. They can also be used to color polyolefins.

209 683/348

ίο

One dyes or prints according to known, z. B. the method described in French patent 1,445,371. The dyeings obtained are extremely fast, e.g. B. excellent thermofixing, subliming, pleating, smoke gas, dyeing, dry cleaning, chlorine and wet fast, z. B. water, wash and sweat resistant. They are extremely resistant to the effects of the various permanent pressing processes. The etchability and reserve of wool and cotton are good. The lightfastness is excellent, even in light shades, so that the new dyes are also very suitable as mixing components for the production of pastel-colored fashion shades. The dyes are verkochbeständig at temperatures up to at least 220 ° C and especially at 80 to 14O ⁰ C. This stability is not adversely affected either by the liquor ratio or by the presence of dye accelerators.

The blue representatives are suitable for production in combination with small amounts of red dyes cheaper, light, wash, sweat, chlorine, sublimated, pleated and uien'iiüuxierechicr as well as etchable navy blue Dyeings and together with red and yellow dyes to produce real black dyeings.

The dyes according to the invention surpass the next comparable ones from the French patent 1 526 338 known dyes in the solvent fastness (dry cleaning fastness) and in the lubricant fastness.

The parts mentioned in the following examples

to are parts by weight and the percentages are percentages by weight.

The temperatures are given in degrees Celsius.

example 1

6.9 parts of sodium nitrite are slowly added to 120 parts of concentrated sulfuric acid at 60 ° to 70 ° with vigorous stirring. The mixture is stirred for a further 10 minutes at 60 ^{° C.} , then cooled to 10 ° and 16.3 parts of 2-amino-5-nitrobenzonitrile are added at this temperature. The diazotization has ended after 3 hours. The sulfuric acid diazonium salt solution is poured into a mixture of 19.1 parts of the compound of the formula

fe te 2i tr

CH ₂ CH ₃ CH ₃ CH ₂

N N

CH ₂ -CO-NH-CH-NH-CO-Ch ₂

CH ₃

100 parts of glacial acetic acid, 750 parts of ice and 10 parts of substance forms immediately and precipitates. It will be filtered off.

Aminosulfonic acid. The coupling is washed free of acid in acid and dried. The thus obtained

Medium by blunting with sodium acetate on dye stains synthetic fibers in ruby red

the pH value 2.0 to 2.5 brought to an end. The dye shades with excellent fastness properties.

Example 2

To 240 parts of concentrated sulfuric acid are slowly added at 60 to 70 ° with vigorous stirring 2,6 - dichloro - 4 - nitro - 1 - aminobenzene. 29.6 parts of 2,6 - dibromo - 4 - nitro - i - aminobenzoi and 200 parts

Given 13.8 parts of sodium nitrite. 45 more glacial acetic acid is stirred in. The mixture is stirred for 3 hours at 10 to 12 ° and 10 minutes at 60 °. then cools to 10 "and adds the resulting diazonium salt solution to one at 10 to 20 "200 parts of glacial acetic acid and then 20.7 parts of a mixture of 99.6 parts of the compound of the formula

CO - CH ₂ - N - CH ₂ CH ₂ OCOCH ₃ NH

CH ₃ - CH
NH

CO - CH ₂ - N - CH ₂ CH ₂ OCOCH ₃

200 parts of glacial acetic acid, 800 parts of ice and 20 parts of aminosulfonic acid. The clutch will be in acidic Medium brought to the end by blunting with sodium acetate to pH 2.0 to 2.5. The dye R

substance forms very quickly and precipitates. It is filtered off washed acid-free and dried. The dye mixture thus obtained dyes synthetic fibers in yellow-brown shades with excellent fastness properties.

Example 3 a) Preparation of the coupling component

A mixture of 279 parts of chloroacetamide, 80 parts of paraldehyde and 12 parts of 10% sulfuric acid is heated for 1 hour on a water bath (bath temperature: 95 to 100 °). Be on it 2000 parts of water were added, dissolved while hot and filtered clear. When the filtrate cools, it crystallizes

Ethylene-bis-chloroacetamide in long white needles out. After cooling well, it is suctioned off and washed with water.

42.6 parts of the ethylene-bis-chloroacetamide obtained, 37 parts of magnesium oxide, 50 parts of monoethylaniline and 1000 parts of dioxane are in one Given autoclave and stirred for 12 to 15 hours at 140 to 150 °. The reaction mixture is then left cool down, the unused magnesium oxide and the resulting magnesium chloride are filtered and the resulting solution is evaporated. The residue is subjected to vacuum distillation, the excess monoethylaniline being distilled off and the coupling component of the formula

CH ₂ CH ₃

- N - CH ₂ - CO - NH CH - CH ₃

remains behind.

N-CH ₂ -CO-NH

CH ₁ CH ₃

b) Preparation of the dye

t. p To 120 parts of concentrated sulfuric acid

e S the slowly at 60 to 70 ° with vigorous stirring η I given 6.9 parts of sodium nitrite. The mixture is stirred for a further 10 minutes at 60 °, then cooled to 10 ° and added at 10 to 20 ° 100 parts of glacial acetic acid and then 20.7 parts 2,6-dichloro-4-nitro-1-aminobenzene and another 100 parts of glacial acetic acid. The mixture is stirred for 3 hours at 10 to 12 ° and pour the resulting diazonium salt solution to a mixture of 19.1 parts of the compound of formula

e
e
d
α

CH ₂ CH ₃ CH ₃ CH

N N

CH ₂ - CO - NH - CH - NH - CO - CH ₂
CH ₃

100 parts of glacial acetic acid. 750 parts of ice and 10 parts Aminosulfonic acid. The coupling is made in acidic medium by blunting with sodium acetate pH 2.0 to 2.5 brought to the end. The dye forms immediately and precipitates. It is filtered off acid-free washed and dried. The dye thus obtained dyes synthetic fibers in yellow-brown shades with excellent fastness properties.

Example 4 a) Preparation of the coupling component

A solution of 4 parts of potassium carbonate in 162 parts of 40% formaldehyde is added Stir in 200 parts of finely powdered monochloroacetamide. One warms up gently on the water bath, until a clear solution is obtained. It is then allowed to cool again, leaving a thick crystal pulp The resulting N-methylolchloroacetamide is formed is filtered off, recrystallized from acetone or benzene and dried.

100 parts of N-methylolchloroacetamide are concentrated in 250 parts with cooling at 20 to 25 ° Dissolved sulfuric acid. This solution is left to stand overnight and the reaction mass is then added dropwise to 2000 parts of ice, the Methykn-bis-chloroacetamide fails. The precipitated product is filtered off, washed with a little cold water and crystallized it out of alcohol. The pure methylenebis-chloroacetamide precipitates in the form of white platelets with a melting point of 175 °.

39.8 parts of the methylene-bis-chloroacetamide obtained, 50 parts of monoethylaniline, 32 parts of magnesium oxide and 1000 parts of dioxane are in one Given autoclave and stirred for 12 to 15 hours at 140 to 150 °. The reaction is then

cool tion mixture and filter it. The filtrate is evaporated and the remaining product Purified by distilling off the unused monoethylaniline. The remaining product corresponds the formula

CH, CH, CH ₂ CH ₃

-CH ₂ -CO-NH-CH ₂ -Nh-CO-CH ₂ -N

b) Preparation of the dye

6.9 parts are added to 120 parts of concentrated sulfuric acid at 60 ° to 70 ° with vigorous stirring Given sodium nitrite. The mixture is stirred for a further 10 minutes

and at 60 ° slowly carries 20.6 parts of 1-amino-2-chloro-20 compound of the formula

4-methylsulfonylbenzene. You keep the temperature for 30 to 40 minutes at 60 ° and then cools to room temperature. The obtained diazonium salt solution is poured into a mixture of 18.4 parts of the compound prepared by the above method.

CH ₂ CH,

CH ₃ CH ₂

CH ₂ -CO-NH-CH ₂ -Nh-CO-CH ₂

300 parts of glacial acetic acid, 750 parts of ice and 10 parts of aminosulfonic acid. The clutch will be in acidic Medium was brought to an end by blunting with sodium acetate to pH 2.0 to 2.5. The dye forms very quickly and fails. It is filtered off, washed free of acid and dried. the The dye obtained in this way dyes synthetic fibers in orange shades with excellent fastness properties.

Dyeing instruction 1

7 parts of the dye obtained according to Example 1 are mixed with 4 parts of dinaphthylmethandisulfonsaurem Sodium, 4 parts of sodium cetyl sulfate and 5 parts of sodium sulfate in a ball mill for 48 hours ground to a fine powder. 2 parts of the dye preparation obtained in this way are dissolved in 3000 parts of water, which is 3 parts of a 30% solution of a highly sulfonated castor oil and 20 parts of an emulsion of a chlorinated benzene, dispersed. 100 parts of polyester fiber fabric are brought at 20 to 25 ° "Dacron" (registered trademark), heats the bath to 95 to 100 ° in about 30 minutes and colors 1 hour at 95 to 100 °. The material to be dyed is taken out of the bath, rinsed, 15 minutes at 70 ° with a 0.1% solution of an alkylphenyl polyglycol ether soaped, rinsed again and dried. You get a ruby red color with excellent fastness properties.

Staining instruction 2

40

45

60

30 parts of the dye mixture obtained according to Example 2 are mixed with 40 parts of dinaphthylmethandisulfonsaurem Sodium, 50 parts of sodium cetyl sulfate and 50 parts of anhydrous sodium sulfate in one Ball mill ground to a fine powder for 48 hours. To 4 parts of the dye preparation obtained 100 parts of purified polyester fiber material "Terylene" are added to 1000 parts of water at 40 to 50 ° C (registered trademark) and warms up slowly. Staining under pressure for about 60 minutes 130 ° and after rinsing, soaking, rinsing and drying it gets a yellow-brown color with excellent Fastnesses.

Dyeing instruction 3

An aqueous, finely disperse suspension of 30 parts of the dye mixture obtained in Example 2. 70 parts of sodium dinaphthylmethanedisulfonic acid and 3 parts of sodium alginate are made up to 1000 parts with water and mixed well. A Polyeslergewebe is padded with the obtained padding liquor at 2Q ^D, treated with air at 60 to 100 ° and then dried with hot, dry air of 230 ° 60 seconds. The fabric is then rinsed, soaped, rinsed again and dried. A yellow-brown, level dyeing with good true heals is obtained.

Dyeing instruction 4

7 parts of the dye obtained according to Example 1 are mixed with 4 parts of dinaphthylmethandisulfonsaurem Sodium, 4 parts of sodium cetyl sulfate and 5 parts of anhydrous sodium sulfate in a ball mill Ground to a fine powder for 48 hours.

2 parts of the dyeing preparation obtained in this way are dispersed in 3000 parts of water which contains 3 parts of a 30% strength solution of a highly sulfonated castor oil. At 20 to 25 ° to 100 parts of cellulose brings ^ ¹ / - acetatfasergewebe and heats the bath in about 30 minutes to 80 to 82 °. This is followed by dyeing at 80 ° to 82 ° for 1 hour. The material to be dyed is taken out of the bath, rinsed, soaped, rinsed again and then dried. A ruby-red dyeing with good fastness properties is obtained.

The following table shows the formulas of further dyes according to the invention.

dye

r-4uance on polyester

O, N

NO ₂

OCH ₂ CH ₃

CH ₂ CH ₂ OCOCH ₃

Br

Γ Vh ₂ CONH CH-

NH-COCH ₃ |

CH ₃

CN

N = N

CH ₂ CH ₂ CN

CN

n = n

CH ₂ CH ₂ CN

CH ₃ COOCH ₂ CH ₂

NH-COCH ₃ NO ₂

-NH CO

CH ₂ CONH

CH,

CN

CH ₂

N = N-

NHCH ₂ CONH

Cl

CH,

-N = N- / V-NO ₂
OCH ₂ CH ₃ Br

NCCH ₂ CH ₂

CH ₂ CONH CH NH COCH ₂

CH ₃

CN

-CH NH COCH ₂ NH

C ₆ H ₅

NC

-N = N

CH ₁ CH,

NHCOCH ₂ \ ^

CH ₁

NO,

blue

Red

Ruby red

orange

continuation

Dye shade on polyester

CN

O ₂ N

Br

OCH ₃

NHCH ₂ NHCOOCH ₃

CONH - CH - NH - CO CH ₃

OCH ₃ CN

N = N

NO,

blue

Cl

O ₇ N

N = N- <> -N

Cl

CH ₂ CH ₂ CN NC-CH ₂ CH ₂

N ^X CH ₂ CONH CH NH CO CH ₂

NHCOOCH,

N = N

Br

Cl

NO ₂

Yellow-brown

O ₂ N-

-N

A-N = N

CH ₃ CH ₂ CH ₂ OCOOCH ₃ Cl

N-CH ₂ CH ₂ OCOOCH,

-N

Cl

-CH ₂ CONHCHNHCOCh ₂ -CH ₃

violet

Cl

-N

CH ₁ SO,

N = N

CH ₂ CH ₂ CN CH ₂ CH ₂ CN

N-red

OCH, OCH ₃

Continuation dye

continuation

Example!

dye

CH,

OCH ₃ OCH

CH,

O ₂ N-

-N

N = N

OCH,

OCH ₃

NHCH ₁ CONH CH NHCOCH ₂ NH

CH ₃

NO,

OCH,

NHCH ₂ CONH CH - NH - CO CH ₂ NH

CH ₂ CH ₃

CN

CH ₁ SO,

-N = N

CH ₂ CH ₃ CN

NCCH ₂ CH ₂

CH ₂ CONH-

CH ₃

-CH-CH ₃

NHCOCH ₂

N = N- <VSO ₂ CH ₃

NHCOCH,

Cl

O ₂ N

CH ₂ CH ₂ OCO

N = N

CH ₂ CH ₂ CN

Cl

CH ₃ CONH CH NH CO CH ₂

CH ₃

-NO,

Cl

0, N-

-N = N

CH ₂ CH ₂ OCOCH ₃

CH ₂ CH ₂ OCOCH ₃
N = N

CN

CH ₇ CONH CH NH CO CH ₂

CH,

NO ₂

Shade on polyester

blue

blue

Ruby red

Scarlet fever

Red

continuation

example

dye

Shade on polyester

CN

CH ₃ SO ₂ \ VN = N

Cl

CH ₂ CH ₂ COOCH ₃

CH ₂ CH ₂ COOCH ₃

CH ₃

CH ₂ CO NH CH NH CO CH ₂

NO ₂

Ruby red

CH ₃

CH,

CH ₃ SO ₂ - <> -N = N- <VN

CH ₃ CH ₃

CH ₂ CONH-NHCOCH ₂ CH ₃

-CH NH-

CH ₃

CH ₂ CH ₂ CN

N— <> —N = N

Cl

SO ₂ CH ₃

orange

Cl

O, N- <V-N = N

Cl

CH ₂ CH ₂ OCOCH ₂ Ch ₃

CH ₂ CH ₂ OCOCh ₂ CH ₃ 9

CH ₂ CO NH CH NH CO CH ₁

CH,

NO ₂

Yellow-brown

Br

O ₂ N

/
Br

N = N

CH ₂ CH ₂ CN

CH ₃

CH, CO-NH-CH-NH-CO CH

CH,

CH ₂ CH ₂ OCOCH ₃

I / - \

«- <f V-N = N

■ 2

Cl Br

NO ₂

Yellow-brown

Br

CH ₇ CH ₂ OCOCH,

CH ₃ SO ₂ ^ VN = N

CH ₂ CH ₂ OCOCH ₃

^N CH ₂ CO-NH-CH-NH-CO CH ₂ X-X

CH ₃

SO ₂ CH;

Scarlet fever

Cl

O ₂ N

N = N

Cl

Cl

O ₂ N-

-N = N-

Cl Cl

O ₂ N

Continuation dye

Cl

CH ₂ CH ₃

CH ₃ CH ₂

N /

^N -CO-N-CH ₂ -CH ₂ -N-CO-CH ₂ N = N

-CO IN ^ n ₂

CH ₃

CH ₃ Cl

Cl

CH ₂ CH ₃

CH ₃ CH ₂

-N

CH ₂ CO-

CH ₂ CH ₂

CH ₂ CH ₂ N-

-N = N

-CO CH ₂

CH ₂ CH ₂ OH CH ₂ CH ₂ OH

Cl

Cl

Cl CH ₃

CH ₂ CO -NH-CH-NH-CO CH ₂

CH ₃ Cl Cl

Cl

Cl

CH ₂ CH ₂ OH

HO-CH ₂ CH ₃ ^N CH ₂ CO-NH-CH - NH - CO ₂ CH

NO ₂

CH ₃

CH ₃ Cl

Cl

Cl

O ₂ N

CH ₂ CH ₂ OH

N = N

HO-CH ₂ CH ₂

NH-CH, -NH-CO CH;

N = N

NO ₂

-NO ₂

NO ₂

NO ₂

Γ1

Cl

Yellow-brown

Yellow-brown

Brown

Brown

Brown

continuation

example O ₂ N- < dye CH ₂ -OCOCH ₃ O Cl
I. Shade on polyester I.
CH ₂
ISTTT fA OTT O 28 CH ₂ CH ₂ OCOCH ₃
-N ^7
X CH ₂ CO - NH --CH - INIl LU Lri2 -NH- CO— CH ₂ - NH - <^ ~~ VN = N — C ₆ H ₅ orange CH ₃ Cl Cl
Br O ₂ N- < -NH-CH ₂ - CO - NH-CH - NH - CO - CH ₂ - NH-sQ> —N = N- O 29 CH ₃ yellow O ₂ N- < -NH-CH ₂ -CO-NH-CH - CH ₂ -OH
CH ₂
I / - \
-NH - CO— CH ₂ - N— <f y- N = N-
OCH ₃ 30th O ₂ N- < CH ₃ NH- CO-CH ₂ -NH - / ~ \ rN = N- Orange red CH ₂ CH ₂ OH
CH ₂ —CO — NH — CH-
CH ₃ CH, ^ -NO ₂ 31 -NH-CH ₂ -CO-NH-CH- CH ₂ OCOCH ₃
CH ₂
NH - CO -CH ₂ -N - (^ VN = N- / Brown 32 orange / ~ \ CH ₂ CH ₂ OCOCH ₃
^N CH ₂ —CO —NH-CH- 33 I.
CH ₃ > - NO ₂ orange H ₅ C Cl
I. ^ -NO ₂ V-NO ₂ Cl
A.
Br ^ CH = N-OH HO-N = CH- / > —N = N- ₆ —N = N- > —N = N- > —N = N- > —N = N— O O Cl OCH ₃ 9- CH ₃

! in V Γ! iNn-

CH ₃ K ^ n ₂ —IN— _x s —N = N-

orange

continuation

example

Dye shade on polyester

Cl

O ₂ N

(CH ₃ ) ₂ N-SO ₂ - <VN = N Cl

CN 0 ₂ N- <VN = N

Cl

N = N

OCH ₃ 0 ₂ N- <> -N = N

CH ₂ CH ₂ OCOCH ₃

CH ₂ OCOCH ₃ CH ₇

CH ₂ -CO-NH-Ch-NH-CO-CH ₂ -N- ^ VN = N
CH ₁

Cl

SO ₂ N (CH ₃ ),

orange

Cl

CH ₂ CH ₂ OCO-C ₆ H ₅

N "CH ₂ -O-CO-C ₆ H ₅ CH ₂

_ co - NH - CH ₂ - NH - CO - CH ₂ - N-

_N = N- <V-NO ₂ CN

CH ₂ CH ₃

N 'CH ₃ CH ₂

¹ CH ₂ -CO-NH-CH-NH-CO-CH ₂ -N N = N

NO ₂

Cl

Cl

CH ₂ CH ₂ CONH,

CH ₂ CONH ₂ CH ₂

_CH2 -CO-NH- CH ₂ - NH - CO - CH ₂ - N- -N = N- (VNO ₂ OCH ₁

Red

Scarlet fever

Scarlet fever

continuation

example O ₂ NK Br dye CH ₂ CH ₂ OH \ / ~ ^N CH ₂ -CO-NH-CH-NH CH ₂ CH ₂ OCOCH ₃
OK CH ₂ CH ₂ OCOH ₃
OK 0
Il \ / ~ ^N Γ ^ ΪΤΓΤϊΜΤΓ / ^ Tf WITH - CO - CH ₂ -OH -NO ₂ \ Shade on polyester (V-N = N- CH ₂ CH ₃ CH ₂ -CO-NH-CH-NH I CH ₂ -CO-NH-CH-NH
NH-CO-CH ₂ CH ₃ Il
CH ₂ CH ₂ OCOCH ₃ ^ n? V ^ w IN ΓΊ \ _ ^ I i 1 τ i. 1 CH ₂
/ \ / \ NO ₂ 38 CH ₃ CH ₃ CH, CH ₂ - N- / VN = N- / y O ₂ NK ^X CH ₂ - CO - NH - CH ₂ - - CO - Γ
Br -NO ₂ Scarlet fever Cl CH ₂ CH ₂ OCH ₃ CH ₂ -OCOCH ₃
CH ₂
/ \ / \ 39 CH ₂ - NK ^ "> - N = NY y O ₂ N- < - CO - Γ
Cl -NO ₂ Scarlet fever (^ V-N = N- CH ₂ -OCOCH ₃
CH ₂
I / - \ / - \ 40 CH ₂ - N - <^ "^ VN = N- / y NHCOCH ₂ CH ₃ Scarlet fever 0
Il -NO ₂ O ₂ NK NH - C ( CH ₂ CH ₂ OCOCH ₃
I / —s. / s. Γ VN = N-
\ / N- / VN = N- / y CH ₃ 41 CH ₃ ^ - CH ₂ Γ
CN Red / N pn CH ₂ CH ₂ OCH ₃
I j - \ N π O ₂ N il ik.T -κ τ
Ll · - N I] M 1
\ s / N- ^ VN = N- \ I 42 / \ / \ c /
(" ¹ TT ° violet CrI ₂

Crt,

ISU ₂

example O ₂ N- < Cl
y L / \ dye CH ₂ CH ₂ OCHO —Ν ⁷ CH ₂ CH ₂ CONH ₂ > —N CH ₂ CO - NH CH ₂ - OH CH ₂ CH ₂ OCHO
I y s. TsTTT f ~ T \ PTT Oh OH \ / " ¹ TT C * f \ TSTTT / ° TT Cl OH Cl - \. Shade on polyester CVn = N-Q \
ηττ r ^ r \ TsTTT / " ¹ TT j N - <(J ^ N = N- IN11, LU CO ₂ I. CH ₂ -CH-CH ₂ -Cl CrI, L-U IN11 CIl VSO ₂ CH ₂ C ₆ H ₅ 43 CrI ₂ CU INIl CIl CH ₂ CH ₂ Cl CH ₂ -CH-CH ₃ / ~ »T_t / ^ O /" ^ T-T
LfIi ^ iT. V ^ O-a I. CH ₂ -CH-CH ₂ Cl r Scarlet fever CI I. \ s
M TST ^ CH ₃ N- <> —N = N- Cl H ₅ C ₆ -CH ₂ C CH ₃ ^N CH _: —CO —NH-CH- CH ₂ CONH ₂ N N ν ^κ v_ / I. CH ₂
I y ν ^ CH ₂ -CO-NH-CH-NH-CO-CH ₂ \ TSTTT PO PTT 1 CN
A _y-s CH ₃ N ^ V-N = N- \ INrI CU CrI ₂ I. Cl \ / N = N ν. -NH CO - CH ₂ CH ₃ Cl YJ) -NO ₂ X N / N ' V-SO ₂ NHCH ₃ 44 CH ₂ CH ₂ Cl
I / - \ χ- CN Red Cl / \ / \ _ CH ₃ HNO ₂ ) ₂ skC ~ ^^ ^{n = n} ~ \ -NH-CO-CH ₂ Γ Cl 45 orange Cl
J ν <V-N0 ₂ Cl / \ y Γ O Ν— < S- /) ^ N-N ^ Cl r 46 Cl Scarlet fever Cl
y—- -ι. j- - ι Vy \ _ / Yl I Γ Brown Cl Cl

continuation

ispiei O ₂ Ν-κ O ₂ N S. VN = N
/ _{/ C} Hj V-N CH, Color TsTTT / Τ » CH ₂ N Shade on polyester i Red 8th I 935 2 48 -N = N- / / " ¹ TI ι OK
CH; fNll CU CH ₂ CH
/ - -N = N-H Ruby red **> O ₂ N- r
NHCOCH ₃ -N = N- /
^X CIl ₂ > CH ₂ CH ₃ ^ O TsTTT i ^ TT .M 3 O ₂ N- < ( _/ CH ₂ CH ₃ ^> - N ^X ^ U IN Ii CIl
CH ₃ CH ₂ ^ v I Red Ϊ ~ ΊΤ violet 49 O ₂ N- N -N = N- / : Hj INrI CU Shade on polyester
L ·. ^ " NCS \ _c / ~ ] ■ "Ό" NTTT / ^ ¹ TT CH ₃ CH ₂ CH ₂ CH ^) - N = N- ω CH ₃ "^ V-NH-CH ₂ - ^ U INrI CxI
CH ₃ ί
-CO-NH-CH-NH-CO-Ch ₂
CH ₃ NHCOCH ₃ Red / · Cl -N = N - <^ ^ HCOCH ₃ CH ₃ CH ₂ 50 CH ~ Λ _ violet SO ₂ N (CH ₃ ) ₂
(VN = N - / ^ r ~ * r \ XTTT / " ¹ TI -NH - <^ NHCOOCH ₃ 51 CN pi T LU iNii ■ CIl ₂ ■ NO ₂
^ -s / - ¹ V NHCOOCH ₃ CH / \ _
\ / -CO —NH-CH- (> NO ₂ CH ₃ CH ₂ r
SO ₂ N (CH ₃ ), 52 NO ₂ / \ pA TSTTT / " ¹ TT ~ \ - N = N- < NHCOCH ₃ 53 CU ΓΝΜ CIl
j
CH ₃ dye
__—— 3 ^ CH ₃ _ / - NH CO—- ^S NO ₂ Cl
I. NH-CO-CH ₂ - CN XTi T / ~ "/" V INIi LU ■ —— ___ ■ -

example

CH,

dye

Cl

Cl

O ₂ N-

Cl

-N = N- <r V-NH-CH ₂ -CO-Nh-CH ₂ -NH-CO-CH ₂ -NH-NHCOCH ₂ CH ₂ Cl -N = I

CH ₃

-N = N-

C ₆ H

6 "5

Br
O ₂ N ^^ ~ VN = N

Cl Cl

Cl

O ₂ N-

-N = N

Cl

Cl

NHCOCH ₂ CH ₂ Cl

CH, CH,

-N

CH ₂ —CO -

NH-CH-NH CH ₃

CO-

-N = N

CH ₃

C ₆ H ₅

Br

CH ₂ -C ₆ H ₅

_[2 __CO- NH-CH-NH CO CH ₂

CH ₃

N = N- <V-NO ₂ Cl Cl

CH ₂ CH ₂ OCOOCh ₂ CH ₃ CH ₂ OCOOCH ₂ CH ₃
CH,

Cl

Shade on polyester

₂ -CO-NH-CH-NH CO CH ₂

CH ₃

NO ₂

Cl

Ruby red

yellow

Brown

-A

Yellow-brown

example

CN

CH ₃ O ₂ S ^ f VN = N

Cl

CH ₃ O ₂ S ^ VN = N

O ₂ N

CN

^^ V-N = N-Br

SO ₂ CH ₃

N = N

continuation

dye

CH ₂ CH ₃

CH ₂ CH ₃

^S CH ₂ CO - NH CH - NH CO CH ₂

C ₂ H ₅

CH ₂ CH ₃

CH ₂ CH ₃

^ CH ₂ - CO - NH - CH - NH CO CH ₂

CH ₂ CH ₃

-N

^S CH ₂ —CO - NH CH - NH CO-

CH ₂ CH ₂ -S-CH ₃

CH ₂ CH ₃

N -CH ₂

CH ₅ CH,

CH ₂ CH ₃

"CH ₂ - CO - NH - CH - NH CO CH

N = N- <VSO ₂ CH,

N = N ^ VSO ₂ CH ₃ Cl

CN

Ν ₌ Ν — ζ ~~ \ - NO ₂ Br

Shade on polyester

Red

orange

violet

N = N- <V-NO ₂ SO ₂ CH ₃

Red

CO-NH CH NH

CO NH CH NH

CO -NH-CH-NH

OCH,

example

CN

O ₂ NC> - N = N Cl

O ₂ N

O ₂ N

Cl

N = N

Cl

NO ₂

N = N

CN

Cl

O ₂ N- \ ~ \ - N = N Cl

continuation

Dye Cl

CH ₂ CH ,,

CH ₂ —CO — NH — CH — NH CO

CH ₂ CH ₃

CN

OCOCH ₃

CH ₂ CH ₂ OCOCH ₃

^S CH - CO - NH - CH ₂ - NH - CO • CH ₃

CH ₂ CH ₂ OCOCH ₃ CH ₂ OCOCH ₃ CH ₂

Cl

-N = N

CH ₂ CH ₂ OCOCH ₃

Cl

NO ₂

CH _? CO NH CH NH CO-

Cl N- -CH ₂

-N = N - <^ Λ- CN

CH ₃ Cl

CH ₂ CH ₃

CH ₂ —CO-

-NH CH NH-

CH ₂ C ₆ H ₅

CH ₂ CH;

N- -CH ₂

-N = NC / ^ NO ₂ Cl

Shade on polyester

violet

Yellow-brown

violet

Yellow-brown

orange

^N CH ₂ - CO - NH - CH - NH

Cl

O ₂ N

CH ₂ CH ₃

^X > ^ H ₂ -SO ₂ -NH-CH ₂ -Nh-SO ₂ -CH ₂

CH ₂ CH ₃

Cl

CH ₂ CH ₃

N = N

-Sa-NH-CH ₂ -NH-SO ₂ -CH;

CH ₂ - SO;

N = N

NO ₂

CH ₃

CH ₃

CN

Cl

O ₂ N

CH ₂ CH ₃

CH ₂ CH ₃

N = N

V-N = N

NO ₂

Cl

W-CO-NH-CH ₂ -Ch ₂ -NH-CO-CH ₂

CH ₂ CH ₃ Cl
Cl

O ₂ N-

CH ₂ CH ₃

N = N

-N = N

CH;

-CO-NH-CH ₂ - (CH ₂ ) ₂ -CH ₂ -NH-CO-CH ₂ ^

NO ₂

Cl

Cl
CN

CH ₂ CH ₃

CH ₂ -CO-NH-

CH ₂ CH ₃

-NH-CO-CH ₂ -N = N- <

CN

Yellow-brown

Reddish purple

orange

Yellow-brown

Ruby red

Oo

example

O ₂ N

O ₂ N

O ₁ K

O ₂ N

continuation

dye

O ₂ N

Cl

N = N

Cl

N = N Cl Cl

N = N Cl Cl

Br

N = N

Cl

Cl

CH ₂ CH ₃

Cl

CH ₂ CH ₃ -N = N

CH ₂ CO NH-

-NH-CO-CH ₂

Cl

CH ₂ CH ₂ OCOCH ₃ CH ₂ OCOCH ₃
CH ₂

Cl

Cl

CH ₂ CH ₂ CONH - CH ₂ CH ₂ - NH - CO - CH ₂ CH ₂ N = N

Cl Cl

CH ₂ CH ₂ OH

HO-CH ₂ CH ₂ N-CH ₂ CH ₂ CONH - CH ₂ CH ₂ - NH - CO - CH ₂ CH ₂

Cl

CH ₂ CH ₂ OCOOCH ₃ CH ₂ OCOOCH ₃
CH ₂

^{/ Λ} ~~ ^Χ N = N

Cl

Br

/ ^ N

^ CH ₂ CH ₂ CONH - CH ₂ CH ₂ - NH - CO - CH ₂ CH ₂ ^

CH ₃ CH ₂ OCO-C _h H ₅

N = N

CH ₂ CH ₂ OCO-C ₆ H ₅

Cl

Cl

Cl

^X CH ₂ CH ₂ -CONH-CH ₂ CH ₂ -NH-CO-CH ₂ CH ₂ Cl

NO ₂

NO ₂

^N ° 2

NO,

-NO,

Continuation of nuance on polyester

scarlet

Yellow-brown

Brown

Brown

Yellow-brown

Cl

O ₂ N- ^ CN
I. -N = N- CH ₂ CH ₂ OCOCH ₃ CH ₂ CH ₂ -CO-N- CH ₂ CH ₃ / —Ν / hoarding CH ₂ CH ₃ CH ₃ CH ₂ CH CH ₂ OCOCH ₃ CN -NO ₂ Shade on polyester example <> CH dye CH ₂ CH ₂ CH ₂ ^> CH ₂ CH ₂ -CO-NH ^ ^- V-NH-CO-CH ₂ CH ₂ -N- CH ₂ CH ₂ -CO-Nh-CH-NH-CO-CH ₂ CH ₂ -N- ^ CH ₂ CH ₂ -CO-NH-CH-NH-CO-CH ₂ Ch ₂ N— Red 80 O ₂ N- ^ Cl
I. -N = N- CH ₂ CH ₃ CH ₃ - CH ₂ CH ₂ - NH - CO - CH ₂ CH ₂ -NO ₂ ο- o < CH ₂ CH ₂ CN CH ₂ CH ₂ CH ₃ OCH ₃
I CH ₂ CH ₂ OCOCH ₃ ^> ^ "VN-CO-CH ₂ CH ₂ —N— Cl scarlet 81 ₂ CH ₂ CN \ CH ₂ CH ₂ -CO-NH-
NHCOCH ₃ CN
I. -N = N- > "\ -NO ₂ '\ y <> _N = N- CN Ruby red 82 Cl
L. -NO ₂ O ₂ N— ( Cl
A. -N = N- 3 j ν / V-N = N- Cl Cl Yellow-brown 83 OCOCH ₃ NO ₂ -NO ₂ O ₂ N- < NO ₂
/ k -N = N- OCH ₃
.U O ( VN = N- Br Br NHCOCH ₃ blue 84

Example

CN-

O ₂ N

O ₂ N

continuation

dye

CN

OCH ₁

CH ₂ CH ₂ OCOCH ₃ CH ₂ OCOCH ₃
'OCH ₃

Cl

-N = N-C> -N

i ^ CH ₂ CH ₂ -CO-NH-CH ₂ CH ₂ -NH-COCh ₂ CH ₂

NHCOOCH ₃ CH ₂

CN

> —N = N
NHCOOCH ₃ Cl

Shade on polyester

NO ₂

NO,

N = N

OCH ₂ CH ₃

CH ₂ CH ₂ OCOOCH ₃

CH ₂ OCOOCH ₃
'OCH ₂ CH ₃

blue

CN

CH ₂ CH ₂ - CO - N NHCOCH ₂ CH ₃ ^x

CH ₂ CH,

/ V

N-

CH ₂ CH ₂ CH ₂

-CO - CH ₂ CH ₂

NO ₂

NHCOCH ₂ CH ₃

NO ₂

OCH,

CH ₂ CH ₂ OCOCH ₃

CH ₃ COOCH ₂ CH ₂ OCH ₃

CN

NO ₂

-N

CHXH, - CO - NH - CH ₂ - NH - COCH ₂ CH ₂

NHCOCH ₃ NHCOCH ₃

-N = NC V-NO ₂
NHCOCH ₃ NHCOCH ₃

NO ₂ O ₂ N- <VN = N-

OCH ₃

OCOCH ₃ CH ₂ -CH-Ch ₂ -OCOCH ₃ CHXOO-CH-CH ₂ -OCOCh ₃

-N CH,

OCH ₁

NO ₂

CH ₂ CH ₂ CONH - CH ₂ CH ₂ NH - CO - CH ₂ CH ₂ - N- <^ - N = N-

SO ₂ CH ₃ NHCOCH ₃

NO ₂

NHCOCH ₃ SO ₂ CH ₃

blue

blue

blue

continuation

CO CXl

example

dye

Shade on polyester

NHCOCH ₃ SO ₂ CH ₃ I.

continuation

example

Kuance dye on polyester

CN

0, N-

OCH ₃

N = N

CH ₂ CH ₂ OCOCH ₃

OCH ₃
CH ₃ COOCH ₂ CH ₂ I '

CN

CN

NO,

NHCOCH ₃

/ CH ₂ CH ₂ -CO-NH-CH ₂ -CH ₂ -Nh-CO-CH ₂ CH ₂ ^X N - <^ VN = N-

NHCOCH ₃ CN

NO ₂

O ₂ N

N = N

Cl

Cl

OCH ₃
J CH ₂ CH ₂ OH HIGH ₂ CH ₂

/ N-

CH ₂ CH ₂ - CO - NH - CH ₂ - CH ₂ NH - CO - CH ₂ CH ₂ NHCOCH ₃

OCH ₃

-N = N-NHCOCH ₃

NO ₂

NO ₂

0, N

N = N

Cl

CH ₂ CH ₂ OCOCH ₃
n 'CH ₂ CH ₂

CH ₂ CH ₂ - CO - N N-

^X CH ₂ CH ₂

H ₃ COOCH ₂ CH ₂ egg

Cl

COCH ₂ CH ₂ N = N

NO ₂

Cl

O ₂ N- ^ ~ \ -N = N
Cl

CN

CH ₂ CH ₂ OCOCH ₃

^X CH ₂ - SO ₂ - NH - CH ₂ NH SO ₂ CH ₂

CH ₂ CH ₂ OCOCH ₃

N— <> —N = N-

Cl Cl

NO ₅

Cl

CN

Cl

—CH ₂ - SO ₂ NH- CH ₂ CH ₂ - NH- SO ₂ - CH ₂ - ΝΗ- ^ ζ ~ ^ \ - Ν = Ν - <(~~ \

Cl

blue

blue

Yellow-brown

Yellow-brown

orange

continuation

example

dye

Shade on polyester

O ₂ N

CO-C ₆ H ₅

N = N

Cl

Cl

Cl

Cl

N = N Br Cl

Cl

O ₂ N- ^ VN = N Cl

CH ₂ CH ₂ OCOCH,

CH ₂ SO ₂ NH CH ₂ CH ₂ NH SO ₂

CH ₂ CH ₂ OCOCH ₃

I / -χ

Ν— <V-N = N

NO ₂ CO-C ₆ H ₅

CH ₂ CH ₃

CH ₂ CH

₂ CH ₃

CH ₂ CH ₂ CONH

NH - CO - CH ₂ -

Cl

Cl

CH, CH,

CH ₃
CH,

Cl

CH ₂ CH ₂ - CO - NH - CH - NH - CO - CH ₂ --N C ₆ H ₅

N = N

Cl

CH ₂ CH ₂ OCOCH ₃

CH ₂ OCOCH ₃ CH ₂ "CH ₂ CH ₂ - CO - NH-CH- NH-COCH ₂ CH ₂ -N - <^ ~ \ - N = N

CH ₂

C ₆ H ₅ Br

Cl

Cl

NO ₂

NO,

Red

Brown

Brown

co υα cn

ro

Yellow-brown

Claims (1)

i 935 234 claims: 1. Disazo compounds of the formula R ₃ D —N ==] R ₇ R ₈ wherein the two D are unsubstituted or by chlorine or bromine atoms, cyano, nitro, methylsulfpnyl, Benzylsulfonyl, methylaminosulfonyl, dimethylaminosulfonyl, BenzoyJ or acetylamino groups or a group of the formula - CH = N - OH substituted phenyl radicals, unsubstituted or substituted by methyl or nitro groups, thiazolyl radicals, substituted by methylsulfonyl or rhodane groups, benzthiazolyl-3 radicals, the 1-phenyl-3-methylpyrazole radical or the methylsulfonylnaphthyl radical, R ₁ and R ₂ independently of one another hydrogen, chlorine or Bromine atoms, methyl, methoxy, acetylamino, propionylamino, chloropropionylamino or methoxycarbonylamino groups, R ₃ and R ₄ independently of one another are hydrogen, chlorine or bromine atoms, methyl, methoxy or ethoxy groups, R ₅ and R _{6 are} independently hydrogen atoms or alkyl groups with 1 to 3 carbon atoms which are unsubstituted or, as substituents, chlorine or bromine atoms, hydroxy, methoxy, ethoxy, cyano, phenyl, formyloxy, acetoxy, propionyloxy, benzoyloxy, methoxycarbonyl, methoxycarbonyloxy -.Äthoxycarbonyl- ■ oxy or aminocarbonyl groups, R ₇ and R ₈ each have a hydrogen atom or a methyl or cyanoethyl group or together one Ethylene bridge, the two X are each a group of the formula CH, ΠΙ..Π1. (Il CH, and A is a bridge member of the formula
-CH ₂ - -C ₂ H ₄ - -C ₃ H ₆ - Cl > ^fr ~ V C ₄ H ₈ -