DE1923592C - Monoazo dyes - Google Patents

Description

where means

R is a 4-nitrophenyl, 2-trifluprmethyl * 4-iutrophenyl, 2-bromo-6-cyano-4-niirophenyK 2 - chlorine - 6 - cyano - 4 - nitrophenyl, 4 - alkyl sulfonylphenyl, 2 - chloro - 4 - nitrophenyl, 2 - bromine 4 - nitrophenyl, 2 - chloro - 4 - alkylsulfonylphenyl radical or one substituted in the 2- and 4-position by two alkyl radicals Sulfonylphenyl radical or a 2-alkylsulfonyl - 4 - nitrophenyl-, 2 - alkylsulfonyl - 4 - thio-

= N- <f

cyanatophenyl or 2-cyano-4,6-dinitrophenyl radical or a 2-TbiazoJyl-, 2-Benzthiazo-IyI-, 1,3,4-thiadiazol-2-yl-, 1,2,4-thiadiazol-5-yi, 3-pyrazolyl or 2-thienyl radical, each with 1 to 4 carbon atoms in the Alkyl group,

R ^{1 is} an alkanoyl, benzoyl, alkoxycarbonyl, alkylsulfonyl or alkylcarbamoyl radical, each with 1 to 4 carbon atoms in the alkyl group,

R ^{2 is} an alkyl radical having 1 to ο carbon atoms or a radical of the formula

-CH ₂

in which R ⁵ denotes a hydrogen or halogen atom or an alkyl, alkoxy or hydroxyl radical each having 1 to 4 carbon atoms in the alkyl group, and
R ^{4 is} a hydrogen or chlorine atom, an alk> I, alkoxy or hydroxy radical, each with 1 to carbon atoms in the alkyl group.

The invention relates to new, water-insoluble monoazo dyes.

A wide variety of monoazo dyes with a similar basic structure are already known (compare 7 B. French patents 413 474, 1444 036, 1450 955, 1494 489, 1497 263 and Belgian patents 617 127, 662 773, 668 287, 688 712 , 699 118, 705 666 and 706 115).

The coloring properties of the various known monoazo dyes depend on the ones used Coloring conditions and colored substrates very different. It has been shown that in particular Textile structures made of polyesters with the previously known monoazo dyes are not more satisfactory Way can be colored.

There was therefore a need for new monoazo dyes, which close this gap.

The object of the invention was to provide new monoazo dyes with the help of which it is possible, in particular To dye textile structures made of polyester lightfast and abrasion-resistant.

It has now been found that this object can be achieved by certain new monoazo dyes can, although djie the same basic structure as the have known monoazo dyes, but due to their different substituents in their Coloring properties are superior to the previously known monoazo dyes.

The invention relates to monoazo dyes, which are characterized by the general formula are in which means

R is a 4-nilrophenyl-, 2-trifluoromethyl-4-nitrophenyl-, 2-bromo-6-cyano-4-nitrophenyl-, 2-chloro-6-cyano-4-nitrophenyl-, 4-alkylsulfonylphenyl-, 2-chloro-4-nitrophenyl-, 2-bromo-4-nitrophenyl-, - Chlorine - 4 - alkylsulfonylphenyl radical or one substituted in the 2- and 4-position by two alkyl radicals Sulfonylphenyl radical or a 2-alkylsulfonyl-4-nitrophenyl, 2-alkylsulfonyl-4-thiocyanatophenyl or 2-cyano-4,6-dinitrophenyl radical or a 2-thiazolyl, 2-benzthiazolyl, 1,3,4-thiadiazol-2-yl, l, 2,4-thiadiazol-5-yl, 3-pyrazolyl or 2-thienyl radical with in each case 1 to Carbon atoms in the alkyl group,

R ^{1 is} an alkanoyl. Benzoyl, alkoxycarbonyl, alkylsulfonyl or alkylcarbamoyl radical, each with up to 4 carbon atoms in the alkyl group,

R ^{2 is} an alkyl radical having 1 to 6 carbon atoms or a radical of the formula

-CH ₂

in which R ⁵ denotes a hydrogen or halogen atom or an alkyl, alkoxy or hydroxy radical each having 1 to 4 carbon atoms in the alkyl group, and

R ^{4 is} a hydrogen or chlorine atom, an alkyl, alkoxy or hydroxy radical, each with 1 to carbon atoms in the alkyl group.

NHR ¹

With the help of the new monoazo dyes according to the invention, it is possible to produce threads, fibers and from them Manufactured textile structures made of polyester in red, yellow or orange to blue shades with excellent To dye fastness properties when dyed by customary known dyeing methods

UO StC

Pa au ka gs bei ins Su ' di to » I bei

K01 aide switch to E '■? dun one

vlils
) e,
ien

will. The monoazo dyes of the invention feature are characterized in particular by the fact that they are particularly lightfast, sublimation-resistant and abrasion-resistant Discolorations result. Because of their particularly favorable sublimation obscurity properties, S the monoazo dyes of the invention in particular for dyeing textile structures made of polyesters according to customary known thermal fixation dyeing processes.

Particularly advantageous dyes of the invention of the formula I given above are those in which R is a 1-halo-^ nitrophenyl group, a 2-halo-4-alkylsulfonyl group, whose alkyl group has 1 to 4 carbon atoms, one in the 2- and 4-position sulfophenyl radical substituted by an alkyl radical having 1 to 4 carbon atoms, a 2-alkylsilfonyl-4-nitrophenyl radical with 1 to 4 carbon atoms in the alkyl group and in particular a 2-Cvano-4,6-dinitrophenyl radical.

Comparative dyeings on poly (ethylene terephthalate) and cellulose acetate fabrics that help with monoazo dyes of the invention and with from Belgian patents 662 773, 617 127 and 705 666 as well aub of French patent 1,450,955 known azo dyes have been carried out shown that the monoazo dyes of the invention the known azo dyes in their coloring properties, especially with regard to the lightfastness and sublimation fastness as well as abrasion resistance of the obtained colorations, are clearly superior and deliver stronger shades.

The monoazo dyes of the invention can be prepared by known processes by diazotizing amines of the formula R - NH ₂ and coupling the diazonium salt obtained with a compound of the formula

in which R, R ¹ , R ² and R * have the meanings given above.

The coupler compounds of the formula required to prepare the monoazo dyes of the invention II can also be produced using known methods. An advantageous method of manufacture The coupler link then exists, a link the formula

NH ₂

(HI)

NHR ¹

NHR ¹

NH ₂ + X - CH ₂

(HI)

to react with a benzyl halide or an aryl ethyl halide.

Coupler compounds of Formula II can be prepared by reacting 2 equivalents of one Benzyl halide or aryl ethyl halide with an amine of the formula III. But you can, for example also by reacting one equivalent of a benzyl halide or an aryl ethyl halide with an amine of the formula III and reaction of the compound obtained with a second benzyl halide or aryl ethyl halide can be prepared.

The reactions described can be represented by the following reaction schemes:

NH-CH ₂ -

NHR ¹

(IV)

X-CH ₂

fS-R *

NHR ¹

CH ₂ -

/ V-R *

Je- , yl-

out
■ th,

NH ₂

2X - CH ₂

NHR

NHR ¹

X here denotes a halogen atom. 60 used

The compounds of the formula IV can be obtained by condensation of a benzaldehyde or acrylacetaldehyde with an amine of the formula III and subsequent hydrogenation of the anil obtained.

The described synthesis of the coupler compounds can be varied by adding in place of an amine of the formula III a nitroaniline of the formula

NO,

The nitro residue of the intermediate Ν, Ν-disubstituted nitroaniline is then hydrogenated, whereupon the amino residue obtained is acylated.

Id- following should begin with the manufacture of some for the preparation of the monoazo dyes according to the invention suitable coupler compounds described will.

I. Preparation of Couplers
1. Preparation of 3-acetamido-N, N-dibenzylaniline

A mixture of 15.0 g S'-Amincacetanilid, 38.0 g of benzyl chloride and 25 ml of Ν, Ν-dimethylformamide was heated under stirring at 95 to 105 ⁰ C for 2 hours. 10.1 g of triethylamine were then added to the reaction mixture, whereupon the reaction mixture was heated to 110 to 125 ° C. for a further hour. The reaction mixture was then poured into water. The precipitated coupler was filtered off, washed with water and air-dried. The melting point of the compound was 140 to 142 C.

20 1 a) Completion of

N-Benzyl-N-ethyl-m-acetamidoaniline

A mixture consisting of 15.0 g of 3'-aminoacetanilide. 12.7 g of benzyl chloride and 25 ml of Ν, Ν-dimethylformamide were heated to 60 to 65 ° C for 12 minutes. The reaction mixture was then poured into 350 ml of water. The precipitated reaction product was filtered off and recrystallized from a mixture of 250 ml of benzene and 50 ml of hexane. The obtained compound 3-acetamido-N-benzyl aniline had a melting point 129-130 C. ^u

12.0 g of 3-acetamido-N-benzylaniline, 10.9 g of ethyl bromide and 25 ml of triethyl phosphate were heated to reflux temperature for 5 hours, whereupon the The reaction mixture was poured into water. The solution obtained was made by adding ammonium hydroxide neutralized, whereupon the reaction product was extracted with benzene. The matchmaker remained after evaporation of the benzene.

2. Preparation of 3-acetamido-N-benzylaniline

A mixture consisting of 15.0 g 3'-aminoacetanilide, 12.7 g benzyl chloride and 25 ml N.N-dimethylformamide, was heated to 60 to 65 ° C for 12 minutes, whereupon the reaction mixture was poured into 350 ml Water was poured. The reaction product was then filtered off and from a mixture of 250 ml Benzene and 60 ml of hexane recrystallized. The obtained coupler had a melting point of 129 to 130 C.

3. Preparation of 3-acetamido-N-benzylaniline

A mixture consisting of 18.0 g of 3'-nitroacetanilide, 2.0 g of sodium acetate, 31.8 g of benzaldehyde and 150 ml of ethanol was in the presence of 3 g of Raney nickel at a temperature of 75 ° C. and a pressure of 105 kg / cm ² Hydrogenated until there was no more hydrogen absorption. Then 100 ml was added to the reaction product taken out of the autoclave. The reaction product was then brought into solution by heating, after which the Raney nickel catalyst was filtered off. Most of the solvent was removed by evaporation and the residue was poured into water. The reaction product was filtered off, washed with water and air dried. The melting point of the coupler was 128 to 13O ⁰ C.

4 Manufacture of
3-acetamido-N-ethyl-N- (2-phenylethyl) aniline

150ε S'-aminoacetanilide, 18.5 g 2-PhenyläthylbroinidI and 25 ml Ν, Ν-dimethylformamide was heated for 1 »Λ hours at 8O ⁰ C. The reaction mixture was then poured into water. The slightly rubbery reaction product was filtered and dried length of the air. The reaction product bectand from 3-acetamido-N- (2-phenylethyl) aniline. It was converted into 3-acetamido-N-ethyl-N- (2-phenylethyl) aniline by reaction with ethyl bromide, as described in Example 1.

4 a) Preparation of 3-acetamido-N-isobutyl aniline

A mixture consisting of 18.0 g of m-nitroacetanilide, 2.0 g of sodium acetate, 21.6 g of glsobuiyraldehyd and 150 ml of ethanol was hydrogenated in the presence of 1.0 g of Raney nickel at 75 ° C. and a pressure of 105 kg / cm ^{2 until} until there was no more hydrogen absorption. The runoff nickel catalyst was then filtered off, whereupon the ethanol was evaporated. The oily residue was washed twice with water by decanting. When the reaction product was left to stand, it solidified. The yield was 20 g.

5. Manufacture of
3-Acetamido-N-benzyl-N- (2-phenylethyl) aniim

Line mixture consisting of 2.5 g of 3-Acelainido-N- (2-phenylethyl) aniline. 2.5 g benzyl chloride and 3.0 ml NN-dimethylformamide. was heated to 95C for ¹ Z _{2 hours.} Then 2 g of triethylamine were added, whereupon the mixture was heated again for an hour. The reaction product was then poured into water. The coupler was washed with water by decanting. The coupler was light amber in color and made of a viscous product.

5a) Preparation of 3-acelamido-N-sec-butylaniline

54.0 g of m-nitroacetanilide were mixed with 2.16 g of 2-butanone and 2 g of a 1% platinum carbon-platinum catalyst. The mixture was hydrogenated at a temperature of 160 to 165 ° C. and a pressure of 70 kg / cm ^{2 for} 4 hours. After removing the excess 2-butanone, 3-acetamido-N-sec-butylaniline was obtained in quantitative yield. It was slowly crystallizing.

6. Manufacture of
3-acetamido-N, N- (di-p-methylbenzyl) aniline

A mixture of 8.0 g of 3'-aminoacetaniin, 21.0 g of i-chloro-p-xylene and 50 ml of Ν, Ν-dimethylformamide was heated to 95 ° C. for 2 hours with stirring. 25 ml of triethylamine were then added The reaction mixture was then poured into water, whereupon the reaction product was filtered off, washed with water and air-dried. The coupler obtained had a melting point of 161 to 162 ^° C.

6a) Manufacture of
3-acetamido-N- (1,3-dimethylbutyl) aniline

A mixture of 52.0 g of m-nitroacetanilide and 216 g of 4-methyl-2-pentanone was according to the im

A 2-meth <methylf added 2 hours of reactive product 250 ml sized. C 138 to

Procedure described in Example 5 hydrogenated. The coupler was obtained in quantitative yield.

The compounds obtained according to 4a, 5a and 6a could be with benzyl chloride or / 9-phenylethyl chloride to convert to corresponding couplers.

7 to 15. Couplers which have another acylamido radical instead of an acetamido radical can be used easily prepared by reacting m-nitroaniline with the appropriate acylating agent and reduction of the nitroanilide obtained to the

corresponding aminoanilide. The aminoanilide can then be treated with a benzyl halide or phenylethyl halide react, whereupon the intermediate product obtained with an alkyl halide, as under 1 a) and 3 a) described, can be implemented. On the other hand, the nitroanilide can also be mixed with an aldehyde or a ketone, as described under 2a), 4a), 5 a) and 6 a), condense. The ones in the following Couplers listed in Table I were made according to the following

ίο reaction scheme prepared:

/ \ _ _NO acylating agent / V-NO H, 75 ° C

^iNU2 95 to 10O ⁰ C \ / ' ^Uz Raney nickel 105 kg / cm ²

NH ₂ NH acyl

NH,

NH-Acvl

_ _R 3_ /

NH-R

NH-acyl

C ₂ H ₅ Br

NH-acyl

Table I.

No. ι acyl radical Acylating agents R ³ 7th C ₂ H ₅ CO - Propionic anhydride -CH ₂ - 8th HCO- Formic acid - CH ₂ - 9 C ₂ H ₅ OOC - Ethyl chloroformate - CH ₂ CH ₂ - 10 CH ₃ SO ₂ - Methanesulfonyl chloride -CH ₂ - 11th P-CH ₃ -QH ₅ SO ₂ p-toluenesulfonyl chloride - CH ₂ CH ₂ - 12th C ₂ H ₅ NHCO - Ethyl isocyanate -CH ₂ - 13th ι — ι ° 2-furoyl chloride - CH ₂ - O 14th QH ₁₁ CO- Cyclohexyl carbonyl chloride - CH ₂ CH ₂ - 15th QH ₅ CO- Benzoyl chloride -CH ₂ -

16. Manufacture of S-acetamido-N.N-dibenzyl ^ -methoxyaniline

A mixture consisting of 18.0 g of 5-acetamido-2-methoxyaniline, 38.0 g of benzyl chloride and N, N-dimethylformamide was stirred for 1 hour heated to 95 ° C. Then 26 ml of triethylamine were added, whereupon the reaction mixture was added Was heated for 2 hours. After pouring the reaction mixture into water, the reaction product was filtered off and from a mixture of 250 ml of methanol and a little water recrystallized. The coupler had a melting point of 138 to 139.5 ° C

17. Manufacture of Ν, Ν-dibenzyl-m-phenylenediamine

A mixture of 69.0 g of m-nitroaniline, 133.0 g of benzyl chloride and 250 ml of N, N-dimethylformamide was heated to a temperature of 130 ° C. for 6 hours. The reaction mixture was then poured into a hot water-methanol solution. The reaction product crystallized out on stirring. After filtering off the reaction product, it was recrystallized from methanol. In this way, 129 g of solid yellow N, N-dibenzyl-3-nitro aniline with a melting point of 78 to 8O ⁰ C. were obtained.

129 g of N, N-dibenzyl-3-nitroaniline were hydrogenated in 800 ml of alcohol in the presence of 14.0 g of Raney nickel catalyst. The hydrogenation was carried out at a temperature of 75 ° C. and a pressure of 105 kg / cm ² . The hydrogenation time was about 3 hours. The Raney nickel catalyst was then filtered off. The reaction product was caused to precipitate by concentrating the filtrate to about one third of the original volume. It was filtered off and air dried. The yield of the coupler was 103 g. The coupler had a melting point of 98 to 100 ° C.

18. Preparation of N, N-dibenzyl-3-propionamidoaniline

A mixture of 14.4 g Ν, Ν-dibenzyl-m-phenylenediamine, 30.0 ml of toluene and 5.0 ml of propionic anhydride were added for 3 hours with stirring Heated between 95 and 100 ° C. The reaction mixture was then poured into hexane, whereupon the reaction product was filtered off. It was made from a mixed solvent of benzene and hexane in proportion 3: 1 recrystallized. The yield of the coupler was 11.3 g. The coupler had a melting point from 133 to 134 ° C.

Analysis for C ₂₃ H ₂₄ N ₂ O:

Calculated
found .

C 80.2, H 7.04, N 8.13; C 80.35, H 6.97, N 7.83.

19. Preparation of N, N-dibenzyl-3-formamidoaniline

A mixture of 8.64 g Ν, Ν-dibenzyl-m-phenylenediamine, 20.0 ml of toluene and 3.0 ml of formic acid were heated to 95 to 100 ° C. for 4 hours The reaction mixture was then poured into a mixture of water and methanol. The reaction product was filtered off. It had a melting point from 95 to 98 ° C.

Analysis for C ₂₁ H ₂₀ N ₂ O:

Calculated ... C 79.7. H 6.38, N 8.86; found .... C 79.9. H 5.9, N 8.73.

20. Preparation of N, N-dibenzyl-3-ethoxyformamidoaniline

22. Preparation of 3- (p-toluenesulfonamido) -N, N-dibenzylaniline

To a solution of 5.76 g of N, N-dibenzyl-m- ■ phenylenediamine in 15.0 m! Dioxane was 4.75 g p-Toluenesulfonyl chloride added. The reaction mixture was then on the steam bath for 2 hours heated for a long time and then poured into water. The reaction product crystallized out and was filtered off. After recrystallization from methanol, it became the pure coupler compound with a melting point obtained from 134 to 135 ° C.

23. Preparation of N, N-dibenzyl-3- (3-äthylureido) aniline

2.12 g of ethyl isocyanate were added to a solution of 8.64 g of N, N-dibenzyl-m-phenylenediamine in 20 ml of toluene. The reaction mixture was heated on a steam bath for 30 minutes. The coupler crystallized out on cooling the reaction mixture. It was filtered off. After recrystallization from a mixture of methanol and water, the pure coupler with a melting point of 154 to 157 ^° C. was obtained.

Analysis for C ₂₃ H ₂₅ N ₃ O:

Calculated ... C 77.0, H 6.76, N 11.7; found .... C 77.0, H 6.5, N 11.6.

24. Preparation of N.N-Dibenzyl-3- (2-furoylamido) aniline

To a solution of 8.64 g of N, N-dibenzylm-phenylenediamine 4.3 g of 2-furoyl chloride were added to 15 ml of dioxane. The reaction mixture was heated with stirring on a steam bath for 15 minutes and then poured into water. The aqueous portion was then decanted off, whereupon the reaction product was recrystallized from methanol would. The coupler had a melting point of 145 to 148 ° C.

3 °

45

To a solution of 5.76 g Ν, Ν-dibenzyl-mphenylenediamine in 15 ml of dioxane, 2.48 g of ethyl chloroformate were added and the solution was heated on the steam bath for 30 minutes. The reaction mixture was then slowly poured into 400 ml of hexane. The coupler obtained crystallized on stirring. It was filtered off.

21. Production of 3-methanesulfonamido-N, N-dibenzy! Aniline

4.0 g of methane sulfonyl chloride were added to a solution of 8.64 g of N, N-dibenzyl-m-phenylenediamine in 20 ml of pyridine. After stirring for 2 hours at 95 to 100 ° C., the reaction mixture was poured into 600 ml of dilute hydrogen chloride solution. The aqueous portion was decanted dan, the reaction product from ethanol followed was recrystallized The coupler had a melting point 113-114 C. ¹

Analysis for C ₂₅ H ₂₂ N ₂ O ₂ :

Calculated ... C 78.5, H 5.8, N 7.3: found .... C 78.3, H 5.4, N 6.9.

25. Manufacture of

3- (1-cyclohexylfornamidoVN.N-dibenzylaniline

A mixture of 10.9 g of 3-cyclohexylformamidoaniline, 13.35 g of benzyl chloride and 25 ml of N, N-dimethylformamide was heated to 130 ° C. for 4 hours. The reaction mixture was then poured into a mixture of methanol and water. The reaction product crystallized out after brief stirring . The melting point of the coupler was 180 to 181 ° C

26. Preparation of 3- (Benzamido) -N, N-dibenzylaniline

10.6 g of 3'-aminobenzanilide described with 13.35 g of benzyl chloride, such as below 16, together \ reacted. The coupler obtained had a melting point of 169 to 171 ° C.

27. Preparation of 3-acetamido-N, N-bis- (p-cbJorobenzyl) ani1 η

A mixture of 7.5 g of β'-aminoacetanilide, 24.2 g p-chlorobenzyl chloride and 25.0 ml N, N-dimethyl - formamide was heated on a steam bath for 4 hours. 10 ml of Tn-

ai BE

Ni da au to 10 and toilet

the ί

ien-;:
üsoirde;>
; eim = 1
the
aiii- ';
.sser
jnkt i

uten i

sweet. §

irauf ί

lidothyl-;
iitz
lish
ionsaus.
I ⁰ C

»35 g
rnder
enn

14.2 g
rthyl vaccine *
iTri-

ethylamine added. The reaction mixture was then poured into a mixture of 600 ml of water and 50 ml Poured methanol. The reaction product was filtered off, air dried and removed from a Recrystallized mixture of benzene and hexane. The yield of the coupler was 19.7 g. The matchmaker had a melting point of 174 to 177 ° C.

28. Preparation of 5-acetamido-N, N-bis- (p-chlorobenzyl) -2-methoxyaniline

A mixture of 9.0 g of 2-methoxy-5-acetamidoaniline, 15 ml of Ν, Ν-dimethylformamide and 24.2 g p-Chlorobenzyl chloride was for 1 hour on the Steam bath heated. Then 25 ml of triethylamine were added, whereupon the reaction mixture again Was heated for 3 hours. The reaction mixture was then poured into water, whereupon the precipitated Reaction product was recrystallized from a benzene-hexane solution. The yield at Coupler was 20.8 g. The coupler had a melting point of 153 to 158 ° C.

Analysis for C ₂₃ H ₂₂ Cl ₂ N ₂ O ₂ :

Calculated ... C 64.4, H 5.2, N 6.5, Cl 16.5; found .... C 64.4, H 5.5. N 6.4. Cl 16.5.

29. Preparation of 5-acetamido-N, N-bis- (p-methylbenzyl) -2-methoxyaniline

A mixture of 9.0 g of 5-acetamido-2-methoxyaniline, 15 ml of Ν, Ν-dimethylformamide, 17.5 g of p-methylbenzyl chloride and 25 ml of triethylamine was, as described under 19, implemented. The received Coupler had a melting point of 185 to 187 ° C.

30. Preparation of S-acetamido-N.N-dibenzyW-methylaniline

A mixture of 16.4 g of 5-acetamido-2-methylaniline, 50.0 ml of Ν, Ν-dimethylformamide and 37.8 g of benzyl chloride were heated to 110 ° C. for 8 hours. The reaction product was filtered off, washed with water and recrystallized from 200 ml of methanol. The coupler had a melting point of 181 to 182 C.

Analysis for C ₂₃ H ₂₂ N ₂ O:

Calculated ... C 75.8. H 7.1. N 11.0; found C 75.7, H 7.0, N 10.9.

II. Preparation of the dyes

Example 1 Preparation of a dye of the formula

N = N

C ₂ H ₅

I CH ₂

NHCOCH ₃

_{0.72 g of NaNO 2} were added to 5 ml of concentrated sulfuric acid with stirring. The solution was then cooled, whereupon 10 ml of an acid mixture of 1 part propionic acid and 5 parts acetic acid were added. The addition took place below 10 ^° C. 1.72 g of 2-chloro-4-nitroaniline were then added to the mixture obtained with stirring, whereupon another 10 ml of one made from 1 part of propionic acid were added

and 5 parts of acetic acid consisting of an acid mixture at 0 to 5 ° C.

The diazotization mixture was then stirred for 3 hours at 0 to 5 C ^1, whereupon it to a cold solution of 2.68 g of 3-acetamido-N-benzyl-N-ethylaniline, dissolved in 100 ml of of 1 part of propionic acid and 5 parts Acetic acid was added to the existing acid mixture.

The coupling mixture was kept below 5 ° C, followed by the addition of solid ammonium acetate has been buffered. So much ammonium acetate was added until the mixture was opposite Congo red paper reacted neutrally. After a coupling time of 2 hours, the reaction mixture was poured into water, whereupon the dye was filtered off, washed with water and air dried.

The dye dyed threads and fibers made of polyester in strong red shades more excellently Authenticity properties.

Example 2
Preparation of a dye of the formula

CH ₂ CH (CHa) ₂

CH ₃ SO ₂

n = N

CH ₃ SO ₂

NHCOCH,

2.49 g of 2,4-bis (methylsulfonyl) aniline were, as described in Example 1, diazotized and 2.96 g 3-Acetamido-N-isobutyl-N-benzylaniline coupled.

The azo dye obtained dyed threads and fibers made of polyester in strong red shades more excellently Authenticity properties.

Example 3

2.16 g of 2-methylsulfonyl-4-nitroaniline were, as described in Example 1, diazotized and with 2.68 j 3-Benzamido-N-benzyl-N-ethylaniline coupled.

The dye obtained dyed threads and fibers made of polyester in strong red shades
drawn authenticity properties.

Example 4
Preparation of a dye of the formula

-N = N

I CH ₂ -

NHCOCH ₃

6.9 g of p-nitroaniline were concentrated in 5.4 ml Sulfuric acid and 12.6 ml of water dissolved. The solution was then poured onto 50 g of crushed ice, whereupon all at once a solution of 3.6 g of sodium nitride in 8 ml of water was added. The diazotization mixture was stirred at 0 to 5 ° C. for 1 hour

whereupon the solution was added to a cold solution of 13.4 g of S-acetamido-N-benzyl-N-ethylaniline, dissolved in 250 ml of an acid mixture consisting of 1 part of propionic acid and 5 parts of acetic acid. The coupling mixture was maintained at a temperature from 0 to 5 ⁰ C neutralized by addition of ammonium acetate using Kcngorotpapier. After a coupling time of 2 hours, the mixture was poured into water. The dye was filtered off, washed with water and air dried.

B e i s ρ i e 1 6

Making a dye
of the following structural formula:

CN

= N

CH,

NHCOCH ₃

Example 5

Manufacture of a dye
of the following structural formula:

CH ₃ SO ₂

2.05 g of 2-chloro-4-methylsulfonylaniline were, as described in Example 4, diazotized and 3.04 g S-ethoxycarbonylamino-N-ethyl-N ^ '- chlorobenzylaniline coupled.

The azo dye was then isolated as described in the previous examples.

The dye dyed polyester threads and fibers in strong orange tones more excellently Authenticity properties.

2.08 g of 2-cyano-4,6-dinitroaniline were, as described in Example 1, diazotized and 2.68 g 3-acetamido-N-benzyl-N-ethylaniline is coupled.

The obtained dye colored threads and fibers made of polyester in blue tones more excellently Lightfastness and sublimation fastness properties. B e i s ρ i e I e 7 to i s 68

Following the procedures described in Examples 1 to 6, the following Table II listed dyes of the following structural formula:

/ \ -N = N

20th

NH-R ¹

In Table II below, the individual substituents and the color shades obtained when the dyes are dyed onto threads and fibers made from polyesters are given, η = either 1, 2 or 3.

Table II

at
game (X). R ¹ R ² -C ₂ H, R ³ R ⁴ H hue 7th 2-CI-4-NO, QH ₅ CO- -C ₂ H ₅ -CH ₂ - H Red 8th 2-C1-4-NO, CH ₃ SO, - -CH ₂ CH (CH ₃ ), -CH ₂ - H Red 9 2-C1-4-NO, C ₂ H ₅ OOC- -C ₂ H ₅ -CH ₂ - 4-OCH, Red 10 2-C1-4-NO, C ₂ H ₅ NHCO - -C ₂ H ₅ -CH ₂ - 4-OCH ₃ Red 11th 2-Cl ^ -NO ₂ ClCH ₂ CO - -C ₂ H, - CH, - 4-OCH ₃ Red 12th 2-C1-4-NO, C ₆ H ₅ CH ₂ CO - -C ₂ H ₅ -CH, - 4-Cl Red 13th 2-C1-4-NO, CH ₃ CO - -CH (CH ₃ ), -CH, - H Red 14th 2-C1-4-NO, C ₂ H ₅ CO - -C ₂ H ₅ -CH ₂ - H Red 15th 4-NO ₂ CH ₃ SO ₂ - -C ₂ H ₅ -CH ₂ - H scarlet 16 4-NO ₂ C ₆ H ₅ CO- -C ₂ H ₅ -CH ₂ - H scarlet 17th 4-NO, C ₆ H ₅ OOC- -C ₂ H ₅ -CH ₂ - H scarlet 18th 2-0-4-CH ₃ SO ₂ - CH ₃ CO - -C ₂ H ₅ -CH ₂ - H orange 19th 2-01-4-CH ₃ SQ ₂ - CH ₃ SO ₂ - -CH ₂ CH (CH ₃ J ₂ -CH ₂ - 4-Cl orange 20th 2-0-4-CHsSQ ₂ - C ₅ H ₅ CO- -CH (CH ₃ ) CH ₂ CH (CH ₃ ] I ₂ -CH ₂ - H orange 21 2-0-4-CH ₃ SO ₂ - CH ₃ CO- -C ₂ H ₅ -CH ₂ - H orange 22nd 2.4-di-CH ₃ SO, - CH ₃ CO - C ₂ H ₅ CH ₂ - 4-CH ₃ Red 23 2,4-di-CH, SO ₂ - C ₂ H ₅ OOC- -C ₂ H ₅ -CH ₂ - H Red 24 2-CH ₃ SO ₂ ^ NO ₂ CH ₃ CO - C ₂ H ₅ -CH ₂ - H violet 25; 2-COCH3-4-NQ2 C ₆ H ₅ CO- -C ₂ H ₅ -CH ₂ - H Red 26th 2-COCH ₃ ^ NQ ₂ CH ₃ CO - C ₂ H ₅ -CH ₂ - H Red 27: 2-COOCHJ-4-NO, CH ₃ CO-: -C ₂ H ₅ -CH ₂ - 4-CH3 Red 28 2-COOCH ₃ -A-NO ₂ CH ₃ CO- C ₂ H ₅ ; -CH ₂ - H ■ Red 29: 2-01-4,6-Oi-NO ₂ CH ₃ CO- -C ₂ H ₅ -CH ₂ - H ; violet 30th 2-01-4,6- (E-NO ₂ C ₆ H ₅ CO- - CH ₃ - violet

continuation

at
game (X). R ¹ R ² -QH ₅ R * R ⁴ hue 31 2-C-4,6-di-Np2 C ₆ H ₅ CO- -QH ₅ -CH ₂ - 4-Cl violet 32 2-CN-4,6-di-NOj C ₆ H ₅ CO- - CHjCH (CHj) ₂ -CH ₂ - H blue 33 2-CN-4,6-di-NQj CH ₃ CO- -CH ₃ -CH ₂ - H blue 34 2-CN- ^ i-NO ₁ ClCH ₂ CO— -CH, -CH ₂ - 4-OCH3 blue 35 2-CN-4,6-di-NOj C ₂ H ₅ NHCO - -QH ₅ H Blsu 36 2-CN-4,6-di-NOj C ₆ H ₅ CO- -QH ₅ -CH ₂ - 4-OCH ₃ blue 37 2-CN-4,6-di-NOj P-CH ₃ -C ₆ H ₄ -CO- -QH ₅ CHj 4-OCH ₃ blue 38 2-CN-4,6-di-NOj C ₆ H ₅ CO- QH ₅ ~~~ CHj "~~ H blue 39 2-CN-4,6-di-NQj P-CH ₃ -C ₆ H ₄ CO- -QH ₅ H blue 40 2-CN-4,6-di-NO ₂ P-Cl-C ₆ H ₄ CO- - CH ₂ CH (CH ₃ ) J CH ₂ H blue 41 4-CH ₃ SOj-2-NOj CH ₃ CO - -CH, -CH ₂ - H Red 42 4-CH ₃ OOC - C ₂ II ₄ OOC - - CH ₂ CH ₂ CH ₃ ν H ₂ - H orange 43 4-C ₄ H ₉ OOC - Cyclohexyl - CO - -QH, .-CHj- H orange 44 2-CjH, SOj-4,6-di-NO ₂ C ₃ H ₇ CO - -QH, UH ₂ 4-CI blue 45 2-CHjSO ₂ -4,6-di-NOj CH ₃ SO ₂ - -QH, -CHj- H blue 46 2-HCO-2,4-di-NOj C ₆ H ₅ CO- -CH ₃ -CHj- H blue 47 2-COOCH ₃ -2,4-di-NO ₃ C ₂ H ₅ SO ₂ - QH ₅ CHj H blue 48. 2-CF3-4-NO2 HCO- -QH ₅ -CHj- H Red 49 2-CF3-4-NO2 C ₆ H ₅ CO- -QH, - CHj - H Red 50 2-CF ₃ ^ -NO ₂ CH ₃ OOC— -CH ₃ -CHj- H Red 51 2-CF ₃ A6-di-NOj CH ₃ CO - - CH ₂ CH (CH ₃ J ₂ -CH ₂ - H blue 52 2-CF ₃ -4,6-di-NOj CH ₃ SO ₂ - -QH ₅ -CH ₂ - H blue 53 4-CN C ₆ H ₅ CO- -QH ₅ - CHj - 2-CH ₃ orange 54 2,4-di-CN CH ₃ CO - -QH, -CH ₂ - H Red 55 2-Br-6-CN-4-NOj CH ₃ CO - -C ₂ H ₅ -CH ₂ - H Rct blue 56 2-Cl-6-CN-4-NOj C ₂ H ₅ CO - -QH ₅ -CH ₂ - H Red Blue 57 2-Cl-6-CN-4-NOj C ₆ H ₅ CO- -CH ₃ -CH ₂ - 3-Cl Red Blue 58 4-NOj-2-SOjNHj CH ₃ CO - -QH ₅ -CH ₂ - H Red 59 4-NOj-2-SOjN (CH ₃ ) j CH ₃ SO ₂ - -CH ₃ -CH ₂ - H Red 60 4-CH ₃ SO ₂ - CH ₃ CO - QH ₅ - CHj - 4-Cl orange 61 4-CF ₃ C ₆ H ₅ CO- QH ₅ -CHj- H orange 62 4-Cl C ₆ H ₅ SO ₂ - -C ₂ H, -CH ₂ - H yellow 63 4-SO ₂ NH ₂ CH ₃ CO - -QH ₅ - CHj - H orange 64 2-NO ₂ -4-SCN CH ₃ CO - -QH, - CHj - H Red 65 2,6-di-Cl-4-NOj 2-furoyl -QH, -CH ₂ - H Vioicu 66 2-SOjCH ₃ -4-SCN CH ₃ CO - -CH, CH (CH ₃ ) j -CH ₂ - H Red 67 2-SO ₂ CH ₃ -4-SCN CH ₃ CO - -C ₂ H ₅ CH ₂ H Red 68 2-NO ₂ -4-CF ₃ CH3CO - -CH ₂ - H Red

Example 69

Preparation of a dye of the following structural formula:

N = N

NHCOCH,

13.6 ml of concentrated sulfuric acid were added to 2.9 g of 2-amino-5-nitrothiazole in 25 ml of water with stirring admitted. Solution occurred immediately after the addition of the acid. The solution was brought to -10 ° C

cooled, whereupon a solution of 1.4 g of sodium nitrite in 10 ml of concentrated sulfuric acid below -5 ° C was added. Then was still Stirred for 15 minutes at about -5 ° C. The obtained diazonium solution then became a cold one Solution of 5.36 g of 3-acetamido-N-benzyl-N-ethylaniline, dissolved in 100 ml of 15% sulfuric acid and 10OmI of 1 part of propionic acid and 5 parts Acetic acid was added to the existing acid mixture at about 0 ° C. The reaction mixture was then left for 30 minutes left to stand at 0 to 5 ° C for a long time, after which the coupling mixture was poured into water. Dei The resulting dye was filtered off, washed with water and air-dried.

The dye stained threads and fibers made of polyester in strong reddish-blue shades more excellently Authenticity properties.

Example 70

2.9 g of I-amino-S-nitrothiazo. ' were after in Example 69 the process described and diazotized with 6.0 g of S-acetamido ^ -methoxy-N-benzyl-N-ethylaniline coupled, The dye obtained had a dye equivalent to that of Example 69 Formula, with the difference, however, that the remainder of the coupler molecule is in the p-position to the acetamido radical found a methoxy residue.

The dye colored threads and fibers made of polyester in strong blue shades with excellent fastness properties.

example

Preparation of a dye with the following structural formula:

CH ₃

CH ₂ CHCH ₃

NHCOCH,

0.72 g of dry sodium nitrite were added in portions to 5 ml of concentrated sulfuric acid with stirring admitted. The resulting solution was cooled, whereupon 10 ml of one of 1 part propionic acid and 5 parts of acetic acid existing acid mixture below 15 ° C were added. The mix was then with further cooling with 1.43 g of 2-amino-5-carbamylthiazole added, whereupon another 10 ml of 1 part of propionic acid and 5 parts of acetic acid existing acid mixture at 0 to 5 ° C were added. After a diazotization period of 2 hours at a temperature of 0 to 5 ° C, the solution became a cold solution of 3.0 g of 3-acetamido-N-benzyl-N-isobutylaniline, dissolved in 100 ml of 1 part propionic acid and 5 parts acetic acid Acid mixture, added. The coupling gene was removed by adding ammonium acetate.

buffered, up to the neutrality of the coupling mixture indicated by Congo red paper. After a coupling time of 2 hours at 0 to 5 ° C., the reaction mixture was poured into water. The precipitated dye was filtered off with

Washed with water and allowed to air dry.

The azo dye obtained dyed threads and fibers made of polyester in strong red shades more excellently Authenticity properties.

example

Production of an azo dye with the following structural formula:

CH ₃

CH ₂ CHCH ₃

CH, SO,

At 2.2% g of 2-amino-o-methyisuiionyibenzothiazoi, suspended in 24 ml of water, 26.2 g of concentrated sulfuric acid were added. After the amine had dissolved, the solution was cooled, whereupon a solution of 0.84 g of sodium nitrite in 5.0 ml of concentrated sulfuric acid was added in portions below () ° C.

The diazotization mixture was stirred for 2 hours at about 0 ⁰ C and then to a solution of 3.4 g of N-isobutyl-N-jii-phenylethyl-m-äthylureido-

B e i s ρ i

14 ml of concentrated sulfuric acid were added to 1.95 g of 2-amino-6-nitrobenzothiazole suspended in 24 ml of water. The resulting solution was adjusted to - cooled 5 ° C, whereupon a solution of 0.72 g of sodium nitrite in 5 ml of concentrated sulfuric acid below 0 ⁰ C was added wuiJe. After stirring for 2 hours at about 0 ° C, the diazotization solution was a solution of 2.25 g of N-ethyl-Np-chlorobenzyl-m-methylsulfonamidoaniline in a mixture of 50 ml of 15% sulfuric acid and 50 ml of a

CH ₂ CH ₂
NHCONHC ₂ H ₅

aniline, dissolved in 75 ml of 15% strength sulfuric acid, was added below 15 ° C.

The temperature was held at 0 to 5 ° C for a further 1 hour, after which the coupling mixture was diluted with water. The precipitated dye was filtered off, washed with water and dried.

The dye dyed threads and fibers made of polyester in strong red shades more excellently Authenticity properties.

el of 1 part propionic acid and 5 parts acetic acid consisting of an acid mixture at about ⁰ ° C. was added. The coupling mixture was then left to stand at ice bath temperature for 2 hours and then diluted with water.

The obtained azo dye was filtered off, washed with water and air-dried. the Dyestuff dyed threads and fibers made of polyester in strong purple hues with excellent fastness properties on.

ge hi at 6-

SC StI

D be 2, (de be

eti Ni Fa de

it) no

in the

OIyieter

Part iden lisch abipier ment. ) to isen.

isern out-

■ nter-

_; ; at

! ^J arb-

PoIyi neter

: acid: tben.

:, With . The .star real

19th

Example 74 Preparation of a dye with the following structural formula:

NC

JLn-n - ^^ - K

C ₂ H ₅

ag? * £ 76 g Natriumnitnt were added in portions to 5 ml * jarazentrierter sulfuric acid was added, the ^ obtained was then cooled in an ice bath solution, _s qrauf 10 ml of of 1 part of propionic acid and! 'parts of acetic acid existing acid mixture was added. The temperature was kept below 15 ° C. The resulting mixture was then stirred at 0 to 5 ° C., 1.75 g of 2-amino-6-cyanobenzothiazole and also 10 ml of the acid mixture described, consisting of propionic acid and acetic acid, being added . The diazotization mixture was then stirred for 2 hours at 0 to 5 ° C., after which it was added to a solution of 2.68 g of 3-acetamido-N-benzyl-N-ethylaniline in 100 ml of the acid mixture described, consisting of propionic acid and acetic acid.

The coupling mixture was then buffered by the addition of solid ammonium acetate and allowed to stand at about 5 ° C for about 2 hours. After pouring into water, the precipitated one became Dye filtered off, washed with water and air dried.

The dye dyed threads and fibers made of polyester in strong red hues with excellent colors Authenticity properties.

example

To 2.28 g of 2-amino-6-methylsulfonylbenzothiazole, suspended in 24 ml of water, were added 26.2 g of concentrated NHCOCH ₃

given trated sulfuric acid. After the amine had dissolved, the solution was cooled, whereupon a solution of 0.84 g of sodium nitrate in 5.0 ml of concentrated sulfuric acid was added in ^{portions below 0 ° C.}

The diazotization mixture was then stirred for 2 hours at about 0 ^° C., whereupon the solution was added to a cold solution of 2.68 g of 3-acetamido-N-benzyl-N-ethylaniline in 50 ml of 15% strength sulfuric acid and 50 ml of the from 1 Part of propionic acid and 5 parts of acetic acid consisting of an acid mixture at about 5 ° C was added.

After a coupling time of 1 hour at 0 to 5 ° C, the dye was precipitated in water, filtered off, washed with water and air-dried.

The dye dyed threads and fibers made of polyester in strong red shades more excellently Authenticity properties.

Examples 76 to 85

Following the procedures described in Examples 72 to 75, the following Table IV compiled dyes by diazotization of the corresponding 2-aminobenzothiazoles and coupling of the diazonium compounds obtained with the corresponding 3-acylamido-N-benzylanilines. All of the dyes produced conformed to the following formula:

(R ⁵ L-

N = N

NH-R ¹

The meaning of the individual substituents as well as the color tones used when dyeing the dyes on threads and polyester fibers are shown in Table IV below.

Table IV

at
game (R ⁵ L R ¹ R ² R ³ R ⁴ H hue 76 6-SO ₂ CH ₃ - COCH ₃ - C ₄ H ₉ -Ii -CH ₂ - H Red 77 6-NO ₂ - COCH ₂ OCH ₃ -C ₂ H ₅ - CH, - H violet 78 6-CN -COOC ₂ H ₅ C ₂ H ₅ -CH, - 3-OCH ₃ Red 79 6-SO ₂ CH ₂ CH ₂ CN -COC ₂ H ₅ QH ₁₁ -CH, - H · Red 80 6-Cl - COCH ₃ - CH (CH ₃ ), - CH ₂ CH ₂ - 4-CH ₃ Red 81 6-N HCOCH ₃ -COC ₆ H ₁₁ - CH ₂ CH (CH ₃ ), -CH ₂ - H Red 82 4,6-di-Cl - COOC ₁ H ₉ -Ii -C ₂ H ₅ CH2 H Red 83 6-SO ₂ NH, - COCH ₃ -C ₂ H ₅ - CH2 - H Red 84 6-SO ₂ CH ₃ -SO ₂ C ₆ H ₄ -P-Cl -C ₂ H ₅ -CH ₂ - H Red 85 6-SO ₂ CH ₃ - COC ₂ H ₄ Cl -C ₂ H ₅ -CH, - Red

Example 86

22nd

To 1.63 g of 2-amino-5-methylsuübnyl-1,3,4-thiadiazole, Slurried in 24 ml water, 14 ml concentrated Sulfuric acid added. The resulting solution was cooled to 0 ° C, followed by a solution of 1.44 g of sodium nitrite in 10 ml of concentrated sulfuric acid was added below 5 ° C. The diazotization mixture was stirred at ice bath temperature for 2 hours. Then she became to a cold solution of 3.3 g of 3-benzamido-N-ethyl-N-benzylaniline in 100 ml of an acid mixture consisting of 1 part propionic acid and 5 parts acetic acid.

The coupling mixture was then buffered by the addition of solid ammonium acetate and for 2 hours left standing for a long time. The mixture was then poured into water. The failed dye was filtered off, washed with water and air dried.

The azo dye obtained dyed threads and fibers made of polyester in strong red shades with excellent fastness properties.

Example 87

Preparation of a dye of the following
f

Structural formula:

C ₂ H ₅

CH ₁ S-

-N = N

NHCOCH, by diazotization of, for example, 1.47 g
5-Amino-3-methylttoo-lA4-thiadiazole and coupling
with 2.68 g of S-acetamido-N-benzyl-N-äthylanihn
the procedure described in Example 87 leave
For example, an azo dye can be one of the following
Create structural formula:

30th

35 - '' J i

-4

CH ₃ S

C ₂ H ₅

CH,

NHCOCH ₃

The dye dyed threads and fibers made of polyester in strong red tones more excellently
Authenticity properties. .

Example 88

Making a dye
of the following structural formula:

0.72 g of sodium nitrite was added in portions to 5 ml of concentrated sulfuric acid. The received Solution was cooled, whereupon 10 ml of one consisting of 1 part propionic acid and 5 parts acetic acid Acid mixture below 15 ° C were added. The cold mixture was then mixed with 1.47 g of 2-amino-5-methylthio-1,3,4-thiadiazole added and furthermore with 10 ml of 1 part of propionic acid and 5 parts of acetic acid existing acid mixture. The addition of the thiadiazole and the acid mixture took place below 5 C. After stirring for 2 hours at 0 to 5 ° C., the diazonium solution became a cold solution of 2.68 g of 3-acetamido-N-benzyl-N-ethylaniline in 100 ml of the acid mixture consisting of propionic acid and acetic acid were added below 5 ° C. Ammonium acetate was added to the cold reaction mixture until the coupling mixture was neutral to Congo red paper. After a coupling time of 1 hour at about 5 ° G, the reaction mixture was poured into water.

The precipitated dye was filtered off, washed with water and air-dried.

The dye dyed threads and fibers made of polyester in strong red shades more excellently Lightfastness properties and sublimation fastness properties.

Dyes of the invention having a 1,2,4-thiadiazol-5-yl-diazo radical can be prepared by using the isomer 5-amino-1,2,4-thiadiazole Place of the 2-amino-l, 3,4-thiadiazole, following the procedures described in Examples 89 and 90 can be worked.

NHCOCH ₃

To 5 ml of concentrated sulfuric acid were under
Stirring added 0.72 g of sodium nitrite in portions.
The nitrosylsulfuric acid solution was cooled,
whereupon 10ml of 1 part propionic acid and 5 parts
Acetic acid existing acid mixture below
10 ⁰ C were added. Then the sour one
2-Amino-3-nitro-5-propionylthiophene solution was added. Thereafter, another 10 ml of one were made
Part of propionic acid and 5 parts of acetic acid were added to the existing acid mixture. The additives were
all added at a temperature of 0 to 5 ° C.
The resulting mixture was then 1 hour
stirred at 0 to 5 ° C. for a long time. The resulting diazonium solution then became a cold solution of 2.68 g
3-Acetamido-N-benzyl-N-ethylaniline, dissolved in 75 ml
des from 1 part propionic acid and 5 parts acetic acid
existing acid mixture added. The coupling mixture was stirred occasionally, whereupon
it was diluted with water after 1 hour. the
Dye was filtered off, washed with water
and air dried.

The dye dyed polyester threads and fibers in strong blue tones more excellently
Authenticity properties.

Example 89

Preparation of a dye of the following
Structural formula:

-COOCH

CH ₂ CH (CH ₃ ) ₂

NHCOCH ₃

ml of one of 1 part propionic acid and 5 parts
Acetic acid mixture was too

ei d> b. w b <w se 5 'd; N ai bt sä ni da Iu to ab

Sau The 1.7: unites Sau mis

amigeir geb hall Am mis ( greed became Farl der Dester lEchi

added to a solution of nitrosylsulfuric acid, which was prepared from 0.72 g of sodium nitrite and 5 ml of sulfuric acid. The solution was cooled to 3 ° C., whereupon 1.41 g of methyl S-aminopyrazoM-carboxylate were added below 5 ° C. Then another 10 ml of the acid mixture were added. The mixture was diazotized at 3 to 5 ^° C. for 2 hours with stirring. The resulting diazo solution was then added to a cold solution of 3.3 g of 3-acetamido-Np-chlorobenzyl-N-isobutylaniline in 100 ml of an acid mixture consisting of 1 part of propionic acid and 5 parts of acetic acid. The mineral acid was then neutralized by adding solid ammonium acetate at a temperature of 0 ° C or below. After the coupling had ended, 500 ml of water were added with vigorous stirring. The yellow dye which had precipitated out was filtered off and washed with water.

The dye dyed polyester threads and fibers in strong yellow tones more excellently Authenticity properties.

B e i s ρ i e 1 e 90 to 95

Following the procedure described in Example 89, additional azo dyes of the following structural formula were obtained manufactured:

R ²

NH-R ¹

The meaning of the individual substituents of the dyes produced results from the following Table VII.

Table VII

at
game R ⁵ R ⁶ R ⁷ R ¹ R ² R ³ R * 90 H - COOC ₂ H ₅ -C ₆ H ₅ - COOC ₂ H ₅ -CH (CH ₃ I ₂ CHj H 91 H - COOCH (CH ₃ ) I ₂ -SO ₂ QH ₅ -COC ₆ H ₅ -C ₂ H ₅ OtJ H 92 H - CONH ₂ -C ₂ H ₅ -SO ₂ QH ₅ -C ₂ H ₅ CHj 4-CH ₃ 93 H - CONH ₂ - SO ₂ C ₂ H ₅ -CONHC ₂ H ₅ -C ₂ H ₅ -CH ₂ - H 94 -CH ₃ - CN -CH ₃ - COCH ₃ -C ₂ H ₅ -CH ₂ H 95 H -COOCH ₃ H -COQH ₅ -C ₂ H ₅ -CH ₂ - H

if
: r
η

Example 96

Preparation of a dye of the following
Structural formula:

CH,

O, N

N = N

CH ₂

NHCOCH,

Example 97

2.49 g of 2,4-bis (methylsulfonyl) aniline were diazotized according to the method described in Example 186 and coupled with 3.30 g of 3-acetamido-N, N-dibenzylaniline. In this way it was used as an azo dye 4 - (2,4 - Dimethylsulfonylphenylazo) - N, N - dibenzyl-3-acetamidoaniline receive.

The dye dyed threads and fibers made of polyester in brilliant red shades more excellently Authenticity properties.

0.72 g of sodium nitrite was added to 5 ml of concentrated sulfuric acid with stirring. The solution was then cooled, whereupon 10 ml of an acid mixture consisting of 1 part propionic acid and 5 parts acetic acid below 10 ^° C. were added. The mixture obtained was admixed with 1.72 g of 2-chloro-4-nitroaniline with stirring, whereupon another 10 ml of the acid mixture were added at a temperature of 0 to 5 ° C. The diazotization mixture was stirred for 3 hours at 0 to 5 ° C, after which it was added to a cold solution of 3.30 g of 3-acetamido-N, N-dibenzylaniline dissolved in 100 ml of the acid mixture of acetic acid and propionic acid. The coupling mixture was kept below 5 ° C. and buffered by adding solid ammonium acetate until the coupling mixture reacted neutrally to Congo red paper. After coupling for 2 hours, the mixture was poured into water and the dye was filtered off, washed with water and air dried.

The dye dyed threads and fibers made of polyester in strong red shades more excellently Authenticity properties.

45

Example 98

2-Methylsulfonyl-4-nitroaniline was diazotized according to the procedure described in Example 154 and then with 3-acetamido-N, N-bis (p-methylbenzyijaniline coupled In this way, 4- {2-methylsulfonyl-4-nitrophenylazo) -N, N-dibenzyl-3 ^ acetamidoaniline was obtained as the azo dye receive.

The dye dyed threads and fibers made of polyester in strong purple hues more excellently Authenticity properties.

Example 99

Preparation of an azo dye of the following
Structural formula:

-N-N

209430/256

26th

6.9 g of p-nitroaniline were dissolved in 5.4 ml of concentrated sulfuric acid and 12.6 ml of water. The received Solution was then poured onto 50 g of crushed ice, followed by a solution of 3.6 g of sodium nitrite in one go in 8 ml of water was added. The diazotization mixture was then left at 0-5 ° C for 1 hour stirred for a long time, after which the solution was dissolved into a cold solution of 16.5 g of S-acetamido-NjN-dibenzylaniline in 250 ml of an acid mixture consisting of 1 part propionic acid and 5 parts acetic acid would. The coupling mixture was kept at 0 to 5 ° C, followed by the addition of Ammonium acetate was neutralized using Congo red paper as an indicator. After a Coupling time of 2 hours, the mixture was poured into water. The precipitated dye was filtered off, washed with water and air-dried.

The dye dyed threads and fibers made of polyester in strong scarlet shades more excellently Authenticity properties. B e i s ρ i e 1 e 100 to

According to those described in Examples 154-157 Processes other azo dyes were made by diazotizing each 0.01 mole of an amine of the formula

ίο

NH,

where Y is a substituent given in Table VIII below and η = 1, 2 or 3. The resulting diazonium compounds were then coupled with 0.01 mol of a compound of formula II.

The azo compounds obtained corresponded to the formula I, in which R is the phenyl radical of the above Amine formula corresponds. The following table also shows the dyeing of the dyes Shades achieved on polyester fibers are indicated.

Table VIII

example

(Y) "

R ²

R ³

R *

hue

2-CI-4-NO2

101 2-Cl-4-NO ₂ 102 2-Cl-4-NOj 103 2-Cl-4-NOj 104 2-Cl-4-NOj 105 2-CI-4-NO ₂ 106 2-C1-4-NO,

2-Cl-4-NOj

108 2-Br-4-NOj 109 2-Br-4-NO ₂ 110 2-0-4-NO ₂ 111 2-Cl-4-NOj

4-NO ₂ -

4-NO ₂ -4-NO ₁ -4-NO ₂ -

-COOC ₂ H ₅

- SO ₂ CH ₃ -COC ₆ H ₅ -SO ₂ C ₆ H ₅ -COC ₆ H _n

- CONHCjH ₅

- CONHQH ₅

- COCH ₃

-COCH ₃

- COCH ₃ -COCH ₃ -SO ₂ CH ₃

-COCH ₃

-COCH ₃ -COCH ₃ -COOC ₂ Hj -CH ₂

-CHj

-CH ₂

-CH ₂

CH ₃

Cl

-CH ₂ -

CH2 '

- CH ₂ -

- CH ₂ -

-CH ₂ - -CH ₂ -

CH2

-CH ₂ -

-CH ₂ - -CH ₂ - -CH ₂ -

-CH ₂ -

-CH ₂ -CH ₂ -

HHHH HH

4-CH ₃

4-0CH ₃

4-Cl

4-Cl

3-CH ₃

4-Cl 3-Cl 3-Cl

Red red red red red red red

Red

Red

Red Red Scarlet

scarlet

Scarlet scarlet scarlet j

!give"
tialten

> beü vsr

ai
■ just.

example

116 117 118 Π9 120

121

122

123 124

125 126! 127

j. 128 * 129

Ir '

130th 131

132

133

134

; 135

i '136

continuation

28

4-NO ₂ -

2-CN-4-NO ₂

2-CN-4-NO ₂

2-CN-4-NO ₂

2-CN-4-NO ₂

2-CN-4,6-di-NO ₂ 2-Cl-4-SO ₂ CH ₃

2-0-4-SO ₂ CH ₃ 2- C1-4-SO ₂ CH ₃

4-SO ₂ CH ₃ 4-SO ₂ CH ₃ 4-SO ₂ C ₁ H ₉

2,4-di-SO ₂ CH ₃

2,4-di-SO ₂ CH ₃

2,4-di-SO ₂ CjH ₅

2,4-di-SO ₂ CH ₃

2-SO ₂ CH ₃ ^ -NO ₂

2-SO ₂ CH ₃ ^ NO ₂

2-SO ₂ CH ₃ -4-NO ₂

4-SO ₂ NH ₂

4-COOC _{2 HY}

R ¹

- COOC ₂ H ₅

- COOC ₂ H ₅

- COCH ₃

- COC ₂ H ₅ -COC ₃ H ₇ Oi)

- COCH ₃ -COCH ₃

- COCH ₃

- COOC ₂ H ₅

- COOC ₃ H ₅ -COCH ₃

- COCH ₃

- COCH ₃

- COOC ₂ H ₅

- COC ₆ H ₅

- CONHC ₂ H ₅ -COCH ₃ -COCH ₃

- COOC _{2 HY}

- COOC _{2 HY}

- COOC _{2 HY}

R ²

-CH ₂ CH ₂ CH ₂ CH ₂

-CH ₂ CH ₃

CH ₃

CH ₃

-CH ₃

-CH ₂

Cl

- CH.

-CH ₂ -CH ₂

-CH ₂ -CH ₂

~~ CH2

CH ₃

CH ₃

CH ₃

CH ₃

R ³ R ⁴ H CH ₂ - H CH ₂ - H CH ₂ - H CH ₂ - H CH ₂ - H CH ₂ - H CH ₂ - 4-CH ₃ CH ₂ - H CH ₂ - H CHj H CH ₂ - H CH ₂ - 4-CH ₃ CH ₂ - - H CH, - - H CH ₂ - IJ CH ₂ - - H CH ₂ - - H CH ₂ - - H CH ₂ - CH ₂ - - H CH ₂ -

hue

Scarlet rol

violet

violet

violet

violet

Red-blue scarlet!

Scarlet: Scarlet

Orange orange orange

Red

Red

Red

Red

violet

violet

Violet Orange Orange.

29

continuation

example

00 »

R ¹

R ²

R ³ R * CH, - - Η CH, - -H - Η CH, - - Η CH, - - Η CH, - TJ CH, - Tl
ΓΤ CH, - - Η CH, - - Η CH, - - Η CH, - - Η CH, - TT CH, - - Η CH ₂ - - Η CH ₂ - - ^Η CH, - - Η CH ₂ - TJ CH ₂ - - Η CH ₂ - TJ CH ₂ - γ *! CH ₂ - TJ V0H2 - Η H CH ₂ - H CH ₂ - H

hue

140
141
142
143
144
145

4-CN
4-CN
2,4-di-CN

2,4-di-CN

2,4-di-CN

2,4-di-CN

2-0-4-COOC ₂ H ₅

2-C1-4-CN

4-CHO

146 4-COCH3 147 2-CI-4-COCH3 148 4-CF3 149 2-CF3-4-NO, 150 2-COOCH3-4-NO, 151 3.5-di-COOCH, 152 2-NO ₂ -4-SCN 153 2-NO ₂ -4-SCN 154 2-Br-6-CN-4-NO ₂ 155 4-a 156 2-COOCH ₃ -4-NO, 157 2-COCH ₃ A6-di-Br 158 2-CONH ₂ ^ NO ₂ 159 ' 2-a-4-NO ₂ 160 2-0-4-NO ₂ 161 2-0-4-NO ₂

-COOC ₂ H ₅ -COCH ₃

- COCH ₃

- COCH.,

-SO ₂ -C ₆ H ₄ -P-CH ₃ -CO-C ₆ H ₄ -P-CH ₃ -COCH ₃

- COCH ₃ -COCH ₃

- COCH ₃

- COCH ₃ -COCH ₃

- COCH3

- COCH ₃

- COCH ₃

- COCH ₃

-SO ₂ -C ₆ H ₄ -P-CH ₃ -COCH ₃

- COCH ₃

- COCH ₃ -COCH ₃

- COCH ₃ -COC ₂ Hs -CHO

- Sq ₂ C ₂ H ₄ Cl

-CH,

CH ₃

CH,

-CH, -

-CH,

-CH,

-CH,

■ OCH,

-CH ₂

-CH ₂

-CH,

orange
orange
Red

Red

Red

Red

Red

Red

orange

orange

Red

orange

Red

Red

orange

Red

Red

Reddish blue

yellow

Red

Red

violet

Red

Red

scarlet

d; N fe m b «

in at ge

av av

Continuation of Fh

at
game (Y). 162 2-01-4-NO ₂ 163 2-01-4-NO ₂ 164 2-01-4-NO ₂ 165 2-Cl-4-NO ₂ 166 2-0-4-NO ₂ 167 2-CI-4-NO, 168 2-C1-4-NO, 169 2-C1-4-NO, 170 2-C1-4-NO, 171 2-C1-4-NO,

R ¹ R »

R *

hue

-COQH ₄ OH

- COCH ₂ Q -COCH ₂ C ₆ H ₃ 2-fufoyl -CO-C ₆ H ₄ -P-CH ₃

-CO-QH ₄ -P-OCH ₃ O

Il

-CO-C ₆ H ₅

- COCH (CH ₃ ), -COCH ₃

- COCH ₃

-CH, - -CH, -

-CH, - CH ₂ - CH, -

CH, - -CH, - -CH, -

H H H H H H

H H

4-Cl H

Red red red red red red

Red

Red

scarlet

Red

Example 172
Preparation of an azo dye of the following formula:

O, N

N = N-

NHCOCH,

40

45

To a suspension of 2.9 g of 2-amino-5-nitrothiazole in 25 ml of water, 13.6 ml of concentrated sulfuric acid were added with stirring. Dissolution of the thiazole occurred immediately. The solution was cooled to -1O ⁰ C, was added followed by a solution of 1.4 g of sodium nitrite in 10 ml concentrated sulfuric acid, below ⁰ -5 C. The mixture was then stirred for about 15 minutes at about -5 ° C. The resulting diazonium solution was then added to a cold solution of 7.6 g of 3-acetamido-Ν, Ν-dibenzylaniline, dissolved in 100 ml of 15% sulfuric acid and 100 ml of an acid mixture consisting of 1 part of propionic acid and 5 parts of acetic acid at about 0 ⁰ C added. The reaction mixture was then allowed to stand at 0-5 ° C for 30 minutes. The coupling mixture was then poured into water. The precipitated dye was filtered off, washed with water and air-dried.

The azo dye obtained dyed threads and fibers made of polyester in strong reddish blue shades excellent fastness properties.

Example 173

Preparation of an azo dye of the following structural formula:

H ₂ NCO

Γ Vo

0.72 g of dry sodium nitrite were added in portions to 5 ml of concentrated sulfuric acid with stirring. The resulting solution was cooled on WOI 10 ml of a part of a propionic acid and 5 parts of acetic acid existing mixture below 15 ⁰ C were added. "The mixture was further cooled, to which 1.43 g of 2-amino-5-carbamylthiazol and then again 10 ml of the acid mixture described were added at 0 to 5 ° C. After a diazotization time of 2 hours at 0 to 5 ° C., the solution was added to a cold solution of 3.30 g of 3-acetamido-N, N-dibenzylaniline, dissolved in 100 ml of the acid mixture described was added. The coupling mixture was then buffered with ammonium acetate until Congo red paper reacted neutrally. After a coupling time of 2 hours at 0 to 5 ° C., the reaction mixture was poured into water. The reaction product was filtered off, washed with water and treated with Air dried.

The dyestuff obtained dyed threads and fibers made of polyester in the strongest red shades more excellently Authenticity properties.

Example 174

Preparation of an azo dye of the following
Structural formula:

ic

. NHCOCH ₃

0.76 g of sodium nitrite were added in portions to 5 ml of concentrated sulfuric acid. The solution was cooled in an ice bath and 10 ml of an acid mixture consisting of 1 part propionic acid and 5 parts acetic acid was added. The temperature was kept below 15 ° C. The mixture was then cooled to 0 ° to 5 ° C. with stirring, whereupon 1.75 g of 2-amino-6-cyanobenzothiazole were added. Subsequently * were ßend another 10 ml of the acid mixture described added the diazotization mixture was then stirred at a temperature from 0 to 5 ^C C for 2 hours and then added to a solution of 3.30 g of 3-acetamido-N, N-dibenzylaniline in 100 ml of the acid mixture described was added. The coupling mixture was then buffered by adding solid ammonium acetate and left to stand at about 5 ^° C. for 2 hours. After the reaction mixture was poured into water, the dyestuff which had precipitated out was filtered off, washed with water and air-dried.

The dye dyed threads and fibers made of polyester in strong red shades more excellently Authenticity properties.

Example 175 Preparation of an azo dye of the following structural formula:

CH ₃ SO ₂ -L II

NHCOCH ₃

To a slurry of 2.28 g of 2-amino-6-methylsulfonylbenzothiazole in 24 ml of water was added 26.2 g of concentrated sulfuric acid. After the amine had dissolved, the solution was cooled, whereupon a solution of 0.84 g of sodium nitrite in 5.0 ml of concentrated sulfuric acid below 0 ° C. was added in portions. The diazotization mixture was stirred for 2 hours at about 0 ^° C., whereupon the solution was added to a cold solution of 3.30 g of 3-acetamido-N, N-dibenzylaniline in 50 ml of 15% strength sulfuric acid and 50 ml of one made from 1 part propionic acid and 5 parts of acetic acid existing acid mixture at about 5 ⁰ C was added. After a coupling time of one hour at 0 to 5 ^° C., the mixture was poured into water, whereupon the precipitated dye was filtered off, washed with water and dried in the air.

The obtained dye colored threads and fibers made of polyester in strong red tones more excellently Authenticity properties.

Example 176 Preparation of an azo dye of the following structural formula:

NHSO ₂ CH ₃ Cl

A solution of 0.72 g of sodium nitrite in 5 ml of concentrated sulfuric acid was cooled to about -5.degree. C. and added to 1.95 g of 2-amino-6-nitrobenzothiazole in 24 ml of water and ¹ ml of concentrated sulfuric acid below 0.degree. After stirring for 2 hours at about 0 ⁰ C, the diazotization solution was added to a solution of 2.25 g of N, N-di (p-chlorobenzyl) -3-methylsulfonamidoanilin in a mixture of 50 ml I5% sulfuric acid and 50 ml of a I Part of propionic acid and 5 parts of acetic acid consisting of an acid mixture ^{at about O 0 C}

60 give. The coupling mixture was allowed to stand for 2 hours at ice bath temperature and then in water poured. The precipitated azo dye would be filtered off, washed with water and allowed to air

65 dried. The dye obtained dyed threads and fibers made of polyester in strong violet hues more excellently Authenticity properties.

hear iino-mieiurehung ratur sung K) ml

The: from the nth it looks like

Polyineter

35

(I.

Examples 177 to 201

According to the method described in Examples 245 to 247, further dyes of the foloden Structural formula made:

NH-R ¹

■ The meaning of the individual substituents results from the following table X, in which the color | ones are given which were obtained when dyeing the resulting dyes on polyester fibers.

example

(R ⁵ L

177 o-CN

178

179

.'pion- 180 6-SO ₂ CH ₃ acid- To 0 to 181 6-SO ₂ CH ₃ ahead Vasser 182 6-SO ₂ CH ₃ Fibers] excellent • 183 6-NOj

'zugelang at jj in what- \,' became; he air ι

', Fibers i

ien aus- ϊ

184 185 186 187

188

189 190

6-CN

6-SO ₂ CH ₃

6-NOj 6-NO ₂ 6-NOj 6-NO ₂

6-NO ₂

4,6-di-NOj 4-C1-6-CN

Table X

R ¹

- COCH ₃

- COCH ₃

- COOC ₂ H ₅ -COC ₆ H ₅

- CONHC ₂ H ₅ 2-furoyl

- COCH ₃

- COOC ₂ H ₅ -COC ₂ H ₅

- COC ₂ H ₅ -COC ₂ H ₅

- COCH ₃

- COCH ₃

- COCH ₃

-CH ₂ CH ₂

-CH ₂

-CH

-CH ₂

-CH, -

-CH ₂ -

-CH ₂

- CH ₂ -

hue

4-CH,

4-CH ₃

CH ₂ - - H Red CHj - TJ Red CH ₂ - - H Red CH ₂ - - H violet CH ₂ - - H violet CH2 yy violet CHj- - H violet CH ₂ - H violet

- H

- H

Red

Red

Red

violet

blue

violet

37

continuation

38

example

191 192 193 194 195 196

(R ⁵ L

6-SCN 6-SCN 6-SCN 6-SCN 4-CI-6-SCH3 6-Cl

6-Cl

6-Br 6-SO ₂ NH ₂ 6-SO ₂ N (CH ₃ ) ₂ 6-SO ₂ C ₂ H ₄ CN

-COCH ₃ -COOC ₂ H ₅

- COCH ₃

- COCH ₃ -COCH ₃

- COCH ₃

- COCH ₃

- COCH ₃ -COCH ₃

- COCH ₃

- COCH ₃

-CH ₂ -

- CH ₂
-CH ₂

- CH ₂
-CH ₂ -
-CH ₂ -

-CH ₂ -

- CrI ₂ ■
-CH ₂ -

- CH, -

- H

- H

- H
4-CH ₃
H

H
H
H
H

»US!

Red,

Red

Red

Red

Red

Red

Red

Red
Red
Red
Red

example

Preparation of a dye with the following structural formula:

N-

-N

n = n- / ~ S-n

NHCOCH ₃

added acid mixture below 5 ° C
The reaction mixture was kept cold, whereupon ₂ l ammonium acetate was added until the
Coupling mixture reacted neutrally to Kongcrctpspicr. After a coupling time of ²¹ hours at about 5 ^° C., the reaction mixture became
poured in water. The precipitated dye was filtered off, washed with water and left in the air
dried. 21

The dye dyed threads and fibers made of polyester in strong red shades more excellently
Lightfastness and sublimation fastness properties ^{- 2I} '

Example 203

0.72 g of sodium nitrite were added in portions to 5 ml. concentrated sulfuric acid. The solution was then cooled, whereupon 10 ml below 15 ° C

an acid mixture consisting of 1 part propionic acid and 5 parts vinegar - preparation of a dye of the following * acid - was added - structural formula:
the. The mixture was with further cooling:; |

with 1.61 g of 2-amino-5-ethylthio-l, 3,4-thiadiazole comparable Cj_j / \ S | ²¹⁷

sets as well as further 10 ml of the described- NN / ² X = ^ A II

benen acid mixture. The thiadiazole and the acid mixture were added at below 5 ° C. After stirring for 2 hours at 0 to 5 ° C., the diazonium solution became a cold solution of 3.30 g of 3-acetamido-N, N-dibenzylaniline in 100 ml of be-CH ₃ SO ₂ -

-N = N

CH ₂
NHCONHC ₂ H ₅

39

24

40

To a solution of nitrosyl sulfuric acid prepared by careful addition of 0.72 g of sodium nitrite to 5 ml of concentrated sulfuric acid below 80 ⁰ C and cooling to 15 ° C in an ice bath, 10 ml of of 1 part of propionic acid and 5 parts of acetic acid existing acid mixture added . The resulting solution was then cooled to 3 ° C., whereupon 1/79 g of 5-methylsulfonyl-2-amino-1,3,4-thiadiazole was added with stirring. A further 10 ml of the acid mixture described were then added below 5 ° C., whereupon the solution X ¹ I was stirred at 0 to 5 ° C. for _{2 hours.} The diazotization solution was then added to a cold solution of 3.59 g of N, N-dibenzyl-3-ethylureidoaniline in 25 ml of the acid mixture described. The solution was then neutralized by adding enough ammonium acetate to cause congo red paper to turn brown. The solution was then left to stand at ice bath temperature for 2 hours and then poured into water. The precipitated dye was filtered off and washed with water.

The dye dyed polyester threads and fibers brilliantly in strong red hues Authenticity properties.

Examples 204 to 243

Following the procedures described in Examples 202 and 203, additional thiadiazolylazo dyes were made of the following structural formula

The meaning of the individual substituents is also reflected in the color tones that are used in the coloring of the her Dyes made on fibers made of polyester were obtained from the following Table XI

Table XI

example

R ⁵

R ³ (R *). -CHj - Η Cri2 4-CH ₃ -CHj- 4-CH ₃ -CH ₂ - - Η CH2 - Η CH2 - Η - CHj - - Η -CH ₂ - - Η -CH ₂ - TJ -CH ₂ - - Η -CH ₂ - - Η -CH ₂ - 4-ΟΗ -CH ₂ - 4-ΟΗ -CH ₂ - 4-ΟΗ -CH ₂ - , χτ -CH ₂ - - Η

hue

; ben.
jrauf
> the

new one
hung
/ urde

Polymeter
sheep-

204 205 206

207 208 209 210 211 212 213 214 215 216 217 218 219

CH ₅ S-CH ₃ S-CH ₃ S-

CH ₃ S QH ₅ S-QH ₅ S-NCQH ₄ S -NCQH ₄ Sn-QHjS -

-QH ₅

-CH ₃

QH ₅

-C ₆ H ₄ -DO • -QH ₄ -P-OCH ₃ - NHCOCH ₃

- COCH ₃

- COCH ₃

- COCH ₃

- COOQH ₅ -COQH ₅ -COC ₀ H ₁₁ -COCH ₃ -COCH ₃

COCH ₃

COCH ₃

-COCH ₃

-COCH ₃

COCH ₃

-COCH ₃

-COCH ₃

CHj

- CHj CH ₃

OH

OH

- CH ₂ Red red red

Red Red Red Red Red Red Red Red Red Red Red Red Red

continuation

42

at
game R ⁵ -Cl R ¹ 220 -Br -COCH ₃ 221 - H - COCH ₃ 222 - SCH ₃ - COCH ₃ 223 -SCH ₃ -COC ₂ H ₅ 224 CH ₃ S- -CHO 225 CH ₃ S- -COCH ₃ 226 CH ₃ S- -COCH ₃ in C ₆ H ₅ CH ₂ S-. - COCH ₃ 228 C ₆ H ₅ CH ₂ S- - COCH ₃ 229 C ₆ H ₅ CH ₂ S- - COCH ₃ 230 p-Cl —C ₆ H ₄ S- -COCH ₃ 231 P-CH ₃ C ₆ H ₄ S -COCH ₃ 232 -SCN -COCH ₃ 233 -SCN - COCH ₃ 234 -SCN - COCH ₃ 235 -SCN - COCH ₃ 236 -S-CH ₂ COOC ₂ H ₅ - COCH ₃ 237 - SC ₂ H ₄ OH - COCH ₃ 238 -SC ₂ H ₄ OOCCH ₃ -COCH ₃ 239 - SCHjCN -COCH ₃ 240 -SCHjCOC ₆ B ₅ -COCH ₃ 241 -SC ₂ H ₄ Cl - SOCH ₃ 242 -SCH ₂ CH ₂ C ₆ Hj -COCH ₃ 243 -COCH ₃

(R ⁴ ).

hue

CH ₂ CH ₂

CH ₂

-CH ₂

CH,

■ CH ₂ - ^ y ~ Cl

- CH ₂ -

Cl

Cl

-CH ₂ -

-CH ₂

CH ₂

-CH ₂

-CH ₂ -

CHj

Cl

-CH ₂ - -CH ₂ - -CH ₂ - -CH ₂ - -CH ₂ - -CH ₂ - -CH ₂ - -CH ₂ - -CH ₂ - -CH ₂ - -CH ₂ - -CH ₂ - -CH ₂ - -CH ₂ -— CH ₂ - -CH ₂ - -CH ₂ -

-CH ₂ - -CH ₂ -

ir

IJ

LJ

- H

TJ

- H 4-Cl

- H

-CH ₂ -

-CHj-

-CH ₂ -

-CH, -

4-Cl

- Η

- Η

- Η

Tj

IJ

4-Cl

- Η

- Η

| Τ

- Η

- Η

- Η

- Η

Red

Red

Red

Red

Red

Red

scarlet

scarlet

Red

Red

scarlet

Red

Red

Red

Red

Red

Red red red red red red

Red

net ran, all right

24?

250 251 252

253 254 255 256

43

example

Preparation of an azo dye with the following structural formula:

CH, S

Examples 245-264

Following the procedures described in Examples 282 and 283, additional azo dyes were obtained following structural formula:

R ⁵

-N

N
\

-N = N

IO

NHCOCH,

1.47 g of S-amino-S-methylthio-l ^ -thiadiazole were diazotized according to the method described in Example 233 and then with 3.3 g of 3-acetamido-N, N-dibenzylaniline coupled.

The obtained azo dye had an excellent affinity for fibers made of polyesters and provided brilliant red shades with excellent fastness properties.

NH-R ¹

starting from the corresponding 5-amino-1,2,4-thia · diazoles and S-acylamido-HN-diaralkylanilines.

The meaning of the individual substituents dei

produced dyes as well as the shades that are used when dyeing the dyes on fibers made of polyesterr are obtained from the following

Table XIl. example

245 246 247 248

249

250 251 252

253 254 255 256

CH ₃ S-

CH ₃ S-CH ₃ S - CH ₃ S-

CH ₃ S-

CH ₃ SO ₂ -CH ₃ SO ₂ -

CH ₃ SO ₂ -

CH ₃ CH ₃ -CH-S

Ti-C ₄ H ₉ S-

CH ₃ S-

CH ₃ S-

Table XII

- COCH ₃

- COCH ₃ -COOC ₂ H ₅ -COC ₆ H ₁₁

-COC ₆ H ₅

- COCH ₃ -COOC ₂ H ₅

- CO ₂ CH ₃

-COCH ₃

- COCH ₃ -CHO ~~ COCH3

- H 4-CH ₃ 4-CH ₃ H

hue

Red red red red

Red

- H violet - H violet - H violet - H Red - H Red - H Hot 4-CI Red

continuation

10 dei Wr wt 1

est Ec

Example.

R ¹ R ²

(R ⁴ ). hue 4-Cl Red 4-Cl Red 4-Cl Red 4-Cl Red 4-Cl Red - H Red - H Red - H Red

258-

CH ₃ S-

CH ₃ S-

CH, S -

CH ₃ S

QH ₅ CH ₂ S-

P-Cl-QH ₄ CH ₂ S-

P-CH ₃ QH ₄ CH ₂ S-

0-CH ₃ -C ₆ H ₄ CH ₂ S-

-SO ₂ QH ₄ -P-CH ₃

- NHCONHC ₂ H ₅

- COOCH ₃

- COOC ₄ H, -n

- COCH ₃

- COCH ₃

- COCH ₃

- COCH ₃

. , ", _R · B eis ρ ie 1 266

Example 265

_ ,,. , 2.14g 2-amino-5-isobutyrvl-3-nitrothiophene was

Production of a monoazo dye of the following _{the ver described in Beispje} , ^ 55.

drive diazotized and coupled with 3.30 g of 3-acetamido-N, N-dibenzylaniline.

The dye colored threads and fibers made of polyester in strong shades of excellent light

Structural formula:

C ₂ H ₅ CO

NHCOCH ₃

0.72 g of sodium nitride were added in portions to 5 ml of concentrated sulfuric acid with stirring. The resulting nitrosylsulfuric acid solution was then cooled, whereupon 10 ml of one of 1 part Propionic acid and 5 parts of acetic acid existing acid mixture below 15 ° C were added. Then 2.0 g of 2-amino-3-nitro-5-propionylthiophene and also another 10 ml of the acid mixture described at 0 to 5 ° C was added. The reaction mixture was then 1 hour stirred for a long time at 0 to 5 ° C. The diazonium solution then became a cold solution of 3.30 g 3-Acetamido-N, N-dibenzylaniline, dissolved in 75 ml of the acid mixture described, was added. The coupling mixture was then left for 1 hour left to stand with occasional stirring, after which it was poured into water.

The precipitated blue dye was filtered off, washed with water and air-dried

The dye dyed polyester threads and fibers in strong blue tones more excellently Lightfastness and sublimation fastness properties on.

fastness and sublimation fastness properties Example 267

Preparation of an azo dye with the following structural formula:

CH,

NHCOCH ₃

10 ml one of 1 part propionic acid and 5 parts. Acetic acid existing mixture of acids were too

added to a solution of nitrosylsulfuric acid, which consists of 0.72 g of sodium nitrite and 5 ml of sulfuric acid was prepared. The solution was cooled to 3 ° C. whereupon 1.41 g of methyl S-aminopyrazole ^ carboxylate below 5 ° C were added. Thereupon

another 10 ml of the acid mixture described were added at the same temperature The diazotization mixture was then stirred at 3 to 5 ° C. for a further 2 hours. The obtained diazo solution then became a cold solution of 3.86 g '-Acet-

amido-RN-di-p-toryltnethylaniline in 100 ml of the described Acid mixture given. The mineral acid was then made by adding solid ammonium acetate neutralizes the temperature at

wur-ver-'4-di-

> olyicht-) i an.

ZS "

10 ° C or below. After finishing fprmel established: 500 ml of water were added to the coupling with vigorous stirring. The precipitated yellow dye was filtered off and washed thoroughly with water.

The dye colored threads and fibers made of polyesterg in strong yellow shades more excellently Authenticity properties.

Examples 268-274

ίο The meaning of the individual substituents results can be found in the following Table XIV. When the dyes on fibers made of polyesters were in After the process described in Example 267, strong yellow shades are more excellent in all cases Further azo dyes with the following structure fastness properties were obtained.

Table XIV

hurry ■ n to even,; acid cools,

.ufh -

aure-the

at
game R ^1J R ¹³ - CN R " H R ¹ R ² R ³ (R ⁴ ). 268 H -COOCH (CH ₃ I ₂ -SO ₂ C ₆ H ₅ - COCH ₃ -CH ₂ - - H 269 H - CONH ₂ CjHj -COC ₆ H ₅ - CH ₂ - ^ 3> -OC ₂ H ₅ -CH ₂ 4-OC ₂ H ₅ 270 H -SO ₂ C ₆ H ₅ -CH ₂ -Z ^ -OH - H - CN -SO ₂ C ₆ H ₅ HO 271 -CN -CONH ₂ -SO ₂ C ₂ H ₅ -COC ₆ H ₄ -P-CH ₃ - CH ₂ - ^ ^> -CH ₂ - - H 272 H -COOCH ₃ H -CONHCjH ₅ - CH ₂ - <^ ^> -CH ₂ - it 273 H -COOCH ₃ H - COCH ₃ - CH ₂ - <^ ^> -CH ₂ - - H 274 H -COQH ₅ -CH ₂ - - H

Claims (1)

Claim: Monoazo dyes, characterized by the general formula R - (I) ⁴ Ch-TVr *