DE2628185A1 - ORGANIC COMPOUNDS - Google Patents

Description

SANDOZ-PATENl ¹ - GMBH 7850 Loerrach

Case 150-3766

Organic compounds

The invention relates to azobenzene disperse dyes, their preparation and use for dyeing hydrophobic fibers.

The new compounds correspond to the formula I.

(D,

bO988S / 1 1 S4

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wherein R- is a group of the formula -CH CH ₀ OH,

-CH ₂ CHOHCH ₂ OH, -CH COCH ₃ , -CH COC H,

-CHCOC H Br or - ^,

^R 9 R_ halogen or cyan,

one of R and R 'is hydrogen, the other is hydrogen

or halogen,

R hydrogen, chlorine, bromine, methyl, methoxy or ethoxy,

R chlorine, bromine, cyano or acylamino or

if R _{1 is} a group of the formula -CH CH OH,

-CH ₀ CH ₀ OHCH ₀ OH, CH ₀ COCH ₀ , -CH _o C0C _c H _c or ZZZ ZJ Aod

-CH ₃ COC ₆ H ₄ Br is also methyl, methoxy

or ethoxy,

RC. Alkyl or C-. -Alkenyl, R ₇ C ^ .- alkyl, C _.- _o alkenyl or phenyl-C, ₂ ~

alkyl,
R ₀ hydroxy-c _o -alkyl and

ο Z ~ ο

R is hydrogen, C. -Alkyl, hydroxy-C ₂ _-, - alkyl or cyano-C ₁ _ ₂ -alkyl.

Halogen is to be understood as meaning fluorine, chlorine, bromine and iodine, preferably chlorine and bromine.

Acyl groups (in acylamino) include, for example, formyl, trifluoroacetyl, C.sub.1-alkyl-carbonyl, C. or c. _{1-alkylsulfonyl} into consideration, where the alkyl and alkoxy groups, one or two chlorine or bromine atoms or a substituent selected from the group consisting of cyano, hydroxy, C. ₁ alkoxy, C ₁ "-C alkoxy _0th-alkoxy , Benzyloxy, phenyl or phenoxy, but acetals are excluded here.

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In each case, independently of the other symbols, the following preferably mean:

R, a group of the formula -CH ₂ CH ₂ OH, "CH ₀ COCH, -CH ₂ CHOHCH ₂ OH, -CH ₂ COC ₆ H ₅ , -CH ₂ CO - ^) - Br or -NR ₀ R ₀ , in particular -CH ₀ CH ₀ OH, -CH ₀ COCH- or -CH ₂ CHOHCH ₂ OH, especially -CH ₂ CH ₂ OH or -CH ₂ COCH ₃ and especially -

R "Chlorine, bromine, iodine or cyan

R_ and R 'one hydrogen, the other chlorine or Bromine, especially R_ hydrogen, chlorine or bromine and R 'hydrogen, especially R_ and R' hydrogen?

R _{4 is} hydrogen, methoxy or ethoxy, especially hydrogen;

R is chlorine, bromine, cyano, methyl, methoxy, ethoxy, formylamino, C. _{1-alkyl-carbonylamino,} the one or two substituents from the group chlorine, bromine, hydroxyl, cyano, C _1-3 -alkoxy, benzyloxy, phenyl or Can carry phenoxy, C _1. -Alkoxycarbonylamino, chloro- or BrOm-C ₁ , -alkoxycarbonylamino, C. _ ₂ -alkoxy-C ₂ _. ~ -Alkoxy-carbonylamino-, methoxyethoxy-ethoxycarbonylamino, phenoxy-C "-alkoxy- carbonylamino-, benzyloxycarbonylamino, benzoylamino, toluylcarbonylamino, phenoxycarbonylamino, allyloxycarbonylamino, trifluoroacetylamino, para-tert.-butylcyclohexyloxycarbonylamino, dioxanylmethoxycarbonylamino, vinylcarbonylamino, methylvinylcarbonylamino, methylvinylcarbonylamino, methylvinylcarbonylamino, or methylvinylcarbonylamino

in particular C _n "-alkyl-carbonylamino, the one

X ~ Δ

Substituents from the group hydroxy, chlorine, bromine or C ₁ "alkoxy can carry, C, _ -alkoxy-carbonylamino, methoxyethoxycarbonylamino, acryloylamino,

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Allylcarbonylamino, allyloxycarbonylaniino, methylvinylcarbonylamino (α- or β-), benzoylamino, phenoxycarbonylamino, trifluoroacetylamino, formylamino or methylsulfonylamino,

especially acetylaminO / propionylamino, chloro- or bromo-acetyl- or -propionylamino, methoxy- or ethoxyacetyl- or -propj.onylamino, acryloylamino, allylcarbonylamino, methacryloylamino, methoxy- or ethoxamino, methoxy- or ethoxlyamino, methoxy-ethoxy-carbonylamino, especially acryloxy-carbonylamino, or above all aethoxlyamycarbonylamino , Propionylamino, methoxy- or ethoxyacetyl amino;
R and RC. -Alkyl, especially ethyl.

The new disperse dyes are made by coupling the Diazonium compound from an amine of the formula II

^NH 2 (II)

^R 3 ^R 3

with a compound of the formula III

(III)

produced according to well known methods.

The compounds of the formula I in which R is cyano and R 'is hydrogen can also be prepared by condensation of a compound of the formula I in which R _{9 is} halogen and hydrogen with a salt of hydrocyanic acid,

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be prepared analogously to generally known methods.

The preparation of the compounds of the formula II in which R one bonded to the SO_ group via a methylene group The remainder can, for example, by condensation of one mole of a compound R -Hal (Hal = Cl, Br or I) with one mole of a Compound of formula IV

NaSO - \ Q \ -NE acyl (IV)

(Acyl is preferably acetyl)

and saponification of the acylamino group.

The condensation is usually carried out in an inert solvent, for example water, dioxane, and at temperatures between 20 and 100 ^° C., preferably 20 to 85 ^° C. The saponification is carried out in a generally known manner, preferably by acidification with dilute mineral acid.

Compounds of the formula II in which R is hydroxyalkyl, can also be obtained by adding one mole of a corresponding compound of the formula IV (which is in the form of the free acid reacts) with an alkylene oxide and subsequent saponification of the acylamino group by acidification, getting produced.

Compounds of the formula II, in which R 1 is a group of the formula _ _N '8, can by condensation of a

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Amine of the formula HN with one mole of a sulfonic acid halide of Formula V

¹ p

(V)

(Acyl is preferably acetyl)

and subsequent saponification of the acylamino group.

This condensation takes place in an inert solvent such as water or dioxane at temperatures between 0 and 50 ⁰ C instead.

The processing of the new compounds of the formula I into coloring preparations takes place in a generally known manner, e.g. by grinding in the presence of dispersants and / or fillers. With the possibly in a vacuum or by After adding more or less water, you can spray dried preparations in a so-called long or dye, pad or print short liquor.

The dyes are often obtained in polymorphic, thermally unstable form and are then advantageous after a converted into their thermostable modification by the following methods:

a) stirring in water at temperatures between 20 and 100 ° C, preferably soluble or at 50-100 ⁰ C, in the presence or absence of a surfactant or a water-insoluble

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organic solvent, for 5-300 minutes (usually 15-45 minutes are sufficient);

b) as a), but in an autoclave at 100-150 ° C, preferably at 125-135 ° C;

c) by drying under vacuum or at atmospheric pressure at temperatures between 50 ° and 140 ⁰ C, preferably between 100 and 140 ° C;

d) by recrystallization from an organic solvent;

e) by heating the reaction mixture after the completion of coupling to 50-100 ⁰ C, preferably 60-9O ^0, where, in order to avoid saponification of the pH value of the suspension is preferably adjusted to 4-7 C;

f) in exceptional cases, the stabilization can be obtained by milling the dye in the presence of water and dispersing agents, and then heating to 50-100 ⁰ C, preferably 60-9O ⁰ C can be performed, but it must be ensured that by the heating no enlargement of the particles takes place.

Also by performing the coupling reaction in the presence of surfactants or of organic solvents the formation of thermally unstable crystal modifications avoided in some cases will.

With the described conversions into the thermostable form, the following advantages, among others, can be achieved:

Improvement of dispersibility (in most In some cases, the production of sufficiently stable dispersions at dyeing temperatures is only possible with thermally stable dispersions ("heat-treated") pigments possible);

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- Improvement of the pulling properties (tends to be less common);

Increasing the dry content of the press cake (is often important in the production of liquid Coloring preparations).

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. They are particularly suitable for dyeing or printing textile material made of linear, aromatic polyesters, as well as cellulose 2-l / 2-acetate, cellulose triacetate and, if the dyes are in which R _{1 contains} at least one hydroxyl group, in particular synthetic polyamides, one dyed or printed according to known per se, for example that in French patent specification no. 1.445.371 described procedure.

The dyeings obtained have good all-round fastness properties; to be emphasized are the lightfastness, the thermosetting, Fastness to sublimation and pleating in particular dry cleaning-proof, rubbing, over-dyeing, ozone, smoke gas and chlorine law; They are very resistant to the effects of the various permanent pressing processes and the so-called "soil release" equipment. The resistance to reduction (when dyeing with wool) and the reserve of wool and cotton are good.

In the following examples, parts are parts by weight and percentages are percentages by weight. The temperatures are given in degrees Celsius.

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Example 1

a) Manufacture of the diazo components

234 grams of 4-acetylamino-3-chlorobenzenesulfinic acid are added to a solution of 800 ml of water and 48 grams of sodium hydroxide. The temperature rises from 25 ° to approx. 45 °. 100 grams of ethylene chlorohydrin are added to the suspension obtained in the course of 20-30 minutes, a brownish solution being formed. The reaction mixture is stirred for 3 hours at reflux ^{temperature (87 °} C.), it is then allowed to cool to room temperature, the product which has precipitated in crystalline form is filtered off and washed with a little water.

The filter residue is in a mixture of 800 ml of water and 500 ml of concentrated hydrochloric acid during Boiled at reflux for 45 minutes. 5 grams of decolorizing charcoal are added to the resulting solution and the mixture is stirred a few minutes and filtered off. The clear-filtered solution is diluted with water to a volume of 2000 ml ■ set.

200 ml of the solution thus obtained are cooled to 0 ° by adding 100 grams of ice and then with a solution of 6.9 grams of sodium nitrite in 50 ml of water in 30 to 60 minutes. One stirs Another 30 minutes, the resulting solution is mixed with 5 grams of aminosulfonic acid and filtered.

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The diazonium salt solution thus obtained is slowly added to a mixture of 2O ₇ 6 grams of 3-acetylamino-1 ~ N, N-diethylaminobenzene, 50 ml of glacial acetic acid and 100 grams of ice, with sodium acetate until a pH of 2.0 to 2.5 is reached added and stirred at 0-5 ° for a further 1 to 2 hours until the coupling has ended. The dye formed is filtered off, washed with water, then rinsed with 1000 ml of water in an autoclave and stirred at 130 ° for 2 hours. After cooling to room temperature, the dye is filtered off and dried.

The dye thus obtained corresponds to the formula

: h CH

HOCH ₂ CH ₂ O ₂ S- ^ (ΪΥ-U = Ν— (Γ ^ V- no

IHCOCH

and dyes synthetic fibers in bright red shades with very good fastness properties.

example

6.9 parts are powdered to 100 parts of concentrated sulfuric acid at 60 ° to 70 ° with vigorous stirring Given sodium nitrite. The mixture is stirred for a further 10 minutes at 60 °, cooled to 10 ° and added slowly at 10-15 ° 100 parts of glacial acetic acid and then 24.7 parts of the compound of the formula

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and 100 parts of glacial acetic acid. The mixture is stirred for 2 hours and the resulting diazonium salt solution is poured into a device of 20.6 parts of S-acetylamino-l-N / N-diethylaminobenzene, 50 parts of glacial acetic acid, 300 parts of ice and 10 parts of sulfamic acid. The clutch is in acidic Medium was brought to an end by blunting with sodium acetate to pH 2.0-2.5. The dye is formed immediately and fails. It is filtered off, washed free of acid and dried.

The dye of the formula thus obtained

CH -C-CH -O S - ((JVN = N- ((J h < (a)

^T 2 ^CH 3

dyes synthetic fibers in brilliant red tones with excellent fastness properties.

46.5 parts of this dye can, in 200 parts of dimethylformamide suspended, heated with 10.4 parts of Cu-I cyanide for 180 minutes with stirring to 130 °, wherein one contains the corresponding 2-cyano substituted dye. This dye dyes polyester fiber material also in red nuances with good fastness properties.

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COLOR EXAMPLE 1

18 parts of the dye prepared according to Example 1 are dinaphthylmethanedisulfonic acids with 11.1 parts! Sodium, 11.1 parts sodium cetyl sulfate and 13.9 parts Anhydrous sodium sulfate was ground to a fine powder in a ball mill for 48 hours. 1.5 parts of the thus obtained dye preparation are in 3000 parts of water, which 3 parts of a 30% solution of a contains highly sulfonated castor oil and 20 parts of an emulsion of a chlorinated benzene in water, dispersed. At 20-25 °, 100 parts of polyester fiber fabric are introduced and the bath is heated up in about 30 minutes 95-100 ° and stains at 95-100 ° for 1 hour. The material to be dyed is taken out of the bath and rinsed for 15 minutes at 70 ° with a 0.1% solution of an alkylphenyl polyglycol ether soaped, rinsed again and then dried. A bright red color is obtained with excellent fastness properties.

COLOR EXAMPLE 2

11.7 g of the dye (a) prepared according to Example 2 and 19.3 g of a commercially available lignosulfonate will be in 10-15 ml of water with 100 g of siliquarzite beads and a two-plate stirrer for 2-8 hours Milled 3000-2500 revolutions per minute. Then you dilute the grinding mixture with about 30 ml of water and filter it through a G 1 glass funnel into a 1000 ml pear flask Adhesive dye and dispersant textiles are with

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As little water as possible rinsed quantitatively into the pear flask. The dispersion obtained in this way is 10% strength Phosphoric acid adjusted to pH 6-6.5 and then on a rotary evaporator at a maximum outside temperature of 60 ° Evaporated dry.

100 g of purified polyester fiber material are added to 2 g of the dye preparation obtained in 1000 ml of water at 40 ° -50 ° "Terylene" (registered trademark) and slowly heats up. You dye under for about 60 minutes Print at 130 ° C and after rinsing, soaking, rinsing and drying it gets a red color with excellent Fastnesses.

FAERBEE EXAMPLE 3

An aqueous, finely dispersed suspension of 10 parts of the dye of Example 28

(Prepared analogously to the procedure of Example 1), 20 parts of sodium and dinaphthylmethandisulfonsaurem 3 parts of sodium alginate are made up to 1000 parts with water and mixed well. A polyester fabric comes with the padding liquor obtained padded at 20 °, squeezed to a water content of 70%, with air from 60-100 ° and then treated with hot, dry air at 230 ° for 60 seconds.

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Then the fabric is rinsed, soaped, rinsed again and dried. A red coloration with excellent results is obtained Fastnesses.

COLOR EXAMPLE 4

10.5 g of the dye obtained according to Example 1 and 19.5 g are placed in a 200 ml beaker at 20-30 ° of a commercially available lignosulfonate in 10-15 ml of water with 100 g of siliquarzite beads and a two-plate stirrer milled for 2-8 hours at 2000-2500 revolutions per minute. Then you dilute the grind with approx. 30 ml of water and filter it through a G 1 glass funnel into a 1000 ml pear flask Dye and dispersant particles adhering to silica-quartzite beads are quantitatively converted with as little water as possible rinsed the pear butt. The dispersion obtained in this way is adjusted to pH 6-6.5 with 10% strength phosphoric acid and then evaporated to dryness on a rotary evaporator at max. 60 ° outside temperature.

A solution of 3 parts of Na PO..10 H „0 in 4000 parts Water is made with NaH-PO. adjusted to pH 9 and then with 1 part of an adduct of 25 mol of ethylene oxide added to 1 mole of oleyl alcohol. First 1 part of the solution obtained according to the above procedure is added to this solution Dye preparation then 100 parts of nylon carpet fabric (Du Pont Nylon 846) and heats the bath inside 30 minutes at 98 °. The dyeing is carried out for 60 minutes at 98 °, the material to be dyed is taken out of the bath, and then rinsed with warm water with cold water and dry it. "The result is a red dyeing with excellent fastness properties.

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COLOR EXAMPLE 5

20 parts of the dye of Example 42

(prepared analogously to the procedure of Example 1), 55 parts of sulfite cellulose liquor powder and 800 parts of water are ground in a ball mill until the size of the dye particles is below 1 μ .

The colloidal solution obtained is mixed with 25 parts of β-hydroxyethoxy-2-n-butoxyethane and 400 parts of 6% strength Carboxymethyl cellulose mixed. This printing paste is very suitable for Vigoureux printing on polyester sliver. The printing takes place with the help of two rollers (coverage 78%), whereupon steamed without intermediate drying at 120 ° will. Red prints with good fastness properties are obtained.

In the following tables, further dyes of the formula I are given which are analogous to the procedure of the Example 1 or 2 can be produced.

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Case 150-3766

Table 1

In the examples of this table, R, -CH CH.OH, R 'and R. _{denote hydrogen and R 5} denote -NHCOR,.

R 1 and R 1 mean in Examples 3 to 22, 24 to 6 /

and 41-48 -C ₂ H, in examples 23, 35, 49 and 50 nC H, in example 38 -CH, in example 36 nC H and in example 3 4 -CH ₂ -CH = CH ₂ ; in Examples 37 and 3 9

is R ,. -C _n H ₁ . and R_ -CH "C _r H _c , or -CH _o CH _o C _r H _c , in the case of -625 7 265 2265

Game 40 is R ₅ -CH ₂ -CH = CH ₂ and R ₇ -CH ₂ CgH ₅ . All dyes dye polyester fiber material in red shades with good fastness properties.

E.g.
No. ^R 2 ^R 3 ^R l0 3 Br H -CH ₃ . 4th Cl H ■ 5 Cl H -CH ₂ CH ₂ CH ₃ 6th Cl H H 7th Br H -CH ₂ OH 8th Cl H -CH ₂ OCH ₃ 9 Br H -CH ₂ OC ₂ H ₅ 10 Cl H -CH ₂ OC ₆ H ₅ 11 Cl Cl -CH ₂ OCH ₂ C ₆ H ₅ 12th Cl Cl -CH ₂ CH ₂ Cl 13th Cl Cl -CHClCH 14th Cl Cl -CH ₂ CH ₃ Br 15th Br Br -CF ₃ 16 Cl Cl -CHOHCH 17th Cl Cl -CH, 18th Cl Cl / —V
/ V "\\ /" »ti

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Case 150-3766

E.g.
No. ^R 2 ^R 3 ■ ^R io 19th Cl Cl -CH ₂ OCH ₂ CH ₂ CH ₃ 20th Br H —CH ₀ C H_
2 6 5 21 Cl H 22nd Cl Cl -CH CN 23 J H do. 24 Br Br -OCH ₃ 25th Br Br 26th Cl H -OCH CH Cl 27 Cl H -OCH ₂ CH ₂ OCH ₃ 28
29 Cl
Cl Cl
H -OCH ₂ CH ₂ OC ₂ H ₅
-0CH "CH _o 0CH _o CH _o 0CH_ 30th Cl H -OCH ₂ C ₆ H ₅ 31 Cl Cl -OCH ₂ CH (CH ₃ ) ₂ 32 Cl Cl -CH ₂ CH ₂ OH 33 Cl Cl -CH ₂ CHCl ₂ 34 Cl Cl ~ ^CH 3 35 Br H do. 36 Cl H do. 37 Cl H do. 38 Cl H 85/1 do. 39 Cl H do. 40 Cl H do. 41 Cl Cl -CH ₂ -CH = CH ₂ 42 Cl Cl -CH ₂ OC ₂ H ₅ 43 Cl Cl 44 Cl Cl -OCH ₂ -CH = CH ₂ 45 Cl H " ^C 6 ^H 5 46 Cl Cl -CH ^ OC ₆ H ₅ 47 Cl Cl -0- (Hj-C (CH ₃ ) ₃ 48 Cl Cl -0-CH ₂ - ^ 49 Cl Cl -CH ₃ 50 Cl H
6 0 9S -CH ₀ OCH ₀ CH-
154 2 2 3

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In the dyes of Examples 1 and 2 and in those of Table 1, R can also be -CH ₂ CHOHCH OH, -CH ₂ COCH,

-CH ₀ COC ^ H ₁ -, -CH ₀ CO- ^ o) -Br, -NHCH ₀ CH ₀ CH ₀ OH and Zoo Z > - ' Z δ δ

-N (CH ₂ CH ₂ OH).

All of these dyes are similar in shade and fastness properties to those in the table.

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Case 150-3766

Table 2

In the examples of this table, R- -NR R, R 'and R. are hydrogen, R and R are -C "H ^, R ₅ is

All dyes in which R is Cl or Br are red, the others bluish-red.

I.
E.g
No. • ^R 2 ^R 3 ^R 8 ^R 9 ^R io 51 Cl H -CH ₃ -CH ₂ CH ₂ OH -CH ₃ 52 Br Br " ^C 2 ^H 5 do. - ^C 2 ^H 5 53 Cl Cl do. do. -CH ₂ OCH ₃ 54 Br H -CH ₂ CH ₂ CN do. -OC ₂ H ₅ 55 -CN H - ^C 2 ^H 5 do. -OCH ₃ 56 do. Cl do. do. -CH ₂ CH ₂ Cl 57 do. Br do. do. -OCH ₂ C ₆ H ₅ 58 do. Cl -CH ₂ CH ₂ CN do. -CH ₃ 59 do. H " ^C 2 ^H 5 do. -CH OH 60 do. Cl do. do. -CH ₀ OC, !!,.
λ 6 5 61 do. Cl do. do. -OCH ₂ C ₆ H ₅ 62 do. Cl -CH ₂ CH ₂ CN do. " ^C 2 ^H 5 63 do. H -C ₂ H ₅ do. do. 64 do. Br do. do. -CH ₂ OC ₂ H ₅ 65 do. Cl -CH ₂ CH ₂ CN do. -C ₂ H ₅ 66 do. H - ^C 2 ^H 5 do. -CF ₃

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Table 3

In the examples in this table, R, -CH means CH OH.

i
E.g,
No. ^R 2 ^R 3 ^E 3 ^R 4 ^R 5 ^R 6 ^R 7 Nuance on
polyester S. do. 67 Cl H H H -CH ₃ -C ₂ H ₅ -C ₂ H ₅ orange do. 68 Br H H H -OCH ₃ do. do. do. do. 69 Cl H H H -Cl do. do. do. orange 70 Cl H H H -Br . do. do. do. do. 71 Cl H H H -CN do. do. do. reddish
yellow 72 Cl H Cl H -CH ₃ do. do. do. orange 73 Br H Br H do. do. do. do. 74 Br H Br -OCH ₃ -OCH ₃ - do. do. do. 75 Cl H Cl do. do. do. -CH -C ₆ H do. 76 Cl H Cl -CH ₃ do. do. do. do. 77 Cl Cl H -OCH ₃ do. do. do. scarlet 78 Cl Cl H Cl -CH ₃ do. ~ ^C 2 ^H 5 do. 79 Cl Cl H Br do. do. do. do. 80 Br Br H H do. -CH ₂ -CH = CH ₂ -CH-CH = CH do. 81 Cl Cl H H do. -C ₃ H ₇ ~ ^C 3 ^H 7 do. 82 Cl Cl H H do. " ^C 4 ^H 9 do. 83 Cl Cl H H do. do. -CH ₂ CH ₂ -C ₆ H 84 Cl Cl H H do. do. 85 Cl Cl H H do. -CH ₃ do. 86 Cl Cl H H -CN -C ₂ H ₅ " ^C 2 ^H 5 87 Cl H Cl H -NHCOCH do. do. 88 Cl H Cl H -Ϊ IHCOCIL CH_
ti * 3
0 do. do. 89 Cl H Cl H H do. do. 90 Cl II Cl H - NHSO ₂ CH ₃ do. do.

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Table 4

In the examples of this table, R 'means water

material,

and R_ -C-H.

All dyes give red shades of color to polyester fiber material.

E.g.
No. ^R i ^R 2 ^R 3 ^R 4 ^R io 91 "CH ₂ CH ₂ OH Cl H -OCH ₃ -CH ₃ 92 do. Br H ' -OC ₂ H ₅ " ^C 2 ^H 5 93 do. Cl Cl do. -OCH ₂ CH ₂ OCH ₃ 94 do. Cl Cl -OCH ₃ -OCH ₂ CH ₃ 95 -CH ₂ COCH ₃ Cl H do. -OCH ₂ CH ₂ OCH ₂ CH ₃ 96 do. Br H -OCH ₂ CH ₃ do. 97 -CH CH-CH -OH Cl H do. -CH ₃ 98 OH
do. Cl H do. -OCH ₃ 99 -NHCH CH OH Cl Cl do. do. 100 do. Cl Cl do. -CH ₃ 101 —XT f Γ * ΛΆ / " ¹ LJ ΠΐϊΛ
Vi \\ jil _r . \ Sxl. _r .yj £ lj _ Cl Cl do. do. 102
103
104 -N-CH CH OH
1 LL
CH ₂ CH ₃
-N (CH CHCH)
Z, OL
OH
-NHCH CH OH Cl
Cl
Cl Cl
Cl
Cl do.
do.
H do.
do.
do. 105 do. Cl Cl H ~ ^C 2 ^H 5 106 do. Cl Cl H 107 -CH ₂ COCH ₃ Cl H H -OCH ₂ CH (CH ₃ ) ₂ 108 do. Cl H H -OCH CH = CH 109 do. Cl Cl H -CHClCH

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Claims (1)

Claims R, one of wherein R _{n is} a group of the formula - -CH CHOHCH ₀ OH, -CH ₀ COCH ₀ , -CH ₀ COC H, / L £ Zt, pj Ζ, UJ -CH ₀ COC, .H. Br or -W, 2 6 4 Rg Halogen or cyan, R and R 'hydrogen, the other hydrogen or halogen, Hydrogen, chlorine, bromine, methyl, methoxy or ethoxy, chlorine, bromine, cyano or acylamino or, if R _{1 is} a group of the formula -CH ₀ CH ₀ OH, -CH CHOHCH OH, -CH COCH, -CH COC H or - CH ₂ COC ₆ H ₄ Br is also methyl, methoxy or ethoxy, C 1, -alkyl or C ", -alkenyl, C" - alkyl, C ₂ , -alkenyl or phenyl- -C ₁ _ ₂ -alkyl, _ c _o hydroxy---alkyl and Signify hydrogen, C _1-4 -A ^ yI, hydroxy-C _0. ~ - alkyl or cyano-C ₁ _ _o -alkyl. R R, 609885/1 154 Case 150-3766 2. Azo disperse dyes according to claim 1, the formula NSO N = N where R, one of and Chlorine, bromine, iodine or cyan, R and R 'hydrogen, the other water substance, chlorine or bromine, Hydrogen, chlorine, bromine, methyl, methoxy or ethoxy, Cyan or a group of the formula -NHR, C. -Alkyl or C -.- alkenyl, C. -Alkyl, C -.- alkenyl or phenyl- ~ ^C l-2 ~ ^{alkyl /} hydroxy-C ₂ __- alkyl, Hydrogen, C,.-Alkyl, hydroxy-C__ ~ - -alkyl or cyano-C, ~ -alkyl Χ - Δ C .__- alkyl-carbonyl, which can carry a substituent from the group hydroxy, chlorine, bromine or C-_ ₂ ~ alkoxy, C. -alkoxy-carbonyl, methoxyethoxycarbonyl, ethoxyethoxycarbonyl, vinylcarbonyl, allylcarbonyl, allyloxycarbonyl, methylvinylcarbonyl, benzoyl , Phenoxycarbonyl, trifluoroacetyl, formyl or methylsulfonyl mean. 609885/1 15A - 24 - Case 150-3766 Azo disperse dyes of the formula I according to Claim 1, where R, one of Chlorine, bromine or cyano,
R_ and R 'hydrogen, the other hydrogen, chlorine or bromine, a group of the formula -CH CH "OH, -CH ₂ COCH ₃ or -CH ₂ CHOHCH ₂ OH, hydrogen, chlorine, bromine, methyl, methoxy or ethoxy,
Chlorine, bromine, cyano, methyl, methoxy, ethoxy, formylamino, C. -Alkyl-carbonylamino, which have one or two substituents from the group of chlorine, bromine, hydroxy, cyano, C -alkoxy, benzyloxy, phenyl or phenoxy can, C. -alkoxy-carbonylamino, chloro- or bromine ~ -C -alkoxy-carbonylamino, C -alkoxy- -C -alkoxy-carbonylamino, methoxyethoxyethoxycarbonylamino, phenoxy- -C "_ ^ - alkoxy-carbonylamino-, benzoyloxycarbonylamino, benzoylamino , Toluylcarbonylamino, phenoxycarbonylamino, allyloxycarbonylamino, trifluoroacetylamino, para-tert-butylcyclohexyloxycarbonylamino, dioxanylmethoxycarbonyl, vinylcarbonylamino, allylcarbonylamino, methylvinylcarbonylamino or methylsulfonylamino,
C alkyl or C alkenyl, 609885/1 1 5 Λ Case 150-3766 and RC _1-4 -alkyl, C -alkenyl or phenyl- - _{Cl- 2} -alkyl
mean. 4. azo disperse dyestuff according to claim 3, where R, Means hydrogen and the rest Symbols have the meanings given there. Azo disperse dyestuff according to claim 1, the formula R ₁ -SO ₂ exnes from 11 N = N NHR wherein R is a group of the formula -CH CH ₃ OH, -CH ₂ COCH or -CH ₂₂ , chlorine, bromine or cyan,
R and R 'is hydrogen, the other is hydrogen, chlorine or bromine, or C ₂ _ ₄ alkenyl, C ~ _.- alkenyl or phenyl- -C, "-alkyl and C _n _ -alkyl-carbonyl, which can carry a substituent from the group consisting of hydroxy, chlorine, bromine or C _{1 o} -alkoxy, C ₁ "-A1-koxycarbonyl, methoxyethoxycarbonyl, ethoxyethoxycarbonyl, vinylcarbonyl, allylcarbonyl, allyloxycarbonyl, methylvinylcarbonyl, Benzoyl, phenoxycarbonyl, trifluoroacetyl, formyl or methylsulfonyl mean. 609885/1154 - 26 - Case 150-3766 6. Azo disperse dyes according to claim 1, the formula ^R 2 wherein R is a group of the formula -CH ₃ CH OH or -CH ₂ COCH, R "chlorine or bromine,
R_ hydrogen, chlorine or bromine and R, methyl, ethyl, chloromethyl, bromomethyl, chloroethyl, bromoethyl, methoxymethyl, Ethoxymethyl, methoxyethyl, ethoxyethyl, Vinyl, allyl, methylvinyl, methoxy, ethoxy, methoxyethoxy, ethoxyethoxy or allyloxy. 7. Azo disperse dyestuff according to claim 1, of the formula ^{N =} wherein R "is chlorine or bromine and R, methyl, ethyl, methoxymethyl or ethoxymethyl. 609885/1 - 27 - Case 150-3766 8. Process for the preparation of the disperse dyes of formula I according to claim 1, characterized in that the diazonium compound from an amine of the formula II ? 2 R ₁ -SO ₂ - (OV-NI ^ (ID with a compound of Formula III '' (in) clutch. 9. Use of the compounds of the formula I according to claim 1 for dyeing or printing fibers or threads or materials made therefrom made of fully or semi-synthetic, hydrophobic, high molecular weight organic matter. 10. Process for dyeing or printing fibers or threads or materials made therefrom from fully or semi-synthetic, hydrophobic, high molecular weight organic substances, characterized in that azo disperse dyes of the formula I according to claim I are used. 11. The materials dyed or printed according to claim 10. « _{N ft Λ} . _ SANDOZ-PATENT-GMBH 609885/1154 I * 3700 / HW / HSc _#