DE1444715C - - Google Patents

Description

The invention relates to a process for the preparation of basic dyes of the formula

CH ₃

y -N-CH ₃
NH ₂ '

m®

-Y Z)"

H ₃ C

N® -NH ₂

(III)

introduces or converts Z into such, where B for A or the remainder of a for the formation of a dye A is a capable compound and Z is a substituent which is represented by a group of the formula (III) can be replaced or converted into such, means and, if B stands for the remainder, for formation of a dye is a compound capable of converting the reaction product into a dye of the formula (I) convicted.

A special process for the production of the new basic dyes is characterized by that one mole of a compound of the formula

B-ey-E) "(IV)

wherein E is the acid residue of an ester and n, y and B are as defined above, with η mol of a compound of the formula

N-NH,

H ₃ C

and when B denotes the residue of a compound capable of forming a dye, that obtained Reaction product converted into the dye of the formula (I).

But you can also use a compound of the formula

-y-N-CH ₃
NH ₂

(VI)

wherein n, y and B are as defined above, quaternize with methyl group donating agents, and if B denotes the remainder of a compound capable of forming a dye, the reaction product convert into the dye of the formula (I).

The new basic dyes of the formula (I) can also be obtained by using a compound the formula '.

Β

' yNH
NH,

(VII)

where A is the radical of a dye free of carboxylic acid and sulfonic acid groups, y is an optionally substituted methylene group or a divalent radical bonded to the adjacent N via one of these, η is the number 1 or 2, m is the number 1 or 2 when η is 1 , and 2, when η is 2, and X is each an anion equivalent to a dye cation, which is characterized in that a compound of the formula

wherein n, y and B are as defined above, quaternized with methyl group donating agents and, if B is the radical of a compound capable of forming a dye, the reaction product is converted into the dye of the formula (I), or if 1 mol of an amine is used the formula

with a compound which, in place of Z, the remainder III

H, C \

B-y-N

R,

R,

(VIII)

where R _{1 is} hydrogen or the methyl group and R _{2 is} hydrogen or the methyl group, and n, y and B are as defined above, with η mol of a halogenamine, when R ₁ and / or R _{2 are} hydrogen, donating the reaction product with methyl groups Agents quaternized and, if B denotes the remainder of a compound capable of forming a dye, the reaction product is converted into the dye of the formula I, it being possible for quaternization and conversion to a dye to be carried out in any order.

For example, such residues are used as dye residues

the nitro, styryl, methine and polymethine, anthraquinone, quinophthalone, azomethine, or in particular the azo dye series into consideration. It is also possible to use such azo dye residues which contain coordinated metal atoms. The azo dye residues mainly include where appropriate substituted mono- or disazo dyes. Components B, which are used to build up the dye residue A appear suitable are preferably those which are obtained by reacting with a diazonium salt or a couplable compound can be converted into the above-mentioned azo dye residues.

The azo coupling is carried out in a known manner, advantageously in a weakly alkaline to acidic, optionally buffered, medium.
In addition, compounds are also suitable as components B which contain a functional group or one which can be converted into one by reacting these with a component used to build up the dye radical A to give the final dye of the formula (I).

Suitable methylating agents to convert compounds of the formulas (VI), (VII) and, if necessary, (VIII) into the color salts which can be prepared according to the process are to be transferred, for. B. Esters of strong mineral acids and organic Sulphonic acids, such as methyl chloride, methyl bromide and methyl iodide or dimethyl sulphate, methyl esters of low molecular weight Alkanesulfonic acids or benzenesulfonic acid. The alkylation or quaternization preferably takes place in an inert solvent

or optionally in aqueous suspension or without a solvent in an excess of the alkylating agent and at elevated temperature and in an optionally buffered medium.

Anion X is to be understood as meaning both organic and inorganic ions, such as, for. B. methyl sulfate, Sulphate, disulphate, perchlorate, chloride, bromide, iodide, phosphorus molybdate, phosphotungsten molybdate, Benzenesulfonate or 4-chlorobenzosulfonate ions.

An optionally substituted methylene group or a divalent radical bonded to the adjacent N via one of these, for example - (CH ₂ ) _p -, where ρ is the number 1 to 6, are preferably suitable as bridge member y

-CH ₂ -CH-CH ₃ .
-NH-CO-CH ₂ -
-NH-CO-C ₂ H ₄ -
-0-C ₃ H ₆
-CO-C ₂ H ₄ -
-CO-NH-C ₃ H _n -
-CO-NH-C ₂ H ₄ -
-CO-OC ₂ H ₄ - 'SO ₂ - ■ C ₂ H ₄

Alkyl ^;

CiHU

-0-C ₂ H ₄ -

Alkyl

Alkyl

-N-CH ₂ -

NH — Arylalkyl — NH-CH ₂ -CO-CH ₂ -

-NH-CH ₂ -CHOH-CH ₂ -

-NH-

-NH

CH ₂ - NH - CO - CH - CH ₃

NH-CO —CH, -

-SO ₂ -NH-C ₃ H ₆ -

-NH-CO-CH ₂ -OC ₂ H ₄ -
-NH-CO-CH ₂ -SC ₂ H ₄ -
-NH-CO-CH-CH-CH ₂ -
-CH ₂ -CHOH-CH ₂ -

- CO - NH - <^ ~ y

CH ₂ -

-C ₂ H ₄ -O-CO-CH ₂ -

V-Fl ₂ ν-ΓΙν / Γΐ V-Ii ₂

ETC. .

Examples of acid radicals E are those of sulfuric acid (E = SO ₄ H), a sulfonic acid (E = SO ₃ R, where R is an optionally substituted hydrocarbon radical of hydrogen sulfide (E = SH), but preferably those of hydrohalic acids (E = CI, Br etc.) into consideration.

The reaction of a compound of formula (IV) with a hydrazine of formula (V) is preferably carried out in an organic solvent and at temperatures of -50 to + 250 ⁰ C. The reaction may however also in an aqueous medium, optionally with the addition of an organic Solvent, or carry out completely without a solvent at the temperatures mentioned above.

Reacting an amine of formula (VIII) with a halogen amine is preferably carried out in an organic solvent and at temperatures of -50 to + 8O ⁰ C. Mankann the reaction but also in an aqueous medium, optionally with the addition of an organic solvent at the abovementioned temperatures to perform wherein the haloamine can be used either in gaseous form or in an organic solvent or in water or in mixtures thereof.

The dyes formed are separated off

after one of the usual basic operations, such as filtration, evaporation and filtration, precipitation in a suitable medium and filtration.

The new dyes are preferably used for dyeing, padding and printing of structures from polymers with more than 80% acrylonitrile, for example polyacrylonitrile, and copolymers 80 to 90% acrylonitrile and 20 to 10% vinyl acetate, methyl acrylate or methyl methacrylate

The dyeings have good light, washing, perspiration, sublimation, pleating, Decatur, ironing, water, sea water, bleach, dry cleaning, over-dyeing and solvent

60. authenticity. .

Compared to the closest comparable dyes known from British patent specification 807 241 the dyes obtainable according to the invention are distinguished by a significantly better migration.

The dyeing with the claimed dyes is advantageously carried out in an aqueous medium, whereby it is advisable to work in a neutral or acidic medium at boiling temperature.

i 444 715

The use of commercially available retarders is not a problem, although the new dyes are particularly suitable for achieving very level colorations on the abovementioned polymers even without a retarder. The dyeing can of course also be carried out in a closed vessel at elevated temperature and under pressure, since the new dyes are extremely resistant to overcooking. With the dyes according to the definition, mixed fabrics which contain a proportion of polyacrylonitrile fibers can also be dyed very well. Some of them are also suitable for dyeing polyacrylonitrile in bulk in lightfast and wetfast shades. Some of those derivatives which have good solubility in organic solvents are also suitable for coloring oils, paints, plastic compounds, plastics and for spinning plastic compounds dissolved in organic solvents. Furthermore, some of the new basic dyes can be used for many other purposes, such. B. for dyeing tannin cotton, wool, silk, regenerated cellulose, synthetic polyamide fibers and paper in every manufacturing stage. It has been shown that mixtures are also advantageous _; can use from two or more dyes of the formula (I).

The new dyes are characterized by good combinability, so that dye salts of the same or different dye classes can be used for a wide variety of nuance adjustments.

The azo dyes which can be prepared according to the invention! .. can, for example, be of the benzene-azo-benzene range, the benzene-azo-naphthalene series, the benzene-azo-pyrazolone series, the benzene-azo-acylacetic acid-arylamide series, the benzene-azo-phenol series, the benzene-azobenzene-azo-phenol series, the thiazole-azo-benzene series, the thia-diazole-azo-pyrazolone series, the pyridine-azoindole series, - belong to the quinoline-azo-benzene series, etc. You can either by coupling with diazotized amines by known methods Azo components or by oxidative coupling. The hydrazinium group can via an optionally substituted methylene group or via one to the adjacent N bonded divalent radical, optionally in addition to other cationic groups, to the diazo and / or be connected to the azo component.

For the production of the invention for. Azo dyes used are diazo compounds the benzene, naphthalene and heterocyclic series are suitable. As a substituent in these Compounds are preferably those which are in the known acetate silk and Polyester dyes are used. Particularly suitable are: Halogen such as chlorine. Bromine, fluorine; Nitrile, nitro, alkyl, trihaloalkyl, alkylsulfonyl, Sulfonamide, monoalkyl and dialkylsulfonamide, carbalkoxy, carboxamides, hydroxyl, Alkoxy, carbalkoxy groups, etc.

Suitable coupling components are derivatives of the benzene, naphthalene and heterocyclic compounds Row. Those substituted by optionally substituted alkyl groups are particularly suitable Aminobenzenecrivate and by in the aromatic nucleus, z. B. by optionally substituted alkyl, Alkoxy, halogen, cyano, trifluoromethyl, alkanoylamino, Alkylsulfonylamino inter alia. substituted descendants. The term alkyl radical does not have valid only for hydrocarbon residues such as methyl, ethyl, propyl and butyl etc., but also for their substitution products (cf. also scientific treatise on "Anthracene and Anthraquinone" by

E. der Barry, Barnett, London 1921, p. 24) 7). As substituents or substitution products are to mention: halogen, hydroxyl, such as in chlorine .propyKHydroxyäthyKDihydroxypropylradika ^ also Ethers and esters, such as methoxyethyl, acetoxyalkyl radicals, the esters of carboxylic and sulfonic acids, such as in the carbalkoxyalkyl radical, the nitrile group, e.g. B. in the cyanoethyl radical.

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

Example l · ■

18.4 parts of N-ethyl-N-ß-chloroethyl-aminobenzene are dissolved in 100 parts of methanol and the solution after the addition of 7.2 parts of 1,1-dimethylhydrazine Heated to boiling under reflux for 24 hours. The solvent is then evaporated off and washed the powdered residue with a little benzene. The dried product is dissolved in 400 parts of water and with a hydrochloric acid prepared in the usual way from 16 parts of 1-amino ^ -chloro ^ -nitro-benzene Diazonium salt solution coupled. If necessary, something is used to precipitate the dye Sodium chloride, filtered, washed with 1% sodium chloride solution and dried. It results in a dark brown-red powder with a melting point of 220 to 221 °; the dye purified by recrystallization melts at 234 to 236 °.

Dyeing example A

20 parts of the dye obtained according to Example 1 are initially mixed with 80 parts of dextrin. in a Ball mill thoroughly mixed for 48 hours.

Then it will be. 1 part of the preparation obtained in this way made into a paste with 1 part acetic acid 40%. the pulp with constant shaking with 400 parts distilled Pour over 60 ° water and briefly boil the whole thing. It is diluted again with 7600 parts distilled water, adds 2 parts of glacial acetic acid and goes into the at 60 ° with 100 parts of polyacrylonitrile fibers Dye bath. The material was soaked in a bath of 8,000 parts of water at 60 ° for 10 to 15 minutes and 2 parts of glacial acetic acid pretreated. It is now heated to 100 "within 30 minutes For 1 hour and rinse. A level red dyeing of excellent lightfastness and very good is obtained good wet fastness properties.

a) Example of padding

50 g / l of dye are used to produce the padding paste

(corresponding to the dye preparation prepared in the previous dyeing example),
3 g / l sodium alginate,
5 g / l acetic acid concentrated,

20 g / l of a cationic plasticizer z. B. a condensation product of 1 mole of stearic acid and 1 mole of triethanolamine.
25 g / l Glauber's salt.

Polyacrylonitrile fibers are padded cold on a 2- or 3-roll pad using conventional methods. The squeezing effect is 80%. After a short intermediate drying at 90 in the stenter, hot flue or with the help of an infrared heater in the nozzle clamping frame at 170 to 190 ° for Ί to 3 minutes Fixed with dry air, then rinsed, soaped and rinsed again. You get a red coloration with excellent lightfastness properties.

b) Printing dye example:

A printing paste is made up of
75 parts of dye

(corresponding to the dye preparation prepared in the above dyeing example), 10 parts of acetic acid concentrated,
450 parts sodium alginate thickener,
25 parts of a cationic plasticizer, e.g. B. a condensation product of 1 mole of stearic acid and 1 mole of triethanolamine.
25 parts of Glauber's salt
415 parts of water.
1000 parts

Polyacrylonitrile fibers are printed using the customary hand printing process, followed by the fiber material air-dried in a star steamer with saturated steam for 20 to 30 minutes steamed, then rinsed, soaped and rinsed again. The result is a red print with very good fastness properties receive.

Example 2

37.5 parts of the dye 2-chloro-4-nitro-4 '- (N-äthy! -N-dimethylaminöäthyl) -amino-l, r-azobenzene are dissolved in 900 parts of chlorobenzene at room temperature. To this solution one leaves im Pass 7.1 parts of freshly made gaseous chloramine at 30 for one hour with vigorous stirring initiate. The color salt formed precipitates and can be isolated from the chlorobenzene by filtration will.

After drying, a dry one is obtained. Powder, the "Orion" (registered trademark) in dyes level red shades with good light and wet fastness properties. .

The preparation of chloramine takes place in each case according to the usual methods described in the literature Methods, (compare e.g. G. H. Co I em an, Inorganic Syntheses I [1939]. P. 59; H. H. S i s 1 c r and Omictamski, Inorganic Syntheses, Vol. V, P. 92; Gmelins Handbuch der Inorganic Chemistry, 8th edition [1926]. P. 418).

An ethereal chlorine solution can be used instead of gaseous chloramine. Representation, for example, according to Inorganic Syntheses L for this according to the invention Procedures are used.

In the latter I all are used to produce colors 37.5 parts of the dye 2-chloro-4-nilro-4 '- (N-ether-N-dimethylaminoethyl / amino-U'-azobenzene dissolved in 1500 parts of chlorobenzene at room temperature. This solution is allowed to die over the course of one hour with vigorous stirring at 25 ° to 30 ° Ether solution containing about 7 parts of chloramine flow in. The color salt precipitates and can be filtered off will.

Example3

19.7 parts of the in the usual way. Diazo solution prepared from 1-amino ^ -cyan ^ -nitro-o-chloro-benzene be · with an aqueous solution containing 23.0 parts of the compound of formula

CH ₃

ν ⁷ 9 ^H * er

CH ₂ -CH ₂ -Im-CH ₃

NH,

contains, coupled at 0 to 5 ° with the addition of ice. The coupling is ended with the addition of sodium acetate in portions. The obtained, water-soluble Monoazo dye is precipitated from the aqueous solution by adding sodium chloride, filtered and washed with a dilute sodium chloride solution. After drying, one obtains a dark powder, the polyacrylonitrile fibers in level bluish red tones with good light and good Dyes wet fastness.

Dyeing example B

20 parts of the dye obtained according to Example 2 are first mixed with 80 parts of dextrin in a ball mill intimately wed for 48 hours.

Then 1 part of the preparation obtained in this way is made into a paste with 1 part of 40% acetic acid, the porridge under Constant shaking with 400 parts of distilled water of 60 "pour over it and the whole thing briefly boiled. It is diluted again with 7600 parts of distilled water, 2 parts of glacial acetic acid are added and goes into the dyebath at 60 "with .100 parts of acrylonitrile fibers. The material was 10 to 15 minutes long pretreated at 60 ° in a bath of 8000 parts of water and 2 parts of glacial acetic acid. One warms up now to 100 within 30 minutes, boil for 1 hour and rinse.

Dyeing Example C

The coloration of the - obtained according to Example 3 Dye can after grinding the dye with dextrin or Glauber's salt or with a other organic or inorganic coupage. as indicated under dyeing example B carried out will. Instead of 2 parts of glacial acetic acid, either a mixture of 5 parts can be added to the dye bath Glauber's salt. 3 parts of sodium acetate and 2 parts of acetic acid or 2 parts of concentrated sulfuric acid to add.

Example 4

10

The cold diazonium salt solution is pre-

2-chloro-4-nitrobenzene prepared hydrochloric acid diazo placed and 34 parts of a with vigorous stirring

nium salt solution is at 0 ° with sodium acetate on 5 compound of the formula
set a pH value of 5 to 6. After a clear

NH ₂

'^ C ₂ H ₄ -N- (CH ₃ J ₂ N
^ C ₂ H ₄ -N- (CH ₃ ),

NH ₂

2Cl '

dissolved in 290 parts of water, added. The dye 20 saline and dries. The result is the color fall immediately off. It is filtered and washed with dilute salt of the formula

Cl

O ₂ N

N = N

NH ₂ C ₂ H ₄ -N- (CH ₃ ),

C ₂ H ₄ -N- (CH ₃ J ₂ NH ₂

2Cl

The dye melts at 248 ° and stains polyacrylic 4 n sodium nitrite solution within 30 minutes

nitrile fibers in even, deeply colored, orange tones. The diazonium salt solution becomes almost quantitative at 0 °

The colorations have very good light, wet, thermo-formed,
fastness to fixation and smoke gas. By adding 21 parts of a compound of

Formula for the coupling component listed above
obtained by reacting 1 mol of di (dimethylaminoethyl) aniline of the formula

X ₂ H ₄ -N (CH ₃ J ₂

CH ₃

C ₂ H ₄ -N (CH ₃ ) ₂

CH ₃ C ₂ H ₄ -N-NH ₂

C ₂ H ₅

with 2 moles of chloramine. The salt melts at 215 °

with decomposition. '

dissolved in 100 parts of glacial acetic acid at 0 ″, the desired dye formation begins immediately 55 accelerated in its process when adjusted to a weakly acidic pH value with sodium acetate will. After the coupling has ended, it is filtered, 17.25 parts of 1-amino - ^ - chloro-nitrobenzene are rinsed, are free of salt with water and dried.

in finely divided form in 100 parts of 15% hydrochloric acid. The resulting dye, which is sparingly soluble in water

at 0 ". By adding 27 parts of a 6o of the formula

Example 5

Cl

CH ₁

/ CH,

O ₂ N

N = N

/ C ₂ H ₄ -N

on the one hand can be used directly for dyeing polyacrylonitrile can be used by applying from an acidic, preferably mineral acidic, dye bath.

The resulting colorations do not matter, they draw are characterized by good fastness properties.

The azo compound used to prepare the dye just described can be prepared by a method known per se, e.g. B. by reacting N- ^ chloroethyl-N-ethylmetatoluidine with an excess of monomethylhydrazine at about 100 ^c , the reaction product is then separated off and, if necessary, distilled in a high vacuum.

B e i s ρ i e 1

42.05 parts of the dye-man described in Example 5. stirred for a further 2 hours at 80 to 90, leaves

substance are cooled in 1000 parts of chlorobenzene at 80, filtered off and dried. You get

solved. While stirring, 19 parts of dimethyl- the desired color salt are left as a dark red powder. the

sulfate, dissolved in 19 parts of chlorobenzene, are added dropwise. 15 compound of formula

Cl

CH ₁

O ₁ N

C ₂ H ₄ -N- (CH ₃ ),

-N = N-

NH,

, Η,

CH ₃ OSO ₃

colors polyacrylonitrile in dark red tones.

B e i s ρ i e 1

The same dye as described in Example 6, but consisting of an anion mixture of Cl and CHj OSO ₃ , is obtained when primarily 20.7 parts of the intermediate product

CH ₃

/ C ₂ H ₄ -N-NH ₂

in chlorobenzene with 19 parts of dimethyl sulfate into the hydrazinium salt of the formula

CH ₃

CH ₃

, C ₂ H ₄ -N-NH ₂
CH ₃

CH ₃ OSO ₃

are transferred and then prepared with a from 17.25 parts of l-amino-2-chloro-4-nitrobenzene hydrochloric acid diazonium salt solution are combined and the color salt is isolated by known methods.

The pure chloride can be produced with the help of an anion exchanger. The dye of the formula

Cl

O ₁ N- <

N = N -ί

C ₂ H ₊ N- (CH ₃ ),

NH ₂
C ₁ H

I ¹¹ p

Cl

melts at 218 to 219.

example

To 105 parts of sulfuric acid (96%) are pulverized 8 parts in a temperature range of 60 to 70, anhydrous sodium nitrite entered. After complete dissolution, the one formed is cooled Nitrosylsulfuric acid to 15 to 20, allows 100 parts of glacial acetic acid to flow in at 20, followed by sprinkling in 16.3 parts of 2-amino-5-nitrobenzonitrile and a further 100 parts of glacial acetic acid.

The mixture is stirred at 15 for 2 to 3 hours, destroys the excess nitrite by adding 5 parts of urea and then loads to 350 parts Water out. The diazonium salt solution of 0 becomes

'S then filtered and treated with 24.4 parts of a compound of the formula

NH,

-N

C ₂ H ₄ -N- (CH,),

C ₂ H ₅

Cl

dissolved in 200 parts of water, added.

The clutch starts slowly; one turns off. so that immediately filtered, rinsed and dried who-adding ammonia to a pH of 5.5. can. The color salt of the formula At this pH value, the clutch is currently running 20

CN

O, N

-N -C ₂ H ₄ -N- (CH ₃ ),
NH,

Cl

With a melting point of 1% to 199, polyacrylonitrile fibers dyes ruby red tones.

In the example mentioned, the diazo compound 2-amino-5-nitrobenzonilril is replaced by 26.2 parts of 2,4-dinitro-6-bromaniline replaced, the result is a corresponding color salt that melts at 180 to 189 and polyacrylonitrile fibers and dyes modified polyester fibers by acidic groups in red-brown tones.

The dye, made from the diazo compound 2-bromo-4-nitroaniline, melts at 226-228. ϊλ dyes polyacrylonitrile fibers a strong red.

If, instead of 2-bromo-4-nitroaniline, the diazo compound is 2-MethyIsulfonyl-4-nitroaniline, this is how the ruby-colored dye of the formula results

O, N

SO ₂ CH ₃

V-N = N-

V ''

CH ₃

C ₂ H ₄ -N-CH ₃
NH,

Cl

with a melting point of 229 to 230.

Other valuable basic monoazo dyes, which are prepared according to the information in the examples given above are described in Table A below:

They correspond to the formula '

Anion

Possible anions are those listed in the description.

example R ₅ 4-nitrophenyl V X * H Y Z CH ₃ (CH ₃ ), /
—N CH ₂ -CH ₂ -N-NH, —N CH ₂ -CH ₂ -N-NH, C ₂ H ₅ Nuance of
Coloring on
Polyacrylonitrile C ₄ H ₉ (CH ₃ K. C ₂ H ₄ -CN
/ "» H H ■ H H -N (CH ₃ ^ ₂ CH ₂ -CH-N-NH ₂
I. orange 4-nitro-2-bromophenyl- H- \
CH ₂ -CH ₂ -N-NH ₂ (CH ₃ ), C ₂ H ₄ -OH
-N (CH ₃ ),
CH ₂ -CH ₂ -N-NH ₂ -N (CH ₃ ), IO H H H H C ₂ H ₄ -O-CO-CH ₃
—N ■. \ I. .
CH ₂ -CH ₂ -N-NH ₂ Red 4-nitro-2-bromophenyl- CH ₂ -CH ₂ -N-NH ₂ the same H (CH ₃ ), Il H H H H Scarlet fever the same - H 12th H H H Red the same -OC ₂ H ₅ 13th H H H Red 4-chloro-2-nitrophenyl- 14th H H H orange 4-nitro-2-cyanophenyl- 15th 2,4-dinitrophenyl H -CH ₃ H ruby 16 H -CH ₃ H Red-violet

■ "\ v. 1 V 2-chlorophenyl H continuation X Y. Z R. H Nuance of
Coloring on
Polyacrylonitrile violet example -N (CH ₃ ),
C ₂ H ₄ -N-NH ₂ Yellow-brown Z4-Dinitrophenyl- H H -CH = CH-CH = CH- C ₂ H ₄ -O-CO-CH ₂ -N-NH,
-N (CH ₃ I ₂
C ₂ H ₅ blue 17th C ₂ H ₅
-N (CH ₃ ),
CH ₂ -CH ₂ -N-NH, ruby the same Scarlet fever 2,4-dinitro-6-chlorophenyl H H H H C ₂ H ₅
-N (CH ₃ ),
CH ₂ -CH ₂ -N-NH ₂ Yellow-brown orange 18th the same 2,4-dinitro-6-cyanophenyl- H H -CH ₃ H the same Red-violet Scarlet fever 19th C ₂ H ₅
-N (CH ₃ J ₂ ,
C ₂ H ₄ -OC ₂ H ₄ -N-NH ₂ - 4-nitro-2-cyano-6-chlorophenyl- H H H H C ₂ H ₅
-N ^ (CH ₃ J ₂ orange 20th ü ^ -pinitro-o-bromophenyl- H • H H H CH ₂ -CHOH-CH ₂ -N-NH ₂ 21 C ₂ H ₅
-N (CH ₃ ),
CH ₂ -CH ₂ -N-NH ₂ Yellow orange 4-nitro-2-methylsulfonphenyl- .H iH -CH ₃ H ■ the same 22nd 2,4-dimethylsulfonphenyl :H H -CH ₃ H 23 4-sulfonamide-2-chloφhenyl- -H <H H H 24 4-monomethylsulfonamide-2-chlorophenyl- H H H H 25th 4-nitro-2-dimethylsulfonamidophenyl- H Ή. -Cl V
H 26 · H -CF ₃ H 27

. ■ ι • - - -, .. V: continuation X Y Z R. C ₂ H ₅ Nuance of
Coloring on
Polyacrylonitrile example -N (CH ₃ I ₂
CH ₂ -CH ₂ -N-NH ₂ 2-cyanophenyl- ■ ι iH H ^ -NH-CO-CH ₃ H the same Reddish
orange 28 2,5-dicyanophenyl -OC ₂ H ₅ -NH-CO-C ₂ H ₅ H also · Red 29 2-cyano-5-chlorophenyl-I .H -OC ₂ H ₅ -NH-CO-CH ₃ H the same ^:. Red 30th 4-chloro-2-trifluoromethyl phenyl-. i ;H -OCH ₃ -NH-CO-CH ₃ H ^ ₂ H ₅ Red 31 —N
\
. QH ₅ 4-Niιro-2-methylphenyl- _; iH H -0-C ₂ H ₄ -N- (CH ₃ J ₂ H the same Red 32 NH ₂ 4-nitro-2-methoxyphenyl-. ; • :H H -QC ₃ H ₆ -N-NH ₂ H the same orange 33 ; (CH ₃ J _{2 /} QH _S
—N NH ₂ 2-methoxyphenyl- ". 'I H H -CO-C ₂ H ₄ -N-NH ₂ H C ₂ H ₄ -N- (CH ₃ J ₂ Yellow orange 34 4-nitro-2-bromophenyl- H H (CH ₃ J ₂
CH ₃ H QH ₅
—N
\
QH ₅ Red 35 C ₃ H, 3-nitrophenyl H H -C ₂ H ₄ -N-NH ₂ H —N
\
C ₃ H, Yellow 36 (CH ₃ J ₂ ^s 4-cyano-2-ethoxyphenyl- .H H -NH-CO-C ₂ H ₄ -N-NH ₂ H orange 37 (CH ₃ J ₂ ■

R ₅ V continuation X Y H Z- R. -N (CHj) ₂ Nuance of
Coloring on
Polyacrylonitrile Example I. 4-cyano-2-iithylmucuptophenyl H H -Cl H C ₃ H ₄ -N-NHj orange 38 H the same 4-hydroxy-2-ethoxyphynyl- H H -Cl H H - N NH,
CH ₂ -CHOH-CH ₂ - N- (CHj), Rotstichiu-
yellow .M 4-chloromethylsulfone-2-bromophenyl- H H H H the same Reddish
yellow 40 4-carbomethoxyphenyl- H H Br H C ₂ H ₄ -CN Rotstichiü-
yellow 41 H —N
\
C ₂ H ₄ -OH 4-carbomethoxy-2-chlorophenyl- H H -NH-CO-CH ₂ -N-NH ₂
(CH ₃ ), H the same Reddish
yellow 42 Phenyl H -OC ₂ H ₅ the same H C ₂ H ₅
-N (CHj) ₂
C ₂ H ₄ -N-NH ₂ orange 43 4-nitro-2,6-dichlorophenyl- H H H the same Yellow-brown 44 the same 4-benzoylaminophenyl- H H H the same Yellow . 45 4-acetylaminophenyl H H H CH.
-N (CHj) ₂
C ₂ H ₄ -N-NH, - yellow 46 4-dimethylamihosulfaminophenyl- H H H yellow 47 4-methylsulfonyl-2-chlorophenyl- H H H orange 48

- 52 ^ '! "■■■■■■■ - R ₃ - ■■ V continuation X H Y Z R. _{/ C} Hj Nuance of
Coloring on
Polyacrylonitrile example i
(CHj) ₂ -N (CHj) ₂ 53 4-nitrophenyl H H H -C = CH-CH = CH- -NH-C ₂ H ₄ -N-NH ₂ C ₂ H ₄ -N-NH ₂ violet 49 OH the same 54 also · - OH - CO —NH- < ^/ ~ ^Λ > H -CH = CH-CH = CH- H C ₂ H ₅ Red-violet 50 55 H ₂ NN-CH ₂ -N (CHj) ₂ 56 (CHj) ₂ H CH ₂ -CH ₂ -N-NH ₂ 57 H the same 6-nitrobenzothiazolyl-2- H H -Cl H the same violet 51 58 H the same 6-methylsulfonylbenzothiazolyl-2- H -Cl H the same . violet H C ₂ H ₄ -O-CO-CH ₃
—N
\
C ₂ H ₄ -O-CO-CH ₃ 5-nitrothiadiazolyl-2- H H H blue 4-phenylthiadiazolyl-2- -CHj H H Reddish
blue 5-nitrothiazolyl-2- -CH ₃ H H blue 5-nitro-4-methylthiazolyl-2- -CH ₃ H H blue 3-nitro-5-acetylthienyl-2- -CH ₃ H ^ H blue 5-cyanthiazolyl-2- H -NH-CO-C ₂ H ₄ -N-NH ₂
(CHj) ₂ H Reddish
blue

example 1,2,4-triazolyl-3- V • X ^r Y Z R. C ₂ H ₅ (CH ₃ ): /
—N
\ J-NH ₂ Nuance of
Coloring on
^ olyacrylnitri: —N (CH ₃ ): C ₂ H ₄ -T 59 S-methyl-U ^ -triazolyl-S- H H H H CH ₂ -CH ₂ -N-NH ₂ C ₂ H ₄ -N-NH ₂ Red 4-methylpyridyl-2- the same (CH ₃ ), 60 BenzimidazoJyI-2- H H H H the same C ₂ H ₅
—N NH ₂ Red 6t Benzoxazolyl-2- H H ■ —CN H the same C ₂ H ₄ -N- (CH ₃ ): Red-violet 62 l, 3.5-triazolyl-2- H -OCH ₃ , OCH ₃ H the same Red 63 Tetrazolyl-5- H -OCH ₃ OCH ₃ H ti
the same Red 64 Diphenyl-4- H H H H the same Red 65 H -OCH ₃ -CH ₃ ΓΤ C ₂ H ₄ NH ₂
-N N-CH ₂ -CH ₂ -N (CH ₃ ):
\ / Red 66 Dipheny! Amine-4- H H H H C ₂ H ₄ yellow 4-methoxy-l, l'-diphenylamine-4- the same 67 H H H H the same yellow 68 H H H H yellow 4-nitrophenyl 69 H H H H Orange ' 4-sulfonamidophenyl 70 H H H' V
H yellow

'.R ₅ 4-nitro-2-cyanophenyl ■ V -*·· Continuation Y the same - the same Z ■. . R. - N CH ₂ -CH ₂ -O-CO-CH ₃ . — N C ₂ H ₄ -OH C ₂ H ₄ -CN /
—N
\ C ₂ H ₅ /
- N C ₂ H ₅ Nuance of
Coloring on
Polyacrylonitrile example ■. -χ (CH ₃ ), CH ₂ -CH ₂ -CN
/ C ₂ H ₄ -CN
/ C ₂ H ₅ C ₂ H ₅ • (CH ₃ ), ... I.
C ₂ H ₄ -N-NH,
/ —N
\
CH ₂ -CH ₂ -O-CO-CH ₃ —N
\ H ■ '.' "" 'H ■ -C ₂ H ₄ -N-NH, -QC ₃ H ₆ -N-NH ₂ H —N ■. C ₂ H ₄ -OH Red 71 the same H (CH ₃ ), C ₂ H ₄ -N-NH ₂ (CH ₃ ), the same CH ₂ -CH ₂ -O-CO-CH ₃
/ ■ the same H -NH-CO-C ₂ H ₄ -N- (CH ₃ ), H Blue red H NH, the same H H Blue red 73 H 4-sulfonamidophenyl H H Red 74 H the same H H Yellow orange 75 H the same H H orange 76 H H H orange 77 H

29

Support of the hydrazine moiety does not necessarily need one, as is shown in the above examples To be coupling components of the benzene or naphthalene series, but also heterocyclic coupling components, such as B. in the following dyes of the formulas

Example 78 ',

NO,

N = N-CH-CCH ₃

O = C N

NH,

NH-CO-C ₂ H ₄ -N- (CH ₃ J ₂

Anion® yellow

Example 79

NH ₂

O, N

- ^ "VN = N-CH - C-NH - CO -CH ₂ -N- (CH ₃ J ₂

O = C N

Anion = yellow

O, N

Example 80

Cl

N = N-CH-C-CH ₃

I Il

O = C N

NH,

NH - CO -CH ₂ -N- (CH ₃ J ₂

Anion® yellow

Cl

Example 81

NO ₂

N = N-CH-C-CH,

HN = C N \ /

NH ₂
NH - CO -CH ₂ -N- (CHj) ₂

Anion ¹ 'yellow

1 444 715 31 B e i s ρ i ei 82 (CH ₃ ), H ₂ NNC ₂ H ₄ -O- CO - / ~~ \ -N = N-CH-C - I Il
O = CN
\. /
N

32

Anion® yellow

Example 83

NO ₂ '.

X ~ \ _N = N-CH-C-CH ₃

O = C N

Cl

O ₂ N

NH ₂
SO ₂ -NH-C ₂ H ₄ - N- (CH ₃ J ₂

Example 84

NH ₂ N = N-CH-C-CO-NHQH ₄ N (CHa) ₂

O = C N

Anion® yellow

Anion® Orange

Example 85

'NH ₂ .

H ₃ C-OOC- / ~ \ -N = N-CH-CC ON HQH ₆ N (CH ₃ J

O = C N

\ /
NH

Example 86

NH ₂ . H ₃ C - <(VN = N-CH-C-CO-NH-QH ₄ N (CH ₃ J ₂

O = C N

Anion »yellow

NO ₂

Anion ^e reddish yellow

Some of the dyes built up with a heterocyclic N-containing diazo compound, accordingly The types listed several times in the table above can be used with suitable quaternizing agents be converted into multi-charged color cations. The quaternization of a ternary, heterocyclic nitrogen atom is known. The methods described in the literature are suitable. The resulting reaction products, on the other hand, are new. This is characteristic of their constitution simultaneous presence of hydrazinium and cycloammonium groups. A suitable manufacturing method is described in the following example.

example

2.5 parts of the dye · of the formula

-N

CH, O

C-N = N

, C ₂ H ₄ -N-NH ₂

HSO ₄ Q

were dissolved in 50 parts of nitromethane and heated to 80 °. The temperature range from 80 to 90 ° is allowed Add 0.8 parts of dimethyl sulfate dropwise. The mixture is stirred for a further 12 hours at 80 ° and then distilled Solvent from under reduced pressure. The dry distillation residue is then mixed Water — alcohol absorbed, dissolved hot, and allowed to cool after a clear filtration. The failing one Dye of the formula

CH ₃ O

N = N

(CH ₃ I ₂
, C ₂ H ₄ -N-NH ₂

is obtained in excellent yield. It dissolves in water with a blue color and stains polyacrylonitrile fibers in brilliant blue tones from acetic, neutral and mineral acid baths, in which it is resistant to overcooking.

The dyeing on polyacrylonitrile fibers has excellent light, washing, perspiration, sublimation, rubbing, Wet and dry fastness to ironing, sea water, flue gas, bleaching, dyeing and dry cleaning.

The dye reserves wool and cellulose fibers that are present in the same dye bath. The colorations are irrelevant in shade, and the dyes have a better leveling power than those similar to them Constitutions, for example made from the same diazo compound and diethylaminobenzene as a coupling component. .

Further basic dyes of the type mentioned, which were prepared according to Example 87, are: ■

OC ₂ U _{5 C2} H ₄ _ _N _ _NH2

CH ₃

C ₂ H ₄ -N-CH ₃
NH-CO-CH ₃ ^ ₁

2C1®

blue

© φ

Cl ". Blue

C ₂ H ₅ -O-SO ₃ ¹ =

Cl- violet

CH ₃ OSO ₃ ^

N = N

C ₂ H ₄ O-CO-CH ₃

^ ₂ H ₄ -O-CO-CH ₃
CH ₃

NH - CO -CH ₂ -N-CH ₃

NH ₂

Cl ^e purple

CH ₃ OSO ₃ *

The possibility of variation of the dyes that can be produced according to the invention is thereby increased even more, that the diazo compound can also be a carrier of the hydrazinium base.

In addition to the aforementioned, suitable azo compounds are suitable for the preparation of the dyes according to the invention in particular: azo compounds of the benzene and naphthalene series, such as z. E.g .: 4-methylphenol, 4-tert-butylphenol, 2-methoxy-5-methylaniline, N-ethylaniline, 2,5-dimethoxy-N-ethylaniline, J-acetylamino-HN-acetoxyethylaniline, 3-propionylamino- ^ N-diacetoxyethylaniline, N-methoxyethyl-N-cyanoethylaniline, N-cyanoethoxy-N-ethylaniline, 3-chloro-N-chloroethyl-N-ethylaniline, N-dimethylaminoethyl-N-ethylaniline, Pheriylcarbamic acid - (/ i-ethyl-3-toluidino) -ethyl ester, aniline-N, N-dicarbamic acid ethyl ester, 2-methoxy-5-cyano-N- / i-y-dihydroxypropyl - N - cyanoethylaniline, compounds capable of coupling of the naphthol-AS type, derivatives of diphenylamine, 3-nitro-5-cyanoethyl-N-ethyl-ani-Hn, S ^^ S-tetrahydro ^ -hydroxynaphthalene, 1-amino ^ -oxynaphthalene ethyl ether, S-acetylamino ^ -naphthol, 2-aminonaphthalene, 1-cyanoethylaminonaphthalene, Oxethylaminonaphthalene.

In addition, the usual heterocyclic coupling components and / or those with a active methylene group worth mentioning. Examples are: 8-hydroxyquinoline-, 1-phenyl-3-methylpyrazolone-5 and substitution products derived therefrom, such as l- (3'-chlorophenyl) -3-methyI-pyrazolon-5, l-ethyl-3-carboxamide-pyrazolon-5, 1 - cyanoethy 1 - 3 - carbäthoxypyrazolon - 5; 1 - phenyl-3-methyl-5-aminopyrazole, 2-methylindole, N-phenyl-3-oxypyrrolidine, «-Cyanacetophenön, acetoacetylanilide and derivatives derived therefrom, 1,3-diketones and derivatives derived therefrom, such as B. Indandione.

Examples of dyes of this type:

92

CH ₃

H ₂ NNC ₂ H ₄ - CO-NH
CH ₃

I = N

CH ₂ -CH ₂ -CO- OCH ₃

CH ₂ -CH ₇ -CN

Anion®
orange

H ₂ NN-CH ₂ - CH = CH - CO - NH

N = N-CH-C-CH ₃

Anion®
Yellow orange

CH ₃

H ₂ NNC ₂ H ₄ -CO
CH ₃

N = N

CH ₃

C ₂ H ₄ -N-NH ₂
N ·. CH ₃

C ₂ H ₅

Anion? ³ ©

37 38

H ₂ NNC ₂ H ₄

N = N

NH

H ₂ NNC ₂ H ₄ -S-CH ₂ -CO-NH - <(^^ N = N — CH-C—

CH ₃

O = CN
\ /
NH

CH ₃

H ₂ NNC ₂ H ₄ -O CH ₃

OH

N = N-CH-C-CH,

HN = C N \ /

CH ₃ H ₂ NNC ₂ H ₄ -NH-CO

¹ A

^CH 3

QH ₅

CF,

NH ₂ (CH ₃ ) ZNC ₂ H ₄ -O-CO

CO-CH ₃ N = N-CH

CO-NH

NH ₂ (CH ₃ ^ -NC ₂ H ₄ -O-CO

N = N-CH \

CO-N

CO-N Anion® red

Anion® yellow

Anion®

Reddish yellow

Anion® yellow orange

Anion® yellow

Anion® yellow

The ο, ο'-dioxy or ο, ο'-oxyamino compounds obtained diazonium salt are added to a sodasind suitable, together with heavy metal ions, such as alkaline solution containing 24.5 parts of the Kupp-Fe, Cu, Ni, Cr, Mn, 1: 1 or 1: 2 complex dyes 6o development component of the formula to build. -

example

25.6 parts of the monoazo dye 4'-nitro-4-amino-2-methylazobenzene prepared by a known method are diazotized ^{in finely dispersed form in aqueous hydrochloric acid with 20 parts of a 4N aqueous sodium nitrite solution at 10 to 2O 3.} The CH ₃
NH - CO -CH ₂ -N-NH ₂

<Q> -OH

39 40

The clutch is currently working. To isolate the dye, it is acidic with aqueous hydrochloric acid placed, the dye filtered off, rinsed and dried.

The obtained dye of the formula

CH ₁

O ₇ N

CH ₃
NH - CO -CH ₂ -N-NH ₂

OH 'Cl ^Θ

dyes polyacrylonitrile fibers in orange tones. Other valuable basic disazo dyes correspond to the formulas:

102

0, N

Cl

N = N

OCH,

N = N

CH ₃
NH - CO -CH ₂ -N-NH ₂

OH 'Anion® reddish orange

103

CF ₃ OCH ₃

N = N-

CH ₃

NH - CO -CH ₇ -N-NH,

Anion® scarlet fever

104

NO ₂

OCH ₃

OCH ₃

CH ₃ C ₂ H ₄ -N-NH ₂

\ CH ₃

C ₂ H ₅ ■■ - ■ Anion® Orange

109636/49

41

42

CH ₃

H ₂ NNC ₂ H ₄ -O CH ₃

N = N

N = N

Ο - C ₂ H ₄ - OH

OH

Anion® yellow

Ο, Ν

CH ₃

CH ₃

0-C ₂ H ₄ -N-NH ₂
CH ₃

OH

Αηΐοη ^θ orange

CH ₃

Ο — C ₂ H ₄ -N-NH ₂
CH ₃

OH

Anion® red

O ₂ N

CN

N = N HO

N = N

NH ₂

NH-C ₂ H ₄ -N- (CH ₃ J ₂

CI

NO ₂

Anion® blue-gray

Example 109

45 parts of sulfuric acid monohydrate are added. After the reaction has ended, the reaction

4.46 parts of 1,4-di- (2 ', 6'-dimethyl) -phenyl- 65 product on 400 parts of ice at 10 to 15 °, and the precipitated product is filtered off

aminoanthraquinone and leaves until it is completely connected and then rinses with cold

Stir the solution. In the temperature interval from 10 to water. !; > ··

15 "3 parts of dichlorodimethyl ether are added. 5.43 parts of 1,4-di- (2 ', 6'-dimethyl-3'-dichloromethy!) -

phenylaminoanthraquinone are introduced into a mixture of tert-butyl alcohol and ethanol at 20 to 30 °. It is then heated to 80 ^u and left at this temperature in the course of 30 minutes 1 part of asymmetric dimethylhydrazine, dissolved in

10 parts of ethanol are added dropwise. After completion of the implementation the solvents are distilled off in vacuo and the dry residue from water-: Recrystallized ethanol. The blue dye of the formula is obtained in good yield

example

9.8 parts of the from 1-methylamino-4-toluidinpanthraquinone through. Sales with dichlorodiethyl ether obtainable monochloromethylated reaction product with "the, melting point of 190 to 192 °, the temperature is entered into 90 parts of methanol then increased to the boiling point and at this temperature a solution of 1.7 parts of 1,1-dimethylhydrazine add dropwise in 10 parts of methanol

35 let. The temperature is maintained at 65 to 70 "for 24 hours and allowed to cool.

The precipitate formed is filtered off, washed with methanol and dried. He solves in concentrated sulfuric acid with green-blue, in hot water with blue color, melts at 228 to 234 ° and corresponds to the formula

O NH-CH ₃

CH ₃
CH ₂ -N-NH ₂

Cl

Polyacrylonitrile fibers are dyed in brilliant, greenish blue tones.

Further dyes are given in the following table. The symbols R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ in the general formula

^R n 9

R ₁₀ Ό R ₉ have the meaning given in the table.

example . * · '■■ - OH R, .- R, NH ₂ • I — CH ₃ CH ₃ ' CF T M PIT Rio CH ₃ R ₁ , π X Nuance of
Coloring on
Polyacrylonitrile
fibers. NH ₂ "N H C» 2 H4 1 CH ₃ NH \ y ~ " - I.
/ ^ TT vi TsTTT 111 -NH-C ₂ H ₄ -N-CH ₃ - OH H H H - NH- <(y- NH- CO- CH, CHj ^f H L, ri2 N- IN H2
/ ■ H 1 Cl Orange brown CH ₃
CH ₃ H ₃ CN-NH ₂ ^ H, -NH - (^) - CH ₃ ^CHi CH ₂ N-CH ₃ CH ₃
CH ₃ 112 -NH- ^ CH ₃ ™> H H ■ H CH ₂ N-NH, H H 1 Cl Red-brown -OH -NH- / / -CH ₃ ^CH3 CH ₂ N-CH ₃ 113 the same H H H NH ₂
I. -NH- <3-CH ₃ ^N «: H 2 Cl Red-violet - OH -NH-C ₂ H ₁ -N-CH ₃ 114 H H CH ₃ H H 1 Cl violet 115 ■ H H H H 1 Cl Blue violet - OH 116 H H H H 1 Cl violet 117 H H OH like ri, 2 Cl blue H H OH ΐ Cl 118 Blue green

—NH ₂ ... H R ₈ *-*"" Continuation CH ₃ CHj Ν -NHj CH ₂ -NH-CO- CH-CH ₃ Rio Ru η X Nuance of
Coloring on
Polyacrylonitrile
fibers example • -NH- ^ y -CH ₃ ^CH > _ _NH _ ^ ~ y_ _CH H ₃ CN-CH ₃
NH ₂ ■ H H H CH ₃
CH ₃ CH ₃ H H 1 Cl Violet blue 119 —NH ₂ CH ₃ NH-CO-CH ₂ -Ν-NH ₂
\ __ /. I. -NH-C ₂ H ₄ -N-CH ₃ • -NH- / J.- CH ₃ ^CH3 NH ₂ I -NHj -CH ₃ H /
CH ₃
CH ₃ NH ₂ H H 1 Cl Violet blue 120 —Br -NH ₇ -Z ^- VN-CO-C ₂ H ₄ -N-CH ₃ H CH ₃
NH ₂ H H 1 CI blue 121 -NH ₂ -CH ₃ CH ₂ N-CH ₃ —NH ₂ -NH - ^) - CH ₃ ^CH 3 H the same
NH ₂ H H 1 CI blue 122 -NH ₂ —Σ H CH ₃ . CH ₂ -NH-CO-CH ₂ -N-CH ₃ H . H 1 CI blue 123 - NH- / ~ V ^CH3 . · · H H CH ₃ H H 1 Cl Violet blue 124 -NH ₂ -NH-CH ₃ - Η H H 1 CI blue 125 H H H 1 Br blue 126

• 131 ■■ ■ .. *, ■ .. ■; R ₇ R ₈ continuation CH ₃ CH ₃ -NH- <5 CH ₃ CH ₃ H R ₁₁ η X Nuance of
Coloring on
'' Polyacrylonitrile
fibers "S .:
J R ₉ '. -NH-C ₂ H ₄ -N-CH ₃ " CO-CH ₂ -N-CHj -NH-CH ₂ -CHOH-Ch ₂ -N-CH ₃ CH ₂ N-NH, -NH-CH ₃ H H NH ₂ NHj -NH ^> CHj CH ₃ H 1 Cl blue 127 132 CH ₃ CH ₃ CH ₂ N-NH, H - NH - <^) ^ CH ₃ ^CH;> -NH-CH ₃ H H H H 1 Cl blue 128 NH, - NH-CH ₃ H H - NH -C ₃ H ₆ -N-CH ₃ H 1 Cl blue 129 CH ₃ H -NH ₂ OCHj H H I. Cl violet 130 I. H -NH ₂ U
λ H H 1 Cl violet φ H C ₅ H ₁₁ -NH, a H Η " 1 Cl . violet "Λ ΐ
< L.

R ₆ - CH ₃ -NH ₂ - H .R ₈ NH,
I. continuation CH ₃ -NH, Rio ■ H . . R ₁ , ; H . I! X Nuance of
Coloring on
Polyacrylonitrile
fibers * example CH ₂ N-NH ₂ -N (CH ₃ ), R ₉ -NH- / "V-NH-CO-CH ₂ -N-CH ₃ Blue green - ^NH - <_> ^CH > ^CH3 H 'CH ₃ NH ₂ Tx NH ₂ H CH, N-NH, H H H 2 Cl green .133 -NH- <^ V-CH3 H ₃ CN-CH ₃ ■ / \ ΓΉ
-NH- / V-CH ₃ ^CHj CH ₂ -NH-CO-CH ₂ H H CH ₃ H 2 Cl green blue 134 'CH ₃ CH ₂ -NH-CO-CH-CH ₃ - NH - <^ ~ \ -CH _{3 HC} _ _N _CH -NH-Z ^ -CH ₃ H ₃ CN-CH ₃ CH ₂ -NH-CO-CH, H \ / t
/ ■ NH ₂
CH ₃ H CH ₃ CH ₂ -NH-CO-CH-CHj H 2 Cl blue 135: '.' . . . CH ₃ H _ _NH ^^> _ CH ₃ Hj "cN-CHj H CO-CH ₂ -N-CH ₃ / ^ NH,
CHj - ^nh -O, H CHj CH ₃ H CO-CH ₂ -N-CH ₃ H 2 Cl green .136 H CH ₃ H H 1 Cl 137 R ₇ together with R ₈ -CO I.
-CO 1 Cl 138

53 54

From the series of anthraquinone pyridines and pyridones are mentioned:

Example 139

O NH

CH ₃ CH ₃ Cl ⁰ red

Example 140

CH ₃

NH,

C.
CO-C NH

YY CH ₃ CH ₂ -NH-CO-CH ₂ -N-CH ₃

o I> - <I

- ^ "V- CH ₃

CH ₃ red

B e i s ρ i e 1 141

CH,

H ₅ C ₂ -CO ₂ -CN

Br

O NH

NH ₂ NH - CO -CH ₂ -N-CH ₃

CH ₃ _j

Example 142

CH,

H ₅ C ₂ -CO ₂ -CN

CH ₃

CH ₃

O NH-C ₂ H ₄ -N-CH ₃ NH ₂ Cl ^θ orange

Cl ^s Orange Ί

example

56

Ν — S

NH,

NH - CO -C ₂ H ₄ -Ν - CH ₃ CH ₃

CI ^Q yellow

35 parts of the dye

example

■ CN

CH = C

■ CN

Cl ¹

20 parts of Glauber's salt and 45 parts of polyvinyl alcohol and drying gives a brilliant green-yellow color are dyeing of good general fastness properties in a roller mill for 48 hours, ground. 1.5 parts of this are divided into 3000 parts. Real dyeings are also obtained with color

Suspended and dissolved water at 40 °. After adding substances of the following constitution: 5 parts of glacial acetic acid are added at 50 ^J with 100 parts of 35
Well-cleaned piece of polyacrylonitrile of the type
»Orion« 42 (registered Schulz brand) and R ₁₃

increases the temperature with a steady increase | X

to boiling point within 45 minutes. You dye at the boil for 1 hour, then rinse the dyed Material and then soaps N for 20 minutes

in a boiling bath containing 1 g / l of a non-ionic detergent. After rinsing again

R ₁₃ -NO

CH = M

Anion ⁰

example R ₁₂ R | 3 R, 4 R | 5 R ₁ , X M. CN
/ COO-CH ₃ COO-C ₂ H ₄ -CN SO ₂ - / "S-CH ₃ hue /
\ CN
/ CN
/ 145 -CH ₃ -CH ₃ / ~ * TJ
C ₂ M ₄ H C ₂ H ₅ -CH ₃ - /
\ /
= C
\ · yellow 146 -CH ₃ -CH ₃ -C ₂ H ₄ - H C ₂ H ₅ H yellow 147 -CH ₃ -CH ₃ C ₂ H ₄ H C ₂ H ₅ H yellow it · ,:

58

Methine and cyanine dyes are just as suitable as the styryl dyes mentioned above. In addition, can the process according to the invention also applied to (oxy) quinophthalones. Examples are:

CHj

H ₂ NN-CH ₂ -OCO

NC

QH

H ₅ CHj

COOCH ₂ -N-NH,
CH = C CHj

CN

2 anion "yellow

O, N

NH-CjH ₁₁ -N-NH ₂

© θ.

2 anion "

Greenish tint) 'yellow

Φ 'Η

2 anion ¹ 'blue

Example 151

2 parts of the soluble color salt of the formula

C ₂ H ₅ -O NO,

SO, N

C ₂ H ₃

"C ₂ H ₄ -N-NH ₂

CHj ..

Cl

are made into a paste with 2 parts of acetic acid (80%) and by adding 8000 parts of hot water in Solution brought. Another 2 parts of acetic acid (80%), 6 parts of sodium acetate and 10 parts are used a condensing agent of oleyl alcohol and 20 mol of ethylene oxide and goes with 2 (X) parts of polyacrylonitrile fiber one. The bath is heated to 85 "within 30 minutes and the temperature range is passed through from 85 to 97 ° within 20 minutes and then colored at the boil for one hour. The dye bath is almost completely exhausted. The dyed material is then under for 15 minutes Addition of a non-ionic detergent, soaped, rinsed and dried. The polyacrylonitrile fiber is Dyed in a brilliant yellow of excellent fastness properties .;

Similar colorations are obtained with other nitro dyes. Examples are:

NH NO ₂

CH ₅

SO ₂ -N

\ 'I
C ₂ H ₄ -N-NH,

Anion
yellow

I 444

Cl-

NH

SO ₁ -N

60

CH,
"'CFI.,

NO,

SO, —N

C ₂ H ₄ -N-NH ₂

CHj

CH ₃ C ₂ H ₄ -N-NH ₂
CH ₃

NO,

NH ₂ -NC ₂ H ₄ -NH

SO, - NH-

NO,

Nil— S Ο-, N =

CHj

C ₂ H ₄ -N-NH,

CHj

H V-NH

example

40 parts of the dye of the formula anion.
yellow

Anion
yellow

Anion
yellow

2 anion
yellow

Anion
yellow

NO,

CH ₃

SO ₂ -NH-C ₃ H ₆ -N

NH,

are prepared with 20 parts of that in Example 110 Grind the dye together with 40 parts of Glauber's salt in a ball mill for 48 hours.

2 parts of the preparation obtained in this way are made into a paste with 2 parts of acetic acid (40%), the color paste pour 4 (X) parts of distilled water at 60 ° over it and boil the whole thing briefly.

It is then diluted with a further 7600 parts of distilled water, and 2 parts of concentrated sulfuric acid are added and goes into the dyebath at 60 "with 100 parts of polyacrylonitrile fiber.

The temperature is increased to 90 '' within 30 minutes and colored for 1 hour in the temperature interval from 90 to 97 °. Then it is soaped and rinsed. The green coloring is characterized by Levelness, brilliance and good fastness properties.

Example 159

Polyacrylonitrile fibers are introduced into an aqueous bath at 50 ° in a liquor ratio of 1:40, the 0.6 part of glacial acetic acid, 0.3 part of sodium acetate and 0.6 part of the reaction product per liter asymmetric dimethylhydrazine and the azo

61

62

methine dye from 4-no chlorine-N-biitylamino-benz- rinsed and dried. The fibers are reddish yellow

contains aldchyd and l-amino-4-methoxy-benzene. Man colored. The Bchtheilsnivcau is extraordinarily high,

heated to boil within 30 minutes and in principle all known azomethine

Holds the bath for 30 to 60 minutes when boiling. Constitutional for dyeing polyacrylonitrile fibers.

Period. After the dyeing is finished, the product is soaped. 5 Of interest are e.g. B. dyes of the formulas

CH ₃

H ₁ NN-GH ₄

j CH ₃

N-

CH = N

QH

H ₅

CI "

Greenish yellow

CH ₃

H ₂ NNC ₂ H _4n CH ₃

CH = -N

CH ₃

CH,

Cl 'orange

According to the information in Example 1, the dyes of the following formulas can also be prepared:

Cl Br

(CH,), N - SO ₂ -ί

N = N-

NH,

C ₂ H ₅ -N (CH ₃ J ₂

Cl

O, N

N = N

C ₂ H ₄ -N (CH ₃ ),

Cl orange

Cl red

CN

CN CN

CH ₃
■ LC ₂ H ₅

-N = N- \> —N ι

V ₂ H ₄ -N (CH ₃ ),

N = N

Cl orange

Cl

Cl

CH ₃

(CH ₃ ) ₂ N - SO ₂

egg

CI CH ₃

(CH ₃ J ₂ N - SÖ ₂ ^ ~ \ -N = N— <.> —N

■■ ■ ': α ■■'. '"

C ₂ H ₄ -N (CH ₃ ), C ₂ H ₅ ·

K'T ²

X ₂ H ₄ -N (CH ₃ J ₂

'NH ₂

CH ₂ -CH-N (CH ₃ ), CH ₃

CI Orange

. e-

CI scarlet fever

CI scarlet fever

C ₂ H ₅

\ Γ ²

^ C ₂ H ₄ -N (CHj) ₂ NH ₂

C ₂ H ₄ -N (CH ₃ ), Cl orange

Cl ¹ orange

Claims (1)

. Palent claims: 1. Process for the preparation of basic dyes of the formula y, η and B are as defined in claim 1, with η moles of a compound of the formula CH ₃ - y - N - CH ₃
NH, 20 111® X U) ' 30th where A is the radical of a dye free of carboxylic acid and sulfonic acid groups, y is an optionally substituted methylene group or a divalent radical bonded to the adjacent N via one of these, η is the number 1 or 2, »1 is the number 1 or 2, if η is 1 stands, and 2, when 11 stands for 2, 'and X is each an anion equivalent to a dye cation, thereby geke η η ζ calibrated η et that a compound of the formula 40 tYZ) _n (H) with a compound which, instead of Z, has the remainder (III) " H ₃ C H ₃ C N - NH ₇ (III) H ₁ C H ₃ C N-NH, (V) converts and, if B denotes the remainder of a compound capable of forming a dye, the reaction product is converted into the dye of the formula I. 3. The method according to claim 1, characterized in that there is a compound of the formula B- -y-N-CH ₃
NH ₂ (VI) wherein 17, y and B are as defined in claim 1, quaternized with methyl group donating agents and, if B is the remainder, to form a Dye-capable compound means the reaction product in the dye of the formula I. convicted. 4. The method according to claim 1, characterized in that that one is a compound of the formula —Y — Ν — Η
NH ₂ (VII) introduces or Z converts into such, where B for A or the remainder of a to form a Dye A is a capable compound and Z is a substituent which is represented by a group of the formula (III) or can be converted into such and, if B for the Rest of a compound capable of forming a dye, the reaction product in the Dye of the formula I transferred. 2. The method according to claim 1, characterized in that I Mo | a connection of formula B - (- y - E) ₁ , (IV) 55 60 65 in which II is the acid residue of an ester and in which n, y and B are as defined in claim 1, quaternierl with methyl group donating agents and, if B is the remainder, to form a Dye-capable compound means the reaction product in the dye of the formula I. , convicted. 5. The method according to claim 1, characterized in that one mole of an amine of formula B-- -y-N (VIII) 109 636/4 ' wherein R _{1 is} hydrogen or the methyl group and R _{2 is} hydrogen or the methyl group and n, y and B are as defined in claim 1, with η mol of a halogen amine, when R ₁ and / or R _{2 is} hydrogen, the reac-, tion product quaternized with methyl group donating agents and, if B denotes the remainder of a compound capable of forming a dye, the reaction product in the dye of the formula I converted, with quaternization and conversion into a dye in any order can be carried out. 6. Use of the dyes prepared according to claims 1 to 5 for dyeing fiber materials from acrylonitrile polymers, optionally dissolved plastic plastic compounds and other plastic masses as well as oils and varnishes. ■