DE1644272C - Process for the preparation of water-insoluble azo compounds - Google Patents

Description

The invention provides a method for the production of new water-resistant azo compounds formula

H Y

I I

N = N-C-C = N-R

C - Ν— Ζ

ii!

O H

or mixtures containing such azo compounds are provided, wherein X is an aryl radical b ^ w. heterocyclic radical, Y an alkyl radical, aryl radical or substituted aryl radical, Z an aryl radical or substituted aryl radical and R represents an aminoalkyl radical or substituted aminoalkyl radical and η is 1 or 2.

Examples of aryl radicals for which X can stand are phenyl, 3 "3'-dichloro-4,4'-diphenylene, 4-methyl-2-nitrophenyl and 4-chloro-2-nitrophenyl radicals mentioned.

Examples of heterocyclic radicals for which X can stand are the T-chloro ^ -hydroxy- ^ methylquinolin-6-yl radical mentioned.

As examples of aryl groups or substituted aryl groups, which Z can represent include phenyl, o-anisyl and 2,4-dimethylphenyl radicals.

A's examples of radicals for which Y can stand are alkyl radicals, such as the methyl radical, aryl radicals, such as the phenyl radical, and substituted aryl radicals, such as by a group of the form!

C (NR) • CH (CO • NHZ) N = N-X

substituted phenyl radicals mentioned.

A's examples of radicals for which R can stand are 3-octadecylaminopropyl, 3-dimethylaminopropyl and 2-dimethylaminoethyl groups mentioned.

Examples of azo compounds of the invention are 2 - benzene azo - 3 - cyclohexyliminobutyranilide, 2,2 '- (3,3' - dichloro - 4,4 '- diphenylene-disazoj-3,3'-di- (3 - octadecylaminopropylimino) - bis - butyranilide and 2,2 '- (3,3' - dichloi: - 4,4 '- diphenyfendisazo) -3,3' - di - (3 - dimethylaminopropylimino) - bis - butyr-2-methoxyanilide mentioned.

Belgian patent 635 490 and French patent 1283 382 refer to Pigments derived from acetoacetarylamides as coupling components

If, according to the present invention, these known pigments are used as a starting point and If these are reacted with an amine, the paints and inks produced with them result in stronger paints and inks Discoloration when it could be produced with the corresponding known paints.

The subject of the invention is a process for the preparation of water-insoluble azo compounds, which is characterized in that a mixture of an azoacylacetarylamide of the formula in which X is an aryl radical or a heterocyclic radical, Y an alkyl radical, aryl radical or substituted aryl radical and Z an aryl radical or substituted Represents aryl radical and η is 1 or 2 with an amine of the formula

/
R - N ^/

wherein R represents an aminoalkyl or substituted aminoalkyl radical, heated to form a compound of Formula I.

X-

H Y

I I

_N = NCC = NO
I.
C — In — Z

I! I.

O H

H Y

i
-N = NCC = O

C-N-Z

; f

ο π

wherein X, Y, Z, η and R have the meanings given above, optionally using the amine, based on the azoacylacetarylamide, in an insufficient amount of preferably 1 to 50 ° / ₀ , so that only part of the azoacylacetarylamide is converted into the azo compound of the formula (I).

The heating can be carried out with the reactants alone or in solution in a solvent such as toluene or xylene, or in suspension in an aqueous medium. Usable temperatures are 70 to 200 ⁰ C.

It is often expedient to use this process with the preparation of the azoacylacetarylamides in the Way to combine that the amine after coupling the diazonium compound and the acylacetarylamides obtained aqueous slurry is added and the mixture is heated and thereafter is filtered to isolate the azo compound of the invention.

Depending on the relative proportion and type of amine used, the specific azoacylacetarylamide and the reaction conditions are compounds in which all available acyl groups or only part of the available acyl groups with the amine have been implemented.

D-also suitable azoacylacetarylamides for use in the manufacture of those according to the invention Compounds are 2 - benzene azoacetoacetanilide, 2,2 '- (3,3' - dichloro - 4,4 '- diphenylenedisazo) bis (acetoacetanilide) and 2 - (4 - chloro - 2 - nitrobenzolazo) acetoacetanilide.

Amines useful for use in preparing the compounds of the invention include 3-dimethylaminopropylamine and 3-octadecylaminopropylamine.
The azo compounds of the invention can also be prepared by condensing the amine with the appropriate acylacetarylamide by conventional procedures and coupling the resulting product with the appropriate diazonium compound. The condensation product can be prepared, for example, by heating the two components in boiling ethanol and adding the cooled ethanol solution to a stirred aqueous solution of the diazonium acetate.

3 4

The azoacylacetarylamides are generally acetic acid and 285 parts of water for aqueous yellowing compounds, and the suspension derived therefrom by tetrazotizing 126.5 parts Azo compounds of the invention are also colored, 3,3'-dichlorobenzidine and domes of 177 parts whereby the introduction of the imino groups produces a batho-acetoacetanilide-obtained yellow pigment color chrome hue change caused. 5 Index Pigment Yellow 12 added. It was

The azo compounds of the invention are in organic aqueous sodium hydroxide to increase the pH value

niche solvents and in the example tes added to 12, whereupon the suspension on

Easily soluble media used for printing inks, ^{heated to 9O 0} C, which leads to complete

and, as fuel-soluble dyes, they lead to the fouling of the pigment. The suspension was

For example, when dyeing gasoline, pickling io then filtered, and the solid material obtained was with

and varnishes for wood of value. Water washed and put in an air oven at 70 ° C

The azo compounds are very effective dispersed dry. The dried product, which to

powder was ground in organic powders for azoacylacetarylamides.

Solvents. As many of the Azoacylacetarylamide that it is in organic solvents in the medium

are valuable pigments, the incorporation of a 15 for gravure inks gives instant dispersion

A. part of a »on these derived or similar, whereby one can be formed without any grinding

Azo compound according to the invention is a pigment which or without any further treatment for printing

Ches in eintr ', for example as a medium for printing-suitable fine dispersion resulted. The untreated

The organic pigment used in paints or paints had to be ground in the medium before

Solvents such as toluene, mineral spirits, light petroleum - the printing ink could be used from it,

fractions or / 3-ethoxyethanol, without mechanical. 17th

Milling process can be dispersed very easily, Example I.

resulting from satisfactory dispersions, 27 parts of commercially available 3-octadecyl-

the aminopropylamine used for printing, for example, in a Beken duplex mixer

be able. Such azoacylacetarylamide preparations 25 are weighed out and allowed to melt to a temperature

with a content of the azo compounds of the invention of 60 ° C. There were 73 parts dry

can be done in various ways, for example by means of yellow Pigment Color Index Pigment Yellow 12

Reacting the azoacylacetarylamids with a slow added, and the temperature was ^ n: f

schüssigen Anunmenge of 1 to 50 ° / _0, preferably from 140 ⁰ C increased. A plastic mass was created,

from 2.25 to 25 ° / ₀ , the weight of the azoacylacetaryl 30 and there was a clear change in color from greenish

amides, or by making the azoacylacetaryl yellow to reddish brown. The mass was cool

amide in the presence of N ^'i .nge from the left thereof, whereupon it solidified. After removal

derived azo compound can be obtained. Those from the mixer turned the lumps into powder

Azo compounds of the invention can also be used as mill. The one obtained by this treatment

Dispersing aid when grinding the azoacyl- 35 pigment mass was characterized by the same dispersing

acetarylamide, for example, with gravure-printing-erosion properties like the pigment mass of the

ben media are used, whereby they have a stability game 1 from. The X-ray examination of the

against the dead-grinding. Pigment mass showed an X-ray diagram that of

Azo compounds of the invention with particularly that of the untreated pigment clearly

high dispersibility will be different due to the 40 different.

Twist obtained from aliphatic diamines, in B is η ie 1 3
which one of the amino groups is a primary amino

group and the other either secondary or the procedure of Example 2 was reconditioned is tertiary amino group. fetches, but the commercially available 3-octadecyl

Pigments containing 2-dimethyl aminopropylamine was replaced by commercially available dodecylaminoethylamine or 3-dimethylaminopropylamine aminopropylamine. A similarly derived azo compounds according to the invention were obtained as in Example 2,
genes when grinding, for example with engraving _R. -14
Printing ink media have particularly good stability Example 4
In terms of dead-milling and better flow properties, a mixture of 20 parts of the yellow shaft was obtained. Pigments Color Index Pigment Yellow 12 and

The resulting from the use of amines with additional 60 parts of commercially available 3-octadecylaminopropyl

basic amino groups in the molecule are formed on / n for 16 hours at a temperature of 90

Resulting azo compounds of the invention are in up to 100 ^° C. and then at 150 ^° C. for 30 minutes

soluble in aqueous acids. Particularly suitable 55 stirred. The product was heated in 216 parts

Amines for use in the manufacture of this toluene are dissolved and added by 792 parts

Azo compounds include 3-dimethylaminopropyl- hot methanol precipitated. The solid fabric was

amine and 2-dimethylaminoethylamine. filtered off, treated with 396 parts of hot methanol

The invention is based on the following do not wash and dry, resulting in 28.3 parts

Examples to be understood as limiting are closer to an amorphous brown which is readily soluble in toluene

with all parts being by weight and all sticky solid.

Unless otherwise stated, percentages are percentages by weight. . ,,

is specified. Example 5

There were 79 parts of commercially available 3-octadecyl

B e i s ρ i e 1 1 65 aminopropylamine dissolved in 79 parts of hot ethanol.

After cooling to 35 ° C, 36.6 parts of aceto

A solution of 53 parts of hand ice acetanilide was added. The solution came to a boil

Brought conventional 3-Octadccyliaminopropylamin in 16 parts, during 45 minutes to 35 ° C cool

left, whereupon another 158 parts of ethanol were added.

There were 500 parts of an aqueous solution of tetrazotized 3,3'-dichlorobenzidine (from 25.3 parts Diclilorbenzidin manufactured) stirred in an ice bath, 36 parts of sodium acetate crystals were added until the solution was no longer against Congo Red was pissed off. The alcoholic solution from above was added to the aqueous solution over 2 minutes. After stirring for 15 minutes, 464 parts of 2-ethoxyethanol were added. After 30 minutes Ammonia was added to stirring until the solution was alkaline to brilliant yellow. The amorphous brown product was extracted with 745 parts of chloroform, and after separation of The chloroform solution was filtered off from the aqueous phase from a trace of insoluble material and concentrated to 300 parts. 237 parts of hot methanol were added and the product became filtered off, washed with 395 parts of hot methanol and dried. The product was similar like that of example 4.

Example 6

A mixture of 5 parts of the yellow pigment Color Index Pigment Yellow 12 and 20 parts of 3-dimethylaminopropylamine was stirred for 16 hours at a temperature of 90 to 100.degree. After diluting with 120 parts of water, the solid product obtained was filtered off, washed with water and dried. The yield was 6.7 parts. It was easily soluble in cold dilute acetic acid. The melting point of the condensate was about 237 to 239 ^° C., but it depends on the heating rate. During this isolation it forms a dihydrate which crystallizes unchanged from chlorobenzene, but is dehydrated ^{by heating to 100 ° C. for several hours under reduced pressure.}

The analysis of the dihydrate showed a content of 60.8% carbon, 6.2% hydrogen and 17.0% Nitrogen. The theoretical values for

C ₄₂ H ₅₀ Cl ₂ N ₁₀ O ₂ · 2 H ₂ O

are: 60.5% carbon, 6.5% hydrogen and 1C, 8% nitrogen. The product made free of water of crystallization contained 62.6% carbon, 6.3% hydrogen and 17.4% nitrogen. The theoretical values for

C ₄₂ H ₅₀ Cl ₂ N ₁₀ O ₂

are: 63.2% carbon, 6.3% hydrogen and 17.6% nitrogen.

Example; 7th

88.5 parts of acetoacetanilide were gradually added to 56.7 parts of 3-dimethylaminopropylamine with stirring. An immediate exothermic reaction occurred, the temperature rising ^{to 68 ° C. by itself.} The reaction was completed by stirring at 90 ° C for 30 minutes. A viscous gum formed on cooling, which slowly crystallized out on standing (faster after inoculation). The solid was a hydrate; on drying over sulfuric acid in a vacuum desiccator, it formed a gum which, in turn, could be crystallized as a hydrate by stirring with water and seeding. The solid, after filtering and washing with water, could be dried over sodium chloride in a vacuum desiccator.

The / J-3-dimethylaminopropylaminocrotonanilide thus obtained melted in a sealed tube at 58 to 60 ° C and analysis indicated the composition

C ₁₅ H ₂₃ N ₃ O · '/. H ₄ O

(found: 66.6% carbon and 8.9% hydrogen). It is very sensitive to acids; even in cold, dilute acetic acid, it was rapidly hydrolyzed to regenerate acetoacetanilide, and for this reason it is best coupled with diazonium salts in such a way that a gradual Addition of an alcoholic solution of the / 5-3-DimethylaminopropylaminocrotonaniIides to a buffered solution of the diazonium salt takes place, whereupon it couples immediately.

There were 400 parts of an aqueous solution of

ao tetrazotised 3,3'-dichlorobenzidine (made from 25.3 parts dichlorobenzidine, stirred in ice, during which 36 parts sodium acetate crystals were added until the solution was no longer acidic to congo red paper. A solution of 70 parts isO-dimethylaminopropylaminocrotonanilidine 158 parts ethanol was added for 2 minutes, added as needed ice to keep the temperature below 2O ⁰ C. after 5 minutes of stirring, ammonia was added until the suspension to Brilliant Yellow (Brilliant Yellow) was alkaline. the product was filtered, washed with water washed, dried and uricrystallized from chlorobenzene.It was identical to the product of Example 6.

Examples

There were 100 parts of the yellow pigment Color Index Pigment Yellow 12 and 10 parts of 3-dimethylaminopropylamine For 16 hours by rumming in a cylindrical container on a horizontal plane

Rollers mixed. The mixture was for 6 hours at atmospheric pressure at a temperature of 80 to 85 ° C and then A ¹ J ₁ hour maintained at a pressure of 20 mm Hg at 8O ⁰ C for. After cooling, the product was ground and passed through a 0.5 mm sieve. Compared to the untreated Color Index Pigment Yellow 12, the treated pigment when used in a gravure printing ink gave a much less viscous base, a better Drixk surface quality and a larger

greater coloring power. In this example, the yellow pigment Color Index Pigment Yellow 12 can be obtained from the Yellow Pigment Color Index Pigment Yellow 3 can be replaced, with a similar improvement being obtained will.

Example 9

There were dissolved 10 parts of the product of Example 4 in 100 parts of / 3-ethoxyethanol at a temperature of 90 ⁰ C and the solution was added to 3000 parts of an aqueous slurry containing 90 parts of Color Index Pigment Yellow 12th After filtering, washing and drying, the treated pigment, which was ground into a powder, was easily dispersed in organic solvents or a medium for gravure inks to give a fine dispersion suitable for printing without further milling or other treatment.

Example 10

1.25 parts of the product prepared as described in Example 6 and 48.75 parts of the yellow pigment Color Index Pigment Yellow 12 were added to 950 parts of a gravure printing ink medium based on an aromatic hydrocarbon (containing 400 parts of resinous zinc and 550 parts of solvent) were mixed in, and the mixture was stirred for 20 minutes with a high-speed stirrer. The resulting gravure ink had much better flow properties than a similar ink from which the product of Example 6 was omitted. On prolonged milling, the strength of the paint containing the product of Example 6 was not appreciably reduced, while the paint containing no product of Example 6 resulted in a serious loss of strength.

Example 11 _ao

There were 25.3 parts of SJ'-dichlorobenzidine in known Way tetrazoticrt with hydrochloric acid and sodium nitrite and filtered, and the filtrate was washed with water diluted to 800 parts.

36.0 parts of acetoacetanilide and 8.2 parts of »5 caustic soda were dissolved in water, and the solution was filtered and diluted to 800 parts with water. 7.0 parts of the product of Example 6 as a solution in 6 parts of acetic acid and 150 parts of water were added at 20 ^° C. to this solution. The acetoacetanilide was precipitated by adding 10 parts of acetic acid dissolved in 50 parts of water over a period of 10 minutes. Then 70 parts of sodium acetate crystals were added.

The tetrazo compound solution was added to the anilide suspension over 90 minutes until only a very small excess of acetoacetanilide remained uncoupled, the temperature being maintained at 10-20 ° C. When the coupling was over, caustic soda solution was added until the yellow suspension was alkaline to brilliant yellow. The alkaline suspension was ^{heated to 90 °} C., kept at this temperature for one hour and filtered, and the solid substance was washed with water until the electrolyte was removed.

The resulting pigment composition was dried in an oven at 65 ° C to give a yellow powder which was easily dispersed in gravure ink media and had increased color strength, gloss and flow compared to the normally prepared pigment led.

Patent claims:

1. Process for the preparation of water-insoluble azo compounds, characterized in that one is a mixture of one Azoacylacetarytamide of the formula

H Y

N = NCCO
i
CNZ

S:

O H

60

where X is an aryl radical or a heterocyclic radical, Y is an alkyl radical, aryl radical or substituted aryl radical and Z is an aryl radical or substituted aryl radical and η is 1 or 2, with an amine of the formula

R-N

wherein R is aminoalkyl or substituted aminoalkyl, heated to form a compound of formula I.

HY
N = N-C-C-NO

C —Ν —Ζ

!
OH

(D

wherein X, Y, Z, η and R have the meanings given above, optionally using the amine, based on the azoacylacetarylamide, in an urterschüssigen amount of 1 to 50 ° / ₀ , so that only part of the azoacylacetarylamide in the azo compound of the formula I is converted.

2. The method according to claim 1, characterized in that one carries out the heating at a temperature of 70 to 200 ⁰ C.

3. The method according to claim 1 or 2, characterized in that the implementation of the Performs reactants in suspension in an aqueous medium.

4. A process for the preparation of the azo compounds of the formula (1) obtainable according to claim 1, in which X, Y, Z, η and R have the meanings given in claim 1, as a modification of the process according to claim 1, characterized in that one of an amine of the formula

, W

Χ — Ι — Ν

Diazunium compound derived from the condensation product of an acylacetarylamide formula

OHO

I i!

Y — C — C — C —Ν — Ζ

! I.

H H

and an amine of the formula

R-N

clutch.