CH620698A5 - Process for the preparation of novel dyestuffs of the perylene-3,4,9,10-dicarboximide series - Google Patents

Description

The invention relates to a process for the preparation of new dyes of the perylene-3,4,9,10-tetracarboxylic acid diimide series and their use as pigments.

From DE-PS 386 057 is the N, N'-bis (4'-chlorophenylimide) and the N, N'-bis (4-methoxyphenylimide) and from DE-OS 2 120 207 the N, N'-bis (4-bromophenylimide) of the peryl-entetracarboxylic acid is known. Compared to these compounds, the process products show a significantly better absorbency on cellulose.

The new dyes have Formula 1

H.

(4)

in the

Z for a radical of the formula ✓R3 bound in the 3- or 4-position of the rings A.

—N — C — N \

I II \ R2

R1 O stands in which

R1 and R2 each represent a hydrogen atom or the same or different alkyl having 1 to 4 carbon atoms,

R3 is a hydrogen atom, alkyl having 1 to 8 carbon atoms, cycloalkyl having 6 to 8 carbon atoms, phenyl, naphthyl or phenyl substituted by C 1 -C 4 -alkyl, methoxy, ethoxy, chlorine, bromine or fluorine, the number of Is substituent on phenyl 1 or 2 and the substituents can be the same or different, or the group • R2

—N \ a saturated 5-, 6- or 7-membered heterocy-

Kr.

used, wherein Y, Z and n have the meaning given above.

2. The method according to claim 1, characterized in that amines of formula 4 are used in which R1 and R2 are hydrogen or methyl, Y is methyl, chlorine, methoxy or ethoxy and n = 0 or 1 and Z has the meaning given in claim 1 Has.

3. The method according to claim 1, characterized in that • amines of the formula 4 are used, in which n = 0 and Z for a group of the formula —NH-C -NH-R '

II

O

is where R 'is Cr to C8-alkyl, cyclohexyl, phenyl or 1 or 2 times substituted ring, substituted with chlorine, bromine, methyl or fluorine, which additionally contain -O-, -S- or another -N- as a ring member can mean,

Y represents alkyl having 1 to 4 carbon atoms, chlorine, bromine, fluorine, methoxy, or ethoxy, where the radicals Y can be the same or different, and n represents the numbers 0, 1 or 2, where n = 2 in each of the rings A only one Y may be in the 2- or 6-position.

The new dyes are obtained by condensation of perylene-3,4,9,10-tetracarboxylic acid or its dianhydride with substituted phenylic amines in inert, higher-boiling solvents or diluents in the heat and in the presence or absence of condensing agents, if the amines are aminophenylureas Formula 4

3rd

620 698

h2n- ^ y n

(4)

used, where Y, Z and n have the meaning given above.

The dyes are very suitable as vat dyes for dyeing cellulose fibers, such as cotton, and fiber material made from regenerated cellulose.

The new dyes are also pigments. The dyeings obtained have good fastness properties.

As Cr to C4-alkyl for R1 and R2 e.g. in particular into consideration: methyl, ethyl, n- or isopropyl, n-butyl, isobutyl, sec-butyl. For R1 and R2, methyl and hydrogen are preferred.

For R3, in addition to hydrogen, Cr to C8-alkyl and C6 to C8-cycloalkyl are e.g. To name: the alkyl radicals mentioned for R1, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, cyclooctyl.

Suitable phenyl optionally substituted by 1 or 2 radicals for R3 are, for example: phenyl, o-, m- and p-chlorophenyl, o-, m- and p-tolyl, o-, m- and p-methoxy-phenyl, o-, m- and p-ethoxyphenyl, 2,4-, 2,5-, 3,4- and 3,5-dimethylphenyl, 2,4-, 2,5-, 3,4- and 3,5- Dichlorophenyl, 3-methyl-4-chlorophenyl and 3-chloro-4-methylphenyl. Of these residues, phenyl, 3-chlorophenyl, 4-chlorophenyl and 3-chloro-4-methylphenyl are preferred for coloristic reasons.

As residues of saturated 5-, 6- or 7-membered saturated

/ R2

heterocyclic rings are for —N <e.g. to name such

\ R3

nen, which are derived from pyrrolidine, piperazine, N-methylpiperazine, N-ethylpiperazine, piperidine, morpholine, thiomorpholine or hexamethyleneimine.

Suitable Cr to C4-alkyl for Y are those mentioned for R1 and R2 s. Y is preferably methyl, chlorine, methoxy or ethoxy and n is 0 or 1.

For economic and coloristic reasons, compounds of the formula (1) are preferred in which R1 and R2 are hydrogen or methyl, R3 has the meaning given above, Y is methyl, chlorine, methoxy or ethoxy and n is the number 0 or 1.

Of these dyes, especially those of formula 2 are

15 Z I

(2)

preferred, in the Z 'for a 3- or 4-residue radical of the formula

H

-NH-CN-R '

5 II O

is in which R 'is Q- to C8-alkyl, cyclohexyl or phenyl, in which one or two, preferably one, hydrogen atom is substituted by chlorine, methyl, bromine or fluorine and the substituents can be identical or different.

The compounds of the formulas (1) and (2), in which the radical Z is in the 4-position of the rings A, have particularly good coloristic properties.

Dyes of the formula 3 are very particularly preferred

0 0 t

R ^ -HN-C-HN- ^ Ä \ -N y = i

0

"4 nh-c-nh-r

(3)

in which R4 represents one of the following groups: 3-chlorophenyl, 4-chlorophenyl, 3-chloro-4-methylphenyl, phenyl, cyclohexyl or methyl and both R4 are the same.

The higher-boiling inert solvents and diluents 50 used in the process according to the invention, e.g. Naphthalene, trichlorobenzene or preferably quinoline. The condensation is expediently carried out at temperatures between 180 and 230 ° C. The reaction is advantageously carried out in the presence of agents which accelerate the condensation 55, such as zinc chloride, zinc acetate, zinc propionate or hydrochloric acid. The aminophenylureas are expediently used in excess: as a rule, 2 to 3, preferably 2.1 to 2.6, mol of the primary amine per mole of perylene tetracarboxylic acid (dianhydride).

As aminophenylureas (4) e.g. to call:

0

<a> h2n ^ 3- n-c-nh-r

~ h and

60

(4a)

0

<^ V-n-c-

h2n

nh-r

(4b).

h in which R for the groups methyl, ethyl, isopropyl, butyl, cyclohexyl, phenyl, 4'-chlorophenyl, 3'-chlorophenyl, 2'-chlorophenyl, 4'-methylphenyl, 3'-methylphenyl, 2'-methylphenyl , 4'-methoxyphenyl, 3'-methoxyphenyl, 2'-methoxyphenyl, 4'-ethoxyphenyl, 3'-ethoxyphenyl, 2'-ethoxyphenyl, 2 ', 4'-dimethylphenyl, 2', 5'-dimethylphenyl, 3 ', 4'-dimethylphenyl, 3 ', 5'-dimethylphenyl, 2', 4'-dichlorophenyl, 2 ', 5'-dichlorophenyl, 3', 4'-dichlorophenyl, 3 ', 5'-dichlorophenyl, 3-chlorine -4-methylphenyl or naphthyl;

620 698

4th

ch,

O

(b) h2n- <

- -nh-c-nh-r,

ch3 o

II

ß -nh-c-nh-r,

H, N

OCH3

h2n- (Cj) - nh-co-nhr,

ch3

h2n— (çy) -nh-co-nhr, ch,

H, N-

-NH-CO-NHR

91

(o) -nh-co-nhr HgN

h2n-

ch3 I

-n-co-nh-r,

H, N

CH3 I

-N-CO-NH-R,

H, N-

c2hs I

- n -co-nhr and c2h5

- N -CO-NH-R in which R is methyl, butyl, isopropyl, cyclohexyl, phenyl, 4'-

H, N

Chlorophenyl, 3'-chlorophenyl, 4'-methylphenyl, 3'-methylphenyl, 3 ', 4'-dichlorophenyl or 3'-chloro-4-methylphenyl;

O

(c) H2N - <(_)) - NH-C wound

H, N

O II

_NH-C —W, in which W is for dimethylamino, diethylamino, dipropylamino, di-sec.-butylamino, di-n-butylamino or for residues of the formulas

-nQ, -o- -O15, -nO, "ch3 '

-N N-CoHc »N t 2 5

For coloristic reasons, the reaction products of perylene tetracarboxylic anhydride with the following ureas are particularly preferred: N-4-aminophenyl-N'-methylurea, N-4-aminophenyl-N'-phenylurea, N-4-aminophenyl-N '- ( 4'-chlorophenyl) urea, N-4-aminophenyl-N '- (3 chlorophenyl) urea, N-4-aminophenyl-N' - (3'-chloro-4'-methylphenyl) urea and N'- 4-aminophenyl-N'-cyclohexylurea.

The dyes are isolated from the reaction mixture in the customary manner by filtration. The filtration is advantageously carried out at temperatures between 50 and 120 ° C. It may prove expedient to firstly mix the reaction mixture with organic liquids, such as alcohols, e.g. Methanol, ethanol, isobutanol; lower carboxylic acid amides, such as formamide or dimethylformamide, or aromatic hydrocarbons, such as toluene or chlorobenzene. In order to remove any traces of unreacted perylene tetracarboxylic acid or its dianhydride which may still be present, the dyes can be boiled out with dilute sodium hydroxide solution or sodium carbonate solution. If desired, the dyes can also be purified by fractional precipitation from sulfuric acid.

55

Compared to the perylene tetracarboxylic acid bis-p-bromoanilide known from DT-OS 2 120 207, the new dyes, with otherwise comparable properties, have a significantly better absorbency on cellulose fibers. This unpredictable color behavior of the new dyes is essential for technical application.

The process products (1) according to the invention are also pigments. The dyeings obtained have good properties, such as high color strength, light fastness, solvent fastness and plasticizer fastness. They are therefore suitable for coloring paints, resins, printing inks and for mass coloring plastics.

In some cases, the raw dyes obtained in the synthesis can be used directly as pigment dyes. As a rule, the tube dyes will be converted into pigment forms by methods known per se. Such measures include the conversion into a finely divided form by grinding or by reprecipitation from sulfuric acid and, if appropriate, a subsequent recrystallization in water, organic solvents or mixtures thereof at elevated temperature into consideration.

5

620 698

Despite the possible use of the dyes as pigments, their preferred application is in the vat field.

The following examples are intended to explain the invention further. The parts and percentages relate to the weight.

The formulas belonging to the examples are shown on the drawing sheets. Example and formula numbers match.

example 1

8.0 parts of crystallized zinc acetate dehydrate, 11.8 parts of perylene-3,4,9,10-tetra-carboxylic acid and 20 parts of N-p-chlorophenyl-N'-p-aminophenylurea are introduced into 220 parts of quinoline at 100 ° C. While passing a weak stream of nitrogen, the mixture is heated to 220 to 230 ° C. and held at this temperature until a worked-up sample, boiled with dilute soda solution, no longer indicates any perylene tetracarboxylic acid. This is the case after 5 hours. After cooling to about 100 ° C is filtered, the residue washed with quinoline, then with methanol and then with water. The 20 filter material is stirred with about 250 parts of 2% aqueous sodium carbonate solution, heated to 95 ° C., filtered and washed until the filter material is neutral. Traces of any perylene tetracarboxylic acid still present are removed. 21 parts of a red-violet dye are obtained. 25th

Example 2

5.7 parts of zinc acetate dihydrate, 8.6 parts of perylene-3,4,9,10-tetracarboxylic acid dianhydride and 15 parts of Np-aminophenyl-N-methyl-N'-p-chlorophenylurea are dissolved in 165 parts of quinoa-30 lin under a weak nitrogen stream heated to 220 ° C.

After stirring for 4 1/2 hours at this temperature, a sample worked up according to Example 1 no longer shows any unreacted perylene tetracarboxylic acid. The mixture is cooled to about 100 ° C., 300 parts of methanol are added and the mixture is worked up as described in Example 1 35. You get 12 parts of a reddish-black. zen powder.

Example 3

4.3 parts of zinc 40-acetate dihydrate, 7 parts of perylene-3,4,9,10-dicarboxylic acid dianhydride and 11 parts of Np-aminophenyl-N'-cyclohexylurea are added to 120 parts of quinoline at 100 ° C. and added under one weak nitrogen stream stirred at 200 to 220 ° C for 5 hours. Then a sample no longer shows any free perylene tetracarboxylic acid. After cooling to 90 to 100 ° C, 250 parts of methanol are added and the procedure is as in Example 1. Yield: 9 parts of a dark, red powder.

Examples 4 to 39

The procedure is as described in Example 1 and in A parts of quinoline B parts of perylenetetracarboxylic acid dianhydride are reacted with C parts of the amines given in the table, see drawing sheets Nos. 1 to 6, Examples 4 to 39, in the presence of D parts of zinc acetate dihydrate (reaction time: E hours), the corresponding dyes are obtained in good yields. The dyes dye cotton from the vat in the colors specified in column F.

Example of use a) 30 parts of the dye obtainable according to Example 8 are dissolved in 600 parts of 96% sulfuric acid at 0 to 5 ° C. Then you drop on a mixture of water and ice, whereby a temperature of 10 ° C is not exceeded. After filtering and washing neutral with water, the filter material is sucked tightly together and an aqueous dye paste with a dye content of about 17% is obtained.

b) 118 parts of the dye dough obtained according to a) (17%) are processed with 64 parts of a solvent-free, soybean oil-modified alkyd resin and 16 parts of bis-ethylhexyl phthalate on a three-roll mill with 6 passages at 60 atm by flushing to a solid paste.

c) 66 parts of binder, obtained by mixing 70 parts of solvent-free alkyd resin modified with soybean oil, 17.5 parts of bis-ethylhexyl phthalate and 12.5 parts of a solvent-free melamine resin, are mixed with 30 parts of titanium dioxide (rutile) and 4 parts of a colloidal Silicon dioxides are grinded on the three-roll mill at 60 atm with 6 passages to a titanium dioxide paste.

d) 0.4 part of the full-tone paste produced according to b) and 5 parts of the titanium dioxide paste produced according to c) are mixed and triturated on a plate grater. This color paste is used to produce a paint spread that is baked at 120 ° C for 45 minutes. A clear red color is obtained.

6 sheets of drawings

Claims (3)

620 698 2nd PATENT CLAIMS 1. Process for the preparation of dyes of the perylene-3,4,9,10-tetracarboxylic acid diimide series of the formula 1 n (i), in the Z for a radical of the formula bonded in the 3- or 4-position of the rings A. Phenyl stands, where the substituents can be the same or different. 4. The method according to claim 1, characterized in that one uses amines of formula 4, in which Z in ; the 4-position to the amino group. 5. The method according to claim 1, characterized in that amines of the formula 4 are used in which n = 0 and Z is a group of the formula -NH-C -NH-R4 to the amino group in the 4-position II O in which R4 is 3-chlorophenyl, 4-chlorophenyl, 3-chloro-4-methylphenyl, phenyl, cyclohexyl or methyl and both R4 are the same. N-C-N \ R2 R3 R1 O a saturated 5-, 6- or 7-membered heterocy- is in which R1 and R2 each represent a hydrogen atom or the same or different alkyl having 1 to 4 carbon atoms, 25 R3 is a hydrogen atom, alkyl having 1 to 8 carbon atoms, cycloalkyl having 6 to 8 carbon atoms, phenyl, naphthyl or phenyl substituted by Cr to C4-alkyl, methoxy, ethoxy, chlorine, bromine or fluorine, the number of substituents on the phenyl is 1 or 2 and the substituents may be the same or different, or the group / R2 N \ \ R3 clical ring, which may additionally contain -O-, - S— or a further —N— as a 35 ring member, Y represents alkyl having 1 to 4 carbon atoms, chlorine, bromine, fluorine, methoxy or ethoxy, where the radicals Y can be the same or different, and n represents the numbers 0, 1 or 2, in which case n = 2 in w each of the rings A may only have one Y in the 2- or 6-position, by condensation of perylene-3,4,9,10-tetracarbonic acid or its dianhydride with substituted phenylic amines in inert, higher-boiling solvents or diluents in of heat, characterized in that 45 amines aminophenylureas of the formula 4