DE2512516C2 - Perylene-3,4,9,10-tetracarboxylic acid ester - Google Patents

Description

The invention relates to new Peryien-S ^ iMO-tetracarboxylic acid esters, their production and their use as dyes.
The new perylene-3,4,9,10-tetracarboxylic acid esters have the formula

(D

OK

RO-C C-OR

O O

in the one or 2 R for hydrogen and the other. R or all R for alkyl, chloroalky !, hydroxyalkyl, each with 1 to 10 carbon atoms in the alkyl radical, alkoxyalkyl with a total of 3 to 8 carbon atoms, cyanoethyl, j5- (carbolkoxy) ethyl with a total of 4 to 8 carbon atoms , Dialkylaminoalkyl with a total of 4 to 8 carbon atoms, phenalkyl with 7 to 10 carbon atoms or phenyl in which 1 or 2 Η atoms are substituted by alkyl with 1 to 4 carbon atoms, methoxy, ethoxy, chlorine and / or bromine can be, X stands for chlorine or bromine and η stands for a number between 0 and 8 and where the radicals R can be identical or different.

The new Perylenetetracarbonsäureester dye synthetic and semi-synthetic fiber material, such as Fibers made of polyamide, cellulose ester, polyacrylonitrile, especially those made of linear polyesters in brilliant colors Yellow to red tones.

DE-AS 1806403 discloses the use of perylene-3,4,9,10-tetracarboxylic acid or its dianhydride known for pigmenting paints and plastics. In this application, the pigment stays in The form of the fine pigment particles is obtained so that bluish red colorations result, which are more or less are opaque. The prior art pigment is applied to polyester fiber material from an aqueous bath not on.

In contrast, the peryl egg; -3,4,9,10-tetracarboxylic acid esters of the present invention color polyester fiber material from an aqueous bath in brilliant yellow to red tones.

As substituents R, for. B. possible linear or branched alkyl with 1 to 10 carbon atoms: methyl, Ethyl, propyl, butyl, i-butyl, pentyl, hexyl, n-octyl, 2-ethylhexyl, decyl;

Alkoxyalkyl with 3 to 10 carbon atoms: jJ-Methoxyäthyl ^ -Äthoxyäthyl, jß-Butoxyäthyl, y-Methoxy ^ opyl, y-Äthoxypropyl, y-butoxypropyl, ./H/f-AthoxyJ-athoxy-athyl;

Hydroxyalkyl with 2 to 6 carbon atoms: ^ 8-hydroxyethyl, γ-hydroxypropyl, δ-hydroxybutyl, ω-hydroxyhexyl;
Haloalkyl with 2 to 4 carbon atoms: jß-chloroethyl, j ^ chloropropyl:

Dialkylamino-alkyl with a total of 4 to 8 carbon atoms: jß-dimethylaminoethyl, ^ - diethylaminoethyl;
jS-Carboalkoxyäthyl with 4 to 8 C-atoms: ^ Carbomethoxyäthyl.jS-Carboäthoxyäthyl ^ -Carbobutoxyäthyl; Phenyl such as benzyl, β-phenylethyl, as phenyl optionally substituted by chlorine, bromine, lower alkyl, methoxy and / or ethoxy: phenyl, 4-methylphenyl, 3-methylphenyl, ethylphenyl, 4-tert.-butylphenyl, 3- or 4- Chlorophenyl, 3- or 4-bromophenyl, 3- or 4-methoxyphenyl, 4-ethoxyphenyl.

For use as dyes for dyeing synthetic fiber material are dyes of the formula (I), in which one or two R is hydrogen and the remaining 3 or 2 of the radicals R are methyl, ethyl, phenyl or Denote methylphenyl, particularly preferred.

Dyes of the formula la are used for mass coloring of thermoplastics

OR'OR 'O = C C = O

(Ia)

20th

25th

30th

35

40

45

50

55

60

65

preferred in which R 'and R "are methyl, ethyl, benzyl, methylphenyl, phenyl and / or methoxyphenyl, β- hydroxyethyl, X is chlorine or bromine and π are the numbers 0 to 4 or 6 to 8. Particularly preferred are Dyestuffs of the formula Ia in which one R 'and R "each represent the same substituent.

The dyes color polystyrene in bright yellow to red shades. The dyeings have high lightfastness

The perylenetetracarboxylic acid esters of the formula (I) are, for. B. obtained if you click on the corresponding perylenetetracarboxylic dianhydride Lets alkali alcoholates or alkali phenolates act, the S & Ize of the half-esters being formed with cleavage of the dianhydride. Subsequent alkylation of the salts of the half esters with an alkylating agent in the presence of bases, the tri- and tetraesters of perylenetetracarboxylic acid are obtained.

The alkylating agents are those commonly used, such as dialkyl sulfates, dialkyl sulfites, alkyl halides, Acrylonitrile, acrylic acid alkyl ester into consideration. Specifically, for example, are to be mentioned: dimethyl sulfate, diethyl sulfate, Dipropyl sulfite, methyl iodide, methyl bromide, benzyl chloride, methyl acrylate.

The amount of alkylating agent will be measured according to whether tri- or tetraester or mixtures thereof be desired. For the preparation of tetraesters is usually at least 2 mol, preferably 3 to Use 6 moles of alkylating agent per mole of perylene tetracarboxylic acid. The amount of alkylating agent is also depending on whether the alkylating agent is lighter or slower with the base present in excess reacted. The amount of base and in particular of alkylating agent required in the individual case can easily be can be determined by simple preliminary tests.

The reaction of the perylenetetracarboxylic dianhydride with the alkali metal alcoholate or phenolate is carried out expediently in the corresponding alcohols or preferably in aprotic solvents.

Aliphatic, monohydric or dihydric alcohols such as those with 1 to 4 carbon atoms, e.g. Methanol, propanol, isopropanol, ethanol, butanol, ethylene glycol, propylene glycol can be considered. Preferably However, if aprotic solvents such as aromatic hydrocarbons, aromatic halogenated hydrocarbons are used, Nitrobenzene, carboxylic acid dialkylamides, phosphoric acid alkylamides or mixtures thereof. Nitrobenzene, trichlorobenzene, dimethylformamide, dimethylpropionic acid amide and N-methylpyrrolidone are particularly preferred as a solvent.

After the end of the alkylation, the reaction mixture is cooled and diluted with cold water and, if appropriate, ice. The suspension obtained is made slightly alkaline with dilute sodium hydroxide solution and _{stirred for a further 2} to 1 hour, any excess alkylating agent that may be present being saponified. The ester is then in the usual manner, for. B. by filtration, separated and washed neutral.

The Perylenetetracarbonsäureester can also by transesterification z. B. obtained from the methyl or ethyl esters. For this purpose, the ester is dissolved in an excess of the desired alcohol and the mixture is heated ^{to 80 to 200 ° C. for a long time in the presence of a small amount of acid as a catalyst.} The course of the reaction can be followed by chromatography or spectroscopy (nuclear resonance).

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

example 1

392 parts of perylenetetracarboxylic dianhydride are made into a paste with 3000 parts of N-methylpyrrolidone and 216 parts of sodium methylate (in the form of a 30 percent strength by weight solution in methanol) are added while mixing. The mixture is stirred at 40 to 50 ^° C. for 30 minutes. 400 parts of dimethyl sulfate are then added and the mixture is stirred at 40 to 50 ° C. for 2 hours. The reaction mixture is cooled to 0 to 1O ⁰ C, cautiously diluted with 60 to 80 parts of water and ice and rendered weakly alkaline with 2 N sodium hydroxide. It is felt for 30 minutes, then the precipitate is filtered off with suction and washed neutral with water.

Yield: 380 parts of perylene O ^ JO-tetracarboxylic acid tetramethyl ester.

The dye dyes fiber material made of linear polyesters in brilliant yellow shades.

The same result is obtained if the N-methylpyrrolidone is replaced by the same amount of hexamethylphosphoric acid triamide replaced.

Example 2 to 6

The procedure given in Example 1 is followed, using per doc! <Instead of the perylene tetracarboxylic acid chloro- or bromoperylene tetracarboxylic acid and the equivalent amount of the sodium salt of the alcohol R-OH and the corresponding alkylating agent, then one obtains tetraesters of the formula (I) in which X, R and η have the meaning given in the table. The esters obtained dye fiber material made of linear polyesters in the shades given in the table.

60 example X η 2 Cl 1.5 3 Cl 1.5 65 ₄ Cl 4th 5 Cl 7.5 6th Cl 7.5

Color shade on polyester CH ₃ yellow C ₂ H ₅ yellow CH ₃ greenish yellow CH ₃ yellow C ₂ H ₅ golden yellow

Example 7

210 parts of chloro-perylene O ^^. 10-tetracarboxylic acid anhydride (X = CIj,) are mixed ^{with 320 parts of potassium tert-butoxide in 250 parts of N-methylpyirolidone at 40 1} C, then 400 parts of hyaroxypropionitrile are added and the mixture 1 Stirred at 40 to 50 ^° C. for an hour.

Is added to 216 parts of triethylamine and leaves at 20 "C ¹ 500 parts of dimethyl sulfate are added dropwise. The processing takes place as described in Example 1.

Yield: 223 parts of the ester of the formula:

CN-CH ₂ -CH ₂ -O-CO

CO-CH ₂ -CH ₂ -CN

Example 8

275 parts dibromo-perylene-OA ^ lO-tetracarboxylic anhydride are added in 270 parts of N-Methylpyrrolidonangeteigt, under agitation with 320 parts of potassium tert-butoxide and 400 parts of jS-hydroxypropionitrile was added over 45 minutes and 1 hour at 40 to 5O ⁰ C touched.

Then 250 parts of triethylamine and then 500 parts of dimethyl sulfate are added at 20.degree. The mixture is stirred at 40 to 50 ° C. for 1 hour. The reaction mixture is cooled and diluted with ice / water. It is made weakly alkaline by adding 2N sodium hydroxide solution. The ester is filtered off with suction and washed with water.

The yield: 235 parts of the ester of the formula:

CH ₃ OO NC-CH ₂ -CH ₂ OC

Example 9

25 parts of the sodium salt of p-cresol are added to 22 parts of dichloroperylenO ^^ 10-tetracarboxylic anhydride in 220 parts of N-methylpyrrolidone at 40 "C. It is then diluted with 100 parts of water, then 36 parts of triethylamine are added and 55 parts are slowly allowed of dimethyl sulfate are added dropwise. the mixture is stirred for 1 hour at 40 to 50 ⁰ C and overnight at room temperature, then it is mixed with 440 parts of ice, filtered off with suction acetate and washed with water. After drying under reduced pressure at 80 ⁰ C is obtained 8 Parts of the ester with X = Cl, which is a mixture of η = \ and 2:

CH ₃

M.p.

nl; 2
«= U

Example 10

To 14.13 parts of dibromoperylene-S ^^. LO-tetracarboxylic acid anhydride and 150 parts of N-methylpyrrolidone are ^{tert at 40 0} C 14 parts. Potassium butoxide dissolved in 30 parts of glycol was added. The mixture is stirred for 1 stand at 40 to 50 t, then 7.2 parts of triethylamine are run in and then 30 parts (corresponding to 8 moles per mole of acid)

Slowly add dropwise dimethyl sulfate. It is stirred for 1 hour at 40 to 50 ⁰ C and then overnight at room temperature. A lot of ice water is added, the mixture is made slightly acidic and filtered off with suction. After drying under reduced pressure at 80 °, 11 parts of the dye are obtained

HO-CH ₃ -CHjO-C

Br ₂

Examples 11 to 16

If the procedure is as indicated in Examples 7 to 10, but the alkali metal salts used are those of the R ' Lugiuüueltcgcfiucn alcohols or phenols and elkylieri the so crhaitcricn diester with dimethyl or diathy! - sulfate, the corresponding mixed tetraesters of ferylenetetracarboxylic acid are obtained:

From the starting material, perylene-3,4,9,10-tetracarboxylic acid was used in all cases, the mean 1.5 Contains chlorine atoms.

example

R '

R "

Coloring on polyester

11th

CH ₂ -

30 12

-CH ₃

-CH ₃

yellow

orange

13th

14 16

example -C ₂ H ₅ 17th orange HO-CH ₂ -CH ₂ - -CH ₃ golden yellow H ₃ CO - <\ ~~ S— -C ₂ H ₅ golden yellow HO-CH ₂ -CH ₂ - -C ₂ H ₅ golden yellow

72 parts of a 30 percent sodium methylate solution in methanol are added at 40 to 50 ° C. to the suspension of 39 parts of perylene OA ^ 10-tetracarboxylic acid anhydride with 1.5 chlorine atoms in 300 parts of N-methylpyrrolidone. The mixture is stirred for 1 hour at 40 to 50 ° C. and then 600 parts of ice are added. The mixture is then made slightly acidic with dilute hydrochloric acid, and the ester is filtered off with suction and washed with plenty of water. After drying under reduced pressure at 80 ¹ C, 34.1 parts of the diester of the formula are obtained

OCH ₃

C-OH

Example 18

Tetracarboxylic acid lO-To a suspension of 39 parts of perylene-S ^^ that an average of 1.5 chlorine atoms carries (= 1 mole), in 300 parts of N-methylpyrrolidone are added at 40 to 5O ⁰ C 4 Moi Natriumphenoiai and stirred for 3 hours at 50 to 60 ⁰ C after; then add ice and dilute with water. The suspension is then made slightly acidic, the diester is filtered off and washed neutral with water. Yield 45 parts of the diester of the formula

Il

HO-C

Cl ,,

η = 1.5

Coloring on polyester: red

Example 19

The procedure is as in Example 18, but using the equivalent amount of the instead of sodium phenolate Sodium salt of p-cresol, the diester of the formula is obtained in practically the same yield

H ₃ C

CH ₃

The diester stains fiber material made of linear polyesters in red shades.

Examples 20 to 28

The procedure described in Example 17 is repeated, but the sodium salt of the radical R is used Alcohol. After decomposition with ice, however, the alkaline solution / suspension is given to the Radical R to corresponding alkylating agents (dimethyl or diethyl sulfate). The amount (2 to 6 moles) will be determined by how many carboxyl groups should not be esterified.

When the reaction has ended, the suspension is made slightly acidic and the ester mixture is filtered off and washed neutral. Mixtures of di- and triesters or Tn- and tetraesters of perylenetetracarboxylic acid are obtained.

example

η (mean)

Mixture of

Coloring on polyester

Cl Cl Cl Cl

Cl Cl

Ci Cl

Br

Cl

1.5

2.5

1.5

1.5

7.5

2 6.5

2 6.5

(CH ₃ ),
(CH ₃ ), H and yellow (CHj) ₃
(CH ₃ ), H and yellow (CH ₃ ),
(CHj), 2H
H and orange (CHj),
(CHj), H and yellow (C ₂ Hs) ₃ 2 H
H and Orange red (CH ₃ ) J.
(CH ₃ ), H and yellow (CH ₃ ), H orange (CHj) ₂ 2H and orange (CR ₁ ) I. H orange (CHj) ₃
(CH ₃ ), H and yellow-orange

Example 30

0.05 parts of the dye obtained according to Example 1 are dry-mixed with 100 parts of ground polystyrene block polymer in a drum mixer. The mixture is melted at the temperature of a screw press at a Zylin-5 from 200 to 250 ⁰ C and homogenized. The colored plastic mass is granulated by hot knocking on the nozzle head. The granulate obtained in this way is then injected into shaped bodies in an injection molding device at 200 to 250 ° C. or pressed into any desired bodies on presses. Bright yellow injection molded parts with excellent lightfastness and fluorescent in a similar hue are obtained.

10 Example 31

0.5 part of the dye from Example 8 is mixed with 100 parts of granulated butadiene / styrene block polymer and 1 part of titanium dioxide. The mixture is melted in a screw press at 220 to 250 ^° C. and homogenized. The colored mass is granulated by drawing it into threads with cooling. The granules obtained in this way are pressed into molded bodies. Bright yellow colored compacts with very good lightfastness are obtained.

Claims (6)

Patent claims: 1. Perylene-3,4,9,10-tetracarboxylic acid ester of the formula
OO I! Il RO-C C-OR RO-C C-OR O O in the one or 2 R for hydrogen and the other R or all R for alkyl, chloroalkyl, hydroxyalkyl, each with 1 to 10 carbon atoms, alkoxyalkyl with a total of 3 to 8 carbon atoms, cyanoethyI, _ /? - (carbalkoxy) -ethyl with a total of 4 to 8 carbon atoms, dialkylaminoalkyl with a total of 4 to 8 carbon atoms, pbenalkyl with 7 to 10 carbon atoms or phenyl in which 1 or 2 H atoms are replaced by alkyl with 1 to 4 carbon atoms, Methoxy, ethoxy, chlorine and / or bromine can be substituted, X stands for chlorine or bromine and η stands for a number between 0 and 8 and where the radicals R can be identical or different. 2. Perylene-3,4,9,10-tetracarboxylic acid ester of the formula according to claim 1, in which R is methyl, ethyl, propyl, Butyl, j8-hydroxyethyl, y-hydroxypropyUjS-methoxyäthyl, jS-ethoxyethyl,) * - methoxypropyl, y-ethoxypropyl, Benzyl, j3-phenylethyl, phenyl, methylphenyl, methoxyphenyl, chlorophenyl or bromophenyl, X for Chlorine or bromine and π are 0 to 4 or 6 to 8 and the radicals R are the same or different can. 3. Perylene-3,4,9,10-tetracarboxylic acid ester according to Claim 1 of the formula O = C C = O R "O OR" in the R 'and R "for methyl, ethyl, benzyl, methylphenyl, phenyl, methoxophenyl, j3-hydroxyethyl, X for Chlorine or bromine and η stand for 0 to 4 or 6 to 8 and where R 'and R "can be identical or different. 4. A process for the preparation of PerylenO ^^. LO-tetracarboxylic acid esters according to claim 1, characterized in that characterized in that PerylenO ^^ JO-tetracarboxylic anhydride in the presence of at least 2 mol of the alkali metal salt of the hydroxyl compound of the formula RAW converts to the half ester and optionally after the addition of further alkali metal salts of lower ones Alcohols the alkali salts of the half esters in the presence of 4 to 10 moles of an alkylating agent per mole Perylenetetracarboxylic anhydride alkylated. 5. Use of the PerylenO ^^. LO-tetracarboxylic acid esters according to claim 1 for dyeing synthetic fibers and cellulose esters from an aqueous bath. 6. Use of the perylene-3,4,9,10-tetracarboxylic acid esters according to Claim I for the mass coloring of thermoplastic Plastics.