DE1569759A1 - Perylene series dyes and process for their preparation - Google Patents

Description

FARBENFABRiKENBAYERAG ^1569759

LEVERKUSEN·

Pfy / Τ ©

Perylenrel dyes and process for their preparation

The present invention relates to dyes of the perylene series of the general formula

ff \ VV = /

in which R stands for hydrogen, an optionally substituted alkyl, cycloalkyl, aralkyl or aryl group and R, an optionally substituted alkyl, cycloalkyl, aralkyl or aryl group or an alkoxy group or a heterocyclic radical and d @ r further - may have substituents,

as well as a ¥ ai ^r fsh £ »en ad äoVQzi manufacture.

BeTOL "- ^: .-,;. '.. c- Γι-Γ'ϋ ^' -: .- ^ ί i .: ^ L · ^ a & üsi such dsl ³ general · Ρο: & ά :. {! /. , w ^ i: i Π Ur wac ^ epstoff stands and R ₁ die

toi ti »* J1-, '= -.

ÄGfe « _it > ife X--

Hydroxy groups, alkoxy groups, alkoxycarbonyl groups, carbonamides or may have sulfonamide groups. Alkylgruppeη of the mentioned Type are, for example, methyl, ethyl, propyl, butyl, methoxy-ethyl, ethoxyethyl, methoxycarbonylethyl or ethoxy carbonyl ethyl groups.

Cycloalkyl groups that may be mentioned in particular are cyclohexyl and cyclopentyl groups.

Aralkyl groups that may be mentioned are, in particular, benzyl groups and the benzyl groups substituted by alkyl groups in the CH «group, the phenyl radicals optionally being further Substituents such as halogen, for example fluorine, chlorine or bromine, nitro groups, hydroxyl groups, alkoxy groups, in particular Solohe with 1-4 carbon atoms, carbonamide groups or sulfonamide groups, alkoxycarbonyl groups, especially such bits 1-4 carbon atoms, as well as alkyl groups, in particular those with 1-4 carbon atoms, may have.

Particularly suitable aryl groups are phenyl groups and naphthyl groups as well as residues of the anthraquinones called, these residues Substituents such as halogen, for example fluorine, chlorine or bromine, nitro groups, hydroxyl groups, alkoxy groups, especially those with 1-4 carbon atoms, alkoxycarbonyl groups, in particular those with 1-4 carbon atoms, carbonateid groups or suIf on-

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may have amide groups.

As heterocyclic radicals are in particular those of Thiazole-, Benzimidazole-, Benzoxazole- »Benzthiazole-, SuIfolan-, Triazole, pyridine, quinoline, quinoxaline and the Called the phthalimide series.

Examples of substituents in the perylene radical are halogen atoms such as chlorine or bromine * alkoxy groups, especially those with 1-4 carbon atoms, such as methoxy groups, xthoxy groups, or butoxy groups, as well as nitro groups or hydroxyl groups in Question.

The new dyes of the formula (I) are prepared by reacting optionally substituted perylene-jJ.4.9.10-tetr & carboxylic acids or their acid derivatives with compounds the general formula

V ₂ (II)

or their salts,

in which R and T ^ have the meaning given above in a molar ratio of about 1: 2.

Acid derivatives are understood to mean, in particular, acid anhydrides, acid chlorides and acid esters. It is of course also possible to use those perylene derivatives which

at the same time carboxylic acid groups and functional ones. Derivatives of

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Have carboxylic acid groups, for example anhydride groups, ester groups or acid chloride groups.

Suitable for the preparation of the dyes of the formula (I) Perylene compounds are, for example, perylene-O.A. ^ lO-tetracarboxylic acid, Perylene-O. ^. O / .lO-tetracarboxylic acid dianhydride, dichloroperylene-j3.4.9.10-tetracarboxylic acid, Tetrachloro-perylenjj. 4.9.10-tetracarboxylic acid, dichloroperylene-3.4.9.10-tetraearboxylic acid dianhydride, Tetrachloroperylene - ^^. G.lO-tetracarboxylic dianhydride, Dimethoxy-perylene-3.4.9.10-tetracarboxylic acid and Dime thoxy-perylene-3.4.9.10-tetracarboxylic acid dianhydride.

Suitable compounds of the formula (II) are the following: ß-cyanoethyl hydrazine, ß-hydroxyethyl hydrazine, hydrazinocarboxylic acid ethyl ester, 1,1-dimethylhydrazine, 2-chlorophenylhydrazine, 3-chlorophenylhydrazine, 4-chloro-phenylhydrazine, 2,4-dichloro-phenylhydrazine, 2,5-dichloro-phenylhydrazine, 2,6-dichloro-phenylhydrazine, 2-nitrophenylhydrazine, ^ -Nitro-phenylhydrazine, 2,4-dinitro-phenylhydrazine, 2-chloro-4-nitro-phenyinydrazine, 4-chloro-j5-nitro-pheny! Hydrazine, o-tolylhydrazine, m-tolylhydrazine, p-tolylhydrazine, 2-methoxyphenylhydrazine, 3-methoxyphenylhydrazine, 4-methoxyphenylhy4razia, 2-methoxy-5-methyl-phenylhydrazine, 4-hydrazino-benzoic acid araid, 3-hydrazino-benzenesulphonic acid amide, 4-hydrazino-benzenesulphonic acid amide, 1-hydrazino-anthraquinone, 2-hydrazino-thiazole, 4-methyl-2-hydrazino thiazole, 4-phenyl-2-hydrazino-thiazole, 4,5-diniethyl-2-hydra2inothiazole, 2-hydrazino-benzimidazole, 2-hydrazino-5-sulfonaeido »benzimidazole, 2-hydrazinobenzoxazole, 2-hydrazinobenzothiazole, 6-carbon

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BATH ORIGINAL

amido-2-hydrazino-benzothiazole, 6 »ethoxy-2-hydrazino-benzothiazole, jJ-hydrazino-suxfolan, 3-hydrazino-1,2,4-triazole, 2-hydrazinopyridine, 2-hydrazino-quinoline, 2-hydrazino-4 = methyl-quinoline, 2-hydrazino-pyrimidine, 2-hydrazino-ehinoxaline, 4-hydrazinophthalimide, 4-hydrazino-phthalic acid-N-methylimide.

The reaction of components I and II is carried out at ordinary or erhöntem pressure by heating the starting materials at temperatures of 100-300 ⁰ C, preferably 15O 24ö ° C, optionally in the presence of solvents and / or diluents such as chlorinated hydrocarbons, for example chlorobenzene, D "icniorbenzoi, triculobenzoi, chlorotoluenes, chloronapnthalins or higher-boiling heterocyclic bases such as quinoline or pyridine. An addition of acidic condensation salts such as ηκho- or cadmium salts, for example zinc chloride or zinc acetate and the corresponding cadamium acid, phosphoric acid, and hydrochloric acid, sulfuric acid, as well as hydrochloric acid proves to be advantageous $ phoric acid #

The new properties obtainable by the process according to the invention Bia violet dyes are valuable pigment dyes and fall in high yield in the process described above in mostly crystalline form. You stand out for being good Heat resistance, solvent fastness, migration fastness, overcoating fastness, light fastness, hone color strength, clarity and Brilliance of the color shades and are therefore suitable, if necessary after conversion into a finely divided form, for coloring Lacquers and plastics and for the manufacture of printing inks

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and pigment pastes. For example, they are also used for spin dyeing suitable for synthetic fibers.

The parts mentioned in the following examples are components.

\ Example 1;

10 T »i £ t Perylene 3.4.9» ^ and 11.4

Parts of phenylhydrazine - ^ - sulfonic acid aflild hydrochloride are ^{stirred in 60 parts of quinoline at 20O 0} C for 4 hours. After it has cooled down, it is suctioned off, the residue level is boiled with water,

'h "ifl vacuumed, washed with ethanol and dried" Man j receives «inen leuai) $ itncl red color to f f.

j 10 part * of the dye thus obtained »by grinding in a

Ball mill old 120 parts of sodium chloride and washing out the

Salad bowl »finely divided, become all one! Stoving enamel made of 25 parts Kolcosölalkydharz (* 0% coconut oil), 10! Parts of melanin resin, 5 parts of toluene and 7 parts of Olykolmonome thy lather rubbed on an automatic Hoover-Muller grinding machine. Man carries the mixture to be painted backing up, curing the paint by baking at 130 ⁰ C and gets: brilHftnte red coatings with very good light, Uberlackier- / and weather resistance ·.

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Example 2;

10 parts of perylene - ^^. ^ LO-tetracarboxylic acid dianhydride and 8.6 parts 2-Nitro-pheny! Hydrazine in 50 parts of quinoline are 4 hours corrugated at 180 C. After the cold it is suctioned off, the filter residue is boiled with ethanol, suctioned off while hot and dried. A red dye is obtained.

A mixture of 65 parts of polyvinyl chloride, 35 parts of di-isooctyl phthalate, 2 parts of dibutyl tin mereaptide, 0.5 part of titanium dioxide and 0.5 part of the above dye, which can be obtained by milling Sodium chloride was brought into a fine distribution, is colored on a mixing roller mill at 105 ° C. You get one red-colored mass, which is used for the production of foils or moldings can serve. The colorations are characterized by high light and MifT »ation center.

example Ii '

10 parts of Perylen-J.JJ.SMO-tetracarboxylic acid dianhydride and 8.3 parts 2-hydrazino-benzimidazole are quinoline in 30 parts for 4 hours Stirred l60 ° C. After cooling, it is suctioned off, the filter residue is boiled out with ethanol, suctioned off and dried. Nan contains a red dye which, when incorporated into plastics, results in dyeings with high migration and lightfastness.

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Example 4;

IC parts Ferylfcii -.. ^ ^^ lO-tetracarboxylic dianhydride and 9.2 parts of 2-hydrazino ~ beii2, tfiiazül are stirred for 4 hours at 200 ^c C in 50 parts of quinoline. After cooling, it is suctioned off, the filter residue is boiled with Ätirianoi, suctioned off while hot and dried. A red dye is obtained which gives organic paints colors of very good overcoating and lightfastness.

Example 5t

10 parts of perylene-3 « ⁱ + .9.10-tetracarboxylic dianhydride and 9 parts of 2-hydrazino-quinoxaline are stirred in 50 parts of quinoline for 4 hours at 220.degree. After cooling, it is suctioned off, the filter residue is boiled up with ethanol, suctioned off while hot and dried. A red dye with good fastness properties is obtained.

Example 6t

10 parts of perylene-jJ ^^. 10-tetracarboxylic dianhydride and 8.} parts 3-hydrazino-bulfolan are quinoline in 50 parts for 4 hours Stirred at 180 ° C. After cooling down, the filter residue is sucked off boiled out with ethanol, filtered off with suction while hot and dried. Man receives a red dye with good fastness properties.

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GINAL

Γ Λ Π T Γ

h h M / hi

Example 7s

10 parts perylene = 5 "'^" 9 <> 10 = fcetracarbonsäur @ diariii3rdr-i <i and 4 · 3 parts of 2-Hydrazinoäthanol are stirred for 4 hours at 200 ⁰ C in 50 Teilao quinoline "After cooling, extracted the filter residue is treated with ethanol boiled "sucked hot and dried. A purple-tinged red dye with good fastness properties is obtained in good yield »

Example 8;

10 parts of perylene - ^. ^. ^ LO-tetracarboxylic acid dianhydride and 5.8 parts Ethyl hydrazine carboxylates are stirred in 50 parts of quinoline at 10 ° C. for 5 hours. After cooling down, the Filter residue boiled with ethanol, suctioned off while hot and dried. A purple-tinged red one is obtained in good yield Dye with good fastness properties,

If, instead of Hydrazincarbonsäureäthylester the hydrazines listed below * is obtained at reaction temperatures of l60 »200 ° C and reaction times of 3 - ^ - Sturiden also red pigment dyes with good Eöhfeheitseigenschaften _B The numbers in parentheses indicate the G@vjj.chtst" eil @ ά <&τ> hydrazine derivatives to which 4 tetracarboxylic anhydride have been reacted with 10 ßeviichtteile-en o

ie a 11 uv j 9 cnr? ' ^s ί / π482

2-chloro-phenylhydrazine (8), 3-chloro-phenylhydrazine (8), 4-chloro-phenylhydrazine (8), 2,4-dichloro-phenylhydrazine (10), 2,5-dichloro-phenylhydrazine (10), 2 , 6-dichloro-phenylhydrazine (10), 2,4-Dlnitro-phenylhydrazine (11.1), o-tolylhydrazine (6.9), m-Toly.lhydrazin (6,9) "p-tolylhydrazine (6.9 ) » 4-methoxyphenylhydrazine (7 * 8), 3-hydrazino-benzenesulphonic acid amide (11 ** 0 * 4-hydrazino-benzoic acid amide (8.4), 1-hydrazino-anthraquinone (13.2), 2-hydrajsino ^ bertzimidazo 1 (8, ^), 2-hydrazino-benzoxazole (8, J), 2-hydrazino-benzothiazole (9,3), 2-hydrazino-pyridine (6,1), 2-hydrazino-4-methyl-quinoline (8.4).

Example 9t

10 parts of perylene-3 «4.9.10-tetracarboxylic acid dianhydride and 6.1 parts of 2-hydrazino-pyrimidine are ^{stirred in 75 parts of trichlorobenzene at 210 °} C. for 4 hours. After cooling, the residue is filtered off with suction, the PilttrrUckstand boiled with ethanol, filtered off with suction while hot and dried. A red dye of excellent lightfastness and very good paint and migration fastness is obtained.

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Claims (9)

1 Γ Γ "- Π / 1. ^ Dyes of the Psrylenrelhe general in white R for hydrogen an optionally substi · = tuierte -Alkyl- · =, C ^ eioailq / i ^ Äraüsyi.- or / is ^ igs'iipp «stands and R, a rf plane if substituted alkyl =;, cycloalkyl,. Araikyl- or Arylf, ruppe or an alkoxycarbonyl group or means a heterocyclic radical and the can have further substitutes α 2. Process for the preparation of dyes of general formula r; TC- /, λ- / Λ-c ο- y vy in white F for hydrogen, an optionally substituted one Alkyl, cycloalkyl, aralkyl or aryl group and R, an M-e ^ likewise substituted alkyl, cycloalkyl, Aralkyl or aryl group or an alkoxycarbonyl group or denotes a heterocyclic radical and the perylene radical can have further substituents, gekennzeicnnet that optionally in the perylene radical PeK ', ylen-3. ^ C9 ° 10-tetracarboxylic acids having substituents LeA, 107C-υ " 009822 / 0A62 / Il or their acid derivatives with compounds of the general formula ^R l \ R- ^N - ^NH 2
or their salts, in which R represents hydrogen, an optionally substituted alkyl, cycloalkyl, aralkyl or aryl group and R _{1 represents} an optionally substituted alkyl, cycloalkyl, aralkyl or aryl group or an alkoxycarbonyl group or a heterocyclic radical, in a molar ratio of about 1: 2. 3. The method according to claim 2, characterized in that one carries out the reaction at temperatures of about 100-300 ⁰ C. K. The method according to claim 2, characterized in that the reaction is carried out in the presence of solvents and / or diluents. 5. The method according to claim 2, characterized in that the reaction is carried out in the presence of solvents and / or diluents as well as acidic condensing agents. 6. A method for coloring paints, plastics and for the production of printing inks and pigment pastes, characterized in that that one uses those of claim 1 as the dye. 7. Paints, plastics, printing inks and pigment pastes colored with or containing dyes of claim 1. Le A 11 ü7C -12- 009822/0462 8. Reaction products of optionally substituted perylene-> .4.9'10-tetracarboxylic acids or their acid derivatives with compounds the formula or their salts, in which R stands for hydrogen, an optionally substituted alkyl, cycloalkyl, aralkyl or aryl group and R, an optionally substituted alkyl, cycloalkyl, aralkyl or aryl group or an alkoxycarbonyl group or means a heterocyclic radical. 9. Reaction products from 1 mole of an optionally substituted one Perylene-3.4.9.10-tetracarboxylic acid or its acid derivatives with about 2 moles of a compound of the formula R ₁ or their salts, in which R stands for hydrogen, an optionally substituted alkyl, cycloalkyl, aralkyl or aryl group and R, an optionally substituted alkyl, cycloalkyl, aralkyl or aryl group or an alkoxycarbonyl group or means a heterocyclic radical. Le A 11 over 70 - 13 - 009822/0462