CH448339A - Process for the production of dyes - Google Patents

Description

  

      Process for the preparation of dyes The invention relates to a process for the preparation of dyes of the formula
EMI0001.0004
    wherein F is the radical of a dye, the radicals A, B, D and E are identical or different, optionally substituted and optionally containing heteroatoms, R is the radical -CO-X- or -X-CO-, X is the group -NH - or an oxygen atom, m is 0 or a lower, whole number and n is one of the numbers 1 or 2, which is characterized by

   that one mole of an amino dye of the formula
EMI0001.0013
    with n mol of a functional derivative of a dicarboxylic acid of the formula HOOC-A-COOH (III) and then with n mol of a hydroxy compound of the formula HO-B- (R-D) m R-E (IV).



  Functional derivatives of a dicarboxylic acid of the formula (III) are, for. B. the esters or anhydrides and especially the halides.



  As dyes, those of the most varied classes can be used, e.g. B. mono-, dis- or polyazo dyes, which can be metallizable or metallized, nitro, dioxazine, quinophthalone, perinon, thiazine or perylene dyes and preferably anthraquinone dyes. The dye residues can carry any substituents.

   Substituents which do not render water-soluble, eg. B. hydroxyl groups, optionally substituted alkoxy groups, halogen atoms, optionally substituted aryl, amino or alkylamino:

  groups or hydroxyaryl, alkoxyaryl or haloaryl groups. The anthraquinone dyes in particular can contain fused iso- or heterocyclic rings, preferably 5- or 6-rings.

   Some preferred anthraquinone dyes are as follows: 1-amino-anthraquinone; 1,4-; 1.5-; 1,6-; 1,7- or 1,8-diaminoanthraquinone; 1-amino-4-hydroxy-anthraquinone; 1-amino-4-methoxy-anthraquinone; 1-amino-3-, -4-, -5-, -6-, -7- or -8-chloro-anthraquinone; 1-amino-6,7-dichloro-anthraquinone; 1-amino-4-, -5- or -8-benzoylamino-anthraquinone;

          1-amino-5,8-di-benzoyl-amino-anthraquinone; 1,5-diamino-4-hydroxy-anthraquinone; 4-amino-1,9-isothiazole-anthrone; 1,5-diamino-4,8-dihydroxy-anthraquinone; 1-amino-2-methyl-anthraquinone; 2-bromo-1,4-diamino-anthraquinone; 1,4-diamino-2-methoxy-anthraquinone; 1-amino-4- or -5-phenyl-amino-anthraquinone;

          1-amino-4- or -5- (2 ', 4', 6'-trimethyl) -phenyl-amino-anthraquinone; 1-amino-4- (4'-chloro) -phenylamino-6-chloro-anthrachinone; 1-amino-4-p @ henyl-mercapto-anthraquinone; 1-amino-4- (4'-, 3'- or 2'-chloro) phenyl mercapto-anthrachinone; 1-amino-4- (4'-, 3'- or 2'-methyl) -phenyl-mercapto-anthraquinone; 1-amino-4- (1'-naphthyl) - mercapto-anthraquinone;

          1- (4'-amino) -phenyl-amino-anthraquinone; or dyes of the formulas
EMI0002.0001
    Azo dyes containing amino groups can be z.

   B. Monoazo dyes of the Hansa yellow G type or the naphthol-A-S-red type, the coupling component of which contains the reactive amino group on an aryl radical, preferably phenyl radical, attached via a carbonamide group, in the para position.

   Furthermore, disazo dyes from tetrazotized 4,4'-diamino-diphenylene, in particular 3,3'-dihalo-4,4'-diamino-diphenylene, and acylacetyl-amino-benzenes with an amino group in the para position of the benzene nucleus.



  The radicals A, B, D and E are to be understood as meaning any optionally substituted and optionally containing heteroatoms, the radicals A, B and D having two free valences and the radical E having one free valence. Substituents which do not render water soluble are preferred, e.g. B. halogen, nitro, low molecular weight alkyl or low molecular weight alkoxy. Preferred radicals A are e.g. B.

    phenyl radicals which are optionally substituted one or more times by halogen or low molecular weight alkyl and unsaturated in the 1- and 4-positions, in particular phenylene, 2-chlorophenylene or 2,5-dichlorophenylene, naphthylene radicals with unsaturated 1- and 4-positions Position, diphenylene radicals whose 4- and 4'-positions are not saturated,

       Azobenzene residues with free valences in the 4- and 4'-position or pyridine residues with free valences in the 2- and 5-position. As radicals B or D come z.

   B. phenylene which is optionally substituted one or more times by halogen or low molecular weight alkyl and which has free valences in the 1- and 4-positions, as well as alkylene optionally substituted by hydroxyl or alkoxy groups or halogen atoms, eg. B. -CH. CH.-, -C1.-CHü-CH. and also
EMI0002.0068
    into consideration. Preferred residues E are e.g. B.

    optionally by haloene, low molecular weight alkyl. Low molecular weight alkoxy or nitro mono- or polysubstituted alkyl radicals with 1-6 carbon atoms, especially the methyl, ethyl, propyl or butyl radical, cycloalkyl radicals, especially the cyclohexyl radical, phenyl radicals, especially the phenyl radical,

       a fluorophenyl, chlorophenyl or bromophenyl radical, dichlorophenyl radical, a methylphenyl radical and di- or trimethylphenyl radical, a methoxyphenyl radical, di- or trimethoxyphenyl radical, or heteroxyclic radicals, for example the furan radical or the pyridine radical.



  To prepare the new dyes one can proceed so that one z. B. glycol with a benzoylating agent on one side benzoylated or z. B. 2-aminoethanol or 4-amino-1-hydroxybenzene benzoylated with a benzoylating agent on the amino group. n moles of the chain obtained are then introduced into the condensation product which is obtained when one in a dye of the formula
EMI0003.0002
    the n-amino groups with z.

   B. terephthalic acid or one of its functional derivatives, e.g. B. a mono- or di-ester or the mono- or dihalide, condensed.



  The preferred benzoylating agent is benzoyl chloride; but other benzoylating agents can also be used, e.g. B. 4-chlorobenzoyl chloride, 3,4-dichlorobenzoyl chloride, 4-methylbenzoyl chloride, 4-bromobenzoyl chloride, 3-chlorobenzoyl chloride, 4-methoxybenzoyl chloride, 4-benzoylamino-benzoyl chloride, etc.



  The acylation or amidation or esterification reaction is preferably carried out in a diluent, e.g. B. an aromatic, optionally halogenated or nitrated hydrocarbon, an ether or an optionally substituted acid amide, at temperatures between about 80 and 160 C, made.

   It is advantageous to add an acid-binding agent, for example pyridine, trimethylamine, sodium carbonate or sodium bicarbonate.



  If the dyes produced in this way do not contain any water-solubilizing groups, they are valuable pigment dyes. You can in suitable Maschi nen, such as roller mills or mills, optionally with the addition of dispersants, eg. B. condensation products from naphthalenesulfonic acids and form aldehyde, processed into commercial pigment dough. These can, for. B. by atomization, dry. They are valuable for pigmenting semi-synthetic or fully synthetic plastic compounds, natural or synthetic resins or their solutions, natural or synthetic rubber or paper. The plastic compounds include, for.

   B. those made from esterified cellulose, for example cellulose 21/2 acetate, triacetate or nitrocellulose; Furthermore, polymers or copolymers formed by condensation, addition or polymerization from low molecular weight compounds, e.g. B. polyolefins, polystyrene, polyvinyl chloride, polyamides, linear or crosslinkable polyesters, polycarbonates, polyurethanes or polyacrylic nitriles.

    



  They are also suitable for pigmenting natural binders, e.g. B. of starch, alginates, tragacanth, British gum, crystal gum, locust bean gum or of collagens, such as gelatin.



  Spinning masses can also be pigmented with dyes of the formula (I) or with pigment preparations which contain dyes of the formula (I). Spinning masses are solvent-based or solvent-free, semi-synthetic and fully synthetic substances that are spun into textile fibers, e.g.

   B. viscose, cellulose esters such as cellulose 21 /, - acetate or triacetate, linear aromatic polyesters, in particular polyethylene terephthalate, synthetic polyamides, for example polycondensation products from amino carboxylic acids or from dicarboxylic acids and diamines or polylactams, or polyolefins, eg. B. polypropylene.



  The dyeings obtained are distinguished by their color strength, thermal stability, chemical resistance, and migration and lightfastness.



  The parts mentioned in the examples are parts by weight. The temperatures are given in degrees Celsius.



  <I> Example 1 </I> 30 parts of terephthalic acid dichloride are dissolved in 150 parts of anhydrous nitrobenzene, and 10 parts of finely divided 1-aminoanthraquinone are gradually added at 70-80 parts with stirring. The temperature is maintained at 70-80 until aminoanthraquinone is no longer detectable, then cooled to 30, stirred for a further 2 hours, the precipitate is filtered off and washed with anhydrous nitrobenzene to remove the unreacted terephthalic acid dichloride.

   The residue is then suspended in 150 parts of nitrobenzene and 11 parts of 2-benzoylaminoethanol and 5 parts of pyridine are added. The reaction mixture is heated to 140 and allowed to react at 140 for 5 hours with stirring. It is then filtered at 140, the residue is washed first with nitrobenzene, then with ethanol and finally with water and dried at 100.



  10 parts of the dye obtained are boiled in 200 parts of dimethylformamide for 1 hour. It is allowed to cool to 20, the dye is filtered off, washed with dimethylformamide and then with water. After drying, a dye is obtained which, further processed by one of the customary methods for pigment production, dyes polyvinyl chloride in yellow shades that are fast to migration.



  <I> Example 2 </I> According to Example 1, 10 parts of the condensation product of 1 mole of 1-amino-4-benzoylamino-anthraquinone and 1 mole of terephthalic acid dichloride are added to 11 parts of 2-benzoylamino-ethanol was prepared according to Example 1, act in 200 parts of nitrobenzene at 130-140. The dye obtained is a red pigment that is fast to migrate.



  <I> Example 3 </I> In 150 parts of anhydrous nitrobenzene, 30 parts of terephthalic acid dichloride are dissolved and 15 parts of 1-amino-4-phenylmercapto-anthraquinone are gradually added at 70-80 degrees with stirring. The temperature is maintained at 70-80 until no more amine can be detected, cooled to 20, stirred for a further 16 hours, the precipitate is filtered off and washed with anhydrous nitrobenzene to remove excess terephthalic acid dichloride. The filter cake is then suspended in 150 parts of nitrobenzene, and 11 parts of 2-benzoyloxyethanol and 5 parts of pyridine are added.

   The reaction mixture is heated to 150 and allowed to react at 150 for 5 hours with stirring. The dye is then filtered off at 150, washed first with nitrobenzene, then with ethanol and finally with water, and dried at 100.



  10 parts of the dye obtained are boiled in 200 parts of dimethylformamide for 1 hour. It is allowed to cool to 20, the precipitate is filtered off, washed with dimethylformamide and then with water. After drying, a dye is obtained which is further processed by one of the customary methods for pigment production and colors polyvinyl chloride in red shades that are fast to migration.

 

Claims (1)

PATENT CLAIMS I. Process for the preparation of dyes of the formula EMI0004.0001 wherein F is the radical of a dye, the radicals A, B, D and E are identical or different, optionally substituted and optionally heteroatoms containing hydrocarbon radicals, R is the radical -CO-X- or -X-CO, X is the group -NH- or an oxygen atom, m is 0 or a lower, whole number and n is one of the numbers 1 or 2, characterized in that that one mole of an amino dye of the formula EMI0004.0010 with n mol of a functional derivative of a dicarboxylic acid of the formula HOOC-A-COOH (III) and then with n mol of a hydroxy compound of the formula HO-B-M-D) m R-E (IV). II. Use of the dyes according to claim I for coloring plastic compositions.