CH430001A - Process for the production of chromium-containing reactive dyes - Google Patents

Description

  

  Process for the production of chromium-containing reactive dyes. The present invention relates to a process for the production of new chromium-containing reactive dyes.



  It has been found that new valuable chromium-containing reactive resins can be obtained by reacting a chromium-containing dye of the formula I,
EMI0001.0021
         in A1 a radical free of reactive groups:

  the benzene or naphthalene series, B a radical of the benzene, naphthalene or pyrazole series free of reactive groups, where A1 and B contain the oxygen -O Je in the = o-position to the azo bond,

       n is a positive whole number of at most 3 and A2 one of reactive groups: free sulfated radical; the benzod or N, a phthalene series, which in addition to sulfonic acid group:

  en does not contain any other -ionogenic-n substituents, and the benzene ring D can also contain lower alkyl and alkoxy groups, with:

  converts a compound which donates the radical Z to a chromium-containing reactive dye of the formula II,
EMI0001.0073
      in the one given for Al, B, n, A2 and D Idas under formula I anld Z is a fiber-reactive group (means,

         which contains at least one substituent which can be split off as an anion or at least one multiple bond capable of addition.



  If A1 and B are a residue of the naphthalene series, this is either bonded to the azo group in the 1 position and to the -O atom in the 2 position, or vice versa.



  If B is a residue of the pyrazole series, it is primarily the residue of a 1-:

  Arylhpyr- azoles, in particular 1- # phenyl-3-methylpyrazole, which is bonded to the azo group in the 4-position and to the -O- atom in the 5-position.



  If A means one; The rest of the naphthalene series, see above. it can be a 1- or a 2-naphthyl radical. A2 preferably denotes a sulfated radical of the benzene series free of reactive groups,

      which contains no other ionic substituents besides sulfonic acid groups.



       The aromatic rings of Al, B and A can, within the scope of the definition, contain common substituents in azo resins, for example lower alkyl groups such as methyl, ethyl or Itert. Bloodyl group, lower alkoxy groups,

          such as the methoxy or ethoxy group, halogens such as fluorine, chlorine or bromine, sulfonic acid and acid groups, lower alkylsulfonyl groups or the nitro group.



       The radical A2 N = N in the benzene ring D advantageously occupies the p-position, -O- to the oxygen, and the benzene ring D contains no further substituents.



       The fiber-reactive group Z contains primarily mobile halogen atoms, preferably chlorine, or also Bronn, and fluorine, whose mobility, for example, depends on the bond to a- or,

  ss carbon atoms in negatively substituted aliphatic radicals, to the S02 group in the case of fluorine the (the presence of electrophilic substituents in the o- or / and p-position in aromatic <RTI

   ID = "0002.0159"> residues or (the presence of tertiary ring nitrogen atoms in heterocycles of aromatic character, in this case preferably 61-membered heterocycles with at least two tertiary ring nitrogen atoms.



  As mobile substituents (which can be split off as anions, there are also hydroxyl groups esterified with strong acids of aliphatic radicals electrophilic substituted in the ss-position,

      For example, ß-hydroxyalkylsulfonyl and suäamyl groups esterified with sulfuric acid ..



  A multiple bond capable of addition is, for example, the -C = C or -C = C group located in the vicinity of an electrophilic group;

       Examples of groups capable of addition are the vinyl sulfone group, the acroyl or methacroyl radical, and the remainder of propidyl acid.



  Accordingly, Z denotes, for example, the radical of aliphatic halocarboxylic acids, such as the radical of chloric or bramessaic acid, β-chloro or β-bromopropionic acid, α or β-chloro or -Bromoacrylic acid, the a,

  ss- dichloric or a, ss d-diibromoacrylic acid, a.- or ss-chloro or bromerotonic acid, a, ss-dichlorocrotonic acid, chloro- or bromomaleic acid, or fumaric acid. qder the rest of the fluoro-nitro:

  or chloro-nitro-benzene-canboxylic acid or the fluorine-nitro-moder chloro-nitro-benzoxulfonic acid, in which the fluorine lbzw. Chlorine atom is in o- or / and p-position to the nitro group or groups.



       Advantageously, Z denotes the radical of a cyclic imide halide of carbonic acid which is directly or via a -CO;

  group is connected to the -NH-igruppe, in particular at least one mobile halogen atom. containing triazinyl or diazinyl radical, for example a chlorine or bromine @ srtriazinyl radical,

      as another. Substituents Halqgen, the primary or a secondary amino group, an alkoxy, alkylthio, phenoxy or phenyl group can contain;

          In particular, Z denotes the di- or trichloro or di- or tribromo-Ipyrimidylrest, or then the remainder of the 2,4-dichloro-Ipyrimidine 6-, carboxylic acid or 2,3-dichloroquinoxaline-6-carboxylic acid.



  The starting material of Formula 1 is obtained, for example, by converting a complex chromium compound of Formula IH
EMI0002.0325
    with a metallizable amine indisazo dye of the formula IV
EMI0002.0330
    in what formulas. Al, B, A2,

      D and n halve the meaning given in formula I.



  The components of the formulas III and IV are expediently reacted in an aqueous solution at a pH of approximately 4 to 8 and at an elevated temperature of around 70 to 20 ° C.

       The output product of the formula I obtained in this way can in some cases be isolated with a residue Z without being isolated. Connection can be implemented directly.



       All compounds (which give off the remainder of Z) are the halides: the carboxylic and sulphanic acids mentioned in the discussion of Z, in particular 2,4-dichloropyrimidine 6@canb.onsäureahlorid and above all more than one mobile Halogen atom, halogen triazines and diazines,

          especially tetrachloropyrimidine.



  The reaction of the chromium-containing dye of formula I with the compounds giving the fiber-reactive radical Z albumin takes place in the usual way, expediently in an aqueous medium, optionally in the presence of inert, easily removable,

          organic solvents such as lower aliphatic ketones, for example acetone, and preferably in the presence of mineral acid blunting agents such as sodium or potassium carbonate, sodium or potassium acetate or tertiary nitrogen bases such as pyridine.



  The new chromium-containing 2: 1 complexes of formula II can in some cases be salted out, but in most cases it is necessary to concentrate the aqueous solution to dryness,

      to isolate the final product. They represent dark powders: represent, are in the form of their alkali salts;

  very well soluble in water and stains cellulose material such as rayon, yurt, ramie, hemp and especially cotton, as well as fiber material containing polyamides, for example natural, such as wool and silk, or synthetic, such as nylon,

      in brown-black to green-black shades.



  These materials are colored with: the dyes obtainable according to the invention: by known methods. The cellulose material is impregnated or printed, for example, at a low temperature, such as at 20 to 50 C,

   with the optionally thickened dye solution and then fixes the dye by treating with acid-binding agents.

   Sodium carbonate, potassium carbonate, di- and trisodium phosphate, sodium hydroxide solution, for example, and, at temperatures above 50 ° C., potassium or sodium bicarbonate can also be considered as such.

   The treatment with these agents can take place at room temperature or at an elevated temperature. Instead of subjecting the impregnated fabrics to an alkaline post-treatment,

   In many cases, the acid-binding agent can also be added to the impregnation liquors or and the development of the color can then be brought about by brief heating to temperatures above 100 C to 16.0 C or by prolonged storage at room temperature.



       Treatment with acid-binding agents makes the new dyes chemical. bound to the fiber. The cellulose stains are excellent after soaping, as the unfixed dye can be washed out very easily.



       Natural polyamide fibers are used in hot, weakly acidic, for example acetic acid, baths in the presence of auxiliaries that improve the uniformity of the dyeing, such as fatty acid-alkanolamine polycondensation products, as well as;

  optionally colored in the presence of salts such as sodium chloride or sodium sulfate. Synthetic polyamide fibers are expediently: dyed in a hot acidic bard, then rinsed and treated in a boiling alkaline bath.



  The dyes obtainable according to the invention give very deep colorations and are therefore particularly suitable for producing deep black tones.



  In the following examples, unless otherwise noted, parts mean

       Parts by weight. The temperatures are given in degrees Celsius. Parts by weight are related to parts by volume as g is to cms.
EMI0003.0151
           119 parts of the chromium complex of Formei
EMI0004.0005
    apply as the sodium salt in 7.00 parts. Water of 80 neutral <RTI

   ID = "0004.0012">; dissolved and reacted with 23 parts of 2,4,5,6-tetrachloropyrimidine while stirring at this temperature. The pH is kept between 5.5 and 6 by adding caustic soda.

   After the reaction has ended, the reaction mixture is cooled to 40 ', the reaction solution is clarified by filtration and the filtrate is concentrated to dryness in vacuo. A dark powder is obtained which dissolves very easily in water.



  The starting dye for the above process is obtained by using the known chromium complex compound of the formula
EMI0004.0052
         in neutral or: weakly alkaline solution at 80 to 9.0 with equivalent parts of the mexallisable disazo dye of the formula
EMI0004.0061
    implements.

         Wind cotton with an 8% aqueous solution of the same dye, which also contains 5% urea and 2% sodium carbonate, ibel 50 padded,

          then at 80, dried, then steamed for 5 to 10 minutes and soaped at the boil, the result is a washfast, deep black color.



       Dyes with similar properties are obtained if the chromium complexes listed in the table below in column II are mixed with those in column IH:

  The above-mentioned compounds releasing the remainder of Z in the case of Aden in column IV converts the temperature values noted and otherwise proceeds as indicated in the example. Column IV:

  indicates the color tones of the dyeings on blue wool of the corresponding reactive dyes.
EMI0005.0001
  
    <I> table </I>
<tb> I <SEP> II <SEP> III <SEP> <B> IV <SEP> V </B>
<tb> No.

   <SEP> Chvomkomplex <SEP> the <SEP> rest <SEP> Z <SEP> Tempe- <SEP> color tone
<tb> sending <SEP> connection <SEP> ratur <SEP> on
<tb> cotton
<tb> p
<tb> <B> H03S <SEP> N = N </B>
<tb> 0 \ <SEP> / 0 <SEP> GI <SEP> j <SEP> GI
<tb> Gr
<tb> <B> 0 @ <SEP> \ 0 <SEP> NH2 <SEP> H </B> <SEP> <SEP> <B> N <SEP> 0-50 <SEP> stichi </B>
<tb> g
<tb> <B> Y </B> <SEP> black
<tb> / <SEP> <B> N = N </B> <SEP> / <SEP> <B> \ <SEP> GI </B>
<tb> <B> H03S <SEP> S03H </B>
<tb> <B> H03S <SEP> N = N </B>
<tb> <B> S03H </B>
<tb> e.
<tb> <B> H03S </B> <SEP> \ <SEP> / <SEP> <B> N = N </B>
<tb> GI <SEP> COGI
<tb> 0 \ / Gr @ O <SEP> <SEP> N \ <SEP> N <SEP> 0-5 <SEP> bl:

  au <B> 0 / <SEP> 0 <SEP> NHZ <SEP> H </B>
<tb> key
<tb> 3 <SEP> @ <SEP> w @
<tb> GI
<tb> / <SEP> <B> N = N </B> <SEP> /
<tb> <B> H03S <SEP> S03H </B>
<tb> <B> H03S </B>
<tb> <B> N = N </B>
<tb> SO <SEP> 3H
EMI0006.0001
  
    <I> <U> Table <SEP> (continued) </U> </I>
<tb> I <SEP> II <SEP> III <SEP> IV <SEP> V
<tb> No.

   <SEP> Cheom complex <SEP> the <SEP> rest <SEP> Z <SEP> Tempe- <SEP> color tone
<tb> sending <SEP> connection <SEP> ratur <SEP> on cotton
<tb> <B> N02 <SEP> CH3 <SEP> O </B>
<tb> <B> \ <SEP> N = N </B>
<tb> O @ C @@ O <SEP> SU3H <SEP> <SEP> CI- @ CH2 <SEP> G <SEP> H2 <SEP> <B> _ </B> COCI
<tb> 0 / <SEP> \ 0 <SEP> NH2 <SEP> H <SEP> <B> 0-Jr </B> <SEP> blue cast
<tb> black
<tb> / <SEP> N = N <SEP> / <SEP> \
<tb> II <SEP> \ <SEP> H035 <SEP> \ <SEP> / <SEP> 503H
<tb> N
<tb> S03H
<tb> <B> N02 <SEP> H035 <SEP> 503H </B>
<tb> N = <SEP> N <SEP> \ <SEP> / <SEP> GI
<tb> 0 <SEP> 0 <SEP> <B> NH </B> -CO <SEP> n \ <SEP> @ <SEP> Cl <SEP> / <SEP> C @ <SEP> <B> YI </B>
<tb> C <SEP> H <SEP> N
<tb> N <SEP> 80-90 <SEP> green <SEP> <B> <I> 5 </I> <SEP> 0 <SEP> 0 </B> <SEP> NH2 <SEP> <B> GI </B> <SEP> black
<tb> <B> S03H </B> <SEP> / <SEP> <B> N = N </B>
<tb> \
<tb> <B> N </B> <SEP> H035 <SEP> S03H
<tb>

  <B> -N </B>
<tb> 503H <I> Table. </I> (continued) I II IIi IV V No. Chromium complex the remainder of the Z Tempe color-releasing compound on cotton N02 H035 503H \ IN == N \ I / er Br < B> 0 0 </B> NH-CO \ <B> NN </B> r H 80-90 green- \\ stichi 0 @

  _0 NH2 8r black <B> 503H </B> / <B> N </B> -N / <B> I \ </B> H035 503H <B> N = N </B> S0'3H <B > N02 </B> CH3 / H03S ... \ -N == N- 0 \ I \ / 0 \\ G. 3 Cr I / N OGH H 7 N 'Z # 2, N 20-30 black <B> 0 </B> NH2 <B> GI </B> <B> S03H </B> -N- N H035 S03H S03H

 

Claims (1)

PATENT CLAIM Process for the production of chromium-containing reactive dyes, characterized in that a chromium-containing dye of the formula I, EMI0008.0011 in the A, . a radical of the benzene or naphthalene series free of reactive groups, B a radical of the benzene, naphthalene or pyrazole series free of reactive groups, where A ,. and B contain the oxygen -O- each in the .o position to the azo bond, n is a positive whole number of not more than 3%, and Aa is a sulfated radical of the benzene or napkin series which is free of reactive groups and which, besides sulfonic acid groups, contains no other ionic substituents, and the benzene ring D can still contain lower alkyl and alkoxy groups, with a compound donating the radical Z to form a chromium-containing active dye of the formula II, EMI0008.0062 in ider for Al, B, n, A2 and D the given under formula I applies and Z denotes a fiber-reactive group which has at least one; as an anion: Contains adaptable substituents or at least one multiple bond capable of addition. SUBCLAIMS 1. Process according to patent claim, characterized by the use of a chromium-containing dye of the formula I in which the radical Az -, N = N- San B.enzolkern D occupies the p-position to the -O atom and the benzaking D has no further substituents. contains. 2. A method according to claim and sub-claim 1, characterized by the use of a chromium-containing dye of the formula I, in which A2 is an isolated radical of the benzene series which is free from reactive groups, which contains no other ionogenic substances besides sulfonic acid groups. 3. The method according to claim and sub-claims 1 and 2, characterized in that as, the compound releasing rice Z uses a cyclic imide halide of carbonic acid. 4. The method according to claim and sub-claims 1 to 3, characterized in that: that 2,4-dichloropyrimidine-6-carboxylic acid chloride or tetraahlorpyrimidine is used as the compound which releases the radical Z.