CH585778A5 - Sulphonated azo cpd. prodn. from (1-di)-sulpho-aryl-pyrazole - by coupling with diazotised trifluoromethyl-aniline and use as dyes - Google Patents

Abstract

Prodn. of sulphonated azo cpds. of formula A-N-B (I) is described) where A is of formula R is H, halogen, or CF3. R1 is OH, NH2 or -NHSO2R4.R2 is H, alkyl or alkoxy. R3 is opt. halogen-, alkyl- or alkoxy -substd. diphenylyl, naphthyl or tetrahydronaphthyl, pref. a naphthyl gp. with only the So3H substits. R4 is alkyl or opt. substd. phenyl). The process involves coupling a diazo cpd. of an amine of the formula A-NH2 with a coupling component of the formula H-B. Cpds. (I) are used for dyeing or printing non-textile organic materials, esp. leather and paper. (I) can also be used for dyeing substrates dyed by anionic dyes, e.g. natural or synthetic polyamides, basic modified fibres (polypropylene, polyurethane, polyvinyl alcohol) and natural or regenerated cellulose. They give bright (greenish) yellow shades. In an example, (I) was prepd. by coupling diazotised 1-amino-4-chloro-2-trifluoromethylbenzene with 1-(2'-naphthyl)-3-methyl-5-aminopyrazole-6',8'-disulphonic acid.

Description

  

  
 



   The main patent relates to a process for the preparation of compounds of the formula
EMI1.1
 where R is hydrogen or halogen, Rs is OH, NH2, -OSO2R4 or -NHSO2R4, R2 is hydrogen, an optionally substituted alkyl or alkoxy radical, R3 is a phenyl, naphthyl or tetrahydronaphthyl radical which is optionally substituted by halogen, alkyl or alkoxy, R4 is an optionally substituted one Hydrocarbon radical, m 0 or 1, n 0 or 1 and m + n 1 or 2, that is, compounds with one or two sulfo groups are prepared according to the invention, where a sulfo group is present either in the diazo component or in the radical R3 located, and if two sulfo groups are present, the diazo component and the radical R3 each carry a sulfo group.



   As an extension of the main patent, the subject of the present additional patent is a process for the preparation of analogous compounds which contain two sulfo groups in the radical R3, according to the formula
EMI1.2
 where R is hydrogen, halogen or trifluoromethyl, R1 is OH, NH2 or -NHSO2R4, R2 is hydrogen, alkyl or alkoxy, R3 is phenyl, diphenylyl, naphthyl or tetrahydronaphthyl and R4 is alkyl or optionally substituted phenyl, characterized that one can produce a diazo compound from an amine of the formula
EMI1.3
 on a coupling component of the formula
EMI1.4
 coupling, the compounds of the formula (I) prepared by the process and their use.



   Halogen generally represents fluorine, chlorine, bromine or iodine, of which chlorine is preferred.



   Alkyl radicals contain z. B. 1-12, advantageously 1-6, preferably 1, 2, 3 or 4 carbon atoms and can be linear or optionally branched and / or cyclized.



  The alkoxy radicals preferably contain 1, 2, 3 or 4 carbon atoms.



   Preferred compounds of the formula (I) are those in which R 1 denotes NH 2. R2 preferably represents linear alkyl having 1-4 carbon atoms, in particular methyl. R3 preferably stands for a naphthyl radical which is further unsubstituted by the sulfo groups. The radical R4-SO2- advantageously represents the acyl radical of an optionally substituted benzenesulfonic acid, preferably an alkylbenzenesulfonic acid, e.g. B. benzene, toluene, xylene, ethylbenzene, n-hexylbenzene or iso-octylbenzenesulfonic acid.



   When R denotes CF3, the two trifluoromethyl groups are preferably in the meta or para position to one another. Preferred compounds of the formula (I) correspond to the formula
EMI2.1
 where R'3 denotes a naphthyl radical which, apart from the sulfo groups, carries no further substituents.



   The diazotization of the compounds of formula (II) he follows by customary methods, advantageously in a strongly acidic, preferably sulfuric or hydrochloric acid medium at low temperatures, for. B. 0-30 "C.



   The coupling is also carried out by customary methods.



   It is preferable to work in an aqueous reaction medium, specifically for compounds in which Ro is OH, in an alkaline, neutral or acidic medium, for compounds in which R is NH2 or -NHSO2R4, preferably in an acidic medium, e.g. B. in the temperature range from -10 "C to +80" C, preferably between 0 and +30 "C.



   The compounds of formula (I) are normally obtained in the form of the free acid, but can optionally, e.g. B. with neutral or alkaline coupling, also in the form of the corresponding salts.



   The compounds of the formula (I) are anionic dyes and can be used for dyeing substrates which can be dyed with anionic dyes; they are mainly used for dyeing by any suitable method, e.g. B. after the exhaust process, or for padding or printing natural polyamides, such as wool and silk or synthetic polyamides, such as. B. Various types of nylon; also of basic modified fibers, such as. B. base modified polypropylene fibers or polyurethane fibers or polyvinyl alcohols, and also natural or regenerated cellulose.



  The dyes can also be used advantageously for dyeing leather or paper.



   The compounds of the formula (I), colored on the substrates mentioned, have a brilliant yellow to greenish yellow shade and, especially on polyamides, such as. B. nylon, generally good light fastness and good wet fastness, such as good wash, water, sea water and perspiration fastness; They also have good neutral drawability, good build-up capacity and can be easily combined with other anionic dyes with comparable properties. The dyes according to the invention also cover the streakiness of streaky nylon fabric.



   In the following examples, the parts are parts by weight, the percentages are percentages by weight; the temperatures are given in degrees Celsius.



  example 1
9.8 parts of 1-amino-4-chloro-2-trifluoromethylbenzene are introduced into 75 parts of 65/0 sulfuric acid and the mixture is cooled to zero. At this temperature, 3.45 parts of sodium nitrite, dissolved in 12 parts of water, are added dropwise over a period of 30 minutes. A solution consisting of 19.2 parts of 12'-naphthyl> 3.methyl-5.aminopyrazole-6 ', 8'-disulfonic acid, dissolved in 100 parts of water with the addition of 3.0 parts of sodium carbonate, is within half a Added to the diazo solution at 0-5 "for one hour, during which time the dye precipitates. The pH is then adjusted to 2.5-3.0 with the aid of an aqueous sodium hydroxide solution.

  The precipitate is filtered off, washed with a 5% sodium chloride solution and dried.



   The dye obtained corresponds to the formula
EMI2.2
  and dyes wool and synthetic polyamide fibers in pure, greenish yellow shades with good lightfastness and good wetfastness.



   The table below lists further dyes of the formula (I) which can be prepared according to Example 1 and are characterized by the compounds of the formulas (II) and (III) used and the shade of the dye on nylon.



   Table Ex. Amine of the formula Coupling component shade of no. (II) of the formula (III) Coloring on nylon 2 1-amino-3,5-1 2'-naphthyl> 3-greenish tinged bis (trifluoromethyl-5-aminopy - Yellow ethyl benzene razol-6 ', 8'-disulphonic acid 3 1-amino-chloro-142'-naphthylS3- greenish tint
2-trifluoromethyl-5-aminopy-yellow ethylbenzene razol-1 ', 5'-disulphonic acid 4 1-amino-6-chloro-12'-naphthyl3-greenish tint
3-trifluoromethyl-5-aminopy- yellow ethylbenzene razol4 ', 8'-disulphonic acid 5 1-amino-3-tri- 1 <2'-naphthyl-3-greenish fluoromethylbenmethyl-5-aminopy- yellow zol razol-5 ', 7'-disulphonic acid staining instructions
In one of 4000 parts of water,

   10 parts of anhydrous sodium fullate and 2 parts of the dye from Example 1 are introduced into 100 parts of pre-wetted nylon cloth (nylon 66) at 40.



   The dye liquor is heated to boiling temperature over the course of 30 minutes, kept at this temperature for 1 hour, 4 parts of glacial acetic acid are added and dyeing is ended by heating to boiling temperature for a further 30 minutes. During the dyeing process, the evaporated water is continuously replaced. Then take the green-tinged yellow nylon cloth from the liquor, rinse it with water and dry it. Wool can also be dyed using the same procedure. The dyeings have good light fastnesses and good wet fastnesses.

 

Claims (1)

PATENT CLAIMS I. Process for the preparation of sulfonic acid group-containing azo compounds of the formula EMI3.1 wherein R is hydrogen, halogen or trifluoromethyl, R1 is OH, NH2, - NHSO2R4, R2 is hydrogen, alkyl or alkoxy, R3 is phenyl, diphenylyl, naphthyl or tetrahydronaphthyl and R4 is alkyl or optionally substituted phenyl, characterized that one can produce a diazo compound from an amine of the formula EMI3.2 on a coupling component of the formula EMI3.3 clutch. II. The compounds of the formula (I) prepared by the process according to claim I. III. Use of the compounds of the formula (I) according to claim II for dyeing or printing non-textile organic materials. SUBCLAIMS 1. The method according to claim I, characterized in that compounds of the formula EMI3.4 where R'3 denotes a naphthyl radical which, apart from the sulfo groups, bears no further substituents 2. Use according to claim III, characterized in that leather is dyed. 3. Use according to claim III, characterized in that paper is dyed