Patent Publication Number: US-5428141-A

Title: Azo dyestuffs containing fluorotriazinyl and vinylsulfonylmethyl-type reactive groups

Description:
The invention relates to new azo reactive dyestuffs containing a monofluorotriazinyl and vinylsulphonyl reactive radical. It is true that combinations of reactive components are disclosed in EP-A-94,055, EP-A-85,025, EP-A-65,732, US-A-4,730,038 and EP-A-307,817, but this prior art still presents problems in terms of practical application. 
     The present invention relates to mono and disazo reactive dyestuffs which, as the free acid, have the formula (1) ##STR3## in which Y denotes CH═CH 2 , CH 2  CH 2  OSO 3  H or CH 2  CH 2  Cl, 
     R denotes H or C 1  -C 3  -alkyl, which may be substituted by OH, CO 2  H or CN, in particular CH 3 , C 2  H 5 , C 3  H 7 , CH 2  CH 2  OH, CH 2  CH 2  CO 2  H, CH 2  CO 2  H or CH 2  CH 2  CN, 
     Z denotes H, C 1  -C 4  -alkyl or C 1  -C 4  -alkoxy, in particular CH 3 , C 2  H 5 , OCH 3 , OC 2  H 5  or OC 3  H 7 , and 
     D denotes a phenyl or naphthyl radical substituted by SO 3  H, CO 2  H, CH 2  --SO 2  W, SO 2  W, NH--COCH 3 , C 1  -C 4  -alkyl and/or C 1  -C 4  -alkoxy, W having one of the meanings given under Y, or denotes a radical of the structure ##STR4## K denotes ##STR5##  the bonding to the triazinyl radical taking place in each case via the amino function of K, 
     A denotes H, C 1  -C 4  -alkyl or C 1  -C 4  -alkoxy, 
     B denotes H, C 1  -C 4  -alkyl, halogen, C 1  -C 4  -alkoxy, OH--, SO 3  H- or OSO 3  H-substituted C 1  -C 4  -alkyl, NHCONH 2 , NHCO-(-C 1  -C 4  -alkyl), NHCOCH 2  OSO 3  H, NHCO-(--CH 2  --) 1-3  SO 3  H, NHCOCH 2  OH or NHCO-(--O-C 1  -C 4  -alkyl). 
     Preferred representatives of the formula (1) in which K is ##STR6## are dyestuffs of the formula (2) ##STR7## in which R, Y and Z have the abovementioned meaning and the phenyl or naphthyl radical D can be additionally substituted by C 1  -C 4  -alkyl, C 1  -C 4  -alkoxy, NHCOCH 3 , CH 2  SO 2  W or SO 2  W, W having one of the meanings given under Y. 
     Particular preference is given to dyestuffs, in particular, of the formula (2) in which D represents a radical of the formula (3) and (4). ##STR8## 
     Particular preference is also given to dyestuffs of the formula (5) and (6) ##STR9## in which V denotes H, CH 3 , OCH 3 , OC 2  H 5  or NHAcyl, in particular NH--CO--CH 3 , 
     p,m, independently of one another, denote 0 or 1, 
     R denotes H or C 2  H 5 , 
     W,Y, independently of one another, denote CH═CH 2  or CH 2  CH 2  OSO 3  H, and 
     Z denotes H, CH 3  or OCH 3   
     Very particular preference is given to dyestuffs of the formula (7) and (8) ##STR10## in which p,m, independently of one another, denote 0 or 1, 
     R denotes H or C 2  H 5 , 
     Y denotes CH═CH 2  or CH 2  CH 2  OSO 3  H, 
     and 
     Z denotes H, CH 3  or OCH 3 . 
     Preferred representatives of the formula (1) in which K is ##STR11## are dyestuffs of the formula (9) ##STR12## in which A, B, R, Y and Z have the meanings mentioned for formula (1). 
     The phenyl or naphthyl radical D can be additionally substituted by C 1  -C 4  -alkyl, C 1  -C 4  -alkoxy, NHCOCH 3 , CH 2  SO 2  W or SO 2  W. 
     Particular preference is given to dyestuffs of the formulae (10) and (11) ##STR13## in which X denotes H, CH 3 , OCH 3 , OC 2  H 5 , CH 2  SO 2  W or SO 2  W, and 
     A, B, R, W and Z have the meanings given for formula (1), B in formula (10) representing in particular H, CH 3 , C 1  -C 4  -alkoxy, NH--CO-(C 1  -C 4  -alkyl), NHCOCH 2  OH, NHCOCH 2  OSO 3  H or NHCO(--CH 2 ) 1-3  -SO 3  H. 
     Very particular preference is given to dyestuffs of the formula (10) and (11) in which 
     A is H, 
     B is NHCOCH 3 , NHCONH 2  or NHCOCH 2  OSO 3  H, in formula (10) in particular CH 3 , OCH 3 , NHCOCH 3  or NHCOCH 2  OSO 3  H, 
     R is H or C 2  H 5 , 
     W,Y, independently of one another, are CH═CH 2  or CH 2  CH 2  OSO 3  H, and 
     Z is H, CH 3  or OCH 3 . 
     Formulae (1) to (11) represent the sulpho-containing dyestuffs in the form of free acids. In general, the preparation gives the salts, in particular the alkali metal salts, such as sodium salts, potassium salts or lithium salts. The dyestuffs can be obtained and used as powders or as concentrated aqueous solutions. 
     Preparation of the dyestuffs (1) in which K is ##STR14## is carried out, for example, by the following procedure: 
     Diazotisation of amines D-NH 2  and coupling of the resulting diazonium compounds to aminonaphtholsulphonic acid derivatives of the formula (12). ##STR15## 
     The intermediates (12) are prepared, for example, condensing aminonaphtholmono- or -disulphonic acids or (aminobenzoyl)aminonaphtholmono- or -disulphonic acids at the amine function by known methods (for example EP-A-40,806, DE-A-2,711,150, EP-A-172,790 or DE-A-2,747,014) with trifluoro-s-triazine and reacting the difluorotriazinyl compounds obtained with amines of the formula (13) ##STR16## in the presence of acid-binding agents. Details of further possibilities of synthesis can be seen from Examples 1-93. Examples of aminonaphtholsulphonic acids are: ##STR17## 
     Examples of suitable amines of the formula (13) are: ##STR18## 
     Preparation of the dyestuffs (1) in which K is ##STR19## is carried out, for example, by the following procedure: 1. By condensation of trifluoro-s-triazine with a dyestuff base of the formula (14) ##STR20##  in the presence of acid-binding agents, followed by a second condensation of the resulting difluorotriazine compounds of the formula (15) ##STR21##  with amino compounds of the formula (13) ##STR22## 2. By condensation of trifluoro-s-triazine with amino compounds of the formula (13) in the presence of acid-binding agents, followed by a second condensation of the resulting difluorotriazine compound of the formula (16) ##STR23##  with dyestuff bases of the formula (14). 
     Examples of dyestuff bases (14) include: ##STR24## 
     Suitable amines of the formula (13) have already been mentioned above by way of example. 
     The dyestuffs according to the invention are highly suitable for the dyeing and printing of natural and synthetic OH- and/or amido-containing materials, in particular those made of cellulose and polyamides. They are particularly suitable for the dyeing of cellulose materials, such as cotton or staple viscose, by the exhaust and cold pad-batch methods. 
     The dyestuffs can be used in a mixture with other dyestuffs for trichromatic dyeing. 
     Dyeings having good general fastness properties, in particular wetfastness properties, are obtained in combination with good build-up properties and high fixation yields. 
    
    
     EXAMPLE 1 
     0.1 mol of the amino compound of the formula ##STR25## is stirred and dissolved in 100 ml of water and 100 g of ice. After addition of 0.1 mol of sodium bicarbonate, 0.11 mol of trifluoro-s-triazine are added dropwise at 0° C. over a period of 10 minutes. About 250 ml of an aqueous solution of the condensation product of the formula ##STR26## are obtained. 
     EXAMPLE 2 
     0.1 mol of 4-amino-5-hydroxy-2,7-naphthalenedisulphonic acid is suspended in 150 ml of water and dissolved under neutral conditions using a 10% strength lithium hydroxide solution. The above condensation solution (Example 1) is then added, and the pH is simultaneously maintained between 4.0 and 4.5 by addition of lithium carbonate. The second condensation is complete after about 6 hours at 10 to 20° C. 
     0.1 mol of 2-amino-1,5-naphthalenedisulphonic acid is diazotised in a known manner, and the resulting diazonium salt mixture is added to the solution of the coupling component at pH 6.5-7.5 at 20° C. Isolation and drying give about 45 g of a salt-containing red powder of the following structure ##STR27## which dyes cotton by the dyeing and printing processes customary for reactive dyestuffs in red hues. (λ max  =517, 540 nm (H 2  O)). 
     By varying the amine component in Example 1 and the coupling or diazo component in Example 2, further valuable red reactive dyestuffs can be obtained (see Table 1). 
     
                                           TABLE 1                                 
__________________________________________________________________________
 ##STR28##                                                                
                   Position                                               
Ex.                                                                       
   D               SO.sub.3 H                                             
                        R       Z    CH.sub.2 SO.sub.2 Y                  
__________________________________________________________________________
    ##STR29##      3    H       H    4-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4  
                                     OSO.sub.3 H                          
4  &#34;               3    C.sub.2 H.sub.5                                   
                                H    &#34;                                    
5  &#34;               3    C.sub.2 H.sub.5                                   
                                H    3-CH.sub.2 SO.sub. 2 C.sub.2 H.sub.4 
                                     SO.sub.3 H                           
6  &#34;               3    H       4-OCH.sub.3                               
                                     &#34;                                    
7  &#34;               3    H       4-CH.sub.3                                
                                     &#34;                                    
8  &#34;               3    C.sub.2 H.sub.5                                   
                                4-OCH.sub.3                               
                                     &#34;                                    
8a &#34;               3    C.sub.2 H.sub.5                                   
                                4-CH.sub.3                                
                                     &#34;                                    
9                                                                         
    ##STR30##      4    C.sub.2 H.sub.5                                   
                                H    3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4  
                                     OSO.sub.3 H                          
10 &#34;               4    H       H    &#34;                                    
11 &#34;               4    H       H    4-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4  
                                     OSO.sub.3 H                          
12 &#34;               4    C.sub.2 H.sub.5                                   
                                H    &#34;                                    
13 &#34;               3    H       H    4-CH.sub.2 SO.sub.2 CHCH.sub.2       
14 &#34;               3    C.sub.2 H.sub.5                                   
                                H    4-CH.sub.2 SO.sub.2 CHCH.sub.2       
15 &#34;               3    H       H    3-CH.sub.2 SO.sub.2 CHCH.sub.2       
16 &#34;               3    H       H    3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4  
                                     Cl                                   
17                                                                        
    ##STR31##      3    H       H    3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4  
                                     OSO.sub.3 H                          
18 &#34;               3    H       H    4-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4  
                                     OSO.sub.3 H                          
19 &#34;               3    C.sub.2 H.sub.5                                   
                                H    3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4  
                                     OSO.sub.3 H                          
20                                                                        
    ##STR32##      4    C.sub.2 H.sub.5                                   
                                H    3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4  
                                     OSO.sub.3 H                          
21                                                                        
    ##STR33##      3    H       H    3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4  
                                     OSO.sub.3 H                          
22 &#34;               4    H       H    &#34;                                    
23 &#34;               3    C.sub.2 H.sub.5                                   
                                H    &#34;                                    
24 &#34;               3    C.sub.2 H.sub.5                                   
                                H    4-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4  
                                     OSO.sub.3 H                          
25 &#34;               3    H       4-OCH.sub.3                               
                                     3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4  
                                     OSO.sub.3 H                          
26                                                                        
    ##STR34##      3    H       H    &#34;                                    
26a                                                                       
   &#34;               3    H       4-CH.sub.3                                
                                     &#34;                                    
27                                                                        
    ##STR35##      3    H       H    4-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4  
                                     OSO.sub.3 H                          
28 &#34;               3    C.sub.2 H.sub.5                                   
                                H    &#34;                                    
29 &#34;               3    CH.sub.2 CH.sub.2 CO.sub.2 H                      
                                H    &#34;                                    
30 &#34;               3    C.sub.2 H.sub.5                                   
                                H    3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4  
                                     OSO.sub.3 H                          
31 &#34;               4    H       H    &#34;                                    
32                                                                        
    ##STR36##      3    H       H    &#34;                                    
33 &#34;               3    C.sub.2 H.sub.5                                   
                                H    &#34;                                    
34 &#34;               3    H       H    4-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4  
                                     OSO.sub.3 H                          
34a                                                                       
    ##STR37##      3    H       H    3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4  
                                     OSO.sub.3 H                          
34b                                                                       
   &#34;               3    H       4-CH.sub.3                                
                                     &#34;                                    
34c                                                                       
   &#34;               3    C.sub.2 H.sub.5                                   
                                4-CH.sub.3                                
                                     &#34;                                    
34d                                                                       
   &#34;               3    C.sub.2 H.sub.5                                   
                                4-OCH.sub.3                               
                                     &#34;                                    
35                                                                        
    ##STR38##      3    H       H    4-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4  
                                     OSO.sub.3 H                          
36                                                                        
    ##STR39##      3    H       H    3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4  
                                     OSO.sub.3 H                          
37 &#34;               3    C.sub.2 H.sub.5                                   
                                H    &#34;                                    
38                                                                        
    ##STR40##      3    H       H    3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4  
                                     OSO.sub.3 H                          
39                                                                        
    ##STR41##      3    H       H    4-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4  
                                     OSO.sub.3 H                          
40 &#34;               3    C.sub.2 H.sub.5                                   
                                H    &#34;                                    
41                                                                        
    ##STR42##      3    H       H    3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4  
                                     OSO.sub.3 H                          
42                                                                        
    ##STR43##      3    H       H    4-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4  
                                     OSO.sub.3 H                          
43 &#34;               3    CH.sub.2 CH.sub.2 CO.sub.2 H                      
                                H    &#34;                                    
44                                                                        
    ##STR44##      3    H       H    4-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4  
                                     OSO.sub.3 H                          
45 &#34;               2    H       H    3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4  
                                     OSO.sub.3 H                          
46 &#34;               3    C.sub.2 H.sub.5                                   
                                H    &#34;                                    
47 &#34;               3    C.sub.2 H.sub.5                                   
                                H    4-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4  
                                     OSO.sub.3 H                          
48 &#34;               4    C.sub.2 H.sub.5                                   
                                H    &#34;                                    
__________________________________________________________________________
 
    
     Dyestuff Examples 2 to 48 are also available by the following synthesis sequence: 
     First, 0.1 mol of 4-amino-5-hydroxy-2,7 (or 1,7)-naphthalenedisulphonic acid is condensed with 0.11 mol of cyanuric fluoride at 0° C. and pH 4.0 to 4.5 in a known manner, and the monocondensation product is then reacted with 0.1 mol of the amine component in an increasing temperature range from 0° to 20° C. and at pH 4.0 to 6.5. pH control takes place by means of aqueous sodium carbonate solution or potassium bicarbonate solution. In the last step of the reaction sequence, suitable diazonium salts (0.1 mol) are then coupled to the biscondensation product at 10° to 20° C. and pH 6.5 to 7.5. Isolation of the dyestuffs is then carried out as described in Example 2. 
     Example 2 is repeated, using the corresponding N-(4-aminobenzoyl) derivatives instead of 4-amino-5-hydroxy-2,7 (or 1,7)-naphthalenedisulphonic acid, giving the following red dyestuffs: 
     EXAMPLE 49 ##STR45## 
     EXAMPLE 50 ##STR46## 
     If the above variation is carried out with Example 26, likewise a valuable red reactive dyestuff is obtained. 
     EXAMPLE 51 ##STR47## 
     EXAMPLE 52 
     0.1 mol of the monoazo compound of the formula ##STR48## is dissolved under neutral conditions in 500 ml of water. The ice-cold condensation solution from Example 1 is added to this solution, and the pH is kept constant between 6.5 and 7.0 with 20% strength sodium carbonate solution. After stirring at 10° to 25° C. and pH 7.0 for about 6 hours, the dyestuff is precipitated by addition of common salt, isolated by suction filtration and dried, giving about 60 g of salt-containing red dyestuff powder which has the formula ##STR49## and dyes cotton in orange-red hues (485 nm). By varying the amine component in Example 1 and the coupling or diazo component in Example 52, further valuable orange and scarlet reactive dyestuffs can be obtained (Table 2). 
     
                                           TABLE 2                                 
__________________________________________________________________________
 ##STR50##                                                                
                         Posi-                                            
Ex.                                                                       
   D                     tion-NH                                          
                              R  Z    CH.sub.2 SO.sub.2 Y                 
__________________________________________________________________________
53                                                                        
    ##STR51##            3    H  H    4-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4 
                                      SO.sub.3 H                          
54 &#34;                     3    C.sub.2 H.sub.5                             
                                 H    &#34;                                   
55 &#34;                     3    C.sub.2 H.sub.5                             
                                 H    3-CH.sub.2 SO.sub.2 C.sub. 2        
                                      H.sub.4 OSO.sub.3 H                 
56 &#34;                     3    H  4-OCH.sub.3                              
                                      &#34;                                   
57 &#34;                     3    H  4-CH.sub.3                               
                                      &#34;                                   
58                                                                        
    ##STR52##            2    H  H    3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4 
                                      SO.sub.3 H                          
59 &#34;                     2    C.sub.2 H.sub.5                             
                                 H    &#34;                                   
60 &#34;                     2    C.sub.2 H.sub.5                             
                                 H    4-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4 
                                      SO.sub.3 H                          
61                                                                        
    ##STR53##            2    H  H    4-CH.sub.2 2C.sub.2 H.sub.4         
                                      OSO.sub.3 H                         
62 &#34;                     2    H  H    4-CH.sub.2 SO.sub.2 CHCH.sub.2      
63 &#34;                     2    H  H    3-CH.sub.2 SO.sub.2 CHCH.sub.2      
64 &#34;                     4    H  H    3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4 
                                      SO.sub.3 H                          
65                                                                        
    ##STR54##            3    H  H    &#34;                                   
66                                                                        
    ##STR55##            3    H  H    &#34;                                   
66a                                                                       
   &#34;                     3    C.sub.2 H.sub.5                             
                                 H    &#34;                                   
66b                                                                       
   &#34;                     3    H  4-OCH.sub.3                              
                                      &#34;                                   
67                                                                        
    ##STR56##            2    H  H    &#34;                                   
68                                                                        
    ##STR57##            3    H  H    3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4 
                                      SO.sub.3 H                          
69 &#34;                     3    H  H    4-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4 
                                      SO.sub.3 H                          
70 &#34;                     3    C.sub.2 H.sub.5                             
                                 H    &#34;                                   
71 &#34;                     2    C.sub.2 H.sub.5                             
                                 H    &#34;                                   
72                                                                        
    ##STR58##            2    H  H    &#34;                                   
73                                                                        
    ##STR59##            3    H  H    3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4 
                                      SO.sub.3 H                          
74 &#34;                     3    H  H    4-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4 
                                      SO.sub.3 H                          
75                                                                        
    ##STR60##            3    H  H    &#34;                                   
76                                                                        
    ##STR61##            3    H  H    4-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4 
                                      SO.sub.3 H                          
77 &#34;                     3    C.sub.2 H.sub.5                             
                                 H    3-CH.sub.2 SO.sub.2 CHCH.sub.2      
78                                                                        
    ##STR62##            3    H  H    3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4 
                                      SO.sub.2 H                          
78a                                                                       
   &#34;                     3    H  4-OCH.sub.3                              
                                      &#34;                                   
78b                                                                       
   &#34;                     3    C.sub.2 H.sub.5                             
                                 4-OCH.sub.3                              
                                      &#34;                                   
78c                                                                       
   &#34;                     3    H  4-CH.sub.3                               
                                      &#34;                                   
79 &#34;                     3    H  H    4-CH.sub.2 SO.sub.2 C.sub.2         
                                      H.sub.4OSO.sub.2 H                  
80 &#34;                     3    C.sub.2 H.sub.5                             
                                 H    &#34;                                   
81 &#34;                     3    C.sub.2 H.sub.5                             
                                 H    3-CH.sub.2 SO.sub.2 C.sub.2         
                                      H.sub.4OSO.sub.3 H                  
81a                                                                       
   &#34;                     3    C.sub.2 H.sub.5                             
                                 4-CH.sub.3                               
                                      &#34;                                   
82                                                                        
    ##STR63##            3    H  H    3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4 
                                      SO.sub.3 H                          
83 &#34;                     3    C.sub.2 H.sub.5                             
                                 H    &#34;                                   
83a                                                                       
   &#34;                     3    H  4-CH.sub.3                               
                                      &#34;                                   
83b                                                                       
   &#34;                     3    H  4-OCH.sub.3                              
                                      &#34;                                   
83c                                                                       
   &#34;                     3    C.sub.2 H.sub.5                             
                                 4-CH.sub.3                               
                                      &#34;                                   
83d                                                                       
   &#34;                     3    C.sub.2 H.sub.5                             
                                 4-OCH.sub.3                              
                                      &#34;                                   
84                                                                        
    ##STR64##            3    H  H    3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4 
                                      SO.sub.3 H                          
85 &#34;                     3    H  H    4-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4 
                                      SO.sub.3 H                          
86                                                                        
    ##STR65##            3    H  H    4-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4 
                                      SO.sub.3 H                          
87 &#34;                     3    H  H    3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4 
                                      SO.sub.3 H                          
88 &#34;                     3    C.sub.2 H.sub.5                             
                                 H    &#34;                                   
88a                                                                       
   &#34;                     3    C.sub.2 H.sub.5                             
                                 H    4-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4 
                                      SO.sub.3 H                          
89                                                                        
    ##STR66##            3    H  H    3-CH.sub.2 SO.sub.2 C.sub.2         
                                      H.sub.5 OSO.sub.3 H                 
90 &#34;                     2    H  H    &#34;                                   
91                                                                        
    ##STR67##            3    H  H    &#34;                                   
92                                                                        
    ##STR68##            3    H  H    &#34;                                   
93                                                                        
    ##STR69##            3    H  H    3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.5 
                                      SO.sub.3 H                          
__________________________________________________________________________
 
    
     Dyestuff Examples 52 to 93 are also available by the following synthesis sequence: 
     First, 0.1 mol of amino-4-hydroxy-2-naphthalenesulphonic acid is reacted with the condensation solution from Example 1 at 0° C. and pH 4.5. During the reaction time of about 3 hours, it is quite possible for the reaction temperature to rise to room temperature. At pH 6.5-7.5 (sodium carbonate solution), suitable diazonium salts (0.1 mol in each case) are then coupled onto the colourless biscondensation products. The dyestuffs are isolated by salting out and suction filtration. 
     Dyestuff mixtures, for example a mixture of Example 2 and 3, can be obtained by using in Example 1 a mixture of two isomers, i.e., 3- and 4-[(2-sulphatoethylsulphonyl)methyl]aniline instead of 3-[(2-sulphatoethylsulphonyl)methyl]aniline. 
     EXAMPLE 94 
     23.6 g of 7-amino-1,3-naphthalenedisulphonic acid monosodium salt are stirred in 150 ml of water/30 g of ice and 20 ml of concentrated hydrochloric acid, and an aqueous sodium nitrite solution is added dropwise at 5° to 10° C. After stirring at 5° to 10° C. for one hour, excess nitrous acid is removed with sulphamic acid. 
     This cream-coloured suspension is metered into a neutral solution of the coupling component prepared from 13.5 g of N-(3-aminophenyl)acetamide hydrochloride, 50 ml of water, 50 g of ice and about 30 ml of a 10% strength aqueous lithium hydroxide solution over a period of 30 minutes. During this addition, the pH of the reaction mixture is kept constant at 6.0 to 6.5 with 20% strength aqueous potassium bicarbonate solution at a maximum temperature of 10° C. After addition is complete, stirring is continued for 30 minutes, during which the pH is still kept constant. 
     Ice is now added to this orange-coloured coupling solution until a temperature of 0° C. is reached. 12 g of cyanuric fluoride are swiftly added, and the pH is simultaneously kept constant at 6.0 to 6.2 by addition of a 20% strength potassium bicarbonate solution. Condensation is complete after 10 minutes. A neutral solution of 21.5 g of 3-[(2-sulfatoethylsulfonyl)methyl]aniline in 100 ml of water is now slowly metered into this mixture while keeping the pH constant at 6.5 to 7.0 by addition of 20% strength sodium carbonate solution. The reaction mixture is then warmed to 20° C. over a period of 2 hours and with further pH control (6.5 to 7.0). Isolation and drying give 65 g of an orange-red powder (λ max  =389 nm (H 2  O)) of the structure ##STR70## which dyes cotton in reddish yellow hues. 
     The same dyestuff is also obtained by first condensing 11 g of cyanuric fluoride with 21.5 g of 3-[(2-sulphatoethylsulphonyl)methyl]aniline in 150 ml of water/50 g of ice at 0° C. at a constant pH of 6.0, and reacting the resulting condensation product with the abovementioned coupling solution. 
     By varying the diazo component D-NH 2 , the aniline coupling component containing A and B and the amino compound of the sulphonylmethyl structure, further valuable reactive dyestuffs of the formula ##STR71## for example those of the table below, can be obtained analogously to Example 94. 
     Dyestuff mixtures, for example a mixture of Example 1 and 3, can be obtained by using in Example 1 a mixture of the two isomers, i.e., 3- and 4-[(2-sulphatoethylsulphonyl)methyl]aniline instead of 3-[(2-sulphatoethylsulphonyl)methyl]aniline. 
     
         __________________________________________________________________________
Ex.                                                                       
   D                B           A   R       Z    CH.sub.2 SO.sub.2        
__________________________________________________________________________
                                                 Y                        
95                                                                        
    ##STR72##       NHCOCH.sub.3                                          
                                H   C.sub.2 H.sub.5                       
                                            H    3-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
96 &#34;                &#34;           H   H       H    4-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
97 &#34;                &#34;           H   C.sub.2 H.sub.5                       
                                            H    &#34;                        
98 &#34;                &#34;           OCH.sub.3                                 
                                    C.sub.2 H.sub.5                       
                                            H    &#34;                        
99 &#34;                NHCOCH.sub.2 OSO.sub.3 H                              
                                H   H       H    3-CH.sub.2 SO.sub.2      
                                                 CHCH.sub.2               
100                                                                       
   &#34;                NHCOCH.sub.3                                          
                                H   H       4-OCH.sub.3                   
                                                 3-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
101                                                                       
   &#34;                NHCONH.sub.2                                          
                                H   C.sub.2 H.sub.5                       
                                            H    &#34;                        
102                                                                       
   &#34;                CH.sub.3    H   H       H    4-CH.sub.2 SO.sub.2      
                                                 C.sub.2                  
                                                 H.sub.4 OSO.sub.3 H      
103                                                                       
   &#34;                H           OCH.sub.3                                 
                                    C.sub.2 H.sub.5                       
                                            H    &#34;                        
104                                                                       
   &#34;                NHCOCH.sub.2 OH                                       
                                H   H       4-CH.sub.3                    
                                                 3-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
105                                                                       
    ##STR73##       NHCOCH.sub.3                                          
                                H   H       H    4-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
106                                                                       
   &#34;                &#34;           H   C.sub.2 H.sub.5                       
                                            H    &#34;                        
107                                                                       
   &#34;                &#34;           H   C.sub.2 H.sub.5                       
                                            4-OCH.sub.3                   
                                                 3-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
108                                                                       
   &#34;                &#34;           H   H       H    &#34;                        
109                                                                       
   &#34;                OCH.sub.3   OCH.sub.3                                 
                                    H       H    &#34;                        
110                                                                       
   &#34;                NHCONH.sub.2                                          
                                H   C.sub.2 H.sub.5                       
                                            H    3-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
111                                                                       
    ##STR74##       NHCOCH.sub.3                                          
                                H   H       H    3-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
112                                                                       
   &#34;                &#34;           H   H       4-OCH.sub.3                   
                                                 &#34;                        
113                                                                       
   &#34;                &#34;           H   C.sub.2 H.sub.5                       
                                            H    &#34;                        
114                                                                       
   &#34;                &#34;           H   H       H    4-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
115                                                                       
    ##STR75##       NHCOCH.sub.3                                          
                                H   C.sub.2 H.sub.5                       
                                            H    4-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
116                                                                       
   &#34;                NHCONH.sub.2                                          
                                H   C.sub.2 H.sub.5                       
                                            H    &#34;                        
117                                                                       
   &#34;                &#34;           H   H       H    &#34;                        
118                                                                       
   &#34;                &#34;           H   H       H    3-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
119                                                                       
   &#34;                &#34;           H   C.sub.2 H.sub.5                       
                                            H    &#34;                        
120                                                                       
   &#34;                &#34;           H   C.sub.2 H.sub.5                       
                                            4-OCH.sub.3                   
                                                 3-CH.sub.2 SO.sub.2      
                                                 CHCH.sub.2               
121                                                                       
   &#34;                &#34;           H   H       H    3-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub. 4         
                                                 OSO.sub.3 H              
122                                                                       
    ##STR76##       NHCOCH.sub.3                                          
                                H   C.sub.2 H.sub.5                       
                                            H    3-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
123                                                                       
   &#34;                NHCOCH.sub.2 OSO.sub.3 H                              
                                H   H       H    &#34;                        
124                                                                       
   &#34;                &#34;           H   H       H    4-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
125                                                                       
   &#34;                NHCOC.sub.2 H.sub.4 SO.sub.3 H                        
                                H   C.sub.2 H.sub.5                       
                                            H    &#34;                        
126                                                                       
    ##STR77##       OCH.sub.3   H   CH.sub.2 CH.sub.2 CO.sub.2 H          
                                            H    4-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
127                                                                       
   &#34;                CH.sub.2 SO.sub.3 H                                   
                                H   H       H    &#34;                        
128                                                                       
    ##STR78##       NHCOCH.sub.3                                          
                                H   H       H    3-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
129                                                                       
   &#34;                &#34;           H   C.sub.2 H.sub.5                       
                                            H    &#34;                        
130                                                                       
   &#34;                &#34;           H   H       H    4-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
131                                                                       
   &#34;                NHCONH.sub.2                                          
                                H   H       H    &#34;                        
132                                                                       
   &#34;                &#34;           H   C.sub.2 H.sub.5                       
                                            H    &#34;                        
133                                                                       
   &#34;                &#34;           H   H       4-OCH.sub.3                   
                                                 3-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
134                                                                       
   &#34;                &#34;           H   H       H    &#34;                        
135                                                                       
    ##STR79##       NHCONH.sub.2                                          
                                H   H       H    3-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
136                                                                       
   &#34;                &#34;           H   H       4-OCH.sub.3                   
                                                 &#34;                        
137                                                                       
   &#34;                &#34;           H   C.sub.2 H.sub.5                       
                                            H    &#34;                        
138                                                                       
   &#34;                &#34;           H   H       H    4-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
139                                                                       
   &#34;                NHCOCH.sub.3                                          
                                H   H       H    &#34;                        
140                                                                       
   &#34;                &#34;           H   H       H    3-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
141                                                                       
   &#34;                &#34;           H   C.sub.2 H.sub.5                       
                                            H    &#34;                        
142                                                                       
    ##STR80##       NHCONH.sub.2                                          
                                H   H       H    &#34;                        
143                                                                       
   &#34;                &#34;           H   H       H    4-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
144                                                                       
   &#34;                &#34;           H   C.sub.2 H.sub.5                       
                                            H    &#34;                        
145                                                                       
    ##STR81##       NHCOCH.sub.3                                          
                                H   H       H    4-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
146                                                                       
   &#34;                &#34;           H   H       H    3-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
147                                                                       
   &#34;                NHCONH.sub.2                                          
                                H   C.sub.2 H.sub.5                       
                                            H    &#34;                        
148                                                                       
   &#34;                &#34;           H   H       H    4-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub. 
                                                 3 H                      
149                                                                       
    ##STR82##       NHCOCH.sub.3                                          
                                H   H       H    4-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
150                                                                       
   &#34;                &#34;           H   H       H    3-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
151                                                                       
   &#34;                NHCONH.sub.2                                          
                                H   C.sub.2 H.sub.5                       
                                            H    &#34;                        
152                                                                       
   &#34;                &#34;           H   H       H    4-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
153                                                                       
   &#34;                OCH.sub.3   OCH.sub.3                                 
                                    H       H    &#34;                        
154                                                                       
    ##STR83##       NHCOCH.sub.2 OSO.sub.3 H                              
                                H   H       H    3-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
155                                                                       
   &#34;                &#34;           H   C.sub.2 H.sub.5                       
                                            H    &#34;                        
156                                                                       
   &#34;                NHCOCH.sub.2 CH.sub.2 SO.sub.3 H                      
                                H   H       H    4-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
157                                                                       
   &#34;                CH.sub.2 SO.sub.3 H                                   
                                H   C.sub.2 H.sub.5                       
                                            H    &#34;                        
158                                                                       
    ##STR84##       NHCOCH.sub.2 OSO.sub.3 H                              
                                H   H       H    4-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
159                                                                       
   &#34;                &#34;           H   H       H    3-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
160                                                                       
    ##STR85##       &#34;           H   H       H    &#34;                        
161                                                                       
    ##STR86##       NHCOCH.sub.3                                          
                                H   H       4-CH.sub.3                    
                                                 &#34;                        
162                                                                       
    ##STR87##       NHCOCH.sub.3                                          
                                H   C.sub.2 H.sub.5                       
                                            4-OCH.sub.3                   
                                                 3-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
163                                                                       
   &#34;                NHCOCH.sub.3                                          
                                H   C.sub.2 H.sub.5                       
                                            4-CH.sub.3                    
                                                 &#34;                        
164                                                                       
    ##STR88##       NHCONH.sub.2                                          
                                H   H       H    3-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
165                                                                       
    ##STR89##       NHCOCH.sub.3                                          
                                H   H       4-CH.sub.3                    
                                                 3-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
166                                                                       
   &#34;                &#34;           H   H       4-OCH.sub.3                   
                                                 3-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
167                                                                       
   &#34;                &#34;           H   C.sub.2 H.sub.5                       
                                            H    4-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
168                                                                       
   &#34;                &#34;           H   C.sub.2 H.sub.5                       
                                            4-CH.sub.3                    
                                                 3-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
169                                                                       
    ##STR90##       NHCOCH.sub.3                                          
                                H   H       4-CH.sub.3                    
                                                 3-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
170                                                                       
   &#34;                NHCOCH.sub.3                                          
                                H   C.sub.2 H.sub.5                       
                                            4-CH.sub.3                    
                                                 &#34;                        
171                                                                       
   &#34;                NHCOCH.sub.3                                          
                                H   C.sub.2 H.sub.5                       
                                            4-OCH.sub.3                   
                                                 3-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
172                                                                       
   &#34;                NHCONH.sub.2                                          
                                H   H       4-CH.sub.3                    
                                                 3-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
173                                                                       
   &#34;                &#34;           H   H       4-OCH.sub.3                   
                                                 3-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
174                                                                       
   &#34;                &#34;           H   C.sub.2 H.sub.5                       
                                            4-OCH.sub.3                   
                                                 3-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
175                                                                       
    ##STR91##       NHCONH.sub.2                                          
                                H   C.sub.2 H.sub.5                       
                                            H    4-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
176                                                                       
    ##STR92##       NHCONH.sub.2                                          
                                H   C.sub.2 H.sub.5                       
                                            4-CH.sub.3                    
                                                 3-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
177                                                                       
   &#34;                NHCONH.sub.2                                          
                                H   C.sub.2 H.sub. 5                      
                                            4-OCH.sub.3                   
                                                 3-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
178                                                                       
   &#34;                NHCONH.sub.2                                          
                                H   H       4-CH.sub.3                    
                                                 3-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
179                                                                       
   &#34;                NHCONH.sub.2                                          
                                H   H       4-OCH.sub.3                   
                                                 3-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
180                                                                       
   &#34;                NHCOCH.sub.3                                          
                                H   C.sub.2 H.sub.5                       
                                            H    4-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
181                                                                       
   &#34;                NHCOCH.sub.3                                          
                                H   C.sub.2 H.sub.5                       
                                            4-CH.sub.3                    
                                                 3-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.4 OSO.sub.3
                                                  H                       
182                                                                       
   &#34;                NHCOCH.sub.3                                          
                                H   C.sub.2 H.sub.5                       
                                            4-OCH.sub.3                   
                                                 3-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.5 OSO.sub.3
                                                  H                       
183                                                                       
   &#34;                NHCOCH.sub.3                                          
                                H   H       4-CH.sub.3                    
                                                 3-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.5 OSO.sub.3
                                                  H                       
184                                                                       
   &#34;                NHCOCH.sub.3                                          
                                H   H       4-OCH.sub.3                   
                                                 3-CH.sub.2 SO.sub.2      
                                                 C.sub.2 H.sub.5 OSO.sub.3
                                                  H                       
__________________________________________________________________________
 
    
     The table examples are characterised by the following λ max  values (H 2  O): 
     
         ______________________________________                                    
Example              nm                                                   
______________________________________                                    
 3                   518, 540                                             
 4                   518, 540                                             
 7                   519, 540                                             
 8                   518, 540                                             
 21                  521, 545                                             
 34a                 521, 544                                             
 44                  519, 540                                             
 53                  486                                                  
 54                  486                                                  
 56                  485                                                  
 66                  483                                                  
 66a                 482                                                  
 66b                 483                                                  
 78                  502                                                  
 78b                 501                                                  
 78c                 502                                                  
 79                  503                                                  
 80                  501                                                  
 82                  497                                                  
 86                  513                                                  
 87                  514                                                  
 88a                 512                                                  
 95                  389                                                  
 96                  390                                                  
 97                  389                                                  
100                  389                                                  
105                  388                                                  
106                  388                                                  
107                  388                                                  
108                  387                                                  
111                  397                                                  
112                  399                                                  
113                  397                                                  
114                  396                                                  
115                  400                                                  
116                  416                                                  
117                  416                                                  
118                  416                                                  
119                  416                                                  
120                  418                                                  
135                  388                                                  
136                  389                                                  
137                  388                                                  
138                  388                                                  
147                  390                                                  
148                  390                                                  
151                  407                                                  
152                  407                                                  
172                  397                                                  
165                  388                                                  
166                  388                                                  
167                  388                                                  
171                  399                                                  
173                  417                                                  
174                  418                                                  
175                  388                                                  
177                  388                                                  
179                  389                                                  
______________________________________