Patent Publication Number: US-4254027-A

Title: Disperse monoazo dyestuffs for coloring synthetic textile materials

Description:
This invention relates to disperse monoazo dyestuffs which are valuable for colouring synthetic textile materials, particularly aromatic polyester textile materials. 
     According to the invention there are provided the disperse monoazo dyestuffs of the formula: ##STR2## wherein T 1  and T 2  are each independently hydrogen or lower alkyl, Z is hydrogen, lower alkyl or lower alkoxy, Y is hydrogen, lower alkyl, lower alkoxy, chlorine bromine, --NHCOX 1  or --NHSO 2  X 2 , X 1  is lower alkyl, lower alkoxy, amino or N-lower alkylamino, X 2  is lower alkyl, A 1  and A 2  are each independently lower alkylene, R 1  and R 2  are each independently lower alkyl or hydroxylalkyl containing from 2 to 4 carbon atoms, and the benzene ring B can contain additional substituents apart from sulphonic acid groups. 
     Throughout this Specification the terms &#34;lower alkyl&#34; and &#34;lower alkoxy&#34; are used to denote alkyl and alkoxy radicals respectively containing from 1 to 4 carbon atoms, whilst &#34;lower alkylene&#34; denotes alkylene radicals containing from 1 to 6 carbon atoms. 
     As examples of lower alkyl represented by T 1 , T 2 , Z, Y, X 1 , X 2 , R 1  and R 2  there may be mentioned methyl, ethyl, n-propyl, isopropyl, isobutyl, sec-butyl and n-butyl. As examples of lower alkoxy represented by X 1 , Z and Y there may be mentioned ethoxy and preferably methoxy. As examples of lower alkylene represented by A 1  and A 2  there may be mentioned methylene, trimethylene, propylene, tetramethylene, hexamethylene and, above all, ethylene. As examples of hydroxyalkyl represented by R 1  and R 2  there may be mentioned β-hydroxyethyl, β-or γ-hydroxypropyl and β-, γ- or δ-hydroxybutyl. As examples of N-lower alkylamino represented by X 1  there may be mentioned methylamino and ethylamino. 
     As examples of additional substituents which may be present on the benzene ring B there may be mentioned chlorine, bromine, nitro, lower alkyl such as methyl, and lower alkoxy such as methoxy. 
     A preferred class of the dyestuffs of the invention comprises the dyestuffs of the formula: ##STR3## wherein T 1 , T 2 , Y, Z, R 1  and R 2  have the meanings stated. Preferably Y is hydrogen or lower alkylcarbonylamino. It is further preferred that R 1  and R 2  are both lower alkyl. 
     According to a further feature of the invention there is provided a process for the manufacture of the said dyestuffs which comprises diazotising an amine of the formula: ##STR4## and coupling with a coupling component of the formula: ##STR5## wherein T 1 , T 2 , Z, Y, A 1 , A 2 , R 1 , R 2  and B have the meanings stated. 
     The process of the invention can be conveniently carried out by, for example, adding sodium nitrite to a solution or suspension of the amine in an aqueous solution of a strong inorganic acid, or by adding the amine to a solution of nitrosulsulphuric acid. Sulphamic acid can then be added, if desired, to destroy any residual nitrous acid, and the resulting solution or suspension of the diazo compound is then added to a solution of the coupling component in water containing an acid and/or a water-soluble organic liquid such as acetone. The pH of the resulting mixture is then, if desired, adjusted so as to facilitate coupling, and when this is complete the resulting dyestuff is isolated in conventional manner. 
     As examples of the said amines there may be mentioned 2-, 3- or 4-carbamoylaniline, 2-, 3- or 4-[N-(methyl, ethyl, n-propyl or n-butyl) carbamoyl]aniline, 2-, 3- or 4-[N:N-di(methyl, ethyl, n-propyl or n-butyl) carbamoyl]aniline, 2- carbamoyl -4- or 5-chloroaniline, 2-carbamoyl-4- or 5-bromoaniline, 2-carbamoyl-4- or 5-nitroaniline and 2-carbamoyl-4:6-dinitro aniline. 
     As examples of the said coupling components there may be mentioned N:N-di(β-methoxycarbonylethyl)-aniline, -m-toluidine, -m-chloroaniline, -m-acetylaminoaniline or -2:5-dimethoxyaniline, and N:N-di[β-(β&#39;-hydroxyethoxycarbonyl)ethyl]-aniline, -m-toluidine, -m-chloroaniline, -m-acetylaminoaniline, -o-toluidine, -2-methoxy-5 acetylaminoaniline or -2:5-dimethoxyaniline. 
     The azo dyestuffs of the invention when dispersed in aqueous medium are valuable for colouring synthetic textile materials for example cellulose acetate, nylon and especially aromatic polyester textile materials. The said colorations can be obtained by dyeing, padding or printing processes using the conditions and other additives which are conventional in colouring such textile materials. At the conclusion of the said processes the coloured textile materials are rinsed in water and then preferably given a clearing treatment in order to remove loose dyestuff from the surface of the textile material. Whilst this clearing treatment can comprise immersion in a warm aqueous alkaline solution of sodium hydrosulphite it is found that the presence of the sodium hydrosulphite is not essential and treatment for a few minutes in an aqueous alkaline solution of pH between 10 and 13.5 and at a temperature of between 50° and 85° C. (for example in an aqueous solution of sodium carbonate or sodium hydroxide) completely removes loose dyestuff. 
     When so applied the azo dyestuffs of the invention yield yellow to blue shades having excellent fastness to the tests conventionally applied to synthetic textile materials. 
     The azo dyestuffs of the invention can also be used for the mass coloration of aromatic polyesters, or can be used to colour synthetic textile materials by the transfer printing process optionally under vacuum or under wet or humid conditions. 
    
    
     The invention is illustrated but not limited by the following Examples in which the parts and percentages are by weight. 
     EXAMPLE 1 
     18.4 parts of sulphuric acid are added to a solution of 2.54 parts of 2-(N:N-dimethylcarbamoyl)-4:6-dinitroaniline in 50 parts of acetic acid at a temperature below 25° C. The mixture is cooled to 5° C. and 7 parts of a 14% aqueous solution of sodium nitrite added at a temperature below 10° C. The mixture is stirred for 15 minutes at the same temperature and is then added to a mixture of 3.25 parts of 2-methoxy-5-acetylamino-N:N-di(methoxycarbonylethyl)aniline, 0.5 parts of sulphamic acid, 20 parts of acetone and 200 parts of ice/water. The pH of the mixture is adjusted to 5 by the addition of sodium acetate, the mixture is stirred for 1 hour, and the precipitated dyestuff is then filtered off, washed with water and dried. 
     The dyestuff is converted into an aqueous dispersion and this is incorporated into a print paste which is then applied onto a polyethylene terephthalate textile material in conventional manner, after which any unfixed dyestuff is removed by treatment in an aqueous solution of sodium carbonate at 80° C. A bright reddish blue print is obtained which has excellent fastness to light, to wet treatments and to dry heat treatments. 
     Further dyestuffs of the invention are obtained by diazotising 2-(N:N-dimethylcarbamoyl)-4-nitroaniline and coupling with the coupling components listed in the second column of Table I using methods similar to that described in Example 1. The shades obtained from the resulting dyestuffs are given in the third column of the Table. 
     
                                           TABLE I                                 
__________________________________________________________________________
Coupling Component                     Shade                              
__________________________________________________________________________
1  2-methoxy-5-methyl-N:N-di(β-methoxycarbonylethyl)aniline          
                                       Bluish-red                         
2  2-methoxy-5-acetylamino-N:N-di(β-ethoxycarbonylethyl)aniline      
                                       Reddish-violet                     
3  3-methyl-N:N-di(β-methoxycarbonylethyl)aniline                    
                                       Red                                
4  N:N-di(β-methoxycarbonylethyl)aniline                             
                                       Scarlet                            
5  2:5-dimethoxy-N:N-di(β-ethoxycarbonylethyl)aniline                
                                       Violet                             
6  2:5-dimethoxy-N:N-di(β-methoxycarbonylethyl)aniline               
                                       &#34;                                  
7  2:5-dimethoxy-N:N-di(δ-methoxycarbonylbutyl)aniline              
                                       &#34;                                  
8  2:5-dimethoxy-N:N-di(β-methoxycarbonylpropyl)aniline              
                                       &#34;                                  
9  2-methoxy-5-methyl-N:N-di(δ-methoxycarbonylbutyl)aniline         
                                       Rubine                             
10 2-methoxy-5-methyl-N:N-di[β-(γ&#39;-hydroxypropoxycarbonyl)ethyl
   ]aniline                            &#34;                                  
11 3-methyl-N:N-di(β-ethoxycarbonylethyl)aniline                     
                                       Red                                
12 3-methyl-N:N-di(β-n-propoxycarbonylethyl)aniline                  
                                       &#34;                                  
13 3-methyl-N:N-di(β-isopropoxycarbonylethyl)aniline                 
                                       &#34;                                  
14 3-methyl-N:N-di(β-n-butoxycarbonylethyl)aniline                   
                                       &#34;                                  
15 3-methyl-N:N-di[β-(β&#39;-methyl-n-propoxycarbonyl)ethyl]aniline 
                                       &#34;                                  
16 3-methyl-N:N-di[β-(α&#39;-methyl-n-propoxycarbonyl)ethyl]aniline
                                       &#34;                                  
17 3-methyl-N:N-di(γ-methoxycarbonylpropyl)aniline                  
                                       &#34;                                  
18 3-methyl-N:N-di(methoxycarbonylmethyl)aniline                          
                                       Reddish-orange                     
19 3-methyl-N:N-di(ethoxycarbonylmethyl)aniline                           
                                       &#34;                                  
20 3-methyl-N:N-di(δ-methoxycarbonylbutyl)aniline                   
                                       Red                                
21 3-methyl-N:N-di(β-methoxycarbonylpropyl)aniline                   
                                       &#34;                                  
22 2-ethoxy-N:N-di(β-methoxycarbonylethyl)aniline                    
                                       Bluish-red                         
23 2-ethoxy-N:N-di(methoxycarbonylmethyl)aniline                          
                                       Red                                
24 2-ethoxy-N:N-di(ethoxycarbonylmethyl)aniline                           
                                       &#34;                                  
25 2-ethoxy-N:N-di(β-methoxycarbonylpropyl)aniline                   
                                       Bluish-red                         
26 2-methoxy-5-chloro-N:N-di(β-methoxycarbonylethyl)aniline          
                                       Red                                
27 2-methoxy-5-bromo-N:N-di(β-methoxycarbonylethyl)aniline           
                                       &#34;                                  
28 2:5-diethoxy-N:N-di(β-methoxycarbonylethyl)aniline                
                                       Violet                             
29 2-methoxy-5-methyl-N:N-di(β-methoxycarbonylethyl)aniline          
                                       Reddish-violet                     
30 2-methoxy-5-methyl-N:N-di(β-ethoxycarbonylethyl)aniline           
                                       &#34;                                  
31 2-methoxy-5-methyl-N:N-di(methoxycarbonylmethyl)aniline                
                                       Rubine                             
32 2:5-dimethoxy-N:N-di(ethoxycarbonylmethyl)aniline                      
                                       &#34;                                  
33 2-methoxy-5-methyl-N:N-di(ethoxycarbonylmethyl)aniline                 
                                       &#34;                                  
34 2-ethoxy-5-methyl-N:N-di(β-methoxycarbonylethyl)aniline           
                                       Reddish-violet                     
35 2-ethoxy-5-methyl-N:N-di(methoxycarbonylmethyl)aniline                 
                                       Rubine                             
36 3-chloro-N:N-di(β-methoxycarbonylethyl)aniline                    
                                       Scarlet                            
37 3-bromo-N:N-di(β-methoxycarbonylethyl)aniline                     
                                       &#34;                                  
38 3-chloro-N:N-di(β-ethoxycarbonylethyl)aniline                     
                                       &#34;                                  
39 3-chloro-N:N-di(γ-methoxycarbonylpropyl)aniline                  
                                       &#34;                                  
40 3-chloro-N:N-di(methoxycarbonylmethyl)aniline                          
                                       Orange                             
41 3-chloro-N:N-di(methoxycarbonylmethyl)aniline                          
                                       &#34;                                  
42 3-chloro-N:N-di(β-methoxycarbonylpropyl)aniline                   
                                       Scarlet                            
43 3-acetylamino-N:N-di(β-methoxycarbonylethyl)aniline               
                                       Bluish-red                         
44 3-acetylamino-N:N-di(β-ethoxycarbonylethyl)aniline                
                                       &#34;                                  
45 3-acetylamino-N:N-di(γ-methoxycarbonylpropyl)aniline             
                                       Rubine                             
46 3-acetylamino-N:N-di(ethoxycarbonylmethyl)aniline                      
                                       Scarlet                            
47 3-acetylamino-N:N-di(β-methoxycarbonylpropyl)aniline              
                                       Bluish-red                         
48 3-propionylamino-N:N-di(β-methoxycarbonylethyl)aniline            
                                       &#34;                                  
49 3-n-propylcarbonylamino-N:N-di(β-methoxycarbonylethyl)aniline     
                                       &#34;                                  
50 3-isopropylcarbonylamino-N:N-di(β-methoxycarbonylethyl)aniline    
                                       &#34;                                  
51 3-methoxycarbonylamino-N:N-di(β-methoxycarbonylethyl)aniline      
                                       &#34;                                  
52 3-ethoxycarbonylamino-N:N-di(β-methoxycarbonylethyl)aniline       
                                       &#34;                                  
53 3-ureido-N:N-di(β-methoxycarbonylethyl)aniline                    
                                       &#34;                                  
54 3-N-methylureido-N:N-di(βmethoxycarbonylethyl)aniline             
                                       &#34;                                  
55 3-N-ethylureido-N:N-di(β-methoxycarbonylethyl)aniline             
                                       &#34;                                  
56 3-methylsulphonylamino-N:N-di(β-methoxycarbonylethyl)aniline      
                                       &#34;                                  
57 3-methylsulphonylamino-N:N-di(β-ethoxycarbonylethyl)aniline       
                                       &#34;                                  
58 3-ethylsulphonylamino-N:N-di(β-methoxycarbonylethyl)aniline       
                                       &#34;                                  
59 2-methoxy-5-propionylamino-N:N-di(β-methoxycarbonylethyl)aniline  
                                       Reddish-violet                     
60 2-ethoxy-5-acetylamino-N:N-di(β-methoxycarbonylethyl)aniline      
                                       &#34;                                  
61 3-methoxy-N:N-di(β-methoxycarbonylethyl)aniline                   
                                       Bluish-red                         
62 3-methyl-N:N-di[β-(β&#39;-hydroxyethoxycarbonyl)ethyl]aniline    
                                       Red                                
63 2-methoxy-N:N-di[β-(β&#39;-hydroxyethoxycarbonyl)ethyl]aniline   
                                       Bluish-red                         
64 2:5-dimethoxy-N:N-di[β-(β&#39;-hydroxyethoxycarbonnyl)ethyl]anili
   ne                                  Violet                             
65 3-methyl-N:N-di[γ-(β&#39;-hydroxyethoxycarbonyl)propyl]aniline  
                                       Red                                
66 3-methyl-N:N-di[(β&#39;-hydroxyethoxycarbonyl)methyl]aniline          
                                       Reddish-orange                     
67 3-methyl-N:N-di[δ-(β&#39;-hydroxyethoxycarbonyl)butyl]aniline   
                                       Red                                
68 3-methyl-N:N-di[β-(β&#39;-hydroxyethoxycarbonyl)propyl]aniline   
                                       &#34;                                  
69 2-ethoxy-N:N-di[β-(β&#39;-hydroxyethoxycarbonyl)ethyl]aniline    
                                       Bluish-red                         
70 2-methoxy-5-chloro-N:N-di[β-(β&#39;-hydroxyethoxycarbohyl)ethyl]a
   niline                              Red                                
71 2-methoxy-5-bromo-N:N-di[β-(β&#39;-hydroxyethoxycarbonyl)ethyl]an
   iline                               &#34;                                  
72 2-methoxy-5-methyl-N:N-di[β-(β&#39;-hydroxyethoxycarbonyl)ethyl]a
   niline                              Reddish-violet                     
73 3-chloro-N:N-di[β-(β&#39;-hydroxyethoxycarbonyl)ethyl]amiline    
                                       Scarlet                            
74 3-bromo-N:N-di[β-(β&#39;-hydroxyethoxycarbonyl)ethyl]aniline     
                                       &#34;                                  
75 3-acetylamino-N:N-di[β-(β&#39;-hydroxyethoxycarbonyl)ethyl]anilin
   e                                   Reddish-blue                       
76 3-acetylamino-N:N-di[β-(β&#39;-hydroxyethoxycarbonyl)propyl]anili
   ne                                  &#34;                                  
77 3-propionylamino-N:N-di[β-(β&#39;-hydroxyethoxycarbonyl)ethyl]ani
   line                                &#34;                                  
78 3-ethylsulphonylamino-N:N-di[β-(β&#39;-hydroxyethoxycarbonyl)ethy
   l]aniline                           &#34;                                  
79 3-acetylamino-N:N-di[β-(β&#39;-hydroxyethoxycarbonyl)ethyl]      
   aniline                             Bluish-red                         
80 3-acetylamino-N:N-di[β-(γ&#39;-hydroxypropoxycarbonyl)ethyl]anil
   ine                                 &#34;                                  
81 3-acetylamino-N:N-di[β-(δ&#39;-hydroxybutoxycarbonyl)ethyl]anili
   ne                                  &#34;                                  
82 3-acetylamino-N:N-di[β-(β&#39;-hydroxypropoxycarbonyl)ethyl]anili
   ne                                  &#34;                                  
83 3-acetylamino-N:N-di[β-(α&#39;-methyl-β&#39;-hydroxypropoxycarb
   onyl)ethyl]aniline                  &#34;                                  
84 N:N-di[β-(β&#39;-hydroxyethoxycarbonyl)ethyl]aniline             
                                       Scarlet                            
85 3-acetylamino-N:N-di(β-n-propoxycarbonylethyl)aniline             
                                       Bluish-red                         
86 3-acetylamino-N:N-di(β-isopropoxycarbonylethyl)aniline            
                                       &#34;                                  
87 3-acetylamino-N:N-di(β-n-butoxycarbonylethyl)aniline              
                                       &#34;                                  
88 3-acetylamino-N:N-di(β-sec-butoxycarbonyl)ethyl)aniline           
                                       &#34;                                  
89 3-acetylamino-N:N-di(β-isobutoxycarbonyl)ethyl)aniline            
                                       &#34;                                  
90 3-acetylamino-N:N-di(methoxycarbonylethyl)aniline                      
                                       Scarlet                            
91 3-acetylamino-N:N-di(δ-methoxycarbonylbutyl)aniline              
                                       Rubine                             
92 2-methyl-5-methoxy-N:N-di(β-methoxycarbonylethyl)aniline          
                                       Red                                
__________________________________________________________________________
 
    
     Further dyestuffs of the invention are obtained when the 2.54 parts of 2-(N:N-dimethylcarbamoyl)-4:6-dinitroaniline used in Example 1 are replaced by equivalent amounts of the amines listed in Table II. The shades obtained from the resulting dyestuffs are also listed in the Table. 
     
                       TABLE II                                                    
______________________________________                                    
Amine                   Shade                                             
______________________________________                                    
A   2-carbamoyl-4:6-dinitroaniline                                        
                            Blue                                          
B   2-carbamoyl-4-nitroaniline                                            
                            Reddish-violet                                
C   2-(N-methylcarbamoyl)4:6-dinitroaniline                               
                            Reddish-blue                                  
D   2-(N-ethylcarbamoyl)-4:6-dinitroaniline                               
                            &#34;                                             
______________________________________                                    
 
    
     Further dyestuffs of the invention are obtained by diazotising the amines listed in the first column of Table III and coupling with each of the coupling components listed in the second column of the Table, the reference numbers for the coupling components referring back to Table I. The dyestuffs were obtained using methods similar to that described in Example 1. The shades of the dyestuffs ranged from yellow to blue. 
     
                       TABLE III                                                   
______________________________________                                    
                        Coupling                                          
         Amine          Component                                         
______________________________________                                    
2-(N:N-dimethylcarbamoyl)-4:6-dinitroaniline                              
                         6,43                                             
2-carbamoyl-4-nitroaniline                                                
                        43                                                
2-(N-methylcarbamoyl)-4-nitroaniline                                      
                        43                                                
2-(N-ethylcarbamoyl)-4-nitroaniline                                       
                        43                                                
2-(N-n-propylcarbamoyl)-4-nitroaniline                                    
                        43                                                
2-(N-isoprropylcarbamoyl)-4-nitroaniline                                  
                        43                                                
2-(N-n-butylcarbamoyl)-4-nitroaniline                                     
                        43                                                
2-(N:N-diethylcarbamoyl)-4-nitroaniline                                   
                        43                                                
2-(N-methyl-N-ethylcarbamoyl)-4-nitroaniline                              
                        43                                                
2-(N:N-dimethylcarbamoyl)-5-nitroaniline                                  
                        43                                                
2-(N:N-dimethylcarbamoyl)-4-nitro-6-                                      
                        43                                                
chloroaniline                                                             
2-(N:N-dimethylcarbamoyl)-4-nitro-6-bromo-                                
                        43                                                
aniline                                                                   
2-(N-methylcarbamoyl)4:6-dinitroaniline                                   
                        43                                                
4-(N:N-dimethylcarbamoyl)aniline                                          
                        3                                                 
3-(N-ethylcarbamoyl)aniline                                               
                        3                                                 
2-carbamoylaniline      3                                                 
2-chloro-4-(N:N-dimethylcarbamoyl)aniline                                 
                        3                                                 
2-bromo-4-(N:N-dimethylcarbamoyl)aniline                                  
                        3                                                 
2:5-dichloro-4-(N:N-dimethylcarbamoyl)aniline                             
                        3                                                 
2-chloro-6-bromo-4-(N:N-dimethylcarbamoyl)                                
                        3                                                 
aniline                                                                   
______________________________________                                    
 
    
     Further dyestuffs of the invention are obtained by replacing the 3.25 parts of 2-methoxy-5-acetylamino-N:N-di(β-methoxycarbonylethyl) aniline used in Example 1 by equivalent amounts of the following coupling components. In all cases the dyestuffs yielded reddish blus shades. 
     2-methoxy-5-propionylamino-N:N-di(β-methoxycarbonylethyl)aniline, 
     2-ethoxy-5-propionylamino-N:N-di(β-methoxycarbonylethyl)aniline, 
     2-methoxy-5-n-propylcarbonylamino-N:N-di(β-methoxycarbonylethyl)aniline, 
     2-methoxy-5-methoxycarbonylamino-N:N-di(β-methoxycarbonylethyl)aniline 
     2-methoxy-5-ureido-N:N-di(β-methoxycarbonylethyl)aniline, 
     2-methoxy-5-N-ethylureido-N:N-di(β-methoxycarbonylethyl)aniline, 
     2-ethoxy-5-methoxycarbonylamino-N:N-di(β-methoxycarbonylethyl)aniline, 
     2-ethoxy-5-ureido-N:N-di(β-methoxycarbonylethyl)aniline, 
     2-methoxy-5-ureido-N:N-di(β-ethoxycarbonylethyl)aniline, 
     2-methoxy-5-methoxycarbonylamino-N:N-di(β-ethoxycarbonylethyl)aniline, 
     2-ethoxy-5-acetylamino-N:N-di[β-(β&#39;-hydroxyethoxycarbonyl)ethyl]aniline, 
     2-methoxy-5-acetylamino-N:N-di[β-(β&#39;-hydroxyethoxycarbonyl)ethyl]aniline, 
     The amines used in the above Examples were themselves obtained by converting the corresponding nitrobenzene carboxylic acid to the acid chloride, condensing with the appropriate amine of the formula: NHT 1  T 2 , and finally reducing the nitro group to an amino group, or by converting the corresponding acetylamino benzenecarboxylic acid to the acid chloride, condensing with an amine of the formula: HNT 1  T 2 , and finally hydrolysing off the N-acetyl group.