Patent Publication Number: US-4650860-A

Title: Benzisothiazolazo, diaminopyridine dyes

Description:
This application is a continuation of application Ser. No. 454,246, filed Dec. 29, 1982, now abandoned. 
    
    
     SUMMARY OF THE INVENTION 
     Azo dye having either 2-arylamino-5-cyano-6-alkylamino- or 2-alkylamino-5-cyano-6-arylamino-pyridine as coupling component general formula I ##STR3## where X is hydrogen, chlorine or bromine, B is hydrogen, methyl, ethyl or propyl, and one of the radicals R 1  or R 2  is phenyl which is unsubstituted or mono- or poly-substituted by chlorine, methyl, ethyl, t-butyl, phenoxy, methoxy, ethoxy, propoxy or butoxy, and the other is C 2  -C 8  -alkyl which is unsubstituted or substituted by C 1  -C 8  -alkoxy or phenyl, or is allyl, cyclopentyl, cyclohexyl, methylcyclohexyl, ##STR4## 
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     Specific examples of alkyl radicals R 1  and R 2  are C 2  H 5 , n--C 3  H 7 , i--C 3  H 7 , n-- or i--C 4  H 9 , n-- or i--C 5  H 11 , n-- or i--C 6  H 13 , n-- or i--C 7  H 15 , n-- or i--C 8  H 17 , C 2  H 4  OCH 3 , C 2  H 4  OC 2  H 5 , C 2  H 4  OC 3  H 7 , C 2  H 4  OC 4  H 9 , (CH 2 ) 3  OCH 3 , C 2  H 4  OCH(CH 3 ) 2 , (CH 2 ) 3  OC 2  H 5 , (CH 2 ) 3  OC 3  H 7 , (CH 2 ) 3  OC 4  H 9 , (CH 2 ) 3  OC 6  H 13 , (CH 2 ) 3  OC 8  H 17 , ##STR5## 
     The compounds of the formula I can be prepared by reacting a diazo compound of an amine of the formula ##STR6## with a coupling component of the formula ##STR7## in a conventional manner. Details may be found in the Examples, in which parts and percentages, unless indicated otherwise, are by weight. 
     The compounds of the formula I are preferably used for fixative printing (known under the tradename DYBLN, cf. eg. German Pat. No. 1,811,796 or U.S. Pat. No. 3,706,525), in which tone-on-tone dyeings can be produced on mixtures of cellulose fibers and polyester. Blue to black dyeings with very good fastness characteristics in comparison with conventional dyes, in particular lightfastness and wetfastness, and also a high stability to live steam, are obtained. 
     Particularly important compounds are those of the formula I a ##STR8## where R 1  and R 2  have the above meanings, but R 2  is preferably ##STR9## and R 1  is preferably ##STR10## always in combination with an unsubstituted or substituted alkyl radical of the type defined, and alkyl is methyl, ethyl or t-butyl. 
     Examples of preferred unsubstituted or substituted radicals R 1  and R 2  are --CH(CH 3 ) 2 , ##STR11## 
     Combinations where R 1  is C 6  H 5  and R 2  is ##STR12## are also preferred. 
    
    
     EXAMPLE 1 
     19.6 parts of the diazo component of the formula ##STR13## are prepared and diazotized with nitrosylsulfuric acid, by the process described in German Pat. No. 2,412,975. The finished diazonium salt solution is then run into a suspension of 31.1 parts of the coupling component of the formula ##STR14## in a mixture of 400 parts of water and 900 parts of ice. About 30% strength sodium formate solution is added to the coupling mixture, until the pH of the suspension has risen to 0.3-0.7, during which time the temperature is kept at below +5° C. by addition of ice. The coupling has ended after about 30 minutes, and the precipitated dye is isolated, washed salt-free and dried, in a conventional manner. 49 parts of a bluish black powder of the formula ##STR15## are obtained. The dye melts at from 225° C. to 230° C. and dyes cotton, polyester and polyester/cotton union fabric in lightfast reddish blue to navy shades. 
     If, instead of the above coupling component, the coupling component mixture formed when 2,6-dichloro-3-cyano-4-methylpyridine is reacted first with 2-methoxyethylamine and then with 2-methoxyaniline, as described in German Pat. No. 2,260,827, is used, the corresponding amount of a dye mixture is obtained which, in addition to the above dye, contains a minor amount of the dye of the formula ##STR16## The mixture melts at from 185° to 229° C., 
     The absorption maximum of a solution of the dye in dimethylformamide (about 10 mg/l) is 589.5 nm. 
     The dye mixture dyes or prints cotton, polyester and polyester/cotton union fabric in highly lightfast clear blue to navy hues at a slightly lower temperature than the pure dyes. The dyeings or prints have good wetfastness, even when the hues are deep, and they are also stable to hot steam. 
     An example of a suitable dyeing method is the procedure described in European Pat. No. 0,012,935, and an example of a suitable printing method is that of German Pat. No. 1,811,796. 
     EXAMPLE 2 
     27.5 parts of the diazo component of the formula ##STR17## are stirred into 200 parts of 96-98% strength sulfuric acid at from 10° to 15° C. The mixture is then cooled to 0°-10° C., and a mixture of 100 parts by volume of glacial acetic acid and 17 parts of propionic acid is added dropwise at this temperature. 33 parts of 42-44% strength nitrosylsulfuric acid solution is then added dropwise at 0°-4° C. in the course of from 20 to 30 minutes, with cooling. The diazotization mixture is subsequently stirred at from 0° to 4° C. for from 31/2 to 4 hours, and is then run, with stirring, into a suspension of 31.1 parts of the mixture of coupling components of the formulae ##STR18## which is described in Example 1, in a mixture of 400 parts of water and 900 parts of ice. 
     After the diazonium salt solution has been added, the pH of the coupling mixture is increased to 0.5-10 with approximately 30% strength sodium formate solution, during which the temperature is kept at from -3° to +5° C. by addition of ice. 
     The reacted coupling mixture is heated to 85° C. with steam and is kept at from 85° to 95° C. for 15-30 minutes, and the precipitated dye is washed salt-free in a conventional manner and dried to give 57 parts of a black powder of the formulae ##STR19## The mixing ratio of the dyes is the same as that of the coupling components used. 
     The dye mixture is soluble in dimethylformamide, giving a blue solution, and dyes or prints cotton, polyester or polyester/cotton union fabric in blue to navy hues. The resulting dyeings or prints have good lightfastness and wetfastness. 
     EXAMPLE 3 
     19.6 parts of the diazo component of the formula ##STR20## are prepared and diazotized by the process described in German Pat. No. 2,412,975. The diazonium salt solution is then run into a suspension of a mixture of 20.6 parts of the coupling component of the formula ##STR21## and 9.8 parts of the coupling component of the formula ##STR22## (which, because of the method of synthesis, each contain a relatively small amount of the 2,6-isomeric coupling component) in a mixture of 400 parts of water and 900 parts of ice. The individual coupling components are prepared from 2,6-dichloro-3-cyano-4-methylpyridine by a method similar to that described in German Pat. No. 2,260,827, by reacting the heterocyclic compound first with the aliphatic amine and then, in a second step, with the aromatic amine. 
     The coupling is brought to completion by a procedure similar to that described in Example 1, and the dye is worked up in a conventional manner. 47.5 parts of dye powder are isolated. A dye mixture is obtained, containing individual components of the formulae ##STR23## and relatively small amounts of ##STR24## 
     The dye mixture melts in the range from 185° to 198° C. and its powder is bluish black and dissolves in dimethylformamide giving a blue solution. 
     Pale dyeings or prints on polyester, cotton or polyester/cotton union fabrics are reddish blue, whilst deeper dyeings are clear navy. 
     The dye mixture dyes polyester and cotton with a good matching of hue. The dyeings have good fastness characteristics in use. 
     The dyes listed in the Tables can be prepared by a procedure similar to that described in the Examples. Where two hues are given for dyeings or prints, the first refers to a lighter dyeing (or print) using about 0.2-0.4% of dye, and the second refers to a dyeing (or print) using not less than 0.8% of dye. 
     
                                           TABLE 1                                 
__________________________________________________________________________
 ##STR25##                                                                
No. R.sup.1       R.sup.2        R.sup.3                                  
                                     Hue                                  
__________________________________________________________________________
 4                                                                        
     ##STR26##    C.sub.6 H.sub.5                                         
                                 CH.sub.3                                 
                                     reddish blue navy                    
 5                                                                        
     ##STR27##    &#34;              &#34;   &#34;                                    
 6                                                                        
     ##STR28##    &#34;              &#34;   &#34;                                    
 7                                                                        
     ##STR29##    &#34;              &#34;   &#34;                                    
 8  C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                      
                  &#34;              &#34;   &#34;                                    
 9                                                                        
     ##STR30##    &#34;              &#34;   &#34;                                    
10  C.sub.2 H.sub.4 OC.sub.3 H.sub.7 (n)                                  
                  &#34;              &#34;   &#34;                                    
11  C.sub.2 H.sub.4 OC.sub.4 H.sub.9 (n)                                  
                  &#34;              &#34;   &#34;                                    
12                                                                        
     ##STR31##    &#34;              &#34;   &#34;                                    
13  C.sub.3 H.sub.6 OCH.sub.3                                             
                  &#34;              &#34;   &#34;                                    
14  C.sub.3 H.sub.6 OC.sub.2 H.sub.5                                      
                  &#34;              &#34;   &#34;                                    
15                                                                        
     ##STR32##    &#34;              &#34;   &#34;                                    
16                                                                        
     ##STR33##    &#34;              &#34;   &#34;                                    
17                                                                        
     ##STR34##    &#34;              &#34;   &#34;                                    
18                                                                        
     ##STR35##                                                            
                   ##STR36##     &#34;   &#34;                                    
19                                                                        
     ##STR37##    &#34;              &#34;   &#34;                                    
20                                                                        
     ##STR38##    &#34;              &#34;   &#34;                                    
21                                                                        
     ##STR39##    &#34;              &#34;   &#34;                                    
22  C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                      
                  &#34;              &#34;   &#34;                                    
23  C.sub.2 H.sub.4 OC.sub.3 H.sub.7 (n)                                  
                  &#34;              &#34;   &#34;                                    
24  C.sub.2 H.sub.4 OC.sub.4 H.sub.9 (n)                                  
                  &#34;              &#34;   &#34;                                    
25                                                                        
     ##STR40##    &#34;              &#34;   &#34;                                    
26  C.sub.3 H.sub.6 OCH.sub.3                                             
                  &#34;              &#34;   blue navy                            
27  C.sub.3 H.sub.6 OC.sub.2 H.sub.5                                      
                  &#34;              &#34;   &#34;                                    
28                                                                        
     ##STR41##    &#34;              &#34;   &#34;                                    
29                                                                        
     ##STR42##                                                            
                   ##STR43##     &#34;   &#34;                                    
30  C.sub.2 H.sub.4 OCH.sub.3                                             
                  &#34;              &#34;   &#34;                                    
31  C.sub.3 H.sub.6 OCH.sub.3                                             
                  &#34;              &#34;   &#34;                                    
32                                                                        
     ##STR44##    CH.sub.2 CHCH.sub.2                                     
                                 &#34;   &#34;                                    
33                                                                        
     ##STR45##                                                            
                   ##STR46##     &#34;   &#34;                                    
34                                                                        
     ##STR47##                                                            
35                                                                        
     ##STR48##    &#34;              &#34;   &#34;                                    
36                                                                        
     ##STR49##    &#34;              &#34;   &#34;                                    
37  C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                      
                  &#34;              &#34;   &#34;                                    
38  C.sub.2 H.sub.4 OC.sub.3 H.sub.7 (n)                                  
                  &#34;              &#34;   &#34;                                    
39  C.sub.2 H.sub.4 OC.sub.4 H.sub.9 (n)                                  
                  &#34;              &#34;   &#34;                                    
40  C.sub.3 H.sub.6 OCH.sub.3                                             
                  &#34;              &#34;   &#34;                                    
41  C.sub.3 H.sub.6 OC.sub.2 H.sub.5                                      
                  &#34;              &#34;   &#34;                                    
42                                                                        
     ##STR50##    &#34;              &#34;   &#34;                                    
43  C.sub.3 H.sub.6 OCH.sub.3                                             
                   ##STR51##     &#34;   dull blue bluish black               
44                                                                        
     ##STR52##    &#34;              &#34;   &#34;                                    
45                                                                        
     ##STR53##    &#34;              &#34;   &#34;                                    
46                                                                        
     ##STR54##                                                            
                   ##STR55##     &#34;   greenish blue bluish black           
47                                                                        
     ##STR56##    &#34;              &#34;   &#34;                                    
48                                                                        
     ##STR57##    &#34;              &#34;   &#34;                                    
49                                                                        
     ##STR58##    &#34;              &#34;   &#34;                                    
50  C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                      
                  &#34;              &#34;   &#34;                                    
51                                                                        
     ##STR59##    &#34;              &#34;   &#34;                                    
52  C.sub.2 H.sub.4 OC.sub.3 H.sub.7 (n)                                  
                  &#34;              &#34;   &#34;                                    
53  C.sub.2 H.sub.4 OC.sub.4 H.sub.9 (n)                                  
                  &#34;              &#34;   &#34;                                    
54                                                                        
     ##STR60##    &#34;              &#34;   &#34;                                    
55  C.sub.3 H.sub.6 OCH.sub.3                                             
                  &#34;              &#34;   &#34;                                    
56  C.sub.3 H.sub.6 OC.sub.2 H.sub.5                                      
                  &#34;              &#34;   &#34;                                    
57  CH.sub.2 CH.sub.2 OCH.sub.3                                           
                  &#34;              &#34;   dull blue bluish black               
58  C.sub.3 H.sub.6 OCH.sub.3                                             
                  &#34;              H   &#34;                                    
59                                                                        
     ##STR61##                                                            
                   ##STR62##     CH.sub.3                                 
                                     &#34;                                    
60                                                                        
     ##STR63##    &#34;              &#34;   &#34;                                    
61                                                                        
     ##STR64##    &#34;              &#34;   &#34;                                    
62                                                                        
     ##STR65##    &#34;              &#34;   &#34;                                    
63  C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                      
                  &#34;              &#34;   &#34;                                    
64  C.sub.2 H.sub.4 OC.sub.3 H.sub.7 (n)                                  
                  &#34;              &#34;   &#34;                                    
65  C.sub.2 H.sub.4 OC.sub.4 H.sub.9 (n)                                  
                  &#34;              &#34;   &#34;                                    
66                                                                        
     ##STR66##    &#34;              &#34;   &#34;                                    
67  C.sub.3 H.sub.6 OCH.sub.3                                             
                  &#34;              &#34;   &#34;                                    
68  C.sub.3 H.sub.6 OC.sub.2 H.sub.5                                      
                  &#34;              &#34;   &#34;                                    
69  C.sub.2 H.sub.4 OCH.sub.3                                             
                  &#34;              &#34;   &#34;                                    
70  C.sub.3 H.sub.6 OCH.sub.3                                             
                  &#34;              H   &#34;                                    
71  &#34;             &#34;              C.sub.2 H.sub.5                          
                                     &#34;                                    
72  C.sub.4 H.sub.9 (n)                                                   
                  &#34;              CH.sub.3                                 
                                     &#34;                                    
73  C.sub.3 H.sub.6 OCH.sub. 3                                            
                   ##STR67##     &#34;   &#34;                                    
74                                                                        
     ##STR68##                                                            
                   ##STR69##     &#34;   bluish grey coal black               
75                                                                        
     ##STR70##    &#34;              &#34;   &#34;                                    
76                                                                        
     ##STR71##    &#34;              &#34;   &#34;                                    
77                                                                        
     ##STR72##    &#34;              &#34;   &#34;                                    
78  C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                      
                  &#34;              &#34;   &#34;                                    
79  C.sub.2 H.sub.4 OC.sub.3 H.sub.7 (n)                                  
                  &#34;              &#34;   &#34;                                    
80  C.sub.2 H.sub.4 OC.sub.4 H.sub.9 (n)                                  
                  &#34;              &#34;   &#34;                                    
81                                                                        
     ##STR73##    &#34;              &#34;   &#34;                                    
82  C.sub.3 H.sub.6 OCH.sub.3                                             
                  &#34;              &#34;   &#34;                                    
83  C.sub.3 H.sub.6 OC.sub.2 H.sub.5                                      
                  &#34;              &#34;   &#34;                                    
84                                                                        
     ##STR74##                                                            
85                                                                        
     ##STR75##    &#34;              &#34;   &#34;                                    
86                                                                        
     ##STR76##    &#34;              &#34;   &#34;                                    
87  C.sub.2 H.sub.4 OCH.sub.3                                             
                  &#34;              &#34;   &#34;                                    
88  C.sub.3 H.sub.6 OCH(CH.sub.3).sub.2                                   
                  &#34;              &#34;   &#34;                                    
89  C.sub.3 H.sub.6 OC.sub.8 H.sub.17 (i)                                 
                  &#34;              &#34;   &#34;                                    
90  C.sub.3 H.sub.6 OCH.sub.3                                             
                  &#34;              H   &#34;                                    
91  &#34;             &#34;              C.sub.2 H.sub.5                          
                                     &#34;                                    
92  C.sub.3 H.sub.6 OC.sub.2 H.sub.5                                      
                  &#34;              H   &#34;                                    
93                                                                        
     ##STR77##                                                            
                   ##STR78##     CH.sub.3                                 
                                     dull blue coal black                 
94                                                                        
     ##STR79##    &#34;              &#34;   &#34;                                    
95                                                                        
     ##STR80##    &#34;              &#34;   &#34;                                    
96                                                                        
     ##STR81##    &#34;              &#34;   &#34;                                    
97  C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                      
                  &#34;              &#34;   &#34;                                    
98                                                                        
     ##STR82##    &#34;              &#34;   &#34;                                    
99  C.sub.2 H.sub.4 OC.sub.3 H.sub.7 (n)                                  
                  &#34;              &#34;   &#34;                                    
100 C.sub.2 H.sub.4 OC.sub.4 H.sub.9 (n)                                  
                  &#34;              &#34;   &#34;                                    
101                                                                       
     ##STR83##    &#34;              &#34;   &#34;                                    
102 C.sub.3 H.sub.6 OCH.sub.3                                             
                  &#34;              &#34;   &#34;                                    
103 C.sub.3 H.sub.6 OC.sub.2 H.sub.5                                      
                  &#34;              &#34;   &#34;                                    
104                                                                       
     ##STR84##    &#34;              &#34;   &#34;                                    
105                                                                       
     ##STR85##    &#34;              &#34;   &#34;                                    
106                                                                       
     ##STR86##    &#34;              &#34;   &#34;                                    
107 C.sub.2 H.sub.4 OCH.sub.3                                             
                  &#34;              &#34;   &#34;                                    
108 C.sub.3 H.sub.6 OCH.sub.3                                             
                   ##STR87##     &#34;   bluish grey coal black               
__________________________________________________________________________
 
    
     
                       TABLE 2                                                     
______________________________________                                    
 ##STR88##                                                                
No.  R.sup.1        R.sup.2       R.sup.3                                 
                                      Hue                                 
______________________________________                                    
109                                                                       
      ##STR89##                                                           
                     ##STR90##    H   blue navy                           
110                                                                       
      ##STR91##     &#34;             &#34;   blue navy                           
111                                                                       
      ##STR92##     &#34;             &#34;   blue navy                           
112                                                                       
      ##STR93##     &#34;             &#34;   blue navy                           
113  C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                     
                    &#34;             &#34;   blue                                
                                      navy                                
114                                                                       
      ##STR94##     &#34;             &#34;   blue navy                           
115  CH.sub.2 CH.sub.2C.sub.6 H.sub.5                                     
                    &#34;             &#34;   blue                                
                                      navy                                
116                                                                       
      ##STR95##     &#34;             &#34;   blue navy                           
117  C.sub.2 H.sub.4 OC.sub.3 H.sub.7 (n)                                 
                    &#34;             &#34;   blue                                
                                      navy                                
118  C.sub.2 H.sub.4 OC.sub.3 H.sub.7 (i)                                 
                     ##STR96##    H   blue navy                           
119  C.sub.2 H.sub.4 OC.sub.4 H.sub.9 (n)                                 
                    &#34;             &#34;   blue                                
                                      navy                                
120  C.sub.3 H.sub.6 OCH.sub.3                                            
                    &#34;             &#34;   blue                                
                                      navy                                
121  C.sub.3 H.sub.6 OC.sub.2 H.sub.5                                     
                    &#34;             &#34;   blue                                
                                      navy                                
122  C.sub.3 H.sub.6 OC.sub.3 H.sub.7 (n)                                 
                    &#34;             &#34;   blue                                
                                      navy                                
123  C.sub.3 H.sub.6 OC.sub.8 H.sub.17 (i)                                
                    &#34;             &#34;   blue                                
                                      navy                                
124                                                                       
      ##STR97##     &#34;             &#34;   blue navy                           
125                                                                       
      ##STR98##     &#34;             Cl  blue navy                           
126                                                                       
      ##STR99##                                                           
                     ##STR100##   H   blue navy                           
127                                                                       
      ##STR101##    &#34;             Cl  blue                                
128                                                                       
      ##STR102##    &#34;             &#34;    &#34;                                  
129                                                                       
      ##STR103##    &#34;             &#34;    &#34;                                  
130  C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                     
                     ##STR104##   H   blue navy                           
131  C.sub.2 H.sub.4 OC.sub.3 H.sub.7 (n)                                 
                    &#34;             &#34;   blue                                
                                      navy                                
132  C.sub.2 H.sub.4 OC.sub.2 H.sub.7 (i)                                 
                    &#34;             &#34;   blue                                
                                      navy                                
133  C.sub.2 H.sub.4 OC.sub.4 H.sub.9 (n)                                 
                    &#34;             &#34;   blue                                
                                      navy                                
134  C.sub.3 H.sub.6 OCH.sub.3                                            
                    &#34;             &#34;   blue                                
                                      navy                                
135  C.sub.3 H.sub.6 OC.sub.2 H.sub.5                                     
                    &#34;             &#34;   blue                                
                                      navy                                
136  C.sub.3 H.sub.6 OC.sub.3 H.sub.7 (n)                                 
                    &#34;             &#34;   blue                                
                                      navy                                
137  C.sub.3 H.sub.6 OC.sub.8 H.sub.17 (i)                                
                    &#34;             &#34;   blue                                
                                      navy                                
138                                                                       
      ##STR105##                                                          
                     ##STR106##   &#34;   navy bluish black                   
139                                                                       
      ##STR107##    &#34;             &#34;   navy  bluish black                  
140                                                                       
      ##STR108##    &#34;             &#34;   navy bluish black                   
141                                                                       
      ##STR109##    &#34;             &#34;   navy bluish black                   
142  C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                     
                    &#34;             &#34;   navy                                
                                      bluish                              
                                      black                               
143  C.sub.2 H.sub.4 OC.sub.3 H.sub.7 (n)                                 
                     ##STR110##   H   navy bluish black                   
144  C.sub.2 H.sub.4 OC.sub.3 H.sub.7 (i)                                 
                    &#34;             &#34;   navy                                
                                      bluish                              
                                      black                               
145  C.sub.2 H.sub.4 OC.sub.4 H.sub.9 (n)                                 
                    &#34;             &#34;   navy                                
                                      bluish                              
                                      black                               
146  C.sub.3 H.sub.6 OCH.sub.3                                            
                    &#34;             &#34;   navy                                
                                      bluish                              
                                      black                               
147  C.sub.3 H.sub.6 OC.sub.2 H.sub.5                                     
                    &#34;             &#34;   navy                                
                                      bluish                              
                                      black                               
148  C.sub.3 H.sub.6 OC.sub.3 H.sub.7 (n)                                 
                    &#34;             &#34;   navy                                
                                      bluish                              
                                      black                               
149  CH(CH.sub.3).sub.2                                                   
                    &#34;             &#34;   blue                                
                                      navy                                
150                                                                       
      ##STR111##                                                          
                     ##STR112##   H   blue navy                           
151                                                                       
      ##STR113##    &#34;             &#34;   blue navy                           
152                                                                       
      ##STR114##    &#34;             &#34;   blue navy                           
153                                                                       
      ##STR115##    &#34;             &#34;   blue navy                           
154  C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                     
                    &#34;             &#34;   blue                                
                                      navy                                
155  C.sub.2 H.sub.4 OC.sub.3 H.sub.7 (n)                                 
                    &#34;             &#34;   blue                                
                                      navy                                
156  C.sub.2 H.sub.4 OC.sub.3 H.sub.7 (i)                                 
                     ##STR116##   H   blue navy                           
157  C.sub.2 H.sub.4 OC.sub.4 H.sub.9 (n)                                 
                    &#34;             &#34;   blue                                
                                      navy                                
158  C.sub.3 H.sub.6 OCH.sub.3                                            
                    &#34;             &#34;   blue                                
                                      navy                                
159  C.sub.3 H.sub.6 OC.sub.2 H.sub.5                                     
                    &#34;             &#34;   blue                                
                                      navy                                
160  C.sub.3 H.sub.6 OC.sub.3 H.sub.7 (n)                                 
                    &#34;             &#34;   blue                                
                                      navy                                
161  C.sub.3 H.sub.6 OC.sub.8 H.sub.17 (i)                                
                    &#34;             &#34;   blue                                
                                      navy                                
162                                                                       
      ##STR117##                                                          
                     ##STR118##   &#34;   navy                                
163                                                                       
      ##STR119##    &#34;             &#34;    &#34;                                  
164                                                                       
      ##STR120##                                                          
                     ##STR121##   &#34;   greenish  blue navy                 
165                                                                       
      ##STR122##    &#34;             &#34;   greenish blue navy                  
166                                                                       
      ##STR123##    &#34;             &#34;   greenish blue navy                  
167                                                                       
      ##STR124##    &#34;             &#34;   greenish blue navy                  
168  C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                     
                    &#34;             &#34;   greenish                            
                                      blue                                
                                      navy                                
169                                                                       
      ##STR125##                                                          
                     ##STR126##   H   greenish blue navy                  
170  CH.sub.2 CH.sub.2C.sub.6 H.sub.5                                     
                    &#34;             &#34;   greenish                            
                                      blue                                
                                      navy                                
171                                                                       
      ##STR127##    &#34;             &#34;   greenish blue navy                  
172  C.sub.2 H.sub.4 OC.sub.3 H.sub.7 (n)                                 
                    &#34;             &#34;   greenish                            
                                      blue                                
                                      navy                                
173  C.sub.2 H.sub.4 OC.sub.3 H.sub.7 (i)                                 
                    &#34;             &#34;   greenish                            
                                      blue                                
                                      navy                                
174  C.sub.2 H.sub.4 OC.sub.4 H.sub.9 (n)                                 
                    &#34;             &#34;   greenish                            
                                      blue                                
                                      navy                                
175  C.sub.3 H.sub.6 OCH.sub.3                                            
                    &#34;             &#34;   greenish                            
                                      blue                                
                                      navy                                
176  C.sub.3 H.sub.6 OC.sub.2 H.sub.5                                     
                    &#34;             &#34;   greenish                            
                                      blue                                
                                      navy                                
177  C.sub.3 H.sub.6 OC.sub.3 H.sub.7 (n)                                 
                    &#34;             &#34;   greenish                            
                                      blue                                
                                      navy                                
178  C.sub.3 H.sub.6 OC.sub.8 H.sub.17 (i)                                
                    &#34;             &#34;   greenish                            
                                      blue                                
                                      navy                                
179                                                                       
      ##STR128##    &#34;             &#34;   greenish blue navy                  
180  C.sub.2 H.sub.4 OCH.sub.3                                            
                    &#34;             &#34;   greenish                            
                                      blue                                
                                      navy                                
181                                                                       
      ##STR129##                                                          
                     ##STR130##   &#34;   blue navy                           
182                                                                       
      ##STR131##    &#34;             &#34;   blue navy                           
183                                                                       
      ##STR132##                                                          
                     ##STR133##   H   blue navy                           
184                                                                       
      ##STR134##    &#34;             &#34;   blue navy                           
185  C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                     
                    &#34;             &#34;   blue                                
                                      navy                                
186  CH.sub.2 CH.sub.2C.sub.6 H.sub.5                                     
                    &#34;             &#34;   blue                                
                                      navy                                
187                                                                       
      ##STR135##    &#34;             &#34;   blue navy                           
188  C.sub.2 H.sub.4 OC.sub.3 H.sub.7 (n)                                 
                    &#34;             &#34;   blue                                
                                      navy                                
189  C.sub.2 H.sub.4 OC.sub.3 H.sub.7 (i)                                 
                    &#34;             &#34;   blue                                
                                      navy                                
190  C.sub.2 H.sub.4 OC.sub.4 H.sub.9 (n)                                 
                    &#34;             &#34;   blue                                
                                      navy                                
191  C.sub.3 H.sub.6 OCH.sub.3                                            
                    &#34;             &#34;   blue                                
                                      navy                                
192  C.sub.3 H.sub.6 OC.sub.2 H.sub.5                                     
                    &#34;             &#34;   blue                                
                                      navy                                
193  C.sub.3 H.sub.6 OC.sub.3 H.sub.7 (n)                                 
                    &#34;             &#34;   blue                                
                                      navy                                
194  C.sub.3 H.sub.6 OC.sub.8 H.sub.17 (i)                                
                    &#34;             &#34;   blue                                
                                      navy                                
195                                                                       
      ##STR136##    &#34;             &#34;   blue navy                           
196  C.sub.2 H.sub.4 OCH.sub.3                                            
                    &#34;             &#34;   blue                                
                                      navy                                
197                                                                       
      ##STR137##                                                          
                     ##STR138##   H   blue navy                           
198                                                                       
      ##STR139##                                                          
                     ##STR140##   &#34;   blue navy                           
199                                                                       
      ##STR141##    &#34;             &#34;   blue navy                           
200                                                                       
      ##STR142##    &#34;             &#34;   blue navy                           
201                                                                       
      ##STR143##    &#34;             &#34;   blue navy                           
202  C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                     
                    &#34;             &#34;   blue                                
                                      navy                                
203  C.sub.2 H.sub.4 OC.sub.3 H.sub.7 (n)                                 
                    &#34;             &#34;   blue                                
                                      navy                                
204  C.sub.2 H.sub.4 OC.sub.3 H.sub.7 (i)                                 
                    &#34;             &#34;   blue                                
                                      navy                                
205  C.sub.2 H.sub.4 OC.sub.4 H.sub.9 (n)                                 
                    &#34;             &#34;   blue                                
                                      navy                                
206  C.sub.3 H.sub.6 OCH.sub.3                                            
                    &#34;             &#34;   blue                                
                                      navy                                
207  C.sub.3 H.sub.6 OC.sub.2 H.sub.5                                     
                    &#34;             &#34;   blue                                
                                      navy                                
208  C.sub.3 H.sub.6 OC.sub.3 H.sub.7 (n)                                 
                    &#34;             &#34;   blue                                
                                      navy                                
209  C.sub.3 H.sub.6 OC.sub.8 H.sub.17 (i)                                
                    &#34;             &#34;   blue                                
                                      navy                                
210                                                                       
      ##STR144##                                                          
                     ##STR145##   H   navy                                
211  &#34;              C.sub.3 H.sub.6 OCH.sub.3                             
                                  &#34;    &#34;                                  
212                                                                       
      ##STR146##                                                          
                     ##STR147##   &#34;   blue navy                           
213                                                                       
      ##STR148##    &#34;             &#34;   blue navy                           
214                                                                       
      ##STR149##    &#34;             &#34;   blue navy                           
215                                                                       
      ##STR150##    &#34;             &#34;   blue navy                           
216  C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                     
                    &#34;             &#34;   blue                                
                                      navy                                
217  C.sub.2 H.sub.4 OC.sub.3 H.sub.7 (n)                                 
                    &#34;             &#34;   blue                                
                                      navy                                
218  C.sub.2 H.sub.4 OC.sub.3 H.sub.7 (i)                                 
                    &#34;             &#34;   blue                                
                                      navy                                
219  C.sub.2 H.sub.4 OC.sub.4 H.sub.9 (n)                                 
                    &#34;             &#34;   blue                                
                                      navy                                
220  C.sub.3 H.sub.6 OCH.sub.3                                            
                    &#34;             &#34;   blue                                
                                      navy                                
221  C.sub.3 H.sub.6 OC.sub.2 H.sub.5                                     
                    &#34;             &#34;   blue                                
                                      navy                                
222  C.sub.3 H.sub.6 OC.sub.3 H.sub.7 (n)                                 
                    &#34;             &#34;   blue                                
                                      navy                                
223  C(CH.sub.3).sub.3                                                    
                     ##STR151##   &#34;   blue navy                           
224  C.sub.6 H.sub.5                                                      
                     ##STR152##   &#34;   blue navy                           
225  C.sub.4 H.sub.9 (n)                                                  
                     ##STR153##   &#34;   blue navy                           
226                                                                       
      ##STR154##    C.sub.6 H.sub.5                                       
                                  &#34;   blue navy                           
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