Patent Publication Number: US-4317929-A

Title: Tetraphenylketazines and isoindolinone pigments obtained therefrom

Description:
This is a divisional of application Ser. No. 007,549, filed on Jan. 30, 1979, now U.S. Pat. No. 4,231,931. 
    
    
     The invention provides novel isoindolinone pigments of the formula ##STR4## wherein X 1 , X 2 , X 3  and X 4  represent hydrogen or halogen atoms, or one or two of X 1  -X 4  represent alkoxy groups of 1 to 4 carbon atoms or phenoxy groups and the others represent hydrogen or halogen atoms, R and R&#34; represent hydrogen or halogen atoms or methyl or methoxy groups, R 1 , R 2 , R 4  and R 5  represent hydrogen, chlorine, or bromine atoms or alkyl groups of 1 to 2 carbon atoms, R 3  and R 6  represent hydrogen or halogen atoms, alkyl or alkoxy groups of 1 to 2 carbon atoms or radicals of the formula ##STR5## Q represents a direct bond or a p-phenylene group, n is 1 or 2 and X represents a group of the formula ##STR6## wherein R 7  and R 8  represent hydrogen or chlorine atoms or methyl groups. 
     Preferred pigments are those of the formula (I) containing iminoisoinodolinone radicals of the formula ##STR7## wherein Hal represents a chlorine or bromine atom, Y and/or Z represent chlorine or bromine atoms or alkoxy groups of 1 to 4 carbon atoms, and, in particular, those pigments of the formula (I) wherein X 1 , X 2 , X 3  and X 4  represent chlorine atoms. 
     Particularly preferred pigments are those of the formula (I) wherein R 3  and R 6  represent hydrogen, chlorine or bromine atoms, methyl or methoxy groups in the para-position to X, and especially those of the formula (I), wherein Q is a direct bond and n is 1. 
     The pigments of the present invention are obtained by condensing 2 or 4 moles of an isoindolinone of the formula ##STR8## wherein X 1 , X 2 , X 3  and X 4  are as previously defined and A represents a group of the formula ##STR9## wherein Y 1  represents an imino or thio group and Y 2  represents a halogen atom, an alkoxy group of 1 to 4 carbon atoms or a secondary amino group, with 1 mole of an amine of the formula ##STR10## wherein R, R&#34;, R 1 , R 2 , R 4  and R 5  are as previously defined and R 3  &#39; and R 6  &#39; represent hydrogen or halogen atoms, alkyl or alkoxy groups of 1 to 2 carbon atoms or amino groups in the para-position to X, and Q is a direct bond or represents a p-phenylene group. 
     The preferred starting materials are isoindolinones of the formula ##STR11## wherein the symbols R&#39; represents alkyl groups of 1 to 4 carbon atoms, Y and Z are as previously defined, and especially those isoindolinones wherein X 1  -X 4  in formula (II) represent chlorine atoms. 
     Examples of such isoindolinones are: 
     3-imino-isoindolinone 
     3-imino-4-chloro-isoindolinone 
     3-imino-5-chloro-isoindolinone 
     3-imino-6-chloro-isoindolinone 
     3-imino-7-chloro-isoindolinone 
     3-imino-5,6-dichloro-isoindolinone 
     3-imino-4,5-dichloro-isoindolinone 
     3,3-dimethoxy-4,5-dichloro-isoindolinone 
     3,3-dimethoxy-4,7-dichloro-isoindolinone 
     3,3-dimethoxy-4,5,6,7-tetrachloro-isoindolinone 
     3,3,6-trimethoxy-4,5,7-trichloro-isoindolinone 
     3,3-dimethoxy-4,5,7-trichloro-6-ethoxy-isoindolinone 
     3,3-dimethoxy-4,5,7-trichloro-6-n-propoxy-isoindolinone 
     3,3-dimethoxy-4,5,7-trichloro-6-n-butoxy-isoindolinone 3,3-dimethoxy-4,5,7-trichloro-6-phenoxy-isoindolinone 3,3,4,6-tetramethoxy-5,7-dichloro-isoindolinone. 
     The compounds are known ones or compounds which can be obtained by known methods. 
     The invention also provides the novel amines of the formula ##STR12## wherein R, R&#34;, R 1 , R 2 , R 4 , R 5 , R 3  &#39;, R 6  &#39;, Q, X and n are as previously defined. They are obtained by condensation of 1 mole of hydrazine with 1 mole of an amine of the formula ##STR13## and with 1 mole of an amine of the formula ##STR14## 
     Amines used for the manufacture of the pigments of the formula (I) are preferably those of the formula (III), wherein R 3  &#39; and R 6  &#39; represent hydrogen, chlorine or bromine atoms, methyl or methoxy groups in the para-position to X, and especially those wherein Q is a direct bond and n is 1. 
     The nomemclature used in the following Examples is derived from the tetraphenylketazine of the formula ##STR15## with the indicated numbering. 4,4&#39;-diamino-tetraphenylketazine 
     4,4&#39;-diamino-4&#34;,4&#34;&#39;-dichloro-tetraphenylketazine 
     4,4&#39;-diamino-4&#34;,4&#34;&#39;-dimethyl-tetraphenylketazine 
     4,4&#39;-diamino-4&#34;,4&#34;&#39;-dimethoxy-tetraphenylketazine 
     4,4&#39;-diamino-3,3&#39;,4&#34;,4&#34;&#39;-tetramethyl-tetraphenylketazine 
     4,4&#39;-diamino-3,3&#39;-dimethyl-4&#34;,4&#34;&#39;-dimethoxy-tetraphenylketazine 
     4,4&#39;-diamino-4&#34;,4&#34;&#39;-diphenoxy-tetraphenylketazine 
     4,4&#39;-diamino-4&#34;,4&#34;&#39;-diphenyl-tetraphenylketazine 
     4,4&#39;-diamino-3,3&#39;-dimethyl-4&#34;,4&#34;&#39;-diphenyl-tetraphenylketazine 
     4,4&#39;-diamino-3&#34;,3&#34;&#39;,4&#34;,4&#34;&#39;-tetrametheyl-tetraphenylketazine 
     4,4&#39;-diamino-2&#34;,2&#34;&#39;,4&#34;,4&#34;&#39;-tetrachloro-tetraphenylketazine 
     4,4&#39;-diamino-3,3&#39;,3&#34;,3&#34;&#39;,4&#34;,4&#34;&#39;-hexamethyl-tetraphenylketazine 
     4,4&#39;-diamino-3,3&#39;-dimethyl-2&#34;,2&#34;&#39;,4&#34;,4&#34;&#39;-tetrachloro-tetraphenylketazine 
     4,4&#39;-diamino-3&#34;,3&#34;&#39;,4&#34;,4&#34;&#39;-tetramethoxy-tetraphenylketazine 
     4,4&#39;,4&#34;,4&#34;&#39;-tetramino-tetraphenylketazine 
     3&#34;,3&#34;&#39;,4,4&#39;-tetramino-tetraphenylketazine 
     3&#34;,3&#34;&#39;,4,4&#39;-tetramino-4&#34;,4&#34;&#39;-dichloro-tetraphenylketazine 
     4,4&#39;-diamino-4&#34;,4&#34;&#39;-di-(o-aminophenoxy)-tetraphenylketazine 
     4,4&#39;-diamino-4&#34;,4&#34;&#39;-di-(p-aminophenoxy)-tetraphenylketazine 
     4,4&#39;-diamino-4&#34;,4&#34;&#39;-di-(p-amino-o-chlorophenoxy)-tetraphenylketazine. 
     The above amines can be obtained by condensation of the corresponding aminobenzophenones with hydrazine. 
     Where 3-imino-, 3-thio- or 3,3-bis-sec-amino-4,5,6,7-tetrachloroisoindolin-1-ones or alkali salts of 3,3-dialkoxy-4,5,6,7-tetrachloroisoindolin-1-ones are used as starting materials, then it is advantageous to use water-miscible organic solvents, e.g. lower aliphatic alcohols, such as lower alkanols, for example methanol, isopropanol or butanol, lower cyclic ethers, such as dioxan, ethylene glycol monomethyl ether, lower aliphatic ketones, such as acetone. In doing so, the condensation is able to take place even at relatively low temperatures. It is advantageous to perform the reaction in the presence of an agent binding alkali and organic bases, for example a lower fatty acid which can be used simultaneously as solvent, especially acetic acid. 
     If the starting material is a 3,3-dihalogeno-4,5,6,7-tetrachloroisoindolin-1-one, it is preferred to use an organic solvent that does not contain hydroxyl groups, for example an aromatic hydrocarbon, such as benzene, toluene, xylene, tetrahydronaphthalene or diphenyl; a cycloaliphatic hydrocarbon, for example cyclohexane; a halogenated aliphatic hydrocarbon, for example carbon tetrachloride or tetrachloroethylene, or a halogenated aromatic hydrocarbon, for example chlorobenzene or di- and trichlorobenzene; also a nitrated hydrocarbon, for example nitrobenzene; an aliphatic ether, for example dibutyl ether; an aromatic ether, for example diphenyl ether, or a cyclic ether, for example dioxan; also a ketone, for example acetone; or an ester, for example an ester of a lower fatty acid with a lower alkanol, for example ethyl acetate, in the presence of an acid acceptor. 
     Directly after their formation the pigments of the present invention precipitate from the reaction medium. For certain purposes they can be used direct as crude pigments; but their properties, especially with respect to purity, form, and hiding power, can also be improved by known methods, for example by extraction with organic solvents or by grinding with grinding assistants which can afterwards be removed, for example salts, or by precipitation with an alkali. 
     The new colourants constitute valuable pigments which, in finely divided form, can be used for pigmenting organic material of high molecular weight, for example cellulose ethers and esters, such as ethyl cellulose, acetyl cellulose, nitrocellulose, polyamides and polyurethanes or polyesters, natural resins or synthetic resins, such as polymerisation or condensation resins, for example aminoplasts, in particular urea/formaldehyde and melamine/formaldehyde resins, alkyd resins, phenolic plastics, polycarbonates, polyolefins, such as polystyrene, polyvinyl chloride, polyethylene, polypropylene, polyacrylonitrile, polyacrylates, thermoplastic or curable acrylic resins, rubber, casein, silicon and silicone resins, singly or in mixtures. 
     It is immaterial whether the cited materials of high molecular weight are in the form of plastics, melts or of spinning solutions, lacquers, paints or printing inks. Depending on the use to which they are put, it is advantageous to use the new pigments as toners or in the form of preparations. 
     The colourations obtained are characterised by high colour strength, great purity of shade, and good fastness to alkali, overstripe bleeding, light, migration and atmospheric influences. 
    
    
     The invention is illustrated by the following Examples in which the percentages are by weight. 
     EXAMPLE 1 
     17.25 g of 3,4,5,6-tetrachlorocyanobenzoic acid methyl ester are stirred with 57.5 ml of a 1 N sodium methylate solution in methanol until a clear solution is obtained. The sodium salt of 3,3-dimethoxy-4,5,6,7-tetrachloroisoindolin-1-one forms. With good stirring, 11.5 g of 4,4&#39;-diamino-4&#34;,4&#34;&#39;-dichloro-tetraphenylketazine (ground and sieved) and 100 ml of o-dichlorobenzene are added. As a bath temperature of 110° C., the internal temperature is raised in the course of 2 hours to 90° C. while distilling off methano, whereupon the sodium salt of the pigment precipitates without a clear solution having formed. The batch is diluted with a further 100 ml of o-dichlorobenzene and, when the internal temperature has reached 100° C. (bath temperature 130° C.), acidified with 20 ml of glacial acetic acid. The temperature is raised to 140°-150° C. and kept thereat for 2 hours with good stirring. The insoluble pigment is filtered off at 120°  C., washed with methanol, acetone and water, and dried, to yield 24 g of a productive orange pigment, which in the form in which it is obtained, or after it has been ground by one of the conventional methods, can be used for colouring plastics and for obtaining printing pastes and lacquers. The orange colourations obtained therewith are characterised by outstanding fastness properties. 
     
         ______________________________________                                    
Analysis                                                                  
______________________________________                                    
calculated:   C 50.8    H 1.8   N 8.4                                     
found:        C 51.0    H 2.1   N 8.8                                     
______________________________________                                    
 
    
     EXAMPLE 2 
     An orange pigment with similar properties obtained by using 3,4,5,6-tetrabromo-o-cyanobenzoic acid methyl ester instead of 3,4,5,6-tetrachloro-o-cyanobenzoic acid methyl ester. 
     EXAMPLE 3 
     By using equimolar amounts of 3,4,6-trichloro-5-methoxy-o-cyanobenzoic acid methyl ester instead of 3,4,5,6-tetrachlorocyanobenzoic acid methyl ester, an orange pigment is obtained which, when incorporated into plastics, printing pastes and lacquers, has similarly good properties. 
     EXAMPLES 4 TO 40 
     Table I lists further pigments which are obtained by condensing an isoindolinone of the formula ##STR16## wherein Y 1  and Z 1  have the indicated meanings, with a diamine of the formula ##STR17## wherein R, R 1 , R 2 , R 3 , R 4  and Q have the indicated meanings. 
     
                                           TABLE I                                 
__________________________________________________________________________
No Y.sub.1                                                                
       Z.sub.1                                                            
           R  R.sub.1  R.sub.2                                            
                           R.sub.3                                        
                               R.sub.4                                    
                                   Shade                                  
__________________________________________________________________________
1 Q = direct bond                                                         
5  Cl  Cl  H  H        H   H   H   scarlet                                
6  Cl  Cl  CH.sub.3                                                       
              H        H   H   H   scarlet                                
7  Cl  Cl  H  CH.sub.3 H   H   H   scarlet                                
8  Cl  OCH.sub.3                                                          
           H  CH.sub.3 H   H   H   orange                                 
9  Cl  Cl  CH.sub.3                                                       
              CH.sub.3 H   H   H   red                                    
10 Cl  Cl  H  OCH.sub.3                                                   
                       H   H   H   red                                    
11 Cl  Cl  CH.sub.3                                                       
              OCH.sub.3                                                   
                       H   H   H   red                                    
12 OCH.sub.3                                                              
       OCH.sub.3                                                          
           H  Cl       H   H   H   yellow                                 
13 Cl  Cl  CH.sub.3                                                       
              Cl       H   H   H   orange                                 
14 Cl  Cl  H  Br       H   H   H   orange                                 
15 Cl  Cl  CH.sub.3                                                       
              Br       H   H   H   orange                                 
16 Cl  Cl  H  phenyl   H   H   H   scarlet                                
17 Cl  Cl  CH.sub.3                                                       
              phenyl   H   H   H   red                                    
18 Cl  Cl  H  phenoxy  H   H   H   yellow                                 
19 Cl  Cl  H  CH.sub.3 CH.sub.3                                           
                           H   H   scarlet                                
20 Cl  OCH.sub.3                                                          
           H  CH.sub.3 CH.sub.3                                           
                           H   H   orange                                 
21 Cl  Cl  CH.sub.3                                                       
              CH.sub.3 CH.sub.3                                           
                           H   H   red                                    
22 Cl  Cl  H  CH.sub.3 H   CH.sub.3                                       
                               H   yellow                                 
23 Cl  Cl  H  OCH.sub.3                                                   
                       OCH.sub.3                                          
                           H   H   yellow                                 
24 Cl  Cl  H  OCH.sub.3                                                   
                       H   OCH.sub.3                                      
                               H   yellow                                 
25 Cl  Cl  H  Cl       Cl  H   H   orange                                 
26 Cl  OCH.sub.3                                                          
           H  Cl       Cl  H   H   yellow                                 
27 Cl  Cl  CH.sub.3                                                       
              Cl       Cl  H   H   orange                                 
28 Cl  OCH.sub.3                                                          
           CH.sub.3                                                       
              Cl       Cl  H   H   yellow                                 
29 Cl  Cl  H  Cl       H   Cl  H   yellow                                 
30 Cl  Cl  H  OC.sub.2 H.sub.5                                            
                       H   H   H   orange                                 
31 Cl  Cl  H  F        H   H   H   yellowish orange                       
32 Cl  Cl  H  C.sub.2 H.sub.5                                             
                       H   H   H   orange                                 
33 Cl  Cl  H  H        H   OCH.sub.3                                      
                               OCH.sub.3                                  
                                   yellow                                 
34 Cl  Cl  CH.sub.3                                                       
              F        H   H   H   orange                                 
35 Cl  Cl  H  Cl       H   CH.sub.3                                       
                               CH.sub.3                                   
                                   yellow                                 
36 Cl  Cl  H  Cl       H   OCH.sub.3                                      
                               OCH.sub.3                                  
                                   yellow                                 
37 Cl  Cl  H  H        H   CH.sub.3                                       
                               CH.sub.3                                   
                                   yellow                                 
38 Cl  Cl  CH.sub.3                                                       
              OC.sub.2 H.sub.5                                            
                       H   H   H   red                                    
39 Cl  Cl  CH.sub.3                                                       
              C.sub.2 H.sub.5                                             
                       H   H   H   scarlet                                
40 Cl  Cl  CH.sub.3                                                       
               ##STR18##                                                  
                       H   H   H   orange                                 
 ##STR19##                                                                
41 Cl  Cl  H  H        H   H   H   orange                                 
42 Cl  Cl  H  CH.sub.3 H   H   H   yellow                                 
43 Cl  Cl  H  OCH.sub.3                                                   
                       H   H   H   yellow                                 
44 Cl  Cl  H  Cl       H   H   H   yellow                                 
__________________________________________________________________________
 
    
     EXAMPLE 45 
     17.25 g of 3,4,5,6-tetrachloro-o-cyanobenzoic acid methyl ester are stirred with 57.5 ml of 1 N sodium methylate solution in methanol until a clear solution is obtained, whereupon the sodium salt of 3,3-dimethoxy-4,5,6,7-tetrachloroisoindolinone forms. Then 5.25 g of 4,4&#39;,4&#34;,4&#34;&#39;-tetraamino-tetraphenylketazine (finely ground and sieved) are stirred in and the reaction flask is subsequently rinsed with methanol. The reaction mixture is then kept gently at the boil at a bath temperature of 80° C. The temperature is raised to 100° C. while distilling off methanol. The reaction mixture is diluted with a further 100 ml of o-dichlorobenzene and acidified with 20 ml of glacial acetic acid. The temperature is raised to 140°-145° C. and kept thereat for 2 hours with good stirring. The pigment is collected by filtration at 120° C. and the filter cake is washed with methanol, acetone and water and dried, affording 18 g of a productive orange pigment which, in the form in which it is obtained or after it has been ground by one of the conventional methods, can be used for the preparation of lacquers and printing pastes as well as for incorporation in plastics. The resulting orange colourations have outstanding fastness properties. 
     
         ______________________________________                                    
Analysis                                                                  
______________________________________                                    
calculated    C 46.8    H 1.3     N 9.4                                   
found         C 45.9    H 1.6     N 9.3                                   
______________________________________                                    
 
    
     EXAMPLES 46 TO 56 
     Table II lists further pigments which are obtained by condensing an isoindolinone of the formula (IX), wherein Y 1  and Z 1  have the indicated meanings, with the tetraaminoazines also listed in the table. 
     
                       TABLE II                                                    
______________________________________                                    
No.  Y.sub.1                                                              
            Z.sub.1  Tetraaminoazine  Shade                               
______________________________________                                    
46   Cl     Cl       4,4&#39;,3&#34;,3&#34;&#39;-tetraamino-tetra-                        
                                      yellow                              
                     phenylketazine                                       
47   Cl     Cl       4,4&#39;,3&#34;,3&#34;&#39;-tetraamino-4&#34;,4&#34;&#39;-                       
                                      orange                              
                     dichlorotetraphenylketazine                          
48   Cl     Cl       4,4&#39;-diamino-4&#34;,4&#34;&#39;-di(o-amino-                      
                                       &#34;                                  
                     phenoxy)-tetraphenylketazine                         
49   Cl     Cl       4,4&#39;-diamino-4&#34;,4&#34;&#39;-di-(p-amino-                     
                                       &#34;                                  
                     phenoxy)-tetraphenylketazine                         
50   Cl     Cl       4,4&#39;-diamino-4&#34;,4&#34;&#39;-di-(p-amino-                     
                                       &#34;                                  
                     o-chlorophenoxy)-tetraphenyl-                        
                     ketazine                                             
51   Cl     --OCH.sub.3                                                   
                     4,4&#39;,4&#34;,4&#34;&#39;-tetraamino-tetra-                        
                                      yellowish                           
                     phenylketazine   orange                              
52   Cl     Cl       4,4&#39;-diamino-3&#34;,3&#34;&#39;-dichloro-                        
                                      yellow                              
                     4&#34;,4&#34;&#39;-di-[p-aminophenoxy-]-                         
                     tetraphenylketazine                                  
53   Cl     Cl       4,4&#39;-diamino-3&#34;,3&#34;&#39;-dichloro-                        
                                      yellow                              
                     4&#34;,4&#34;&#39;-di-(o-chloro-p-amino-                         
                     phenoxy)-tetraphenylketazine                         
54   Cl     Cl       4,4&#39;-diamino-3,3&#39;-dimethyl-                          
                                      yellow                              
                     3&#34;,3&#34;&#39;-dichloro-4&#34;,4&#34;&#39;-di-                           
                     (o-chloro-p-aminophenoxy)-                           
                     tetraphenylketazine                                  
55   Cl     Cl       4,4&#39;-diamino-4&#34;,4&#34;&#39;-(p-amino-                        
                                      orange                              
                     phenyl)-tetraphenylketazine                          
56   Cl     Cl       4,4&#39;-diamino-3,3&#39;-dimethyl-                          
                                      orange                              
                     3&#34;,3&#34;&#39;-dichloro-4&#34;,4&#34;&#39;-(p-                           
                     aminophenoxy)-tetraphenyl-                           
                     ketazine                                             
______________________________________                                    
 Q = direct bond                                                          
 
    
     EXAMPLE 57 
     The procedure of Example 1 is repeated using 11 g of the 4,4&#34;-diamino-4&#39;-chloro-4&#34;-methyltetraphenylketazine obtained in accordance with Example 213 instead of 11,5 g of 4,4&#34;-diamino-4&#39;,4&#34;&#39;-dichloro-tetraphenylketazine. Yield: 23.2 g of a much redder orange pigment which has similarly good properties when incorporated into the different substrates. 
     EXAMPLES 58 TO 135 
     The following table lists further pigments which are obtained by condensing 3,3-dimethoxy-4,5,6,7-tetrachloroisoindolinone-1 with diamino-tetraphenylketazines of the formula ##STR20## wherein R 1  -R 6  have the meanings indicated in the table. 
     
                       TABLE                                                       
______________________________________                                    
No     R.sub.1                                                            
             R.sub.2                                                      
                    R.sub.3                                               
                           R.sub.4                                        
                                R.sub.5                                   
                                       R.sub.6                            
                                            Shade                         
______________________________________                                    
58    H      H      Cl     H    CH.sub.3                                  
                                       CH.sub.3                           
                                            orange                        
59    H      H      H      H    CH.sub.3                                  
                                       H    orange                        
60    H      H      CH.sub.3                                              
                           H    OCH.sub.3                                 
                                       H    scarlet                       
61    H      H      H      H    Cl     H    orange                        
62    H      H      Cl     H    Br     H    orange                        
63    H      H      Br     H    H      H    orange                        
64    H      H      CH.sub.3                                              
                           H    Br     H    scarlet                       
65    H      H      CH.sub.3                                              
                           CH.sub.3                                       
                                H      H    scarlet                       
66    H      H      CH.sub.3                                              
                           H    CH.sub.3                                  
                                       CH.sub.3                           
                                            scarlet                       
67    H      H      OCH.sub.3                                             
                           H    H      H    scarlet                       
68    H      H      Br     H    OCH.sub.3                                 
                                       H    orange                        
69    H      H                                                            
                     ##STR21##                                            
                           H    CH.sub.3                                  
                                       H    orange                        
70    H      H                                                            
                     ##STR22##                                            
                           H    H      H    orange                        
71    H      H      CH.sub.3                                              
                           CH.sub.3                                       
                                OCH.sub.3                                 
                                       H    red                           
72    H      H      Cl     H    OCH.sub.3                                 
                                       H    orange                        
73    H      H      CH.sub.3                                              
                           H    Cl     Cl   orange                        
74    H      H      H      H    Cl     Cl   orange                        
75    H      H      OCH.sub.3                                             
                           H    Cl     Cl   orange                        
76    CH.sub.3                                                            
             H      Cl     H    H      H    orange                        
77    H      H      Cl     Cl   CH.sub.3                                  
                                       CH.sub.3                           
                                            orange                        
78    H      H      Cl     Cl   Cl     H    orange                        
79    CH.sub.3                                                            
             H      Cl     H    OCH.sub.3                                 
                                       H    orange                        
80    CH.sub.3                                                            
             H      Cl     H    Cl     H    orange                        
81    CH.sub.3                                                            
             H      Cl     H    CH.sub.3                                  
                                       H    orange                        
82    CH.sub.3                                                            
             H      Cl     H    Br     H    orange                        
83    H      H      Br     H    CH.sub.3                                  
                                       CH.sub.3                           
                                            orange                        
84    H      H      Br     H    Cl     Cl   orange                        
85    CH.sub.3                                                            
             H      H      H    H      H    scarlet                       
86    CH.sub.3                                                            
             H      CH.sub.3                                              
                           H    H      H    scarlet                       
87    CH.sub.3                                                            
             H      CH.sub.3                                              
                           H    Cl     H    orange                        
88    CH.sub.3                                                            
             H      H      H    OCH.sub.3                                 
                                       H    orange                        
89    CH.sub.3                                                            
             H      CH.sub.3                                              
                           CH.sub.3                                       
                                CH.sub.3                                  
                                       H    red                           
90    CH.sub.3                                                            
             H      CH.sub.3                                              
                           CH.sub.3                                       
                                OCH.sub.3                                 
                                       H    scarlet                       
91    CH.sub.3                                                            
             H      OCH.sub.3                                             
                           H    CH.sub.3                                  
                                       H    scarlet                       
92    CH.sub.3                                                            
             H      CH.sub.3                                              
                           H    CH.sub.3                                  
                                       H    scarlet                       
93    CH.sub.3                                                            
             H      CH.sub.3                                              
                           H    OCH.sub.3                                 
                                       H    scarlet                       
94    CH.sub.3                                                            
             H      OCH.sub.3                                             
                           H    OCH.sub.3                                 
                                       H    scarlet                       
95    CH.sub.3                                                            
             H      OCH.sub.3                                             
                           H    H      H    scarlet                       
96    CH.sub.3                                                            
             H      H      H    CH.sub.3                                  
                                       H    scarlet                       
97    CH.sub.3                                                            
             H      OCH.sub.3                                             
                           H    Cl     H    orange                        
98    CH.sub.3                                                            
             H      CH.sub.3                                              
                           H    CH.sub.3                                  
                                       CH.sub.3                           
                                            scarlet                       
99    CH.sub.3                                                            
             H      CH.sub.3                                              
                           H    Br     H    orange                        
100   CH.sub.3                                                            
             H      OCH.sub.3                                             
                           H    Br     H    orange                        
101   CH.sub.3                                                            
             H      H      H    CH.sub.3                                  
                                       CH.sub.3                           
                                            scarlet                       
102   CH.sub.3                                                            
             H      CH.sub.3                                              
                           CH.sub.3                                       
                                CH.sub.3                                  
                                       CH.sub.3                           
                                            red                           
103   CH.sub.3                                                            
             H      Cl     H    Cl     Cl   orange                        
104   CH.sub.3                                                            
             H      CH.sub.3                                              
                           CH.sub.3                                       
                                Br     H    orange                        
105   CH.sub.3                                                            
             H      Cl     H    CH.sub.3                                  
                                       CH.sub.3                           
                                            orange                        
106   CH.sub.3                                                            
             H      OCH.sub.3                                             
                           H    CH.sub.3                                  
                                       CH.sub.3                           
                                            red                           
107   CH.sub.3                                                            
             H      H      H    Cl     Cl   orange                        
108   CH.sub.3                                                            
             H      H      H    Br     H    orange                        
109   CH.sub.3                                                            
             H      H      H    Cl     H    orange                        
110   CH.sub.3                                                            
             H      CH.sub.3                                              
                           H    Cl     Cl   orange                        
111   CH.sub.3                                                            
             H      OCH.sub.3                                             
                           H    Cl     Cl   orange                        
112   CH.sub.3                                                            
             H      CH.sub.3                                              
                           CH.sub.3                                       
                                 ##STR23##                                
                                       H    red                           
113   CH.sub.3                                                            
             H      OCH.sub.3                                             
                           H                                              
                                 ##STR24##                                
                                       H    red                           
114   CH.sub.3                                                            
             CH.sub.3                                                     
                    Cl     H    H      H    orange                        
115   CH.sub.3                                                            
             CH.sub.3                                                     
                    CH.sub.3                                              
                           CH.sub.3                                       
                                H      H    red                           
116   CH.sub.3                                                            
             CH.sub.3                                                     
                    CH.sub.3                                              
                           H    H      H    scarlet                       
117   CH.sub.3                                                            
             CH.sub.3                                                     
                    OCH.sub.3                                             
                           H    H      H    red                           
118   CH.sub.3                                                            
             H      CH.sub.3                                              
                           CH.sub.3                                       
                                Cl     Cl   orange                        
119   CH.sub.3                                                            
             CH.sub.3                                                     
                    C.sub.2 H.sub.5                                       
                           H    CH.sub.3                                  
                                       H    red                           
120   CH.sub.3                                                            
             CH.sub.3                                                     
                    C.sub.2 H.sub.5                                       
                           H    OCH.sub.3                                 
                                       H    red                           
121   CH.sub.3                                                            
             CH.sub.3                                                     
                    CH.sub.3                                              
                           H    Cl     H    orange                        
122   CH.sub.3                                                            
             CH.sub.3                                                     
                    CH.sub.3                                              
                           H    OCH.sub.3                                 
                                       H    scarlet                       
123   CH.sub.3                                                            
             CH.sub.3                                                     
                    CH.sub.3                                              
                           CH.sub.3                                       
                                CH.sub.3                                  
                                       H    red                           
124   CH.sub.3                                                            
             CH.sub.3                                                     
                    CH.sub.3                                              
                           CH.sub.3                                       
                                OCH.sub.3                                 
                                       H    red                           
125   CH.sub.3                                                            
             CH.sub.3                                                     
                    OCH.sub.3                                             
                           H    Cl     H    orange                        
126   CH.sub.3                                                            
             CH.sub.3                                                     
                    CH.sub.3                                              
                           CH.sub.3                                       
                                Cl     H    scarlet                       
127   CH.sub.3                                                            
             CH.sub.3                                                     
                    C.sub.2 H.sub.5                                       
                           H    H      H    scarlet                       
128   CH.sub.3                                                            
             CH.sub.3                                                     
                    C.sub.2 H.sub.5                                       
                           H    Cl     H    orange                        
129   CH.sub.3                                                            
             H      C.sub.2 H.sub.5                                       
                           H    CH.sub.3                                  
                                       H    scarlet                       
130   CH.sub.3                                                            
             CH.sub.3                                                     
                    C.sub.2 H.sub.5                                       
                           H    CH.sub.3                                  
                                       CH.sub.3                           
                                            red                           
131   CH.sub.3                                                            
             H      C.sub.2 H.sub.5                                       
                           H    OCH.sub.3                                 
                                       H    red                           
132   CH.sub.3                                                            
             H      C.sub.2 H.sub.5                                       
                           H    Cl     H    orange                        
133   CH.sub.3                                                            
             H      C.sub.2 H.sub.5                                       
                           H    CH.sub.3                                  
                                       CH.sub.3                           
                                            scarlet                       
134   CH.sub.3                                                            
             H      C.sub.2 H.sub.5                                       
                           H                                              
                                 ##STR25##                                
                                       H    orange                        
135   CH.sub.3                                                            
             H      C.sub.2 H.sub.5                                       
                           H    Br     H    orange                        
______________________________________                                    
 
    
     EXAMPLE 136 
     A suspension of 92.4 g of 4-amino-4&#39;-chlorobenzophenone, 1.5 g of zinc chloride and 11 ml of hydrazine hydrate in 200 ml of ethylene glycol monomethyl ether is heated for 22 hours to the boil, in the course of which the internal temperature falls from 116° C. to 112° C. on account of the water which forms, and the odour of hydrazine disappears. Then 125 ml of a mixture of ethylene glycol monomethyl ether/water is distilled off in the descending cooler in the course of 24 hours and simultaneously 100 ml of solvent is added dropwise. The internal temperature rises to 125° C. and a clear solution forms. On cooling, the reaction product crystallises out. The mass is diluted with 200 ml of alcohol and filtered after brief standing. The filter cake is washed with alcohol and dried, affording 65 g of 4,4&#34;-diamino-4&#39;,4&#34;&#39;-dichloro-tetraphenylketazine (71% of theory) with a melting point of 224°-227°  C. A further 18.3 g of reaction product with a melting point of 221°-223° C. are obtained from the mother liquor by evaporating the solvent and stirring the residue in alcohol. The total yield is accordingly 91%. 
     EXAMPLES 137 TO 212 
     Table III lists further ketazines of the formula ##STR26## which are obtained by condensing hydrazine hydrate with a benzophenone of the formula ##STR27## in ethylene glycol monomethyl ether. The position and nature of the substituents are indicated in columns 2 and 3 respectively of the table. In this connection it is to be observed that, depending on their constitution, the tetraphenylketazines are in the form of different stereoisomoic mixtures and can also be processed as such. 
     When using benzophenones which are difficult to condense, in particular 2&#34;- und 2&#34;&#39;-methyl-substituted benzophenones, it is advantageous to replace ethylene glycol monomethyl ether by ethylene glycol monoethyl ether or diethylene glycol dimethyl ether, and to carry out the second step of the reaction at a temperature of 135° to 165° C. 
     
                       TABLE III                                                   
______________________________________                                    
                                Analysis                                  
     Position and nature                                                  
                       Melting  calc.                                     
Ex.  of the substituents of                                               
                       point    found                                     
No.  A         B           in °C.                                  
                                  C%   H%   N%                            
______________________________________                                    
137  2-amino    --         205-207                                        
                                  79.97                                   
                                       5.68 14.35                         
                                  79.8 5.8  14.3                          
138  4-amino    --         223-226                                        
                                  79.97                                   
                                       5.68 14.35                         
                                  79.9 5.7  14.5                          
139  3-amino   4-methyl    168-173                                        
                                  80.35                                   
                                       6.26 13.4                          
                                  79.6 6.3  13.4                          
140  4-amino   &#34;           240-245                                        
                                  80.35                                   
                                       6.26 13.4                          
                                  80.1 6.4  13.5                          
141  4-amino-   --         238-240                                        
                                  80.35                                   
                                       6.26 13.4                          
                                  80.5 6.4  13.5                          
142   &#34;        4-methyl    256-259                                        
                                  80.68                                   
                                       6.77 12.54                         
                                  80.3 6.6  12.6                          
143  4-amino   2,4-di-     200-203                                        
                                  80.7 6.77 12.54                         
               methyl             80.2 6.9  12.5                          
144   &#34;        3.4-di-     198-200                                        
                                  80.7 6.77 12.54                         
               methyl             80.4 6.9  12.5                          
145  4-amino-  2,4-di-     202-204                                        
                                  80.97                                   
                                       7.2  11.8                          
     3-methyl  methyl             80.9 7.3  12.0                          
146   &#34;        3.4-di-     230-232                                        
                                  80.97                                   
                                       7.2  11.8                          
               methyl             80.4 7.3  11.8                          
147  3-amino-   --         191-193                                        
                                  74.64                                   
                                       5.82 12.44                         
     4-methoxy                    74.7 5.9  12.4                          
148  4-amino   4-methoxy   233-236                                        
                                  74.64                                   
                                       5.82 12.44                         
                                  74.8 5.9  12.8                          
149  4-amino-   &#34;          220-223                                        
                                  75.3 6.3  11.7                          
     3-methyl                     75.2 6.5  11.7                          
150   &#34;        4-methyl    175-177                                        
                                  75.3 6.3  11.7                          
                                  75.1 6.4  11.6                          
151  3-amino-  4-methoxy   167-170                                        
                                  70.57                                   
                                       5.9  10.97                         
     4-methoxy                    70.4 6.1  10.9                          
152  4-amino   2,4-di-     240-241                                        
                                  70.57                                   
                                       5.9  10.97                         
               methoxy            70.5 5.9  10.8                          
153   &#34;        3,4-di-     218-221                                        
                                  70.57                                   
                                       5.9  10.97                         
               methoxy            70.4 6.0  11.0                          
154  4-amino   4-ethoxy    219-221                                        
                                  75.3 6.3  11.7                          
                                  75.3 6.7  11.5                          
155   &#34;        4-isopro-   197-199                                        
                                  80.97                                   
                                       7.2  11.8                          
               poxy               80.3 7.3  12.3                          
156   &#34;        4-tert-     157-160                                        
                                  81.2 7.6  11.15                         
               butyl              81.0 7.7  11.1                          
157  4-amino-   --         211-212                                        
                                  68.0 4.4  12.2                          
     2-chloro                     68.0 4.6  12.0                          
158  4-amino   4-bromo     232-245                                        
                                  56.95                                   
                                       3.6  10.2                          
                                  57.1 3.7  10.4                          
159  2-amino-   &#34;          227-230                                        
                                  58.35                                   
                                       4.2  9.7                           
     3-methyl                     58.5 4.2  9.9                           
160   &#34;        4-chloro    216-219                                        
                                  69.0 4.96 11.5                          
                                  68.7 5.1  11.6                          
161  4-amino-  4-methyl    266-268                                        
                                  69.0 4.96 11.5                          
     2-chloro                     68.9 5.1  11.8                          
162   &#34;        4-methoxy   223-226                                        
                                  64.75                                   
                                       4.66 10.8                          
                                  64.9 4.6  10.9                          
163  3-amino-  4-chloro    200-203                                        
                                  64.76                                   
                                       4.66 10.8                          
     4-methoxy                    64.6 4.8  11.0                          
164  3-amino-  4-ethoxy    170-173                                        
                                  65.8 5.15 10.2                          
     4-chloro                     65.7 5.2  10.5                          
165  4-amino-  4-bromo     234-235                                        
                                  50.6 2.94 9.08                          
     2-chloro                     51.0 2.9  9.2                           
166  3-amino-  4-chloro    213-215                                        
                                  59.1 3.4  10.6                          
     4-chloro                     59.3 3.3  10.7                          
167  2-chloro                     59.3 3.6  10.8                          
168  4-amino   2,4-di-     242-245                                        
                                  59.1 3.4  10.6                          
               chloro             58.9 3.7  10.4                          
169  4-amino   3,4-di-     194-198                                        
                                  59.1 3.4  10.6                          
               chloro             58.5 3.6  10.6                          
170  4-amino-  2,4-di-     222-224                                        
                                  60.45                                   
                                       4.0  10.07                         
     3-methyl  chloro             60.4 4.1  10.0                          
171  4-amino-  3,4-di-     219-221                                        
                                  60.45                                   
                                       4.0  10.07                         
     3-methyl  chloro             60.4 4.2  10.1                          
172  4-amino   4-phenyl    261-263                                        
                                  84.1 5.57 10.3                          
                                  83.7 5.6  10.4                          
173   &#34;        4-phenoxy   206-208                                        
                                  79.4 5.26 9.75                          
                                  79.2 5.1  9.8                           
174  4-amino-  4-phenyl    285-288                                        
                                  84.18                                   
                                       6.0  9.8                           
     3-methyl                     83.5 6.1  9.8                           
175   &#34;        4-phenoxy   208-210                                        
                                  79.7 5.7  9.3                           
                                  79.3 5.8  9.4                           
176  3-amino   3-amino     223-224                                        
                                  74.26                                   
                                       5.75 20.0                          
                                  74.2 5.7  19.9                          
177  4-amino   3-amino     247-250                                        
                                  74.26                                   
                                       5.76 20.0                          
                                  74.1 6.0  20.2                          
178   &#34;        4-amino     295-298                                        
                                  74.26                                   
                                       5.75 20.0                          
                                  73.6 5.8  19.9                          
179  3-amino-  3-amino-    202-205                                        
                                  66.65                                   
                                       5.97 15.55                         
     4-methoxy 4-methoxy          66.5 6.0  15.7                          
180  4-amino   3-amino-    243-246                                        
                                  63.93                                   
                                       4.63 17.2                          
               4-chloro           63.6 4.7  17.2                          
181   &#34;        4-o-amino-  215-217                                        
                                  75.48                                   
                                       5.33 13.9                          
               phenoxy            74.8 5.5  13.6                          
182   &#34;        4-p-amino-  285-287                                        
                                  75.48                                   
                                       5.33 13.9                          
               phenoxy            75.2 5.7  13.6                          
183  4-amino-   &#34;          200-203                                        
                                  75.9 5.7  13.28                         
     3-methyl                     75.4 5.6  13.1                          
184  4-amino   4-o-amino-  204-207                                        
                                  67.76                                   
                                       4.5  12.48                         
               p-chloro-          67.3 4.5  12.2                          
               phenoxy                                                    
185   &#34;        4-o-chloro- 245-248                                        
                                  67.76                                   
                                       4.5  12.48                         
               p-amino-           67.8 4.6  12.4                          
               phenoxy                                                    
186  4-amino-  4-o-chloro- 242-245                                        
                                  68.47                                   
                                       4.88 11.98                         
     3-methyl  p-amino-           68.3 4.9  11.8                          
               phenoxy                                                    
187   &#34;        4-o-amino-  213-216                                        
                                  68.47                                   
                                       4.88 11.98                         
               p-chloro-          68.2 4.9  11.70                         
               phenoxy                                                    
188  4-amino   3-chloro-4- 288-291                                        
                                  67.76                                   
                                       4.5  12.48                         
               p-amino-           67.6 4.5  12.4                          
               phenoxy                                                    
189   &#34;        3-chloro-4- 206-209                                        
                                  61.47                                   
                                       3.8  11.3                          
               o-chloro-p-        61.5 4.0  10.8                          
               amino-                                                     
               phenoxy                                                    
190  4-amino   4-fluoro    193-197                                        
                                  73.23                                   
                                       4.7  13.14                         
                                  72.8 4.6  13.5                          
191  4-amino   4-ethyl     217-219                                        
                                  80.68                                   
                                       6.77 12.54                         
                                  80.1 6.8  12.5                          
192  4-amino-  3-chloro-4- 158-160                                        
                                  62.35                                   
                                       4.2  10.9                          
     3-methyl  (o-chloro-p-       62.0 4.3  11.0                          
               aminophenoxy)                                              
193  4-amino   4-(p-amino- &gt;300   79.7 5.6  14.67                         
               phenyl)            79.4 5.7  14.5                          
194  4-amino   2,5-di-     253-256                                        
                                  70.57                                   
                                       5.9  10.97                         
               methoxy            70.1 6.0  10.9                          
195  4-amino-  4-fluoro    255-257                                        
                                  74.0 5.3  8.36                          
     3-methyl                     73.7 5.4  8.2                           
196  4-amino   2,5-di-     256-260                                        
                                  69.9 5.47 10.87                         
               methyl-            69.4 5.6  10.7                          
               4-chloro                                                   
197  4-amino-  4-cyclo-    177-180                                        
                                  82.43                                   
                                       7.96 9.6                           
     3-methyl  hexyl              82.0 8.1  9.6                           
198  4-amino   4-cyclo-    214-218                                        
                                  82.27                                   
                                       7.6  10.1                          
               hexyl              81.9 7.5  9.9                           
199  4-amino   2,5-di-     238-242                                        
                                  62.18                                   
                                       4.87 9.67                          
               methoxy-           61.9 4.9  9.8                           
               4-chloro                                                   
200  4-amino   2,5-di-     241-245                                        
                                  80.68                                   
                                       6.77 12.54                         
               methyl             80.6 6.9  12.5                          
201  4-amino-  4-ethoxy    223-226                                        
                                  75.86                                   
                                       6.76 11.06                         
     3-methyl                     75.8 6.9  11.3                          
202  4-amino-  4-ethyl     221-225                                        
                                  80.97                                   
                                       7.22 11.8                          
     3-methyl                     80.7 7.3  12.0                          
203  4-amino-  4-(p-chloro-                                               
                           195-198                                        
                                  71.5 4.8  8.3                           
     3-methyl  phenoxy)           71.6 5.0  8.3                           
204  4-amino-  2,5-di-     192-198                                        
                                  70.7 5.9  10.3                          
     3-methyl  methyl-                                                    
               4-chloro                                                   
205  4-amino-  2,5-di-     210-211                                        
                                  71.35                                   
                                       6.36 10.4                          
     3-methyl  methoxy            71.2 6.4  10.5                          
206  4-amino-  2,4-di-     219-220                                        
                                  71.35                                   
                                       6.36 10.4                          
     3-methyl  methoxy            71.4 6.5  10.5                          
208  4-amino-  2,5-di-     216-219                                        
                                  63.26                                   
                                       5.31 9.22                          
     3-methyl  methoxy-           62.8 5.5  9.0                           
               4-chloro                                                   
 ##STR28##                                                                
209  4-amino    --         192-196                                        
                                  84.1 5.57 10.32                         
                                  84.7 5.4  10.2                          
210  4-amino   4-methyl    230-233                                        
                                  84.18                                   
                                       6.01 9.92                          
                                  84.0 5.9  9.6                           
211  4-amino   4-methoxy   228-231                                        
                                  79.71                                   
                                       5.69 9.3                           
                                  79.3 5.8  9.1                           
212  4-amino   4-chloro    215-220                                        
                                  74.6 4.6  9.16                          
                                  74.1 4.7  9.2                           
______________________________________                                    
 
    
     EXAMPLE 213 
     To a suspension of 23.1 g of 4-amino-4&#39;-chlorobenzophenone in 100 ml of ethylene glycol monomethyl ether are added 0.75 g of zinc chloride and 5.5 ml of hydrazine hydrate. The reaction mixture is boiled overnight at a bath temperature of 150° C., in the course of which the boiling temperature falls from 118° C. to 115° C. on account of the water which forms. Then 21.1 g of 4-amino-4&#39;-methylbenzophenone are added to the resulting turbid solution. Then 21 ml of solvent are distilled off at a bath temperature of 160° C. and the internal temperature rises to 122°-125° C. This temperature is kept for 24 hours, whereupon a portion of the reaction product crystallises out. After cooling, the resulting 4,4&#34;-diamino-4&#39;-chloro-4&#34;&#39;-methyltetraphenylketazine is collected by filtration, washed with alcohol and water and dried in vacuo at 80° C., affording 30 g (68%) of reaction product with a melting point of 225°-226° C. 
     
         ______________________________________                                    
Analysis                                                                  
______________________________________                                    
calculated                                                                
         C 73.88% H 5.28%   N 12.76% Cl 8.08%                             
found    73.7%    5.3%      13.00%   7.8%                                 
______________________________________                                    
 
    
     Table IV lists further ketazines of the formula ##STR29## which are obtained by condensing 1 mole of 4-amino-benzophenone of the formula ##STR30## and 1 mole of 4-aminobenzophenone of the formula ##STR31## with 1 mole of hydrazine hydrate in ethylene glycol. 
     
                                           TABLE IV                                
__________________________________________________________________________
Ex.                        Analysis                                       
No. A   B   C    D    m.p.(°C.)                                    
                           C   H   N                                      
__________________________________________________________________________
214 --  --  --   4-CH.sub.3                                               
                      196-199°                                     
                           80.17                                          
                               5.98                                       
                                   13.85                                  
                           79.8                                           
                               6.1 13.7                                   
215 --  --  4-CH.sub.3                                                    
                 4-OCH.sub.3                                              
                      217-221°                                     
                           77.39                                          
                               6.03                                       
                                   12.89                                  
                           77.3                                           
                               6.2 12.8                                   
216 --  --  --   4-Cl 190-192°                                     
                           73.49                                          
                               4.98                                       
                                   13.19                                  
                           73.0                                           
                               5.0 13.0                                   
217 --  --  4-Cl 4-Br 222-224°                                     
                           61.98                                          
                               4.0 11.12                                  
                           61.8                                           
                               4.2 11.2                                   
218 --  --  --   4-Br 177-182°                                     
                           66.35                                          
                               4.51                                       
                                   11.94                                  
                           66.1                                           
                               4.6 11.9                                   
219 --  --  4-CH.sub. 3                                                   
                 4-Br 233-235°                                     
                           67.09                                          
                               4.8 11.59                                  
                           67.5                                           
                               5.0 11.7                                   
220 --  --  4-CH.sub. 3                                                   
                 3,4-di-                                                  
                      204-208°                                     
                           80.5                                           
                               6.5 12.95                                  
                 CH.sub.3  80.3                                           
                               6.6 12.9                                   
221 --  --  4-Br 4-OCH.sub.3                                              
                      212-218°                                     
                           64.94                                          
                               4.64                                       
                                   11.22                                  
                           64.8                                           
                               4.7 11.2                                   
222 --  --                                                                
             ##STR32##                                                    
                 --   178-183°                                     
                           82.37 81.9                                     
                               5.62 5.7                                   
                                   12.01 11.7                             
223 --  --  4-OCH.sub.3                                                   
                 3,4-di-                                                  
                      198-201°                                     
                           77.65                                          
                               6.29                                       
                                   12.49                                  
                 CH.sub.3  77.3                                           
                               6.2 12.5                                   
224 --  --  4-Cl 4-OCH.sub.3                                              
                      208-212°                                     
                           71.28                                          
                               5.09                                       
                                   12.31                                  
                           71.0                                           
                               5.2 12.2                                   
225 3-CH.sub.3                                                            
        --  4-Cl --   168-173°                                     
                           73.88                                          
                               5.28                                       
                                   12.76                                  
                           73.5                                           
                               5.3 12.7                                   
226 --  --  3,4-di-                                                       
                 3,4-di-                                                  
                      194-197°                                     
                           69.0                                           
                               4.96                                       
                                   11.5                                   
            CH.sub.3                                                      
                 Cl        68.7                                           
                               5.1 11.5                                   
227 --  --  4-Cl 3,4-di-                                                  
                      188-192°                                     
                           63.24                                          
                               3.88                                       
                                   11.35                                  
                 Cl        63.2                                           
                               4.1 11.5                                   
228 3-CH.sub.3                                                            
        --  4-Cl 4-Cl 148-155°                                     
                           68.5                                           
                               4.7 11.84                                  
                           68.3                                           
                               4.9 11.8                                   
229 3-CH.sub.3                                                            
        --  4-Cl 4-CH.sub.3                                               
                      179-187°                                     
                           74.24                                          
                               5.56                                       
                                   12.37                                  
                           73.6                                           
                               5.6 12.3                                   
230 3-CH.sub.3                                                            
        --  4-Cl 4-Br 176-181°                                     
                           62.62                                          
                               4.28                                       
                                   10.82                                  
                           62.4                                           
                               4.4 10.9                                   
231 --  --  4-Br 3,4-di-                                                  
                      187-191°                                     
                           67.61                                          
                               5.07                                       
                                   11.26                                  
                 CH.sub.3  67.1                                           
                               5.2 11.0                                   
232 --  --  4-Br 3,4-di-                                                  
                      190-198°                                     
                           58.02                                          
                               3.56                                       
                                   10.4                                   
                 Cl        57.8                                           
                               3.7 10.3                                   
233 3-CH.sub.3                                                            
        --  --   --   202-208°                                     
                           80.17                                          
                               6.0 13.85                                  
                           80.1                                           
                               6.2 13.8                                   
234 3-CH.sub.3                                                            
        --  3,4-di-                                                       
                 4-CH.sub.3                                               
                      --   80.68                                          
                               6.77                                       
                                   12.54                                  
            CH.sub.3       80.6                                           
                               6.8 12.4                                   
235 3-CH.sub.3                                                            
        --  3,4-di-                                                       
                 4-OCH.sub.3                                              
                      196-205°                                     
                           77.89                                          
                               6.54                                       
                                   12.11                                  
            CH.sub.3       77.3                                           
                               6.6 12.2                                   
236 3-CH.sub.3                                                            
        --  4-OCH.sub.3                                                   
                 4-CH.sub.3                                               
                      190-195°                                     
                           77.65                                          
                               6.3 12.5                                   
                           77.3                                           
                               6.3 12.5                                   
237 3-CH.sub.3                                                            
        --  4-CH.sub.3                                                    
                 4-CH.sub.3                                               
                      229-234°                                     
                           80.52                                          
                               6.53                                       
                                   12.95                                  
                           80.5                                           
                               6.6 12.6                                   
238 3-CH.sub.3                                                            
        --  4-CH.sub.3                                                    
                 4-OCH.sub.3                                              
                      --   77.65                                          
                               6.3 12.5                                   
                           77.2                                           
                               6.4 12.4                                   
239 3-CH.sub.3                                                            
        --  4-OCH.sub.3                                                   
                 4-OCH.sub.3                                              
                      192-199°                                     
                           74.97                                          
                               6.07                                       
                                   12.06                                  
                           74.4                                           
                               6.1 11.9                                   
240 3-CH.sub.3                                                            
        --  --   4-CH.sub.3                                               
                      --   80.35                                          
                               6.26                                       
                                   13.39                                  
                           79.9                                           
                               6.2 13.3                                   
241 3-CH.sub.3                                                            
        --  4-OCH.sub.3                                                   
                 4-Cl 183-187°                                     
                           71.71                                          
                               5.37                                       
                                   11.95                                  
                           71.2                                           
                               5.5 12.0                                   
242 3-CH.sub.3                                                            
        --  4-CH.sub.3                                                    
                 3,4-di-                                                  
                      228-237°                                     
                           80.68                                          
                               6.77                                       
                                   12.54                                  
                 CH.sub.3  80.4                                           
                               6.8 12.5                                   
243 3-CH.sub.3                                                            
        --  4-CH.sub.3                                                    
                 4-Br --   67.61                                          
                               5.07                                       
                                   11.26                                  
                           67.3                                           
                               5.2 11.3                                   
244 3-CH.sub.3                                                            
        --  --   3,4-di-                                                  
                      --   80.5                                           
                               6.5 12.95                                  
                 CH.sub.3  79.9                                           
                               6.2 13.0                                   
245 3-CH.sub.3                                                            
        --  3,4-di-                                                       
                 3,4-di-                                                  
                      205-215°                                     
                           80.83                                          
                               7.0 12.16                                  
            CH.sub.3                                                      
                 CH.sub.3  80.6                                           
                               7.0 12.1                                   
246 3-CH.sub.3                                                            
        --  4-Cl 3,4-di-                                                  
                      166-170°                                     
                           63.86                                          
                               4.17                                       
                                   11.03                                  
                 Cl        64.0                                           
                               4.2 11.2                                   
247 3-CH.sub.3                                                            
        --  3,4-di-                                                       
                 4-Br 190-205°                                     
                           68.1                                           
                               5.3 10.95                                  
            CH.sub.3       68.5                                           
                               5.5 11.0                                   
248 3-CH.sub.3                                                            
        --  4-Cl 3,4-di-                                                  
                      --   74.58                                          
                               5.83                                       
                                   12.0                                   
                 CH.sub.3  73.8                                           
                               5.7 11.9                                   
249 3-CH.sub.3                                                            
        --  4-OCH.sub.3                                                   
                 3,4-di-                                                  
                      190-196°                                     
                           77.89                                          
                               6.53                                       
                                   12.1                                   
                 CH.sub.3  77.4                                           
                               6.6 12.0                                   
250 3-CH.sub.3                                                            
        --  --   3,4-di-                                                  
                      --   68.5                                           
                               4.7 11.84                                  
                 Cl        68.6                                           
                               4.7 12.1                                   
251 3-CH.sub.3                                                            
        --  4-CH.sub.3                                                    
                  ##STR33##                                               
                      --   82.56 82.1                                     
                               6.11 6.1                                   
                                   11.33 11.1                             
252 3-CH.sub.3                                                            
        --  3,4-di- CH.sub.3                                              
                  ##STR34##                                               
                      --   82.64 82.1                                     
                               6.34 6.3                                   
                                   11.01 10.9                             
253 3-CH.sub.3                                                            
        3-CH.sub.3                                                        
            4-Cl --   186-193°                                     
                           74.24                                          
                               5.56                                       
                                   12.37                                  
                           74.0                                           
                               5.7 12.4                                   
254 3-CH.sub.3                                                            
        3-CH.sub.3                                                        
            3,4-di-                                                       
                 --   --   80.68                                          
                               6.77                                       
                                   12.54                                  
            CH.sub.3       80.4                                           
                               6.7 12.4                                   
255 3-CH.sub.3                                                            
        3-CH.sub.3                                                        
            4-C.sub.2 H.sub.5                                             
                 4-CH.sub.3                                               
                      227-231°                                     
                           80.83                                          
                               7.0 12.16                                  
                           80.9                                           
                               7.1 12.4                                   
256 3-CH.sub.3                                                            
        3-CH.sub.3                                                        
            4-C.sub.2 H.sub.5                                             
                 4-OCH.sub.3                                              
                      228-230°                                     
                           78.12                                          
                               6.77                                       
                                   11.75                                  
                           77.9                                           
                               6.8 11.7                                   
257 3-CH.sub.3                                                            
        3-CH.sub.3                                                        
            4-CH.sub.3                                                    
                 4-Cl 236-240°                                     
                           74.58                                          
                               5.83                                       
                                   12.0                                   
                           75.0                                           
                               6.1 12.1                                   
258 3-CH.sub.3                                                            
        --  4-CH.sub.3                                                    
                 --   --   80.35                                          
                               6.26                                       
                                   13.39                                  
                           80.2                                           
                               6.4 13.3                                   
259 3-CH.sub.3                                                            
        3-CH.sub.3                                                        
            4-CH.sub.3                                                    
                 4-OCH.sub.3                                              
                      234-238°                                     
                           77.89                                          
                               6.54                                       
                                   12.11                                  
                           77.8                                           
                               6.7 12.2                                   
260 3-CH.sub.3                                                            
        3-CH.sub.3                                                        
            3,4-di-                                                       
                 4-CH.sub.3                                               
                      232-234°                                     
                           80.83                                          
                               7.0 12.16                                  
            CH.sub.3       81.0                                           
                               7.2 12.3                                   
261 3-CH.sub.3                                                            
        3-CH.sub.3                                                        
            3,4-di-                                                       
                 4-OCH.sub.3                                              
                      214-217°                                     
                           78.12                                          
                               6.77                                       
                                   11.75                                  
            CH.sub.3       78.2                                           
                               6.8 11.7                                   
262 3-CH.sub.3                                                            
        3-CH.sub.3                                                        
            4-OCH.sub.3                                                   
                 4-Cl 207-210°                                     
                           72.11                                          
                               5.63                                       
                                   11.6                                   
                           71.9                                           
                               5.7 11.6                                   
263 3-CH.sub.3                                                            
        3-CH.sub.3                                                        
            3,4-di-                                                       
                 4-Cl 198-204°                                     
                           74.91                                          
                               6.08                                       
                                   11.65                                  
            CH.sub.3       75.2                                           
                               6.3 11.6                                   
264 3-CH.sub.3                                                            
        3-CH.sub.3                                                        
            4-C.sub.2 H.sub.5                                             
                 --   --   80.68                                          
                               6.77                                       
                                   12.54                                  
                           80.6                                           
                               6.9 12.5                                   
265 3-CH.sub.3                                                            
        3-CH.sub.3                                                        
            4,C.sub.2 H.sub.5                                             
                 4-Cl 205-210°                                     
                           74.91                                          
                               6.08                                       
                                   11.65                                  
                           75.4                                           
                               6.3 11.5                                   
266 3-CH.sub.3                                                            
        --  4-C.sub.2 H.sub.5                                             
                 4-CH.sub.3                                               
                      --   80.68                                          
                               6.77                                       
                                   12.54                                  
                           80.1                                           
                               6.8 12.7                                   
267 3-CH.sub.3                                                            
        3-CH.sub.3                                                        
            4-C.sub.2 H.sub.5                                             
                 3,4-di-                                                  
                      203-207°                                     
                           80.97                                          
                               7.22                                       
                                   11.8                                   
                 CH.sub.3  80.4                                           
                               7.3 11.5                                   
268 3-CH.sub.3                                                            
        --  4-C.sub.2 H.sub.5                                             
                 4-OCH.sub.3                                              
                      197-204°                                     
                           77.89                                          
                               6.54                                       
                                   12.11                                  
                           77.6                                           
                               6.6 12.0                                   
269 3-CH.sub.3                                                            
        --  4-C.sub.2 H.sub.5                                             
                 --   --   80.52                                          
                               6.5 12.95                                  
                           80.0                                           
                               6.5 12.7                                   
270 3-CH.sub.3                                                            
        --  4-C.sub.2 H.sub.5                                             
                 4-Cl --   74.58                                          
                               5.83                                       
                                   12.0                                   
                           74.5                                           
                               6.1 11.9                                   
271 3-CH.sub.3                                                            
        --  4-C.sub.2 H.sub.5                                             
                 3,4-di-                                                  
                      --   80.83                                          
                               7.0 12.16                                  
                 CH.sub.3  80.3                                           
                               7.1 11.8                                   
272 3-CH.sub.3                                                            
        --  4-C.sub.2 H.sub.5                                             
                 4-Br --   68.1                                           
                               5.3 10.95                                  
                           68.4                                           
                               5.5 10.8                                   
__________________________________________________________________________
 
    
     EXAMPLE 273 
     2 g of the pigment obtained in Example 45 are ground with 36 g of toner dehydrate, 60 g of boiled linseed oil of medium viscosity and 2 g of cobalt linoleate on a three roll mill. The orange prints obtained with the resulting colour paste are strong and outstandingly fast to light. 
     EXAMPLE 274 
     0.6 g of the pigment obtained in Example 1 is mixed with 67 g of polyvinyl chloride, 33 g of dioctyl phthalate, 2 g of dibutyl tin dilaurate and 2 g of titanium dioxide and the mixture is processed to a thin sheet for 15 minutes at 160° C. on a roll mill. The orange colouration obtained is strong and fast to migration, heat and light. 
     EXAMPLE 275 
     10 g of titanium dioxide and 2 g of the pigment obtained in Example 5 are ground for 48 hours in a ball mill with 88 g of a mixture of 26.4 g of coconut alkyl resin, 24 g of melamine/formaldehyde resin (30% solids content), 8.8 g of ethylene glycol monomethyl ether and 28.8 g of xylene. The resulting lacquer is sprayed onto an aluminium sheet, predried for 30 minutes at room temperature and then stoved for 30 minutes at 120° C., to give a yellow finish which has very good colour strength and is distinguished by very good fastness to overstripe bleeding, light and atmospheric influences. 
     EXAMPLE 276 
     8.03 g of 3-iminoisoindolin-1-one are added to a hot solution of 12.3 g of 4,4&#34;-diamino-3&#39;,4&#39;,3&#34;&#39;,4&#34;&#39;-tetrachloro-tetraphenylketazine in 150 ml of glacial acetic acid. The reaction mixture is boiled for 10 minutes, whilst the pigment begins to precipitate after about 30 seconds. The precipitate is collected by filtration, washed with methanol, acetone and water and then dried, affording 15.7 g of a yellow pigment which, after it has been ground by one of the conventional methods, can be used for colouring plastics and for the preparation of lacquers and printing pastes. The resulting colourations are strong and distinguished by outstanding fastness properties. 
     
         ______________________________________                                    
Analysis                                                                  
______________________________________                                    
calculated                                                                
        C 64.14%  H 3.08%   N 10.69% Cl 18.03%                            
found   C 64.4%   H 3.22%   N 10.5%  Cl 17.65%                            
______________________________________                                    
 
    
     EXAMPLE 277 
     6.7 g of 4,5-dichloro-2-cyanobenzoic acid methyl ester with a melting point of 129°-130° C. (prepared by the process of Example 1 of British Pat. No. 1,319,731 by reaction of the ammonium salt of 4,5-dichloro-2-cyanobenzoic acid with dimethyl sulfate) are stirred for 2 hours at room temperature with 28.75 ml of 1 N sodium methylate solution in methanol, whereupon a suspension of the sodium salt of 3,3-dimethoxy-5,6-dichloroisoindolin-1-one forms. Then 6.8 g of finely ground 4,4&#34;-diamino-4&#39;,4&#34;&#39;-dibromo-tetraphenylketazine and 150 ml of o-dichlorobenzene are added and the methyl alcohol is distilled off at a bath temperature of 110° C., while the internal temperature rises in the course of 2 hours to 100° C. The sodium salt of the pigment begins to precipitate at 80° C., without the ketazine having dissolved completely. The batch is diluted with a further 50 ml of o-dichlorobenzene and the temperature is kept at 100° C. for 3 hours. After acidification with 10 ml of glacial acetic acid, the internal temperature is raised to 140°-150° C. and the mixture is stirred for  2 hours at this temperature. The insoluble pigment is collected by filtration at 120° C. The filter cake is washed with methanol, acetone and water and dried. 
     Yield: 9.5 g of a productive yellow pigment which, after incorporation into plastics, printing pastes and lacquers, produces colourations distinguished by outstanding fasteness properties. 
     
         ______________________________________                                    
Analysis                                                                  
______________________________________                                    
calculated                                                                
        C 53.4%  H 2.5%   N 8.9% Cl 15.0%                                 
                                        Br 16.9%                          
found   C 53.3%  H 2.6%   N 8.8% Cl 14.7%                                 
                                        Br 16.7%                          
______________________________________