Novel rhodamine dyes

Abstract

There are described novel rhodamine color-forming compounds. The rhodamine color-forming compounds exhibit a first color when in a crystalline form and a second color, different from the first color, when in an amorphous form.

1 . A compound represented by the formula 
       
         
           
           
               
               
           
         
       
       wherein:
 R 1 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8  and R 14  are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, heterocycloalkyl, substituted heterocycloalkyl, alkoxy, substituted alkoxy, substituted carbonyl, acylamino and halogen; 
 R 2  is selected from the group consisting of hydrogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, heterocycloalkyl and substituted heterocycloalkyl; 
 
       or
 R 2  and R 3  taken together with the nitrogen atom to which they are attached form a substituted or unsubstituted saturated heterocyclic ring system; 
 R 9  is absent or selected from the group consisting of hydrogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, heterocycloalkyl, substituted heterocycloalkyl, alkoxy, substituted alkoxy, substituted carbonyl, halogen, aryl, substituted aryl, heteroaryl, substituted heteroaryl, amino, substituted amino, alkylamino, substituted alkylamino, arylamino and substituted arylamino; 
 R 10 , R 11  and R 12  are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, heterocycloalkyl, substituted heterocycloalkyl, alkoxy, substituted alkoxy, substituted carbonyl, halogen, aryl, substituted aryl, heteroaryl, substituted heteroaryl, amino, substituted amino, alkylamino, substituted alkylamino, arylamino and substituted arylamino; 
 R 13  is selected from the group consisting of hydrogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, heterocycloalkyl and substituted heterocycloalkyl; 
 R 14  is selected from the group consisting of hydrogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, heterocycloalkyl and substituted heterocycloalkyl; 
 
       or
 R 13  and R 14  taken together with the atoms to which they are attached form a 5- or 6-membered heterocyclic ring; 
 R 15 , R 16 , R 17  and R 18  are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, heterocycloalkyl, substituted heterocycloalkyl, alkoxy, substituted alkoxy, substituted carbonyl, halogen, aryl, substituted aryl, heteroaryl, substituted heteroaryl, amino, substituted amino, alkylamino, substituted alkylamino, arylamino and substituted arylamino; and 
 X 1  is carbon or nitrogen; 
 provided that only one of R 2  and R 13  is hydrogen. 
 
     
     
         2 . A compound as defined in  claim 1  wherein R 2  and R 3  taken together form a pyrrolidine ring, R 10 , R 11  and R 13  each is hydrogen, X 1  is carbon and R 1 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 12 , R 14  and R 15 -R 18  are as defined in  claim 1 . 
     
     
         3 . A compound as defined in  claim 1  wherein R 2  is hydrogen, R 3  is alkyl, R 10  and R 11  are each halogen, R 13  is alkyl, X 1  is carbon and R 1 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 12 , R 14  and R 15 -R 18  are as defined in  claim 1 . 
     
     
         4 . A compound as defined in  claim 1  wherein R 1 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9  and R 12  are each hydrogen; R 2  is hydrogen or alkyl having from 1-18 carbon atoms, R 3  is alkyl having from 1-18 carbon atoms, or R 2  and R 3  taken together with the nitrogen atom to which they are attached form a pyrrolidine ring; R 10  and R 11  are each independently hydrogen or halogen; R 13  is hydrogen or alkyl having from 1-18 carbon atoms, R 14  is hydrogen or alkyl having from 1-18 carbon atoms, X 1  is carbon and R 15 -R 18  are each independently hydrogen, alkyl having from 1-18 carbon atoms, or halogen.