Process for preparing tetrahydrotetraazapentacenes and derivatives

1. A process for preparing a 5,7,12,14-tetrahydro-5,7,12,14-tetraazapentacene compound of Formula (A):

wherein each of R 1 , R 2 , R 3 , R 4 , R 6 , R 8 , R 9 , R 10 , R 11 , and R 13 is independently selected from hydrogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, acyl, arylalkyl, and halogen; and

each of R 5 , R 7 , R 12 , and R 14 are independently selected from hydrogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, acyl, and arylalkyl;

comprising reacting at least one compound of Formula(I):

wherein R a , R b , R c , and R d are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, acyl, arylalkyl, and halogen; and wherein R′ and R″ are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, and substituted aryl;

with a compound of Formula (II):

wherein R e and R f are independently selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, substituted alkyl, substituted alkenyl, substituted alkynyl, aryl, substituted aryl, and halogen; and R g , R h , R i , and R j are independently selected from the group consisting of hydrogen, alkyl, and substituted alkyl.

2. The process of claim 1 , wherein the at least one compound of Formula (I) and the compound of Formula (II) are mixed together to form a mixture, and the mixture is heated in an inert environment to form the compound of Formula (A).

3. The process of claim 2 , wherein the mixture is heated at a temperature of from 110° C. to 250° C.

4. The process of claim 3 , wherein the mixture is heated for a period of from 30 minutes to 12 hours.

5. The process of claim 2 , wherein the mixture is heated at a temperature above 300° C. for a period of from 30 seconds to 10 minutes.

6. The process of claim 1 , wherein the at least one compound of Formula (I) and the compound of Formula (II) are dissolved in a solvent to form a solution, and the solution is heated to form the compound of Formula (A).

7. The process of claim 6 , wherein the solution is heated at a temperature of from 80° C. to 180° C.

8. The process of claim 6 , wherein the solution is heated for a period of from 30 minutes to 12 hours.

9. The process of claim 6 , wherein the solvent is methanoic acid, ethanoic acid, octadecanoic acid, propanoic acid, benzenecarboxylic acid, propanedioic acid, butanedioic acid, N-methyl pyrrolidone, dimethylformamide, dimethylacetamide, or dimethylsulfoxide.

10. The process of claim 1 , wherein R′ and R″ are both hydrogen.

11. The process of claim 1 , wherein R′ and R″ are identical to each other.

12. The process of claim 1 , wherein R b and R c are identical.

13. The process of claim 1 , further comprising:

isolating the 5,7,12,14-tetrahydro-5,7,12,14-tetraazapentacene compound of Formula (A),

washing the 5,7,12,14-tetrahydro-5,7,12,14-tetraazapentacene compound of Formula (A), and

drying the 5,7,12,14-tetrahydro-5,7,12,14-tetraazapentacene compound of Formula (A).

14. The process of claim 1 , wherein the molar ratio of the at least one compound of Formula (I) to the compound of Formula (II) is from 2:1 to 2.5:1.

15. The process of claim 1 , wherein one molar unit of the compound of Formula (II) is reacted with one molar unit of a first compound of Formula (I) to form an intermediate:

wherein R p is independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, acyl, arylalkyl, and halogen;

and the intermediate is subsequently reacted with one molar unit of a second compound of Formula (I) to form the 5,7,12,14-tetrahydro-5,7,12,14-tetraazapentacene compound of Formula (A),

wherein the first compound of Formula (I) and the second compound of Formula (I) are different.

16. A process for preparing an 5,7,12,14-tetrasubstituted-5,7,12,14-tetraazapentacene of Formula (A):

wherein each of R 1 , R 2 , R 3 , R 4 , R 6 , R 8 , R 9 , R 10 , R 11 , and R 13 is independently selected from hydrogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, acyl, arylalkyl, and halogen; and

each of R 5 , R 7 , R 12 , and R 14 are independently selected from hydrogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, acyl, and arylalkyl;

comprising reacting a 5,7,12,14-tetrahydro-5,7,12,14-tetraazapentacene of Formula (3):

with a sidechain-producing reagent of Formula (B):

X-L-R 15

where X is halogen or hydrogen; R 15 is selected from alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, acyl, and arylalkyl; and L is a divalent linkage selected from carbonyl, ethenyl, or acetvlenvl.