Supernucleophilic 4-substituted-pyridine catalysts, and processes useful for preparing same

A process for preparing a 4-(secondary or tertiary)aminopyridine, comprising:

• reacting a 4-substituted pyridine base having a leaving group as the 4-substituent, with an activating agent of the formula:
• wherein R3 and R4, which may be the same as or may differ from one another, are each —H or a C1-C4 alkyl group, and Z is —OR7 or NR5R6, wherein R5 and R6, which may be the same as or may differ from one another, and may taken together form a ring, are each —H or C1-C8 alkyl;
• and R7 is —H or C1-C8 alkyl;
• so as to form a corresponding 1,4-substituted pyridine, and
• wherein the leaving group is selected from the group consisting of cyano;
• halo;
• arylsulfonyl having from six to ten carbon atoms, optionally substituted with one or more alkyl groups having from one to four carbon atoms;
• arylsulfonyloxy having from six to ten carbon atoms;
• alkylsulfonyloxy having from one to eight carbon atoms;
• aryloxy having from six to ten carbon atoms;
• arylthio having from six to ten carbon atoms;
• and nitro;
• reacting said 1,4-substituted pyridine with a primary or secondary amine to substitute an amino group for the leaving group at the 4-position, and thereby form a corresponding 1-substituted-4-(secondary or tertiary)aminopyridine, wherein said amine is included in a molar ratio of at least about 2:1 relative to the 1,4-substituted pyridine and said reacting is conducted in a substitution reaction medium essentially free from strong base;
• and
• treating the 1-substituted-4-aminopyridine compound to remove the 1-substituent and thereby form a product medium including the 4-(secondary or tertiary) amino-pyridine.