Aminolysis of Amides, Solvent and Catalytic Effects

Abstract

Place L o u i s P a s t e u r , 1 B-1348 Louvain-la-Neuve, Belgium.The k i n e t i c s t u d y o f a m i n o l y s i s o f amides : R-CONR' R"shown d r a m a t i c dependence of t h e t o t a l r a t e o f t h e r e a c t i o n v s ; t h e s t r u cof t h e r e a c t i v e amine HNR1R2.The g e n e r a l r a t e law e x h i b i t f i r s t o r d e r d e p e n d e n c e f o r t h e amide b u t f o r t h e r e a c t i v e amine, t h e o r d e r c a n be f i r s t , second and t h i r d o r a c o m b i n a t i o n of t h e f i r s t and s e c o n d , o r of t h e second and t h e t h i r d , w h e r e i n t h e h ig h e r o r d e r s i n t h e r e a c t i v e amine c h a r a c t e r i z e t h e m o s t r e a c t i v e o n e s . On t h e o t h e r hand, amine o r d e r dependence and t h e t o t a l r a t e o f '<he r e a ct i o n a r e f u n c t i o n o f t h e n a t u r e o f t h e medium and o f t h e p r e s e n c e o f c a t a l y t i c s p e c i e s , e . g . t e r t i a r y amines.S p e c i f i c i n t e r a c t i o n s between t h e r e a c t a n t s a n d / o r t h e i n t e r m e d i a t e s and t h e s o l v e n t c a n be shown by k i n e t i c s t u d y o f t h e r e a c t i o n i n mixed s o l v e n t s : C l a s s i c a l t r e a t m e n t of t h e e x p e r i m e n t a l v a l u e s w i t h s o l v e n t p a r a m e t e r s d o e s n ' t l e a d t o s i m p l e r e l a t i o n s h i p between t h e o b s e r v e d v a r i a t i o n s of t h e r e a c t i v i t y and g e