Synthesis of deuterium-labelled N,N-dimethyl-morpholinium- and N-methyl-N-ethyl-morpholinium- 7,7,8,8-tetracyanoquinodimethane complexes

✍ Scribed by B. H. Kwant

• Publisher: John Wiley and Sons
• Year: 1980
• Tongue: French
• Weight: 755 KB
• Volume: 17
• Category: Article
• ISSN: 0022-2135
• DOI: 10.1002/jlcr.2580170611

✦ Synopsis

Attempted exchange e x p e r i m e n t s o f morpholine, N-methylmorpholine and N -e t h y l m o r p h o l i n e w i t h a d e u t e r i u m donor l e d t o no d e u t e r i u m i n c o r p o r a t i o n i n t h e m o r p h o l i n e r i n g s . Morpholine-dg i s n o t f o u n d i n t h e r e a c t i o n o f bromoethanol-d and ammonia, b u t i t can be p r e p a r e d f r o m e t h y l e n e o x i d e -d 4 an3 ammonia. These r e a c t i o n cond i t i o n s a r e g i v e n f o r t h e H-analog. N-methylmorpholine-d i s p r e p a r e d f r o m e t h y l e n e o x i d e -d 4 and methylamine-d,-; N-ethbhorpholine-d13 i s p r e p a r e d i n an analogous manner. N-methyl-d3-morpholine i s p r e p a r e d f r o m m o r p h o l i n e and diazomethane-d and m e t h y l i o d i d e -d or from 2,2'-bis-(iodoethyl)ether and m e t h y lp r e p a r e 2 f r o m N-methylmorpho?.ine and e t h y l i o d i d e -d 5 . M.E.M.-d16i o d i d e and M.E.M.-iodide a r e o b t a i n e d by a s i m i l a r r o u t e . N,N-di-(methyl-d ) -m o r p h o l i n i u m i o d i d e i s p r e p a r e d f r o m N-methyl-dm o r p h o l i n e and m e t h y l i o d i d e -d 3 and a l s o f r o m m o r p h o l i n e and methy?iodide-d3. M.E.M.-(T.C.N.Q.-d,) ; M.E.M.-d,-(T.C.N.Q.-d ) ; M.E.M.-d16-( T.C .N.Q.-d4)2; M.E.M.-d16-fT.C .N.Q.)2 and N, N-di-(&ghyl-d3)morpholinium-(T.C.N.Q.) a r e p r e p a r e d f r o m t h e d e u t e r a t e d o r u n d e u t e r a t e d m o r p h o l i n i u m i o d i d e s and T.C.N.0. A l l s y n t h e t i c methods a r e d e s c r i b e d i n d e t a i l . or f r o m m o r p h o l i n e amine-d . N-methyl-N-ethyl-d 3 -morpholinium(M.E,M.-d5)-iodide i s 3 2 .