ΜΕΛΕΤΗ ΟΞΕΙΔΩΣΗΣ ΟΞΙΜΙΝΙΚΩΝ ΚΑΙ ΙΜΙΝΙΚΩΝ ΠΑΡΑΓΩΓΩΝ ΚΑΡΒΟΝΥΛΙΚΩΝ ΕΝΩΣΕΩΝ

Abstract

THE REACTION OF ALIPHATIC 1,3-DIOXIMES WITH LEAD TETRAACETATE (LTA) RESULTED MAINLY IN PYRAZOLE- AND PYRAZOLINE - 1,2-DIOXIDES. THE EXACT TYPE OF THE N-OXIDE FORMED, DEPENDS ON THE SUBSTITUENTS ON THE 2-POSITION OF THE DIOXIME. FURTHERMORE, INFLUENCE IS ALSO EXERCISED BY ALKYL OR ARYL GROUPS ADJACENT TO THE =NOH MOIETY. DEOXYGENATION OF THE ABOVE N- OXIDES WITH TRIETHYL PHOSPHITE PROCEEDSVERY DIFFICULTY TO THE PARENT RING SYSTEM, WHEREAS DIELS-ALDER REACTION AND IRRADIATION WITH MERCURY LAMP WERE UNSUCCESSFUL. FURTHERMORE, PRELIMINARY TESTSHAVE SHOWN PROMISING BIOLOGICAL ACTIVITY OF THESE COMPOUNDS. THE OXIDATION WITH LTA OF SOME B-DIOXIMES WITH THE =NOH MOIETIES ATTACHED TO THE CYCLOHEXANE RING LEADS TO PYRAZOLE AND PYRAZOLINE- 1,2 - DIOXIDES OR TO GEM-NITROSO-ACETATES RATHER THAN THEIR ISOMERIC PYRAZOLE- 1,2 - DIOXIDES IS PERSSUMABLY INFLUENCED BY THE CONFORMATIONAL EFFECTS OF THE CYCLOHEXANE RING. TREATMENT OF THE GEM-NITROSOACETATES WITH HYDROGEN PEROXIDE YIELDED THE CORRESPONDING NITRO COMPOUNDS, WHEREAS WITH DILUTE HYDROCHLORIC ACID THE PARENT 1,3-DIKETONES WERE REGENERATED. REACTION WITH ANILINE RESULTED MAINLY IN AZO- AND AZOXY - BENZENE. FURTHERMORE, REACTION OF LTA WITH BIS-SCHIFT BASES, DERIVED FROM THE CONDESATIONOF ETHYLENEDIAMINE WITH AROMATIC CARBONYLS, GAVE HYDROLYSIS INSTEAD OF CYCLISATION PRODUCTS. FINALLY, REACTION OF LTA WITH BIS-SCHIFT BASES OF DIACETYL ANDBENZIL YIELDED SUBSTITUTED ACETANILIDE AND AZOBENZENE. PLANSIBLE MECHANISMS ARE PROPOSED FOR ALL THE ABOVE CASES.

ΣΤΗΝ ΔΙΑΤΡΙΒΗ ΑΥΤΗ ΜΕΛΕΤΑΤΑΙ ΔΙΕΞΟΔΙΚΑ Η ΟΞΕΙΔΩΣΗ Β-ΔΙΟΞΙΜΩΝ, ΚΑΘΩΣ ΚΑΙ ΔΙΠΛΩΝΒΑΣΕΩΝ ΤΟΥ SCHIFT ΜΕ ΤΕΤΡΑΟΞΙΚΟ ΜΟΛΥΒΔΟ. ΕΠΙΣΗΣ ΜΕΛΕΤΑΤΑΙ Η ΧΗΜΕΙΑ ΤΩΝ ΠΡΟΙΟΝΤΩΝ ΠΟΥ ΠΡΟΚΥΠΤΟΥΝ ΑΠΟ ΤΙΣ ΑΝΤΙΔΡΑΣΕΙΣ ΑΥΤΕΣ ΚΑΘΩΣ ΚΑΙ Η ΠΡΑΚΤΙΚΗ ΕΦΑΡΜΟΓΗ ΤΟΥΣ.