THE VALIDATION OF PROTOCOLS FOR CARRYING OUT THE EXPERIMENTAL ANALYSIS OF AMINATION REACTIONS IS OF PARAMOUNT IMPORTANCE TO ENHANCE THE SCIENTIFIC KNOWLEDGE AND REPRODUCIBILITY OF RESULTS. ACCORDINGLY, IN THE PRESENT PAPER, A PROTOCOL HAS BEEN PROPOSED FOR THE STUDY OF THE AMINATION OF CYCLOHEXANONE-TO-SECONDARY AMINES (DIPHENYLAMINE AND N-CYCLOHEXYLANILINE) OVER HETEROGENEOUS CATALYSTS. THE RESULTS OF ACTIVITY AND SELECTIVITY, AND THE ELUCIDATION OF A PLAUSIBLE REACTION PATHWAY WERE DESCRIBED IN A PARENT PAPER. THEREFORE, THE PURPOSE OF THIS DOCUMENT IS TO INFORM ABOUT THE DETAILS OF THE EXPERIMENTAL SETUPS, THE METHODS, AND THE ANALYTICAL TECHNIQUES TO IDENTIFY AND QUANTIFY THE REACTION PRODUCTS. FINALLY, SOME PRACTICAL AND SAFETY CONSIDERATIONS ARE ALSO INCLUDED. ? ONE-POT CATALYTIC AMINATION OF CYCLOHEXANONE WITH ANILINE WAS PERFORMED EFFICIENTLY IN LIQUID PHASE ON PD/C. ? STIRRING, HE ATMOSPHERE AND TEMPERATURE CONTROL WERE CRITICAL TO ACHIEVE REPRODUCIBLE ACTIVITY RESULTS. ? ULTRA-HIGH PERFORMANCE LIQUID CHROMATOGRAPHY ALLOWS IDENTIFYING PRODUCTS AND REACTION INTERMEDIATES, WHILE NONANE PERFORMED WELL AS INTERNAL STANDARD FOR GC-FID QUANTIFICATION.

THE LIQUID PHASE AMINATION OF THE CYCLOHEXANONE (CYO) WITH ANILINE (PHNH2) WAS STUDIED ON A PD/C CATALYST USING NACO2H AS A H-DONOR. CATALYTIC TESTS WERE PERFORMED IN BATCH REACTORS BY VARYING REACTANT CONCENTRATIONS (0, 0.1, 0.2 AND 0.4 MOL/L), THE TEMPERATURE (80?160 °C) AND H2-EQUIVALENTS AVAILABILITY (0, 2 AND 4 H2-EQUIVALENTS WITH RESPECT TO CYO). THE RESULTS INDICATE THAT, THE USE OF NACO2H BARELY AFFECT THE REACTIVITY (MEASURED AS INITIAL REACTION RATE) WHILE IT DOES INFLUENCE THE SELECTIVITY TO SECONDARY AMINES. THIS EFFECT WAS ASCRIBED TO THE LIMITED EFFECTIVITY OF THE H2 TRANSFER, WHICH WAS CONTROLLED BY THE WATER FORMED AFTER THE CONDENSATION OF THE CYO WITH THE PHNH2, HYDROGEN SOLUBILITY IN TOLUENE, AND THE MASS TRANSFER FROM THE LIQUID TO THE CATALYST SURFACE. THE EXPERIMENTAL OBSERVATIONS WERE CONSISTENT WITH A MULTI-STEP MECHANISM CONSISTING IN: A FIRST STEP OF CONDENSATION OF THE KETONE AND THE AMINE TO FORM AN IMINE, FOLLOWED BY THE DISPROPORTIONATION OF THE IMINE INTO SECONDARY AMINES. THE KINETIC MEASUREMENTS AT INITIAL RATE CONDITIONS WERE WELL INTERPRETED BY A LANGMUIR HINSHELWOOD (L-H) KINETIC MODEL, WHICH SUGGEST THAT THE SURFACE REACTION TO FORM THE INTERMEDIARY IMINE IS THE RATE LIMITING STEP (R.L.S).