Mesityl Oxide Reduction by Using Acid-Modified Phonolite Supported NiW, NiMo, and CoMo Catalysts

Mesityl oxide is standardly used to produce methyl iso butyl ketone but it can be also used to produce other useful compounds. Three catalysts were used for the reaction of the mesityl oxide reduction. They were NiW, NiMo, and CoMo supported on phonolite modified by HCl (metals/Ph-HCl). The fresh catalysts were characterized by XRD, XRF, BET surface, Hg porosimetry, SEM, H2-TPR, NH3-TPD, CO2-TPD. The materials were directly used, previously reduced in H2 or sulfided for the mesityl oxide reduction under H2 atmosphere. The reaction was performed in an autoclave at T = 375 °C, p = 50 bar (H2), and TOS = 1.5 h. The products were analyzed by GC/MS, GC/FID-TCD, ATR. The main products were methyl isobutyl ketone, 2-methyl pentane, and 2-methyl-2-pentene. Sulfided metal catalysts were the most active in the methyl isobutyl ketone, where the NiWSx/Ph-HCl catalyst showed the highest activity. For the non-previously-activated and hydrogen activated catalysts the most active catalyst was the NiMo/Ph-HCl for the production of methyl isobutyl ketone. The catalyst CoMo/Ph-HCl activated in hydrogen was the most active for the production of 2-methyl pentane compared to the other two hydrogen-activated materials.

The Molecular Mechanism of the Formation of Four-Membered Cyclic Nitronates and Their Retro (3 + 2) Cycloaddition: A DFT Mechanistic Study

In the present work, the formation of the four-membered cyclic nitronates and the retro (3 + 2) cycloaddition (retro-32CA) reaction of the 4H-[1,2]oxazete 2-oxide were studied using the density functional theory method at the MPWB1K/6-311G(d,p) theoretical level. The electronic structure of 3-tert-butyl-4,4-dimethyl-1,2-dinitro-pent-2-ene was known through electron localization function analysis, natural population analysis, and molecular electrostatic potential analysis. The formation of 4,4-di-tert-butyl-3-nitromethyl-4H-[1,2]oxazete 2-oxide proceeds through a one-step mechanism. The mechanism of the retro-32CA leading to di-tert-butyl ketone and nitrile oxide derivative should be described as an asynchronous two-stage one-step process. The bonding evolution theory study was carried out to clarify the mechanisms of the formation of 4H-[1,2]oxazete 2-oxide and their retro-32CA.

UNIFAC Model for Liquid-Liquid Phase Equilibrium of Penicillin G and 6-APA System

This study investigated the effect of pH and type of solvent on liquid-liquid phase equilibrium in the system of pure penicillin G and mixed penicillin G with 6-APA. Penicillin G extraction was carried out in a pH range of 2.0–5.0 at 4 oC using several types of solvents. The liquid-liquid phase equilibrium mathematical model is prepared assuming that a single stage of thermodynamic equilibrium occurs in a batch process of liquid-liquid extraction. The coefficient of activity was calculated by the UNIFAC method. From the experiment, it was found that the extraction process of penicillin G was strongly influenced by pH of the solution. The highest yield of extraction was achieved with different solvents in the two types of solution. For pure penicillin G system, the highest yields was obtained in n-butyl acetate solvent (95.51%) while for penicillin G mixture with 6-APA, it was obtained in methyl iso-butyl ketone solvent (92.6%). The UNIFAC model have been tested against five three-component liquid-liquid phase equilibrium systems at pH 2.0 and 2.5. It was able to estimate the concentration of penicillin G in the organic phase with a relatively average error between experiment and calculation of 8.32%