Direct Phenolysis Reactions of Unactivated Amides into Phenolic Esters Promoted by a Heterogeneous CeO2 Catalyst.

The direct catalytic esterification of amides that leads to the construction of C-O bonds through the cleavage of amide C-N bonds is a highly attractive strategy in organic synthesis. While aliphatic and aromatic alcohols can be readily used for the alcoholysis of activated and unactivated amides, the introduction of phenols is more challenging due to their lower nucleophilicity in the phenolysis of unactivated amides. Herein, we demonstrate that phenols can be used for the phenolysis of unactivated amides into the corresponding phenolic esters using a simple heterogenous catalytic system based on CeO2 under additive-free reaction conditions. The method tolerates a broad variety of functional groups (>50 examples) in the substrates. Results of kinetic studies afforded mechanistic insights into the principles governing this reaction, suggesting that the cooperative effects of the acid-base functions of catalysts would be of paramount importance for the efficient progression of the C-N bond breaking process, and consequently, CeO2 showed the best catalytic performance among the catalysts explored.

Exposure and health risks of metals in imported and local brands' lipsticks and eye pencils from Bangladesh.

Elemental contamination in cosmetics is a serious health concern as it can pose a cumulative effect on the user's body over a long period. The prime motive of the study was to assess the concentration of 10 concerning chemical elements (Pb, Cd, Cr, As, Co, Ni, Cu, Zn, Fe, and Mn) in imported and local lipsticks and eye pencil samples collected from retail outlets in central Bangladesh (Dhaka city) and to assess their dynamic health risks for users. A total of 18 lipsticks and 24 eye pencils were studied and concentrations of chemical elements were examined with atomic absorption spectrophotometer. The health risk assessment was performed for dermal and ingestion routes of the contaminants. The results reveal that the concentrations of the examined elements vary with colors, brands, and origins. Pb and As concentrations were found below the permissible limit but Cr concentration in some samples exceeded the allowable limit in cosmetics. Cd was not detected in any samples; however, other examined elements such as Co, Ni, Cu, Mn, Zn, and Fe were detected in considerable concentrations. Elements like Mn, Zn, and Fe were found at high levels. In the case of lipstick samples, elemental concentrations followed the order of Fe > Zn > Mn > Ni > Cr > Cu > Pb > Co > As, while the order was Fe > Cu > Mn > Zn > Ni > Cr > Co > Pb > As for eye pencil samples. Results of the hazards quotient (HQ) indicate that there were no non-carcinogenic or carcinogenic risks of elements in samples for dermal exposure. But the cancer risk values of Cr (HQ > 1 for ingestion) in brown color lipsticks and Ni indicate that lipsticks have some carcinogenic effects if they enter the user's body. Dermal cancer risk for eye pencils has also been calculated and for Pb, Cr, Ni, and As; the values were found within the acceptable ranges of 10-6-10-4. It is suggested that the allowable limit of all toxic elements in cosmetics must be established. Furthermore, continuous monitoring is urgently needed for personal care products like lipsticks and eye pencils commonly available in the local markets in the country like Bangladesh.

Selective Transformations of Triglycerides into Fatty Amines, Amides, and Nitriles by using Heterogeneous Catalysis.

The use of triglycerides as an important class of biomass is an effective strategy to realize a more sustainable society. Herein, three heterogeneous catalytic methods are reported for the selective one-pot transformation of triglycerides into value-added chemicals: i) the reductive amination of triglycerides into fatty amines with aqueous NH3 under H2 promoted by ZrO2 -supported Pt clusters; ii) the amidation of triglycerides under gaseous NH3 catalyzed by high-silica H-beta (Hß) zeolite at 180 °C; iii) the Hß-promoted synthesis of nitriles from triglycerides and gaseous NH3 at 220 °C. These methods are widely applicable to the transformation of various triglycerides (C4 -C18 skeletons) into the corresponding amines, amides, and nitriles.