Efficient Synthesis of 2-Ethylhexanoic Acid via N-Hydroxyphthalimide Catalyzed Oxidation of 2-Ethylhexanal with Oxygen.

An efficient method for the synthesis of 2-ethylhexanoic acid has been reported. The method involves the 2-ethylhexanal oxidation using oxygen or air in the presence of N-hydroxyphthalimide in isobutanol as a solvent under mild conditions. A high selectivity of >99% for 2-ethylhexanoic acid was achieved. The influence of catalyst amount, solvent type and quantity, temperature, and reaction time on the product composition was studied. The developed method is in line with the global trends aimed at developing green oxidation processes as well as having potential for implementation in industry due to its high selectivity, cost-effective oxidizing agent, and mild reaction conditions. The use of isobutanol as a solvent is of crucial importance providing an opportunity for potential producers of 2-EHAL from butanal to employ the less valuable alcohol.

Selective Oxidation of Cyclohexanone to Adipic Acid Using Molecular Oxygen in the Presence of Alkyl Nitrites and Transition Metals as Catalysts.

This paper presents a not previously reported catalytic system consisting of transition metals Co2+ and Mn2+ and alkyl nitrites R-ONO for the oxidation of cyclohexanone with oxygen to adipic acid. The influence of type and amount of catalyst, temperature, time, and type of raw material on conversion and product composition were determined. In addition, the oxidation of selected cyclic ketones such as cyclopentanone, cyclohexanone, cyclooctanone, cyclododecanone, 2-methylcyclohexanone, 3-methylcyclohexanone, and 4-methylcyclohexanone in acetic acid as solvent was performed. The results showed that R-ONO systems, under established reaction conditions, form NO·radicals, which oxidize to NO2 under a strong oxidization reaction environment. The Co2+/Mn2+/NO2 system was shown to be highly active in the oxidation of cyclic ketones with oxygen.

Methods to Produce Nicotinic Acid with Potential Industrial Applications.

Nicotinic acid is a naturally occurring pyridine carboxylic acid, contained in vitamin PP, an essential nutrient for humans and animals, and used as an antipelagic agent. Nicotinic acid can be made from tryptophan by plants and animals but is usually not completely bioavailable. Industrially, nicotinic acid is produced mainly by oxidation of 5-ethyl-2-methylpyridine with nitric acid. One of the by-products of the process is nitrous oxide, a gas that is difficult to recycle and manage, with a greenhouse effect 300 times stronger than CO2. A new technology for the industrial production of nicotinic acid is undoubtedly necessary to meet the needs of green chemistry and not burden the environment. We carried out a literature review on ecological methods to produce nicotinic acid from commercially available raw materials such as 3-methylpyridine and 5-ethyl-2-methylpyridine, especially focusing on those methods with potential industrial applications.

Oxidation of Cyclohexane/Cyclohexanone Mixture with Oxygen as Alternative Method of Adipic Acid Synthesis.

Herein, an alternative method for adipic acid (AA) synthesis of industrial importance has been reported. The proposed novel method involves the one-step, solvent-free oxidation of a cyclohexane/cyclohexanone (CH/CH=O) mixture, with a cheap oxidizing agent such as O2 or air under mild conditions in the presence of N-hydroxyphtalimide (NHPI) and transition metals as catalysts. It has been showed that CH/CH=O mixture under applied mild conditions oxidized faster than CH and CH=O separately. This was due to the greater oxidizability of CH=O compared to CH. The peroxyl radicals formed by CH=O oxidation initiated the oxidation of the less reactive CH. Additionally, CH=O increased the polarity of the reaction mixture, promoting the solubility of NHPI. The influence of type and amount of catalyst, cyclohexane to cyclohexanone ratio, temperature, time, type of oxidizing agent on the composition of CH/CH=O oxidation products have been reported.

Influence of the Feedstock on the Process Parameters, Product Composition and Pilot-Scale Cracking of Plastics.

Chemical recycling of polymers can lead to many different products and play a significant role in the circular economy through the use of plastic waste as a feedstock in the production of valuable materials. The polyolefins: polyethylene (PE) and polypropylene (PP), together with polystyrene (PS), can be chemically recycled by the thermal cracking (pyrolysis) process. In this study, continuous cracking of polyolefins and polystyrene in different proportions and with the addition of other polymers, like polyethylene terephthalate (PET) and polyvinyl chloride (PVC), was investigated at the pilot scale in terms of the process parameters and product yields. Gas chromatography with mass spectrometry (GC-MS) was used for the detailed analysis of the products' compositions. The boiling temperature distribution and the bromine number were used for additional characterization of products. It was found that an increase of PP share caused a decrease in the process temperature, an increase of the product yield and a shift of the boiling range towards lighter products, increasing the content levels for unsaturates and branched hydrocarbons. It was observed that the addition of 5% PS, PET and PVC reduced the overall product yield, resulting in the creation of a lower-boiling product and increasing the conversion of polyethylene. An addition of 10% polystyrene increased the PP conversion and resulted in a higher product yield, without significant change in the boiling temperatures distribution.

Transition Metal Salts of Carboxylated Multiwalled Carbon Nanotubes in Combination with N-hydroxyphthalimide as Catalytic Systems for Hydrocarbon Oxidation.

In this study, the transition metal (Co (II), Cu (II), and Mn (II)) salts of carboxylated carbon nanotubes were synthesized and characterized (the determined metal contents were in the range of 0.89-1.16%). The catalytic activity and the possibility for recovery and reuse of the obtained heterogeneous salts were then studied in the solvent-free oxidation of ethylbenzene with oxygen. The oxidation processes were carried out at 80 °C under atmospheric pressure in the presence of N-hydroxyphthalimide. The highest conversion of ethylbenzene, 27%, was obtained with a system consisting of the Cu (II) salt of the carboxylated carbon nanotubes, N-hydroxyphthalimide, and the azo initiator AIBN.

Oxidation of Long-Chain α-Olefins Using Environmentally-Friendly Oxidants.

Studies on the oxidation of α-olefins via the two-stage method are presented. The new method consisted of oxidizing C30+ α-olefins with hydrogen peroxide (2 equiv.) and subsequent oxidation with oxygen. Products with high acid numbers (29-82 mgKOH/g) and saponification numbers (64-140 mgKOH/g) were obtained and compared with products obtained using only hydrogen peroxide or oxygen. It was demonstrated that H2O2 can be partially replaced by oxygen in the oxidative cleavage reaction of α-olefins. N-hydroxyphthalimide in combination with Co(acac)2 demonstrated high activity in the oxidation stage using oxygen.

Recyclable Polymer-Supported N-Hydroxyphthalimide Catalysts for Selective Oxidation of Pullulan.

This paper proposes a convenient route to oxidize the -CH2-OH groups in the water-soluble pullulan, using a new catalytic polymer-supported N-hydroxyphthalimide (NHPI) immobilized on polystyrene. The protocol involves the presence of sodium hypochlorite and sodium bromide. The conversion is possible at room temperature, atmospheric pressure, and pH = 10. The characterization of both the catalysts and oxidized pullulan was done using NMR and FTIR methods. Using polyelectrolyte titration with end-point indication by means of a particle-charge detector (PCD), we were able to assess the degree of electrokinetic charge in all oxidized samples as a consequence of the conversion of the -CH2-OH group into -COOH moieties. The possibility of recovery and recycling of the polymer-supported NHPI catalyst was tested for up to four cycles, since the morphological analyses performed on the catalysts using SEM revealed no significant changes.

Spectroscopic Methods in the Evaluation of Modified Vegetable Base Oils from Crambe abyssinica.

Raw vegetable oil from Crambe abyssinica was subjected to oxidative treatment to enhance its viscosity. The oxidation processes were carried out in the presence of N-hydroxyphthalimide with or without supercritical CO2 as a solvent. Four spectroscopic techniques (Raman, UV-VIS, FT-IR, NMR) were applied to assess the chemical changes taking place during the oxidation. Raman and NMR spectroscopy proved best in the assessment of the chemical transformations leading to increased viscosity of the modified vegetable oil.