Crystal structure of 5-[4-(diethylamino)benzylidene]-2,2-dimethyl-1,3-dioxane-4,6-dione

The title compound, C17H21NO4, consists of substituted Meldrum's acid with a [4-(diethylamino)phenyl]methylidene fragment attached to the fifth position. The heterocycle assumes a distorted boat conformation. The planar part of heterocycle is almost coplanar with the benzene ring due to the presence of a long conjugated system in the molecule. This leads to the formation of C—H...O-type intramolecular contacts. As a result of the absence of hydrogen-bond donors in the structure, the crystal packing is controlled by van der Waals forces and weak C—H...O interactions, which associate the molecules into inversion dimers

Bio-Based Polymer Developments from Tall Oil Fatty Acids by Exploiting Michael Addition

In this study, previously developed acetoacetates of two tall-oil-based and two commercial polyols were used to obtain polymers by the Michael reaction. The development of polymer formulations with varying cross-link density was enabled by different bio-based monomers in combination with different acrylates—bisphenol A ethoxylate diacrylate, trimethylolpropane triacrylate, and pentaerythritol tetraacrylate. New polymer materials are based on the same polyols that are suitable for polyurethanes. The new polymers have qualities comparable to polyurethanes and are obtained without the drawbacks that come with polyurethane extractions, such as the use of hazardous isocyanates or reactions under harsh conditions in the case of non-isocyanate polyurethanes. Dynamic mechanical analysis, differential scanning calorimetry, thermal gravimetric analysis, and universal strength testing equipment were used to investigate the physical and thermal characteristics of the created polymers. Polymers with a wide range of thermal and mechanical properties were obtained (glass transition temperature from 21 to 63 °C; tensile modulus (Young’s) from 8 MPa to 2710 MPa and tensile strength from 4 to 52 MPa). The synthesized polymers are thermally stable up to 300 °C. The suggested method may be used to make two-component polymer foams, coatings, resins, and composite matrices

Crystal structure of 3-hydroxy-2-(4-hydroxy-3-methoxyphenylmethyl)-5,5-dimethylcyclohex-2-enone

In the title compound, C16H20O4, a new starting compound for the synthesis of various heterocycles, the partially saturated six-membered ring adopts a sofa conformation. An intramolecular O—H...O hydrogen bond is observed in the guaiacol residue. In the crystal, molecules are assembled into a sheet structure parallel to the ab plane via O—H...O hydrogen bonds. The hydrogen-bond pattern is described by an R44(28) graph-set motif. The sheets are further linked by C—H...O hydrogen bonds into a three-dimensional network

Crystal structure of 3-(4-hydroxyphenyl)-2-[(E)-2-phenylethenyl]quinazolin-4(3H)-one

The title compound, C22H16N2O2 {systematic name: 3-(4-hydroxyphenyl)-2-[(E)-2-phenylethenyl]quinazolin-4(3H)-one}, consists of a substituted 2-[(E)-2-arylethenyl]-3-arylquinazolin-4(3H)-one skeleton. The substituents at the ethylene fragment are located in trans positions. The phenyl ring is inclined to the quinazolone ring by 26.44 (19)°, while the 4-hydroxyphenyl ring is inclined to the quinazolone ring by 81.25 (8)°. The phenyl ring and the 4-hydroxyphenyl ring are inclined to one another by 78.28 (2)°. In the crystal, molecules are connected via O—H...O hydrogen bonds, forming a helix along the a-axis direction. The helices are linked by C—H...π interactions, forming slabs parallel to (001)

Spent Coffee Grounds Valorization in Biorefinery Context to Obtain Valuable Products Using Different Extraction Approaches and Solvents

The valuable products that can be isolated from spent coffee ground (SCG) biomass consist of a high number of bioactive components, which are suitable for further application as raw materials in various production chains. This paper presents the potential value of the SCG obtained from large and local coffee beverage producers, for the production of valuable, biologically active products. Despite its high potential, SCG has not been utilized to its full potential value, but is instead discarded as waste in landfills. During its decomposition, SCG emits a large amount of CO2 and methane each year. The main novelty of our work is the implementation of sequential extraction with solvents of increased polarity that allows for the maximal removal of the available extractives. In addition, we have compared different extraction techniques, such as conventional and Soxhlet extraction, with more effective accelerated solvent extraction (ASE), which has seen relatively little use in terms of SCG extraction. By comparing these extraction methods and highlighting the key differences between them in terms of extraction yield and obtained extract composition, this work offers key insights for further SCG utilization. By using sequential and one-step accelerated solvent extraction, it is possible to obtain a significant number of extractives from SCG, with a yield above 20% of the starting biomass. The highest yield is for coffee oil, which is obtained with n-hexane ranging between 12% and 14% using accelerated solvent extraction (ASE) according to the scheme: n-hexane→ethyl acetate→60% ethanol. Using single-stage extraction, increasing the ethanol concentration also increases the total phenolic content (TPC) and it ranges between 18.7–23.9 Gallic acid equivalent (GAE) mg/g. The iodine values in the range of 164–174 using ASE and Soxhlet extraction shows that the hexane extracts contain a significant amount of unsaturated fatty acids; coffee oils with a low acid number, in the range of 4.74–6.93, contain few free fatty acids. The characterization of separated coffee oil has shown that it mainly consists of linoleic acid, oleic acid, palmitic acid, stearic acid and a small number of phenolic-type compounds

Novel type of carbon-centered antioxidants arylmethyl Meldrum’s acids inhibit free radicals

art. no. 1700172Arylmethyl Meldrum’s acids should be highlighted as potential antioxidants for increasing oxidative stability of various products containing, for example, esters of poly-unsaturated fatty acids. It should be admitted that the structure of the title compounds can be widely modified by substituents in the aromatic ring without remarkable loss of antioxidant and antiradical activity, but other properties (like solubility) may be improved. In order to apply the title antioxidants into products like cosmetics additional tests regarding toxicity are required. However, these antioxidants can be recommended for increasing oxidative stability for products used in techniqueVytauto Didžiojo universitetasŽemės ūkio akademij

The Synthesis of Bio-Based Michael Donors from Tall Oil Fatty Acids for Polymer Development

In this study, the synthesis of a Michael donor compound from cellulose production by-products—tall oil fatty acids—was developed. The developed Michael donor compounds can be further used to obtain polymeric materials after nucleophilic polymerization through the Michael reaction. It can be a promising alternative method for conventional polyurethane materials, and the Michael addition polymerization reaction takes place under milder conditions than non-isocyanate polyurethane production technology, which requires high pressure, high temperature and a long reaction time. Different polyols, the precursors for Michael donor components, were synthesized from epoxidized tall oil fatty acids by an oxirane ring-opening and esterification reaction with different alcohols (trimethylolpropane and 1,4-butanediol). The addition of functional groups necessary for the Michael reaction was carried out by a transesterification reaction of polyol hydroxyl groups with tert-butyl acetoacetate ester. The following properties of the developed polyols and their acetoacetates were analyzed: hydroxyl value, acid value, moisture content and viscosity. The chemical structure was analyzed using Fourier transform infrared spectroscopy, gel permeation chromatography, size-exclusion chromatography and nuclear magnetic resonance. Matrix-assisted laser desorption/ionization analysis was used for structure identification for this type of acetoacetate for the first time

Impact of Different Epoxidation Approaches of Tall Oil Fatty Acids on Rigid Polyurethane Foam Thermal Insulation

A second-generation bio-based feedstock—tall oil fatty acids—was epoxidised via two pathways. Oxirane rings were introduced into the fatty acid carbon backbone using a heterogeneous epoxidation catalyst-ion exchange resin Amberlite IR-120 H or enzyme catalyst Candida antarctica lipase B under the trade name Novozym® 435. High functionality bio-polyols were synthesised from the obtained epoxidated tall oil fatty acids by oxirane ring-opening and subsequent esterification reactions with different polyfunctional alcohols: trimethylolpropane and triethanolamine. The synthesised epoxidised tall oil fatty acids (ETOFA) were studied by proton nuclear magnetic resonance. The chemical structure of obtained polyols was studied by Fourier-transform infrared spectroscopy and size exclusion chromatography. Average molecular weight and polydispersity of polyols were determined from size exclusion chromatography data. The obtained polyols were used to develop rigid polyurethane (PU) foam thermal insulation material with an approximate density of 40 kg/m3. Thermal conductivity, apparent density and compression strength of the rigid PU foams were determined. The rigid PU foams obtained from polyols synthesised using Novozym® 435 catalyst had superior properties in comparison to rigid PU foams obtained from polyols synthesised using Amberlite IR-120 H. The developed rigid PU foams had an excellent thermal conductivity of 21.2–25.9 mW/(m·K)

Wood pulp industry by-product valorization for acrylate synthesis and bio-based polymer development via Michael addition reaction

It is crucial to adapt the processing of forest bio-resources into biochemicals and bio-based advanced materials in order to transform the current economic climate into a greener economy. Tall oil, as a by-product of the Kraft process of wood pulp manufacture, is a promising resource for the extraction of various value-added products. Tall oil fatty acids-based multifunctional Michael acceptor acrylates were developed. The suitability of developed acrylates for polymerization with tall oil fatty acids-based Michael donor acetoacetates to form a highly cross-linked polymer material via the Michael addition was investigated. With this novel strategy, valuable chemicals and innovative polymer materials can be produced from tall oil in an entirely new way, making a significant contribution to the development of a forest-based bioeconomy. Two different tall oil-based acrylates were successfully synthesized and characterized. Synthesized acrylates were successfully used in the synthesis of bio-based thermoset polymers. Obtained polymers had a wide variety of mechanical and thermal properties (glass transition temperature from –12.1 to 29.6 °C by dynamic mechanical analysis, Young's modulus from 15 to 1 760 MPa, and stress at break from 0.9 to 16.1 MPa). Gel permeation chromatography, Fourier-transform infrared (FT-IR) spectroscopy, matrix-assisted laser desorption/ionization-time of flight mass spectrometry, and nuclear magnetic resonance were used to analyse the chemical structure of synthesized acrylates. In addition, various titration methods and rheology tests were applied to characterize acrylates. The chemical composition and thermal and mechanical properties of the developed polymers were studied by using FT-IR, solid-state nuclear magnetic resonance, thermal gravimetric analysis, differential scanning calorimetry, dynamic mechanical analysis, and universal strength testing apparatus