Amination Of Alcohols Research Articles

Synthesis of Tertiary Fatty Amines in Water: The Dual Role of Dimethylamine as Reagent and Phase Mediator in the Homogeneously Catalyzed Fatty Alcohol Amination

Synthesis of Tertiary Fatty Amines in Water: The Dual Role of Dimethylamine as Reagent and Phase Mediator in the Homogeneously Catalyzed Fatty Alcohol Amination

Ionic Liquid Hydrogen-bonding Promoted Alcohols Amination over Cobalt Catalyst via Dihydrogen Autotransfer Mechanism.

Higher amines are important high-valuable chemicals with wide applications, and amination of alcohols is a green route to them, which however generally suffers from harsh reaction conditions and use of equivalent base. Herein, we report an ionic liquid (IL) hydrogen-bonding promoted dihydrogen autotransfer strategy for amination of bio-alcohols to higher amines over cobalt catalyst under base-free conditions. Co(BF4)2·6H2O complexed with triphos and IL (e.g., tetrabutylphosphonium tetrafluoroborate, [P4444][BF4]) shows high performances for the reaction, and is tolerate to wide scopes of amines and bio-alcohols, affording higher amines in good to excellent yields. Mechanism investigation indicates that the [BF4]- anion activates alcohol via hydrogen bonding, promoting transfer of both hydroxyl H and a-H of alcohol to cobalt catalyst to form aldehyde intermediate and cobalt dihydride complex, which involve in subsequent reductive amination. This strategy provides a green and effective route for alcohol amination, which may have promising applications in alcohol-involved alkylation reactions.

Metal-Free Construction of Multisubstituted Indolizines via Intramolecular Amination of Allylic Alcohols.

An intramolecular amination of allylic alcohols is developed as an efficient and general access to biologically important multisubstituted indolizines and their variants. Two metal-free synthetic platforms including using aqueous hydrochloric acid solution as the solvent and p-toluenesulfonic acid as the catalyst have been established, enabling the divergent synthesis of these valuable compounds in high yields.

Direct Amination of α-Triaryl Alcohols via Vanadium Catalysis

α-Triaryl amines have been used as pharmaceuticals and pharmaceutical intermediates for antifungal and anticancer applications. Current methods to synthesize such compounds require at least two steps, and no direct amination of tertiary alcohols has been reported. Herein, we disclose efficient catalytic conditions for the direct amination of α-triaryl alcohols to access α-triaryl amines. VO(OiPr)3, a commercially available reagent, has been identified as an effective catalyst for the direct amination of several α-triaryl alcohols. This process is scalable, as demonstrated by a gram-scale synthesis, and the reaction still works at as low as a 0.01 mol % catalyst loading with the turnover number reaching 3900. Moreover, commercial pharmaceuticals including clotrimazole and flutrimazole have been successfully prepared rapidly and efficiently using this newly developed method.

Analysis of thermodynamics, kinetics, and reaction pathways in the amination of secondary alcohols over Ru/SiO2

This work considers the Ru-mediated amination of secondary alcohols with ammonia in vapor and liquid media. We map thermodynamic constraints, and we probe the impacts of species partial pressure, residence time, and reaction temperature on rate, selectivity, and catalyst stability. Alcohol amination consumes no H2, and H2 has no significant impact on amination kinetics; however, operating under H2 benefits Ru stability. Primary amine selectivity increases with ammonia pressure and alcohol conversion, and the latter observation is consistent with the formation of primary amines through a network of sequential reactions. Unfortunately, primary amines are susceptible to secondary deamination to form hydrocarbons. As is typical of processes that seek to isolate a reactive intermediate, the main selectivity challenge here is identifying residence times that are long enough to accumulate high substrate conversion but short enough to avoid secondary deamination. In general, moderate residence times will maximize the production of primary amines. Insights extend across a broad substrate scope, and we observe 70 – 90% yield of primary amines from linear, cyclic, and heterocyclic alcohols. That said, heterocyclic alcohols appear susceptible to product inhibition, so achieving high conversions requires longer residence times and/or increased ammonia pressures.

New Ru(II) pyrazolone complex catalyzed direct amination of alcohols: A preliminary mechanistic investigation

A novel Ru(II) complex containing 4‐(2‐hydroxybenzyl)‐3‐methyl‐5‐oxo‐2,5‐dihydropyrazole‐1‐carbothioic acid methylamide has been applied as a catalyst for directly aminating alcohols. Preliminary investigation on the reaction mechanism has been done with the help of NMR spectroscopy recorded for regenerated catalysts and an NMR reaction. In addition, a plausible mechanism for the formation of the coupled product has been proposed.

Preparation and characterization of CO2/O2 selective facilitated transport films by coating polyvinyl alcohol/polyethylene glycol/aminated sodium lignosulfonate on TiO2/ZnO‐modified LDPE

AbstractA novel facilitated transport film was prepared by coating polyvinyl alcohol (PVA)/polyethylene glycol (PEG)/aminated sodium lignosulfonate on TiO2/ZnO‐modified low‐density polyethylene (LDPE). Monoethanolamine (MEA), diethanolamine (DEA), ethylenediamine (EDA), diethylenetriamine (DETA), tetramethylpiperidine amine (TEMP), and acrylamide (AM) were selected to modify sodium lignosulfonate (Ls) for enhancing the selectivity and permeability of CO2/O2. The fabricated Ls were characterized by fourier transform infrared (FTIR), thermogravimetric test (TG), and scanning electron microscopy (SEM). The CO2 permeability and CO2/O2 selectivity were improved with the increase in the amount of amine groups. Compared with the addition of Ls modified by alcohol amine, the composite film has higher selectivity to CO2 after the addition of DETA‐Ls or TEMP‐Ls. The selectivity of the 1:3:3EDA/MEA‐Ls‐g‐AM composite film reached 13.7, and CO2 permeability increased by 5.54 times. The storage test also demonstrated that the composite films have better freshness retention ability. As a result, modified LDPE coated by PVA/PEG/aminated Ls has the potential as an active modified atmosphere packaging material.

Synthesis and characterization of N-acyl alkanolamide surfactant from fatty acids and alcohol amines using sodium methoxide catalyst

Surfactant is a substance added to the liquid that improves the spread's properties by weakening the liquid's surface voltage. Surfactants have a molecular structure consisting of hydrophilic groups and hydrophobic groups. Surfactant needs in Indonesia continue to increase along with the development of industries in Indonesia. This study will be synthesized by the N-acyl surfactant alkanolamide using one type of alcohol amine, namely diethanolamine, through a reaction of amidation between fatty acids and using organic solvents tert-amyl alcohol. The catalyst used is a chemical catalyst, namely sodium methoxide. Furthermore, the purpose of this research is to determine the effect of reaction variables and determine the characteristics of the N-acyl alkanolamide surfactant in the form of acidic numbers and spreading numbers. This study showed for lauric acid, palmitate acid, and the best stearate acid at 90 oC reaction temperatures and 2-hour reaction times, while the best succinic acid at 100 oC and a reaction time of 2 hours. The relationship between reaction rate and time is directly proportional; the longer the reaction time, the higher the rate. The conversion relationship with reaction time is directly proportional, where conversion will increase with the increase in reaction time. However, this does not happen to all fatty acids. Due to the increase in reaction time, it will not provide significant results on surfactant products. The relation between the reaction temperature and the conversion acquisition at the time obtained decreased along with the increase in reaction temperatures. The acid numbers in the best conditions in a row are 40.67 for N-palmitoyl diethanolamine, 47.41 for N-lauroyl diethanolamine, 63.11 for N-succinyl diethanolamine, and 22.44 for N-stearoyl diethanolamine. The saponification number in the best conditions in a row is 36.47 for N-palmitoyl diethanolamine, 23.84 for N-lauroyl diethanolamine, 57.50 for N-succinoyl diethanolamine, and 7.01 for N-stearoyl diethanolamine.

Homogeneous Catalysis at its Edge: High‐Temperature Ru‐Catalysed Amination of Alcohols under Continuous Flow Conditions

AbstractCombining a tubular flow reactor with a robust homogeneous catalyst enabled running the alcohol amination at unique conditions, i. e., very high temperatures at low residence times. Catalytic activities were thus increased to unprecedented values of >900 h−1 in the synthesis of tertiary dimethylalkylamines directly from alcohols with excellent selectivities exceeding 99 %. Furthermore, several alcohols could be converted to the desired tertiary amines.

Metal-free nanodiamond catalyst for alcohol–amine oxidative coupling to imine

Metal-free nanodiamond catalyst for alcohol–amine oxidative coupling to imine

Development of Immobilized Carreira (Phosphoramidite, Olefin) Ligands and Application in Iridium-Catalyzed Asymmetric Allylic Amination

A family of polystyrene-supported (phosphoramidite, olefin) ligands L1-L4, based on the original design by Defieber and Carreira, has been developed and applied in iridium-catalyzed asymmetric allylic amination of unmasked allylic alcohols (27 examples, up to 99% ee). Among them, functional resins L1 and L4 exhibit important advantages such as easy preparation, ligand recyclability, and easy handling for sequential use. As a distinctive advantage, the catalytic use of the iridium complexes of L1 and L4 allows the straightforward reuse of a high percentage of the expensive iridium metal involved in the complexes, which is not achievable under homogeneous conditions with the corresponding monomeric complexes.

Synthesis and properties of aminomethoxy 1-(benzylsulfanyl)octane-2-ol derivatives

A previously unknown sulfur-containing alcohol, 1-(benzylsulfanyl)octane-2-ol, was synthesized in 65% yield. Further, on the basis of the obtained alcohol, formaldehyde, and aliphatic (diethyl-, dibutyl-, dipropyl-, dipentyl-, dihexylamine) or heterocyclic (piperidine, morpholine, hexamethyleneimine) amines, new representatives of 2-aminomethoxy derivatives of 1-(benzylsulfanyl)octane-2-ol were obtained by Mannich condensation. The yield of target products was 68-75%. The physicochemical data of the synthesized compounds were determined. The composition and structure of the obtained compounds were confirmed by elemental analysis, IR, 1H NMR spectroscopy, and mass spectrometry. The resulting products are colorless liquids with a characteristic odor, insoluble in water, and readily soluble in organic solvents. The synthesized compounds were tested for antimicrobial activity against pathogenic and conditionally pathogenic microorganisms. The antimicrobial activity of the substances was studied by the method of serial dilutions. The results obtained showed that the tested compounds exhibit more pronounced antimicrobial activity than alcohol, carbolic acid (phenol), rivanol, nitrofungin, furacillin and chloramine used in practice. The synthesized compounds have also been tested as antimicrobial additives to oils, and it has been found that they effectively suppress the vital activity of microorganisms.

Study the reuse possibility of tempering lubricant for cold‐rolled strip wet‐rolling processing

AbstractIn the wet rolling process of industrial cold‐rolled strips, the tempering lubricant was discarded after one‐time use, which resulted in huge waste and high costs for wastewater treatment. In order to explore the reuse value and feasibility of the tempering lubricant, the influences of industrial rolling were to be studied first. In the comparison of before and after‐use‐ tempering lubricant, the surface tension decreased by 34%, and the physicochemical indicators such as electrical conductivity, pH, and total alkali value decreased by 4%–14.3%. In terms of the components and related effects, about 15% of heavy organic matter, such as fatty acids and alcohol amine was responsible for lubrication, rust prevention, and corrosion inhibition. These heavy organic solutes would reduce by 2%–6%, with impurities increasing after rolling. However, the waste tempering lubricant still had a high reuse value. Further from the influence of impurities and microorganisms, it was concluded that if the solid powders were filtered out, the bacteriostatic agent was added after 3 days, and the changes in the effective substance concentration of the tempering lubricant were mastered to replace 1/3 of it in time during recycling, then the reuse of the tempering lubricant was feasible.

Uncovering Structure-Activity Relationships in Pt/CeO2 Catalysts for Hydrogen-Borrowing Amination.

The hydrogen-borrowing amination of alcohols is a promising route to produce amines. In this study, experimental parameters involved in the preparation of Pt/CeO2 catalysts were varied to assess how physicochemical properties influence their performance in such reactions. An amination reaction between cyclopentanol and cyclopentylamine was used as the model reaction for this study. The Pt precursor used in the catalyst synthesis and the properties of the CeO2 support were both found to strongly influence catalytic performance. Aberration corrected scanning transmission electron microscopy revealed that the most active catalyst comprised linearly structured Pt species. The formation of these features, a function result of epitaxial Pt deposition along the CeO2 [100] plane, appeared to be dependent on the properties of the CeO2 support and the Pt precursor used. Density functional theory calculations subsequently confirmed that these sites were more effective for cyclopentanol dehydrogenation-considered to be the rate-determining step of the process-than Pt clusters and nanoparticles. This study provides insights into the desirable catalytic properties required for hydrogen-borrowing amination but has relevance to other related fields. We consider that this study will provide a foundation for further study in this atom-efficient area of chemistry.

Ring-opening mechanism of epoxides with alcohol and tertiary amines

The ring-opening reaction of epoxides with alcohol and tertiary amines was studied. NMR spectroscopy analysis confirmed that glycidol has a different ring-opening polymerization mechanism than other epoxides in the presence of tertiary amines.

Cheminformatics analysis of chemicals that increase estrogen and progesterone synthesis for a breast cancer hazard assessment

Factors that increase estrogen or progesterone (P4) action are well-established as increasing breast cancer risk, and many first-line treatments to prevent breast cancer recurrence work by blocking estrogen synthesis or action. In previous work, using data from an in vitro steroidogenesis assay developed for the U.S. Environmental Protection Agency (EPA) ToxCast program, we identified 182 chemicals that increased estradiol (E2up) and 185 that increased progesterone (P4up) in human H295R adrenocortical carcinoma cells, an OECD validated assay for steroidogenesis. Chemicals known to induce mammary effects in vivo were very likely to increase E2 or P4 synthesis, further supporting the importance of these pathways for breast cancer. To identify additional chemical exposures that may increase breast cancer risk through E2 or P4 steroidogenesis, we developed a cheminformatics approach to identify structural features associated with these activities and to predict other E2 or P4 steroidogens from their chemical structures. First, we used molecular descriptors and physicochemical properties to cluster the 2,012 chemicals screened in the steroidogenesis assay using a self-organizing map (SOM). Structural features such as triazine, phenol, or more broadly benzene ramified with halide, amine or alcohol, are enriched for E2 or P4up chemicals. Among E2up chemicals, phenol and benzenone are found as significant substructures, along with nitrogen-containing biphenyls. For P4up chemicals, phenol and complex aromatic systems ramified with oxygen-based groups such as flavone or phenolphthalein are significant substructures. Chemicals that are active for both E2up and P4up are enriched with substructures such as dihydroxy phosphanedithione or are small chemicals that contain one benzene ramified with chlorine, alcohol, methyl or primary amine. These results are confirmed with a chemotype ToxPrint analysis. Then, we used machine learning and artificial intelligence algorithms to develop and validate predictive classification QSAR models for E2up and P4up chemicals. These models gave reasonable external prediction performances (balanced accuracy ~ 0.8 and Matthews Coefficient Correlation ~ 0.5) on an external validation. The QSAR models were enriched by adding a confidence score that considers the chemical applicability domain and a ToxPrint assessment of the chemical. This profiling and these models may be useful to direct future testing and risk assessments for chemicals related to breast cancer and other hormonally-mediated outcomes.

Sustainable Amination of Bio-Based Alcohols by Hydrogen Borrowing Catalysis

In this review, we aim to give an overview of the use of the Borrowing Hydrogen (BH) methodology with bio-based alcohols. This methodology only forms water as a by-product, thus providing a sustainable way to amines, which have a large range of applications. This process is of particular interest when related to biomass due to the high abundance of alcohol functions in natural compounds. However, natural compounds often comprise multiple chemical functions that can change the reactivity of the substrate. This comprehensive review, comprising both homogeneous and heterogeneous catalysts, aims at summarizing the recent advancements in biomass amination for every class of substrate, highlighting the key parameters governing their reactivity and the remaining scientific hurdles. Even though most substrates have successfully been converted into the corresponding amines, reaction selectivity and functional group tolerance still need to be improved.

Cover Feature: Visible Light‐Induced Unactivated δ‐C(sp3)−H Amination of Alcohols Catalyzed by Iron (ChemSusChem 20/2022)

The Cover Feature shows a warrior directing a horse, originally from an alto-relievo of the Tang Dynasty in China. The picture is a metaphor of a visible-light-induced δ C(sp3)−H amination of aliphatic alcohols catalyzed with iron. The hydroxy substitute acts as the directing group to realize the selectivity of the reaction through an alkoxyl radical-involved 1,5-hydrogen atom transfer. More information can be found in the Research Article by Z. Jue et al.

Highly Dispersed and Stable Hydrotalcite-Derived NiCu/MgAlO Alloy Catalyst for Efficient Amination of Cyclohexanol to Cyclohexylamine in the Vapor Phase

Developing a mild and efficient method for highly selective amination of alcohols to amines as important versatile compounds is very interesting in the organic synthesis field. In this work, we have developed a simple and efficient approach for high-yield preparation of cyclohexylamine from the vapor-phase catalytic amination of cyclohexanol with ammonia under atmospheric pressure. The results indicated that the hydrotalcite-derived NiCu/MgAlO alloy catalyst exhibited excellent catalytic performance and stability, and 98% cyclohexanol conversion with 95% selectivity toward cyclohexylamine had still been maintained after running for over 300 h at 170 °C. The super high activity and stability of the NiCu/MgAlO catalyst are attributed to the active Ni–Cu alloy nanoparticles with high dispersion and uniform particle size (about 4 nm). DFT calculation results indicated the Ni site of the NiCu alloy (111) facet as the main catalytic active site. The energy profiles for the potential comparative free energy of cyclohexanol to cyclohexylamine on the NiCu alloy (111) facet were calculated. This approach employing a highly dispersed and stable Ni–Cu bimetallic alloy catalyst for efficient amination of cyclohexanol to cyclohexylamine in the vapor phase is promising and has potential industrial application prospects. Especially, the designed Ni–Cu alloy catalyst can also be applied in the amination of other alcohols with ammonia to prepare the corresponding organic amines.

Removing aromatic organic pollutants by cloud point extraction using biodegradable nonionic surfactants: equilibrium constants and diffusion kinetics

ABSTRACT The impacts of inadequate disposal of industrial wastewater cause environmental, economic, social and human health damage. The search for innovative and viable methodologies from a technical and economic standpoint aims to promote suitable management of effluents produced by different industrial activities. The objective of this paper was to study phenol, aromatic alcohol and aromatic amine removal using cloud point extraction based on analysis of extraction capacity, miscibility curves, equilibrium lines, distribution coefficients and mass transfer solubilisation diffusion. The oxo-C10E3P4E2 surfactant produced the best results, exhibiting smaller coacervate volume fractions, low concentration in the diluted phase and efficient extraction (E%) of phenol (81.79%), 1-phenylethanol (67.88%), 2-phenylethanol (65.41%), benzyl alcohol (57.01%), aniline (56.91%), p-toluidine (73.96%) and 2,4-dimethylaniline (84.87%). The ternary phase diagrams revealed a large miscibility area favourable to extraction, with equilibrium lines showing a pronounced slope in favour of the coacervate, indicating high compound concentration factors. Equilibrium isotherms were used to obtain the distribution and solubilisation constants (Log KC/D KS), in the following order: aniline (1.05; 9.15) < p-toluidine (1.35; 20.40) < 2,4-dimethylaniline (1.76; 45.10) and benzyl alcohol (1.07; 8.19) < 2-phenylethanol (1.22; 14.04) < 1-phenylethanol (1.28; 15.23) < phenol (1.59; 36.72). These parameters show a linear correlation with Log KO/W, revealing that micellar solubilisation is governed by the hydrophobic nature of aromatic organic compounds. The evolution of pH demonstrated that the ionised forms of phenol and 2,4-dimethylaniline do not establish interactions (electrostatic, van der Waals, hydrogen bonds) with surfactants. Mass transfer diffusion is governed by hydrophobic compounds, slightly compromising phenol due to its high solubility in water.