- Effect of pH on Carbon-13 NMR Spectra of N-Dodecyl-N,N-dimethylamine Oxide Solution
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Carbon-13 NMR chemical shifts of the non-ionic-cationic surfactant N-dodecyl-N,N-dimethylamine oxide (C12DAO) were measured and identified by an INADEQUATE experiment.On micellization, downfield chemical shifts were found for all carbon atoms except NCH2.The shifts are most pronounced for the carbon atoms in the central part of the chain.Protonation of the micelles resulted in upfield shifts of all the carbon atoms; the magnitudes decreased with increasing distance from the nitrogen atom.A plot of several chemical shifts against pH gave titration curves and pKa values.The pKa values vary with the carbon atom used in the calculation (from pKa = 5.05 to 5.66).An AM1 calculation of the charge densities suggests that these variations in pKa are caused by the electric field of the OH group.The effect of N-oxidation on the chemical shifts of the carbon atoms in five solvents was estimated. Key Words: 13C NMR - INADEQUATE - Dodecyldimethylamine oxide - Micelles
- Brycki, Bogumil,Szafran, Miroslaw
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- Aggregation Numbers of Dodecyldimethylamine Oxide Micelles in Salt Solutions
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Micellel aggregation number m of dodecyldimethylamine oxide was determined as a function of the micelle composition or the degree of ionization of the micelle αM in 0.1 and 0.2 M NaCl at 25 deg C with light scattering and the steady state fluorescence probe method.The two methods gave consistent results in most cases.The aggregation numbers at the critical micelle concentration (cmc) were nearly identical for both cationic and nonionic micelles: about 70 and 80 in 0.1 and 0.2 M NaCl, respectively.The aggregation number increased as αM approached 0.4-0.5.The maximum values were about 100 and 150 for 0.1 and 0.2 M NaCl.At intermediate compositions, the Rayleight ratio of the scattered light incerased with the concentration, and this increase was interpreted as the increase of micelle size with concentration.Apparent aggregation numbers at a finite concentration were evaluated on the assumption of negligible contribution from the second virial coefficient.The idea of the growth of micelles was supported by dynamic light scattering but not by the fluorescence probe method.From the observed variation of the aggregation number at cmc with αM the width of the aggregation number distribution of nonionic micelles is estimated on the basis of a simple theory.
- Kaimoto, Hideki,Shoho, Kouki,Sasaki, Shigeo,Maeda, Hiroshi
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- Novel low viscous, green and amphiphilic N-oxides/phenylacetic acid based Deep Eutectic Solvents
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Four novel Deep Eutectic Solvents (DESs) were prepared by mixing phenylacetic acid (which is a natural molecule present in honey) with amine N-oxides, which are molecules easily biodegradable in nature. Three of these N-oxides are amphiphilic. The novel DESs have very low freezing points (from ??34?°C to 20?°C) and they have very low viscosity, much lower than the most common and used DES in literature so far (choline chloride/urea mixture). The conductivity values resulted low and the ionicity analysis showed these DESs to be “super ionic”. Their polarity resulted high enough and it can be compared with other commonly used solvents or ionic liquids.
- Germani, Raimondo,Orlandini, Matteo,Tiecco, Matteo,Del Giacco, Tiziana
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- Kinetics and Preparation of Amine Oxides
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A kinetic model for the oxidation of dimethyllaurylamine to its amine oxide with hydrogen peroxide was developed.It is a second-order reaction where k=.0250, .0079 and .0037 kg per mol/min at 75, 60 and 50 deg C, respectively.Amine oxides of N-lauryl morpholine, piperidine and 3-methyl piperidine were synthesized, and their rates of formation were determined.Compared to dimethyllaurylamine, the piperidines react slower, while the morpholine reaction is much faster. KEY WORDS: Amine oxides, dimethyllaurylamine, foam stabilizers, hydrogen peroxide, kinetics, morpholine, piperidine.
- Toney, C. Joe,Friedli, F. E.,Frank, P. J.
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- Reduction of Propellane Ketones in Solution Aggregates
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The reduction of propellane diones and ketols has been studied in water containing cationic, anionic and zwitterionic surfactants.From the rate and stereochemistry of the reductions done in these media, the binding of neutral substrates and ionic reagents to surfactant aggregates has been probed.Surface interactions of these variously charged aggregates have been studied, and the behavior of aggregates with like charge but different structure (cationic aqueous micells, vesicles, and reverse micelles) has been compared.A picture of charge distribution at the surface of amine oxide zwitterionic micells has emerged.The oriented propellane binding (polymethylene aligned with surfactant tails and fused five-membered rings tangential to the aggregate surface) first proposed for propellanes bound to cationic micelles has been confirmed and extended to cationic vesicles and to amine oxide micelles.
- Natrajan, Anand,Sukenik, Chaim N.
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- The surface properties of amine oxides with a fluoroether chain
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Persistent organic pollutants (POPs) includes long-chained fluorosurfactants, for instance, perfluorooctanonate (PFOA) and perfluorooctanesulfonate (PFOS). In order to find out alternative fluorosurfactants, we synthesized eight amine oxides with a fluoroether chain. Their surface properties were evaluated and compared with perfluoroalkyl and hydrocarbon analogues. The surface tensions at critical micelle concentration (γcmc) for the eight amine oxides with a fluoroether chain were at a range from 15.5 to 23.0 mN/m, and γcmc of four fluoroether amine oxides were below 17 mN/m comparable to perfluorooctyl analogues (16.4 mN/m) and much lower than perfluorohexyl (20.5 mN/m) and hydrocarbon analogues (24.2 and 24.7 mN/m). The critical micelle concentration (cmc) for the eight amine oxides with a fluoroether chain were 3 to 535 × 10?4 mol/L. The cmc of four fluoroether amine oxides were 3 to 21 × 10?4 mol/L (0.2 to 1.0 g/L) comparable to perfluorooctyl (0.4 g/L) and hydrocarbon analogues (4 and 10 × 10?4 mol/L) and much lower than perfluorohexyl analogue (36.9 g/L). The surface excesses, the limiting molecule areas and the free energies of micellization of amine oxides were calculated. Fluoroether surfactants are promising alternatives for PFOA and PFOS.
- Chen, Qing-Yun,Dai, Longhao,Guo, Yong,Huang, Meiwei,Shen, Qing,Su, Qin,Su, Zhaoben,Wu, Chengying,Zhao, Zhi-Gang
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- A method for preparing an organic amine oxide
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A organic amine oxide preparation method, comprises the following steps: (1) organic amine as the raw material, the organic amine, solvent and the heteropoly acid quaternary ammonium salt catalyst is added to the container, heating (25 - 100 °C); (2) dropping hydrogen peroxide solution, dropping about 1.5 hours, the dropwise insulation reaction; (3) gas chromatographic detection reaction solution, when the organic amine content is reduced to 0.5% when, stopping the reaction, reaction filtering out catalyst, organic phase distillation shall have amine oxide. The invention relates to a method for preparing an organic amine oxide, its production process is simple, low energy consumption, the catalyst can be used repeatedly, can effectively reduce the production cost, and improves the economic benefit.
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Paragraph 0018
(2019/06/13)
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- Novel access to verbenone via ruthenium nanoparticles-catalyzed oxidation of Α-pinene in neat water
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Aqueous suspensions of Ru(0) nanoparticles, stabilized with hydroxyethylammonium salts and possessing sizes around 2 nm, proved to be active and selective in the mild oxidation of α-pinene in the presence of tert-butylhydroperoxide, in neat water. Verbenone, a product of great interest for fine chemistry, was obtained as major product with yield up to 41% under optimized conditions. 2-hydroxy-3-pinanone was identified as a co-product of the reaction, but with very low amount (7%). Kinetic investigations allowed determining the potential reaction intermediates and by-products. Moreover, mechanistic studies with radical scavengers confirmed that α-pinene oxidation mainly implies both carbon- and oxygen-centered radicals.
- Rauchdi, Mariem,Ait Ali, Mustapha,Roucoux, Alain,Denicourt-Nowicki, Audrey
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p. 266 - 273
(2017/12/06)
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- 2,2,2-Trifluoroacetophenone as an organocatalyst for the oxidation of tertiary amines and azines to N-oxides
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A cheap, mild and environmentally friendly oxidation of tertiary amines and azines to the corresponding Noxides is reported by using polyfluoroalkyl ketones as efficient organocatalysts. 2,2,2-Trifluoroacetophenone was identified as the optimum catalyst for the oxidation of aliphatic tertiary amines and azines. This oxidation is chemoselective and proceeds in high-to-quantitative yields utilizing 10 mol% of the catalyst and H2O2 as the oxidant.
- Limnios, Dimitris,Kokotos, Christoforos G.
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supporting information
p. 559 - 563
(2014/04/03)
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- PROCESS FOR PRODUCING NITROGEN-CONTAINING COMPOUNDS
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The present invention relates to a process for producing a tertiary amine in the presence of a catalyst containing copper and at least one element selected from the group consisting of elements belonging to Groups 2, 3, 7 and 12 of the Periodic Table (long form of the periodic table), said process including the steps of (a) reducing an amide compound in a hydrogen atmosphere; and (b) introducing a dialkyl amine containing a linear or branched alkyl group having 1 to 6 carbon atoms into a reaction product obtained in the step (a), and treating the reaction product with the dialkyl amine. The present invention provides a process for producing high-purity aliphatic tertiary amines containing a less amount of by-products by reducing aliphatic acid amides under moderate conditions using a chromium-free catalyst, as well as a process for producing amine derivatives such as amine oxide by using the aliphatic tertiary amines, with a good productivity in an economical manner.
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Page/Page column 25-26
(2009/04/25)
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- METHOD FOR PRODUCING NITROGEN-CONTAINING COMPOUND
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The present invention provides a process for producing high-purity aliphatic tertiary amines containing a less amount of by-products by subjecting aliphatic acid amides to hydrogenation reduction under moderate conditions, as well as a process for producing amine derivatives from the aliphatic tertiary amines, with a good productivity in an economically advantageous manner. The present invention relates to a process for producing an aliphatic tertiary amine by subjecting a specific aliphatic amide to hydrogenation reduction in the presence of a catalyst containing copper and at least one element selected from the group consisting of elements belonging to Groups 2, 3 and 7 of the Periodic Table; the catalyst; and a process for producing amine oxide by reacting the tertiary amide obtained by the above production process with hydrogen peroxide.
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Page/Page column 10
(2008/12/09)
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- Mild and Efficient Flavin-Catalyzed H2O2 Oxidation of Tertiar Amines to Amine N-Oxides
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A mild and highly effective H2O2 oxidation of tertiary amines has been developed by the use of flavin catalysis. Eight aliphatic amines were oxidized to their corresponding N-oxides in fast and selective reactions. For all substrates a considerable rate enhancement was observed compared to the noncatalyzed reactions. The product N-oxides were isolated in good yields using this mild oxidation system based on the environmentally attractive oxidant H2O2. As the catalyst, an N1N5- dialkylated flavin was used as an analogue of the biologically important flavin redox cofactor. The catalytic cycle proposed for the flavin catalysis accounts for the observation that, in addition to the hydrogen peroxide oxidant, molecular oxygen is required for the initiation of the process.
- Bergstad, Katarina,B?ckvall, Jan-E.
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p. 6650 - 6655
(2007/10/03)
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- Amine oxide process with CO2 and aluminum
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Amine oxides which have low levels of nitrosamines or are substantially-free of nitrosamines are made by reacting tert-amines with hydrogen peroxide in the presence of carbon dioxide and aluminum metal.
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- Amine oxide process
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Amine oxides which have decreased levels of nitros-amines are made by reacting tert-amines with hydrogen peroxide in the presence of titanium metal. Addition of carbon dioxide to the process results in a substantially nitrosamine-free amine oxide.
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- Use of amine oxide in the H2 O2 oxidation of aliphatic mercaptan to sulfonic acid
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Hydrocarbyl mercaptans are oxidized to sulfonic acids by reaction with aqueous hydrogen peroxide in the presence of an inorganic base (e.g. sodium hydroxide) and a tert-amine oxide. The product is in the form of a sulfonate salt. The reaction rate is increased and undesirable free-oil by-product is decreased by the inclusion of the amine oxide catalyst.
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- Selective Autoxidation of Electron-Rich Substrates under Elevated Oxygen Pressures
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We report here the observation of a novel autoxidation pathway which occurs with electron-rich substrates.Tertiary amines, dialkyl thioethers, olefins, and alkynes under high oxygen pressures (>20 bars of O2), in polar solvents, and at elevated temperatures (>90 deg C) yield in good to excellent selectivity amine oxides, sulfoxides, and site-specific olefin and alkyne cleavage products, respectively.The results of mechanistic studies, including high oxygen pressure electrochemical studies, are discussed.A mechanism for this novel oxygenation reaction pathway that is consistent with the observed results is proposed.It involves an initial unfavorable electron transfer from the electron-rich substrate to oxygen to yield superoxide and the radical cation, which reacts with triplet oxygen to yield the oxygenated radical cation intermediate, a suspected potent oxidant.Electron transfer to the oxygenated radical cation from additional substrate (chain reaction) or superoxide yields a zwitterionic intermediate.This intermediate either reacts with additional substrate (O-atom transfer) to yield product (sulfoxide and N-oxide, in the case of thioethers and tertiary amines) or is converted with unimolecular reactivity to dioxetane-like (in the case of alkenes) or dioxetene-like (in the case alkynes) derived products.
- Correa, Paul E.,Hardy, Gordon,Riley, Dennis P.
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p. 1695 - 1702
(2007/10/02)
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- An Unprecedented Selective Autoxidation of Tertiary Amines to Amine Oxides
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Tertiary amines have been found to react directly with molecular oxygen under high O2 pressures to give in an unexpected result the corresponding N-oxide in high yields.
- Riley, Dennis P.,Correa, Paul E.
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p. 1563 - 1564
(2007/10/02)
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- AMINE OXIDES-XIII IODINE COMPLEXES WITH NON-AROMATIC AMINE OXIDES
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EDA-iodine complex with trialkylamine oxides in dichloromethane have been investigated spectrophotometrically.Thermodynamic (KADc,-ΔG0) and spectral (ΕADλ) characteristics of these complexes were determined.The absorption band of iodine in the visible region was blue-shifted with a variable maximum, depending on the structure of the amine oxide.The KADc and ΕADλ values were calculated using a modified method.A non-linear relationship KADc=(R), where R is the number of carbon atoms in the alkyl chain, was found.
- Devinsky, F.,Leitmanova, A.,Lacko, I.,Krasnec, L.
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p. 5707 - 5710
(2007/10/02)
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- Topical medicament preparations
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Topical therapeutic compositions are disclosed which contain from about 0.1 to 70 percent by weight of a water-soluble tertiary amine oxide and a therapeutic agent selected from the group consisting of erythromycin, benzoyl peroxide, hydrocortisone, tetracycline, 5-fluorouracil, and propranolol. The amine oxide enhances penetration of the therapeutic agent into and through the skin.
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- Ruthenium Chloride Catalysed Oxidation of Tertiary Amines to Amine Oxides with Molecular Oxygen
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Tertiary amines are catalytically oxidized with molecular oxygen in homogeneous solutions containing RuCl3*xH2O to afford as a major product the corresponding N-oxide, the first example of such an oxidation.
- Riley, Dennis P.
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p. 1530 - 1532
(2007/10/02)
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