Alkyl Glycidyl Ethers Research Articles

Raw and waste plant materials as sources of fungi with epoxide hydrolase activity. Application to the kinetic resolution of aryl and alkyl glycidyl ethers

The by-products of olive oil production can be used as sources of microbial strains. Penicillium sp., Aspergillus terreus, Penicillium aurantiogriseum, Aspergillus tubingensis and Aspergillus niger were selected on the basis of their epoxide-hydrolyzing activity towards racemic rac-glycidyl phenyl ether. We studied the effect on enzymatic activity of adding styrene oxide to the growth medium. It induced the biosynthesis of epoxide hydrolases and reduced cell growth. The resolution capacity of the five fungi was tested on rac-glycidyl phenyl ether, rac-benzyl glycidyl ether, rac-1,2-epoxyhexane and rac-1,2-epoxyoctane. The resolution of rac-glycidyl phenyl ether by A. niger, rac-benzyl glycidyl ether by P. aurantiogriseum and A. terreus, rac-1,2-epoxyhexane by A. tubingensis and rac-1,2-epoxyoctane by A. terreus provided (S)-3-phenoxy-1,2-propanediol (45.1% yield, 51.4% ee), (R)-3-benzyloxy-1,2-propanediol (40.8% yield, 43.3% ee), (S)-3-benzyloxy-1,2-propanediol (45.4% yield, 45.6% ee), (R)-1,2-hexanediol (70.4% yield, 24.4% ee) and (R)-1,2-octanediol (21.4% yield, 27.5% ee), respectively. The (R)-enantiopreference of the epoxide hydrolases from P. aurantiogriseum is unprecedented.

Towards green polyurethane foams via renewable castor oil-derived polyol and carbon dioxide releasing blowing agents from alkylated polyethylenimines

Alternatives to climate changing blowing agents (e.g. chlorofluorocarbons) and petroleum sourced raw materials (e.g. polyether polyols) are very attractive in the polyurethane (PU) foam industry. We explore a series of CO2 adducts from a branched polyethylenimine (bPEI) alkylated with C4 to C16 alkyl glycidyl ethers. These adducts can serve as CO2 releasing blowing agents during the exothermic polymerisation of PUs. A 13% alkylation of the bPEI amine groups enhances the dispersibility of the resultant CO2 adducts into the PU foaming mixtures containing a castor oil-derived polyol. In particular, the CO2 adduct with a C8 alkyl (2-ethylhexyl) side chain possesses the best dispersibility and is among the most effective in decreasing the foam density. It generates PU foams whose density and compressive strength are almost suitable for thermal insulation of underground steel pipes. This is the first report showing that PU foams from biomass polyols can be blown by CO2 adducts that are environmentally neutral.

Merrifield Resin-supported Functionalized Amino Acids as Efficient Catalysts for the Cycloaddition of Carbon Dioxide with Epoxides

Various amino acids were covalently grafted onto DVB cross-linked polystyrene resin (Merrifield resin, PS) and functionalized with alkyl halides of different alkyl chain lengths and counter-anions. The catalysts were characterized by elemental analysis (EA), FT-IR, TGA, XPS, and SEM. The catalysts exhibited good reactivity in the cycloaddition of alkyl glycidyl ether (AGE) and CO2. The effects of the alkyl-halide structure, reaction temperature and CO2 pressure on the reactivity of the catalysts were also investigated. The catalyst could be reused for up to three consecutive runs without a severe reduction in the initial activity. Keywords: Amino acid, carbon dioxide, cycloaddition, epoxide, merrifield resin.

疏水改性玉米淀粉合成研究

本文以玉米淀粉为原料，烷基缩水甘油醚(AGE)为疏水化试剂，氢氧化钠作催化剂，水为溶剂，在较温和反应条件下合成了2-羟基-3-烷氧基丙基淀粉(AHPS)。考察了反应时间、反应温度对取代度和反应效率的影响，确定了最佳反应温度为75℃，最佳反应时间为5 h。用IR、1HNMR对产物结构进行了表征。 2-Hydroxy-3-alkoxypropyl starches (AHPS) were synthesized by an environmentally-friendly process using alkyl glycidyl ether (AGE) as hydrophobic reagent, water as solvent and sodium hy-droxide as catalyst. Effects of reaction time and reaction temperature on molar substitution degree and react efficiency were studied. The optimized reaction time is 5 h and the optimized reaction temperature is 75˚C. IR and 1HNMR were used to analyze the structure of modified products.

Syntheses and physical properties of 1-alkoxydiglycerids as insulating oil

Vegetable oils are used for insulating oil, but the oils can be readily decomposed by moisture and heat to fatty acids and other oxidation compounds. To solve these problems, oils containing two ester groups and one ether group were synthesized by using alkyl glycidyl ethers and alkanoyl chloride. The yields of the products were in the range of 90–95%. The pour point, viscosity, thermal stability, and biodegradability of the products were tested as well. Pour point of the vegetable oil derivatives is low, and the biodegradability of the products is 85% or even higher.

Catalytic performance of montmorillonite clay ion-exchanged with ionic liquids in the cycloaddition of carbon dioxide to allyl glycidyl ether

In this study, various ionic liquids immobilized onto montmorillonite clay (IL-MMT) were prepared by ion-exchange reaction between the ionic liquids and ions in the clay interlayer. Tetra-alkyl ammonium chlorides were used as the ionic liquid precursors. The IL-MMTs were characterized by elemental analyses (EA), BET, XRD, 13C NMR, FT-IR, and SEM. The surface areas and d-spacings of the IL-MMTs increased with increasing alkyl chain lengths. The IL-MMTs showed good catalytic activity for the synthesis of the cyclic carbonate from alkyl glycidyl ether (AGE) and carbon dioxide. The effects of the IL cation structure, and reaction parameters such as temperature and CO2 pressure on the reactivity of IL-MMTs were also discussed. The catalyst could be reused in up to four consecutive runs without a significant reduction in the initial activity.

Syntheses and surface active properties of cationic surfactants having multi ammonium and hydroxyl groups

In this study, cationic surfactants having mono-, di-, and tri-amminium groups were synthesized by the condensation reaction of alkyl glycidyl ether and alkyl amine followed by the quarternization with dimethyl sulfate. The structure of the product was elucidated by 1H NMR and FT-IR. The minimum surface tension achieved using C12-BHDM surfactant was around 28.88mN/m, which suggests that C12-BHDM can be used to reduce the surface tension of primarily aqueous formulations and to act as emulsifiers. Dynamic surface tension measurement using a maximum bubble pressure tensiometer indicated that much longer time was required to reach an equilibrium value presumably due to the low mobility rate of a surfactant molecule with high molecular weight. The interfacial tensions measured between 1wt.% surfactant solution and n-decane were found to be in the same order of magnitude as those exhibited between micellar solutions and nonpolar hydrocarbon oils. It has been observed that the results for foam stability measurement are consistent with those of CMC and contact angle. That is, the percentage of foam volume decrease has been observed to increase with an increase in number of ammonium and hydroxyl groups.

A novel cationic surfactant having two quaternary ammonium ions

Novel cationic surfactants having two hydrophobic groups and two quaternary ammonium ions which are in the middle of alkyl group were prepared by two-step reactions. Three kinds of N,N-bis-(3- n-alkoxy-2-hydroxypropyl)- N,N-dimethyl-1,3-propylenediamine were prepared quantitatively as the intermediate by the condensation reaction between alkyl glycidyl ether and 3-(dimethylamino)-1-propylamine under mild conditions without solvent and catalyst. The intermediates were quaternized with dimethyl sulfate. The structures of the products were characterized by 1H NMR, FAB/MS and FT-IR. The interfacial properties of the synthesized cationic surfactants were measured such as critical micelle concentration, surface tension, interfacial tension, contact angle and foam stability.

Redox initiated cationic polymerization: The unique behavior of alkyl glycidyl ethers

AbstractRedox systems composed of a diaryliodonium or a triarylsulfonium salt together with a silane bearing SiH groups were used for the in situ generation of strong Brønsted acids at room temperature in the presence of alkyl glycidyl ether monomers. Secondary oxiranium intermediates are generated with lifetimes from minutes to hours at room temperature. These systems undergo rapid, exothermic cationic chain polymerization when the temperature is raised. Metastable monomer‐redox initiator systems were also observed to undergo frontal polymerizations when a localized heat source is applied to the sample. The application of these delayed cationic ring‐opening polymerization systems for the development of one‐component structural adhesives that undergo rapid thermosetting at low temperatures are discussed. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

Synthesis of Sulfated Sodium Salts of 1‐Alkylamino‐3‐alkyloxy‐2‐propanols and N,N‐Di‐(2‐hydroxy‐3‐alkyloxy propyl) Alkylamines as Potential Surfactants

Abstract1‐Alkylamino‐3‐alkyloxy‐2‐propanols, V (a–g) and N,N‐di‐(2‐hydroxy‐3‐alkyloxy propyl) alkylamines, VI (a–g) were prepared with the same chain length both for alkyl amino and alkyloxy groups by condensation of alkyl glycidyl ethers with long chain alkylamines by employing thermal and microwave‐assisted methods. All the products were characterized by 1H‐NMR, IR and fast atom bombardment mass spectrometry studies. These compounds were further sulfated and evaluated as their sodium salts for surfactant properties namely surface tension, critical micelle concentration, emulsifying property, wetting, foaming power and calcium tolerance. Sulfated 1‐dodecylamino‐3‐dodecyloxy‐2‐propanol, VII c and sulfated N,N‐di‐(2‐hydroxy‐3‐dodecyloxy propyl) dodecylamine, VIII c were found to exhibit superior surfactant properties among the respective series of monomers and dimers.

Effect of Temperature on the Cationic Photopolymerization of Epoxides

The effects of temperature on the photoinitiated cationic ring‐opening polymerizations of a number of different epoxide monomers were studied with the aid of a modified optical pyrometer instrument. Depending on the structures of the epoxide monomer, various behaviors were observed. The results were interpreted as due to steric and electronic features inherent in the structures of the monomers that affect the stabilization of the secondary oxonium ions, which are formed as intermediates in these polymerizations. At one extreme, cycloaliphatic epoxides such as cyclohexene oxide give highly reactive oxonium intermediates that exhibit high rates of polymerization even at subambient temperatures. At the other extreme, alkyl glycidyl ethers produce oxonium ion intermediates, which are so stable that they do not spontaneously react to form polymer at room temperature. By manipulation of the structure of the epoxide monomer, novel monomers with tailored reactivities can be prepared.

Microwave-Assisted Ring Opening of Epoxides: A General Route to the Synthesis of 1-Aminopropan-2-ols with Anti Malaria Parasite Activities

A series of 1-aminopropan-2-ols were synthesized and evaluated against two strains of malaria, Plasmodium falciparum FCR3 (chloroquine-resistant) and 3D7 (chloroquine-sensitive). Microwave-assisted ring opening of epoxides (aryl and alkyl glycidyl ethers, glycidol, epichlorohydrin) with various amines without catalysts generated the desired library of beta-amino alcohols rapidly and efficiently. Most of the compounds showed micromolar potency against malaria, with seven of them having IC50 values between 1 and 10 microM against both Plasmodium falciparum strains.

Synergistic effects in hybrid free radical/cationic photopolymerizations

AbstractMultifunctional alkyl glycidyl ether and oxetane monomers are usually deemed to be poorly reactive and are consequently of limited use for high speed photocuring applications. However, these monomers can be made to undergo exceedingly rapid exothermic photopolymerization when combined with a multifunctional acrylate monomer and a corresponding free radical photoinitiator. Under optimum UV irradiation conditions, these hybrid photopolymerizations take place rapidly and substantially without an induction period. A mechanism was proposed on the basis of thermal acceleration of the cationic ring‐opening polymerizations induced by the fast exothermic free radical acrylate photopolymerization. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3759–3769, 2007

Design and synthesis of multifunctional glycidyl ethers that undergo frontal polymerization

AbstractAn investigation of the photoactivated cationic ring‐opening frontal polymerizations of a series of alkyl glycidyl ethers has been carried out with the aid of a novel technique, optical pyrometry. With this technique, the effects of the monomer structure on the frontal behavior of these monomers have been examined. Upon irradiation with UV light, the photopolymerizations of many alkyl glycidyl ethers display a prolonged induction period at room temperature as the result of the formation of long‐lived, relatively stable secondary oxonium ions. The input of only a small amount of thermal activation energy is required to induce the further reaction of these species with a consequent autoaccelerated exothermic ring‐opening polymerization. Photoactivated frontal polymerizations have been observed for both mono‐ and polyfunctional alkyl glycidyl ether monomers. The ability of monomers to exhibit frontal behavior has been found to be related to their ability to stabilize the secondary oxonium ion intermediates through multiple hydrogen‐bonding effects to the ether groups present in the molecule. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6435–6448, 2006

Cationic photopolymerization of alkyl glycidyl ethers

AbstractAn investigation of the photoactivated cationic ring‐opening frontal polymerizations of a series of alkyl glycidyl ethers was carried out with the aid of a novel technique, optical pyrometry. With this technique, the effects of various experimental parameters, such as the photoinitiator type and concentration, as well as the effects of the monomer structure on the frontal behavior of these monomers were examined. Upon irradiation with UV light, the photopolymerizations of many alkyl glycidyl ethers displayed a prominent induction period at room temperature as the result of the formation of long‐lived, relatively stable secondary oxonium ions. The input of only a small amount of thermal activation energy was required to induce the further reaction of these species with the consequent autoaccelerated exothermic ring‐opening polymerization. Photoactivated frontal polymerizations were observed for both mono‐ and polyfunctional alkyl glycidyl ether monomers. The ability of monomers to exhibit frontal behavior was found to be related to their ability to stabilize the secondary oxonium ion intermediates through hydrogen‐bonding effects. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3036–3052, 2006

Cleavage of different ether bonds in butyl glycidyl ether and allyl glycidyl ether by K −, K +(15-crown-5) 2

The kind of substituent in alkyl glycidyl ethers affects the course of their reaction with K −, K +(15-crown-5) 2. The cyclic oxirane ring is exclusively cleaved in the case of butyl glycidyl ether whereas the presence of the unsaturated allyl group in the glycidyl ether molecule unexpectedly prefers the scission of the linear ether bond. In both the systems organometallic intermediates are formed. They react with crown ether causing its ring opening. Allylpotassium formed from allyl glycidyl ether reacts also with another glycidyl ether molecule; the oxirane ring is opened in this case.

Core-corona nanoparticles formed by high molecular weight poly(ethylene oxide)- b-poly(alkylglycidyl ether) diblock copolymers

Novel high molecular weight poly(ethylene oxide)- b-poly(alkylglycidyl ether) diblock copolymers have been synthesized by sequential anionic-coordination polymerization using a calcium amide–alkoxide initiating system. The hydrophobic blocks were formed by polymerization of alkylglycidyl ethers differing in the size of the hydrophobe and the length of the oxyethylene spacer between the terminal hydrophobes and the polymerizable epoxy group. The length of the spacer was 0, 2 or 10 oxyethylene units. The content of the hydrophobic groups in the copolymers was about 2 wt% as determined by 1H NMR and the molecular weights were found to be up to 1.8×10 6 g/mol by using GPC and SLS. The aqueous solution properties of the copolymers were studied by static fluorescence, static and dynamic light scattering and transmission electron microscopy. The copolymers were found to self-associate in core-corona type particles in a relatively narrow concentration range. The aggregation numbers and the dimensions of the aggregates were determined by a combination of dynamic and static light scattering molecular weights. Core-corona nanoparticles of low aggregation number (3–5) and slightly extended coronae were found to coexist with unassociated macromolecules in the concentration range between the critical aggregation concentration and the overlap concentration. Both particles were visualized by TEM.

ChemInform Abstract: Newer Synthetic Approaches of Alkyl Glycidyl Ether as C3‐Building Blocks for Molecular Design of Artificial Lipids

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Improvement of the phase‐transfer catalysis method for synthesis of glycidyl ether

AbstractA convenient procedure for the synthesis of aliphatic alkylglycidyl ether has been studied. It has been found that the improved preparation of the alkylglycidyl ether can be achieved by using fatty alcohol such as octanol and octadecanol with epichlorohydrin in the presence of phase‐transfer catalyst (PTC) such as 1‐alkyloxypropan‐2‐ol‐3‐trimethyl ammonium methylsulfate, 1‐alkyloxypropan‐2‐ol‐3‐methyldiethanolammonium methylsulfate, alkyloxy‐2‐hydroxypropyldimethylamine and alkyloxy‐2‐hydroxypropyldiethanolamine, tetrabutylammonium bromide, etc. without water and other organic solvents. This method, carried out in solid phase/organic phase (reactants and product themselves), has the following merits: (i) producing the solid by‐products such as sodium chloride and sodium hydroxide which are easily removed by simple filtration, (ii) saving the amount of reactants used such as sodium chloride and phase‐transfer catalyst, and (iii) increasing the yields of glycidyl ethers. The yields of octylglycidyl ether and octadecylglycidyl ether are 92.0 and 91.7%, respectively. The amount of sodium hydroxide used can be saved by from 1.5 to 0.7 molar ratio with respect to octanol in comparison with those in the conventional method using PTC.

A perspective on the contribution of surfactants and lipids toward “Green Chemistry”: Present states and future potential

Abstract“Green Chemistry” has become a subject of increasing interest in recent years. The goal of efforts in this area is to develop environmentally friendly methods and processes to replace traditional reactions that use organic solvents, consume much energy, and generate undesirable by‐products and/or waste. Utilization of renewable resources is an important component of Green Chemistry. Fats and oils represent one such resource. They can give rise to many types of surfactants and lipids that can modify properties of boundary phases between different phases. Thus, phase‐transfer catalysts (PTC) based on surfactants or lipids have been reported to be useful in reactions such as oxidation and hydration reactions and in glycidyl ether formation. Another approach to satisfying Green Chemistry requirements is the recovery and recycling of reactants and/or substrates used. In the preparation of alkyl glyceryl ethers, the intermediate 1,3‐dioxolane compounds prepared by addition of acetone to alkyl glycidyl ethers can be hydrolyzed to regenerate reusable acetone. Other examples of methodologies based on surfactants or lipids are summarized, and their potential contribution to Green Chemistry is discussed.