Applications of protecting groups in the synthesis of surfactants, lipids, and related compounds

Several types of alkyl ether lipids were prepared in high yield and high purity using protecting groups such as 1,3-dioxolane compounds or allyl ethers. We also succeeded in the industrial production of alkyl glyceryl ethers using the reaction of alkyl glycidyl ethers with acetone to give 1,3-dioxolane compounds, from which the desired alkyl glyceryl ethers were obtained in high quantities. 1,3-Dioxolane (ketal) compounds based on acetone were used in the enzymatic preparation of monoglyceride on an industrial scale. On the basis of these protecting groups, we extended our studies concerning both the preparations and properties of novel polyol ether compounds, beginning with alkyl glycidyl ethers. Another typical property of surfactants containing 1,3-dioxolane units and acetal is degradability under acidic conditions. Several types of destructible/cleavable surfactants based on polyols, such as carbohydrates and polyethyleneglycol, were prepared. As for natural products containing polyol skeletons, much attention has been paid to their molecular design, in which protecting groups such as 1,3-dioxolane compounds or allyl ether have contributed to synthetic strategies.     

氯化N-[3-长链烷氧(双)乙烯氧-2-羟]丙基-N,N,N-三甲基铵的合成及性质

以溴代烷和乙二醇或一缩二乙二醇为原料合成长链烷基（双）氧乙烯醇（收率为７５％ ）,然后在相转移催化条件下和环氧氯丙烷反应得到长链烷基（双）氧乙烯缩水甘油醚（收率为９０％ ）,后者和三甲胺盐酸盐反应得到氯化Ｎ［３长链烷氧（双）乙烯氧２羟］丙基Ｎ,Ｎ,Ｎ三甲基铵（收率为９１％ ）,其结构通过红外光谱、核磁共振氢谱和元素分析结果得以证实,测定了产物的γｃｍ 及ｃｍ ｃ     

Thioether glycidyl resins. II. Products of condensation of bis(4-mercaptomethylphenyl) ether and bis(4-mercaptomethylphenyl)methane with epichlorohydrin

New thioether glycidyl resins produced by condensation of bis(4-mercaptomethylphenyl) ether and bis(4-mercaptomethylphenyl)methane with epichlorohydrin were obtained by heterophase alkaline condensation in water and isopropyl alcohol solution. To define the optimal conditions of condensation, the following factors that influence the process were studied: the mole ratios of epichlorohydrin–mercaptan, alcohol–mercaptan, alkaline hydroxide–mercaptan. For all reaction products, yield, epoxide content, and chlorine content were determined. The structure of thioether glycidyl resins with the highest epoxide content was determined by elemental analysis and infrared and NMR spectra. The physical and chemical properties were defined. Some properties of the resins, cured chemically or thermally with different curatives, and thermal and mechanical properties of the cured compounds were determined.     

Synthesis of derivatives of alkylamino alkyloxy propanol structures by N-alkylation, acylation, and nitration. Application as fuel additives

Polyfunctional compounds were prepared by alkylation, acylation, and nitration of hydroxyl and amine functions of the following alkanolamine ether structures: (di)alkylamino alkyloxy propanol, hydroxy alkyloxy (di)alkylamino propanol, and their dimer compounds. The resulting compounds were characterized by conventional spectroscopic methods, and complete nuclear magnetic resonance data are given. These reactions extented the application of these propanic compounds to use as multipurpose fuel additives. In particular, they enhance phase stability and improve the cetane number in ethanol-diesel fuel blends.     

Thioether glycidyl resins. VII. Products of condensation of bis(4-mercaptophenyl)sulfide and bis(4-mercaptophenyl)sulfone with epichlorohydrin

New thioether glycidyl resins by condensation of bis(4-mercaptophenyl)sulfide or bis(4-mercaptophenyl)sulfone with epichlorohydrin were obtained by heterophase alkaline condensation in aqueous and isopropanol medium using sodium hydroxide. The detailed studies on their structures from elemental analysis and IR and ¹H-NMR spectra, physical and chemical properties, and curing conditions are presented. Thioether glycidyl resins compositions were also prepared using curatives typical for epoxy resins and after curing they were characterized from derivatographic, thermomechanical, and mechanical studies.     

溴化N-[3-长链烷氧(双)乙烯氧-2-羟]丙基-N,N,N-三甲基铵的合成及表面活性

以脂肪醇和乙二醇或一缩二乙二醇为原料合成长链烷基（双）氧乙烯醇，收率为７５％。然后在相转移催化条件下和环氧氯丙烷反应得到长链烷基（双）氧乙烯缩水甘油醚，收率为９０％。后者和三甲胺氢溴酸盐反应得到溴化Ｎ ［３ 长链烷氧（双）乙烯氧 ２ 羟］丙基 Ｎ，Ｎ，Ｎ 三甲基铵，收率为９１％。其结构通过红外光谱、核磁共振氢谱和元素分析结果得以证实，测定了其基本的表面活性，产品的表面张力为３７７～４４６ｍＮ／ｍ，临界胶束浓度（ＣＭＣ）为２５７×１０－３～４６×１０－５ｍｏｌ／Ｌ。     

Glycerol-derived solvents containing two or three distinct functional groups enabled by trifluoroethyl glycidyl ether

Conversion of epichlorohydrin to glycidyl ethers creates versatile precursors that can be transformed into a variety of molecular species with glycerol skeletons, enabling the design of molecules with highly tailored functionalities. The synthesis of 2,2,2-trifluoroethyl glycidyl ether (TFGE, IUPAC name: 2-[(2,2,2-trifluoroethoxy)methyl]oxirane, CAS# 1535-91-7) was optimized to provide high yield/selectivity and good “green metrics.” TFGE was then used as a platform molecule in the synthesis of asymmetric glycerol 1,3-diether-2-alcohol derivatives, which were subsequently transformed to 1,2,3-triethers or 1,3-diether-2-ketones. The density, viscosity, and CO₂ solubility of each molecule were measured and compared with those of other glycerol-derived compounds as well as compounds with similar functional groups. Furthermore, quantum chemical calculations were performed to understand the structure–property–performance relationships of these molecules for CO₂ absorption. Based on the results in this work, we foresee that TFGE (and similar glycidyl ethers) would offer great flexibility in molecular design of green solvents and precursors to more complex compounds.     

New aspects in acceleration of glycidyl ether oligomerization by imidazole compounds

Summary Using simple model compounds the oligomerization of glycidyl ethers accelerated by imidazole and imidazole derivatives was investigated. The formation of oligomers depending on 1,3-diphenoxy-2-hydroxypropane as their starting compound was predominant.In the case of imidazole 1,2-dihydroxy-3-phenoxypropane and the resulting oligomers are further formed. It seems to be obvious that this reaction also occurs in the absence of water.An over-all reaction mechanism including both the main products of the glycidyl ether oligomerization formed and the different imidazole compounds investigated is proposed.     

Investigation of the elementary reactions in the synthesis of poly(hydroxethers) in dipolar,aprotic solvents

The effect of the hydroxyl groups of various phenols on the course of the reaction of their alkali metal salts with epichlorohydrin in dipolar, aprotic solvents has been studied. It was found that the presence of phenols in the system leads to the formation of a complex salt of the type (ArO … H … OAr)^?Mt⁺, and to a considerable decrease in the reaction rate. The mechanism of the reaction of chlorohydrin ethers of phenols with alkali metal phenolates was also studied. The effect of various factors on the course of the reaction of glycidyl ethers with phenols was determined by kinetic measurements.     

Photo-crosslinkable polymers with benzylideneacetophenone (chalkone) structure in the side chains

Four soluble types of polymers have been synthesized by grafting 4- and 4′-chalkonyl glycidyl ethers onto an aromatic polyamine (aniline–formaldehyde linear resin) and a polyamide (condensation product of dimerized linseed oil and an aliphatic polyamine) to obtain photo-crosslinkable chalkone structure in the side chains which are also expected to contain one ? OH group each. The completion of grafting reactions has been followed by the disappearance of the epoxide absorption around 918 cm^?1. The characterization of the resins was done by melting point, solubility, and IR measurements. Irradiation was carried out with a 100-watt Hanovia high-pressure mercury are lamp. Irradiated samples were studied by UV spectral measurements and their insolubility in CHCl₃. It was observed that polymers grafted with 4′-chalkonyl glycidyl ether possibly undergo both isomerization and crosslinking reactions under UV irradiation while those grafted with 4-chalkonyl glycidyl ether undergo crosslinking reaction predominantly.     

Polyurethanes based on 2,2‐Dinitropropane‐1,3‐diol and 2,2‐bis(azidomethyl)propane‐1,3‐diol as potential energetic binders

On the base of 2,2‐bis(azidomethyl)propane‐1,3‐diol (BAMP) and 2,2‐dinitropropane‐1,3‐diol (DNPD) four different polyurethanes were synthesized in a polyaddition reaction using hexamethylene diisocyanate (HMDI) and diisocyanato ethane (DIE). The obtained prepolymers were mainly characterized using vibrational spectroscopy (IR) and elemental analysis. For determination of low and high temperature behavior, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were used. Investigations concerning friction and impact sensitivities were carried out using a BAM drop hammer and friction tester. The energetic properties of the polymers were determined using bomb calorimetric measurements and calculated with the EXPLO5 V6.02 computer code. The obtained values were compared with the glycidyl azide polymer (GAP). The compounds turned out to be insensitive toward friction (>360 N) and less sensitive toward impact (40 J). The good physical stabilities, along with their sufficient thermal stability (170–210 °C) and moderate energetic properties renders these polymers into potential compounds for applications as binders in energetic formul;ations. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43991.     

氟化N-（3-长链烷氧-2-羟）丙基-N，N，N-三烷基铵的合成及性质

脂肪醇和环氧氯丙烷在相转移催化条件下反应得到长链烷基缩水甘油醚，以此为原料和三甲(乙)胺氢氟酸盐反应得到氟化N-(3-长链烷氧-2-羟)丙基-N，N，N-三甲(乙)基铵，其结构通过红外光谱、核磁共振氢谱及元素分析结果得以证实。还测定了所合成产品的表面张力和临界胶束浓度。     

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

“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.     

Synthesis,Characterization and Thermal Properties of Poly(glycidyl azide‐r‐3‐azidotetrahydrofuran) as Azido Binder for Solid Rocket Propellants

Azido polymers have been investigated as energetic binders in the area of solid rocket propellants. However, the low temperature mechanical properties of them are not comparable with the traditional propellant binders. In this work, a new kind of azido binder named poly (glycidyl azide‐r‐3‐azidotetrahydrofuran) (PGAAT) was successfully synthesized. The molecular structures of monomers and copolymers were characterized. The sensitivity and thermal properties of the azido binder were studied. The cationic copolymerization of 3‐methylsulfonyloxytetrahydrofuran with ternary cyclic ethers was confirmed. The PGAAT azido binder exhibited attractive features like low glass transition temperature (T_g, −60 °C) and high energy (1798 J/g). The results indicate that the polymer is a suitable candidate binder for the solid rocket propellants.     

Potential Energetic Plasticizers on the Basis of 2,2‐Dinitropropane‐1,3‐diol and 2,2‐Bis(azidomethyl)propane‐1,3‐diol

Different carboxylic acid derivatives of 2,2‐dinitropropane‐1,3‐diol (DNPD) and 2,2‐bis(azidomethyl)propane‐1,3‐diol (BAMP) were synthesized to investigate their suitability as energetic plasticizers. The syntheses were carried out using acyl chlorides of acetic, propionic, and butyric acid. The obtained products were characterized by elemental analysis, NMR, and IR spectroscopy. The energetic properties of the synthesized compounds were calculated on the basis of the computed heats of formation at the CBS‐4M level of theory using the EXPLO5 version 6.02 computer code. Investigations of physical stabilities were carried out using BAM drop hammer and friction tester. Low and high temperature behavior was determined by differential scanning calorimetry (DSC). The energetic and physical properties of the synthesized compounds were compared to the literature known energetic plasticizers N‐butyl nitratoethylnitramine (BuNENA) and diethylene glycol bis(azidoacetate) ester (DEGBAA). For analyzing the plasticizing abilities, mixtures of glycidyl azide polymer (GAP) and poly(3‐nitratomethyl‐3‐methyloxetan) (polyNIMMO) were prepared with both propionyl based compounds in different ratios and investigated regarding their glass transition temperatures and viscosity. Both compounds showed plasticizing effects in the range of BuNENA.     

Polymerization and characterization of various di(pyridine)bis(trihalophenolato)cobalt(II) complexes in solid and melt states

The syntheses of distorted tetrahedral bis(pyridine)bis(trihalophenolato)cobalt(II) complexes from an aqueus solution were achieved and their characterization by FT‐IR, X‐ray, DSC, UV‐visible and elemental analysis in solid state or in melt form is reported. Polymerizations of these complexes were accomplished either at constant temperature, employing different time intervals or constant decomposition times while varying the temperature range. The slow decomposition at constant temperature leads to long chain products, whereas long chains formed at higher temperatures were during a constant time. The resulting poly(dihalophenylene oxide)s were characterized by FT‐IR, ¹H NMR, ¹³C NMR spectral analysis, differential scanning calorimetry and molecular weight determinations by viscometric method. © 2001 Society of Chemical Industry     

Applications of phase-transfer catalytic reactions to fatty acids and their derivatives: Present state and future potential

Phase-transfer catalysts (PTC), which accelerate reactions between liquid(organic)-liquid(water) and liquidsolid heterogeneous states, have been investigated and developed. Several processes with PTC have succeeded in industrial processes involving fatty acids and their derivatives. For example, preparation of fatty alkyl glycidyl ethers, from which fatty alkyl glyceryl ethers and their derivatives can be obtained, has been carried out with PTC. However, some problems remain to be solved. For example, preparation of the fatty alkyl glycidyl ether by a PTC reaction was considered, but typical problems to be solved included: (i) how to reuse or recover the catalysts; (ii) how to control the heterogeneous reaction without obstacles to produce useful chemical materials; (iii) how to satisfy the environmental requirements for the catalysts; and (iv) are there more effective catalysts? We address these problems based on our own experiences with phase-transfer catalytic Williamson ether syntheses of fatty alkyl glycidyl ethers. Moreover, we describe recent developments in phase-transfer catalytic reactions related to oleochemistry, such as transition metal-catalyzed reactions of long-chain olefins in liquid(organic)-liquid(water) or liquid-solid heterogeneous states. Based on these results, we have considered the potential of PTC as a synthetic tool in oleochemistry.     

Synthesis of novel copoly(ether ether ketones): Property evaluation and microstructure analysis by NMR

A series of copolymers were prepared by the reaction of various bisphenols with a 50:50 molar ratio of two bisfluoro compounds, 4,4′‐bis(1‐fluoro‐2‐trifluoromethyl benzyl) benzene and 4,4′‐difluorobenzophenone. The synthesized polymers were well characterized for their thermal, mechanical, and electrical performances. The copolymers showed a better set of properties than their analogous homopolymers derived from 4,4′‐bis(1‐fluoro‐2‐trifluoromethyl benzyl) benzene and bisphenols. The microstructures of the copolymers were analyzed by ¹H‐, ¹³C‐, ¹⁹F‐, distortionless enhancement by polarization transfer 90, two‐dimensional ¹H–¹H homonuclear correlation spectroscopy, and ¹³C–¹H correlation spectroscopy NMR techniques. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1292–1305, 2005     

The alkyl glycidyl ether as synthetic building blocks

Alkyl glycidyl ether is one of the most useful key materials for industrial applications because the addition reaction of various kinds of nucleophilic reagents to the reactive epoxy bond of the glycidyl ethers has led to glyceryl ether derivatives. Glyceryl ether exhibits many interesting physical and pharmacological properties. The alkyl glycidyl ether can presently be produced at an industrial scale under the phase-transfer catalytic Williamson ether synthesis. We have reviwwed some addition reactions of the alkyl glycidyl ether and possibilities for use as the building blocks for the syntheses of surfactants, pharmaceuticals, etc. that contain glyceryl ether skeletons. Typical examples of alkyl glyceryl ether derivatives include: amino ether as cosmetic material, and isodiglycerin mono- and dialkyl ethers and triglycerin monoalkyl ether as a cosmetic or a pharmacologically useful material, respectively. Another interesting reaction is the rearrangement of the epoxy bond of the alkyl glycidyl ether, which gives alkoxy ketone in a one-pot synthesis.     

Fabrication of transmission holographic gratings with spiroorthoester and trimethylolpropane triacrylate

Spiroorthoester function was found to be polymerizable with visible laser light (λ = 532 nm) in the presence of diphenyliodonium hexafluorophosphate and 3,3′‐carbonylbis(7‐diethylaminocoumarin), as evidenced using Fourier transform infrared spectroscopy. High‐performance holographic gratings were fabricated using siloxane‐containing bis(spiroorthoester) compounds together with trimethylolpropane triacrylate. The volume shrinkage of the grating thus formed was much lower than that prepared with bis(glycidyl) compounds. Copyright © 2006 Society of Chemical Industry