系列缩水甘油醚类β-环糊精衍生物的合成及结构表征

以苯基缩水甘油醚、邻甲基酚缩水甘油醚及苯甲基缩水甘油醚(1～3)和β-环糊精为原料, 分别在弱碱水溶液(1.5%)和强碱水溶液(30%)中制备出系列缩水甘油醚类β-环糊精衍生物, 所得产物用自制硅胶色谱柱分离, 以V(正丙醇)∶V(水)∶V(浓氨水)＝6∶3∶1作为硅胶色谱柱分离纯化的洗脱剂, 得到单2位取代的苯氧基(或邻甲基苯氧基或苯甲氧基-2-羟丙基-β-环糊精(1a～3a)和单6位取代的苯氧基(或邻甲基苯氧基)-2-羟丙基-β-环糊精(1b～2b). 所得产品用薄层色谱、红外光谱、质谱和核磁共振波谱等手段进行了表征.     

系列单取代烷氧基-2-羟丙基-β-环糊精的合成与表征

以环氧氯丙烷和脂肪醇为原料, 通过相转移催化法合成了乙基、正丙基、正丁基和正戊基缩水甘油醚(1～4), 并利用所合成的缩水甘油醚和β-环糊精为原料, 分别在弱碱水溶液(1.5%)和强碱水溶液(30%)中制备并用硅胶柱分离出单2位取代的乙氧基、丙氧基、丁氧基和戊氧基-2-羟丙基-β-环糊精(1a～4a)和单6位取代的丙氧基、丁氧基和戊氧基-2-羟丙基-β-环糊精(2b～4b), 利用薄层色谱、红外光谱、差热扫描量热分析、质谱和核磁共振等手段对所合成的产品进行了表征.     

α-烯基-β-环糊精毛细管电色谱整体柱的制备与评价

将烯丙基缩水甘油醚(AGE)和β-环糊精在碱性条件下作用得到带有α烯基的环糊精衍生物——4(3-烯丙氧-2-羟基)丙氧基-β-环糊精(PCD),利用这种衍生物和甲基丙烯酸甘油酯(GMA)为功能单体,在毛细管中通过原位聚合反应,一步法制备得到了新型β-环糊精聚合物毛细管电色谱手性整体柱.在毛细管电色谱(CEC)模式下,应...     

Biodegradable Polycarbonate Synthesis by Copolymerization of Carbon Dioxide with Epoxides Using a Heterogeneous Zinc Complex

As a means for the chemical fixation of carbon dioxide and the synthesis of biodegradable polycarbonates, copolymerizations of carbon dioxide with various epoxides such as cyclohexene oxide (CHO), cyclopetene oxide, 4-vinyl-1-cyclohexene-1,2epoxide, phenyl glycidyl ether, allyl glycidyl ether, propylene oxide, butene oxide, hexene oxide, octene oxide, and 1-chloro-2,3-epoxypropane were investigated in the presence of a double metal cyanide catalyst (DMC). The DMC catalyst was prepared by reacting K₃Co(CN)₆ with ZnCl₂, together with tertiary butyl alcohol and poly(tetramethylene ether glycol) as complexing reagents and was characterized by various spectroscopic methods. The DMC catalyst showed high activity (526.2 g-polymer/g-Zn atom) for CHO/CO₂ (P_CO2 = 140 psi) copolymerization at 80 °C, to yield biodegradable aliphatic polycarbonates of narrow polydispersity (M_w/M_n = 1.67) and moderate molecular weight (M_n = 8900). The DMC catalyst also showed high activities with different CO₂ reactivities for other epoxides to yield various aliphatic polycarbonates with narrow polydispersity.     

Simultaneous determination of NOGE-related and BADGE-related compounds in canned food by ultra-performance liquid chromatography–tandem mass spectrometry

An improved analytical method enabling rapid and accurate determination and identification of bisphenol F diglycidyl ether (novolac glycidyl ether 2-ring), novolac glycidyl ether 3-ring, novolac glycidyl ether 4-ring, novolac glycidyl ether 5-ring, novolac glycidyl ether 6-ring, bisphenol A diglycidyl ether, bisphenol A (2,3-dihydroxypropyl) glycidyl ether, bisphenol A (3-chloro-2-hydroxypropyl) glycidyl ether, bisphenol A bis(3-chloro-2-hydroxypropyl) ether, and bisphenol A (3-chloro-2-hydroxypropyl) (2,3-dihydroxypropyl) ether in canned food and their contact packaging materials has been developed by using, for the first time, ultra-performance liquid chromatography coupled with tandem mass spectrometry. After comparison of electrospray ionization and atmospheric pressure chemical ionization in positive and negative-ion modes, tandem mass spectrometry with positive electrospray ionization was chosen to carry out selective multiple reaction monitoring analysis of novolac glycidyl ethers, bisphenol A diglycidyl ether, and its derivatives. The analysis time is only 5.5 min per run. Limits of detection varied from 0.01 to 0.20 ng g(-1) for the different target compounds on the basis of a signal-to-noise ratio (S/N) = 3; limits of quantitation were from 0.03 to 0.66 ng g(-1). The relative standard deviation for repeatability was <8.01%. Analytical recovery ranged from 87.60 to 108.93%. This method was successfully applied to twenty samples of canned food and their contact packaging materials for determination of migration of NOGE, BADGE, and their derivatives from can coatings into food.     

Ring Closure of N,N′:N,N′-bis(decamethylene)-1, 4-diamino-2,5-bis(10-cyanodecyloxy)benzene (IV)

Recently, β-chloro-α,β-unsaturated carbonyl compounds have become increasingly useful as intermediates in organic synthesis. For example, reactions involving a number of different cyclic β-chloro-α,β-unsaturated ketones with a variety of reagents (a malonate anion², the anion of the dithiolane derivative of ethyl glyoxalate³, zinc-silver couple in methanol⁴, dimethylsulfoxonium methylide^5,6) have produced a series of structurally diverse and potentially fruitful synthetic intermediates. The second-mentioned reagent has also been successfully reacted with a β-chloro-α,β-unsaturated ester³.     

Chromatographic Purification and Identification of Polar Metabolites of Benazolin-Ethyl from Soybean

Abstract

The metabolism of benazolin-ethyl (4-chloro-2-oxobenzothiazolin-3-ylacetic acid ethyl ester), a post emergence herbicide, has been studied in soybean using (¹⁴C)-phenyl labelled compound. Preliminary studies were performed on excised soybean leaves. Following hydrolysis of the ethyl ester to benazolin acid (4-chloro-2-oxobenzothiazolin-3-ylacetic acid), extensive metabolism to polar conjugates was observed. The polar fraction from a Bligh-Dyer extraction was purified by solvent partitioning, preparative TLC and reverse phase HPLC with ion suppression. The two major metabolites were characterised by fast atom bombardment mass spectrometry with accurate mass determination as an aspartate conjugate and a malonyl-β-glucose ester of benazolin acid. Subsequent experiments were performed by spraying intact plants at growth stage V4. The major polar metabolite isolated one month after treatment was identified as the aspartate conjugate by mass spectrometry and high resolution nuclear magnetic resonance spectroscopy.     

Degradation of Lignin Model Compounds in Organic Solvents. Part 1. Preliminary Studies

Preliminary studies were conducted on the degradation of guaiacylglycerol-β-aryl ether (β-O-4′), phenylcoumaran (β-5′) and biphenyl (5–5′) type lignin model compounds in the organic solvent systems such as ethanol-water (1:1, v/v) and 2-butanone-water (1:1, v/v), in the presence of a di- or trivalent inorganic salt to act as a Lewis acid in the temperature range 140–170°C and with a reaction time up to 60 minutes. The inorganic salts investigated include aluminum chloride, aluminum sulfate, ferric chloride, ferric sulfate, and stannic chloride. The results indicate that lignin model compounds of both phenolic and non-phenolicβ-O-4′ types are susceptible to degradation in organic solvent systems in the presence of one of these salts. Stannic chloride was found to be the most suitable catalyst for the degradation of β-O-4′ type lignin model compounds in the organic solvent systems. In contrast, lignin model compounds of β-5′ and 5–5′ types did not undergo degradation under the same reaction conditions. A possible reaction mechanism for the degradation of β-O-4′ type lignin model compounds in organic solvent system in the presence of stannic chloride is discussed.     

Synthesis and Photopolymerization of Multifunctional Propenyl Ether Monomers

Abstract

A novel and facile synthesis of aromatics containing di- and tetrafunctional propenyl ether monomers is reported. These monomers were prepared by the base-catalyzed condensation of allyl glycidyl ether with a variety of bisphenols followed by allylation of the secondary hydroxyl groups and finally isomerization of the allyl groups by a ruthenium catalyst. The cationic photopolymerization of these novel monomers to give crosslinked network polymers was carried out using a diaryliodonium salt photoinitiator. The reactivity of the multifunctional propenyl ether monomers was studied using real-time infrared spectroscopy and by differential scanning photocalorimetry.     

Synthesis and photopolymerization of 1-propenyl glycidyl ether

The ambifunctional monomer, 1-propenyl glycidyl ether, was prepared from allyl glycidyl ether, by a ruthenium-catalyzed isomerization reaction in high yield. 1-Propenyl glycidyl ether undergoes facile photoinduced cationic polymerization to yield a crosslinked polymer. The structure of this polymer was studied using ¹H- and, ¹³C-NMR spectroscopies and employing well-characterized related polymers as models. The model polymers were prepared by the cationic polymerization of allyl glycidyl ether with BF₃OEt₂ followed by isomerization of the pendant allyl groups by a ruthenium catalyst. Subsequently, the resulting polyether-bearing pendant 1-propenyl ether groups was subjected to a diaryliodonium salt-photoinitiated polymerization. A comparison of the spectra of the polymers indicated the presence of cyclic acetal units in the polymer backbone. © 1994 John Wiley & Sons, Inc.     

Anionic alternating copolymerization of 3,4‐dihydrocoumarin and glycidyl ethers: A new approach to polyester synthesis

Anionic copolymerizations of 3,4‐dihydrocoumarin (DHCM) and a series of glycidyl ethers (n‐butyl glycidyl ether, tert‐butyl glycidyl ether, and allyl glycidyl ether) with 2‐ethyl‐4‐methylimidazole as an initiator proceeded in a 1:1 alternating manner to give the corresponding polyesters, whose structures were confirmed by spectroscopic analyses and reductive scission of the ester bonds in the main chain with lithium aluminum hydride, followed by detailed analyses of the resulting fragments. The polyester obtained by the copolymerization of DHCM and allyl glycidyl ether inherited the allyl groups in the side chain, whose applicability to chemical modifications of the polyester was successfully demonstrated by a platinum‐catalyzed hydrosilylation reaction. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4092–4102, 2008     

Synthesis and Modification of Functional Polycarbonates with Pendant Allyl Groups

Functional aliphatic polycarbonates with pendant allyl groups were synthesised by copolymerization of carbon dioxide and allyl glycidyl ether (AGE) in the presence of a catalyst system based on ZnEt₂ and pyrogallol at a molar ratio 2 : 1. The functionality of some polycarbonates was reduced by replacing a part of allyl ether with saturated glycidyl ether, i.e., butyl glycidyl ether (BGE) or isopropyl glycidyl ether (IGE). Polycarbonates obtained by the copolymerization of AGE and CO₂ or by the terpolymerization of AGE, IGE and CO₂ were oxidized with m‐chloroperbenzoic acid to their respective poly(epoxycarbonate)s. The influence of the AGE/ΣGE ratio in the polycarbonates, the polymer concentration in the reaction solution and the duration of the reaction on the conversion of allyl groups into glycidyl ones was examined. A tendency to gelation of the initial and oxidized polycarbonates during storage was observed. The initial polycarbonates and their oxidized forms were degraded in aqueous buffer of pH = 7.4 at 37°C. The course of hydrolytic degradation was monitored by the determination of mass loss.     

Study of chemical processes in the modification of epoxide polymers by aluminum oxide

The processes occurring during the modification of epoxy polymers by various polymorphic aluminum oxide modifications (γ-AlO(OH), γ-Al₂O₃, α-Al₂O₃) with epoxy groups were studied by the methods of IR Fourier spectroscopy, chemical analysis, and differential scanning calorimetry (DSC) by an example of a model compound (phenyl glycidyl ether). Two types of interactions were revealed: a direct chemical reaction of phenyl glycidyl ether with the surface hydroxy groups of alyminum oxide, and phenyl glycidyl ether homopolymerization. By processing by graphical method the data of chemical analysis on the diminishing in amount of epoxy groups in the course of the polycondensation reaction the value of activation energy 106–110 kJ mol⁻¹ of the process of phenyl glycidyl ether interaction with aluminum γ-oxide was determined.     

Kinetics of the Polymerization of Ethyl Glycidil Ether and Allyl Glycidil Ether with BF3OEt2

The kinetics of the polymerization of ethyl glycidyl ether and allyl glycidyl ether with BF₃OEt₂ as catalyst has been studied. Chain transfer to the monomer has been evidenced. It increased with the monomer concentration and decreased with the increase of the dielectric constant of the solvent used and decreased in the presence of a monomer more basic than glycidyl ethers, for example, 1,3-dioxepane.     

MULTIFUNCTIONAL HYDROPHILIC POLYMERS

ABSTRACT

Different types of multifunctional hydrophilic polymers were synthesized and characterized in view of their possible biomedical application. Several poly(amide)s and poly(ester-amide)s containing oligo(oxyethylene) segments and tartaric or succinic acid residues were prepared by activated polycondensation methods. New functional derivatives of β-cyclodextrin were obtained by reaction with glycidyl ether of protected polyols. The mechanism of β-cyclodextrin polymerization with epichlorohydrine was investigated by ¹³C-NMR spectroscopy.     

Alternative Syntheses of (l→3)-β-D-Galacto-Oligosaccharides

ABSTRACT

Galactosyl halides bearing different substituents at O-3 [i.e. acetyl (15), benzoyl (14), benzyl (3), bromoacetyl (12), and the 2, 3, 4, 6-tetra-O-benzoyl-β-D-galactopyranosyl group (17)] have been prepared, and used to study the stereoselectivity of the coupling reaction to position O-3 of different galactose derivatives [i.e. methyl 2, 4, 6-tri-O-acetyl-(9) and 2, 4, 6-tri-O-benzoyl-β-D-galactopyranoside (7), l, 2, 4, 6-tetra-O-benzoyl-β-D-galactose (6) and O-(2, 4, 6-tri-O-benzoyl-β-D-galactopyranosyl)-(1→3)-β-D-galactose (33)], as well as to benzoic acid. In more polar solvents, using silver trifluoro-methanesulfonate as the promoter, a higher proportion of β-linked products was formed, whereas with silver perchlorate as the promoter the α-linked product predominated. Under basic conditions, applied to prevent anomerisation of 1-O-benzoylated nucleophiles 6 and 33, no orthoesters were found as end products. Under those conditions, a better overall yield of the β-(l→3)-linked galactotriose 31 was obtained by condensation of die disaccharide glycosyl donor 17 and the monosaccharide glycosyl acceptor 6 than by condensation of 14 and 33. The disaccharide glycosyl chloride 17 was obtained in 75% yield by the cleavage of the corresponding methyl glycoside with dichloromethyl methyl ether.     

Synthesis and polymerization studies of several chloro and cyano epoxides

The polar epoxides, glycidonitrile, dimethyl glycidonitrile, tetracyanoethylene oxide, epicyanohydrin, 4,4,4-trichlorobutylene-1,2-epoxide, and 1,1-dichloro-3,4-epoxy-1-butene were prepared, characterized by their infrared and nuclear magnetic resonance spectra and their polymerizations studied. Epicyanophydrin was found to be an unpolymerizable dimer, and those epoxides with a cyano group attached directly to the epoxide ring could not be polymerized. The halogenated epoxides, 4,4,4-trichlorobutylene-1,2-epoxide and its dehydrochlorination product, 1,1-dichloro-3,4-epoxy-1-butene were polymerized to high polymers with a complex catalyst from aluminum alkyl, acetyl acetone, and water. The polymerization of these monomers gave low conversions and required large amounts of catalyst. Higher conversions were obtained by copolymerization with propylene oxide or terpolymerization with propylene oxide and allyl glycidyl ether. The polymerizability of the substituted epoxide in (where X is CH₃? , ClCH₂? , Cl₃CCH₂? , and Cl₂C? CH? ) was found to follow the order: CH₃? > ClCH₂? > Cl₃C? CH₂? > Cl₂C?CH. The polymers of 4,4,4-trichlorobutylene-1,2-epoxide and its dehydrochlorination products were not vulcanizable through the chlorine functionality or the olefinic unsaturation of the type Cl₂C?CH? . The presence of an active third monomer such as allyl glycidyl ether was necessary to facilitate vulcanization. Properties of such vulcanizates are reported.     

聚(β-氯乙基缩水甘油醚)的合成及其酯化反应动力学

本文合成了β-氯乙基缩水甘油醚及其聚合物。结果表明, AlEt3-0.5H2O体系是β-氯乙基缩水甘油醚的一种有效的聚合引发剂。研究了聚(β-氯乙基缩水甘油醚)的酯化反应动力学, 并通过^1H NMR和IR光谱确立了酯化度的计算关系式。最后, 通过光交联的动力学研究发现, 酯化聚合物中的肉桂酰基含量为85%时, 材料的感光灵敏度最高。     

Photochemical Reactions 127th CommunicationPhotochemistry of Epoxy-enones: Intramolecular Trapping of a Carbonyl Ylide

On ¹n, π* -excitation 5, 6-epoxy-2-hydroxy-5, 6-dihydro-β-ionone ((E)-4) shows the typical behaviour of a, β-unsaturated γ, δ-epoxy ketones undergoing primarily C(γ), O-cleavage of the oxiran. However, ¹π, π*-excitation of (E)? 4 leads to enol ether 10 which is formed by intramolecular insertion of the hydroxyl group of the ylide c .     

Synthesis of enantiomerically enriched α,α-disubstituted β,γ-epoxy esters using hydrolytic kinetic resolution catalyzed by salenCo(III)

Novel α,α-disubstituted epoxy esters were prepared in enantiopure form by hydrolytic kinetic resolution (HKR) of the corresponding racemic mixtures using chiral salenCo(III) as catalyst. The methodology provides a convenient route to enantioenriched β,γ-epoxy esters 2a, 2c and 2d.