Meldrum's acids as acylating agents in the catalytic intramolecular Friedel-Crafts reaction

[reaction: see text] The intramolecular Friedel-Crafts acylation of aromatics with Meldrum's acid derivatives catalyzed by metal trifluoromethanesulfonates is reported. Meldrum's acids are easily prepared, functionalized, handled, and purified. The synthesis of polysubstituted 1-indanones from benzyl Meldrum's acids was investigated thoroughly, and it was shown that a variety of catalysts were effective, while accommodating a diversity of functional groups under mild conditions. The scope, limitations, and functional group tolerance (terminal alkene and alkyne, ketal, dialkyl ether, dialkyl thioether, aryl methyl ether, aryl TIPS and TBDPS ethers, nitrile- and nitro-substituted aryls, alkyl and aryl halides) for a variety of 5-benzyl (enolizable Meldrum's acids) and 5-benzyl-5-substituted Meldrum's acids (quaternized Meldrum's acids), forming 1-indanones and 2-substituted-1-indanones, respectively, are delineated. This method was further applied to the synthesis of 1-tetralones, 1-benzosuberones, and the potent acetylcholinesterase inhibitor donepezil. Rate of cyclization as a function of ring size was established for various benzocyclic ketones via competition experiments: 1-tetralones form faster than both 1-indanones and 1-benzosuberones, and 1-benzosuberones cyclize faster than 1-indanones.     

1-茚满酮合成方法研究进展

1-茚满酮类化合物是许多药物和天然产物合成中的中间体, 有关这类化合物的合成方法仍然不断得到更新. 按照关环位点对于这些合成方法进行了综述, 着重介绍了2000以来的合成新进展.     

Boosting Selective Oxidation of Ethylene to Ethylene Glycol Assisted by In situ Generated H2O2 from O2 Electroreduction

Ethylene glycol is a useful organic compound and chemical intermediate for manufacturing various commodity chemicals of industrial importance. Nevertheless, the production of ethylene glycol in a green and safe manner is still a long-standing challenge. Here, we established an integrated, efficient pathway for oxidizing ethylene into ethylene glycol. Mesoporous carbon catalyst produces H₂O₂, and titanium silicalite-1 catalyst would subsequently oxidize ethylene into ethylene glycol with the in situ generated H₂O₂. This tandem route presents a remarkable activity, i.e., 86 % H₂O₂ conversion with 99 % ethylene glycol selectivity and 51.48 mmol g_ecat⁻¹ h⁻¹ production rate at 0.4 V vs. reversible hydrogen electrode. Apart from generated H₂O₂ as an oxidant, there exists ⋅OOH intermediate which could omit the step of absorbing and dissociating H₂O₂ over titanium silicalite-1, showing faster reaction kinetics compared to the ex situ one. This work not only provides a new idea for yielding ethylene glycol but also demonstrates the superior of in situ generated H₂O₂ in tandem route.     

A library of thermoresponsive PEG-based methacrylate homopolymers: How do the molar mass and number of ethylene glycol groups affect the cloud point?

In this study, a novel library of thermoresponsive homopolymers based on poly (ethylene glycol) (EG) (m)ethyl ether methacrylate monomers is presented. Twenty-seven EG based homopolymers were synthesized and three parameters, the molar mass (MM), the number of the ethylene glycol groups in the monomer, and the chemistry of the functional side group were varied to investigate how these affect their thermoresponsive behavior. The targeted MMs of these polymers are varied from 2560, 5000, 8200 to 12,000 g mol⁻¹. Seven PEG-based monomers were investigated: ethylene glycol methyl ether methacrylate (MEGMA), ethylene glycol ethyl ether methacrylate (EEGMA), di(ethylene glycol) methyl ether methacrylate (DEGMA), tri(ethylene glycol) methyl ether methacrylate (TEGMA), tri(ethylene glycol) ethyl ether methacrylate (TEGEMA), penta(ethylene glycol) methyl ether methacrylate (PEGMA), nona(ethylene glycol) methyl ether methacrylate (NEGMA). Homopolymers of 2-(dimethylamino) ethyl methacrylate (DMAEMA) were also synthesized for comparison. The cloud points of these homopolymers were tested in different solvents and it was observed that it decreases as the number of EG group was decreased or the MM increased. Interestingly, the end functional group (methoxy or ethoxy) of the side group has an effect as well and is even more dominant than the number of EG groups.     

Superacid-Promoted Hydroxyalkylation of 1,2-Indandiones

1,2-Indandione reacts efficiently with arenes to give 2,2-diaryl-1-indanones by the hydroxyalkylation reaction. The Brønsted superacid CF₃SO₃H (triflic acid) is an effective catalyst for these condensation reactions. The requisite 1,2-indandiones were prepared from the 1-indanones.     

Headspace gas chromatography analysis of toxic contaminants in ethoxylated alcohols and alkylamines

Summary Headspace-gas chromatography was used to determine the contents of toxic 1,4-dioxane, ethylene oxide and ethylene glycol in ethoxylated alcohols and alkylamines, and in commercial cosmetics and washing products. A Permaphase PEG capillary column was used for the determination of 1,4-dioxane and ethylene oxide and a DB-17 column for ethylene glycol determination. Dimethylformamide was used as the solvent in the determination of 1,4-dioxane and ethylene oxide, and undecanol in the case of ethylene glycol. The detection limits for ethylene oxide, 1,4-dioxane and ethylene glycol are 1,2 and 10 μg·g⁻¹, respectively.     

Phase equilibria of the quaternary system acetic acid—ethylene glycol monoethyl ether acetate—ethylene glycol monoethyl ether—water

The synthesis of ethylene glycol monoethyl ether acetate by esterification of ethylene glycol monoethyl ether with acetic acid is of industrial interest. The following experimental determinations were carried out: vapour—liquid equilibria of the binary systems acetic acid—ethylene glycol monoethyl ether acetate and acetic acid—ethylene glycol monoethyl ether; liquid—liquid equilibrium of the binary system water—ethylene glycol monoethyl ether acetate; solubility curves of the ternary systems water—ethylene glycol monoethyl ether acetate—ethylene glycol monoethyl ether and water—acetic acid—ethylene glycol monoethyl ether acetate.The parameters of a model able to describe the phase equilibria of the whole system have been identified. Liquid—liquid, as well as vapour—liquid equilibrium data, are satisfactorily correlated with an unique choice of parameters.     

3,3]-Sigmatropic rearrangement/5-exo-dig cyclization reactions of benzyl alkynyl ethers: synthesis of substituted 2-indanones and indenes

Substituted benzyl alkynyl ethers, prepared from the corresponding α-alkoxy ketones in a two-step sequence involving enol triflate formation and KOtBu-induced E2 elimination, undergo [3,3]-sigmatropic rearrangement/intramolecular 5-exo-dig cyclization at 60 °C to form substituted 2-indanones in good overall yields. 1,3-cis-Disubstituted-2-indanones are formed preferentially when the benzylic substituent R(1) is bulky. Substituted indenes may be prepared from 2-indanones in high yields by Horner-Wadsworth-Emmons reaction.     

A new synthesis of 2-fluoro-1-naphthols

A general synthesis of 2-fluoro-1-naphthols in two steps from 1-indanones is reported. The 1-indanones are first converted to difluoromethyl 2-fluoro-1-napthyl ethers by reaction with difluorocarbene source, trimethylsilyl 2-fluorosulfonyl-2,2-difluoroacetate (TFDA). These ethers are then converted in high yield to the respective naphthols by heating with a mixture of acetic acid and 48% HBr.     

Triton X-100在乙二醇中的胶体性质

表面活性剂在非水溶剂中聚集态的研究所见的报导与水体系相比要少得多．然而近年来对非水体系的研究日益增多．这是因为表面活性剂在非水溶剂中的应用日趋增加，但与水体系相反，对非水体系的性质了解甚少．对表面活性剂非水体系的研究还有助于对其聚集体的共溶剂效应有更深的认识．TritonX－100（以下简写为TX－100）是典型的非离子表面活性剂，在工业上有着广泛的应用．乙二醇在多醇中与水的化学结构最相近问，然而它却是水结构的破坏剂，加入少量的乙二醇会使水的冰点急剧下降．乙二醇又是蛋白质的变性溶剂．表面活性剂在乙二醇中的胶…     

Modeling of Osmotic Pressure of Aqueous Poly(Ethylene Glycol) Solutions Using the Artificial Neural Network and Free Volume Flory Huggins Model

In this work, the modified Flory-Huggins coupled with the free-volume concept and the artificial neural network models were used to obtain the osmotic pressure of aqueous poly(ethylene glycol) solutions. In the artificial neural network, the osmotic pressure of aqueous poly(ethylene glycol) solutions depends on temperature, molecular weight and the mole fractions of poly(ethylene glycol) in aqueous solution. The network topology is optimized and the (3-1-1) architecture is found using optimization of an objective function with batch back propagation (BBP) method for 134 experimental data points. The results obtained from the neural network in obtaining of the osmotic pressure of aqueous poly(ethylene glycol) were compared with those obtained from the free volume Flory-Huggins model (FV-FH). The results showed that the modified Flory-Huggins model and also the artificial neural network can accurately predict the osmotic pressure of aqueous poly(ethylene glycol) solutions but the accuracy of ANN is much better than the modified Flory-Huggins model.     

Effect of ethylene glycol on the thermodynamic and micellar properties of Tween 20

The aggregation behaviour of Tween 20 in ethylene glycol-water mixed solvents has been investigated using surface tension, density, static and dynamic light scattering, and fluorescence measurements. Micellar and surface thermodynamics data were obtained from the temperature dependence of critical micelle concentrations in various aqueous mixtures of ethylene glycol. In order to evaluate the influence of the cosolvent, the differences in the Gibbs energies of micellization of Tween 20 between water and binary solvents were determined. This study allowed us to conclude that the ability of ethylene glycol to act as a structure breaker and its interaction with the surfactant hydrophilic group are the controlling factors of the micellization process. From the evaluation of the thermodynamics of adsorption at the solution-air interface, it was determined that the surface activity of the surfactant decreases slightly with increasing concentration of ethylene glycol at a given temperature. Partial specific volume data, obtained by density measurements, indicate that the fraction of solvent molecules interacting with the micelle, via hydrogen bonds, remained roughly constant. The effect of cosolvent on the size and solvation of the aggregates was analysed by means of static and dynamic light scattering measurements. It was found that the aggregation number decreased, whereas the whole micellar solvation increased with the ethylene glycol content. Micellar micropolarity was examined using two different probes, pyrene and 8-anilinonaphthelene-1-sulfonic acid, and was found to increase with ethylene glycol addition, accompanied by an enhanced solvation. Fluorescence polarization measurements found by using coumarin 6 as a hydrophobic probe revealed an increase in the micellar microviscosity. The observed trends in these microenvironmental properties were ascribed to a participation by ethylene glycol in the micellar solvation layer.     

New deuterated oligo(ethylene glycol) building blocks and their use in the preparation of surface active lipids possessing labeled hydrophilic tethers

For the introduction of additional analysis protocols of tethered molecules, a method is presented to prepare functionalized, deuterated oligo(ethylene glycols) from ethylene glycol-d4. Partial oligomerization of ethylene glycol-d4 and conversion to ditosylates is accompanied by coupling reactions to prepare doubly benzyl protected oligo(ethylene glycols) with two to five repeating units. The tetramer bearing 16 deuteria was elaborated at both ends to eventually prepare 2,3-di-O-phytanyl-sn-glycerol-1-tetraethylene glycol-d,l-alpha-lipoic acid ester (DPTL), which bears a fully deuterated tetra(ethylene glycol) spacer group. Through linking of functionalized components, an analogue of DPTL possessing an octa(ethylene glycol) spacer group was prepared, both in deuterated and unlabeled form.     

Solvation of amides of carboxylic acids in aqueous solutions of ethylene glycol

Enthalpies of solution of amides of formic, acetic, and propionic acids with different degrees of N-substitution in aqueous solutions of ethylene glycol were measured at 298.15 K. The concentration of ethylene glycol did not exceed 4 mol kg^–1. The reasons for increasing endothermic values of the enthalpies characterizing the amide transfer from water to a mixed aqueous-organic solvent on going from primary to tertiary amides and from formamides to the corresponding acetamides are discussed. The enthalpic coefficients of pair interactions between amides and ethylene glycol in water were calculated. The endothermicity of the interaction of the alkyl groups of the amide molecules with ethylene glycol results in positive values of the coefficients. The coefficient values increase with the enhancement of the hydrophobic properties of hydrophilic non-electrolytes (urea, formamide, ethylene glycol) due to an increase in the contribution of the hydrophobic component and a decrease in the contribution from the interaction of the polar groups of amides to the total interaction.     

Ruthenium complex catalyzed n-heterocyclization. Indoles from aminoarenes and glycols.

N-Methylaniline reacted with ethylene glycol in the presence of a homogeneous ruthenium catalyst (1 mol % based on ethylene glycol) to give 1-Methylindole in 51% yield. Similarly, aniline reacted with 2,3-butanediol affording 2,3-dimethylindole in 58% yield. The yields of indoles were affected by the molar ratio of aminoarene to glycol.     

Rapid determination of ethylene glycol at toxic levels in serum and urine

The rapid gas chromatographic detection and determination of ethylene glycol in biological fluids is described. Phenylboronic acid in acetone was used for the esterification of glycol. The phenylboronates of ethylene glycol and 1,2-propylene glycol are not separated on a packed column of medium polarity (OV-17), but they can be separated on a non-polar column (OV-101). In both instances, 1,3-propylene glycol can be used as an internal standard. The method requires only 100 microliters of serum or urine and is suitable for trace analysis in an emergency toxicological laboratory. The utility of the method is demonstrated on two cases of human intoxication with ethylene glycol.     

Ultrafast dynamics of liquid poly(ethylene glycol)s and crown ethers studied by femtosecond Raman-induced Kerr effect spectroscopy

Ultrafast molecular dynamics of liquid poly(ethylene glycol)s, tetra(ethylene glycol), penta(ethylene glycol), and poly(ethylene glycol) with the molecular weight of 600, and crown ethers, 12-crown-4 and 15-crown-5, have been investigated by means of femtosecond optical heterodyne-detected Raman-induced Kerr effect spectroscopy. Picosecond Kerr transients of poly(ethylene glycol)s and crown ethers are characterized by a biexponential function with the time constants of about 2 and 20 ps. Both the faster and slower time constants do not vary much among the five oligo(ethylene oxide)s. Femtosecond dynamics is discussed based on the Kerr (depolarized Raman) spectra obtained by Fourier transform deconvolution analysis of the high time resolution Kerr transients. The broad low-frequency band (0-200 cm(-1)) in the Kerr spectrum is analyzed by two Brownian oscillators. The spectral shapes of linear poly(ethylene glycol) and cyclic crown ether are very different. Both the low- and high-frequency Brownian oscillators for crown ethers show lower frequency and broader spectral features than those for poly(ethylene glycol)s. The comparison of the low-frequency spectra of poly(ethylene glycol)s and crown ethers shows that the low-frequency spectrum of 15-crown-5 is closer to that of poly(ethylene glycol)s than that of 12-crown-4 is. The difference of the low-frequency spectra between poly(ethylene glycol) and crown ether is discussed with the concepts of molecular conformation and liquid density. The features of the observed intramolecular vibrational bands are also correlated with the molecular conformations.     

乙二醇二缩水甘油醚的合成及作为阳离子型紫外光固化稀释剂性能研究

以三氟化硼乙醚络合物为催化剂,以氢氧化钠为成环反应的闭环剂,利用乙二醇和环氧氯丙烷为原料合成了乙二醇二缩水甘油醚.研究了催化剂三氟化硼乙醚络合物用量、环氧氯丙烷和乙二醇摩尔比、氢氧化钠和乙二醇摩尔比,以及成环反应温度这些因素对合成反应的影响.结果表明较好的合成反应条件是:三氟化硼乙醚络合物质量分数为0.40%,环氧氯丙烷和乙二醇较佳摩尔比为2.4:1,氢氧化钠和乙二醇较佳摩尔比为2.2:1,较佳的成环反应温度为30℃.同时,把乙二醇二缩水甘油醚作为稀释剂加入到环氧树脂E-51中,利用三芳基锍鎓六氟锑酸盐作为引发剂,制备了阳离子型紫外光固化涂料,其紫外光固化膜的拉伸强度为46.25MPa,杨氏模量为1487.26MPa,断裂伸长率为6.27%.     

Separation and confirmation of the product and by products of the reaction of cyclododecanone with phenyl ethylene glycol

It has been proved, by TLC and synthetic methods, that the odoriferous material formed in the reaction of cyclododecanone and phenyl ethylene glycol under acidic condition, was not the ketal of cyclododecanone, but an acetal of phenylacetaldehyde with phenyl ethylene glycol—the by-product formed from phenyl ethylene glycol. The cis-trans isomers of the acetal were separated by chromatography, the configurations were confirmed via the analysis of their ¹H NMR spectra, and the odors were evaluated as well.     

On the role of initiator in emulsion polymerization

The use of nonionic poly(ethylene glycol)-azo-initiators instead of ionic initiators in emulsion polymerizations offers interesting possibilities for modifying the colloidal and polymeric properties of polymer dispersions. Experimental results are presented for various kinds of anionic, cationic, and nonionic stabilizers as well as for peroxodisulfate initiators with different counter ions (ammonium and potassium). For example, in a styrene emulsion polymerization (with monomer to water mass ratio of 1:4 at a given concentration of 1% with respect to monomer mass of either an anionic or a cationic surfactant), the replacement of either peroxodisulfate or 2,2'-azobis(2-amidinopropane)dihydrochloride by a poly(ethylene glycol)-azo-initiator (with a poly(ethylene glycol) molecular weight of 200 g mol^-1) leads to particles with considerably smaller size, polymers with higher molecular weight, and latexes with higher viscosity.