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51.
The separation, characterization, and determination of mixtures of alkyl ether sulfates (AES) and fatty acids (C10-C16) in background electrolytes (BGEs) containing acetonitrile (ACN)-water mixtures is addressed. Due to inhibition of the ionization of the carboxylate groups, the migration time and the resolution between the fatty acids decreased when the water content of the BGE was reduced, but efficiency and resolution between the AES oligomers improved. The migration times increased and resolution improved by substituting 5% ACN by an equivalent amount of dioxane. A complete separation of the two surfactant classes, up to the AES oligomers with 8 ethylene oxide units (EOs) with respect to C10, with excellent resolution between the AES oligomers, while preserving a satisfactory resolution between the fatty acids, was achieved with a BGE containing 5 mM trimethoxybenzoic acid, 7 mM dipentylamine, 85% ACN, 5% dioxane, and 10% water. The two surfactant classes were increasingly resolved by further reducing the water content of the BGE. Thus, C2 (acetate) was resolved from the AES oligomers up to 7 EOs using 90% ACN and 5% dioxane, but the resolution between the heavier fatty acids was poor with this BGE. Identification of the AES oligomers was eased by the excellent regularity of the successive migration times; thus, within each AES subclass or series of oligomers with the same number of carbon atoms in the alkyl chain, the migration times decreased following a mild curve as the number of EOs increased. The way how the data obtained by indirect photometry (corrected peak areas that are proportional to the molar concentrations) should be managed to avoid systematic error when the calibration curve is constructed using an AES standard with an oligomer distribution different from that of the samples is discussed and equations are given. Decyl sulfate was successfully used as internal standard. The detection limits (S/N = 3) were of ca. 2 microM for individual AES oligomers. 相似文献
52.
Silvia Stumpf Gudrun Goretzki Kerstin Gloe Karsten Gloe Wilhelm Seichte Edwin Weber Jan W. Bats 《Journal of inclusion phenomena and macrocyclic chemistry》2003,45(3-4):225-233
The di- and tetra-allyl ethers of tert-butylcalix[4]arene 1 and 2 have been prepared by alkylation of tert-butylcalix[4]arene with allyl bromide and K2CO3 using different reaction times. Solution 1H NMR measurement of the di-allyl ether 1 and X-ray crystal structures of the complexes of 1 with chloroform (1a) or methanol (1b) indicate the cone conformation of 1 in which intramolecular hydrogen bonding can be maximized. The crystalline state conformers 1a and 1b are distorted in different grades depending on the solvent. While methanol is incorporated in the macrocycle, chloroform molecules do not occupy the cage. The solution 1H NMR spectra of tetra-allyl ether 2 show the co-existence of the cone and partial cone conformation. The partial cone conformer of 2 was investigated by X-ray crystallography. In this compound hydrogen bonding is not existent. The conformer distribution is likely affected by steric and template effects. 相似文献
53.
Carboxylate-substituted radicals from phenylselenide derivatives. Designs on models for coenzyme B12-dependent enzyme-catalyzed rearrangements 总被引:1,自引:0,他引:1
Miranda N Daublain P Horner JH Newcomb M 《Journal of the American Chemical Society》2003,125(18):5260-5261
Laser flash photolysis (266 nm) of alpha- and beta-phenylselenyl esters, carboxylic acids, and carboxylates in aqueous acetonitrile media gave the corresponding radicals by homolytic cleavage of the phenylselenyl groups. In the beta-substituted systems, acid and carboxylate radicals reacted in intramolecular reporter reactions with approximately equal rate constants. For the alpha-substituted systems, an ester- and carboxylic acid-substituted radical reacted in an intramolecular reporter reaction with the same rate constants, but the analogous alpha-carboxylate radical, a radical anion, reacted an order of magnitude less rapidly and with an activation energy that is 3 kcal/mol greater than that found for analogues. A kinetic titration of the equilibrating alpha-acid and alpha-carboxylate radicals gave pKa = 4.6. The results indicate that alpha-ester and alpha-carboxylic acid radicals are unlikely to be appropriate models for alpha-carboxylate radicals, the intermediates formed in a large subset of coenzyme B12-dependent enzyme-catalyzed reactions. 相似文献
54.
Miranda LP Lubell WD Halkes KM Groth T Grøtli M Rademann J Gotfredsen CH Meldal M 《Journal of combinatorial chemistry》2002,4(5):523-529
A novel polymer matrix for solid-phase synthesis, SPOCC(194) resin (1), was designed featuring a backbone of homogeneous tetraethylene glycol (TEG(194)) macromonomer linked by quaternary carbon junctions and terminating in primary alcohol functionality. Beaded SPOCC(194) resin was effectively prepared by suspension polymerization of oxetanylated TEG macromonomer 5 in stirred silicon oil. Mechanically stable and inert to a diverse range of reaction conditions, SPOCC(194) possessed a high hydroxyl group loading (0.9-1.2 mmol/g) for substrate attachment and swelled effectively ( approximately 2-4 mL/g) in a variety of organic and aqueous solvents. Developed for solid-phase synthesis at high reactant concentrations for driving organic and aqueous reactions to completion, SPOCC(194) exhibited high functional group density (mmol/mL) similar to that of low-loaded aminomethylated polystyrene-divinylbenzene copolymer (PS-1%DVB) yet significantly higher than that of PEGA(1900), SPOCC(1500), and TentaGel S. High-resolution MAS NMR spectra of Fmoc-derivatized SPOCC(194) indicate that monitoring of functional group transformation is possible. Moreover, by employment of a nonaromatic resin-linker combination, electrophilic chemistry, such as Lewis acid catalyzed glycosylation and Friedel-Crafts acylation, was selectively performed on substrate bound to SPOCC(194) resin. Such properties make SPOCC(194) resin a promising new polymer matrix for the support-bound construction of small organic molecules by parallel and combinatorial synthesis and the scavenging of solution-phase reactants or byproducts. 相似文献
55.
Dimethyl carbonate (DMC) was investigated as a mild, harmless and odorless reagent for pyrolytic methylation of fatty acids. Soybean oil was selected as test material for its high content of (poly)unsaturated fatty acids. Pyrolyses were performed at 500, 700 and 900 degrees C by means of a heated platinum filament pyrolyser on-line and off-line to the GC-MS apparatus. Methyl esters of palmitic, linoleic, oleic and stearic acid were formed as prominent products from off-line pyrolysis of soybean oil in the presence of DMC and zeolite 13X. Fatty acid methyl esters (FAMEs) were not observed at important levels in the absence of zeolite, while on-line Py-GC-MS experiments resulted principally in the formation of free fatty acids and hydrocarbons. The FAME profiles obtained from the DMC/zeolite off-line pyrolysis were compared to those resulting from tetramethylammonium hydroxide (TMAH) thermochemolysis and BF3-methanol procedure. The observed differences between pyrolysis and methanolysis methods were principally attributed to the thermal degradation of unsaturated fatty acids. The effectiveness of the DMC/zeolite pyrolytic methylation was further demonstrated by the analysis of tripalmitine and soybean seeds. 相似文献
56.
Lupane Pentacyclic Triterpenes Isolated from Stems and Branches of Maytenus imbricata (Celastraceae)
Silvia Ribeiro deSouzaeSilva GraciaDivina deFtimaSilva LucaCludio deAlmeidaBarbosa LucienirPains Duarte SidneyAugustoVieira Filho 《Helvetica chimica acta》2005,88(5):1102-1109
Four lupane pentacyclic triterpenes were isolated from the hexane extract of stems and branches of Maytenus imbricata Mart. ex Reissek : 3‐oxolup‐20(30)‐en‐29‐al ( 1 ), 30‐hydroxylup‐20(29)‐en‐3‐one ( 2 ), (11α)‐11‐hydroxylup‐20(29)‐en‐3‐one ( 3 ), and (3β)‐lup‐20(30)‐ene‐3,29‐diol ( 4 ). The structural identification of 1 – 4 was achieved by 1H‐ and 13C‐NMR techniques, including 2D experiments (HSQC, HMBC, and NOESY). 相似文献
57.
Modeling and simulation of free radical polymerization of styrene under semibatch reactor conditions
The first part of this approach is concerned with the elaboration of a radical polymerization model of styrenne, based on
a kinetic diagram that includes chemical and thermal initiation, propagation, termination by recombination and chain transfer
to the monomer. Furthermore, volume contraction during polymerization is considered, as well as the gel and glass effects.
The mathematical formalism that describes the model in terms of moments is explored in detail. The model was then used to
predict the changes in monomer conversion and molecular weight after intermediate addition of initiator and monomer. The results
of this operation are dependent on the conditions of the reaction mass, quantity, and moment of substance addition. Therefore,
the simulations were performed at different times with respect to the gel effect; before, during and after this phenomenon,
and also with respect to different temperatures and initiators. Increasing the initiator concentration before the gel effect
leads to an earlier appearance of the phenomenon and to a decrease in molecular weight. The ratio
reveals a polydispersity index smaller for the intermediate addition of initiator. No significant changes take place during
or after the gel effect. If along with the initiator, unreacted monomver (used to dissolve the initiator) enters the reactor,
a small dip in conversion is observed. The general conclusion of this paper reveals the intermediate addition of initiator
as a method to control polymer properties and to prevent the “dead-end” polymerization of styrene. 相似文献
58.
Dominick Maes Silvia Debenedetti Sven Mangelinckx Norbert De Kimpe 《Tetrahedron》2005,61(9):2505-2511
The synthesis of three highly oxygenated naturally occurring coumarins, 8-methoxy-6,7-methylenedioxycoumarin, 5-methoxy-6,7-methylenedioxycoumarin and 5,8-dimethoxy-6,7-methylenedioxycoumarin is described for the first time, together with a new method for the preparation of ayapin (6,7-methylenedioxycoumarin). Comparison of the spectroscopic data of the synthetic tetraoxygenated coumarin 5,8-dimethoxy-6,7-methylenedioxycoumarin with literature reports resulted in the structural revision of several natural coumarins. Two coumarins, both identified as 5,8-dimethoxy-6,7-methylenedioxycoumarin must have other structures, while the structure of another coumarin, described as the isomeric 7,8-dimethoxy-5,6-methylenedioxycoumarin has to be revised to 5,8-dimethoxy-6,7-methylenedioxycoumarin. 相似文献
59.
60.
[reaction: see text] A new Prins-type cyclization between homopropargylic alcohol and aldehydes in the presence of FeX(3) to obtain 2-alkyl-4-halo-5,6-dihydro-2H-pyrans in good yield is described. Osmium-catalyzed cis dihydroxylation provided direct access to trans-2-alkyl-3-hydroxy-tetrahydro-pyran-4-ones. Anhydrous ferric halides are also shown to be excellent catalysts for the standard Prins cyclization using homoallylic alcohol. Isolation of an intermediate acetal provides substantiation of a proposed mechanism. 相似文献