Spectroscopic characterization of cobalt-containing mesoporous materials

Cobalt-containing mesoporous materials that have been prepared using different procedures have been comparatively characterized by transmission electron microscopy/energy-dispersive X-ray spectroscopy (TEM/EDS), extended X-ray absorption fine structure spectroscopy (EXAFS), X-ray absorption near edge spectroscopy (XANES), and ultraviolet-visible (UV-vis), near-infrared (NIR), and mid-infrared (mid-IR) spectroscopies, and the results provide new insights into the local environment and properties of cobalt in this type of material. TEM/EDS analyses have shown that tetraethyl orthosilicate (TEOS) may be less appropriate as a silicon source during the syntheses of cobalt-containing mesoporous materials, because the distribution of cobalt throughout the framework may become uneven. EXAFS has been determined to be the most suitable method for direct verification of framework incorporation, by identifying silicon as the backscatterer in the second shell. Such a direct verification may not be obtained using UV-vis spectroscopy. From EXAFS analyses, it is also possible to distinguish between surface-bound and framework-incorporated cobalt. There is a good agreement between the results obtained from XANES and UV-vis regarding the coordination symmetry of cobalt in the samples. The presence of cobalt in the silica framework has been determined to create Lewis acid sites, and these acid sites are suggested to be located at tetrahedral cobalt sites at the surface.     

Papain catalyzed estehification of alanine by alcohols and diols

Papain catalyzed esterification of Boc-Ala-OH with various alcohols and diols under biphasic conditions was investigated. Long-chain diols HO(CH₂)nOH gave good yields of esterification up to n=10 whereas the homologous alcohols C_nH_2n+1OH condensed well only for n = 2, 4, 6. Esterification with functionnalized primary alcohols is also described.     

Nucleophilic fluorination of amino alcohols and diols using Deoxofluor

Various fluorinated chiral compounds were synthesized using bis(2-methoxyethyl)aminosulfur trifluoride (Deoxofluor) as a nucleophilic fluorinating reagent. Reactions of Deoxofluor (1) with amino alcohols (2a-d) and diols (2e-g) in methylene chloride at room temperature led to the formation of the corresponding fluoro derivatives (3a-g) in good yields.     

二醇及氨基醇类鬼臼毒素衍生物的合成

以天然产物鬼臼毒素(1)为原料，合成了四种二醇及氨基醇类鬼臼毒素衍生物：4-O-乙基表鬼臼苦醇(4)，(1R,2S,3R,4S)-1-3',4',5'-三甲氧基苯基-2-氨甲基-3-羟甲基-4-乙氧基-6,7-亚甲二氧基-1,2,3,4-四氢萘(5)，(1R,2S,3R,4S)-1-3',4',5'-三甲氧基苯基-3-羟甲基-2-氨基-4-乙氧基-6,7-亚甲二氧基-1,2,3,4-四氢萘(6)和4-O-异丙基表鬼臼苦醇(7)。4～7及中间产物8～11都是新化合物。     

Dielectric characterization of substituted diols

Dielectric properties of four diols having different chemical structures of the hydrophobic part were determined by the time domain spectroscopy method in the frequency range from c. 15MHz to c. 7GHz. The static permittivity clearly reflects the changes in the position of the dipole moments in the molecules. The dielectric relaxation times characterizing the diol part of the molecules are similar for all the substances studied. In the case where the phenylthiadiazole unit is built into the alkyl chain, two well separated processes were observed: one connected with the 'hydrophobic' and the second with the 'hydrophilic' part of the molecule. This emphasizes the amphotropic character of such molecules.     

Fluorination of alcohols and diols with a novel fluorous deoxy-fluorination reagent

We prepared a novel fluorous deoxy-fluorination reagent N,N-diethyl-α,α-difluoro-[3,5-bis(1H,1H,2H,2H-perfluorodecyl)benzyl]amine (1b) from 3,5-diiodobenzoic acid (3b) via N,N-diethyl-3,5-bis(1H,1H,2H,2H-perfluorodecyl)benzamide (2b) in four steps and used it for the fluorination of alcohols and diols. After the fluorination reactions, the isolation of the products and recovery of 2b was performed by extraction with a fluorous/organic solvent system.     

Reactions of terpene alcohols and diols with chlorine dioxide in dimethylformamide

The system chlorine dioxide–dimethylformamide in combination with or without a catalytic amount of MoCl₅, CeCl₃, ZrOCl₂, or VO(acac)₂ induces oxidative chlorination of a number of bicyclic terpene alcohols and vicinal diols. 2α-Chloropinan-3-one, 3α-chloro-10β-pinan-4-one, 5α-chloro-3α-hydroxycaran-4-one, 5β-chloro-3β-hydroxycaran-4-one, and 4α-chloro-2α-hydroxypinan-3-one were thus synthesized in good preparative yields.     

Iridium-catalyzed oxidative methyl esterification of primary alcohols and diols with methanol

Oxidative methyl esterification of primary alcohols and diols with methanol was successfully achieved, using acetone as a hydrogen acceptor, under the influence of an iridium complex combined with 2-(methylamino)ethanol (MAE) as catalyst.     

Polycondensations of dicarboxylic acids and diols derived from optically active amino alcohols

Polycondensations of dicarboxylic acids with diols having amide moieties derived from optically active amino alcohols were carried out. Polymers with M _ns 8,700–17,400 were obtained by the polycondensations using 1.2 eq. of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC·HCl) in DMF at room temperature for 8 h in satisfactory yields. The T_g of the polymer rose with decrease of the methylene chain length of the dicarboxylic acid. In the T_gs of the polymers from L-leucinol, even-odd effect was observed with increase of the methylene chain length of the dicarboxylic acid. The molecular rotation values of the polymers were constant except for the polymer from succinic acid, which showed the negatively largest one. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2925–2934, 1997     

Preparation, characterization and application of polymeric diols with comb-branched structure and their nanocomposites containing montmorillonites

The polymeric diols with comb-branched structure (CPD) and their nanocomposites containing montmorillonites (MMT) were prepared through three-step reaction on basis of molecular design. The effect of experimental parameters, such as molar mass of oligomer polyols, catalysts and MMT on conversion of -NCO group during polymerization was investigated by utilizing FTIR to measure content of -NCO group varied as reaction time. In addition, the structure of comb-branched polymeric diols was characterized by FTIR and ¹H NMR. The results show that the comb-branched chains contain reactive CC double bonds in CPD. The nature of dispersion of montmorillonites in CPD was characterized by X-ray diffraction. The results show that Na⁺-MMT is exfoliated and organo-MMT is intercalated in CPD via in-situ polymerization. Finally, the properties of water-borne polyurethane modified with CPD or CPD/2T-MMT nanocomposite were compared with those of common water-borne polyurethane, and the comb-branched chains and 2T-MMT improve the properties of water-borne polyurethane.     

Polyepichlorohydrin diols free of cyclics: Synthesis and characterization

Polymerization of epichlorohydrin (ECH) in the presence of diols, catalyzed by Lewis or protic acids, proceeds by activated monomer mechanism (AMM), i.e., by subsequent additions of protonated monomer molecules to the terminal hydroxyl groups of the growing chain. As opposed to the typical active chain end mechanism, side reactions, including cyclization, are strongly suppressed in the polymerization by AMM and well-defined linear product are obtained. It follows from kinetic considerations, that in order to achieve the high contribution of AMM, the reaction should be carried out at low instantaneous concentration of monomer, and this can be accomplished by slowly adding ECH to the reaction mixture. Using this approach, polyepichlorophydrin diols have been prepared in the M?_n ～ 2500 products with DP _n = [M]₀/[I]₀ can be obtained practically free of cyclic by-products with the yields approaching quantitative. Polyepichlorohydrin diols obtained by AM polymerization are strictly bifunctional, regular head-to-tail polymers containing mainly (≥ 95%) secondary hydroxyl and groups.     

Selective mono protection of diols, diamines, and amino alcohols using cesium bases

Efficient synthetic methods were developed for the synthesis of mono xanthates, as well as mono dithiocarbamates of diamines and amino alcohols. This protocol utilizes the three component coupling of diols, diamines, and amino alcohols using alkyl bromides and carbon disulfide in the presence of a cesium base and tetrabutylammonium iodide (TBAI).     

Solvent free oxidation of primary alcohols and diols using thymine iron(III) catalyst

In this study, we developed an efficient and selective iron-based catalyst system for the synthesis of ketones from secondary alcohols and carboxylic acids from primary alcohol. In situ generated iron catalyst of thymine-1-acetate (THA) and FeCl(3) under solvent-free condition exhibits high activity. As an example, 1-octanol and 2-octanol were oxidized to 1-octanoic acid and 2-octanone with 89% and 98% yields respectively.     

Photocatalytic Umpolung of N- and O-substituted alkenes for the synthesis of 1,2-amino alcohols and diols

We report an organophotocatalytic 1,2-oxyalkynylation of ene-carbamates and enol ethers using Ethynyl BenziodoXolones (EBXs). 1-Alkynyl-1,2-amino alcohols and diols were obtained in up to 89% yield. Photocatalytic formation of radical cations led to Umpolung of the innate reactivity of the alkenes, enabling addition of a nucleophilic benzoate followed by radical alkynylation.

Photocatalytic Umpolung with organic dyes overcoming the innate nucleophilicity of enecarbamates and enol ethers for oxyalkynylation with EBX reagents to access 1-alkynyl-1,2-amino alcohols and diols.     

Kinetic resolution of diols and pyridyl alcohols by Cu(II)(borabox)-catalyzed acylation

[reaction: see text] Boron-bridged bisoxazoline (borabox) ligands have been used in the copper(II)-catalyzed benzoylation of pyridyl alcohols and 1,2-diols. Efficient kinetic resolution of 1,2-diols was achieved using both borabox and bisoxazoline (box) ligands. Borabox ligands induced high selectivities in the benzoylation of suitable pyridyl alcohols, where they outperformed bisoxazolines. In addition, highly enantioselective Cu(II)(borabox)-catalyzed benzoylation has been used for the synthesis of both enantiomers of a pyridyl alcohol.     

Preparation of alcohols from sulfones and trialkylboranes

The reaction of sulfone anions with trialkylboranes followed by thermal isomerization of the obtained boron compounds in the presence of excess borane-methyl sulfide complex and by alkaline hydroperoxide oxidation yields primary alcohols.