Search results for "alcohols"
showing 10 items of 150 documents
Sequential Iron-Catalyzed C(sp2)–C(sp3) Cross-Coupling of Chlorobenzamides/Chemoselective Amide Reduction and Reductive Deuteration to Benzylic Alcoh…
2023
Benzylic alcohols are among the most important intermediates in organic synthesis. Recently, the use of abundant metals has attracted significant attention due to the issues with the scarcity of platinum group metals. Herein, we report a sequential method for the synthesis of benzylic alcohols by a merger of iron catalyzed cross-coupling and highly chemoselective reduction of benzamides promoted by sodium dispersion in the presence of alcoholic donors. The method has been further extended to the synthesis of deuterated benzylic alcohols. The iron-catalyzed Kumada cross-coupling exploits the high stability of benzamide bonds, enabling challenging C(sp2)–C(sp3) cross-coupling with alkyl Grign…
Selective oxidation of aromatic alcohols in the presence of C3N4 photocatalysts derived from the polycondensation of melamine, cyanuric and barbituri…
2021
AbstractA set of C3N4 samples has been prepared by using melamine, cyanuric acid and barbituric acid as the precursors. The materials were subjected both to physical and chemical characterization and were used as photocatalysts for the selective oxidation of aromatic alcohols in water suspension under UV and visible irradiation. The photoactivity of the materials versus the partial oxidation of four substituted benzyl alcohols was investigated. The type and position of the substituents in the aromatic molecule influenced conversion and selectivity to the corresponding aldehyde. The presence of barbituric and cyanuric acids in the preparation method has changed the graphitic-C3N4 structure, …
A practical entry to β-aryl-β-alkyl amino alcohols: application to the synthesis of a potent BACE1 inhibitor
2012
The 1,2-addition of alkyl Grignard reagents to readily available N-tert-butanesulfinyl ketimines, bearing an α-silyloxy substituent, proceeds in high yields and excellent diastereocontrol. The utility of the present method was demonstrated by the synthesis, in enantiomerically pure form, of one recently disclosed β-secretase (BACE1) inhibitor.
Single-pump bi-dimensional LC applied to the characterization of derivatized fatty alcohol ethoxylates.
2010
A column selection valve and a 6-port 2-position injection valve were combined to implement bi-dimensional LC in a system driven by a single pump. The system was applied to the separation of linear fatty alcohol ethoxylates with 12-18 carbon atoms in the hydrocarbon moiety, previous derivatization with diphenic anhydride. Separation on the first separation dimension (C(1)) was carried out with a propyl-diol column and an acetonitrile/aqueous ammonium acetate gradient. Fatty alcohol ethoxylate hydrocarbon series (oligomers with the same number of carbon atoms in the alkyl chain but differing in the number of ethylene oxide units) were resolved without distinguishing the oligomers within the …
Asymmetric synthesis of fluorinated amino macrolactones through ring-closing metathesis
2007
The synthesis of new chiral fluorinated amino and azamacrolactones of types 1 and 2 is described. A ring-closing metathesis (RCM) reaction constitutes the key step in this methodology, which uses fluorinated amino alcohols 7 as starting materials. The influence of the CF2 group, which is located in the alpha-position relative to the carbon bearing the amino group, on the efficiency of the RCM reaction is noteworthy. This method allows for the preparation of the desired fluorinated macrolactones in excellent yields.
Photoelectrocatalytic selective oxidation of 4-methoxybenzyl alcohol in water by TiO2 supported on titanium anodes
2013
The photoelectrocatalytic partial oxidation of 4-methoxybenzyl alcohol in aqueous solution irradiated by near-UV light was carried out in a three-electrode batch reactor. TiO2 films were either deposited by dip-coating of a TiO2 sol onto a Ti foil and subsequent calcination or generated on Ti plates by thermal oxidation in air at 400-700 degrees C. The effects of the anode preparation method and bias potential values on conversion and selectivity to the corresponding aldehyde were investigated. The photoelectrocatalytic results were compared with the photocatalytic and electrocatalytic ones. The results indicated that no reaction occurred during the electrocatalytic experiments, whereas the…
Single-pump heart-cutting two-dimensional liquid chromatography applied to the determination of fatty alcohol ethoxylates.
2014
Abstract A setup for heart-cutting bi-dimensional liquid chromatography (LC–LC), constructed with a chromatograph provided with a single pump, an auxiliary 6-port 2-position valve (V 6/2 ) and a column selector valve (V CS ), is described. The possible ways of connecting the two valves for LC–LC, namely with V 6/2 first followed by V CS and vice versa, are compared. The possibility of using the setups for preconcentration followed by the backwards transfer of the preconcentrated solutes to the detector or to a second column is also shown. The V 6/2 -first configuration for LC–LC was applied to the characterization of industrial fatty alcohol ethoxylates (FAEs) using UV–vis detection. For th…
On the determination of underivatised fatty alcohol ethoxylates by electrospray ionisation–mass spectrometry
2006
Abstract The oligomers of fatty alcohol ethoxylates (FAEs) exhibit large sensitivity differences in mass spectrometry with electrospray ionisation (ESI–MS) and atmospheric pressure chemical ionization (APCI). Standards of the oligomers from m = 1 to 7 ethylene oxide units (EOs) and linear alkyl chains from n = 10 to 18 carbon atoms were infused to examine the relative sensitivities or response factors in several media. The response factors of the [M + H]+ and [M + Na]+ peaks in 9:1 acetonitrile/water and methanol/water media containing acid buffers increased following irregular patterns when n and m increased. In methanol/water the response factors depended on the parity of m, being larger …
Stereoselectivity in the Addition of Organotitanium Reagents to Carbonyl Compounds
1986
Although great strides have been made in the area of stereoselective C—C bond forming reactions [1], many problems persist. Early studies concerning chemo- selective reactions of organotitanium reagents (Chapter 3) suggested that they might also behave stereoselectively in relevant cases. In fact, the first such observation goes back to 1979 when it was noted that dichlorodi- methyltitanium (2) adds to the ketone 1 in CH2C12 to produce a mixture of tertiary alcohols 4/5 instead of the desired (±) cuparene (3) [2, 3]. The striking aspect of this transformation is the high disastereoselectivity in favor of 4. Methyllithium shows the opposite stereoselectivity (4:5 = 34:66), in line with the s…
SN1 Reactions in Supercritical Carbon Dioxide in the Presence of Alcohols: the Role of Preferential Solvation
2016
Ethanol (3b) inhibits SN1 reactions of alkyl halides 1 in supercritical carbon dioxide (scCO2) and gives no ethers as products. The unexpected behaviour of alcohols 3 in the reaction of alkyl halides 1 with 1,3-dimethoxybenzene (2) in scCO2 under different conditions is rationalised in terms of Bronsted and Lewis acid–base equilibria of reagents, intermediates, additives and products in a singular solvent characterised by: (i) the strong quadrupole and Lewis acid character of carbon dioxide, which hinders SN2 paths by strongly solvating basic solutes; (ii) the weak Lewis base character of carbon dioxide, which prevents it from behaving as a proton sink; (iii) the compressible nature of scCO…