Oxidation of alcohols by dimethyldioxirane

The kinetics of oxidation of a series of monoatomic alcohols (methanol, 2-propanol, 2-butanol, 2-methyl-1-propanol, 2-chloroethanol, 1,3-dichloro-2-propanol, benzyl alcohol), hydroxyacetic acid, and 1,3-butandiol (ROH) by dimethyldioxirane (1) was studied. The reaction kinetics obeys the second order equationw=k[ROH][1]. The rate constants were measured in the range of 7–50†C, and the activation parameters were found. To describe the reaction rate constants as a function of the ROH structure, the two-parametric Taft equation was used, which takes into account both the polar and resonance substituent effects. Alcohol oxidation produces the corresponding carbonyl compounds,viz., ketones from secondary alcohols and aldehydes from primary alcohols, in yields of at least 80%. The results were explained by the competition of the molecular (oxenoid) and radical mechanisms. The introduction of electron-withdrawing substituents into the alcohol molecule increases the contribution of the radical channel of the reaction. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1338–1343, August, 2000.     

Kinetics of hydrolysis of 4-methoxyphenyl-2,2-dichloroethanoate in binary water-cosolvent mixtures; the role of solvent activity and solute-solute interactions

Rate constants are reported for the pH-independent hydrolysis of 4-methoxyphenyl-2,2-dichloroethanoate in aqueous solution as a function of the concentration of added cyanomethane (acetonitrile), polyethylene glycol (PEG 400) and tetrahydrofuran (THF). The concentration of water was varied between ca. 25 and 55.5 M. It was found that the variation in water activity yields only a minor contribution to the observed variation in rate constants. Interestingly, for both cyanomethane and PEG 400 log(k) varies approximately linearly with the molar concentration of water. Medium effects in highly aqueous solutions ([H(2)O] > 50 M) of ethanol, 1-propanol, 2-propanol, 1-butanol and 2-methyl-2-propanol have also been determined. Unexpectedly, in this concentration range the alcohols induce significantly smaller effects per unit volume than cyanomethane. The present results are discussed in terms of pairwise interaction parameters. Isobaric activation parameters have been determined and reveal remarkable differences in the nature of the induced medium effects.     

Liquid chromatographic determination of alcohols in food and beverages with indirect polarimetric detection using a beta-cyclodextrin mobile phase.

An indirect polarimetric detection method for the determination of alcohols has been proposed in liquid chromatography (LC). Optically active mobile-phase additives, such as beta-cyclodextrin (beta-CD), could be used to visualize optically inactive alcohols in reversed-phase LC. The visualization of alcohols is based on a perturbation of the partition of beta-CD caused by the alcohols. The detection limits of the present system at a signal-to-noise ratio of 3 were 0.031, 0.019, 0.018, 0.013, 0.011, 0.008 and 0.008% (v/v) for ethanol, 2-propanol, 1-propanol, 2-methyl-2-propanol, 2-butanol, 2-methyl-1-propanol and 1-butanol, respectively. The method was successfully applied to the determination of ethanol present in food and beverage samples.     

The role of proton donors in SmI2-mediated ketone reduction: new mechanistic insights

The effects of proton donors (alcohols and water) on the rate of reduction of acetophenone by SmI2 have been examined utilizing stopped-flow spectrophotometric studies. The rate orders with respect to proton source and the kinetic isotope effects were determined as well. The reaction was first-order in phenol, 2,2,2-trifluoroethanol, methanol, and ethanol and zero-order in 2-propanol and 2-methyl-2-propanol when 25 equiv of proton source were used in the reduction. Methanol, ethanol, 2,2,2-trifluoroethanol, and phenol also showed a direct correlation between the pKa of the alcohol and the rate of reduction. Under the same conditions, water had a fractional rate order of 1.4. Further studies showed that water has a rate order of 1 at lower concentrations (<8 equiv) and a rate order of 2 at higher concentrations (>80 equiv). These results clearly indicate that the nature of the proton donor and its concentration affects the rates of reduction. Water has a high affinity for SmI2 (compared to that of the alcohols), and the onset of coordination at relatively low concentrations channels the reaction through a mechanistically distinct pathway.     

Reactions of nitro alcohols with n,n-diethyl-1,1,2,3,3,3-hexafluoropropylamine

Fluorination of nitro alcohols with N,N-diethyl-1,1,2,3,3,3-hexafluoropropylamine (PPDA) was investigated. 3-Nitrobenzyl fluoride (II) was obtained from the reaction of PPDA and 3-nitrobenzyl alcohol (I) (yield 66%). The reaction of 2-methyl-2-nitro-1-propanol (IV) with PPDA given 2-methyl-2-nitropropyl 2,3,3,3-tetrafluoropropionate (V). reduction of 3-nitrobenzyl fluoride (II) with lithium aluminium hydride gave the corresponding amino compound, 3-aminobenzyl fluoride (VI) in poor yield.     

Photoinduced electron-transfer substitution reactions via unusual charge-transfer intermediates.

The photoinduced substitution reactions of halogenated alkanes (1-haloadamantanes, 1-haloronorbornanes, menthyl chloride) with a homologous series of amines or alcohols (methylamine, 2-methyl-2-aminopropane, methanol, or 2-methyl-2-propanol) to form the corresponding alkane-substituted amines or ethers and HCl were investigated. The geometry of the bridgehead carbons made S(N)2 reactions impossible. Nonpolar reaction conditions were employed which made classical and nonclassical carbocation S(N)1 reaction pathways unlikely. The reaction rates were measured. Trapping experiments indicated that free radical reactions were uninvolved in the substitution product formation. A novel, photoinduced electron-transfer reaction mechanism involving a charge-transfer intermediate is proposed to explain the observed production of secondary amines and ethers. The excitation wavelength dependence (action spectrum) was measured and found to be comparable to the ultraviolet absorption spectra of the charge-transfer complexes. The stereochemical implications of the reaction mechanism were investigated. The formation of the methyl ether of (1R,2S,5R)-menthol was the only organic reaction product observed in the photoreaction between (1R,2S,5R)-menthyl chloride and methanol.     

Ultrasonic velocities and isentropic compressibilities of N-methyl-2-pyrrolidone with ketones and branched alcohols at 303.15 K

The ultrasonic sound velocities and densities are measured for the binary mixtures of N-methyl-2-pyrrolidone (NMP) with ketones and branched alcohols at 303.15?K. The ketones include methyl ethyl ketone, methyl propyl ketone, diethyl ketone, methyl isobutyl ketone and cyclohexanone. The branched alcohols include 2-propanol, 2-methyl-1-propanol, 3-methyl-1-butanol, 2-butanol and 2-methyl-2-propanol. The ultrasonic sound velocity data were used to compute isentropic compressibilities (k _s). The deviations in the value of k _s from ideal value were computed. Except cyclohexanone all the binary mixtures formed by NMP with ketones at 303.15?K exhibit negative deviation from ideal behaviour over the entire range of composition. Cyclohexanone with NMP exhibit positive deviation over the entire range of composition. An inversion in the sign of Δk _s from positive to negative was observed for 2-propanol system and negative deviation was observed in four binary mixtures formed by NMP with other branched alcohols at 303.15?K. The ultrasonic sound velocities of these mixtures have been analysed is terms of Free Length Theory (FLT), Collision Factor Theory (CFT) and Nomoto's relation.     

Recombination dynamics and hydrogen abstraction reactions of chlorine radicals in solution

We observe chlorine radical dynamics in solution following two-photon photolysis of the solvent, dichloromethane. In neat CH(2)Cl(2), one-third of the chlorine radicals undergo diffusive geminate recombination, and the rest abstract a hydrogen atom from the solvent with a bimolecular rate constant of (1.35 +/- 0.06) x 10(7) M(-1) s(-1). Upon addition of hydrogen-containing solutes, the chlorine atom decay becomes faster, reflecting the presence of a new reaction pathway. We study 16 different solutes that include alkanes (pentane, hexane, heptane, and their cyclic analogues), alcohols (methanol, ethanol, 1-propanol, 2-propanol, and 1-butanol), and chlorinated alkanes (cyclohexyl chloride, 1-chlorobutane, 2-chlorobutane, 1,2-dichlorobutane, and 1,4-dichlorobutane). Chlorine reactions with alkanes have diffusion-limited rate constants that do not depend on the molecular structure, indicating the absence of a potential barrier. Hydrogen abstraction from alcohols is slower than from alkanes and depends weakly on molecular structure, consistent with a small reaction barrier. Reactions with chlorinated alkanes are the slowest, and their rate constants depend strongly on the number and position of the chlorine substituents, signaling the importance of activation barriers to these reactions. The relative rate constants for the activation-controlled reactions agree very well with the predictions of the gas-phase structure-activity relationships.     

Effects of alcohols on CE enantioseparation of basic drugs with native gamma-CD as chiral selector

The effects of alcohol on the CE enantioseparation of selected basic drugs with gamma-CD as the chiral selector was investigated. The enantioseparation behavior of the analytes with gamma-CD in the absence and presence of different alcohols specifically methanol, ethanol, 2-propanol (IPA), and 2-methyl-2-propanol (TBA), the relationship of enantiomeric resolution (R(s)) values with either hydrophobicity or bulkiness of the alcohols, as well as the effect of these alcohols on interaction of the analytes with gamma-CD were studied. Results showed that hydrophobicity and/or bulkiness of alcohols have an influence on the enantioresolution of most of the analytes based on the relatively high correlation coefficients (R) obtained between R(s) versus log P and between R(s) versus ovality (i.e., parameter to indicate bulkiness of a molecule). Comparison of the values of the average binding constants obtained for each enantiomeric pair in the presence and absence of 5% IPA showed that alcohols can increase, decrease, or give a minimal effect on the analyte-gamma-CD interaction depending on the analyte. Furthermore, the significant enhancement in the enantioresolution of both propranolol and pindolol in the presence of either IPA or TBA led to the baseline enantioresolution of both drugs using 35 mM gamma-CD.     

Formation of π-Allyl Palladium Complexes from Tertiary Alcohols

Reactions of 2-methyl-2-propanol, 2-methyl-2-butanol, 2-methyl-2-pentanol, 1-methyl-1-cyclohexanol, and 1-ethyl-1-cyclohexanol with palladium(II) tetraaqua complex in a perchloric acid medium give carbonyl and aromatic compounds, as well as the corresponding palladium -allyl complexes. The complexes were isolated from the reaction mixtures by way of formation of 2,2'-bipyridine complexes and characterized by the elemental analyses and ¹H and ¹³C NMR spectra. The main direction of transformation of acyclic alcohols is formation of complexes with no alkyl substituents at the central carbon atom of the allyl ligand; with cyclic alcohols, exocyclic complexes are formed.     

Control of the porosity of asymmetric TPX membranes

In the present work, the effect of adding nonsolvent in the casting solution on the porosity of asymmetric TPX (poly(4-methyl-1-pentene)) membranes was systematically investigated. A series of alcohols, with carbon number ranging from 2 to 14, was added in the casting solution (TPX/cyclohexane) to alter the porosity of two types of asymmetric TPX membranes, prepared by using ethanol and 1-propanol as the coagulation medium. It was found that the effect of nonsolvent on membrane porosity is different for the two types of membranes and the difference can be reasoned by considering the exchange rate between the polymer solvent and the coagulation medium during membrane formation. The results indicate that, for the membrane formation system with low exchange rate between coagulant and solvent, the membrane porosity is controlled by the coagulation value, defined as the volume of coagulant required to demix the casting solution. On the other hand, for the system with high exchange rate, the membrane porosity is not controlled by the coagulation value but by the penetration speed of the coagulant front moving through the casting solution.     

Thermosolvatochromism of betaine dyes revisited: theoretical calculations of the concentrations of alcohol-water hydrogen-bonded species and application to solvation in aqueous alcohols

Solvatochromic data of 2,6-diphenyl-4-(2,4,6-triphenylpyridinium-1-yl)phenolate (RB) in aqueous methanol, 1-propanol, 2-propanol, and 2-methyl-2-propanol at 25 degrees C were recalculated by employing a recently introduced model that explicitly considers the presence of 1:1 alcohol-water hydrogen-bonded species, ROH-W, in bulk solution and their exchange equilibria with water and alcohol in the probe solvation microsphere. The thermosolvatochromic behavior of RB in aqueous ethanol was measured in the temperature range from 10 to 60 degrees C; the results thus obtained were treated according to the same model. All calculations require reliable values of Kdissoc, the dissociation constant of the ROH-W species. This was previously calculated from the dependence of the density of the binary solvent mixture on its composition. Through the use of iteration, the volume of the hydrogen-bonded species, VROH-W, and Kdissoc are obtained simultaneously from the same set of experimental data. This approach may be potentially problematic because Kdissoc and VROH-W are highly correlated. Therefore, we introduced the following approach: (i) VROH-W was obtained from ab initio calculations, (ii) these volumes were corrected for the nonideal behavior of the binary solvent mixtures at different temperatures, (iii) corrected VROH-W values were employed as a constant in the equation used to calculate Kdissoc (from density vs binary solvent mixture composition). VROH-W calculated by the COSMO-RS solvation model fitted the density data better than those calculated by the IEFPCM model. In all aqueous alcohols, solvation by ROH-W is favored over that by the two precursor solvents. In aqueous ethanol, a temperature increase resulted in a gradual desolvation of RB, due to a decrease in the hydrogen-bonding of both components of the mixture. The microscopic polarities of ROH-W are much closer to those of the precursor alcohols.     

Effect of the Composition of the Aqueous Organic Solvent on the Kinetics of N-Acylation of α-Amino Acids with 4-Nitrophenyl 4-Nitrobenzoate

Equations relating the N-acylation rate constants of glycine, L--alanine, DL-threonine, and L-proline with 4-nitrophenyl 4-nitrobenzoate in water-acetonitrile, water-2-propanol, and water-2-methyl-2-propanol solvents to the composition of the medium were obtained, and reaction rate constants in water were calculated.     

Solvent effects in the reaction of 2-thiophenesulfonyl chloride with aniline

The second order rate constants k₂ and the activation parameters for the reaction of 2-thiophenesulfonyl chloride with aniline together with solution enthalpies of the reactants have been measured in methanol, ethanol, 2-propanol, acetonitrile and acetone. The reaction rates are slower in dipolar aprotic solvents than in protic ones due to a remarkable activation negative entropy. The rate constants k₂ are correlated with empirical solvent polarity parameters. The data seem in accord with a S_AN reaction mechanism.     

Mesoporous silica-supported uranyl: synthesis and photoreactivity

A mesoporous silica-supported uranyl material (U(aq)O(2)(2+)-silica) was prepared by a co-condensation method. Our approach involves an I(-)M(+)S(-) scheme, where the electrostatic interaction between the anionic inorganic precursor (I(-)), surfactant (S(-)), and cationic mediator (M(+)) provides the basis for the stability of the composite material. The synthesis was carried out under acidic conditions, where the anionic sodium dodecyl sulfate provided the template for the uranyl cation and silicate to condense. Excitation with visible or near-UV light of aqueous suspensions of U(aq)O(2)(2+)-silica generates an excited state that decays with k(0) = 1.5 x 10(4) s(-1). The reaction of the excited state with aliphatic alcohols exhibits kinetic saturation and concentration-dependent kinetic isotope effects. For 2-propanol, the value of k(C)3(H)7(OH)/k(C)()3(D)7(OH) decreases from 2.0 at low alcohol concentrations to 1.0 in the saturation regime at high alcohol concentrations. Taken together, the data describe a kinetic system controlled by chemical reaction at one extreme and diffusion at the other. At low [alcohol], the second-order rate constants for the reaction of silica-U(aq)O(2)(2+) with methanol, 2-propanol, 2-butanol, and 2-pentanol are comparable to the rate constants obtained for these alcohols in homogeneous aqueous solutions containing H(3)PO(4). Under slow steady-state photolysis in O(2)-saturated suspensions, U(aq)O(2)(2+)-silica acts as a photocatalyst for the oxidation of alcohols with O(2).     

Electrocatalytic oxidation of alcohols by a carbon-supported Rh porphyrin

A Rh porphyrin on carbon black was shown to catalyze the electro-oxidation of several aliphatic alcohols (ethanol, 1-propanol, and 2-propanol) and benzyl alcohols. The overpotentials for alcohol oxidation were very low. The reaction mechanism and substrate specificity are discussed.     

Excess enthalpies of binary solvent mixtures of 2-butanone with aliphatic alcohols

The molar excess enthalpies of binary solvent mixtures of 2-butanone with methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and 2-methyl-2-propanol have been measured with a flow microcalorimeter at 313.15 K. The excess enthalpies are positive over the whole composition range for all alcohols studied. The values for the primary alcohols increase with the length of the alkyl chain of the alcohol. The values for the secondary and the tertiary alcohol are slightly greater than those for the primary analogues. The partial molar excess enthalpies have also been evaluated. The results are discussed in terms of intermolecular interactions in the mixtures.     

Phosphazene Base tBu-P4 Catalyzed Methoxy–Alkoxy Exchange Reaction on (Hetero)Arenes

The organic superbase tBu-P4 catalyzes methoxy-alkoxy exchange reactions on (hetero)arenes with alcohols. The catalytic reaction proceeded efficiently with electron-deficient methoxy(hetero)arenes as well as with a variety of alcohols, including 3-amino-1-propanol, β-citronellol, menthol, and cholesterol. An intramolecular version of this reaction furnished six- and seven-membered ring compounds.     

Preparation of polysiloxanes from silicic acid. VII. Effects of the degree of esterification and alkyl groups on condensations of silicic acid esters and formation of fibrous silica

Silicic acid esters were prepared by the reaction of the silicic acid in tetrahydrofuran with various alcohols such as such as methanol, ethanol, 2-propanol, 1-butanol, 2-methyl-2-propanol and 1-octanol, using an esterification apparatus designed especially to allow the preparation of silicic acid esters from alcohols with low boiling points or appreciable steric hindrance. With the intent of obtaining a spinnable ester solution by condensation of silicic acid esters, the effects of the degree of esterification (DE) and alkyl group on gel time and spinnability are investigated. An increase in the DE and the size of the alkyl group led to an increase in the gel time of the esters. Esters solutions with a good spinnability were prepared from n-butyl and isopropyl esters with DEs of 40–50%. In addition, the gel permeation chromatography of condensing esters with low DEs showed a rapid increase in molecular weight. The results showed that spinnability depended on DE and the ester's alkyl group. Fibers could be formed with length of about 10–100 cm from ethyl, isopropyl, and n-butyl esters with DEs 40–50% and with length of 10 cm from octyl ester with DE 26%.