Study of pre-equilibrium effects on α-induced reactions on copper

A stack of natural copper was bombarded with -particles. Cumulative cross-sections for⁶⁵Ga,⁶⁶Ga and⁶⁵Zn production, and the excitation functions for⁶⁸Ga and⁶⁷Ga production, were measured using high resolution gamma-ray spectroscopy. The data are compared with the theoretical result provided by equilibrium and pre-equilibrium reaction model, for this purpose we used the code ALICE of Blann. The overall agreement with theory is good. Besides, we present the experimental data obtained by other authors.     

Synthesis and Stereochemistry of α-Aryl-β-Nitroalkylphosphinate

Abstract

Twenty-three new α -aryl-β -nitroalkylphosphinates 3a - g were synthesized in high yields under very mild conditions. Compounds 3 consist of two pairs of diastereomeric isomers (A) and (B)     

Reactions of organometallics with oximes. Synthesis of α-N-hydroxy amino acids

Reaction of organolithium reagents with glyoxylate and pyruvate derived oximes provides a direct route for the synthesis of unusual α-N-hydroxy amino acids.     

Synthesis of α-amino oximes and bis-α-amino oximes from the monoterpene hydrocarbons 3-carene and α-pinene and α,ω-diamines

The reaction of nitroso chlorides of natural monoterpene hydrocarbons, 3-carene and -pinene, with simple ,-diamines (1,2-diaminoethane, 1,3-diaminopropane, piperazine, 1,6-diaminohexane, diethylenetriamine) results in the formation of -amino oximes and bis--amino oximes. The product structures were proved by spectroscopy. The procedures of separation and purification of diamino oximes and diamino dioximes are described. Detailed analysis of the ¹H and ¹³C NMR spectra of the new chiral nitrogen-containing derivatives was carried out.     

Stereoselective synthesis of α-substituted serines from protected erythrulose oximes

The additions of organolithium reagents to the CN bond of several chiral oxime ethers derived from erythrulose afforded protected amino polyols with high diastereoselectivity. Four of the latter compounds have been converted into the α,α-disubstituted α-amino acids (R)-2-(−)-methylserine, (S)-2-(+)-methylserine, (R)-(+)-2-phenylserine and (R)-(−)-2-n-butylserine.     

Enantioseparation of α-cyclohexylmandelic acid by solvent sublation

Herein we focused on using a novel separation technology, solvent sublation, for the enantioseparation of α-cyclohexylmandelic acid (CHMA). The experiment was carried out in a conventional bubble column using d-iso-butyl tartrate (d-IBTA) and sodium dodecyl sulfate (SDS) as a chiral selector and surfactant, respectively (Fig. 7). Several important parameters influencing the separation performance, such as the type of organic phase, the pH in the aqueous phase, and the concentrations of CHMA, d-IBTA, and SDS were investigated. Under the optimal operating conditions, the enantiomeric excess and separation factor were 54.85% and 4.5, respectively. The yields of d-enantiomer and l-enantiomer were 82.20% and 38.94%, respectively. Finally, the thermodynamic properties of the separation were investigated, which indicated an enthalpy-controlled process. This technique is an efficient chiral separation method, with many advantages, such as low amounts of organic solvent and chiral selector required and easier realization of the multi-stage operation.     

Insights for diastereoselective synthesis of cyclic α-sulfinyl and sulfanyl oximes

The comparison in several reaction conditions for synthesis of nonracemic α-methylsulfinylation of 3,4-dihydronaphthalen-1(2H)-one was achieved. The sulfanylation reactions of 3,4-dihydronaphthalen-1(2H)-one-O-methyloxime and 2-(methylsulfinyl)-3,4-dihydronaphthalen-1(2H)-one-O-methyloxime by homogenous reaction medium are reported. The products were obtained in good yields and de. The yields, diastereoselectivity and theoretical calculations to all obtained compounds to support the experimental data are compared and discussed.     

Stereochemistry of Substitution of the α-Dimethylamino Group by Dialkylzinc in Chiral Benzylferrocene

The stereochemistry of the substitution of the α-dimethylamino group by dimethylzinc in the presence of acetyl chloride in the chiral benzylferrocene backbone was examined. The reaction with the benzylferrocene bearing an o-bromo substituent at both ferrocene and the phenyl ring proceeded with inversion of configuration, while the reaction with the benzylferrocene bearing an o-bromo substituent at either ferrocene or the phenyl ring proceeded with retention of configuration.     

Spectrometric Study of α-Phenylcinnamic Acids

TheanalwisofMSdataofl4substitutalatwcbocacidsindicateSaclassofpeificfragmenpeakS(Tatrl)'fllcdevelopn1en1oftLhesefragmentPeaksistnggeredb)].3-shift[1J7-heMSIYapoenta[1onpattenlot'compotmdf;8belou'illustratesthegenera1mechanjs1nScbemc.lTbemajorMShagmentationpatternofa-phenysubstitutedcinnamicacidAstheSCheInshows,afterthel,3-shiftofhydr0xyinCOmpoUndE8-tberesultinginterInwhatewhllosetheRCX=0grOUfollowinthebondeq,chchleadstOtheformationofmlZl25anditscomPleInentaIyPeakYnlzl63,withthebo…     

Assessment of solvent effects: do weak alignment media affect the structure of the solute?

Alignment media used for measuring residual dipolar couplings, such as solutions of filamentous phages, phospholipid mixtures, polyacrylamide gels and various lyotropic liquid crystalline systems were investigated with respect to solvent effects on molecular structure. Structural parameters of the small rigid model compound 13C-acetonitrile were calculated from dipolar couplings and variations from expectation values were used for assessment of solvent effects. Only minor solvent effects were observed for most of the media employed and the measured structural data are in good agreement with microwave data and theoretical predictions.     

Synthesis and Stereochemistry of some New Unsymmetrical Phosphates with α-Poly-fluoroalkylbenzyl Fragments

Abstract

The methods of synthesis unsymmetrical polyfluoroalkyl phosphates (II) by catalytic phosphorylation of phenols or polyfluoroalkanols by chlorophosphates (I) were elaborated     

The Stereochemistry of the Reaction of α-Silyl Lithium Reagents with Cyclic Tert-butyldimethylsilyl Acyloins

The reactions of the tert-butyldimethylsilylated acyloins of five-, six- and seven-membered rings with the lithium reagents of benzyltrimethylsilane, thiophenoxymethyltrimethylsilane and tri-methylsilyl acetonitrile were studied. These reactions favor formation of the substituted (Z) exo methylidene silyl ethers in moderate yields.     

Study of dissociation of α-alkyl-substituted dicarboxylic acids

Dissociation of α-alkyl-substituted dicarboxylic acids low-soluble in water was studied by the method of pH-potentiometry titration. Equilibrium constants of the dissociation at 25°C were determined.     

Partition constants of α-aminophosphonates in two-phase aqueous-organic solvent systems

Two-phase potentiometric titration was used to determine partition constants for a series of -aminophosphonates (RO)₂P(O)CH₂NR¹R² [R = Alk (C₂-C₅), R¹, R² = Me, Et, (CH₂)₅] between water and organic solvents, such as chloroform, carbon tetrachloride, toluene, octane, n-octanol, nitrobenzene, o-xylene, and cyclohexane. Correlations between the partition constants and the number of carbon atoms in substrate molecules were obtained. Solvent effects on partition constants were discussed, and solution parameters of -aminophosphonates were calculated.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 12, 2004, pp. 1998–2002.Original Russian Text Copyright © 2004 by Garifzyanov, Nuriazdanova, Zakharov, Cherkasov.This revised version was published online in April 2005 with a corrected cover date.     

Study on the Reaction of α-Ketohemithioacetal

Aromatic α-sulfinyl carboxylic acids can be rearranged to hemithioacetals or other derivatives of glyoxylic acid under the action of acid reagents was first reported by Pummerer¹. Later, Russell and coworkers applied this rearrangement to β-ketosulfoxides, synthesized α-ketohemithioacetal², which can be transformed to α-keto alcohol, α-keto aldehyde and α-hydroxy alcohol, α-hydroxy acid³. Furthermore, Hall and Poet reported that α-ketohemithio-acetal can be rearranged to the corresponding α-hydroxythioester in the presence of magnesium nitrate and sodium acetate or tertiary amine⁴. However, few reports of reaction of α-ketohemithioacetal can be seen in literature.     

Study on the Reaction of α-Thiobenzoylthioformylmorpholine

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Are the solvent effects critical in the modeling of polyoxoanions?

DFT calculations were driven for a set of differently charged polyoxoanions in the gas phase and in solution. We have calculated and analyzed their geometries and orbital energies to trace simple rules of behavior regarding the modeling of anions in isolated form. We discuss the quality of the results depending on the molecular charge, q, and the size of the cluster in terms of the number of metal centers, m. When the q/m ratio reaches a value of approximately 0.8, DFT calculations for the isolated anion fail to describe the gap between the band of occupied oxo orbitals and the set of unoccupied orbitals delocalized among the metal atoms. In these cases the incorporation of the stabilizing external fields generated by the solvent through continuum models improves the geometries and orbital energies.     

Chemoselective coupling of sugar oximes and α-ketoacids to glycosyl amides and N-glycopeptides

The reaction of unprotected sugar hydroxylamines and oximes with α-ketoacids leads to the chemoselective formation of glycosyl amides following the decarboxylative condensation pathway of Bode’s ketoacid hydroxylamine (KAHA) ligation. Sugar oximes with gluco configuration stereoselectively form β-linked products. This method can be used for the convergent synthesis of N-acylated sugars and oligosaccharides bearing small labels, spacers, or peptides in the acyl part.     

One-pot α-nucleophilic fluorination of acetophenones in a deep eutectic solvent

Two methods of nucleophilic fluorination to prepare α-fluoroacetophenones from α-bromoacetophenones by using KF with PEG-400 or TBAF with ZnF₂ are described. On the fundamental of nucleophilic fluorination, a novel method of one-pot fluorination to prepare α-fluoroacetophenones directly from acetophenones in DES was developed.