C-H stretching frequencies and C-H bond strengths of CH3X compounds

The influence of the X-group in CH₃X type molecules on the frequency of the C-H symmetrical stretching vibration has been investigated by means of normal coordinate analysis and CNDO/2 partial force constant and localized orbital calculations. The frequency of the C—H symmetrical stretching vibration was found to be dependent on the HCH angle α and the C—H symmetrical stretching force constant F_CH. By studying the partial force constants for a number of CH₃X type molecules a distinct relation between F_CH and the C—H bond length could be shown. With the help of localized orbital calculations a relation was found between the C—H bond length and the percentage ionic character of the C—H bond.     

Equilibrium acidities and homolytic bond dissociation energies of acidic C-H bonds in alpha-arylacetophenones and related compounds

The equilibrium acidities (pK(AH)s) and the oxidation potentials of the congugate anions [E(ox)(A(-))s] were determined in dimethyl sulfoxide (DMSO) for eight ketones of the structure GCOCH(3) and 20 of the structure RCOCH(2)G, (where R = alkyl, phenyl and G = alkyl, aryl). The homolytic bond dissociation energies (BDEs) for the acidic C-H bonds of the ketones were estimated using the equation BDE(AH) = 1.37pK(AH) + 23.1E(ox)(A(-)) + 73.3. While the equilibrium acidities of GCOCH(3) were found to be dependent on the remote substituent G, the BDE values for the C-H bonds remained essentially invariant (93.5 +/- 0.5 kcal/mol). A linear correlation between pK(AH) values and [E(ox)(A(-))s] was found for the ketones. For RCOCH(2)G ketones, both pK(AH) and BDE values for the adjacent C-H bonds are sensitive to the nature of the substituent G. However, the steric bulk of the aryl group tends to exert a leveling effect on BDEs. The BDE of alpha-9-anthracenylacetophenone is higher than that of alpha-2-anthracenylacetophenone by 3 kcal/mol, reflecting significant steric inhibition of resonance in the 9-substituted system. A range of 80.7-84.4 kcal/mol is observed for RCOCH(2)G ketones. The results are discussed in terms of solvation, steric, and resonance effects. Ab initio density functional theory (DFT) calculations are employed to illustrate the effect of steric interactions on radical and anion geometries. The DFT results parallel the trends in the experimental BDEs of alpha-arylacetophenones.     

Vibrational spectra of mono-, di- and trichloroacetamide and mono- and trifluoroacetamide

The Raman and infrared spectra of five α-halogenoacetamides; mono-, di- and trichloroacetamide (MCA, DCA and TCA) and mono- and trifluoroacetamide (MFA and TFA), in solid phase (KBr pellets and Nujol dispersion) and in solution in several solvents (ClCH₃, Cl₂CH₂, Br₂CH₂, CH₃CN and benzene), have been recorded in order to assign the fundamental bands. The vibrational assignments, the intermolecular hydrogen bonds and the equilibrium mixture of cis and trans isomers have been discussed.     

Cobalt-catalyzed, room-temperature addition of aromatic imines to alkynes via directed C-H bond activation

A quaternary catalytic system consisting of a cobalt salt, a triarylphosphine ligand, a Grignard reagent, and pyridine has been developed for chelation-assisted C-H bond activation of an aromatic imine, followed by insertion of an unactivated internal alkyne that occurs at ambient temperature. The reaction not only tolerates potentially senstitive functional groups (e.g., Cl, Br, CN, and tertiary amide), but also displays a unique regioselectivity. Thus, the presence of substituents such as methoxy, halogen, and cyano groups at the meta-position of the imino group led to selective C-C bond formation at the more sterically hindered ortho positions. Under acidic conditions, the hydroarylation products of dialkyl- and alkylarylacetylenes underwent cyclization to afford benzofulvene derivatives, while those of diarylacetylenes afforded the corresponding ketones in moderate to good yields. A mechanistic investigation into the reaction with the aid of deuterium-labeling experiments and kinetic analysis has indicated that oxidative addition of the ortho C-H bond is the rate-limiting step of the reaction. The kinetic analysis has also shed light on the complexity of the quaternary catalytic system.     

Radical hydroxyalkylation of C-H bond adjacent to nitrogen of tertiary amides, ureas, and amines

Tertiary amides, ureas, and amines undergo direct intermolecular addition to aldehydes under the Et3B/air conditions, thereby providing a unique and simple means for the radical sp3 C-H transformation of nitrogen-containing molecules.     

Simple method for the chromatographic separation and determination of mono-, di- and tricyclic aromatic hydrocarbons in heavier petroleum fractions

Summary The method described is a simple procedure for separating gas oil boiling range petroleum fraction into its aromatic hydrocarbons of the mono-, di- and trinucleartype. This is accomplished by gradient elution through an alumina adsorption column under established/standardised conditions. Characterisation is performed by UV-absorption. The method can be used also for investigating aromatic hydrocarbon structures from other petroleum fractions.

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Einfaches Verfahren zur chromatographischen Trennung und Bestimmung von mono-, di- und tricyclischen aromatischen Kohlenwasserstoffen in schwereren Erdölfraktionen

Zusammenfassung Zur Trennung der Erdölfraktion vom Siedebereich des Gasöls in die ein-, zwei- und dreikernigen aromatischen Bestandteile wird eine Gradientenelution an einer Aluminiumoxidsäule unter standardisierten Bedingungen angewendet. Zur Charakterisierung dienen UV-spektrometrische Messungen. Das Verfahren kann auch zur Untersuchung von Aromaten aus anderen Erdölfraktionen eingesetzt werden.

     

Highly efficient and enantioselective cyclization of aromatic imines via directed C-H bond activation

The first highly enantioselective catalytic reaction involving aromatic C-H bond activation is communicated. Enantioselective cyclization of aromatic ketimines containing alkenyl groups tethered at the meta position of an imine directing group has been achieved using 5 mol % [RhCl(coe)2]2 and 15 mol % of an (S)-binol-derived phosphoramidite ligand. Selectivities of up to 96% ee and up to quantitative yields were obtained. Moreover, the identified catalyst system enables the intramolecular alkylation reaction to be performed at temperatures 75 degrees C lower than our previously reported achiral system. The reaction can even be performed at room temperature for one of the optimal substrates.     

The Soret effect of mono-, di- and tri-glycols in ethanol

We employed thermal diffusion forced Rayleigh scattering (TDFRS) to investigate the chain length dependence of the thermal diffusion behavior of short glycols in ethanol. We studied three glycols, monoethylenglycol (MEG), diethylenglycol (DEG) and triethylenglycol (TEG), in an ethanol solution. In contrast to the polymer polyethylenglycol, the shorter glycols used within the framework of this study are completely soluble in ethanol, at least for low molar fractions. In order to guarantee a good solubility of the glycols, the measurements were limited to molar fractions of 10% and 20%. As the different glycols only differ by their chain length it will be possible to deduce its influence on the thermal diffusion properties. Due to the fairly short persistence length of the glycols, D(T) reaches already for the dimer a plateau value. This finding agrees with simulation results. Furthermore, the thermal expansion and the kinematic viscosity are measured to investigate if empirical correlations seen for other systems could be confirmed.     

C-H activation of terminal alkynes by tris-(3,5-dimethylpyrazolyl)boraterhodiumneopentylisocyanide: new metal-carbon bond strengths

C-H bond activation of terminal alkynes by [Tp'Rh(CNneopentyl)] (Tp' = hydridotris-(3,5-dimethylpyrazolyl)borate) resulted in the formation of terminal C-H bond activation products Tp'Rh(CNneopentyl)(C≡CR)H (R = t-Bu, SiMe(3), hexyl, CF(3), p-MeOC(6)H(4), Ph, and p-CF(3)C(6)H(4)). A combination of kinetic selectivity determined in competition reactions and activation energy for reductive elimination has allowed for the calculation of relative Rh-C(alkynyl) bond strengths. The bond strengths of Rh-C(alkynyl) products are noticeably higher than those of Rh-C(aryl) and Rh-C(alkyl) analogues. The relationship between M-C and C-H bond strengths showed a linear correlation (slope R(M-C/H-C) = 1.32), and follows energy correlations previously established for unsubstituted sp(2) and sp(3) C-H bonds in aliphatic and aromatic hydrocarbons.     

Facile synthesis of mono-, di-, and trisubstituted alpha-unbranched hydrazines

Methods for the alkylation of di-tert-butyl hydrazine-1,2-dicarboxylate were investigated. It was found that under mild conditions mono- or di-substituted hydrazine derivatives were obtained in good to excellent yield. Furthermore, it was shown that one of the two Boc-groups of the disubstituted derivatives was selectively removed by heating, leading to precursors for trisubstituted hydrazines.     

Thermal analysis of ammonium,mono-, di- and triethanolammonium alginates

Thermal behaviour of ammonium (NH₄alg), mono- (MEAalg), di- (DEAalg) and triethanolammonium (TEAalg) salts of alginic acid (Halg) was investigated by thermogravimetry (TG) and differential scanning calorimetry (DSC). Salts were prepared by the direct reaction of alginic acid with the ammonium hydroxide and with the respective ethanolamines. After preparation the compounds were lyophilized during 24 h and characterized by FTIR spectroscopy and elemental analysis (C, H and N). Under air the compounds exhibited three successive thermal decomposition steps: dehydration, decomposition of the polymeric matrix and finally, burning of carbonaceous residue. Under nitrogen two steps (dehydration and decomposition) were observed. The stability order of this series of compounds was: TEAalg this series of compounds was: TEAalg<DEAalg<NH₄alg<Halg≈MEAalg. DSC curves between –50 and 150°C did not show any thermal events suggesting that after lyophilization probably non-freezing type water is present in the system.     

Synthesis of mono-, di- and trisulfated Lewis x trisaccharides

3′-Sulfated and 3′,6′-disulfated Lewis x trisaccharides have been prepared through selective sulfation of methyl 2-acetamido-6-O-benzyl-2-deoxy-4-O-β-D-galactopyranosyl-3-O-(2,3,4-tri-O-benzyl-α-L-fucopyranosyl)-β-D-glucopyranoside, followed by catalytic hydrogenolysis. In a similar manner, 3′,6-disulfated and 3′,6,6′-trisulfated Lewis x trisaccharides have been selectively obtained from methyl 2-acetamido-2-deoxy-4-O-β-D-galactopyranosyl-3-O-(2,3,4-tri-O-benzyl-α-L-fucopyranosyl)-β-D-glucopyranoside.     

Synthesis of new chiral mono-, di-, tri-, and tetraalkylglycolurils

Two general procedures were developed for the synthesis of chiral N-mono-, N, N′-di-, N, N′ N″-tri-, and N, N′, N″, N′″-tetraalkylglycolurils based on the reactions of 4,5-dihydroxy-imidazolidin-2-ones or glyoxal with one or two moles of alkylureas, respectively, by acid catalysis. The reactions of N-monoalkyl- and N, N′-dialkylureas with glyoxal proceed regioselectively. The mechanism of these reactions was suggested and partly confirmed by quantum-chemical calculations and experimental data. The enantiomeric separation of some chiral glycolurils by chiral-phase HPLC was carried out for the first time.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 680–692, March, 2005.     

Copper-catalyzed oxidative trifluoromethylation of benzylic sp C-H bond adjacent to nitrogen in amines

Copper-catalyzed trifluoromethylation via oxidative sp³ C-H activation at the α-position of nitrogen in tetrahydroisoquinoline derivatives using DDQ and Ruppert-Prakash reagent has been successfully achieved. The reaction of various amines gave the corresponding trifluoromethylated products in 15-90% yields under mild conditions.     

Complexation of zinc octaalkylporphyrin with mono-, di-, and triethylenediamines in toluene

The complexation of zinc octaalkylporphyrin with mono-, di-, and triethylenediamines in toluene was studied by spectrophotometry using the molar ratio method and by ¹H NMR. The effect of the structure of the two-center organic base on the formation of 1 : 1 or 2 : 1 metal porphyrin-ligand complex was established. The stability constants of the resulting complexes were calculated and the concentration ranges of their existence were determined.     

Kinetic thermal analytical study of saturated mono-, di- and tri-glycerides

A thermal degradation study using TG–DTG thermogravimetry was performed on three saturated fatty acids esterified with glycerol (i.e. glyceryl-tristearate (C₁₈), -tripalmitate (C₁₆) and -trimyristate (C₁₄)) at different heating rates. In addition, thermogravimetry (TG) and derivative thermogravimetry (DTG) of glyceryl di-stearate and glyceryl mono-stearate were also carried out at different heating rates. A deconvolution procedure applied to the first process and overlapping at least two steps between about 200 and 350 °C, enabled the activation energy of decomposition to be determined both by the Kissinger and the Ozawa–Flynn–Wall isoconversional methods for the deconvoluted steps of the above-mentioned fatty acids.