Acylation of N-p-toluenesulfonylpyrrole under Friedel-Crafts conditions: evidence for organoaluminum intermediates

The Friedel-Crafts acylation of N-p-toluenesulfonylpyrrole under Friedel-Crafts conditions has been reinvestigated. Evidence is presented in support of the hypothesis that when AlCl₃ is used as the Lewis acid, acylation proceeds via reaction of an organoaluminum intermediate with the acyl halide. This leads to the production of the 3-acyl derivative as the major product. With weaker Lewis acids (EtAlCl₂, Et₂AlCl) or less than 1 equiv of AlCl₃ the relative amount of 2-acyl product is increased. A mechanistic rationalization is presented to explain these data.     

Aerobic alcohol oxidation using a PdCl2/N,N-dimethylacetamide catalyst system under mild conditions

A new and simple PdCl₂/DMA catalytic system for the alcohol oxidation has been developed using molecular oxygen as the sole oxidant under mild conditions. The catalytic system could be reused for three runs without significant loss of catalytic activity. A variety of active and non-active alcohols were oxidized to their corresponding carbonyl compounds in good to excellent yields. Gas-uptake kinetics for the catalytic system was also investigated. The ca. 1:1 molar ratio of O₂ uptake to product yield is observed, suggesting the in situ formation of H₂O₂.     

One pot synthesis using supported reagents system KSCN/SiO2-RNH3OAc/Al2O3: synthesis of 2-aminothiazoles and N-allylthioureas

A simple and efficient method has been developed for the synthesis of 2-aminothiazoles and N-allylthioureas from commercially available materials in one pot by using a supported reagents system, KSCN/SiO₂-RNH₃OAc/Al₂O₃, in which α-halo ketone reacts first KSCN/SiO₂ and the product, α-thiocyanatoketone, reacts with RNH₃OAc/Al₂O₃ to give the final product, 2-aminothiazoles, in good yield and allyl bromide reacts with KSCN/SiO₂ and the product, allyl isothiocyanate, reacts with RNH₃OAc/Al₂O₃ to give N-allylthiourea.     

Distorted-wave calculations for the three dimensional chemical reaction H + H2(v ⩽ 2, j = 0) → H2(v′ ⩽ 2, j′, mj) + H

Calculations of the vibrational—rotational product state population distributions and differential cross sections for the chemical reaction H + H₂(v ? 2, j = 0) → H₂(v′ ? 2, j′, m_j) + H have been carried out on the Porter—Karplus potential energy surface. The vibrationally-adiabatic-distorted-wave (VADW) method has been used. The relative rotational product distributions, differential cross sections and the helicity m_j, dependences of these quantities for the v = 0 reaction agree well with accurate close-coupling results. The absolute integral cross sections are considerably smaller than the accurate quantum values, however. The calculations for the v = 1 reaction agree with the findings of previous sudden quantum, limited close-coupling and quasiclassical theoretical studies and experiments that product H₂(v′ = 1) is more likely to be produced than H₂(v′ = 0). For the reaction with v = 2, it is found that at high translational energies product H₂(v′ = 2) is favoured over H₂(v′ = 1) or H₂(v′ = 0). The VADW differential cross sections for the v = 1 and v = 2 reactions have a similar shape to those of the v = 0 reaction, with backward peaking when summed over all m_j states. The relative rotational distributions for the v = 2, j = 0 → v′ = 2, j and v = 1, j = 0 → v′ = 1, j reactions are also similar to those obtained for the v = 0, j = 0 → v′ = 0, j reaction, with low rotational excitation.     

Highly diastereoselective 1,2-dichlorination of glycals using NCS/PPh3: study of substituent and solvent effects

Highly diastereoselective 1,2-dichlorination of glycals has been achieved at room temperature conditions in good to excellent yields using a milder, more convenient, less hazardous reagent combination NCS/PPh₃ giving only one major product out of four possible diastereomers [either α-gluco (2) or α-manno (4)] depending upon the substituents. The diastereoselectivity is maximum (100% α/β-selectivity as well as cis/trans selectivity) for d-galactal and l-rhamnal derivatives. Detailed studies showed that solvent and substituent effects play a significant role in determining the product distribution.     

Solid state reactions in the system Nb2O5·WO3: An electron microscopic study

Lattice imaging electron microscopy has been used to study the mechanism of solid state reactions of the type: A_s → B_s + C_s, in which the product B is able to intergrow coherently with the starting material A, but the product C cannot do so. C must be formed by a fully reconstructive, heterogeneous process; formation of B is only partially reconstructive, and essentially homogeneous. Reactions were the reversible phase reactions in the system Nb₂O₅WO₃: disproportionation of the (5 × 4)₁ block structures of 8Nb₂O_5·5WO₃, to form (4 × 4)₁ blocks of 7Nb₂O_5·3WO₃ as coherent product, and that of 9Nb₂O_5·8WO₃ (with (5 × 5)₁ blocks), forming (5 × 4)₁ blocks of 8Nb₂O_5·5WO₃ as coherent product. The coherent product structure is formed in isolated rows of blocks, or small packets of such rows, running across each crystal. The reaction does not work in progressively from some surface initiating step, with an interface between unchanged and converted material, but represents a block-by-block conversion, linearly propagated. Nb₂O₅ and WO₃ must be abstracted, in appropriate stoichiometric ratio, from each block but must ultimately reach and react at the surface, to form the incoherent product (a pentagonal tunnel network structure, in both cases). Some homogeneous transport process involving lattice diffusion must be invoked. Domains of highly anomalous structure, regarded as relicts of transient conditions, are occasionally observed. From reactions at relatively low temperatures, these have structures that can be regarded as partially ordered nonstoichiometric solid solutions; after prolonged heating, and at higher temperatures they form well ordered strips of metastable block structures. Both types represent strong, spontaneous fluctuations of composition, which impose a corresponding structure locally. These fluctuations may be associated with the transport of WO₃ and Nb₂O₅ away from the locus of reaction. Evidence about the mechanism of the reactions, the role of dislocations and the nature of cooperative processes is considered.     

Facile oxygenation of organic sulfides with H2O2 catalyzed by Mn-Me3TACN compounds

Two binuclear Mn-Me₃TACN (Me₃TACN is 1,4,7-N,N′,N″-trimethyl-1,4,7-triazacyclononane) compounds catalyze the oxygenation of organic sulfides utilizing H₂O₂ under ambient conditions. Both phenyl sulfide and ethyl phenyl sulfide were converted to the corresponding sulfones and chloroethyl phenyl sulfide proceeds to its elimination product of phenyl vinyl sulfone.     

An unusual oxidation-dealkylation of 3,4-dihydropyrimidin-2(1H)-ones mediated by Co(NO3)2·6H2O/K2S2O8 in aqueous acetonitrile

4-Aryl-6-methyl-3,4-dihydropyrimidin-2(1H)-one (DHPM) scaffolds of Biginelli type were oxidized using Co(II)/S₂O₈²⁻ and the reaction afforded 6-unsubstituted pyrimidin-2(1H)-ones through an unprecedented dealkylation process. 4-Alkyl DHPMs under similar conditions afforded yet another unusual product, ethyl tetrahydropyrimidin-2,4(1H,3H)-dione-5-carboxylate.     

Reaction of RF-palmitic acid-F13 with dicyclohexylcarbodiimide

The 1,3-dicyclohexylcarbodiimide (DCC) adduct of R_F-palmitic acid-F₁₃1 has been synthesized and characterized. The X-ray crystal structure shows that the product arises from an O- to N-acyl migration of an initially formed N,N′-dicyclohexyl-O-R_F-palmitoyl-F₁₃-isourea 2 to give 1-R_F-palmitoyl-F₁₃-1,3-dicyclohexylurea 3. X-ray data for an R_F-palmitic acid-F₁₃ unit are reported for the first time. The product of the reaction of DCC with palmitic acid is also the urea derivative which has been characterized by IR and NMR methods.     

Fe(ClO4)3·×H2O-Catalyzed direct C-C bond forming reactions between secondary benzylic alcohols with different types of nucleophiles

A mild and efficient Fe(ClO₄)₃·×H₂O-catalyzed direct C-C bond coupling reactions of 1,3-dicarbonyl compounds, electron-rich arenes and heteroarenes and 4-hydroxycoumarin with secondary benzylic alcohols have been described. The benzylation of electron-rich arenes and heteroarenes leads to the synthesis of bis-symmetrical triarylmethanes. The present method is also applied to synthesis of an anti-coagulant compound, 4-hydroxy-3-(1,2,3,4-tetrahydronaphthalen-1-yl)-2H-chromen-2-one (Coumatetralyl (B)) from commercially available substrates was obtained in 85% yield. The advantages of this protocol are broad scope, mild conditions, use of inexpensive catalyst and simplicity of operation since water is the only side product.     

A simple conversion of azlactones into indenones via H3PW12O40/Al2O3 catalyzed intramolecular Friedel-Crafts reaction

A rapid and simple procedure for the synthesis of the indenone derivatives, N-(1-oxo-1H-inden-2-yl)benzamides, via intramolecular Friedel-Crafts (IFC) reaction of (Z)-4-arylidene-2-phenyl-5(4)-oxazolones (azlactones) catalyzed by H₃PW₁₂O₄₀ supported on neutral alumina under microwave irradiation has been developed. The reaction is straightforward and allows easy isolation of the product. The catalyst could be re-used up to four times after simple filtration.     

One-pot synthesis of N-allylthioureas using supported reagents

A simple and efficient method has been developed for the synthesis of N-allylthioureas from allylic bromides in one-pot by using a supported reagents system, KSCN/SiO₂-RNH₃OAc/Al₂O₃, in which allyl bromide reacts first with KSCN/SiO₂ and the product, allyl isothiocyanate, reacts with RNH₃OAc/Al₂O₃ to give the final product, N-allylthiourea, in good yield.     

2-(Fluorophenyl)pyridines by the Suzuki-Miyaura method: Ag2O accelerates coupling over undesired ipso substitution (SNAr) of fluorine

Problematic ipso substitution was observed in the Suzuki-Miyaura coupling of pentafluorophenylboronic acid to make 2-pentafluorophenylpyridine. Strong bases favored coupling, but under these conditions fluorine in the product tended to undergo nucleophilic substitution. Inclusion of Ag₂O accelerated coupling over ipso substitution.     

A Novel in Situ Oxidization-Sulfidation Growth Route via self-Purification Process to β-In2S3 Dendrites

A novel in situ oxidization-sulfidation growth route via a self-purification process has been developed to synthesize β-In₂S₃ dendrites. To our best knowledge, this is the first example to prepare dendrites of III-VI compounds, which are expected to show particular physical properties. The X-ray analysis (EDXA), X-ray photoelectron spectra (XPS), Raman spectrum and optical properties of β-In₂S₃ dendrites have also been investigated. It is found that the product is pure In₂S₃ and shows the strong quantum confinement of the excitonic transition expected for the In₂S₃ dendrites.     

N-(ethoxycarbonyl)ferrocenecarboxamide: Synthesis and use as the pronucleophile in the Mitsunobu reaction

The title compound has been synthesized in the reaction of ferrocene with ethoxycarbonyl isocyanate in methanesulfonic acid. It has been found that it undergoes N-alkylation with benzyl alcohols under classical Mitsunobu conditions (PPh₃/DEAD). However, in the reaction with cholesterol and stigmasterol O-alkylation with inversion of configuration occurred (confirmed by hydrolysis of the product obtained from cholesterol to epicholesterol). The structure of the product obtained from p-nitrobenzyl alcohol was determined by X-ray diffraction.     

Intramolecular C-glycosylation of 2-O-benzylated pentenyl mannopyranosides: remarkable 1,2-trans stereoselectivity

The IDCP-promoted intramolecular C-glycosylation of pentenyl α-mannopyranosides carrying, at O-2, an activated benzyl group gave, unexpectedly, the 1,2-trans-fused bicyclic product which corresponds to an α-C-aryl mannopyranose derivative. This remarkable, strained C-glycosyl compound was rapidly epimerized to the more stable 1,2-cis product on treatment with BF₃·Et₂O. The IDCP-reaction product could be elaborated into a 2-(α-C-mannopyranosyl)-3,4,5-trimethoxybenzyl alcohol derivative.     

An investigation of the Cr1−xMnxO2 series and the characterization of orthorhombic CrMnO4

Several members of the Cr_1?xMn_xO₂ series were prepared in the tetrahedral anvil press by the reaction of CrO₂ with MnO₂. The tetragonal, rutile-type products were single-phase and have been characterized by crystallographic and magnetic measurements. The results are consistent with the formulations Cr⁴⁺_1?2xCr³⁺ Mn⁵⁺O₂ for 0 ? x ? 0.5. At low manganese concentration, x < 0.20, the magnetic moments are consistent with ferromagnetic contribution from Mn⁵⁺. A two-phase product was noted at the composition x = 0.90. The CrMnO₄ composition was found to have a powder pattern similar to that of orthorhombic PtO₂.     

In situ Mössbauer spectroscopy studies of the electrochemical reaction of lithium with KFeS2

In situ Mössbauer spectroscopy has been used to study the electrochemical reaction of lithium with KFeS₂. Compositions KLi_xFeS₂ with Δx = 0.25 were obtained by coulometric titration for one complete discharge and recharge. Mössbauer spectra were obtained at each composition. Three new iron sites are identified in addition to Fe³⁺ in KFeS₂. A mechanism to account for the electrochemical and Mössbauer data is proposed. The end product KLiFeS₂ has been synthesized and found to be body-centered tetragonal with a = 3.938(2) Å and c = 13.135(5) Å.     

Synergic effect of hydride and proton donors in the Pd(0)-mediated deprotection of N-Aloc proline derivatives

In this study, the challenging Pd(0)-catalyzed N^α-Aloc removal from a proline residue using Me₂NH·BH₃ or PhSiH₃ as allyl scavengers has been investigated. Standard conditions led to a large amount of an allylamine byproduct. A careful study of the reactions allowed us to design the optimal conditions for the quick and quantitative formation of the desired product, while taking advantage of a synergic effect between hydride and proton donors.     

Decomposition of cis-and trans- potassium diaquobis(oxalato)chromate(III)

The decomposition of cis- and trans-K[Cr(C₂O₄)₂](H₂O)₂] has been studied using differential scanning calorimetry. Dehydration occurs as the first step with activation energies being 27.5 and 13.9 mol^?1, respectively, for the cis and trans complexes. After dehydration, continued heating results in loss of CO amd CO₂. For the trans complex, an additional endothermic peak is seen and the mass loss indicated that CO has been lost in a single step. In both cases, the final product indicated by mass loss data is KCrO₂.