Oxidation of Organic Substrates Using Two Triethylammonium Halochromates(VI), (C2H5)3NH[CrO3X], (X=F,Cl) Supported on Silica Gel

Triethylammonium fluorochromate(VI), (C₂H₅)₃NHCrO₃F, TriEAFC and triethylammonium chlorochromate(VI), (C₂H₅)₃NHCrO₃Cl, TriEACC were prepared, supported on silica gel and used to quantitatively oxidize a number of organic substrates. These supported triethylammonium halochromates are versatile reagents ensuring effective oxidation of organic compounds, in particular of alcohols, under mild conditions. The durability, ease of work up and efficiency of TriEAFC and TriEACC are considerably increased upon their absorption on silica gel.     

Synthesis,characterization, X-ray structural analysis and study of oxidative properties of propyltriphenylphosphonium bromochromate

The complex of propyltriphenylphosphonium bromochromate(VI), PrPh₃P[CrO₃Br] is easily synthesized in nearly quantitative yield using a direct reaction of chromium(VI) oxide and propyltriphenylphosphonium bromide. This compound is a versatile reagent for the efficient and selective oxidation of organic substrates, in particular for alcohols to their corresponding aldehydes or ketones, under mild conditions. This compound was characterized by IR, UV/Visible, ¹³C-n.m.r. and ¹H-n.m.r. techniques. It crystallized in the monoclinic form and its crystal and molecular structure have been determined by X-ray crystallography.     

Synthesis, characterization, X-ray structural analysis and study of oxidative properties of a chlorochromate(VI) complex with benzyltriphenylphosphonium cation

Benzyltriphenylphosphonium chlorochromate(VI), [(PhCH₂)Ph₃P][CrO₃Cl], BTriPPCC, is easily synthesized in a nearly quantitative yield by direct reaction of Cr(VI) oxide and benzyltriphenylphosphonium chloride. The complex was characterized by physico-chemical and spectroscopic methods. The use of phosphonium counter ion, improves the quality of the BTriPPCC crystals. The compound was indeed crystallized and structurally characterized by X-ray diffraction at 170(2) K. This compound is a versatile reagent for the efficient and selective oxidation of organic substrates, in particular of alcohols to the corresponding aldehydes or ketones, in mild conditions. Due to the stability and solubility of BTriPPCC, the reactions can be performed at room temperature and the separation of the products is easy.     

Synthesis,characterization, X-ray structural analysis and study of oxidative properties of tetraethylammonium chlorochromate

Tetraethylammonium chlorochromate(VI), Et₄N[CrO₃Cl] is easily synthesized in nearly quantitative yield using a direct reaction of chromium(VI) oxide and tetraethylammonium chloride and characterized by elemental analysis, IR, UV/Visible, ¹H-NMR and ¹³C-NMR techniques and single-crystal X-ray diffraction analysis (monoclinic system, space group C2(#5), with a = 12.023(3), b = 7.998(2), c = 14.527(4) Å, β = 114.187(4)°, V = 1274.4(6) ų and Z = 4). X-ray data determined the CH ··· O hydrogen bond that forms between the ethyl hydrogen of the cation and oxygen of the anion. This compound is a versatile reagent for efficient and selective oxidation of organic substrates, in particular for alcohols to their corresponding aldehydes or ketones, under mild conditions.     

Synthesis and Characterization of Tetraphenylphosphonium Halochromates

Ion-associated halochromates (halo=F, Cl, Br) from tetraphenylphosphonium cation (Ph₄P⁺) are synthesized by stepwise solvent extraction technique and characterized based on XRD, spectral and thermal studies. The Ph₄P⁺CrO₃Br^- crystal is tetragonal with a=b=12.368 and c=7.511 ∮A. Thermal stabilities of these complexes are found to be decreasing in the order of Ph₄P⁺CrO₃F^-> Ph₄P⁺CrO₃Cl^-> Ph₄P⁺CrO₃Br^-. This revised version was published online in July 2006 with corrections to the Cover Date.     

Tetramethylammonium fluorochromate(VI): a new and efficient oxidant for organic substrates

Tetramethylammonium fluorochromate(VI), (CH₃)₄N⁺CrO₃F⁻ (TMAFC), was prepared and used for quantitative oxidation of several organic substrates. This new compound is more efficient and has certain advantages over similar oxidizing agents in terms of the amount of oxidant and solvent required, short reaction times and high yields.     

A New Oxidative Conversion of Carbohydrate Benzyl Ethers to Benzoyl Esters with RuCl3-NaIO

Abstract

The benzyl group is often used in organic synthesis, especially in carbohydrate chemistry, as one of the most useful of the hydroxyl protecting groups. Benzyl ethers are stable to basic conditions and the benzyl group is removed easily by hydrogenolysis or under Birch reduction conditions. Alternatively, the benzyl ether group is oxidized to benzoyl ester and removed under basic conditions. A few oxidation methods have been reported using more than a stoichiometric amount of chromium reagents such as CrO₃-H₂SO₄ (Jones reagent)¹ or CrO₃-AcOH₂. Here we report a new and mild oxidation of benzyl ether to benzoyl ester with a catalytic amount of RuO₄ derived from RuCl₃ and NaIO₄. This method has proved effective in removing benzyl ether groups chemoselectively in the presence of benzylidene acetal and benzyl glycosidic functions.     

Hydrogen peroxide oxidation of cyclohexane,indane, and styrene in the presence of CrO3 or (Bu3SnO)2CrO2

Cyclohexane, indane, and styrene was oxidized by H₂O₂ in the presence of CrO₃ or (Bu₃SnO)₂CrO₂ in a two-phase system or in an organic solvent with the formation of cyclohexanone, indanone, and benzaldehyde, respectively, as the major products. The oxidation of indane by the adduct of H₂O₂ with urea upon catalysis by CrO₃ in acetone proceeds most efficiently.Université de Reims Champagne-Ardenne.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1454–1457, June, 1991.     

Rational Syntheses of CdII and PbII Metal‐Organic Frameworks for Luminescence Sensing of Nitroaromatics,Ferric and Chromate Ions

The metal‐organic frameworks (MOFs), {[Cd(L)(H₂O)] · CH₃OH · DMF} ( 1 ) and [Pb(L)(DMF)] ( 2 ) (L = 2,4‐dihydroxybenzaldehyde nicotinoylhydrazone), were synthesized and characterized using microanalyses, IR spectroscopy, and single‐crystal X‐ray diffraction. Single crystal X‐ray analyses revealed that both 1 and 2 exhibit 2D grid networks. The photoluminescence investigation indicates that 1 and 2 could be a prospective candidate for developing luminescencent sensors for the selective sensing of nitrobenzene, which is used as a precursor for explosives. The luminescent properties of 1 and 2 in different solvents were investigated and corroborated by theoretical calculations. Additionally compounds 1 and 2 also show selective sensing ability for Fe³⁺ as well as for CrO₄^2– ions.     

Electromediators based on the Ni(II) and Cr(III) complexes with the redox-active ligands in the synthesis of sulfur-containing organic compounds

The chromium(III) tris-o-semiquinolate complex Cr(L^SQ)₃ (L^SQ is 3,6-di-tert-butyl-o-semiquinone) and the monoanionic paramagnetic nickel(II) complex [n-Bu₄N][Ni(L _S ^SQ )(L _S ^DT )] (L _S ^SQ is o-thiosemiquinone, L _S ^DT is benzene-1,2-dithiolate) are considered as electromediators of hydrogen sulfide oxidation in the presence of various organic substrates (hex-1-ene, oct-1-ene, benzene, toluene, and benzoic acid). It is revealed that the electrolysis of hydrogen sulfide at the oxidation potential of the mediators in the presence of the substrates affords the corresponding aliphatic and aromatic thiols in a yield of 62–75%.     

Reactivity investigations of some chosen peroxo-vanadium(V), manganese(III) and chromium(VI) compounds

An interpretative account of the results of reactions in aqueous medium of a highly peroxygenated vanadium(V) complex, K [V(O_{2 3}]·3H₂O, with different organic and inorganic substrates is presented. The reactions were monitored by solution EPR spectroscopy and isolation of products at different stages of the reactions. Redox reactions between diperoxide, K[VO(O₂)₂(H₂O)] and VOSO₄ were conducted. The results of the investigation suggest that secondary oxygen exchange-reaction occurs which not only depends on but also utilises the intermediates in the primary reaction during diperoxovanadate-dependent oxidation of VOSO₄. In an interesting reactiontris(acetylacetonato)-manganese(III), Mn(acac)₃, on being reacted with a hydrogen peroxide adduct, KF·H₂O₂, and bpy and phen afforded crystalline [Mn(acac)₂(bpy)] and [Mn(acac)₂(phen)], respectively. The X-ray structural analysis of [Mn(acac)₂(phen)] showed that the compound crystallised in orthorhombic space groupPbcn. The structure consists of a pseudooctahedral Mn(II) ion being bound to two acac⁻(C₅H₅O ₂ ⁻ ) and a phen ligand with the molecule lying on two-fold axis. Reactivity profiles of two new chromium(VI) reagents viz., pyridinium fluorochromate, C₅H₅NH[CrO₃F] (PFC), and quinolinium fluorochromate C₉H₇NH [CrO₃F] (QFC), have been presented. The compounds are capable of acting as both electron-transfer and oxygen-atom-transfer agents. The X-ray analysis of PFC crystals reveals that the compound crystallises in the orthorhombic space group CmcZ₁. The structure consists of discrete pyridinium cations and CrO₃ F anions with no significant hydrogen bonding. This results in total disorder of the pyridinium cation. The tetrahedral [CrO₃ F]⁻ ion lies on a crystallographic mirror plane.     

Molecular‐Level Understanding of the Photocatalytic Activity Difference between Anatase and Rutile Nanoparticles

The generation of oxidants on illuminated photocatalysts and their participation in subsequent reactions are the main basis of the widely investigated photocatalytic processes for environmental remediation and selective oxidation. Here, the generation and the subsequent diffusion of ^.OH from the illuminated TiO₂ surface to the solution bulk were directly observed using a single‐molecule detection method and this molecular phenomenon could explain the different macroscopic behavior of anatase and rutile in photocatalysis. The mobile ^.OH is generated on anatase but not on rutile. Therefore, the photocatalytic oxidation on rutile is limited to adsorbed substrates whereas that on anatase is more facile and versatile owing to the presence of mobile ^.OH. The ability of anatase to generate mobile ^.OH is proposed as a previously unrecognized key factor that explains the common observations that anatase has higher activity than rutile for many photooxidative reactions.     

Benzyltriphenylphosphonium Chlorochromate: A Mild and Novel Reagent for Oxidation of Benzylic and Allylic Alcohols Under Non-Aqueous and Aprotic Conditions or Microwave Conditions

This paper describes the oxidation of benzylic and allylic alcohols under non-aqueous and aprotic conditions or microwave conditions using benzyltriphenylphosphonium chlorochromate (1) PhCH₂PPh₃CrO₃.HCl which has been prepared by mixing an aqueous solution of benzyltriphenylphosphonium chloride with CrO₃ in 6 N HCl at room temperature. This reagent is stable orange powder which may be stored for months without loss of its activity. This compound is readily soluble in organic solvents such as acetonitrile, chloroform and dichloromethane and slightly soluble in carbon tetrachloride, ether and hexane. the oxidation under microwave conditions is much more faster.     

Catalytic activity and physicochemical properties of Ni-Au/Al<Subscript>3</Subscript>CrO<Subscript>6</Subscript> system for partial oxidation of methane to synthesis gas

This work is focused on the role of gold and Al₃CrO₆ support for physicochemical properties, and catalytic activity of supported nickel catalysts in partial oxidation of methane (POM). Catalysts, containing 5% Ni and 5% Ni-2% Au active phases dispersed on mono- (Al₂O₃, Cr₂O₃) and bi-oxide Al₃CrO₆ support, were investigated by TPR, BET and XRD methods, and the activity tests in POM reaction were carried out. Bimetallic Ni-Au catalysts dispersed on Al₃CrO₆ support remained highly stable and active. The amorphous binary oxide Al₃CrO₆ can stabilize considerable amount of Cr⁴⁺, Cr⁵⁺, and Cr⁶⁺ species in Ni-Au/Al₃CrO₆ catalyst network during its calcination in the air. Nickel supported on binary oxide Ni/Al₃CrO₆ can form Ni(III)CrO₃ bi-oxide phase in reductive conditions. During TPR H2 reduction of Ni-Au/Al₃CrO₆ catalyst chromium(II) oxide Cr(II)O phase is observed. After POM reaction the existence of bimetallic Au-Ni alloy was experimentally confirmed on mono-oxide Al₂O₃ support surface, but its formation was not identified on bioxide Al₃CrO₆ support. Published in Russian in Kinetika i Kataliz, 2009, Vol. 50, No. 1, pp. 149–156. The article is published in the original. Based on a report at the VII Russ. Conf. on Mechanisms of Catalytic Reactions (with international participation), St. Petersburg, July 2–8, 2006.     

Synthesis, crystal structure and properties of a charge-transfer compound [(CH3)3CNH3]3[PMo12O40] · 2H2O

A charge-transfer compound [(CH₃)₃CNH₃]₃[PMo₁₂O₄₀] · 2H₂O was synthesized and characterized by IR, UV, ESR, diffusion reflectance electronic spectrum, cyclic voltammogram and X-ray crystallography. Oxygen atoms of the polyoxometalate anion, N atoms of organic substrates (CH₃)₃CNH₂ and O atoms of water molecules are involved in hydrogen bonding. The solid reflectance electronic spectra and IR data indicate the presence of interaction between the [PMo₁₂O₄₀]³⁻ and the organic substrates in the solid state. Photosensitivity to ultraviolet light was assessed for the compound, showing that charge-transfer resulted from oxidation of the organic substrates and the reduction of the heteropolyanion.     

Instant capture of recoil51Cr(III) from neutron activated K2CrO4

We have recently developed a new method of measuring the initial⁵¹Cr(III) produced from nuclear recoil of K₂CrO₄. In our method, K₂CrO₄ was mixed with MgO in the presence of a small amount of water, and the mixture was irradiated in a nuclear reactor. After irradiation, the mixture was dissolved in water, and MgO precipitate was separated from the solution. The yield of recoil⁵¹Cr(III) could be calculated from the⁵¹Cr activity in the precipitate measured. On the other hand, the yield of retention of⁵¹Cr as chromate could be calcualted from the activity found in the supernatant. The⁵¹Cr(III) yield thus obtained is almost a factor of 2 higher than observed in pure K₂CrO₄ without mixing with MgO, irradiated under the same condition. Another important observation is that the⁵¹Cr(III) yield is independent of irradiation time in the presence of MgO. Without MgO, the observed⁵¹Cr(III) yield decreases with increasing irradiation time, suggesting possible oxidation of Cr(III) to chromate during irradiation. This variation is not observed in the system of K₂CrO₄ containing MgO, indicating that the initial Cr(III) is adsorbed immediately after nuclear recoil by MgO and is protected from oxidation by gamma radiation.     

Carbon–carbon bond fission on oxidation of primary alcohols to carboxylic acids

α-Carbon–carbon bond cleavage is shown to be a general side reaction accompanying the oxidation of unbranched primary alcohols to the corresponding carboxylic acids using HNO₃, CrO₃/H₂SO₄/H₂O/acetone, CrO₃/CH₃COOH, PDC/DMF, H₅IO₆/CrO₃, KMnO₄/H⁺, KMnO₄/HO^?, NiCl₂/NaClO, TEMPO/PhI(OAc)₂. Therefore, the product formed is always contaminated with a carboxylic acid containing one carbon atom less. Systems such as PhI(OAc)₂/TEMPO or H₅IO₆/CrO₃/CH₃CN reduce to a minimum the content of this impurity. Temperature, the order of reagent addition, and additives such as oxalic acid or cerium salts produce a profound effect on the formation of the undesirable impurity during the Jones oxidation of primary alcohols.     

Functionalization at C-12 in labdanic diterpenes: synthesis of the natural diterpenic lactones isolated from cistus ladaniferus L.

Oxidative cyclization of Labdanediol (XII) and methyl Labdanolate (Ib) with Pb(OAc)₄, and subsequent oxidation with reagents as RuO₄, O₃, CrO₃, or (Bu^t)₂ CrO₄ affords, in excellent yield, the natural diterpenic lactones II, III, VII, VIII, XI and XIII, isolated from $\text{Cistus ladaniferus L.}$     

Ca10(CrVO4)6(CrVIO4), a disordered mixed‐valence chromium compound exhibiting inversion twinning

The structure analysis of so‐called 9CaO·4CrO₃·Cr₂O₃ proved it to be the title compound, decacalcium hexakis[chromate(V)] chromate(VI), with the simultaneous presence of unusual chromium oxidation states. The structure determination was carried out on a crystal that had inversion twinning. The Cr^VIO₄ tetrahedron is situated on a threefold axis and is disordered over two possible orientations that share three O atoms, while the Cr^VO₄ tetrahedra are in general positions and are ordered. The charge is balanced by Ca²⁺ cations, one of which is located on a threefold axis. The Ca²⁺ ions are coordinated by six, seven or eight O atoms. The compound is a significant phase in the CaO–CrO_x system and its formation reduces the refractoriness of calcium‐rich compositions in an oxidizing atmosphere.     

Selective oxidation of organic compounds using pyridinium-1-sulfonate fluorochromate, C5H5NSO3H [CrO3F] ( PSFC )

Efficient selective oxidation of primary, secondary, and benzylic alcohols to the corresponding carbonyl compounds by a new chromium oxidizing reagent, pyridinium-1-sulfonate fluorochromate, C₅H₅NSO₃H [CrO₃F] (PSFC) is reported. Various cholesterol derivatives were easily converted to related oxocholesterol from allylic oxidation at lower temperature in comparison to other general oxidants. This oxidation procedure is simple and affords good yields.