Fluorierungseigenschaften von WF6

WF₆ reacts with aliphatic carbonyl- or carboxyl derivates to form the corresponding difluorides or carbonic acid fluorides. Fluorination of carbonyl compounds makes the presence of a Lewis acid like BF₃ necessary.Trifluoromethyl compounds are not available in this way.Selective fluorination of alcoholes with WE₆ is not possible.     

Oxone/iron(II) sulfate/graphite oxide as a highly effective system for oxidation of alcohols under ultrasonic irradiation

Oxone, in the presence of a catalytic amount of iron(II) sulfate and graphite oxide, oxidizes efficiently alcohols into their corresponding carboxylic acid or ketone compounds at room temperature in short reaction times and in good to quantitative yields under ultrasonic irradiation.     

Esterification and Selective Esterification in the Presence of TiCl4

A series of carboxylic acids was esterified to the corresponding esters with TiCl_4 as catalyst at room temperature,in high yields.This catalyst was highly effective for the selective esterification of primary alcohols with carboxylic acids,in the presence of secondary alcohols,and for the selective esterification of saturated acid with alcohol in the presence of conjugated acid or aromatic acid.On account of the high yield,high chemoselectivity,mild condition,and being free of other dehydrants,this is an efficient method.     

Solvent‐free Oxidation of Alcohols by Silica Sulfuric Acid/Sodium Dichromate Dihydrate or Potassium Permanganate/Wet SiO2 System

A combination of silica sulfuric acid and sodium dichromate dihydrate or potassium permanganate in the presence of wet SiO₂ was used as an effective oxidizing agent for oxidation of alcohols to their corresponding aldehydes or ketones in solvent free conditions.     

The first report on the catalytic oxidation of urazoles to their corresponding triazolinediones via in situ catalytic generation of Br using periodic acid or oxone/KBr system

A combination of periodic acid or oxone^® and a catalytic amount of KBr in the presence of few drops of water, were used for the catalytic oxidation of urazoles and bis-urazoles to their corresponding triazolinediones under mild and heterogeneous conditions with moderate to excellent yields.     

Cyclic and stripping voltammetry of tin at mercury hanging drop and film electrodes in acidic o-diphenol media in the presence of lead and cadmium

The influence of catechol, gallic acid and tiron on the voltammetric behaviour of tin(IV) in the presence of lead(II) and cadmium(II) was investigated at hanging drop and mercury film electrodes in perchloric acid, oxalic acid and formate supporting electrolytes. Under cyclic conditions, well separated peaks of tin, lead and cadmium are obtained in oxalic acid and formate solutions containing gallic acid or catechol; tiron suppresses the tin peaks significantly. The efficiency of the deposition of tin in the presence of catechol or gallic acid is less than that of lead, particularly at long deposition time. The best separation of the stripping peaks of tin, lead and cadmium is obtained in oxalic acid solution containing gallic acid or catechol. In perchloric acid solution containing gallic acid or catechol the second peak corresponding to tin oxidation is useful for determinations of tin in the presence of lead. Tin(IV) at the 10^-8 mol l^-1 level can be detemined in various salt solutions and in water samples in the presence of five-fold amounts of lead and cadmium.     

Pallado-catalysed P-arylations and P-vinylation of 2-hydrogeno-2-oxo-1,4,2-oxazaphosphinanes

A simple and effective preparation of 2-aryl- (or 2-vinyl)-1,4,2-oxazaphosphinanes, phosphorus analogues of aryl-morpholinols has been developed, involving palladium catalysed coupling of aryl (or vinyl)-halides with 2-H-1,4,2-oxazaphosphinane in presence of triethylamine. A deprotection step was also proposed to afford the corresponding P-aryl-α-aminobenzylphosphinic acid.     

Oxidation of N-alkyl-N′-tosylhydrazines with Hg(OAc)2. A new synthesis of ethers

N-Alkyl-N′-tosylhydrazines with Hg(OAc)₂ in the presence of alcohols or phenol give high yields of corresponding ethers. Reactions in the presence of acetic acid are also examined.     

Silica Sulfuric Acid/Sodium Dichromate Dihydrate as an Efficient Heterogeneous Method for the Oxidation of Alcohols Under Mild Conditions

A combination of silica sulfuric acid and sodium dichromate dihydrate in the presence of wet SiO 2 were used as an effective oxidizing agent for the oxidation of alcohols to their corresponding aldehyde or ketone derivatives in dichloromethane or toluene with excellent yields.     

Polycondensation of Terephthalic Acid and 3,3′‐Dimethyl Bisphenol A with TsCl/DMF/Py in the Presence of Salts

When activated with TsCl/dimethylformamide/pyridine in the presence of lithium, ammonium, or phosphonium salts, activated terephthalic acid of difficult solubility in pyridine became soluble. Depending on the kind and amount of the salt, terephthalic acid reacted smoothly with 3,3′‐dimethyl bisphenol A to yield the corresponding polymer having high molecular weight. However, this reaction could not be successfully applied to the preparation of polyesters from other dicarboxylic acids of difficult solubility.     

Knoevenagel kondensationen mit TiCl4/base-IV : Umsetzungen von aldehyden und ketonen mit phosphonoessigester und methylendiphosphonsäureestern

In the presence of titanium tetrachloride and an organic base in tetrahydrofurane, triethyl phosphonoacetic acid undergoes condensation with aliphatic and aromatic aldehydes and aromatic ketones to yield the corresponding triethyl alkylidene and arylidene phosphonoacetic acids respectively. Tetraalkyl methylenediphosphonates and aromatic or aliphatic α-branched aldehydes react under identical conditions in the same way. The largely unknown triethyl alkylidene and arylidene phosphonoacetic acids and the new tetraalkyl alkylidene and arylidene methanediphosphonic acids are easily hydrogenated either catalytically or by sodium borohydride in ethanol to give the corresponding saturated compounds in nearly quantitative yields.     

Palladium/phosphite-catalyzed 1,4-addition of arylboronic acids to acrylic acid derivatives

1,4-Addition of arylboronic acids to acrylic acid derivatives proceeds efficiently in the presence of a palladium catalyst system of Pd(OAc)2/(PhO)3P to produce the corresponding 3-arylpropionic acid derivatives. The use of the phosphite ligand is the key to conducting the addition smoothly with suppressing the competing Mizoroki-Heck-type oxidative coupling.     

Efficient synthesis of ferrocenylenones by Friedel-Crafts acylation with EtAlCl2-Me3Al

Efficient synthesis of ferrocenylenones using a Friedel-Crafts acylation reaction is described. Acryloyl, methacryloyl, crotonoyl, cinnamoyl, and β-methylcrotonoyl chlorides react with ferrocene in the presence of a Lewis acid (EtAlCl₂ or EtAlCl₂-Me₃Al) to give the corresponding ferrocenylenones (acryloyl, methacryloyl, crotonoyl, cinnamoyl, and methylcrotonoylferrocenes) in good isolated yields. Besides ferrocenylenones, chloroactylferrocene is also synthesised by this method.     

Synthesis of 6-carboxy-2,2-dimethylchromans and chromenes

The condensation of hydroxybenzoic acids and their methyl esters with isoprene in the presence of orthophosphoric acid gives corresponding 2,2-dimethylchromans, which can be dehydrogenated with DDQ or NBS to give the corresponding 6-carboxy-2,2-dimethylchromenes. The synthesis of β-tubaic acid, a natural compound, has also been achieved.     

Preparation of fluoroalkyl end-capped oligomers/magnetite nanocomposites possessing a good dispersibility and stability

Fluoroalkyl end-capped vinylphosphonic acid cooligomers-encapsulated magnetite nanocomposites were prepared by the magnetization of aqueous ferric and ferrous ions in the presence of the corresponding fluorinated cooligomers and magnetic nanoparticles under alkaline conditions. These fluorinated cooligomers magnetic composites are nanometer size-controlled very fine particles and have a good dispersibility and stability in water and traditional organic solvents. These fluorinated nanocomposites were also applied to the surface modification of poly(methyl methacrylate) to exhibit a good oleophobicity imparted by fluorine on their surface. Fluoroalkyl end-capped 2-methacryloyloxyethanesulfonic acid oligomer-encapsulated magnetite nanocomposites and fluoroalkyl end-capped 2-acrylamide-2-methylpropanesulfonic acid oligomer-encapsulated magnetite nanocomposites were prepared in good isolated yields by the magnetization of iron chlorides in the presence of the corresponding oligomers and magnetic nanoparticles under similar conditions. Colloidal stability of these fluorinated nanocomposites thus obtained in water was demonstrated to become extremely higher than that of fluorinated vinylphosphonic acid cooligomers/magnetic nanocomposites.     

Reductive Deoxygenation of Carbonyl to Methylene by LiAlH4／InBr3

The reductive deoxygenation of aldehydes and ketones into the corresponding alkanes is accomplished by LiAlH4 in the presence of Lewis acid InBr3. It provides a convenient method to complete the transformation from carbonyl compounds to alkanes.     

A novel reduction of polycarboxylic acids into their corresponding alkanes using n-butylsilane or diethylsilane as the reducing agent

A convenient one-pot reaction has been developed for the reduction of polycarboxylic acids on aliphatic and aromatic systems to their corresponding alkanes. The reduction utilises either diethylsilane or n-butylsilane as the reducing agent in the presence of the Lewis acid catalyst tris(pentafluorophenyl)borane.     

PhI- and polymer-supported PhI-catalyzed oxidative conversion of ketones and alcohols to α-tosyloxyketones with m-chloroperbenzoic acid and p-toluenesulfonic acid

Various ketones were converted to the corresponding α-tosyloxyketones with mCPBA and p-toluenesulfonic acid in the presence of a catalytic amount of iodobenzene. Moreover, secondary alcohols were directly converted to the corresponding α-tosyloxyketones using mCPBA and catalytic amounts of iodobenzene and potassium bromide, followed by treatment with p-toluenesulfonic acid in a one-pot manner. Poly(4-iodostyrene) could be also used as a recyclable catalyst for the same α-tosyloxylation of ketone     

A Simple Convenient Method for the Conversion of Primary Alcohols Into Carboxylic Acids Using Nabro3-HBr/CCl4/T-BuOH System

Reaction of primary alcohols with sodium bromate-hydro-bromic acid system in the presence of excess tert-butyl alcohol gives the corresponding carboxylic acids in moderate to good yields.     

Silica Sulfuric Acid/NaNO 2 as a Novel Heterogeneous System for the Chemoselective α-Nitrosation of β-Diketones Under Mild Conditions

A combination of silica sulfuric acid and sodium nitrite in the presence of wet SiO 2 was used as an effective nitrosating agent for the nitrosation of g -diketones to their corresponding f -nitroso or f -oximinoketones under mild and heterogenous conditions in moderate to excellent yields.