Activated Carbonyl Compounds Research Articles

ChemInform Abstract: Synthesis of Highly Functionalized γ‐Butyrolactones from Activated Carbonyl Compounds and Dimethyl Acetylenedicarboxylate.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform Abstract: Synthesis of 1‐(2‐Oxoalkyl)‐2‐acyltetrahydroisoquinolines by α‐ Amidoalkylation of Methylene Active Carbonyl Compounds with N‐ Acyliminium Intermediates.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Synthesis of 1-(2-Oxoalkyl)-2-acyltetrahydro-isoquinolines by α-Amidoalkylation of Methylene Active Carbonyl Compounds with N-Acyliminium Intermediates

Abstract Intermolecular α-amidoalkylation reaction of methylene active carbonyl compounds with N-acyliminium salts of 3,4-dihydroisoquinolines and acyl chlorides has been used for synthesis of 1-(2-oxoalkyl)-2-acyltetrahydroisoquinolines.

Hydride Transfer Reactions of Aminomethylphosphines and Bis(Amino)Methanes with Diphenylboric Acid Ester in the Presence of Carbonyl Compounds

Abstract The interaction of diethylaminomethylphosphines and diphenylboric acid isobutyl ester proceeds only in the presence of active carbonyl compounds, namely alkyl aldehydes, followed by the formation of 1,3,2,5-dioxaborataphosphoniarinanes with the second molecule of the carbonyl compound. Reactions don't take place in the presence of ketones and aromatic aldehydes. Bis(N,N-diethylamino)methane reacts analogously to give corresponding N,B-containing zwitter-iones.

Synthesis of Highly Functionalized gamma-Butyrolactones from Activated Carbonyl Compounds and Dimethyl Acetylenedicarboxylate.

A triphenylphosphine-catalyzed cyclization of alpha-keto esters, alpha-keto nitriles, or alpha,alpha,alpha-trifluoroacetophenone with dimethyl acetylenedicarboxylate is reported to produce highly functionalized alpha,beta-unsaturated gamma-butyrolactones in moderate yields. Thus treating a mixture of methyl 4-nitrophenylglyoxylate and dimethyl acetylenedicarboxylate with 20 mol % of triphenylphosphine afforded 5,5'-disubstituted 3-methoxy-4-(methoxycarbonyl)-2(3H)-furanone in 94% yield. In the reaction of alpha-keto esters R(1)COCOOMe, an electron-withdrawing R(1) substituent is required for satisfactory reactivity. On the other hand, electron-donating R(1) substituents give higher yields with alpha-keto nitriles R(1)COCN. Another electron-deficient carbonyl compound, alpha,alpha,alpha-trifluoroacetophenone, gave the corresponding lactone in good yield. The use of an alpha-hydroxy ketone as an electrophilic carbonyl compound with more than 1 equiv of triphenylphosphine produced dihydrofuran derivatives. One equivalent of triphenylphosphine oxide was obtained as a major product. An intramolecular Wittig reaction is proposed as a reaction mechanism.

Carbonyl-containing bisphosphonate esters as novel antiinflammatory and antiarthritic agents.

A study of the decomposition of the pyrazoline bisphosphonate ester 2 identified 3 as the sole bisphosphonate component. Evaluation in a delayed-type hypersensitivity granuloma model of chronic inflammation in mice (DTH-GRA) showed 3 to be a potent inhibitor of granuloma formation (sc, 10 mg/kg, 45%), but in a murine model of antigen-induced arthritis (AIA), no significant inhibition was observed. As a result, new ketonic bisphosphonate tetraethyl esters were synthesized from vinylidenebisphosphonic acid tetraethyl ester 4 and activated carbonyl compounds in 13-84% yield. 6 significantly inhibited the pathology of both the DTH-GRA (sc, 25 mg/kg, 45%) and AIA models (sc, 25 mg/kg, 55%). Other compounds in the series were not as potent. Our results show that bisphosphonate ester 6 can inhibit the chronic inflammatory response associated with cutaneous granuloma formation and erosive arthritis.

ChemInform Abstract: The Nitration of Activated Carbonyl Compounds (I) in a Two‐Phase System.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Coulometric Study of the Influence of Aldehydes and Ketones on the Karl Fischer Titration of Water Using Standard Pyridine/Methanol Reagents

Conditions for the determination of water in active carbonyl compounds have been studied coulometrically for standard pyridine/methanol KBrl Fischer (KF) reagents. The presence of active carbonyl compounds in the sample is considered to be one of the serious problems associated with the KF method, since they lead to a continuous formation of water through reaction with methanol. This study conforms that such side reactions cannot normally be adequately corrected for simply by subtracting the end-point drift

Addition of primaryN-nitroamides to activated olefins

PrimaryN-nitrosulfamides readily undergo addition to acrolein and vinyl ketones to yieldN-γ-oxoalkyl-N-nitrosulfamides. The presence of a second substituent at the double bond hinders the reaction.N-Nitrourethane reacts with activated carbonyl compounds and α-nitroolefins.

Zinc meso-tetraphenylporphyrin as shift reagent for NADH-models

By the use of zinc meso-tetraphenylporphyrin as a shift reagent the conformations of two new NADH-models have been determined. Induced 1H-NMR shifts up to five ppm have been observed. The conformations determined in this study are consistent with theoretical calculations and NOE-measurements. It has been proven that zinc, which is a co-catalyst in the reduction of activated carbonyl compounds with NADH-models, coordinates to the oxygen of the amide groups in two of our model compounds.

Synthesis of ?-functional nitro compounds by the nitration of activated carbonyl compounds in a two-phase system

2-Nitro-1,3-dicarbonyl and α-nitromonocarbonyl compounds were synthesized in the yields varying from moderate (30 %) to nearly quantitative by the nitration of β-dicarbonyl compounds in a two-phase system: sulfuric/nitric acid mixture-chloroform at - 10÷10 °C. The use of phase transfer conditions made it possible to avoid the formation of furoxans as by-products and to simplify the isolation of products. This method is quite common for preparing various α-functional nitro compounds including those containing a CF3-group. Key words: nitration, α-functional nitro compounds.

The Nitration of Activated Carbonyl Compounds in a Two-phase System

The nitration of activated carbonyl compounds in a two-phase system gives novel possibilities for the synthesis of functional nitro derivatives.

Palladium-catalyzed synthesis of amides and peptides

When the Pd(0)-catalyzed hydrostannolysis of the N-allyloxycarbonyl group is carried out in the presence of an activated carbonyl compound, a coupling product is formed. This new method appears to be applicable to the synthesis of a wide range of amides and peptides.

ChemInform Abstract: α,β‐Unsaturated Derivatives of Trivalent Phosphorus in Reactions with Activated Carbonyl Compounds.

ChemInform Abstract: α,β‐Unsaturated Derivatives of Trivalent Phosphorus in Reactions with Activated Carbonyl Compounds.

On the structure and reactivity of a stabilized phosphorane: methyl (triphenylphosphoranylidene) acetate

In the absence of a source of acidic protons, methyl (triphenylphosphoranylidene)acetate 1 exists as a mixture of the cis and trans isomers even at room temperature. Acidic protons catalyze the interconversion of the two forms and facilitate the reaction of the ylide with active carbonyl compounds such as benzaldehyde or phthalic anhydride. Keywords: stabilized phosphoylide, structure, reactivity.

ChemInform Abstract: Synthesis of New Tricyclic Chiral P‐H Bond Phosphoranes, “Triquinphosphoranes”, from Chiral Diaminodiols. Asymmetric Addition on an Activated Carbonyl Compound.

AbstractThe new class of tricyclic, chiral hydridophosphoranes, the "triquinphosphoranes" (III), are synthesized as shown and characterized NMR spectroscopically.

α,β-Unsaturated Derivatives of Trivalent Phosphorus in Reactions with Activated Carbonyl Compounds

Abstract Dialkyl alkynylphosphonites (I) react with esters and nitriles of α-oxocarboxylic acids to give phosphorylated alkanoates, 1,3,2-dioxaphospholanes and l-phosphabicyclohept-4-enes, depending on the nature of the reagent and conditions of the reaction. The reaction of dialkyl alkenylphosphonites (II) with esters and nitriles of α-oxocarboxylic acids predominantly leads to dioxaphospholane derivatives.

Synthesis of new tricyclic chiral phosphorus-hydrogen bond phosphoranes, "triquinphosphoranes", from chiral diaminodiols. Asymmetric addition on an activated carbonyl compound

Synthesis of new tricyclic chiral phosphorus-hydrogen bond phosphoranes, "triquinphosphoranes", from chiral diaminodiols. Asymmetric addition on an activated carbonyl compound

α,β-Unsaturated Derivatives of Trivalent Phosphorus in Reactions with Activated Carbonyl Compounds

α,β-Unsaturated Derivatives of Trivalent Phosphorus in Reactions with Activated Carbonyl Compounds

Studies on the ageing characteristics of automotive crankcase oils

The ageing characteristics of two competing lubricants, monograde and multigrade crankaase oils, have been studied. A combination of oil acidity, deposit formation and infra-red spectroscopy were used to follow the ageing of the lubricating oils. Both oils showed a similar pattern of ageing. However, the monograde oil, showed a higher tendency to form carbonyl compounds, but the multigrade oils formed more active carbonyl compounds, which polymerized rapidly to form deposits. Consequently, the multigrade oil aged faster than the monograde oil.