Andrzej Jóźwiak

The dual behaviour of N,N-dialkylpyridylcarboxyclic amides in the reaction with lithium diisopropylamide

Abstract The dual behaviour of N,N-diisopropylpyridylcarboxylic amides in the reaction with iPr2NLi depending upon temperature and structure of a given amide, is described.

Application of Organolithium and Related Reagents in Synthesis. Part 23: Synthetic Strategies Based on ortho-Aromatic Metallation. Synthesis of 4b-Arylisoindolo[2,1-a]quinoline derivatives

Abstract The synthesis of the 2-aryl-3-hydroxyisoindol-1-ones 3 and their successive conversion via the reaction with 1-methoxy-1-trimethylsilyloxyethene in the presence of titanium(IV) chloride into 3-carboxymethylphthalimides 7 and subsequent cyclization via sequential treatment with oxalyl chloride and aluminium chloride as a way of regiospecific transformation of the benzenecarbocylic acids into the corresponding isoindolo[2,1-a]quinoline-5,11-diones 5 is described.

Experimental and theoretical electron-density study of three isoindole derivatives: topological and Hirshfeld surface analysis of weak intermolecular interactions

A combined experimental and theoretical study of three isoindole derivatives was made on the basis of a topological analysis of their electron-density distributions. Experimental electron densities were determined from high-resolution X-ray diffraction data sets measured with synchrotron radiation at 100 K, whereas theoretical calculations were performed using DFT methods at the B3LYP\6-311++G(3df,3pd) level of approximation. Both experimental and theoretical models are in good agreement with each other. Since the analysed structures possess a variety of hydrogen-bonding interactions, weak intermolecular contacts of C-H···C(π), C,N(π)···C,N(π) and H···H types were subject to our special interest and are discussed in detail. They were characterized quantitatively and qualitatively by topological properties using Baders Atoms in Molecules theory and by mapping the electron-density distribution, electrostatic potential and a geometric function on the Hirshfeld surface. This way the forces and directions of intermolecular interactions as present on the molecular surfaces were depicted and described. These interactions not only guide crystal packing, but are likewise important for recognition processes involving (aza)isoindole fragments in a biological environment.

Application of organolithium and related reagents in synthesis, part VI. A general study of the lithiation of secondary picoline- and isonicotine amides

SummaryThe lithiation of secondary picoline- (1) and isonicotine-amides (2) and the subsequent reaction of the corresponding (N- and 3-)lithiated amides (3 and4) with N,N-dimethylbenzamide towards the synthesis of the C3-benzoylated picoline (12 a) and isonicotine acids (13 a) has been investigated. The effect of the N-substituent upon the generation of the lithiated amides3 and4 has been studied. As a result it was found that the anilide function should be considered the best choice for direct metallation of the masked picoline- and isonicotinecarboxylic acids. The effects at various temperatures upon the generation of the lithiated reactive intermediates and the problems concerning their reactions with an acid (deuteriation) and an carbonyl electrophile are discussed.ZusammenfassungDie Metallierung sekundärer Amide von Picolin- (1) und Isonicotinsäure (2) und nachfolgende Reaktion der entsprechenden (N- und 3-)metallierten Amide3 und4 mit N,N-Dimethylbenzamid — zur Synthese von C3-benzoylierten Picolin- (12 a) und Isonicotinsäuren (13 a) — wurde untersucht. Der Einfluß des N-Substituenten auf die Bildung der metallierten Amide3 and4 wurde studiert und dabei festgestellt, daß der Anilidrest für eine direkte Metallierung der maskierten Picolin- und Isonicotinsäure gut geeignet ist. Der beobachtete Einfluß des Substituenten bei verschiedenen Temperaturen bei Bildung der metallierten Spezies und die Probleme ihrer Reaktivität gegen Säuren (MeOD) und Carbonyl-Elektrophilen wurden diskutiert.

Application of organolithium and related reagents in synthesis. Part 18. Synthetic strategies based on aromatic metallation. A conversion of methyl ortho-pyridoylbenzoates into aza-anthra-5,10-quinones

Abstract The synthesis of the aza-anthraquinones (16) and (17) via metallation (LDA / THF) of the pyridine nucleus at the C3-carbon atom of the methyl ortho-pyridinecarbonyl benzoates (12) and (13), and then the intramolecular cross addition of the generated lithiated species to the carbomethoxy group is described.

Application of Organolithium and Related Reagents in Synthesis. XV. A Concise Regiospecific Conversion of Picolinic- and Isonicotinic Acids into 2-Benzoyl- and 4-Benzoylnicotinic Acids

Abstract The synthesis of the azaphthalides (7) and (8) and their conversion into the corresponding 2- and 4-benzoyl-3-hydroxymethylpyridines (9) and (10), very useful precursors of the 2- and 4-benzoylated nicotinic acids (11) and (12), as a way of regiospecific transformation of the picolin- and isonicotinanilides (1) and (2) Into nicotinic acid derivatives, is described.

Application of organolithium and related reagents in synthesis. Part 13. Synthetic strategies based on aromatic metallation. A concise regiospecific conversion of benzoic acids into 4-hydroxy-1-arylnaphthalenes

Abstract the synthesis of the 3-unsubstituted phthalides (5) and their conversion into 1-hydroxy-1-arylphthalans (8), very useful precursors of isobenzofurans (10) and subsequent cycloaddition of them to dimethyl acetylenedicarboxylate as a way of regiospecific transformation of benzoic acids into dimethyl 4-hydroxy-1-(2-methoxyphenyl)naphthalene-2,3-dicarboxylates (12) (biaryls highly substituted around the axis), is described.

Thermodynamics of interactions of Na+ ion with 15-crown-5 ether in the mixtures of water with dimethylsulfoxide at 298.15 K

Standard enthalpies of solution of crown ether (15-crown-5 ether) in the dimethylsulfoxide-water-sodium iodide system have been measured at 298.15 K. The equilibrium constants of complex formation of 15-crown-5 with sodium iodide have been determined by the 13C NMR chemical shift of 15-crown-5 ether and by conductivity measurements at various molar ratios of 15-crown-5 ether and sodium iodide in the mixtures of water with dimethylsulfoxide at 298.15 K. The thermodynamic functions of 15-crown-5 ether complex formation with sodium iodide were calculated. The linear enthalpy-entropy relationship for complex formation was discussed. The enthalpies of transfer of the complex from pure dimethylsulfoxide to the examined mixtures were calculated and discussed.

Application of organolithium and related reagents in synthesis. Part 14. Synthetic strategies based on aromatic metallation. A concise regiospecific conversion of benzoic acids into their ortho-pyridoyl derivatives

Abstract The synthesis of the 3-hydroxy-3-pyridyl-isoindolin-1-ones ( 5 ) and ( 6 ) via metallation (n-BuLi) of the benzanilides ( 1 ), and then the reaction of the generated bis lithiated anilides ( 2 ) with N,N-dimethylamides or methyl esters of pyridinecarboxylic acids (benzoylation reagents), and subsequent acidic hydrolysis of ( 5 ) and ( 6 ) as a way (general synthetic strategy) of regiospecific transformation of benzoic acids into their ortho-benzoylated derivatives, is described.

Application of Organolithium and Related Reagents in Synthesis; XX. Synthesis of 4b-Phenylazaisoindolo[2,1-a]quinoline Derivatives

Abstract The synthesis of hydroxyazaisoindolinones 3 and 4 and their successive conversion into azaisoindoleaceic acids 7 and 8 as effective precursors of the corresponding 4b-phenyldihydroazaisoindol[2,1-a]quinolinediones 9 and 10 are described.