1.Isolation and characterization of efficient isoxaben-transforming Microbacterium sp strains from four European soils.
Arrault S1, Desaint S, Catroux C, Sémon E, Mougin C, Fournier JC. Pest Manag Sci. 2002 Dec;58(12):1229-35.
Nutrient-agar plates containing isoxaben (500 mg litre(-1)) were used to isolate isoxaben-metabolising bacteria from four European soils incubated with the herbicide under laboratory conditions. In flask experiments, inoculation of a basal salts medium containing nitrogen and [phenyl-U-14C]isoxaben with an isolate (B2b) resulted in 33% recovery of the initial radioactivity as [14C]carbon dioxide after 2 weeks. A major metabolite identified by GC-MS and NMR analysis as 3-(1-ethyl-1-methylpropyl)isoxazol-5-ylamine accumulated both in basal salts and nutrient broth media. 2,6-Dimethoxybenzoic acid, a suspected metabolite of isoxaben, was not detected in either liquid media. However, the capability of the B2b isolate to use 2,6-dimethoxybenzoic acid as a source of carbon was demonstrated. Soil inoculation with the B2b strain resulted in an increase in the recovery of [14C] carbon dioxide from both [phenyl-U-14C] and [isoxazole-5-14C]isoxaben.
2.Palladium(II)-catalyzed desulfitative synthesis of aryl ketones from sodium arylsulfinates and nitriles: scope, limitations, and mechanistic studies.
Skillinghaug B1, Sköld C, Rydfjord J, Svensson F, Behrends M, Sävmarker J, Sjöberg PJ, Larhed M. J Org Chem. 2014 Dec 19;79(24):12018-32. doi: 10.1021/jo501875n. Epub 2014 Oct 31.
A fast and efficient protocol for the palladium(II)-catalyzed production of aryl ketones from sodium arylsulfinates and various organic nitriles under controlled microwave irradiation has been developed. The wide scope of the reaction has been demonstrated by combining 14 sodium arylsulfinates and 21 nitriles to give 55 examples of aryl ketones. One additional example illustrated that, through the choice of the nitrile reactant, benzofurans are also accessible. The reaction mechanism was investigated by electrospray ionization mass spectrometry and DFT calculations. The desulfitative synthesis of aryl ketones from nitriles was also compared to the corresponding transformation starting from benzoic acids. Comparison of the energy profiles indicates that the free energy requirement for decarboxylation of 2,6-dimethoxybenzoic acid and especially benzoic acid is higher than the corresponding desulfitative process for generating the key aryl palladium intermediate.
3.Supramolecular association in proton-transfer adducts containing benzamidinium cations. II. Concomitant polymorphs of the molecular salt of 2,6-dimethoxybenzoic acid with benzamidine.
Irrera S1, Ortaggi G, Portalone G. Acta Crystallogr C. 2012 Nov;68(Pt 11):o447-51. doi: 10.1107/S010827011204067X. Epub 2012 Oct 18.
Two concomitant polymorphs of the molecular salt formed by 2,6-dimethoxybenzoic acid, C(9)H(10)O(4) (Dmb), with benzamidine, C(7)H(8)N(2) (benzenecarboximidamide, Benzam) from water solution have been identified. Benzamidinidium 2,6-dimethoxybenzoate, C(7)H(9)N(2)(+)·C(9)H(9)O(4)(-) (BenzamH(+)·Dmb(-)), was obtained through protonation at the imino N atom of Benzam as a result of proton transfer from the acidic hydroxy group of Dmb. In the monoclinic polymorph, (I) (space group P2(1)/n), the asymmetric unit consists of two Dmb(-) anions and two monoprotonated BenzamH(+) cations. In the orthorhombic polymorph, (II) (space group P2(1)2(1)2(1)), one Dmb(-) anion and one BenzamH(+) cation constitute the asymmetric unit. In both polymorphic salts, the amidinium fragments and carboxylate groups are completely delocalized. This delocalization favours the aggregation of the molecular components of these acid-base complexes into nonplanar dimers with an R(2)(2)(8) graph-set motif via N(+)-H···O(-) charge-assisted hydrogen bonding.
4.Potential neuroleptic agents. 4. Chemistry, behavioral pharmacology, and inhibition of [3H]spiperone binding of 3,5-disubstituted N-[(1-ethyl-2-pyrrolidinyl)methyl]-6-methoxysalicylamides.
de Paulis T, Kumar Y, Johansson L, Rämsby S, Hall H, Sällemark M, Angeby-Möller K, Ogren SO. J Med Chem. 1986 Jan;29(1):61-9.
A series of 3,5-disubstituted N-[(1-ethyl-2-pyrrolidinyl) methyl]-6-methoxysalicylamides was synthesized, starting from the 2,6-dimethoxybenzoic acids, by boron tribromide demethylation of the corresponding 3,5-disubstituted 2,6-dimethoxybenzamides and separation of the two positional isomers. The correct structure assignments were based on selective decoupling studies on their 13C NMR spectra. The salicylamide derivatives were tested for antidopamine activity in vivo by their ability to inhibit the apomorphine syndrome in the rat and in vitro by their ability to displace [3H]spiperone from striatal preparations of the rat brain. The activity seems to reside exclusively in the S enantiomer. Several compounds were considerably more potent than haloperidol, particularly those having an ethyl group in the 3-position and a halogen atom in the 5-position of the aromatic ring. The corresponding 5-alkyl-3-halogen-substituted compounds were much less active.