Dihydrobenzoxazines and tetrahydroquinoxalines by a tandem reduction‐reductive amination reaction

A tandem reduction‐reductive amination reaction has been applied to the synthesis of 3,4‐dihydro‐2H‐1,4‐benzoxazines and 1‐acetyl‐1,2,3,4‐tetrahydroquinoxalines. The nitroketones required for the benzoxazine ring closures were prepared by (A) alkylation of the anion derived from 2‐nitrophenol with an allylic halide or (B) nucleophilic aromatic substitution of an allylic alkoxide on 2‐fluoro‐1‐nitrobenzene followed by ozonolysis. Precursors for the quinoxalines were prepared by alkylation of the anion of 2‐nitroacetanilide with an allylic halide followed by ozonolysis. Catalytic hydrogenation of the nitroketones using 5% palladium‐on‐carbon in methanol then gave the target heterocycles by a reduction‐reductive amination sequence. The N‐methyl derivatives for both ring systems were easily prepared by adding 5‐10 equivalents of aqueous formaldehyde prior to the reduction. The dihydrobenzoxazines were isolated in high yield following purification by chromatographic methods; tetrahydroquinoxalines were isolated in a similar manner and possessed differentiated functionality on the two nitrogens.     

Peptides-XXXXVI: Studies in the synthesis of an analogue of hen egg white lysozyme

The previously synthesised (1–37), (38–75), (76–93), (94–104), (105–117) and (118–129) fragments of the analogue were combined making extensive use of the DCCI/HONSu method. The final coupling involved the (1–75) and (76–129) sub-fragments. Aggregation of the latter fragment caused problems in purification by routine gel filtration methods employing Enzacryl K2 or Sephadex LH60. The fully protected (1–129) product was partially purified by washing, then deprotectcd and purified by gel filtration and ion exchange chromatography. Satisfactory removal of the acetamidomethyl group used for cysteine protection could not be achieved.     

On-line determination of organophosphorus pesticides in water by solid-phase microextraction and gas chromatography with thermionic-selective detection

This paper describes the extraction of 49 organophosphorus pesti-cides (OPPs) from water samples using solid-phase microextraction (SPME). Three fibers, including a 15-μm XAD-coated fiber, a 85-μm polyacrylate-coated fiber, and a 30-μm polydimethylsilox-ane-coated fiber (PDMS), were evaluated here. The effects of stirring and the addition of NaCl to the sample were examined for the polyacrylate-coated fiber. The precision of the technique was examined for all three fibers and the extraction kinetics were investigated using the XAD- and polyacrylate-coated fibers. With some exceptions, the XAD- and polyacrylate-coated fibers performed better than the PDMS-coated fiber. The superiority of the XAD-nd polyacrylate-coated fiber. The superiority of the XAD- and polyacrylate-coated fibers over the PDMS-coated fibers can be attribuibuted to the aromatic functionalities of the XAD and the polar functionalities in the polyacrylate. The relatively high percent RSDs indicate that the SPME technique needs to be further refined before it can be used for anything other than screening. A more effective form of agitation than mechanical stirring may be neccessary to reduce variability and achieve a faster equilibrium between the sample and the SPME fiber.     

Syntheses and reactions of some 4,5-dihaloimidazole-2-carboxylic acid derivatives

The preparation of 5H,10H-diimidazo[1,2-a:1′,2′-d]pyrazine-5,10-dione ( 2a ) and its 2,3,7,8-tetrabromo- and 2,3,7,8-tetrachloro- analogs ( 2b and 2c , respectively) is reported. These dimers, when allowed to react with various anilines, afford imidazole-2-carboxamides ( 3a-c ).     

(1-Adamantanethio)pyridines and tetrahydropyridines from the reaction of 1-adamantanethiol with pyridine I-oxide in acetic anhydride

The reaction of pyridine 1-oxide with 1-adamantanethiol in acetic anhydride produced a mixture of 2- and 3-(1-adamantanethio)pyridines, 1-aeetyl-2-(1-adamantanethio)-3-hydroxy-4-acetoxy-1,2,3,4-telrahydropyridine and the corresponding 3-acetoxyderivative. Pure substances were separated by means of column chromatography on alumina. The tetrahydropyridines were identified by means of their proton magnetic and mass spectra. 4-(1-Adamantanethio)pyridine was synthesized from 4-chloropyridinc and 1-adamantanethiol. The three isomeric (1-adamantanethio)-pyridines were, each, cleaved by concentrated hydrochloric acid to give 1-chloroadamantane and the corresponding pyridinethiol.     

Reductive claisen rearrangements of anthraquinone allyl ethers

Gentle heating of allyloxyanthraquinones with sodium dithionite in dimethylformanide - water effects a rapid and controlled rearrangement to give high yields of 2-allyanthraquinones.     

Effects of ground loop currents on signal intensities in electrospray mass spectrometry

The occurrence of electrochemical processes during the operation of an electrospray ionization (ESI) source is well established. In the positive ion mode, electrons are drawn from the ESI metal capillary to a high voltage power supply. These electrons are the product of charge-balancing oxidation reactions taking place at the liquid/metal interface of the ion source. In a recent study, (Anal. Chem.2001, 73, 4836-4844), our group has shown that the introduction of a ground loop can dramatically enhance the rate of these oxidation processes. Such a ground loop can be introduced by connecting the sample infusion syringe (or the liquid chromatography column, in the case of LC-MS studies) to ground. The magnitude of the ground loop current can be controlled by the electrolyte concentration in the analyte solution, and by the dimensions of the capillary connecting the syringe needle and the ESI source. Using ferrocene as a model system, it is demonstrated that the introduction of such a ground loop can significantly enhance the signal intensity of analytes that form electrochemically ionized species during ESI. However, analytes that form protonated molecular ions, such as reserpine, also show higher signal intensities when a ground loop is introduced into the system. This latter observation is attributed to the occurrence of electrolytic solvent (acetonitrile and/or water) oxidation processes. These reactions generate protons within the ion source, and thus facilitate the formation of [M + nH](n+) ions. Overall, this work provides an example of how the careful control of electrochemical parameters can be exploited to optimize signal intensities in ESI-MS.