Applications of benzotriazole methodology in heterocycle ring synthesis and substituent introduction and modification

Applications of benzotriazole methodology for the preparation of heterocyclic compounds are reviewed. The characteristic advantages of benzotriazole as a synthetic auxiliary are first briefly considered. This is followed by a summary of its use in ring synthesis in which the construction of small; five-membered; six-membered; and larger heterocyclic rings using benzotriazole methodology are each examined separately. Finally, consideration of the use of benzotriazole in the ring annulation - particularly benzannulation - of heterocycles. Subsequent sections deal with the introduction of substituents into aromatic heterocycles; the ring substitution of saturated heterocycles; and benzotriazole assisted modification of heterocyclic substituents. The present review supplements a recent comprehensive review of benzotriazole chemistry [1] which covers the literature through 1996.     

CORRELATION BETWEEN THE BINDING OF FORMATE AND DECREASED RATES OF CHARGE TRANSFER THROUGH THE PHOTOSYSTEM II QUINONES

Abstract— The binding parameters of bicarbonate to the thylakoid membrane at different formate concentrations have been established [Stemler and Murphy (1983) Photochem. Phorobiol. 38, 701–707]. Based on these parameters, predictions could be made concerning the effects of bicarbonate and formate on photosynthetic electron flow. In this work these effects of various concentrations of bicarbonate and formate are measured and compared to predictions from the binding study. Electron flow is measured between Q_A and Q_B (the primary and secondary quinone acceptors) and Q_B and the plastoquinone pool. Also, these same concentration effects are determined for silicomolybdate supported oxygen evolution. It is found that the results of the bicarbonate binding study are in good agreement with the concentration dependence determined for the quinone reactions, as well as the silicomolybdate reaction. The bicarbonate concentrations required for half-maximal effects are approximately 100 μM, 300 μM and 1.3 mM in the presence of 0, 20 mM and 100 mM formate, respectively. It is concluded that a hierarchy of possible electron flow rates exist. The slowest rates occur when formate is bound. A substantially higher rate occurs when neither formate nor bicarbonate (< 2 μM) are present, but only chloride is present. The highest rates of electron flow occur when bicarbonate is bound. The Q_A- Q_B→ Qa Qb^? Qa^? Qb^2– PQ → Q_a Q_b- PQ^2–, and the silicomolybdate reactions all have the same concentration dependence on formate and bicarbonate. From this it is concluded that a single binding site for formate and bicarbonate affect all of these reactions. The possibility that multiple sites exist with approximately equal affinities for bicarbonate cannot be excluded.     

A simplified synthesis of the hexamethylplatinate(IV) ion

Tetra-n-butylammonium hexachloroplatinate (IV) reacts with lithium methyl/lithium iodide in ether to give a solution containing lithium hexamethylplatinate (IV). With lithium methyl/lithium bromide in ether however, tetrabutylammonium hexamethylplatinate (IV) is precipitated together with lithium halides. Solid [Bu₄N)₂[Pt(Ch₃)₆] is stable under nitrogen at room temperature, but ether solutions of [Pt(Ch₃)₆]^2- decompose in a few minutes at room temperature in the absence of excess lithium methyl.     

A general and efficient synthesis of sulfonylbenzotriazoles from N-chlorobenzotriazole and sulfinic acid salts

One-pot reactions of sulfinic acid salts (produced from organometallic reagents with SO2) with N-chlorobenzotriazole gave the corresponding N-alkane-, N-arene-, and N-heteroenesulfonylbenzotriazoles 3a-j in 41-93% yields. Reagents 3a-j are efficient sulfonylating agents, reacting at 20-80 degrees C with various primary and secondary aliphatic amines to yield the corresponding sulfonamides in 64-100% yields.     

Flow-injection amperometric determination of oxalate with immobilized oxalate oxidase

Oxalate is immobilized on controlled-pore glass and is used on-line in a glass minicolumn (2.5×25 mm). The hydrogen peroxide formed is detected amperometrically. Oxalate (6×10^?6?9×10^?4 M) is determined in a flowing stream of pH 3.5 citrate (or succinate) buffer. As little as 20 ng (in 40 μl; 5.7×10^?6 M) of oxalate can be detected. Copper inhibition can be removed either by adding EDTA to the carrier stream or incorporating a chelating-resin minicolumn into the flow system prior to the enzyme column.     

Hole and Electron Doping of the 4d Transition-Metal Oxyhydride LaSr3NiRuO4H4

Hole or electron doping of phases prepared by topochemical reactions (e.g. anion deintercalation or anion-exchange) is extremely challenging as these low-temperature conversion reactions are typically very sensitive to the electron counts of precursor phases. Herein we report the successful hole and electron doping of the transition-metal oxyhydride LaSr₃NiRuO₄H₄ by first preparing precursors in the range La_xSr_4−xNiRuO₈ 0.5<x<1.4 and then converting into the corresponding La_xSr_4−xNiRuO₄H₄ phases. This is particularly noteworthy as the (Ni/Ru)H₂ sheets in the La_xSr_4−xNiRuO₄H₄ phases are structurally analogous to the CuO₂ sheets in cuprate superconductors and hole doping (Ni^1+/2+, Ru²⁺) or electron doping (Ni²⁺, Ru^1+/2+) yields materials with partial occupancy in Ni/Ru –H 1s bands which are analogous to the partially occupied Cu –O 2p bands present in the CuO₂ sheets of doped superconducting cuprates.     

Flow-injection determination of sulphite and assay of sulphite oxidase

Sulphite (1–80 × 10^?5 M) in formaldehyde-stabilized solutions is determined by injection into a flowing stream of pH 8.5 phosphate buffer, passing through a mini-column of sulphite oxidase immobilized on controlled-pore glass, with amperometric detection of the hydrogen peroxide produced. Sulphite oxidase (5–100 U l^?) is determined by injection into a flowing stream of formaldehyde-stabilized 2 × 10^?3 M sodium sulphite in pH 8.0 phosphate buffer; hydrogen peroxide is again monitored.     

Synthesis and characterisation of a series of alkylmagnesium amide and related oxygen-contaminated "alkoxy" compounds

Synthesised either by an unusual tert-butyl metathesis between tert-butyllithium and a n,s-butylmagnesium amide or by reaction of an alkyl Grignard reagent and a sodium amide, five tert-butylmagnesium amides, Bu(t)MgDBA (5)(DBA=dibenzylamide), Bu(t)MgDA (6)(DA=diisopropylamide), Bu(t)MgHMDS (7)(HMDS=1,1,1,3,3,3-hexamethyldisilazide), Bu(t)MgTMP (8)(TMP=2,2,6,6-tetramethylpiperidide) and Bu(t)MgNCy2 (9)(cy=cyclohexyl) have been isolated as crystalline solids. All five amides have been characterised by X-ray crystallography and solution NMR spectroscopic studies. The former studies reveal a common dimeric molecular structure with amido bridges in a planar (MgN)2 ring and terminal Bu(t) ligands on the Mg atoms. Also described is the dodecameric primary amide [Bu(n)MgN(H)Dipp]12 (10a) and its monomeric solvate Bu(n)MgN(H)Dipp.TMEDA (10b)(Dipp=2,6-diisopropylphenyl; TMEDA=N,N,N',N'-tetramethylethylenediamine). The crystal structures of the oxo-insertion products Bu(t)MgOBu(t).THF (11), Bu(t)Mg(mu-OBu(t))(mu-TMP)MgTMP (12) and Mg(OBu(n))HMDS.solv [solv=THF (13a) or Et2O (13b)], made fortuitously during the course of this work, are also presented.     

Some past achievements and future perspectives in main group chemistry

A survey of some recent developments and past achievements in low-valent main group chemistry is presented. Some emerging implications of this area of chemistry in materials science, catalysis and new reagent development are also discussed.