Use of t-butyllithium as a reducing agent

Details of the first reported use of an alkyllithium reagent for the reduction of a CO bond are presented.     

Dihaloindium hydride as a novel reducing agent

Dihaloindium hydrides (X2InH) are novel reducing reagents, which act in both an ionic and a radical manner. The hydrides were easily generated from InX3 and Bu3SnH to reduce a variety of functionalities such as aldehydes, ketones, enones, and imines. The combination of a phosphine and Cl2InH accomplished the selective transformation from acid chlorides to aldehydes. One-pot treatment of Cl2InH, enones, and aldehydes achieved reductive aldol reactions, in which the predominant reduction of enones was followed by an aldol reaction between the resulting indium enolates and the remaining aldehydes. It is noteworthy that both anti- and syn-selective aldols were obtained by the use of THF and an aqueous solvent, respectively. The replacement of Bu3SnH with Et3SiH as a hydride source allowed the catalytic use of InBr3 to give the syn-selective aldols. The dehalogenation of alkyl halides was achieved by a catalytic amount of InCl3 in the presence of Bu3SnH. This procedure was applied to some representative cyclizations as radical proof. A simple and non-toxic system, NaBH4/InCl3, also promoted dehalogenation, intramolecular cyclization, and intermolecular coupling reactions. In addition, the Et3SiH/InCl3 system was found applicable to an effective intramolecular cyclization of enynes.     

Use of sodium diisobutylaluminum dihydride as a reducing agent

Summary It has been found that sodium diisobutylaluminum dihydride can be applied for the reduction of different functional groups of organic compounds. Both hydrogen equivalents of the complex are utilized.     

Quinquevalent tungsten as a reducing agent in potentiometric titrations

Qmnquevalcnt tungsten prepared by the electrolytic reduction of tungstate in ION HC1 is sufficiently stable when kept in strong acid solutions under COg to be used as an effective reducing agent in potcntiometric titrations. It can be accurately standardised with dichromate. The formal redox potentials of the $\text{W}{}^{\mathrm{+6}}\text{W}{}^{\mathrm{+5}}$ system as determined at different acidities indicate that quinquevalent tungsten is more reducing than the corresponding molybdenum compound.Quinquevalent tungsten can be applied successfully as a volumetric reagent in the potentiometric titration of ferric iron in 8-ioN HC1 or in a mixture of HCl and H3PO4 0.5.N each and of cupric copper in 8N HCl at 80° C. It can also be applied for the estimation of iodate, provided that the latter is used as the titrant.     

Trivalent molybdenum as volumetric reducing agent

Summary The purpose of the present investigation is to introduce trivalent molybdenum as a new analytical reducing agent, in hydrochloric as well as sulphuric acid media.The solution is prepared in 9N acid by electrolytic or mercuryreduction of the hexavalent form. It is preferentially stocked and used in high acid concentrations, whereby its stability in air is optimal, falling to half its titer after nearly two months. It has been tested with success as reductant for ceric, dichromate, ferric and vanadate. It has the advantage of being used in ordinary opened burettes. Titrations were followed potentiometrically in general, and alternately visually in decinormal media, whereby molybdenum blue appears at the end-point. The percentage error in fifteen discussed experiments never surpassed ±1%. Some oxidation titrations were also undertaken using iodate and bromate, with the same degree of accuracy, provided they were conducted in 6N acid. In weaker acid concentrations, equilibria were more slowly attained, with a more or less pronounced deviation, due to some oxidisability that necessitates controlled inert atmosphere.     

Carbon monoxide as a selective reducing agent in organic chemistry

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Rieke zinc as a reducing agent for common organic functional groups

The ability of Rieke zinc to reduce common organic functional groups has been studied. Nitrobenzene, conjugated aldehydes, arylacetylenes, and phenylpropiolates are readily reduced under mild conditions. Benzonitrile, alkylacetylenes, ketones, unconjugated aldehydes, and alkenes are not reduced.     

Aluminumoxyhydride: improved synthesis and application as a selective reducing agent

Aluminumoxyhydride (HAlO) has been obtained by the reaction of aluminum hydride with the siloxane (Me2HSi)2O or the stannoxane (Bu3Sn)2O as an amorphous colorless insoluble powder. The highest-purity product resulted from the reaction of H3Al.NMe3 with (Me2HSi)2O. However, HAlO suspensions in tetrahydrofuran (THF) of sufficient quality for synthetic applications can be prepared from commercially available reagents with only minor precautions. A LiAlH4 solution in THF was treated successively with Me3SiCl and (Me2HSi)2O, followed by heating at 60 degrees C for 20 h. The resulting suspensions are 0.4-0.5 M in active hydride content and selectively reduce aldehydes and ketones to the respective alcohols in the presence of any other common nonprotic functional group.     

Biocompatible reduced graphene oxide prepared by using dextran as a multifunctional reducing agent

A large-scale, cost-effective, and environmentally friendly synthetic strategy for biocompatible reduced graphene oxide (RGO) by using dextran as a reducing and stabilization agent has been developed. Dextran-coated RGO (D-RGO) was readily soluble in water with high biocompatibility.     

Volumetric determination of iron (III) with hydroxylamine as a reducing agent

Summary A new volumetric method has now been developed for the determination of iron(III) through reduction to iron(II) with excess of hydroxylamine. The reduction is completed at the temperature of the boiling water bath in 10 min, keeping the acidity at 0.2–0.5 N sulphuric acid. The mixture is cooled and treated with enough 1 1 sulphuric acid to bring up the acidity to 6 N. It is then titrated with a standard solution of sodium vanadate, using N-phenyl anthranilic acid as inside indicator. Diphenyl benzidine, barium diphenyl sulphonate, or 1,10-phenanthroline cannot be used as indicators in this titration, because of the interference of the unreacted hydroxylamine.The method has been found to be very precise, and convenient. It has also the advantage that it is subject to fewer interferences than the existing methods.One of us, Mrs. G. Somidevamma, desires to thank the Ministry of Education Government of India for the award of Research Fellowship which enabled her to take part in this investigation.     

Synthesis of thiol-capped gold nanoparticle with a flow system using organosilane as a reducing agent

Synthesis of thiol-capped gold nanoparticle is carried out by mixing of a THF solution of HAuCl₄·4H₂O and ⁿC₁₂H₂₅SH with a THF solution of triethylsilane in a flow system that consists of polytetrafluoroethylene tubing. The effect of residence time and reaction temperature on the particle size is examined.     

Precipitation of dispersed silver particles using acetone as reducing agent

A novel environmentally friendly solution-based method for preparing dispersed silver particles is described. The simple and convenient approach consists in heating silver oxide particles dispersed in a highly alkaline water/acetone mixture. The data presented clearly show that acetone reduces completely and rapidly Ag(2)O particles to metallic silver at 60°C. A mechanism explaining the provenance of the electrons responsible for the reduction of silver is proposed.     

Trivalent molybdenum as volumetric reducing agent for admixed oxidizing agents

Summary The aim of this study was to test the applicability of trivalent molybdenum as a volumetric reducing agent for mixtures of two and three oxidizing agents. The oxidizing agents used were ceric, vanadate dichromate and ferric solutions. All possible combinations of two and three ions were attempted. With the exception of a few cases, successful results were obtained with mixtures of two ions. Accurate determinations with three ions admixed could not be achieved; however, a close estimation was possible in some cases.     

Diborane as a reducing agent IX: Reduction of aTris(trifluoroacetyl)enaminospiroindoline

Summary Reduction of the title compound (2) with diborane furnishes 1-trifluoroethyl-3-(2-(trifluoroethylamino)ethyl)-3-vinylindoline (4), 1-hydroxy-trifluoroethyl-3-(2-(trifluoroethylamino)ethyl)indole (5), and 1-methyl-2-trifluoroethyl-1,2,3,4-tetrahydro--carboline (6). However, treatment of2 with lithium aluminum hydride, H₂/Pd on charcoal, and sodium borohydride affords hydroxyspiroindolenine8, hydroxy-bis(trifluoroacetyl)enaminospiroindoline9, andN-ethyltryptamine7, respectively. The results are discussed and the mechanisms of the reactions leading to4–8 are presented.

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Diboran als Reduktionsmittel, 9. Mitt.: Reduktion einesTris(trifluoroacetyl)enaminospiroindolins

Zusammenfassung Reduktion der Titelverbindung (2) mit Diboran ergibt 1-Trifluoroethyl-3-(2-(trifluoroethylamino)ethyl)-3-vinylindolin (4), 1-Hydroxy-trifluoroethyl-3-(2-(trifluoroethylamino)ethyl)indol (5) und 1-Methyl-2-trifluoroethyl-1,2,3,4-tetrahydro--carbolin (6). Behandlung von2 mit Lithiumaluminiumhydrid, H₂/Pd auf Aktivkohle und Natriumborhydrid führt jedoch zu Hydroxyspiroindolenin8, Hydroxy-bis(trifluoroacetyl)enaminospiroindolin9 und N-Ethyltryptamin (7). Die Ergebnisse werden diskutiert und die Mechanismen der zu den Produkten4–8 führenden Reaktionen werden vorgestellt.

     

Biodegradable and Biocompatible Silatrane Polymers

In this study, new biodegradable and biocompatible amphiphilic polymers were obtained by modifying the peripheral hydroxyl groups of branched polyethers and polyesters with organosilicon substituents. The structures of the synthesized polymers were confirmed by NMR and GPC. Organosilicon moieties of the polymers were formed by silatranes and trimethylsilyl blocks and displayed hydrophilic and hydrophobic properties, respectively. The effect of the ratio of hydrophilic to hydrophobic organosilicon structures on the surface activity and biological activity of macromolecules was studied, together with the effect on these activities of the macromolecules’ molecular weight and chemical structure. In particular, the critical micelle concentrations were determined, the effect of the structure of the polymers on their wetting with aqueous solutions on glass and parafilm was described, and the aggregation stability of emulsions was studied. Finally, the effect of the polymer structures on their antifungal activity and seed germination stimulation was examined.     

Transformation of glutaryl chloride to 4,5-dibromopentanoic acid in the presence of a saturated hydrocarbon as a reducing agent and AlBr3 as the brominating agent

Conclusions Glutaryl chloride in the complex, ClCO(CH₂)₃COCl·4AlBr₃, reacts with normal alkanes and cycloalkanes with the formation of 4,5-dibromopentanoic acid after hydrolysis.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1170–1173, May, 1989.The authors express their gratitude to V. I. Dostovalova for a discussion of the PMR and¹³C NMR spectra.     

Triethylsilane as a mild and efficient reducing agent for the preparation of alkanethiol-capped gold nanoparticles

The reaction of HAuCl(4).4H(2)O and n-C(12)H(25)SH with 1 equiv. of Et(3)SiH in an organic solvent affords spherical gold nanoparticles (AuNPs) with narrow dispersity.