Phenyliodoso Acetate Research Articles

Approaches to α-amino acids via rearrangement to electron-deficient nitrogen: Beckmann and Hofmann rearrangements of appropriate carboxyl-protected substrates

The titled approaches were effected with various 2-substituted benzoylacetic acid oximes 3 (Beckmann) and 2-substituted malonamic acids 9 (Hofmann), their carboxyl groups being masked as a 2,4,10-trioxaadamantane unit (an orthoacetate). The oxime mesylates have been rearranged with basic Al2O3 in refluxing CHCl3, and the malonamic acids with phenyliodoso acetate and KOH/MeOH. Both routes are characterized by excellent overall yields. Structure confirmation of final products was conducted with X-ray diffraction in selected cases. The final N-benzoyl and N-(methoxycarbonyl) products are α-amino acids with both carboxyl and amino protection; hence, they are of great interest in peptide synthesis.

Kinetics and Oxidation of Substituted Benzyl Alcohols by Phenyliodoso Acetate

Oxidation of benzyl alcohol and some meta‐ and para‐ substituted alcohols by phenyliodoso acetate (PIA) in t‐butyl alcohol–water medium (50:50) leads to the formation of corresponding benzaldehyde. The stoichiometry of the reaction was found to be 1:1. The reaction was first order each in substrate and oxidant concentrations. This reaction was studied at four different temperatures and the activation parameters were calculated. Correlation analysis was carried out using Taft’s and Swain’s dual substituent parameter (DSP) equation. The rate data of meta‐ compounds showed good correlation with (F,R) values, para‐substituted benzyl alcohols showed good correlation with σIσR+ A suitable mechanism has been proposed.

Determination of bromide and nitrite by indirect redox titration using phenyl iodosoacetate

Bromide has been determined by its oxidation with an excess of phenyl iodosoacetate in the presence of acetanilide to give bromine which subsequently reacts with acetanilide to form 4-bromoacetanilide. The residual amount of phenyl iodosoacetate was evaluated iodometrically. Thus, for every mol of bromide one mol of phenyl iodosoacetate was consumed. For the determination of bromine in organic compounds, the test substance was decomposed by fusion with alkali peroxide to liberate bromide which was then evaluated by the phenyl iodosoacetate method. For its determination, nitrite has been reacted with an excess of isoniazid in acid medium to form isonicotinyl azide (which does not react with phenyl iodosoacetate) and the residual amount of isoniazid was titrated with phenyl iodosoacetate in the presence of acidified bromide and methyl red indicator (when isoniazid and phenyl iodosoacetate react in a 1∶2 molar ratio). Each mol of nitrite is equivalent to 2 mol of phenyl iodosoacetate.

ChemInform Abstract: Oxidative Cyclization of Diamides by Phenyliodoso Acetate.

AbstractThe title reaction of carboxamides, e.g. (I), (III) and (V), proceeds via an initially formed isocyanate.

Oxidative Cyclization of Diamides by Phenyliodoso Acetate

Carboxamides containing a suitably situated nucleophilic group ( carboxamide , N-substituted carboxamide, or hydroxymethyl ) undergo oxidation by phenyliodoso acetate to afford heterocyclic products through internal attack on the initially formed isocyanate. N- Substituted carboxamido groups are the least effective of these internal traps. Phenyliodoso acetate is much superior to lead(IV) acetate for oxidative cyclization of maleamide and various substituted propanediamides, but is not suitable for butanediamide.

ChemInform Abstract: Chemistry of 1,5‐Diketone Derivatives. Part 3. Oxidation of Araliphatic 1,5‐Diketones by Phenyliodoso Acetate.

AbstractThe reaction between the 1,5‐diketones (I) or (VI) and PhI(OAc)2 is investigated for the first time with the aim to synthesize 2‐hydroxy‐1,5‐diketones.

ChemInform Abstract: Spectral Evidence for the Formation of Active Intermediates from RuCl3 and RuC12(PPh3)3 with N‐Methylmorpholine N‐Oxide (NMO) and Phenyliodosoacetate (PIA) as Mild Oxidants.

AbstractIR, electronic, and EPR spectroscopic investigations show evidence for the formation of the three active intermediates ‐ Ru(VIII), Ru(V)‐oxo species, and Ru(II)‐triphenylphosphine oxide complex ‐ in the case of the RuC13/PIA system in acetic acid, RuC13/NMO system in DMF, and RuC12(PPh3)3/NMO system, respectively.

Spectral evidence for the formation of active intermediates from RuCl 3 and RuCl 2(PPh 3) 3 with N-methylmorpholine N-oxide (NMO) and phenyliodosoacetate (PIA) as mild oxidants

Electronic, EPR and IR spectral evidence are given for the formation of the following active species: (1) ruthenium(VIII) in ruthenium(III)-PIA system, (2) ruthenium(V) oxo species in ruthenium(III)- N- oxide system, and (3) ruthenium(II)-phosphine oxide complex in ruthenium(II) N-oxide system. Cyclic voltammetric studies also suggest the formation of Ru(V) in ruthenium(III)- N-oxide system.

Pathways in aromatic oxidations by PIA

A kinetic study of the oxidation of phenanthrene and acenaphthene by phenyliodosoacetate (PIA) in aqueous acetic acid-perchloric acid medium is reported. The order with respect to oxidant, substrate(s) and acid is each unity. A suitable mechanism is proposed and a corresponding rate law derived.

Kinetic and mechanistic aspects of redaction of lead tetraacetate and phenyl iodoso acetate by L-ascorbic acid in aqueous acetic acid

Kinetic and mechanistic aspects of redaction of lead tetraacetate and phenyl iodoso acetate by L-ascorbic acid in aqueous acetic acid

Kinetic and mechanistic aspects of redaction of lead tetraacetate and phenyl iodoso acetate by L-ascorbic acid in aqueous acetic acid

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ChemInform Abstract: KINETICS AND MECHANISM OF OXIDATION OF CYCLOPENTANONE, CYCLOHEXANONE, CYCLOHEPTANONE AND CYCLOOCTANONE BY PHENYL IODOSOACETATE

Chemischer InformationsdienstVolume 10, Issue 38 Preparative Organic Chemistry ChemInform Abstract: KINETICS AND MECHANISM OF OXIDATION OF CYCLOPENTANONE, CYCLOHEXANONE, CYCLOHEPTANONE AND CYCLOOCTANONE BY PHENYL IODOSOACETATE S. C. PATI, S. C. PATISearch for more papers by this authorB. R. DEV, B. R. DEVSearch for more papers by this author S. C. PATI, S. C. PATISearch for more papers by this authorB. R. DEV, B. R. DEVSearch for more papers by this author First published: September 18, 1979 https://doi.org/10.1002/chin.197938149AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume10, Issue38September 18, 1979 RelatedInformation

Oxidation of organic compounds by phenyl iodoso acetate (II). Kinetics and mechanism of oxidation of aldo-sugars

Kinetics of oxidation of five aldo-sugars by phenyl iodoso acetate in aqueous acetic acid medium in presence of perchloric acid has been investigated. The reaction has first order dependence on both substrate and oxidant. The reaction is retarded by perchloric acid and has unit inverse dependence on acidity. Increase in acetic acid in the solvent composition decreases the rate. A suitable mechanism involving the complex formation between the oxidant and substrate is postulated which explains the observed kinetic data.

Chemistry of trivalent iodine:part II mechanism of action of phenyliodoso acetate on p-substituted acetanilides and N-alkylanilines

Chemistry of trivalent iodine:part II mechanism of action of phenyliodoso acetate on p-substituted acetanilides and N-alkylanilines

ChemInform Abstract: THE FORMATION OF ALKYL ACETATE IN THE REACTION OF TRIALKYLBORANE WITH LEAD(IV) ACETATE OR PHENYLIODOSO ACETATE

AbstractDie Trialkylborane (I) (dargestellt aus den entsprechenden 1‐Alkenen und BH3 in THF) reagieren mit Pb‐tetraacetat in Benzol unter Bildung der Ester (II), wobei 2/3 der Alkylgruppen des Borans umgesetzt werden.

The Formation of Alkyl Acetate in the Reaction of Trialkylborane with Lead(IV) Acetate or Phenyliodoso Acetate

Abstract In the reaction of trialkylborane with lead(IV) acetate or phenyliodoso acetate in benzene, about two thirds of the alkyl groups of trialkylborane were converted to the corresponding alkyl acetate without any isomerization of the alkyl group. Lead(IV) acetate reacted preferentially with the secondary alkyl group, while phenyliodoso acetate reacted only with the primary alkyl group. In either reaction, one mole of oxidizing agent was consumed for the formation of one mole of alkyl acetate.

Volumetric determination of thioureas and mercaptans with phenyl iodosoacetate

Volumetric determination of thioureas and mercaptans with phenyl iodosoacetate

Iodonium derivatives of heterocyclic compounds

Reaction of indole with phenyl iodosoacetate in alkaline media leads to the unstable Β-phenyliodonioindole betaine, the more stable tosylate and fluoborate of which were used for the introduction of a pyridine, quinoline, and isoquinoline molecule into the Β-position of indole to give the corresponding tosylates and fluoborates of Β-(N-pyridinio)-, Β-(N-quinolinio)-, and Β-(N-isoquinolinio)indole. Intramolecular charge transfer from the donor indole system to the acceptor onium systems is detected from the UV spectral data. The acidity constants of a number of Β-onium derivatives of indole were determined by spectrophotometry.

The reaction of phenyliodoso acetate with substituted acetanilides in the presence of perchloric acid

The reaction of phenyliodoso acetate with substituted acetanilides appears to be quite complex in the presence of perchloric acid. Although there is no change in the reaction products (at least initially), there is evidence for a change in mechanism on the addition of acid. Experimental evidence suggests that the reaction involves an electrophilic substitution-yielding an acetoxy derivative in the case of p-methyl and p-methoxy compounds.

Solutions of phenyliodoso acetate. Decomposition in acetic acid and the effect of perchloric acid

Phenyliodoso acetate appears capable of sustaining both free-radical and ionic reactions. Conductivity studies on solutions of phenyliodoso acetate in acetic acid indicate a small degree of ionic dissociation at temperatures above room temperature. Photolysis of the iodoso compound is a zero-order reaction and a homolytic mechanism is proposed for the decomposition. Evidence from conductivity and spectroscopic studies indicates that there is interaction between the iodoso compound and hydrogen ions. The decomposition of phenyliodoso acetate in acetic acid is markedly accelerated by the addition of perchloric acid. In the absence of acid no conclusion about mechanism is possible; when acid is present decomposition occurs by an ionic mechanism.