Ferric Chloride Oxidation Research Articles

Synthesis and Characterization of Polythiophene Derivatives Containing Electron Transporting and Hole Transporting Moieties

Novel luminescent copolymers, poly(3-(2-benzotriazoloethyl)thiophene-co-octylcarbazolylene) ([(BET)m-OcCz2]n) that contain both electron transporting benzotriazole and hole transporting octylcarbazole moiety were synthesized by oxidation of ferric chloride with changing the composition ratio of BET and OcCz. The absorption peak of UV-VIS was blue-shifted from λmax=440 nm in poly(3-(2-benzotriazoloethyl)thiophene) (PBET) to λmax= 412 nm in [(BET)4-OcCz2]n. The photolumine scence (PL) and electroluminescence (EL) intensities of the polymers were decreased with presence of carbazole moieties in the copolymer.

Synthesis of Triphenylene-Based Discotic Liquid Crystal Monomer Containing Azobenzene Moieties

ABSTRACTThe synthesis of a novel discotic liquid crystal monomer was carried out based on vinyl monomer whose molecular architecture consists of a triphenylene as central core and the peripheral cores were linked to the central core through an alkyl chain spacer. Consequently, a disk-like poymerizable monomer 2, 3, 6, 7, 10, 11-hexakis-[11-(4-{4-(acryloxy)phenylazo}phenoxy)undecanoxy]triphenylene was prepared by using a ferric chloride oxidation method. Polarizing optical microscopy and DSC analysis shows that the monomer exhibited a wide columnar mesophase. UV-vis spectra of the azobenzene mesogens showed that a significant tailing, which would allow the use of laser in the visible range to photoinduce isomerization and reorientation of the azo groups.

Extended triphenylenes: synthesis, mesomorphic properties and molecularly resolved scanning tunneling microscopy images of hexakis(dialkoxyphenyl)triphenylenes and dodeca(alkoxy)tris(triphenylenylene)s

Palladium-catalyzed cross-coupling between 3,4-dialkoxyphenylboronic acids (1a–d) and 2,3,6,7,10,11-hexabromotriphenylene (2) provided 2,3,6,7,10,11-hexakis[3,4-bis(alkoxy)phenyl]triphenylenes, C18H6[C6H3(OCnH2n + 1)2]6 where n = 6, 8, 10, and 12 (3a–d). Cyclodehydrogenation of the aryl-substituted triphenylenes 3a–d using ferric chloride oxidation followed by methanol reduction produced 6,6′,6″,7,7′,7″,10,10′,10″,11,11′,11″-dodecaalkoxy-2,3′:3,2″:2′,3″-tris(triphenylenylene)s, C54H18(OCnH2n + 1)12 where n = 6, 8, 10, and 12 (4a–d). The mesomorphic properties of the compounds 3a–d and 4a–d were investigated by differential scanning calorimetry (DSC) measurements, polarizing microscopy, and wide angle X-ray diffraction (WAXD). The triphenylenes 3a–d exhibited a columnar mesophase in the range of 111–126, 85–104, 74–103, and 47–101 °C, respectively. Upon oxidation of the moiety, the columnar mesophases shift to higher temperatures and exist in a much broader range of temperatures: for the tris(triphenylenylene)s 4a–d, they have been observed in the range of 180–430, 150–370, 120–322, and 104–306 °C, respectively. Finally, the self-assembly at the interface between a solution of 4c and a graphite substrate has been studied by scanning tunneling microscopy. Molecularly resolved imaging revealed a highly ordered monolayer exhibiting a two-dimensional hexagonal lattice.

Photoactivated Ferric Chloride Oxidation of Carotenoids by Near-UV to Visible Light

When canthaxanthin (I) and β-carotene (II) dichloromethane solutions are treated with small amounts of ferric chloride (≤0.26 mol equiv), extensive photodegradation of the remaining unreacted neutral carotenoid occurs upon subsequent irradiation with near-UV to visible light. The rate of this photodegradation is independent of the neutral carotenoid concentration at a given initial FeCl3 concentration and first-order in initial FeCl3 (k1 = 1.43 and 3.30 min-1 for I and II, respectively). The data are consistent with a mechanism in which Fe(II) is photochemically converted in the presence of CH2Cl2 to Fe(III), which then oxidizes unreacted neutral carotenoids. We also report that canthaxanthin radical cations in dichloromethane form cation dehydrodimers at low temperature or upon irradiation with near-UV to visible light, which have an absorption maximum near 770 nm and a reduction peak at 20 mV in cyclic voltammetry. It is proposed that radical cations associate with parent molecules and then undergo two ...

Derivate des 1.3-BenzdioxoIs, 52 Darstellung und Reaktionen von 1.3-Dioxolo[4.5-b]phenazinen / Derivatives of 1,3-Benzdioxoles, 52 Preparation and Reactions of 1,3-Dioxolo[4,5-b]phenazines

We describe the preparation of the 1,3-dioxolo[4,5-b]phenazines 4 a -p formed by ferric chloride oxidation of the corresponding 2,2′-diaminodiphenylamines. They are obtained by condensing the o-nitrohalogenbenzenes 1 a -g with o-nitroanilines 2 a-i and reduction of the resulting 2,2′-dinitrodiphenylamines 3 a -p with H2/Pd.

Ferric chloride oxidation of isoeugenol

Ferric chloride oxidation of isoeugenol gave 5 products. The elucidation of the structures of those products and the mechanism of their formation are discussed.

Quinones. Part 2. General synthetic routes to quinone derivatives with modified polyprenyl side chains and the inhibitory effects of these quinones on the generation of the slow reacting substance of anaphylaxis (SRS-A)

General synthetic routes to quinone acids (8), quinone amides (9), quinone alcohols (10), and quinone methylketones (11) with polyprenyl side chains, in which allylic alcohols (3) are employed as the key intermediates, are described. The Claisen rearrangements and the Carrot reactions of the allylic alcohols (3) with ethyl orthoacetate and diketen produced the ethyl esters (4) and the methylketones (5), respectively. Quinone products (8), (10), and (11) were recovered by oxidative demethylation of hydroquinone dimethyl ethers (4), (5), and (7) or by acid hydrolysis of hydroquinone bis(methoxymethyl) ethers (4) and (5) followed by ferric chloride oxidation. Amidation of quinone acids (8) led to the formation of quinone amides (9). Inhibitory effects of these quinone derivatives on the generation of the slow reacting substance of anaphylaxis (SRS-A) in the lungs of sensitised guinea pigs are evaluated.

ChemInform Abstract: PHOTOCHEMICAL OXIDATION OF ALCOHOLS USING FERRIC CHLORIDE

Chemischer InformationsdienstVolume 8, Issue 20 Preparative Organic Chemistry ChemInform Abstract: PHOTOCHEMICAL OXIDATION OF ALCOHOLS USING FERRIC CHLORIDE V. I. STENBERG, V. I. STENBERGSearch for more papers by this authorS. P. SINGH, S. P. SINGHSearch for more papers by this authorN. K. NARAIN, N. K. NARAINSearch for more papers by this authorS. S. PARMAR, S. S. PARMARSearch for more papers by this author V. I. STENBERG, V. I. STENBERGSearch for more papers by this authorS. P. SINGH, S. P. SINGHSearch for more papers by this authorN. K. NARAIN, N. K. NARAINSearch for more papers by this authorS. S. PARMAR, S. S. PARMARSearch for more papers by this author First published: May 17, 1977 https://doi.org/10.1002/chin.197720152Read the full textAboutPDF 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 onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume8, Issue20May 17, 1977 RelatedInformation

Reduction and azo coupling of quinones. A histochemical study of human cutaneous melanin and adrenochrome.

Cutaneous melanin in formol fixed skin and adrenochrome in dichromate fixed monkey adrenal after adequate bisulfite or dithonite reduction were found to give definite azo coupling reactions. Weaker reactions were obtained on unreduced material, and these disappeared on ferric chloride oxidation. Both cutaneous melanin and adrenochrome appear to exist in a quinhydrone status. Prolongation of dichromate treatment weakens or abolishes azo coupling capacity of adrenochrome. The findings support the concept of quinonization and reduction to prevent and restore azo coupling of enterochromaffin cells and noradrenaline islets of the adrenal. The most effective diazos for melanin were p-nitrodiazobenzene, fast black K and the diazosulfanilic acid, pH 1 pyronin B procedure, for adrenochrome. Diazosafranin and 2-chloro-4-nitrodiazobenzene were also useful. Blue and violet coupling products from toluidine blue and methylene violet RR fail to yield sufficient contrast to be convincing.

Volubilinin, a new isoflavone- C-glycoside from Dalbergia volubilis flowers

Abstract Dalbergia volubilis flowers after successive extraction with light petroleum, benzene and alcohol yielded β-sitosterol, stigmasterol, biochanin-A and a new isoflavone- C -glycoside named volubilin. The glvcoside on boiling with HI and phenol gave genistein and on ferric chloride oxidation rhamnose. The compound was identified as 8- C -rhamnopyranosyl-genistein-4′,7-dimethyl ether by means of chemical reactions as well as from spectral data.

Volubilin, a new isoflavone- C-glycoside from Dalbergia volubilis flowers

Dalbergia volubilis flowers after successive extraction with light petroleum, benzene and alcohol yielded β-sitosterol, stigmasterol, biochanin-A and a new isoflavone- C-glycoside named volubilin. The glvcoside on boiling with HI and phenol gave genistein and on ferric chloride oxidation rhamnose. The compound was identified as 8- C-rhamnopyranosyl-genistein-4′,7-dimethyl ether by means of chemical reactions as well as from spectral data.

Formation of indole derivatives by phenolic oxidative coupling

Ferric chloride oxidation of 3-hydroxy-4-methoxyphenethylamine (3) and N-(3-hydroxy-4-methoxyphenethyl)-ethylamine (6) afforded the corresponding indole derivatives (10) and (11), respectively, in moderate yield. The synthesis of the indole derivative (13) from N-(3-hydroxybenzyl)dopamine (7) by phenolic oxidative coupling with potassium ferricyanide is also described.

The oxidation products of crude mesobilirubinogen.

Bile pigment esters were separated by ascending t.l.c. Apparently pure pigments, obtained by ferric chloride oxidation of crude mesobilirubinogen, derived from commercial bilirubin by reduction with sodium amalgam, were shown to be complex mixtures. Successive chromatography of their dimethyl esters on silica gel in methyl acetate-methyl propionate-dichloromethane-carbon tetrachloride (1:1:1:1, by vol.), ethyl methyl ketone-1,2-dichloroethane (1:2, v/v) and benzene-ethanol (100:3, v/v) revealed two major blue pigments (verdins), six major violet pigments (violins) and a red pigment (rhodin) together with numerous minor components. i-Urobilin dimethyl ester, prepared from mesobilirubinogen by dehydrogenation with aqueous iodine, was resolved into three major and at least four minor components on silica gel-kieselguhr (3:1, w/w) in benzene-ethanol (25:2, v/v). The chemical nature of these pigments was investigated by oxidation, by visible and u.v. spectroscopy, by mass spectrometry and by n.m.r. spectrometry. The evidence suggests unusual rearrangement of bilirubin during reduction leading to the formation of IIIalpha and XIIIalpha isomers. Isomeric forms of mesobiliviolin IXalpha and of i-urobilin IXalpha may also be formed.

Mass spectrometry and ferric chloride oxidation applied to urobilinoid structures

The mass spectra of a large number of bilirubinoid and urobilinoid substances have been measured. The time-varying intensities in the parent ion regions of these materials have been scrutinized and interpreted in terms of oxidation and reduction reactions taking place prior to volatilization and electron impact. Structural and stereochemical implications of the ferric chloride oxidation method for the urobilinoids are discussed. Correlations of the results of this method with mass spectrometric data provide a basis for the categorization of urobilinoids into three classes: Dipyrrolinone (e.g. d-urobilins, mol wt 588 and 590), pyrrolinone-pyrrolidone (e.g., half-stercobilin mol wt 592), and dipyrrolidone (e.g., stercobilin mol wt 594).

A new method of interpretation of the ferric chloride oxidation patterns of the urobilinoids

A new and more definitive interpretation of the results of a standard method of FeCl 3 oxidation of the urobilinoids is presented. This interpretation is based on the actual yields of mesobiliviolin, glaucobilin, or unchanged urobilinoid. The yields are used to calculate the two distinctive ratios characteristic of urobilinoid type. Correction is made for the effects due to overlapping of spectra and the method has been programmed for a digital computer. Blind analyses of appropriate known mixtures of l-stercobilin, mesobiliviolin, and glaucobilin have given satisfactory results. Comparison of the ratios following FeCl 3 oxidation of binary mixtures of representative urobilinoids permits analysis of their composition. Evidence is presented that the FeCl 3 method involves two types of oxidation: (a) Dehydrogenation to mesobiliviolin and glaucobilin, the extent of oxidation depending on saturation or unsaturation of the end rings. Stercobilin, with both end rings saturated, yields neither mesobiliviolin or glaucobilin; half-stercobilin with one end ring saturated yields stable mesobiliviolin and unreacted urobilinoid; and the urobilins proper, with both end rings unsaturated, are converted first to labile mesobiliviolin then to glaucobilin. (b) All three types also undergo some degradative oxidation as indicated by the presence of ethylmethylmaleimide from unsaturated, and ethylmethylsuceinimide from saturated end rings.

C-Glycosylflavonoids. The chemistry of orientin and iso-orientin

1. The structures of orientin and iso-orientin have been investigated by periodic acid and ferric chloride oxidation of the tetra-O-methyl derivatives and by identification of the products of oxidation. 2. The preparation and properties of the 3',4',7-trimethyl ethers of orientin and iso-orientin are described, and the nuclear-magnetic-resonance spectra of orientin, iso-orientin and their tri- and tetra-O-methyl derivatives are discussed. 3. Orientin and iso-orientin are formulated as 8- and 6-C-beta-d-glucopyranosyl-luteolin respectively.

The Ferric Chloride Oxidation of 5-Substituted o-Semidines and the Polarographic Properties of the Products

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTThe Ferric Chloride Oxidation of 5-Substituted o-Semidines and the Polarographic Properties of the ProductsAlfred P. Kottenhahn, Eddie T. Seo, and Hosmer W. StoneCite this: J. Org. Chem. 1963, 28, 11, 3114–3120Publication Date (Print):November 1, 1963Publication History Published online1 May 2002Published inissue 1 November 1963https://doi.org/10.1021/jo01046a043RIGHTS & PERMISSIONSArticle Views135Altmetric-Citations10LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (918 KB) Get e-Alerts Get e-Alerts

Über die Chemie des Vitamins E. 1. Mitteilung. Die Umkehrung der Konfiguration am Kohlenstoffatom 2 von natürlichem (2 R, 4′ R, 8′ R)‐α‐Tocopherol

Abstract(2 S, 4′R, 8′R)‐α‐Tocopherol with unnatural configuration at C‐2 is prepared by oxidation of natural, so called d‐α‐tocopherol (I), which has the (2R, 4′R, 8′R)‐configuration, to α‐tocopherylquinone (II), followed by recyclization of the corresponding α‐tocopherylhydroquinone (III). Experiments showed that the configuration of carbon atom 2 of natural α‐tocopherol is retained during the ferric chloride oxidation (I →II) and is predominantly inverted by zinc chloride cyclization of α‐tocopherylhydroquinone (III).

Phenazines—III : The synthesis of 7-aminophenazine-1-, 7-aminophenazine-2- and 8-aminophenazine-2-carboxylic acids

Ferric chloride oxidation of 2,4′-diamino-4- and -5-cyanodiphenylamines led to 2-amino-8- and -7-cyanophenazines respectively which could be hydrolysed to the corresponding 7- and 8-aminophenazine-2-carboxylic acids. 8-Aminophenazine-2-carboxylic acid was also made by the oxidative cyclization in boiling nitrobenzene of 2,4′-diaminodiphenylamine-4-carboxylic acid; 4′,6-diaminodiphenylamine-2-carboxylic acid similarly gave 7-aminophenazine-1-carboxylic acid.