Ring Contraction Through Epoxide Rearrangement: A Formal Synthesis of Capsorubin

An eight-step synthesis of the cyclopentane keto-alcohol 2, which has previously been converted in one step into the carotenoid pigment capsorubin (1), is described. The key step in our synthesis is a stereospecific epoxide rearrangement with ring contraction, thus producing the cyclopentane ring from an epoxide of a cyclohexene.     

The Identification and Quantitative Analysis of Unusual Keto-Carotenoids in Ripe Fruits of Maclura tricuspidate and Its Potential as a Valuable Source of Cryptocapsin

Ripe fruits of Maclura tricuspidata (MT) are used as food material and a natural colorant in Korea. Although MT fruits have a deep red color due to carotenoid-like pigments, their chemical nature has not been explored in detail so far. The present study aimed at elucidating the chemical structures and composition of carotenoids in MT fruits and changes at different maturity stages. Two carotenoids from saponified MT fruit extract were isolated using repeated silica gel column chromatography. Based on interpretations of spectroscopic data, these compounds were determined as keto-carotenoids, i.e., capsanthin (3,3′-dihydroxy-β,κ-caroten-6′-one) and cryptocapsin (3′-hydroxy-β,κ-caroten-6’-one), and the contents of individual carotenoids were quantified with HPLC based on calibration curves obtained from authentic standards. The contents of capsanthin and cryptocapsin in the sample of saponified MT fruits were 57.65 ± 1.97 µg/g and 171.66 ± 4.85 μg/g as dry weight base (dw). The majority of these keto-carotenoids in the MT fruits were present in esterified forms with lauric, myristic or palmitic acid rather than in their free forms. The results also showed that esterification of these compounds occurred starting from early stage (yellow-brownish stage) of maturation. Considering the high cryptocapsin content, MT fruits can be applied as a potentially valuable source of cryptocapsin for food and medicinal application as well as a source of provitamin A.     

Reduction and determination of dixanthogens

A convenient method for the reduction and determination of dixaathogen has been developed. It is based on the quantitative reaction of dixanthogen with zinc amalgam to form xanthate; the latter can be determined by iodine titration, potentiometric titration with silver nitrate or by spectrophotometry at 310 mmu. Dixanthogen can be determined in mixtures containing xanthate, by titration of aliquots with and without reduction. Higher dixanthogens can also be determined, and flotation liquors analysed.     

广义氧化还原

在提出广义氧化还原新概念的基础上，利用广义氧化还原电极电势判断无机化学反应的方向、顺序和计算反应的平衡常数，使溶液中无机化学反应系统化。     

Reduction and Oxidation of Simple Oxocuprates

Oxidation-reduction reactions were studied for the following oxocuprates: LiCuO, Li₂CuO₂, SrCu₂O₂, Sr₂CuO₃, SrCuO₂, BaCu₂O₂, BaCuO₂,LaCuO₂, La₂CuO₄, Ca₂CuO₃ and Bi₂CuO₄. Transformation schemes have been proposed for the anionic sub-lattices of these salts and the effect of cations on the properties of the anionic sub-lattices in oxidation-reduction reactions was determined. This revised version was published online in August 2006 with corrections to the Cover Date.     

Synthesis and Electrochemical Reduction of Nitro-Alkanephosphonates

Abstract

As a continuation of our research program [l, 2], directed to the synthesis of aminoalkanephosphonates, we present here the synthesis of 1-amino-nitroalkanephosphonid acids 5, prepared according to eq. 1. The electrochemical reduction of amino acids 5 to the derivatives 6 and 7 (eq. 2) have been investigated.     

Reduction of dichlorodiphenylstannane

Reduction of dichlorodiphenylstannane with lithium followed by treatment with methyl iodide gave methyltriphenylstannane, dimethyldiphenylstannane and 1,2‐dimethyldistannane. 1,2‐Dilithiodistannane and triphenylstannyllithium were intermediates of this reaction. Copyright © 2005 John Wiley & Sons, Ltd.     

Reduction of bis

The reduction of symmetric, fully-substituted titanocene dichlorides bearing two pendant omega-alkenyl groups, [TiCl2(eta5-C5Me4R)2], R = CH(Me)CH= CH2 (1a). (CH2)2CH=CH2 (1b) and (CH2)3CH=CH2 (1c), by magnesium in tetrahydrofuran affords bis(cyclopentadienyl)titanacyclopentanes [Ti(IV)[eta1:eta1: eta5:eta5-C5Me4CH(Me)CH(Ti)CH2CH(CH2(Ti))CH(Me)C5Me4]] (2a), [Ti(IV)[eta1:eta1:eta5: eta5-C5Me4(CH2)2CH(Ti)(CH2)2CH(Ti)(CH2)2C5Me4]] (2b) and [Ti(IV)[eta1:eta1:eta5:eta5-C5Me4(CH2)2CH(Ti)CH(Me)CH(Me)CH(Ti)(CH2)2C5Me4]](2c), respectively, as the products of oxidative coupling of the double bonds across a titanocene intermediate. For the case of complex 1c, a product of a double bond isomerisation is obtained owing to a preferred formation of five-membered titanacycles. The reaction of the titanacyclopentanes with PbCl2 recovers starting materials 1a from 2a and 1b from 2b, but complex 2c affords, under the same conditions, an isomer of 1c with a shifted carbon - carbon double bond, [TiCl[eta5-C5Me4(CH2CH2CH=CHMe)]2] (1c'). The titanacycles 2a-c can be opened by HCl to give ansa-titanocene dichlorides ansa-[[eta5:eta5-C5Me4CH(Me)CH2CH2CH(Me)CH(Me)C5Me4]TiCl2] (3a), ansa-[[eta5:eta5-C5Me4(CH2)8C5Me4]TiCl2] (3b), along with a minor product ansa-[[eta5:eta5-C5Me4CH2CH=CH(CH2)5C5Me4]TiCl2] (3b'), and ansa-[[eta5:eta5-CsMe4(CH2)3CH(Me)CH(Me)CH=CHCH2C5Me4]TiCl2] (3c), respectively, with the bridging aliphatic chain consisting of five (3a) and eight (3b, 3b' and 3c) carbon atoms. The course of the acidolysis changes with the nature of the pendant group; while the cyclopentadienyl ring-linking carbon chains in 3a and 3b are fully saturated, compounds 3c and 3b' contain one asymetrically placed carbon-carbon double bond, which evidently arises from the beta-hydrogen elimination that follows the HCl addition.     

Temperature Programmed Reduction and Spectroscopic Studies of Reduction Behavior of fe/tiO2 Catalyst

Fe/TiO₂ catalyst was prepared by incipient wetness impregnation of TiO₂ with aqueous solution of ferric nitrate. The reduction behavior of the catalyst was studied by temperature programmed reduction profiles, Mössbauer spectroscopy, x-ray diffraction and x-ray photoelectron spectroscopy. The results show that the reduction of Fe/TiO₂ was accompanied by a phase transition of anatase to rutile titania. α-Fe₂O₃ was reduced to Fe₃O₄ in the initial reduction stage. Due to the strong support effect of TIO₂, FeTiO₃ was gradually formed as the reduction temperature reached 450°C. Complete reduction to the metallic Fe° particles occurred at temperatures higher than 670°C. The anatase-rutile transition was initiated by the reduced Ti³⁺ ions and led to the formation of TiO_x. At higher reduction temperature, TiO_x migrated to the surface of metallic Fe° particles forming FeTiO_x in the so-called strong metal-support interaction (SMSI) state.     

meso-Arylporpholactones and their Reduction Products

The rational syntheses of meso-tetraaryl-3-oxo-2-oxaporphyrins 5, known as porpholactones, via MnO(4)(-)-mediated oxidations of the corresponding meso-tetraaryl-2,3-dihydroxychlorins (7) is detailed. Since chlorin 7 is prepared from the parent porphyrin 1, this amounts to a 2-step replacement of a pyrrole moiety in 1 by an oxazolone moiety. The stepwise reduction of the porpholactone 5 results in the formation of chlorin analogues, meso-tetraaryl-3-hydroxy-2-oxachlorin (11) and meso-tetraaryl-2-oxachlorins (12). The reactivity of 11 with respect to nucleophilic substitution by O-, N-, and S-nucleophiles is described. The profound photophysical consequences of the formal replacement of a pyrrole with an oxazolone (porphyrin-like chromophore) or (substituted) oxazole moiety (chlorin-like chromophore with, for the parent oxazolochlorin 12, red-shifted Q(x) band with enhanced oscillator strengths) are detailed and rationalized on the basis of SAC-CI and MNDO-PSDCI molecular orbital theory calculations. The single crystal X-ray structures of the porpholactones point at a minor steric interaction between the carbonyl oxygen and the flanking phenyl group. The essentially planar structures of all chromophores in all oxidation states prove that the observed optical properties originate from the intrinsic electronic properties of the chromophores and are not subject to conformational modulation.     

黄鸣龙还原法

综述了黄鸣龙还原法的发展历史、发现经过、反应机理、应用范围和限制以及实验时应注意之处.     

广义氧化还原滴定

根据广义氧化还原新概念 ,提出了广义氧化还原滴定。广义氧化还原滴定包括酸碱滴定、沉淀滴定、配位滴定和氧化还原滴定。它们的滴定曲线可以由相同的原理绘出     

Reduction of isocyanates and carbodiimides via hydrosilylation

The hydrosilylation of isocyanates is promoted by palladium catalysts and affords N-silylformamides or C-silylamides. The orientation of the reaction depended upon the structure of isocyanates. The reaction of carbodiimides with silicon hydrides, catalyzed by PdCl₂ or (Ph₃P)₃RhCl, required higher temperatures to give N-silylformamidines. The adducts obtained in these reactions are precursors to formamides, formamidines, and their N-acetyl derivatives.     

Polarographic Reduction of Alkylarsonic and Dialkylarsinic Acids

Abstract

The polarographic reduction of the alkylarsonic acids, C_nH_2n+1AsO₃H₂ (n=1–8) and the dialkylarsinic acids (C_nH_2n+1)₂AsOOH (n=2–4; c-C₆H₁₁) by differential pulse polarography is described.     

Reduction of 9-aminoarylacridines and their salts

9-Formamidoarylacridans are obtained in the reduction of 9-aminoarylacridines with a free amino group by means of formic acid in the presence of triethylamine. Under these conditions N,N-dialkyl derivatives are cleaved to 9-unsubstituted acridan and dialkylanilines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 814–816, June, 1975.