A copper complexes

The Colour Index (up to June 1991) Hsts 21 direct violets with disclosed chemical constitutions. Commercially important are Cl Direct Violet 9 [6227-14-1] (79) (Cl 27885) (sulfanihc acid coupled to cresidiue followed by alkaline coupling to V-phenyl J-acid) and Cl Direct Violet 66 [6798-03-4] (80) (Cl 29120) (a copper complex of 2-arniao-l-phenol-4-sulfonarnide (2 mol) coupled to 6,6 -imiQobis-l-naphthol-3-sulfonic acid). 

The Ag complex 121 in the presence of CuCl H O or CuCOTO CgHg catalyses the allylic alkylations of allyl phosphates by diaUcylzinc reagents with high enantiose-lectivity (Scheme 2.23). A copper complex 122 which is the precursor to the catalytic species was also isolated and structurally characterised (Figs. 2.21 and 2.22) [99]. 

The yellow ink jet dyes (and pigments) are metal-free azo dyes, such as Cl Direct Yellow 132 and Cl Acid Yellow 23 (Tartrazine).48,49 Most of the magentas are azo dyes derived from H-acid (l-amino-8-naphthol-3,6-disulfonic acid), such as (62), and xanthenes, such as Cl Acid Red 52 and Cl Acid Red 289.48,49 Where high lightfastness is a requirement, a copper complex azo dye, Cl Reactive Red 23 (63), is used. However, such dyes are dull (see Section 9.12.3.2). Nickel complex PAQ dyes, such as (22), are claimed to be brighter and to have similar high lightfastness... 

A number of heteroaromatic monothiocarboxylic acids are formed by Pseudomonas sp. From P. putida, there was isolated pyridine-2,6-di-(mon-othiocarboxylic acid) 46 (Scheme 16). Of interest is the fact that in P. stutzeri KC, a copper complex of 46 is the active agent for a one electron transfer in the bacterial biodegradation of CCI4. Methylation of P. putida extracts provides a number of related structures such as 47. In addition, a P. fluorescens sp. contains 8-hydroxy-4-methoxy-quinoline-2-monothiocarboxylic acid 48.98... 

Copper-catalyzed ATRP is a multicomponent system, consisting of a monomer, an initiator with a transferable (pseudo)halogen, and a copper complex (composed of a copper (pseudo)halide and nitrogen-based complexing ligand). For a successful... 

A combination of the SNAr feature and the coordination ability of a copper complex has led to the development of a new O-arylation method that makes use of a triazene as an activating and directing group (Equation (2)).32,33 This protocol, though necessitating a three-step removal sequence of the triazene moiety, has been successfully applied to the total synthesis of vancomycin1 6 and extended to a solid-phase synthesis in which the triazene unit serves as an anchor to the resin.37... 

When a copper complex of 83 is used as the catalyst, the reaction can also proceed with excellent selectivity (98% de and >98% ee for the enJo-isomer).30 Note that 83 is similar to 81, but in this compound the two phenyl groups are replaced by two t-butyl groups. 

Chapter 2 to 6 have introduced a variety of reactions such as asymmetric C-C bond formations (Chapters 2, 3, and 5), asymmetric oxidation reactions (Chapter 4), and asymmetric reduction reactions (Chapter 6). Such asymmetric reactions have been applied in several industrial processes, such as the asymmetric synthesis of l-DOPA, a drug for the treatment of Parkinson s disease, via Rh(DIPAMP)-catalyzed hydrogenation (Monsanto) the asymmetric synthesis of the cyclopropane component of cilastatin using a copper complex-catalyzed asymmetric cyclopropanation reaction (Sumitomo) and the industrial synthesis of menthol and citronellal through asymmetric isomerization of enamines and asymmetric hydrogenation reactions (Takasago). Now, the side chain of taxol can also be synthesized by several asymmetric approaches. 

Diels-Alder reactions are one of the most famous examples which are accderated by a Lewis acid. Various water-stable Lewis adds such as Ln(OTf)3,1371 methylrhenium trioxide,1381 copper nitrate,1391 copper bis(dodecyl sulfate) (4b),1401 indium chloride,1411 and bismuth triflate1421 have been used for Diels-Alder and aza-Diels-Alder reactions in water. Furthermore, a catalytic asymmetric Dids-Alder reaction in water using a copper complex of an amino... 

The presence of residual unbound transition-metal ions on a dyed substrate is a potential health hazard. Various eco standards quote maximum permissible residual metal levels. These values are a measure of the amount of free metal ions extracted by a perspiration solution [53]. Histidine (5.67) is an essential amino acid that is naturally present as a component of perspiration. It is recognised to play a part in the desorption of metal-complex dyes in perspiration fastness problems and in the fading of such chromogens by the combined effects of perspiration and sunlight. The absorption of histidine by cellophane film from aqueous solution was measured as a function of time of immersion at various pH values. On addition of histidine to an aqueous solution of a copper-complex azo reactive dye, copper-histidine coordination bonds were formed and the stability constants of the species present were determined [54]. Variations of absorption spectra with pH that accompanied coordination of histidine with copper-complex azo dyes in solution were attributable to replacement of the dihydroxyazo dye molecule by the histidine ligand [55]. 

Bleomycin (BLM) was first isolated as a copper complex from a culture of Streptomyces verticillus. Since then numerous analogs have been prepared by modifying the conditions of fermentation. Bleomycins (114, bleomycin A2) are used clinically in combination cancer chemotherapy for the treatment of head and neck cancer, certain lymphomas, and testicular cancer (555). 

A typical nitrogen ENDOR spectrum of a copper complex (Cu(sal)2) with two magnetically equivalent 14N nuclei and with the EPR observer at mF = 0 (two sets of six ENDOR lines) is shown in Fig. 9. The pronounced splitting of the lines into a doublet structure is described by the term 4/Jai. The splitting of the more intense lines by 4/ a3 is not resolved (see B5). 

The list ends here other heterocycles have failed to gain significance as coupling components for diazonium salts. The only exception is 2,4-hydroxyquinoline, which is used as a starting material for a copper complex pigment (Sec. 2.10.1.1). 

A copper complex of chlorophyll in amounts not higher than 1 pg per g of product is used for coloring preserved vegetables, however the complex cannot contain more copper than 200 pg per g (Dz. U., 2003). Non-organic copper compounds were used in the past for food coloration in the 19th Century in England, copper salts were used to color food products and condiments. 

Of the other possible structures (95) of the condensation product, the Schiff s base (CXXX) is not resolvable, nor, because of the tautomeric nature of the guanidine system, is the four-membered ring compound (CXXXI). A compound of the improbable structure (CXXXII) should yield a copper complex, which the condensation products failed to do. 

A Copper-Complexed [2]Catenane in Motion with Three Distinct Geometries... 

A different type of rearrangement involves cycloaddition of dimethyl acetylenedicarboxylate on to a copper complex which serves to activate the ligand (Scheme 73).229 The reaction is similar in some respects to that shown in equation (42), and indicates the difficulty in the categorization of many of the reactions of coordinated ligands according to mechanism. Consequently, the above account is of necessity somewhat subjective. 

The reaction is catalyzed by cupric ions and presumably results from a copper-complexed carbene.8 The electron-deficient carbene with only six electrons in its outer valence shell is known to add across the O—H bonds of un-ionized carboxyl groups to form the methyl ester. 

Robinson, N. J. Thurman, D. A. (1986). Isolation of a copper complex and its rate of appearance in roots of Mimulus guttatus. Planta 169, 192-7. 

Figure 9-4. The reaction of dioxygen with the copper complex of ascorbic acid generates a copper complex of dehydroascorbic acid.

Oxidative coupling polymerization provides great utility for the synthesis of high-performance polymers. Oxidative polymerization is also observed in vivo as important biosynthetic processes that, when catalyzed by metalloenzymes, proceed smoothly under an air atmosphere at room temperature. For example, lignin, which composes 30% of wood tissue, is produced by the oxidative polymerization of coniferyl alcohol catalyzed by laccase, an enzyme containing a copper complex as a reactive center. Tyrosine is an a-amino acid and is oxidatively polymerized by tyrosinase (Cu enzyme) to melanin, the black pigment in animals. These reactions proceed efficiently at room temperature in the presence of 02 by means of catalysis by metalloenzymes. Oxidative polymerization is observed in vivo as an important biosynthetic process that proceeds efficiently by oxidases. 

II. Claims 7 and 8, drawn to a copper complex, classified in class 556, subclass 1. 

Interestingly, when using copper(I)triflate, the cyclopentadiene dimer 14 reacts in an intermolecular way, leading to the cydobutane 15 (reaction 5) [22], When the same substrate is transformed in the presence of the triplet sensitizer acetone, an intramolecular [2 + 2] cycloaddition takes place and the cage hydrocarbon compound 16 is formed. Obviously, the formation of a copper complex intermediate involving both alkene double bonds of the substrate is unfavorable in this case. 

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