Group copper complexes

The introduction of copper into conventional substantive dyes often increases their light and wetfastness considerably, since complexing blocks the hydrophilic groups. Copper complexes of o,o -disubstituted azo dyes are chiefly of interest for direct dyes. Substituents especially capable of complexing are hydroxyl, meth-oxy, carboxy, and carbomethoxy groups. BASF developed the oxidative copper treatment process in which on the basis of o-hydro xyazo dyes, copper complexes of the corresponding o,o -dihydroxyazo dyes are obtained [9],... 

A substantial fraction of the named enzymes are oxido-reductases, responsible for shuttling electrons along metabolic pathways that reduce carbon dioxide to sugar (in the case of plants), or reduce oxygen to water (in the case of mammals). The oxido-reductases that drive these processes involve a small set of redox active cofactors , that is, small chemical groups that gain or lose electrons. These cofactors include iron porjDhyrins, iron-sulfur clusters and copper complexes as well as organic species that are ET active. 

Direct Blue 218 had reported sales of 623 t valued at 4.4 million ia 1987. It is produced from Direct Blue 15 (76) by metallizing and elimination of methyl groups from the methoxide to form the copper complex. Direct Blue 15 (76) is prepared by coupling o-dianisidine [119-90-4] to two moles of H-acid (4-amiQO-5-hydroxy-2,7-naphthalenedisulfonic acid) under alkaline pH conditions. Other important direct blues iaclude Direct Blue 80 (74), (9-dianisidine coupled to two moles of R-acid (3-hydroxy-2,7-naphthalenedisulfonic acid [148-75-4]) followed by metallizing to form a bis copper complex, and Direct Blue 22 (77), an asymmetrical disazo dye, prepared by coupling o-dianisidine to Chicago acid [82-47-3] and 2-naphthol. Direct Blue 75 (78) is an example of a trisazo dye represented as metanilic acid — 1,6-Q.eve s acid — 1,6-Q.eve s acid — (alb) Ai-phenyl J-acid. 

Potassium sodium copper chlorophyllin (chiorophyllin—copper complex)—A green-black powder obtained from chlorophyll by replacing the methyl and phytyl ester groups with alkaH and replacing the magnesium with copper. The source of the chlorophyll is dehydrated alfalfa. 

Forma n dyes bear a formal resemblance to a2o dyes, since they contain an a2o group but have sufficient stmctural dissimilarities to be considered as a separate class of dyes. The most important forma2an dyes are the metal complexes, particularly copper complexes, of tetradentate forma2ans. They are used as reactive dyes for cotton (81) is a representative example. 

The series M(PP)C1 (PP = 2,ll-bis(diphenylphosphinomethyl)benzo[c]-phenanthrene M = Cu, Ag, Au) is interesting in showing group trends (Table 4.7) where the silver and copper complexes have trigonal coordination and the gold member is linear [50]. 

Complexes III and IV have Fe-porphyrin prosthetic groups (hemes), complex IV also contains copper atoms which are involved in electron transport. Complexes I, III, and IV use the energy of electron transport to pump protons out of the matrix so as to maintain a pH gradient and an electrical potential difference across the inner membrane required for ATP synthesis (see below and Appendix 3). It is important to remember that all dehydrogenations of metabolic substrates remove two protons as well as two electrons and that a corresponding number of protons are consumed in the final reduction of dioxygen (Figures 5, 6). 

This group showed that isolable silver(I) diaminocarbene complexes can be use in situ instead of free carbenes, to generate the copper carbene complex. The silver salts that precipitates during the formation of the copper complex have not any negative effect on the conversion. This method is advantageous since most of the silver complexes are isolable, air-stable and easily obtained by treatment of the corresponding imidazohnium salt by 0.5 equiv of silver oxide (Scheme 53). The solid structure of 78 was analyzed by X-ray diffraction. 

The treatment of LB films of copper behenate (10-50 layers) with H2S gas resulted in formation of the semiconductor CU2S [177]. In this case, the LB films of behenic acid alone were formed and then exposed to solutions of copper chloride. Conversion of the carboxyl groups to carboxylate groups upon copper complexation was confirmed by infrared spectroscopy. Resistivity measurements versus temperature confirmed the formation of semiconducting CU2S in one case, and showed a linear increase in log(R) versus IT K). All of the samples became insulators on exposure to air maintaining the conductivity required storage under vacuum. The formation of CuiS sheets in some of the sample was concluded from optical microscopy and resistivity data. 

The hydrosilylation of carbonyl compounds by EtjSiH catalysed by the copper NHC complexes 65 and 66-67 constitutes a convenient method for the direct synthesis of silyl-protected alcohols (silyl ethers). The catalysts can be generated in situ from the corresponding imidazolium salts, base and CuCl or [Cu(MeCN) ]X", respectively. The catalytic reactions usually occur at room tanperature in THE with very good conversions and exhibit good functional group tolerance. Complex 66, which is more active than 65, allows the reactions to be run under lower silane loadings and is preferred for the hydrosilylation of hindered ketones. The wide scope of application of the copper catalyst [dialkyl-, arylalkyl-ketones, aldehydes (even enoUsable) and esters] is evident from some examples compiled in Table 2.3 [51-53],... 

In addition, the same group has used copper complexes of these ligands as efficient catalysts for enantioselective Cu-catalysed aza-Diels-Alder reactions of A-sulfonyl imines with Danishefsky s dienes, providing the corresponding six-membered heterocycles with enantioselectivities of up to 80% ee. ... 

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... 

Bis(oxazoline)-copper complexes 158 have been used by Evans group as chiral catalysts for the enantioselective aziridination of olefins.116 Aryl-substituted olefins have been found to be particularly suitable substrates, which can be efficiently converted to A-tosylaziridines with ee of up to 97% (R = Ph... 

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