Cobalt sulfonates

It was suspected that some of the cobalt sulfonate added to the jet fuel had decomposed and the cobalt had plated onto the walls of the container before the cooperating laboratory had started the analysis. This type of loss, however, was not confirmed in a long-term stability study by neutron activation analysis, which showed that cobalt sulfonate was stable... 

The cobalt sulfone polymer was prepared by hydrogen peroxide oxidation of the corresponding sulfoxide polymer. 

Air oxidation of dyestuff waste streams has been accompHshed using cobalt phthalocyanine sulfonate catalysts (176). Aluminum has been colored with copper phthalocyanine sulfonate (177,178). Iron phthalocyanine can be used as a drier in wood oil and linseed oil paints (179). 

Photooxidafions are also iudustriaHy significant. A widely used treatment for removal of thiols from petroleum distillates is air iu the presence of sulfonated phthalocyanines (cobalt or vanadium complexes). Studies of this photoreaction (53) with the analogous ziuc phthalocyanine show a facile photooxidation of thiols, and the rate is enhanced further by cationic surfactants. For the perfume iudustry, rose oxide is produced iu low toimage quantifies by singlet oxygen oxidation of citroneUol (54). Rose bengal is the photosensitizer. 

Nitroso-l-napbthol-4-sulfonic acid (3H2O) [3682-32-4] M 316.3, m 142-146°(dec), pK ,t -6.3 (OH). Crystd from dilute HCl soln. Crystals were dried over CaCl2 in a vacuum desiccator. Also purified by dissolution in aqueous alkali and pptn by addition of water. Reagent for cobalt. 

Anionic complexes can easily be prepared by the sulfonation of the aromatic rings in the complexes. Sulfonated cobalt phthalocyanine intercalated in a layered double hydroxide host was a stable catalyst for the oxidation of thiols162,163 and phenol derivatives.164 It was concluded that the complex has been intercalated with the plane of the phthalocyanine ring perpendicular to the sheet of the host (edge-on orientation) (Fig. 7.2). 

Merox [Mercaptan oxidation] A process for removing mercaptans from petroleum fractions by extracting them into aqueous sodium hydroxide and then catalytically oxidizing them to disulfides using air. The catalyst is an organometallic compound, either a vanadium phthalocyanine supported on charcoal, or a sulfonated cobalt phthalocyanine. Developed by UOP in 1958 and widely licensed by 1994, more than 1,500 units had been built, worldwide. Unzelman, G. H. and Wolf, C. J., in Petroleum Processing Handbook, Bland, W. F. and Davidson, R. L., Eds., McGraw-Hill, New York, 1967, 3-128. 

In abroad sense, the model developed for the cobaloxime(II)-catalyzed reactions seems to be valid also for the autoxidation of the alkyl mercaptan to disulfides in the presence of cobalt(II) phthalocyanine tetra-sodium sulfonate in reverse micelles (142). It was assumed that the rate-determining electron transfer within the catalyst-substrate-dioxygen complex leads to the formation of the final products via the RS and O - radicals. The yield of the disulfide product was higher in water-oil microemulsions prepared from a cationic surfactant than in the presence of an anionic surfactant. This difference is probably due to the stabilization of the monomeric form of the catalyst in the former environment. 

ABS AE AE/P AES AG AOS APEO APG AS BiAS BM c6(EO)3 CNPEC CTAS D DATS DCPEG DEEDMAC branched alkylbenzene sulfonate alcohol ethoxylate alcohol ethoxylate/propoxylate alkylether sulfate alkyl glucamide a-olefin sulfonate alkylphenol ethoxylate alkyl polyglucoside alkyl sulfate bismuth active substances alkyldimethylbenzyl ammonium triethylene glycol monohexyl ether carboxylated nonylphenoxy carboxylates cobalt thiocyanate active substances R2S10(o.5)2 dialkyl tetralinsulfonate dicarboxylated PEG ditallow ester of di(hydroxyethyl)dimethyl ammonium chloride... 

The commonly used separator material now is the surface treated polypropylene. The surface treatment helps in making the polypropylene permanently wettable. Surface treatments involve the grafting of a chemical such as acrylic acid to the base fibers to impart wettability and is accomplished using a variety of techniques such as UV or cobalt radiation. Another method of imparting wettability to the polypropylene is a sulfonation treatment where the base fiber material is exposed to fuming sulfuric acid. The separator surface is designed to be made hydrophilic to the electrolyte. 

In 1975 Kuntz has described that the complexes formed from various rhodium-containing precursors and the sulfonated phosphines, TPPDS (2) or TPPTS (3) were active catalysts of hydroformylafion of propene and 1-hexene [15,33] in aqueous/organic biphasic systems with virtually complete retention of rhodium in the aqueous phase. The development of this fundamental discovery into a large scale industrial operation, known these days as the Ruhrchemie-Rhone Poulenc (RCH-RP) process for hydroformylation of propene, demanded intensive research efforts [21,28]. Tire final result of these is characterized by the data in Table 4.2 in comparison with cobalt- or rhodium-catalyzed processes taking place in homogeneous organic phases. 

For simple acidic extractants, such as carboxylic or sulfonic acids, the similarity in formation constants does not produce cobalt-nickel separation factors (Sn° 2) sufficiently large for commercial operation (Fig. 11.4). Data for pH versus extraction for some chelating acid extractants does seem to offer the possibility of separation [e.g., for the hydroxyoxime Acorga P50, the pHso for nickel(II) is 3.5 and for cobalt(II) 5.0]. Normally, this pH difference would be suitable for a separation process, but this particular system has hidden complications. The rate of nickel extraction is very slow compared with cobalt and, in addition, although cobalt is initially extracted... 

Earlier it was noted that nickel and cobalt could be extracted by carboxylic and sulfonic acids, with nickel being extracted at the lower pH. However, with alkylphosphorus acids, a selectivity reversal is observed, with cobalt being favored under acid conditions. The cobalt-nickel separation factor has been shown to depend upon metal concentration, reagent structure, diluent, temperature, and the presence of a diluent modifier. Thus, with increasing cobalt concentration the color of the extractant phase changes... 

Chemicals which can damage (a) the liver include carbon tetrachloride, paracetamol, bromobenzene, isoniazid, vinyl chloride, ethionine, galactosamine, halothane, dimethyl-nitrosamine (b) the kidney include hexachlorobutadiene, cadmium and mercuric salts, chloroform, ethylene glycol, aminoglycosides, phenacetin (c) the lung include paraquat, ipomeanol, asbestos, monocrotaline, sulfur dioxide, ozone, naphthalene (d) the nervous system include MPTP, hexane, organophosphoms compounds, 6-hydroxydopamine, isoniazid (e) the testes include cadmium, cyclophosphamide, phthalates, ethanemethane sulfonate, 1,3-dinitrobenzene (f) the heart include allylamine, adriamycin, cobalt, hydralazine, carbon disulfide (g) the blood include nitrobenzene, aniline, phenyl-hydrazine, dapsone. 

Hydrolysis of peptides,84 amides,85 phosphate esters,86 sulfonate esters87 and acetals88 can also be metal catalyzed. The hydrolysis of a phosphate ester coordinated to cobalt(III) also occurs at an increased rate (Scheme 19).89 A rather similar reaction occurs in the amine exchange of coordinated dithiocarbamates (equation 21).90 The conversion of imidates to amidines has been mentioned previously and is a similar type of reaction (see Section 7.4.2.2.1). 

Potassium nitrosodisulfonate, 258 Trimethylsilyl chlorochromate, 327 By hydrolysis of acetals or thioacetals Amberlyst ion-exchange resin, 152 Methylthiomethyl p-tolyl sulfone, 192 By isomerization of allylic alcohols N-Lithioethylenediamine, 157 By oxidation of aromatic side chains Trimethylsilyl chlorochromate, 327 From oxidative cleavage of alkenes [Bis(salicylidene-7-iminopropyl)-methylamine]cobalt(II)... 

The fact that only one proton is lost from an o.o -diaminodiarylazo compound on metal complex formation is not only of theoretical interest but has important practical implications in the synthesis of unsymmetrical 2 1 chromium(III) and cobalt(III) complex dyestuffs for wool. The most important complexes of these types are those which are doubly negatively charged (Section 58.1) and are obtained from one molecule of a sulfonated tridentate azo compound and one molecule of an unsulfonated tridentate azo compound. In general the latter are insoluble in water and it is necessary to use organic solvents in the manufacture of complexes such as (10). This is very undesirable from the point of view of the dyestuffs manufacturer and any means of avoiding the use of solvents is attractive to him. The use of sulfonated o,u -diaminodiarylazo compounds in combination with, for example, sulfonated o,o -dihydroxydiarylazo compounds opened up one such possibility, e.g. (77), although this has not yet been exploited commercially. 

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