Manganese amine

Polyphenylene oxide. Oxidative polymerization of 2,6-xylenol to the engineering resin polyphenylene oxide (PPO) is catalyzed by copper and manganese amines. Pyridine is a typical amine used in the polymerization. 

Divalent copper, cobalt, nickel, and vanadyl ions promote chemiluminescence from the luminol—hydrogen peroxide reaction, which can be used to determine these metals to concentrations of 1—10 ppb (272,273). The light intensity is generally linear with metal concentration of 10 to 10 M range (272). Manganese(II) can also be determined when an amine is added to increase its reduction potential by stabili2ing Mn (ITT) (272). Since all of these ions are active, ion exchange must be used for deterrnination of a particular metal in mixtures (274). 

Mn2(H2P202)2) is the stable product in the potentiometric deterrnination of manganese. Manganese(III) does not coordinate with amines or nitro complexes, but it does make manganicyanides of the types M2(Mn(CN)g) and M2(Mn(CN) (OH)), which are similar to the ferricyanides. The K", Na", LC and manganicyanides have been prepared and slowly hydroly2e in water to MnO(OH). 

Catalysts used for preparing amines from alcohols iaclude cobalt promoted with tirconium, lanthanum, cerium, or uranium (52) the metals and oxides of nickel, cobalt, and/or copper (53,54,56,60,61) metal oxides of antimony, tin, and manganese on alumina support (55) copper, nickel, and a metal belonging to the platinum group 8—10 (57) copper formate (58) nickel promoted with chromium and/or iron on alumina support (53,59) and cobalt, copper, and either iron, 2iac, or zirconium (62). 

Phenols. Phenols are unreactive toward chloroformates at room temperature and at elevated temperatures the yields of carbonates are relatively poor (< 10%) in the absence of catalysis. Many catalysts have been claimed in the patent Hterature that lead to high yields of carbonates from phenol and chloroformates. The use of catalyst is even more essential in the reaction of phenols and aryl chloroformates. Among the catalysts claimed are amphoteric metals or thek haUdes (16), magnesium haUdes (17), magnesium or manganese (18), secondary or tertiary amines such as imidazole (19), pyridine, quinoline, picoline (20—22), heterocycHc basic compounds (23) and carbonamides, thiocarbonamides, phosphoroamides, and sulfonamides (24). 

Nickel peroxide is a solid, insoluble oxidant prepared by reaction of nickel (II) salts with hypochlorite or ozone in aqueous alkaline solution. This reagent when used in nonpolar medium is similar to, but more reactive than, activated manganese dioxide in selectively oxidizing allylic or acetylenic alcohols. It also reacts rapidly with amines, phenols, hydrazones and sulfides so that selective oxidation of allylic alcohols in the presence of these functionalities may not be possible. In basic media the oxidizing power of nickel peroxide is increased and saturated primary alcohols can be oxidized directly to carboxylic acids. In the presence of ammonia at —20°, primary allylic alcohols give amides while at elevated temperatures nitriles are formed. At elevated temperatures efficient cleavage of a-glycols, a-ketols... 

At the end of the reaction time there was no unreacted amine as shown by the following test A 10-ml. aliquot was filtered through Supercel to remove the manganese dioxide, and the filtrate was added to a mixture of 25 ml. of benzene and 25 ml. of water. Extraction of the benzene layer with 10% hydrochloric acid, followed by the addition of sodium hydroxide, gave no oil layer or characteristic odor of the free amine. 

Zhang H, C-H Huang (2005) Oxidative transformation of fluoroquinolone antibacterial agents and structu-iraloly related amines by manganese dioxide. Environ Sci Technol 39 4474-4483. 

Another situation is observed when salts or transition metal complexes are added to an alcohol (primary or secondary) or alkylamine subjected to oxidation in this case, a prolonged retardation of the initiated oxidation occurs, owing to repeated chain termination. This was discovered for the first time in the study of cyclohexanol oxidation in the presence of copper salt [49]. Copper and manganese ions also exert an inhibiting effect on the initiated oxidation of 1,2-cyclohexadiene [12], aliphatic amines [19], and 1,2-disubstituted ethenes [13]. This is accounted for, first, by the dual redox nature of the peroxyl radicals H02, >C(0H)02 and >C(NHR)02 , and, second, for the ability of ions and complexes of transition metals to accept and release an electron when they are in an higher- and lower-valence state. 

Maleic anhydride Manganese dioxide Alkali metals, amines, KOH, NaOH, pyridine Aluminum, hydrogen sulfide, oxidants, potassium azide, hydrogen peroxide, peroxosulfuric acid, sodium peroxide... 

The XPS results for cobalt at pH 4, particularly the Co 2p splitting (15 eV) and the absence of shake-up satellite structure, are indicative of cobalt(III). However, the N(amine)/Co atomic ratio of 2.7 indicates that some ammonia ligands have been displaced. Since it is known (22) that hydrolysis rates for cobalt(III) complexes are very slow, the presence of cobalt with a low number of coordinated amines, suggests that hydrolysis is induced via an interaction with the birnessite surface. The cobalt to manganese ratios for bulk and surface measurements are equivalent within experimental error, a result which is consistent with a reaction process occurring primarily at the surface. It is... 

Clearly an unambiguous examination of the chemical nature of sorbed complexes using SIMS in these measurements is complicated by the presence of manganese and manganese-cobalt containing ions in the spectra. The greater relative ion intensities and the intensity distribution differences for the pH 10 sample compared to the pH 7 material, may arise due to the presence of different surface amine species. Alternatively, the difference may be related to different secondary ion formation processes for sorbed species. 

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