Mercuric nitrate, catalysts

On the basis of his own experiments, Zakharov suggested a different mechanism of reaction. He believed that the catalyst initially weakens the stability of the aromatic ring by the rupture of a double bond on the attachment of mercuric nitrate, e g. ... 

The reaction takes place in the presence of mercuric nitrate as a catalyst at... 

Various forms of inorganic mercury are used in industry in battery production and as catalysts. Mercuric nitrate was previously used in tanneries and the fur trade (see pp. 166-7). Clearly these can cause both pollution and human poisoning. However, the form of mercury most likely to be associated with environmental pollution and to cause problems is organomercury. This is because in this form mercury is soluble in fat and can accumulate in animals in the food chain. The cases of serious environmental mercury pollution and poisoning illustrate this well. 

A review on mercuric salts in nitration was given by Titov and Laptev (79. Japanese authors Tsutsumi and Iwata [80], Osawa and co-workers [81 j have found that mercuric oxide and mercuric nitrate were catalysts of nitration with nitric acid. Komoto and co-workers [82] found that mercuric acetate catalysed nitration of toluene with nitric and acetic acid at 80 C. 

The effect of various metal salt catalysts [29-33] on the production of olefin-sulfiir dioxide copolymers was studied earlier by Frey, Snow, and Schulze [33]. It was found that the soluble catalysts (silver nitrate, lithium nitrate, ammonium nitrate, and dilute alcoholic nitric acid) are much more effective than insoluble salts (barium nitrate, zirconium nitrate, titanium nitrate, strontium nitrate, and mercuric nitrate) which usually have long induction periods for reactions as shown in Table III [33]. 

Use of mercuric catalysts has created a serious pollution problem thereby limiting the manufacture of such acids. Other catalysts such as palladium or mthenium have been proposed (17). Nitration of anthraquinone has been studied intensively in an effort to obtain 1-nitroanthraquinone [82-34-8] suitable for the manufacture of 1-aminoanthraquinone [82-45-1]. However, the nitration proceeds so rapidly that a mixture of mono- and dinitroanthraquinone is produced. It has not been possible, economically, to separate from this mixture 1-nitroanthraquinone in a yield and purity suitable for the manufacture of 1-aminoanthraquinone. Chlorination of anthraquinone cannot be used to manufacture 1-chloroanthraquinone [82-44-0] since polychlorinated products are formed readily. Consequentiy, 1-chloroanthraquinone is manufactured by reaction of anthraquinone-l-sulfonic acid [82-49-5] with sodium chlorate and hydrochloric acid (18). 

Methylene groups adjacent to aromatic rings are oxidized to keto groups by oxygen with chromium sesquioxide as a catalyst [1128] or by mercuric bromide [11], ceric ammonium nitrate [380, 417, 422], selenium dioxide [509], sodium dichromate [622, 625], pyridinium chlorochromate [607], manganese dioxide [814], potassium permanganate [866, 877], and alkyl nitrites [452]. 

Color reactions Boric acid (hydroxyquinones). Dimethylaminobenzaldehyde (pyrroles). Ferric chloride (enols, phenols). Haloform test. Phenylhydrazine (Porter-Silber reaction). Sulfoacetic acid (Liebermann-Burchard test). Tetranitromethane (unsaturation). Condensation catalysts /3-Alanine. Ammonium acetate (formate). Ammonium nitrate. Benzyltrimethylammonium chloride. Boric acid. Boron trilluoride. Calcium hydride. Cesium fluoride. Glycine. Ion-exchange resins. Lead oxide. Lithium amide. Mercuric cyanide. 3-Methyl-l-ethyl-2-phosphoiene-l-oxlde. 3-Methyl-1-phenyi-3-phoipholene-1-oxide. Oxalic acid. Perchloric acid. Piperidine. Potaiaium r-butoxIde. Potassium fluoride. Potassium... 

In contrast to aliphatic alcohols, which are mostly less acidic than phenol, phenol forms salts with aqueous alkali hydroxide solutions. At room temperature, phenol can be liberated from the salts even with carbon dioxide. At temperatures near the boiling point of phenol, it can displace carboxylic acids, e.g. acetic acid, from their salts, and then phenolates are formed. The contribution of ortho- and -quinonoid resonance structures allows electrophilic substitution reactions such as chlorination, sulphonation, nitration, nitrosation and mercuration. The introduction of two or three nitro groups into the benzene ring can only be achieved indirectly because of the sensitivity of phenol towards oxidation. Nitrosation in the para position can be carried out even at ice bath temperature. Phenol readily reacts with carbonyl compounds in the presence of acid or basic catalysts. Formaldehyde reacts with phenol to yield hydroxybenzyl alcohols, and synthetic resins on further reaction. Reaction of acetone with phenol yields bisphenol A [2,2-bis(4-hydroxyphenyl)propane]. 

Ethanol is produced from ethylene and liquid water under high pressure and at temperatures of 200° to 300° C. in the presence of dissolved or suspended salts such as silver nitrate, cuprous chloride, and mercuric chloride which have an affinity for ethylene. Bomb experiments only are described. For instance, by operating with 20 cc. of water in a 150 cc. bomb and 40 atmospheres of ethylene cold, and by heating to 300° C. for six hours without a catalyst only one per cent conversion of ethylene to ethanol is obtained. However, by using water saturated with mercuric chloride under otherwise the same conditions, a 10 per cent ethylene conversion is obtained.81... 

SULKOL (7704-34-9) Combustible solid (flash point 405°F/207°C). Finely divided dry material forms explosive mixture with air. The vapor reacts violently with lithium carbide. Reacts violently with many substances, including strong oxidizers, aluminum powders, boron, bromine pentafluoride, bromine trifluoride, calcium hypochlorite, carbides, cesium, chlorates, chlorine dioxide, chlorine trifluoride, chromic acid, chromyl chloride, dichlorine oxide, diethylzinc, fluorine, halogen compounds, hexalithium disilicide, lampblack, lead chlorite, lead dioxide, lithium, powdered nickel, nickel catalysts, red phosphorus, phosphorus trioxide, potassium, potassium chlorite, potassium iodate, potassium peroxoferrate, rubidium acetylide, ruthenium tetraoxide, sodium, sodium chlorite, sodium peroxide, tin, uranium, zinc, zinc(II) nitrate, hexahydrate. Forms heat-, friction-, impact-, and shock-sensitive explosive or pyrophoric mixtures with ammonia, ammonium nitrate, barium bromate, bromates, calcium carbide, charcoal, hydrocarbons, iodates, iodine pentafluoride, iodine pentoxide, iron, lead chromate, mercurous oxide, mercury nitrate, mercury oxide, nitryl fluoride, nitrogen dioxide, inorganic perchlorates, potassium bromate, potassium nitride, potassium perchlorate, silver nitrate, sodium hydride, sulfur dichloride. Incompatible with barium carbide. 

The synthetic utility of the mercuration reaction derives from subsequent transformations of the arylmercury derivatives. As indicated in Chapter 6, arylmer-cury compounds are only weakly nucleophilic but the carbon-mercury is reactive toward various electrophiles. The nitroso group can be introduced by reaction with nitrosyl chloride" or nitrosonium tetrafluoroborate" as the electrophile. Arylmercury compounds are intermediates in nitrations carried out in nitric acid using mercuric acetate as a catalyst." ... 

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