Amines mercury salts

Acetoiicetyliition Reactions. The best known and commercially most important reaction of diketene is the aceto acetylation of nucleophiles to give derivatives of acetoacetic acid (Fig. 2) (1,5,6). A wide variety of substances with acidic hydrogens can be acetoacetylated. This includes alcohols, amines, phenols, thiols, carboxyHc acids, amides, ureas, thioureas, urethanes, and sulfonamides. Where more than one functional group is present, ring closure often follows aceto acetylation, giving access to a variety of heterocycHc compounds. These reactions often require catalysts in the form of tertiary amines, acids, and mercury salts. Acetoacetate esters and acetoacetamides are the most important industrial intermediates prepared from diketene. 

The covalent character of mercury compounds and the corresponding abiUty to complex with various organic compounds explains the unusually wide solubihty characteristics. Mercury compounds are soluble in alcohols, ethyl ether, benzene, and other organic solvents. Moreover, small amounts of chemicals such as amines, ammonia (qv), and ammonium acetate can have a profound solubilizing effect (see COORDINATION COMPOUNDS). The solubihty of mercury and a wide variety of mercury salts and complexes in water and aqueous electrolyte solutions has been well outlined (5). 

Only certain specific environments appear to produce stress corrosion of copper alloys, notably ammonia or ammonium compounds or related compounds such as amines. Mercury or solutions of mercury salts (which cause deposition of mercury) or other molten metals will also cause cracking, but the mechanism is undoubtedly differentCracks produced by mercury are always intercrystalline, but ammonia may produce cracks that are transcrystalline or intercrystalline, or a mixture of both, according to circumstances. As an illustration of this, Edmundsfound that mercury would not produce cracking in a stressed single crystal of brass, but ammonia did. 

The present procedure2 describes the conversion of resin-bound, primary aliphatic amines into isothiocyanates and the conversion of the latter into 3-aminothiophenes. The generation of isothiocyanates is related to known procedures,3 in which amines are first treated with carbon disulfide and the resulting dithiocarba-mates are desulfurized by treatment with a condensing agent (alkyl chloroformates, carbodiimides, lead or mercury salts, etc.). The presence of resin-bound isothiocyanates on the polystyrene support could be qualitatively ascertained by infrared spectroscopy (KBr-pellet strong absorption at 2091 cm-1). 

Nitrotetrazole is readily prepared from the diazotization of 5-aminotetrazole in the presence of excess sodium nitrite and is best isolated as the copper salt complex with ethylenediamine. The salts of 5-nitrotetrazole have attracted interest for their initiating properties. The mercury salt is a detonating primary explosive. The amine salts of 5-nitrotetrazole are reported to form useful eutectics with ammonium nitrate. ... 

DOT CLASSIFICATION 6.1 Label Poison SAFETY PROFILE A poison by ingesdon. Moderately toxic by skin contact. Explosive reacdon with halogens or amine metal salts. When heated to decomposidon it emits very toxic fumes of CF, NO, and Hg. See also MERCURY COMPOUNDS. 

The mercury-promoted amination of double bonds proceeded in an anti mode with >99% diastereoselectivity. By treating (Z)-2-butene with dimethylamine in the presence of mer-cury(II) chloride, the syn-adduct of 1 was obtained, while ( )-2-butene under the same conditions afforded the anti-adduct. However, by treating alkenes with ammonia and mercury salts, only ammonia-mercury complexes were formed8-14,171. 

Acetylene is condensed to vinylacetylene and divinylacetylene by cuprous chloride and ammonium chloride. Similar additions of other compounds containing an active hydrogen atom occur in the presence of various catalysts. Mercury salts ate most effective in the vapor-phase reaction of acetylene with hydrogen chloride to give vinyl chloride (100%). Basic catalysts such as potassium hydroxide, potassium ethoxide, or zinc oxide are used for the vinylation of alcohols, glycols, amines, and acids. Most of these reactions involve the use of acetylene under pressure, and few have been described as simple laboratory procedures. Chloroacetic acid, however, reacts with acetylene at atmospheric pressure in the presence of mercuric oxide to yield vinyl chloro-acetate (49%). ... 

DIMETHYLNITROMETHANE (79-46-9) Forms explosive mixture with air (flash point 75°F/24°C). Violent reaction with strong oxidizers, chlorosulfonic acid, hydrocarbons, hydroxides calcium or potassium hydroxide, oleum. May explode on heating (burns even in absence of air), causing fast rise in pressure closed containers may explode. Decomposition is promoted by the presence of acids, amines, or bases. Forms heat-, friction-, or shock-sensitive explosive products with acids, amines, inorganic bases, mercury salts, nitrous acid, silver salts. The presence of metal oxides increases the explosive sensitivity of this compound. Incompatible with isocyanates, potassium hydride. Attacks some plastics, rubber, and coatings. 

Because of the relatively easy oxidation of mercury, anodic waves are observed with the DME only for the strongest reducing agents such as hydroquinones, enediols (e.g., ascorbic acid), phenylhydroxylamine derivatives, and certain aldehydes. Numerous organic substances nevertheless yield anodic waves corresponding to mercury-salt formation, e.g., thiols and other derivatives of bivalent sulfur, amines, and some... 

A further complication in the equilibrium is shown in Fig. 8.3-7, which shows the mercury distribution coefficient as a function of amine concentration for a fixed level of mercuiy. At low amine concentrations the distribution coefficient increases with amine level in the way that is expected for reaction (8.2-7) or (8.2-8), but above a certain amine level the distribution coefficient becomes constant. This behavior indicates that some separate phenomenon, such as limited solubility or association of the amine-hydrochloride salt, keeps its activity constant with increasing concentraticm. This is a common experimental observation in such systems. 

While ethylene hydroamination with secondary amines was reported by Coulson using Rh as a catalyst in 1971 [86], unfortunately, despite decades of research in the area, there are no catalysts for this reaction across a broad range of substrates. Significant early work in d-block-metal-hydroamination catalysis took advantage of the controlled reactivity provided by mercurial salts. However, the toxicity and ensuing environmental problems of using Hg " " salts demanded an improvement in catalytic protocols. Indeed, steady advancement in the application... 

Mercuration-demercuration of enamines with ionic mercury salts gives tertiary amines (485). Mercuration-demercuration of allylethers (486) or iV-allylamino-alcohols (487) gives morpholines. ... 

There also exists an acidregioselective condensation of the aldol type, namely the Mannich reaction (B. Reichert, 1959 H. Hellmann, 1960 see also p. 291f.). The condensation of secondary amines with aldehydes yields Immonium salts, which react with ketones to give 3-amino ketones (=Mannich bases). Ketones with two enolizable CHj-groupings may form 1,5-diamino-3-pentanones, but monosubstitution products can always be obtained in high yield. Unsymmetrical ketones react preferentially at the most highly substituted carbon atom. Sterical hindrance can reverse this regioselectivity. Thermal elimination of amines leads to the a,)3-unsaturated ketone. Another efficient pathway to vinyl ketones starts with the addition of terminal alkynes to immonium salts. On mercury(ll) catalyzed hydration the product is converted to the Mannich base (H. Smith, 1964). 

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