Amines, metallation

Anionic extractants are commonly based on high molecular weight amines. Metal anions such as MnO or ReO can be exchanged selectively with inorganic anions such as Cl or The equiHbrium for a quaternary onium compound of organic radicals R for two anion species A and B ... 

Method 2. Alcohol amination—metal cataly2ed amination of an alcohol over a metal catalyst under reducing conditions. 

Polymerization of ethylene oxide can occur duriag storage, especially at elevated temperatures. Contamination with water, alkahes, acids, amines, metal oxides, or Lewis acids (such as ferric chloride and aluminum chloride) can lead to mnaway polymerization reactions with a potential for failure of the storage vessel. Therefore, prolonged storage at high temperatures or contact with these chemicals must be avoided (9). 

Optical recording systems, 6, 126 Optical resolution amine metal complexes, 2,25 Oral contraceptives iron deficiency, 6, 764 Orbital angular momentum quenching, 1,262 /-Orbital systems... 

Azo, azoxy, and hydrazo compounds can all be reduced to amines. Metals (notably zinc) and acids, and Na2S204, are frequently used as reducing agents. Borane reduces azo compounds to amines, though it does not reduce nitro compounds. " Lithium aluminum hydride does not reduee hydrazo compounds or azo compounds, though with the latter, hydrazo compounds are sometimes isolated. With azoxy compounds, LiAHLj gives only azo compounds (19-48). 

A corrosion inhibitor with excellent film-forming and film-persistency characteristics is produced by first reacting Cig unsaturated fatty acids with maleic anhydride or fumaiic acid to produce the fatty acid Diels-Alder adduct or the fatty acid-ene reaction product [31]. This reaction product is further reacted in a condensation or hydrolyzation reaction with a polyalcohol to form an acid-anhydride ester corrosion inhibitor. The ester may be reacted with amines, metal hydroxides, metal oxides, ammonia, and combinations thereof to neutralize the ester. Surfactants may be added to tailor the inhibitor formulation to meet the specific needs of the user, that is, the corrosion inhibitor may be formulated to produce an oil-soluble, highly water-dispersible corrosion inhibitor or an oil-dispersible, water-soluble corrosion inhibitor. Suitable carrier solvents may be used as needed to disperse the corrosion inhibitor formulation. 

Freeder, B. G. et al., J. Loss Prev. Process Ind., 1988, 1, 164-168 Accidental contamination of a 90 kg cylinder of ethylene oxide with a little sodium hydroxide solution led to explosive failure of the cylinder over 8 hours later [1], Based on later studies of the kinetics and heat release of the poly condensation reaction, it was estimated that after 8 hours and 1 min, some 12.7% of the oxide had condensed with an increase in temperature from 20 to 100°C. At this point the heat release rate was calculated to be 2.1 MJ/min, and 100 s later the temperature and heat release rate would be 160° and 1.67 MJ/s respectively, with 28% condensation. Complete reaction would have been attained some 16 s later at a temperature of 700°C [2], Precautions designed to prevent explosive polymerisation of ethylene oxide are discussed, including rigid exclusion of acids covalent halides, such as aluminium chloride, iron(III) chloride, tin(IV) chloride basic materials like alkali hydroxides, ammonia, amines, metallic potassium and catalytically active solids such as aluminium oxide, iron oxide, or rust [1] A comparative study of the runaway exothermic polymerisation of ethylene oxide and of propylene oxide by 10 wt% of solutions of sodium hydroxide of various concentrations has been done using ARC. Results below show onset temperatures/corrected adiabatic exotherm/maximum pressure attained and heat of polymerisation for the least (0.125 M) and most (1 M) concentrated alkali solutions used as catalysts. 

Aromatic amines, Metal compounds Rastogi, R. P. et al., Indian J. Chem., 1964, 2, 301-307... 

Boche and coworkers drew attention to the solid state structure of mixed amine-metal amide99 and silylamide-nitrile complexes100 as models of reaction intermediates. 

Decarboxylation of p-oxoacids. Beta-oxoacids such as oxaloacetic acid and acetoacetic acid are unstable, their decarboxylation being catalyzed by amines, metal ions, and other substances. Catalysis by amines depends upon Schiff base formation,232 while metal ions form chelates in which the metal assists in electron withdrawal to form an enolate anion.233 235... 

Odta — see Acetic acid, octamethylenediaminetetra-Optical resolution amine metal complexes, 25 Ore-forming solutions metal sulfides, 525 Organometallic complexes solubility... 

Organic solutions of a tertiary amine saturated with molybdenum214 were found to have an amine metal ratio of 1 2. In accordance with the species known to be present in moderately acidic solutions of molybdenum(VI), the most probable mechanism of extraction is... 

Although no polynuclear molybdenum(VI) species containing less than seven metal atoms is known in aqueous solution,215 this does not preclude the existence of such species in organic extracts, the observed amine metal ratio also being consistent with the extraction of Mo4Ot32 or Mo207 species. 

These compounds do not readily react with epoxy resins except in the presence of water, alcohol, or some other base, called an accelerator. Tertiary amines, metallic salts, and imidazoles often act as accelerators for anhydride cured epoxy systems. The reaction between acid anhydride and epoxy resins is illustrated in Fig. 5.7. 

Amine metal oxosalts metal compounds with coordinated ammonia, hydrazine, or similar nitrogenous donors and ionic chlorate(Vll), nitrate(V), manganate(VIl), or other oxidizing group Azides, including metal, nonmetal, and organic azides Chlorate(lll) salts of metals... 

To activate carbon dioxide for chemical reactions, it is advantageous to fix and destabilize this rather inert molecule. An important strategy to control and influence the reactivity of CO2 is its coordination to amines, metal-bound imido moieties, or metal centers (144), which leads to a decrease of the CO bond order, while the molecule in most cases becomes considerably bent. In biochemical pathways, the CO2 adduct of the coenzyme biotin (17) is involved in various carboxylation and transcarboxylation reactions (146). Similar structural motifs could become important functional building blocks for bioinspired photoreactions involving carbon dioxide activation steps (Fig. 18). 

Amine-metal-carbonyl reactions are limited to complexes in which the calculated C—O force constant (FC) is greater than ca. 17.2 mdyne A. Carbonyl complexes that have C—O force constants (FC) between 16.0 and 17.2 mdyne A react with amines to form an equilibrium mixture of reactants and products from which the product cannot be isolated e.g., in the reaction of [Mn(CO)3(mes- / )]PF6 (mes = mesitylene) and CyNHj in CHjClj the following equilibrium is established ... 

Reactions of cationic carbonyl complexes with alcohols are less common than with amines ( 5.8.2.12.4). They occur only with the most reactive carbonyl complexes with high C—O force constants this is because alcohols are poorer nucleophiles and also less basic than amines. Metal carbonyls react with alkoxide ions. See Table 1 for complexes of the Mn, Fe and Co subgroups ". ... 

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