Reaction with ammonium salts

Reaction with ammonium salts gives biguanide salts which react further with the ammonium salt forming guanidine salts. Guanidine nitrate [506-93 ] is manufactured by this route (46). 

Use of TMSCl in combination with HMPA, DMAP, or TMEDA all favored 1,2-addition over 1,4-addition. Sequential a-alkoxyalkylcuprate conjugate addition, enolate trapping with TMSCl, and silyl enol ether alkylation provides a one-pot synthesis of tetrahydrofurans (Scheme 3.35) [129]. Cyclic enones afford as-fused tetrahydrofurans, while acyclic systems give complex mixtures of diastereomers. a-Alkoxyalkylcopper reagents also participate in allylic substitution reactions with ammonium salts [127]. 

Violent reactions with ammonium salts, chlorate salts, beryllium fluoride, boron diiodophosphide, carbon tetrachloride + methanol, 1,1,1-trichloroethane, 1,2-dibromoethane, halogens or interhalogens (e.g., fluorine, chlorine, bromine, iodine vapor, chlorine trifluoride, iodine heptafluoride), hydrogen iodide, metal oxides + heat (e.g., beryllium oxide, cadmium oxide, copper oxide, mercury oxide, molybdenum oxide, tin oxide, zinc oxide), nitrogen (when ignited), silicon dioxide powder + heat, polytetrafluoroethylene powder + heat. 

Amides of fatty adds are also formed from fatty acids during thermal treatments by reaction with ammonium salts, amines or amino acids (see Section 8.2.10.1.3). 

The transesterification reaction was carried out in a 50 mL stainless steel autoclave equipped with a magnetic stirrer. For each typical reaction, quaternary ammonium salt (2 mmol), propylene carbonate (25 mmol) and excess methanol (200 mmol) were charged into the reactor, and the CO2 was introduced at room temperature to a preset pressure. The reaction was started by stirring when the desired tranperature and pressure were attained The reachon was performed in a batch operation... 

Transformations to polymer-bound amino compounds, which are often useful as ligands for metals ions or other free species (67), employ a wide selection of organic reactions. Quaternary ammonium salts result from heating isolated polymer tosylate with tertiary amine they may also be prepared in one step from (hydroxyethyl)polystyrene and toluenesulfonyl chloride and a two-fold excess of amine. 

MRH Aluminium 10.71/33, iron 4.35/50, magnesium 10.88/40, manganese 5.06/50, sodium 5.56/55, phosphorus 7.32/25, sulfur 4.27/20 Mixtures of the chlorate with ammonium salts, powdered metals, phosphorus, silicon, sulfur or sulfides are readily ignited and potentially explosive [1], Residues of ammonium thiosulfate in a bulk road tanker contaminated the consignment of dry sodium chlorate subsequently loaded, and exothermic reaction occurred with gas evolution during several hours. Laboratory tests showed that such a mixture could be made to decompose explosively. A reaction mechanism is suggested. 

The synthesis of lanthanide chemical shift reagents has been the objective of many groups owing to their effect on NMR spectra simplification. A drawback of the commonly used reagents is their sensitivity to water or acids. Tris(tetraphenylimido diphosphinatojpraseodymium [Pr(tpip)3] has been developed as a CSR for the analysis of carboxylic acids.17 Furthermore, it has been found that dinuclear dicarboxylate complexes can be obtained through reactions with ammonium or potassium salts of carboxylic acids, and these compounds can be used to determine the enantiomer composition of carboxylic acids.18... 

Greater durability of the colloidal Pd/C catalysts was also observed in this case. The catalytic activity was found to have declined much less than a conventionally manufactured Pd/C catalyst after recycling both catalysts 25 times under similar conditions. Obviously, the lipophilic (Oct)4NCl surfactant layer prevents the colloid particles from coagulating and being poisoned in the alkaline aqueous reaction medium. Shape-selective hydrocarbon oxidation catalysts have been described, where active Pt colloid particles are present exclusively in the pores of ultramicroscopic tungsten heteropoly compounds [162], Phosphine-free Suzuki and Heck reactions involving iodo-, bromo-or activated chloroatoms were performed catalytically with ammonium salt- or poly(vinylpyrroli-done)-stabilized palladium or palladium nickel colloids (Equation 3.9) [162, 163],... 

The problems encountered in the catalytic transfer of highly hydrophilic anions from aqueous solutions into the organic phase can be countered by the use of anhydrous solid salts the organic reactant is dissolved in the organic solvent or, if liquid, may be used neat. Solid liquid two-phase reactions using ammonium salts have widespread application (see, for example, the many examples cited in later chapters) frequently with shortened reaction times, lower reaction temperatures, and higher yields [e.g. 66, 67] and are generally superior to solidrliquid reactions catalysed by crown ethers [68]. The process is particularly useful in base-initiated reactions with fluorides, hydroxides or carbonates. 

Ammonium nitrate alternatively may be prepared by double decomposition reactions of ammonium salt with a nitrate salt e.g., ammonium sulfate and sodium nitrate ... 

Aqueous solutions of ammonium nitrate undergo a double decomposition reaction with metal salts. NH4NO3 acts as an oxidizing agent in aqueous solutions and is reduced by various metals at ambient temperatures. 

The hydroxide is strongly basic. It reacts with acids undergoing neutralization reactions i.e., reaction with HCl or HNO3 yields hydrated salt of lanthanum chloride or nitrate on evaporation and crystalhzation of the solution. It reacts with ammonium salts displacing ammonia ... 

Reaction with ammonium chloride yields yellow precipitate of the complex salt, ammoniumhexachloroplumbateflV) ... 

Reactions with ammonium chloride or other ammonium salts form a lemon yellow precipitate of ammonium hexachloroplatinate, (NH4)2PtCl6 ... 

The direct electrochemical synthesis (Scheme 2) of the addncts of organomagnesinm halides with 2,2 -bipyridine (6) and salts of organodihalogenomagnesinm(II) anions (7) was reported by Hayes and coworkers . Adducts of different stoichiometry and 7 were obtained in the electrochemical oxidation of magnesium in ACN solutions containing organic halides RX (8), a.ro-dihalides XR X (9) and 8 with ammonium salts R NX, respectively. All new products showed none of the typical reactions of Grignard reagents. 

The preparation of a quinoxalinylthiophosphate (121) in biphasic systems from 2-quinoxalinone and ClPS(OEt)2 with TBAB-NaOH has been recently described by Gore et o/.187 the reaction was catalyzed with ammonium salts and with N-methylimidazole. 

Elguero and Espada29S have used this dealkylation reaction with quaternary salts of heterocyclic compounds. Another application is the preparation of tertiary amines functionalized in the <5 position.296 In these reactions, the ammonium salt 196 is both the catalyst and the reagent. 

It was shown from the study of styrene and MMA in a KNOa-DMF system using tracer techniques for the composition analysis that the free-radical contribution is apparently confined to the first few percent of polymerization, whereas at later stages the reaction is anionic (34). This is consistent with the inhibitor studies. On the same monomer pair with a variety of solvents with ammonium salts, only with tetrahydrofuran did a possible free-radical reaction accompany the anionic propagation, with the others, DMF and dimethylacetamide, as well as without solvent, an anionic reaction accompanying the free radical one was assumed (35). 

Aluminum in solution of its salts is detected by the reaction (1) with ammonium salt of aurin tricarboxylic acid ( aluminon ), which yields a red precipitate persisting in NH4OH solution, (2) with alizarin red S. which yields a bright red precipitate persisting in acetic acid solution. 

Cyanamide is also acted upon directly by ammonium salts in aqueous and non-aqueous solutions.17-20 Since it is of decided advantage to avoid the isolation of pure cyanamide, methods have been developed in which aqueous solutions of cyanamide are prepared from calcium cyanamide and are then permitted to react with ammonium salts. However, guanidine nitrate may also be prepared directly from commercial calcium cyanamide by the action of ammonium nitrate. This reaction takes place readily in the fused state, in concentrated aqueous solution,21 or by direct admixture of solid ammonium nitrate with calcium cyanamide and subsequent heating to 100°C.22 The latter procedure is to be preferred, since better yields are obtainable and the hazard of fusion with ammonium nitrate is obviated. The directions given for procedure B require the use of a fairly good grade of unoiled calcium cyanamide containing approximately 65 per cent CaNCN. 

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