Salts, acid ammonia derivatives

Ethylamines. Mono-, di-, and triethylamines, produced by catalytic reaction of ethanol with ammonia (330), are a significant outlet for ethanol. The vapor-phase continuous process takes place at 1.38 MPa (13.6 atm) and 150—220°C over a nickel catalyst supported on alumina, siUca, or sihca—alumina. In this reductive amination under a hydrogen atmosphere, the ratio of the mono-, di-, and triethylamine product can be controlled by recycling the unwanted products. Other catalysts used include phosphoric acid and derivatives, copper and iron chlorides, sulfates, and oxides in the presence of acids or alkaline salts (331). Piperidine can be ethylated with ethanol in the presence of Raney nickel catalyst at 200°C and 10.3 MPa (102 atm), to give W-ethylpiperidine [766-09-6] (332). 

Acids, bases, and salts.—To distinguish between the ordinary oxygen salts, acids, and bases and those compounds which bear an analogous relation to ammonia, E. C. Franklin applies the term hydro-salts, hydro-acids, and hydro-bases to those compounds which are related to water, like the ammono-salts, ammom-acids, and ammono-bases are related to the corresponding ammonia derivative. The terms... 

Aoids (709) 69. Imidodiphosphoric or Imidopyropbosphoric Aoid (712) 70. Amides and Imides of the Higher Phosphoric Acids (714) 71. The Meta-phosphimic Acids and their Salts (716) 72. Phosphorus Chloronitrides or Phosphonitrilic Chlorides (721) 73. Ammonia Derivatives of Thiophosphoric Acid (725). 

In a conventional process, ammonium salts of organic acids are derived first by fermentation and then catalytically cracked to yield the acid. The acid then reacts with C1-C4 alcohols to form the ester. The reaction products include the acid ester, unreacted alcohol, water, and ammonia ... 

A crystalline acid salt, NiF2.5HF.6HaO, and an ammonia derivative, 5NiF2.6NH3.8H20, have been described.7 Other derivatives and double salts are known.8... 

Hydrazoic Acid.—The third compound, which is the other one containing only nitrogen and hydrogen, is not an ammonia derivative. It is known as hydrazoic acid or tri-azoic acid. Its formula is N3H. It is a mono-basic acid while ammonia, NH3, is a base. It forms a salt with ammonia, NH4N3, ammonium hydrazoate. Hydrazoic acid was also discovered by Curtius in 1890. 

Derivation (1) Form G acid by heating sodium salt with ammonia and sodium bisulfite solution in an autoclave under pressure. (2) Sulfonation by (3-naphthylamine. 

Adding ammonia derivatives to cyanamide leads to guanidines. Salts of unsubstituted guanidine are obtained by melting dicyanodiamide with ammonium salts, e.g., with ammonium nitrate.43 Amines react smoothly with cyan-amide only if presented as hydrochlorides the components are boiled in anhydrous ethanol under reflux.44 This process fails with too feebly basic amines, e.g., with nitroanilines however, even in such cases almost quantitative yields of guanidines can be obtained by melting the amine with an excess of cyanamide and treating the product with an excess of concentrated hydrochloric acid.45... 

Contents Background and Technical Aspects of the Chemical Industry. - Air Quality and Emission Control. - Water Quality Emission Control. - Natural and Derived Sodium and Potassium Salts. - Industrial Bases by Chemical Routes. - Electrolytic Sodium Hydrocide and Chlorine and Related Commodities. -Sulfur and Sulfuric Add. - Phosphorus and Phosphoric Acid. - Ammonia, Nitric Add and their Derivatives. - Aluminium and Compounds. - Ore Enrichment and Smelting of Copper. - Production of Iron Steel. - Production of Pulp and Paper. - Fermentation Processes. - Petroleum Production and Transport. - Petroleum Refining. - Formulae and Conversion Factors. - Subject Index. 

The primary use of ammonia ( 80%) in the United States is in fertilizers, either as anhydrous ammonia or as the salts ammonium nitrate and ammonium sulfate. Other uses include conversions to nitric acid and urea. The reaction for the syntheses of the ammonia derivatives are as follows. 

Derivatives. Boil the substance with alkali to remove ammonia, acidify, and isolate the acid. Prepare derivatives of the latter (page 123). (Some colour tests for carboxylic acids may be made directly on the ammonium salt.)... 

This p. is based on - undecylenic acid, which derives from - castor oil and represents a p. of type II. Undecylenic acid is reacted with HBr in the presence of peroxides or air in, e.g., toluene at 30°C. 11-Bromo-undecanoic acid is formed in over 95% yield. Further reaction with 25% aqueous ammonia gives the desired 11-amino-undecanoic acid. Repeated crystallization enhances the pinity of the monomer. The polycondensation is carried out in a column with three zones melting, main reaction and equilibration of m.w. Phosphorous and phosphoric acids and their salts act as catalysts. The resulting p. (m.p. 190 °C) is very hydrophobic, has a low moisture content and is therefore used in electrical insulation. Other applications are as filament, powder - coatings and - molded goods. Castor oil consumption for this area was 35000 mt (1988). 

Colorations or coloured precipitates are frequently given by the reaction of ferric chloride solution with.(i) solutions of neutral salts of acids, (ii) phenols and many of their derivatives, (iii) a few amines. If a free acid is under investigation it must first be neutralised as follows Place about 01 g. of the acid in a boiling-tube and add a slight excess of ammonia solution, i,e., until the solution is just alkaline to litmus-paper. Add a piece of unglazed porcelain and boil until the odour of ammonia is completely removed, and then cool. To the solution so obtained add a few drops of the "neutralised ferric chloride solution. Perform this test with the following acids and note the result ... 

Arsenic pentasulfide (arsenic(V) sulfide), As S q, is stable in air up to 95°C, but at higher temperatures begins to dissociate into arsenous sulfide and sulfur. It is prepared by the fusion of arsenic with sulfur foUowed by extraction with ammonia and reprecipitation at low temperatures by addition of hydrochloric acid. Arsenic pentasulfide is precipitated at low temperatures from strongly acidic arsenate solutions by a rapid stream of hydrogen sulfide. It is hydrolyzed by boiling with water, yielding arsenous acid and sulfur. Salts derived from a number of thioarsenic acids are formed from arsenic pentasulfide and alkaH metal sulfides. 

Isatin (190) is a compound with interesting chemistry. It can be iV-acetylated with acetic anhydride, iV-methylated via its sodium or potassium salt and O-methylated via its silver salt. Oxidation of isatins with hydrogen peroxide in methanolic sodium methoxide yields methyl anthranilates (81AG(E)882>. In moist air, O-methylisatin (191) forms methylisatoid (192). Isatin forms normal carbonyl derivatives (193) with ketonic reagents such as hydroxylamine and phenylhydrazine and the reactive 3-carbonyl group also undergoes aldol condensation with active methylene compounds. Isatin forms a complex derivative, isamic acid (194), with ammonia (76JCS(P1)2004). 

Laudanine, C20H25O4N, was isolated by Hesse. The crude alkaloid is purified by recrj stallisation from dilute alcohol for the removal of small quantities of cryptopine, or it may be dissolved in acetic acid and the solution poured into dilute caustic soda, when this impurity is precipitated and laudanine may be recovered from the filtrate by addition of ammonium chloride. It still contains its isomeride laudanidine, which may be separated by repeated crystallisation of the hydrochlorides, laudanidine accumulating in the aqueous mother liquors. The base crystallises from dilute alcohol, or from a mixture of alcohol and chloroform in rhombic prisms, m.p. 166°, [a]o 0°. It dissolves in solutions of alkali hydroxides, fornung metallic derivatives, which are precipitated by excess of alkali, but is nearly insoluble in solution of ammonia. The salts crystallise well ... 

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