Ammonia derivatives

Nitrogen, phosphorus and arsenic form more than one hydride. Nitrogen forms several but of these only ammonia, NHj, hydrazine, N2H4 and hydrogen azide N3H (and the ammonia derivative hydroxylamine) will be considered. Phosphorus and arsenic form the hydrides diphosphane P2H4 and diarsane AS2H4 respectively, but both of these hydrides are very unstable. 

Place 200 ml. of absolute ethyl alcohol in a 500 ml. aU-glass wash bottle, and cool to — 5° by immersion in a bath of ice and salt. Pass a slow stream of ammonia, derived from a cylinder and dried by passage through a tower filled with small pieces of quicklime, into the alcohol until the... 

Caprolactam [105-60-2] (2-oxohexamethyleiiiiriiQe, liexaliydro-2J -a2epin-2-one) is one of the most widely used chemical intermediates. However, almost all of the aimual production of 3.0 x 10 t is consumed as the monomer for nylon-6 fibers and plastics (see Fibers survey Polyamides, plastics). Cyclohexanone, which is the most common organic precursor of caprolactam, is made from benzene by either phenol hydrogenation or cyclohexane oxidation (see Cyclohexanoland cyclohexanone). Reaction with ammonia-derived hydroxjlamine forms cyclohexanone oxime, which undergoes molecular rearrangement to the seven-membered ring S-caprolactam. 

The process for the production of the ionone referred to in the second claim, consisting in treating the pseudo-ionone referred to in the first claim or its ketone condensation products with phenylhydrazine or other ammonia derivatives, finally with acids, substantially as described. 

Amines are ammonia derivatives in which one or more hydrogen atoms have been replaced by an organic radical. Amines are sometimes called nitrogen bases. Basic chemistries include fatty amines (as primary, secondary, tertiary, and polyamines), amine salts, quaternary ammonium compounds, amine oxides, and amides. 

While ammonia, derived mainly from the a-amino nitrogen of amino acids, is highly toxic, tissues convert ammonia to the amide nitrogen of nontoxic glutamine. Subsequent deamination of glutamine in the liver releases ammonia, which is then converted to nontoxic urea. If liver function is compromised, as in cirrhosis or hepatitis, elevated blood ammonia levels generate clinical signs and symptoms. Rare metabolic disorders involve each of the five urea cycle enzymes. 

With such a diversity of N-nItrosatlon pathways theoretically possible. It Is comforting to note that only a few combinations of circumstances have been Implicated In environmental nitrosamlne formation thus far. Two of these are so facile and prevalent that, as of 20 years ago, they were the only recognized mechanisms of N-nItrosatlon. They Involve the Interaction of di-or trisubstituted ammonia derivatives with a nitrite Ion, as Illustrated In Figure 1 for the secondary amines, under the catalytic Influence of acid. Note the Important special cases of nucleophilic displacement of water from the nitrous acldlum Ion, H20-N0 , by a second nitrite Ion to yield NoOo (as in the reaction at the top of Figure 1), and by nitrate (bottom of Figure... 

In 1956 Brown, in a series of patents(68-75), disclosed that clays could be treated with di-, tri-, or tetra-substituted ammonia derivatives. Later, McLaughlin, et al.(76,77), introduced cationic polymers as permanent clay protective chemicals. A series of published results describing laboratory and field applications soon became available(78-81). Structural details of the cationic polymers appeared in patents(82-85). In general the polymers are polyamine derivatives, mostly quaternary in nature. Theng(86,87) has discussed how the multiple cationic centers in these polymers can interact and permanently protect clays. Callaway(88) et al. has noted that cationic polymers may interfere with the performance of crosslinked fracturing fluids. 

The pKa of ammonia derived from these data agrees with literature data within 0.1 pH unit at 25°C and 0.42 pH unit at 80°C. 

Inorganic chemicals and fertilizers include acids (e.g., sulfuric, nitric) and alkalies (e.g., caustic soda, soda ash), chlorine, ammonia, and ammonia-derived fertilizers. They also include fluorine derivatives (e.g., hydrogen fluoride), phosphates, potash, pigments (e.g., titanium dioxide), and certain metals such as mercury. 

Next, we consider ammonia and its derivatives in the top 50 chemicals. We have completed a study of the number one inorganic chemical sulfuric acid and its derivatives and have also studied industrial gases from which ammonia is made. Ammonia is in the top 10 chemicals and some important ammonia derivatives are listed in the top 50 ammonium nitrate, nitric acid, urea, and ammonium sulfate. Most ammonia eventually ends up in fertilizers of one type or another. The manufacturing chemistry for these chemicals is outlined below. 

Although urea is an organic compound, it is best discussed with other ammonia-derived synthetic nitrogen compounds, especially in view of its importance to the fertilizer industry like the other compounds in this chapter. It is made easily from ammonia and carbon dioxide. 

Ammonia Derivatives Methyl t-butyl ether -Butyraldehyde Dimethyl terephthalate Methanol Formaldehyde Acetic acid... 

This method of phytochemical reduction may also be extended to homologs of thioacetaldehyde. In this way Nord converted the ammonia derivatives of n-thiobutyraldehyde and thioisovaleraldehyde to n-butyl and isoamyl mercaptans, respectively. 

Nucleophilic addition to C=0 (contd.) ammonia derivs., 219 base catalysis, 204, 207, 212, 216, 226 benzoin condensation, 231 bisulphite anion, 207, 213 Cannizzaro reaction, 216 carbanions, 221-234 Claisen ester condensation, 229 Claisen-Schmidt reaction, 226 conjugate, 200, 213 cyanide ion, 212 Dieckmann reaction, 230 electronic effects in, 205, 208, 226 electrons, 217 Grignard reagents, 221, 235 halide ion, 214 hydration, 207 hydride ion, 214 hydrogen bonding in, 204, 209 in carboxylic derivs., 236-244 intermediates in, 50, 219 intramolecular, 217, 232 irreversible, 215, 222 Knoevenagel reaction, 228 Lewis acids in, 204, 222 Meerwein-Ponndorf reaction, 215 MejSiCN, 213 nitroalkanes, 226 Perkin reaction, 227 pH and, 204, 208, 219 protection, 211... 

Problem 15.28 Write the formula for the solid derivative formed when an aldehyde or ketone reacts with each of the following ammonia derivatives ... 

Problem 15.30 Explain why formation of oximes and other ammonia derivatives requires slightly acidic media (pH = 3.5) for maximum rate while basic or more highly acid conditions lower the rate. ... 

The only salt corresponding to the mercuro-ammines which seems capable of existence is the hydrazine derivative of mercurous nitrate, [Hg(N2II4)2]N03, prepared by Hoffmann and Marburg.2 The corresponding ammonia derivative has not been obtained. 

Ammino-mercuric Salts.—Several types of ammoniaeal derivatives of mercuric salts have been described, but little is known of their constitution. Many of them are insoluble in ordinary solvents and decompose on volatilisation hence, moleeular-weight determinations are difficult. Originally all compounds were shown as derivatives... 

The ammonia additive compounds of arsenic trihalides all react energetically on addition of cold concentrated sulphuric acid with formation of arsenic trilialides, a fact which Besson regards as evidence that the ammonia derivatives are true additive compounds. 

Preparation of Ammonia Derivatives of Metallic Salts.— The principles just described will now be illustrated by directions for the preparation of some typical salts. 

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