Ammonia and its derivatives

Reaction of Diazonium Compounds with Nucleophiles I. Ammonia and its derivatives 

In his classical work on diazonium compounds, Griess demonstrated that bcnzenediazonium tribromide reacts with ammonia to give phenyl azide in high yield (equation 113). It has since been estab- 

Boyer and Canter suggested that the reaction proceeds through the intervention of a triazene, and further implied that this intermediate is subsequently oxidized to the azide by halogen or the anion (equation 114). In support of this suggestion it has been observed that in the absence of oxidant some diazonium compounds form tri-azenes with ammonia. 

For example, the triazene (228) is obtained from ditizotized anthra-quinone and ammonium carbonate under these conditions (equation 115). Further, the formation of aryl azides by oxidation of aryl triazenes with hypochlorite solution has been reported In a related 

Glusius and co-workershave established by N-labelling experiments that in the reaction between benzenediazonium per-bromide and ammonia, the terminal nitrogen of the azido group originates from a molecule of ammonia as shown in. equation (117). 

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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. 

It might also be argued that ammonia and its derivatives are all petrochemicals since the hydrogen is derived from methane or natural gas. Many ammonia plants are near oil refineries. Urea even contains carbon and is considered an organic chemical. But because all these nitrogen... 

Addition of ammonia and its derivatives to carbonyl compounds preparation of oximes and imine derivatives (Schiff s bases)... 

The reaction of furans with ammonia and its derivatives is of considerable synthetic utility (B-73MI31 too). Substituted furan-2-carbaldehydes and 2-acylfurans on heating with ammonia and ammonium salts, often under pressure, yield 3-hydroxypyridines. The mechanism of this reaction is thought to involve nucleophilic attack of ammonia at the 2-position. Ring opening affords an amino aldehyde or ketone and thence, by reclosure, the 3-hydroxy-pyridine (Scheme 29). A wide range of substitutents is tolerated. Primary amines with furan-2-carbaldehydes yield A-substituted pyrroles, the closure of the intermediate... 

Ammonia and its derivatives are very prone to react in this way thus conjugate addition provides a method for the preparation of j8-amino carbonyl compounds. 

Ammonia and its derivatives, HN03, NH4N03, and CO(NH2)2, are key fertilizers and ingredients for explosives, and their production consumes nearly 5 percent of the world s natural gas. 

Synthesis gas is the starting material for the manufacture of ammonia and its derivatives and also for methanol, as well as for other... 

It may be added that, according to Bredig this law of dissociation holds for weak bases (ammonia and its derivatives) as well as for weak acids hence in solutions of bases (e. g. ammonia) we may assume the state of equilibrium expressed by... 

In the examples we have just seen, the nucleophilic reagent, Z, is either the strongly basic anion, CN , or a neutral base like ammonia and its derivatives, NH2 G. These are the same reagents which, we have seen, add to the carbonyl group of simple aldehydes and ketones. (Indeed, nucleophilic reagents rarely add to the carbon-carbon double bond of a,)8-unsaturated aldehydes but rather to the highly reactive carbonyl group.)... 

Iran s petrochemical industry is striving to be a major player in the region. There are eight government-owned petrochemical production companies and three privately owned petrochemical/chemical companies. The major petrochemical products are ethylene and its derivatives, propylene and its derivatives, benzene, toluene, xylenes, pyrolysis gasoline, propane, butane, pentane, ethylbenzene, and styrene, as well as sulfur, ammonia, and its derivatives. In early 1999 there were 21 construction projects in the areas of petrochemicals, petroleum, and environmental cleanup [13]. 

In this connexion only the addition of ammonia and its derivatives to carbon disulfide is of preparative interest this gives dithiocarbamates which find use as intermediates in manifold syntheses. 

Two fundamentally different types of reaction of esters with ammonia and its derivatives must be distinguished, although in both cases oxygen is replaced by nitrogen ... 

Colorless gas, characteristic unpleasant odor. B.p. —20.2°C m.p. —161.5°C ( ock and Zeidler). Ignites and burns with a green flame on exposure to air. Not attacked by water at room temperature. At higher temperatures, reaction with water in a sealed tube yields methyl borates and methane. Absorption by aqueous KOH and NH3 solutions is violent. Ammonia and its derivatives give addition products with trimethylboron. 

In Chapter 11, we found that salts with their formal electrostatic intermolecular attractions had low vapor pressures and thus highboihng points. Ammonia and its derivatives (anunes) are molecules with dipole-dipole attractions as long as the nitrogen has one direct N-H bond, the molecule will have hydrogen... 

In Chapter 11, we found that salts with their electrostatic intermolecular attractions had low vapor pressmes and thus high boiling points. Ammonia and its derivatives (amines) are molecules with dipole-dipole attractions. If the nitrogen has one direct N-H bond, the molecule will have hydrogen bonding. Even so, these molecules will have much weaker intermolecular attractions than ionic species and hence higher vapor pressures. Thus, if we could convert the neutral armnonia-type molecules into salts, their vapor pressures, and thus associated odors, would decrease. Lemon juice contains acids which can react with ammonia-type (amine) molecules to form ammonium salts. 

Before the availability of synthetic ammonia and its derivatives, sodium nitrate of natural origin was the primary source of nitric add and chemical nitrogen for fertilizer purposes in many countries. Most of this nitrate originated in Chile, where it is found prindpally in a large ore body nearly 500 miles lor and 10-15 miles wide on the eastern part of the Chilean coastal range. Nitrate production remains a primary industry in Chile. 

More recent studies were carried out with coals (lignite and subbituminous), enriched with nitrogen, before carbonization and activation, by treatment with ammonia and its derivatives, mainly urea [36,37]. The ammoxidation reaction (reaction with an ammonia-air mixture) is another route to obtaining nitrogen-enriched precursors of active carbons from various carbonaceous materials, such as pine wood, peat, lignite, subbituminous coal [38], and cellulose [39]. 

In these studies, the nitrogen was introduced in the already activated carbons. Another way to prepare such active carbons is to start from coals enriched in nitrogen before the step of pyrolysis or activation [36,37], Two coals were selected a Polish subbituminous coal, preoxidized with performic acid, and a Russian lignite. Ammonia and its derivatives (ammonium carbonate, hydrazine, hydroxylamine, and urea) were applied as N-reagents [36,37], The N-rich-acti-vated carbons showed good oxidative removal activity for traces of hydrogen sulfide and for its oxidized by-products (elemental sulfur and sulfur dioxide) [36],... 

Addition of Ammonia and Its Derivatives Formation of Imines (Section 16.8A)... 

Molecular inversion involves tunnelling between two equivalent configurations that are related by a planar reflection of one or more atoms. Inversion occurs for all non-planar molecules, but it is of thermodynamic significance only for the few molecules, such as ammonia and its derivatives, that have low inversion barriers. 

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