Addition of ammonia

How ever, the Mn(II) ion forms a variety of complexes in solution, some of which may be more easily oxidised these complexes can be either tetrahedral, for example [MnClJ , or octahedral, for example [Mn(CN)f,] Addition of ammonia to an aqueous solution of a manganese(II) salt precipitates Mn(OH)2 reaction of ammonia with anhydrous manganese(II) salts can yield the ion [MnfNH y T... 

In aqueous solution at 100° the change is reversible and equilibrium is reached when 95 per cent, of the ammonium cyanate has changed into urea. Urea is less soluble in water than is ammonium sulphate, hence if the solution is evaporated, urea commences to separate, the equilibrium is disturbed, more ammonium cyanate is converted into urea to maintain the equilibrium and evfflitually the change into urea becomes almost complete. The urea is isolated from the residue by extraction with boiling methyl or ethyl alcohol. The mechanism of the reaction which is generally accepted involves the dissociation of the ammonium cyanate into ammonia and cyanic acid, and the addition of ammonia to the latter ... 

It has been tentatively suggested that one mechanism underlies the Willgerodt reaction and the Kindler modification of it. A labile intermediate is first formed which has a carbon—carbon bond in the side chain. The scheme is indicated below it postulates a series of steps involving the addition of ammonia or amine (R = H or alkyl), elimination of water, re addition and eUmination of ammonia or amine until the unsaturation appears at the end of the chain then an irreversible oxidation between sulphur and the nitrogen compound may occur to produce a thioamide. 

Direct addition of ammonia to olefmic bonds would be an attractive method for amine synthesis, if it could be carried out smoothly. Like water, ammonia reacts with butadiene only under particular reaction conditions. Almost no reaction takes place with pure ammonia in organic solvents. The presence of water accelerates the reaction considerably. The reaction of aqueous ammonia (28%) with butadiene in MeCN in the presence orPd(OAc)i and PhjP at 80 C for 10 h gives tri-2,7-octadienylamine (47) as the main product, accompanied by a small amount of di-2,7-octadienylamine (46)[46,47], Isomeric branched... 

Uses. 3-Pentenenitrile, 3PN, is used entirely by the manufacturers to make adiponitrile. i7j -2-Pentenenitrile, 2PN, can be cycli2ed catalyticaHy at high temperature to produce pyndine, a solvent and agncultural chemical intermediate. 2PN is also chlorinated to manufacture pentachloropyndine, an intermediate in the insecticide Dursban produced by Dow. Addition of ammonia to 2PN foUowed by reduction leads to 1,3-pentadiamine (Dytek ep), which is used as a curing agent for epoxy coatings and as a chain modifier in polyurethanes. 

Primary amines form Schiff bases, (CH3 )2C=NR. Ammonia induces an aldol condensation followed by 1,4-addition of ammonia to produce diacetone amine (from mesityl oxide), 4-amino-4-methyl-2-pentanone [625-04-7] (CH2)2C(NH2)CH2COCH2, and triacetone amine (from phorone),... 

Many of these reactions are reversible, and for the stronger nucleophiles they usually proceed the fastest. Typical examples are the addition of ammonia, amines, phosphines, and bisulfite. Alkaline conditions permit the addition of mercaptans, sulfides, ketones, nitroalkanes, and alcohols to acrylamide. Good examples of alcohol reactions are those involving polymeric alcohols such as poly(vinyl alcohol), cellulose, and starch. The alkaline conditions employed with these reactions result in partial hydrolysis of the amide, yielding mixed carbamojdethyl and carboxyethyl products. 

Unsubstituted Amides. The most widely used synthetic route for primary amides is the reaction of fatty acid with anhydrous ammonia (11). Fatty acid and ammonia are allowed to react at approximately 200°C for 10 to 12 h under a constant vent of excess ammonia and water by-product. A pressure of 345—690 kPa (50—100 psi) is maintained by the addition of ammonia while the venting of water faciUtates the completion of the reaction. 

Addition of ammonia to the hydrogenator, 1.5 to 5 parts per 100 parts aniline, has been reported to selectively yield cyclohexylamine (49). The reduction is carried out at 160 to 180°C and 2 to 5 MPa (20 to 50 atm) with a mthenium-on-carbon catalyst. 

This is an example of an ammonolytic reaction ia which a chemical bond is broken by the addition of ammonia. It is analogous to the hydrolysis reactions of water. An impressive number of inorganic and organic compounds undergo ammonolysis. 

For direct precipitation of vanadium from the salt-roast leach Hquor, acidulation to ca pH 1 without the addition of ammonia salts yields an impure vanadic acid when ammonium salts are added, ammonium polyvanadate precipitates. The impure vanadic acid ordinarily is redissolved in sodium carbonate solution, and ammonium metavanadate precipitates upon addition of ammonium salts. Fusion of the directly precipitated ammonium salts can yield high purity V20 for the chemical industry. Amine solvent extraction is sometimes used to recover 1—3 g/L of residual V20 from the directly precipitated tail Hquors. 

Potassium and ammonium dichromates are generally made from sodium dichromate by a crystallization process involving equivalent amounts of potassium chloride or ammonium sulfate. In each case the solubiHty relationships are favorable so that the desired dichromate can be separated on cooling, whereas the sodium chloride or sulfate crystallizes out on boiling. For certain uses, ammonium dichromate, which is low in alkaH salts, is required. This special salt may be prepared by the addition of ammonia to an aqueous solution of chromic acid. Ammonium dichromate must be dried with care, because decomposition starts at 185°C and becomes violent and self-sustaining at slightly higher temperatures. 

Kamisako et al., 1988) or alternatively, an addition of ammonia gas leads to a different route for achieving the same product by die photolysis of arnmonia to produce hydrogen atoms... 

HCl aq EtOH). Recrystd from warm, acidified EtOH by addition of ammonia. The crude material (Ig) can be extracted with EtOH (50mL) in a Soxhlet apparatus for lOh to remove impurities. Impurities can be detected by paper electrophoresis. [Petrova et al. Anal Lett 5 695 1972.]... 

Two classes of resol are generally distinguished, water-soluble resins prepared using caustic soda as catalyst, and spirit-soluble resins which are catalysed by addition of ammonia. The water-soluble resins are usually only partially dehydrated during manufacture to give an aqueous resin solution with a solids content of about 70%. The solution viscosity can critically affect the success in a given application. Water-soluble resols are used mainly for mechanical grade paper and cloth laminates and in decorative laminates. 

There is reeent evidenee that stabilization to elevated temperatures (over 350°C) yields a strueture with additional intermoleeular eross-linking that results in improved mechanieal properties in earbonized fibers [10,11]. In addition, it has been noted that the addition of ammonia to the stabilizing environment aeeelerates stabilization [12]. 

Reactions.—i. A small cpiantity of the alloxan solution is evaporated to dryness on the water-bath in a porcelain iDasin. A reddish residue is left, which turns purple on the addition of ammonia (murexide). See Appendix., p. 26S. 

Arynes are intermediates in certain reactions of aromatic compounds, especially in some nucleophilic substitution reactions. They are generated by abstraction of atoms or atomic groups from adjacent positions in the nucleus and react as strong electrophiles and as dienophiles in fast addition reactions. An example of a reaction occurring via an aryne is the amination of o-chlorotoluene (1) with potassium amide in liquid ammonia. According to the mechanism given, the intermediate 3-methylbenzyne (2) is first formed and subsequent addition of ammonia to the triple bond yields o-amino-toluene (3) and m-aminotoluene (4). It was found that partial rearrangement of the ortho to the meta isomer actually occurs. 

Those reactions of halogenopyridines with potassium amide and lithium piperidide which proceed via 3,4-pyridyne form the 3- and 4-substituted pyridine derivatives in ratios of 1 2 and 1 1, respectively (see Section II, A, 1). It appears that the ring nitrogen atom has an orienting effect on these additions, but the quantitative divergence of the addition of ammonia and piperidine is not understood at present. 

According to Roberts et al. the direction of addition of ammonia to 3-substituted benzynes might be predicted by considering the amide ion to add so as to provide the most favorable location of the negative charge with respect to the inductive effect of the orienting substituent. Thus, ammonia adds to 3-methoxybenzyne (39) producing chiefly n-aminoanisole (40). 

A new example of the reactivity of 3,4-pyridyne as a dienophile was reported (the conversion by cyclopentadiene ) and a remarkable orienting effect of the amino group on the addition of ammonia to the triple bond in amino derivatives of 3,4-pyridyne, e.g., the addition of the amide ion to C-4 in 5-amino-3,4-pyridyne. ... 

The reaction seems to involve double addition of ammonia to the ketone 102 (at the methoxyethenyl group and the triple bond) to form the diamine 104 which further undergoes cyclization to aminopyridine 103 by elimination of water and methanol. 

Another pathway for the aromatization of the cr -adducts was found in the reactions of 3-pyrrolidino-l,2,4-triazine 4-oxide 81 with amines. Thus the treatment of 1,2,4-triazine 4-oxide 81 with ammonia leads to 5-amino-1,2,4-triazine 4-oxides 54—products of the telesubstitution reaction. In this case the cr -adduct 82 formed by the addition of ammonia at position 5 of the heterocycle undergoes a [l,5]sigmatropic shift resulting in 3,4-dihydro-1,2,4-triazine 83, which loses a molecule of pyrrolidine to yield the product 54. This mechanism was supported by the isolation of the key intermediates for the first time in such reactions—the products of the sigmatropic shift in the open-chain tautomeric form of tiiazahexa-triene 84. The structure of the latter was established by NMR spectroscopy and X-ray analysis. In spite of its open-chain character, 84 can be easily aromatized by refluxing in ethanol to form the same product 54 (99TL6099). 

It was clearly shown by NMR spectroscopy that the addition of ammonia or primary or secondary alkylamines at position 5 of the 1,2,4-triazine 4-oxides to give the adducts 89 is a kinetically controlled process, while addition at position 3 to form the ring-opening products 85 is a thermodynamically controlled process. 

There have been extensive investigations on the reaction mechanism. In most cases the reaction proceeds via initial nucleophilic addition of ammonia 2 to formaldehyde 1 to give adduct 5, which is converted into an iminium ion species 6 (note that a resonance structure—an aminocarbenium ion can be formulated) through protonation and subsequent loss of water. The iminium ion species 6 then reacts with the enol 7 of the CH-acidic substrate by overall loss of a proton ... 

The large Kf value means that the forward reaction goes virtually to completion. Addition of ammonia to a solution of AgN03 will convert nearly all the Ag+ ions to Ag(NH3)2+ (see Example 15.6). 

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