Ammonia halides

Linear polysilazane oligomers H2N(SiMe2NH) -SiMc2NH2 with a degree of polymerization of ca. 15 are obtained in the reaction of cyclosilazanes in liquid Polymers A and B are formed in reactions of cyclosilazanes with hot ammonium halides (160-300°C, 1-45% ammonia halid) . ... 

NH Cl and NH F are the most acceptable ammonia halides for the use in SHS-Az processes. The reason is that they are safe to handle and there is presently sufficient base of initial products for it. The chemical reaction equations with the use of halides of ammonia have the form ... 

The results in Table 6.2 suggest that no unique order of reactivity applying in all reactions can be given. However, an approximate order of decreasing reactivity [1,32] that applies to most situations is NHj" > > RS >AlkO > PhO > piperidine > OH > aniline > ammonia > halide ions > water. 

CH rCHCH NHCSNH. Colourless crystalline solid with a faint garlic-like odour m.p. 74 C. Manufactured by treating propenyl isothiocyanate with a solution of ammonia in alcohol. It has been given by injection in the treatment of conditions associated with the formation of excessive fibrous tissue. Toxic side reactions may occur. Propenyl thiourea is a chemical sensitizer for photographic silver halide emulsions. 

Towards a simple Lewis base, for example the proton, phosphine is a poorer electron donor than ammonia, the larger phosphorus atom being less able to form a stable covalent bond with the acceptor atom or molecule. Phosphine is, therefore, a much weaker base than ammonia and there is no series of phosphonium salts corresponding to the ammonium salts but phosphonium halides. PH4X (X = Cl, Br, I) can be prepared by the direct combination of phosphine with the appropriate hydrogen halide. These compounds are much more easily dissociated than ammonium halides, the most stable being the iodide, but even this dissociates at 333 K PH4I = PH3 -t- HI... 

Silver chloride is readily soluble in ammonia, the bromide less readily and the iodide only slightly, forming the complex cation [Ag(NH3)2]. These halides also dissolve in potassium cyanide, forming the linear complex anion [AglCN) ] and in sodium thiosulphate forming another complex anion, [Ag(S203)2] ... 

In its chemistry, cadmium exhibits exclusively the oxidation state + 2 in both ionic and covalent compounds. The hydroxide is soluble in acids to give cadmium(II) salts, and slightly soluble in concentrated alkali where hydroxocadmiates are probably formed it is therefore slightly amphoteric. It is also soluble in ammonia to give ammines, for example Of the halides, cadmium-... 

The preparation of pure primary amines by the interaction of alkyl halides and ammonia is very difficult, because the primary amine which is formed reacts with unchanged alkyl halide to give the secondary amine the latter... 

To determine which halogen is present, take 1-2 ml. of the filtrate from the sodium fusion, and add dilute sulphuric acid until just acid to litmus. Add about 1 ml. of benzene and then about 1 ml. of chlorine water and shake. A yellowish-brown colour in the benzene indicates bromine, and a violet colour iodine. If neither colour appears, the halogen is chlorine. The result may be confirmed by testing the solubility of the silver halide (free from cyanide) in dilute ammonia solution silver chloride is readily soluble, whereas the bromide dissolves with difficulty, and the iodide not at all. 

C) Phenacyl and p-Bromophenacyl esters. Ammonium salts in aqueous-ethanolic solution do not however usually condense satisfactorily with phenacyl and />-bromophenacyl bromide. The aqueous solution of the ammonium salt should therefore be boiled with a slight excess of sodium hydroxide to remove ammonia, and the solution then cooled, treated with hydrochloric acid until just alkaline to phenol-phthalein, and then evaporated to dryness. The sodium salt is then treated as described (p. 349) to give the ester. Filter the ester, and wash with water to remove senium halide before recrystallisation. 

The hydrogenolyaia of cyclopropane rings (C—C bond cleavage) has been described on p, 105. In syntheses of complex molecules reductive cleavage of alcohols, epoxides, and enol ethers of 5-keto esters are the most important examples, and some selectivity rules will be given. Primary alcohols are converted into tosylates much faster than secondary alcohols. The tosylate group is substituted by hydrogen upon treatment with LiAlH (W. Zorbach, 1961). Epoxides are also easily opened by LiAlH. The hydride ion attacks the less hindered carbon atom of the epoxide (H.B. Henhest, 1956). The reduction of sterically hindered enol ethers of 9-keto esters with lithium in ammonia leads to the a,/S-unsaturated ester and subsequently to the saturated ester in reasonable yields (R.M. Coates, 1970). Tributyltin hydride reduces halides to hydrocarbons stereoselectively in a free-radical chain reaction (L.W. Menapace, 1964) and reacts only slowly with C 0 and C—C double bonds (W.T. Brady, 1970 H.G. Kuivila, 1968). 

Nucleophilic substitution by ammonia on a halo acids (Section 19 16) The a halo acids obtained by halogenation of car boxylic acids under conditions of the Hell-Volhard-Zelinsky reaction are reac tive substrates in nucleophilic substitu tion processes A standard method for the preparation of a ammo acids is dis placement of halide from a halo acids by nucleophilic substitution using excess aqueous ammonia... 

Alkylamines are in principle capable of being prepared by nucleophilic substitution reactions of aUtyl halides with ammonia... 

Although this reaction is useful for preparing a ammo acids (Table 22 3 fifth entry) it IS not a general method for the synthesis of amines Its major limitation is that the expected primary amine product is itself a nucleophile and competes with ammonia for the alkyl halide... 

Because alkylation of ammonia can lead to a complex mixture of products it is used to prepare primary amines only when the starting alkyl halide is not particularly expensive and the desired amine can be easily separated from the other components of the reaction mixture... 

Aryl halides do not normally react with ammonia under these conditions The few exceptions are special cases and will be described m Section 23 5... 

A method that achieves the same end result as that desired by alkylation of ammonia but which avoids the formation of secondary and tertiary amines as byproducts is the Gabriel synthesis Alkyl halides are converted to primary alkylamines without contam mation by secondary or tertiary amines The key reagent is the potassium salt of phthal imide prepared by the reaction... 

The reaction of amines with alkyl halides was seen earlier (Section 22 7) as a complicat ing factor in the preparation of amines by alkylation of ammonia... 

Ammonia can act as a nucleophile toward primary and some secondary alkyl halides to give primary alkylamines Yields tend to be modest because the primary amine IS itself a nucleophile and undergoes alkylation Alkylation of ammonia can lead to a mixture containing a primary amine a secondary amine a tertiary amine and a quaternary ammonium salt... 

Nitric acid, fuming Organic matter, nonmetals, most metals, ammonia, chlorosulfonic acid, chromium trioxide, cyanides, dichromates, hydrazines, hydrides, HCN, HI, hydrogen sulflde, sulfur dioxide, sulfur halides, sulfuric acid, flammable liquids and gases... 

Nickel halide complexes with amines give mixtures of linear polymer and cychc trimers (30). Nickel chelates give up to 40% of linear polymer (31). When heated with ammonia over cadmium calcium phosphate catalysts, propargyl alcohol gives a mixture of pyridines (32). 

A number of 2eohtic materials have been claimed to cataly2e this reaction and reaction temperatures are on the order of 200—350°C with pressures as high as 18000 kPa (2600 psi) reported. This is a low conversion process and recycle of the unconverted starting materials is necessary to provide an economical process. Amination of ethylene to produce ethylamines cataly2ed by ammonium iodide is reported, but not beheved to be practiced commercially (15,16). Alkyl Halide Amination (Method 7). The oldest technology for pioducing amines is the reaction of ammonia with an alkyl hahde. This... 

Silver Chloride. Silver chloride, AgCl, is a white precipitate that forms when chloride ion is added to a silver nitrate solution. The order of solubility of the three silver halides is Cl" > Br" > I. Because of the formation of complexes, silver chloride is soluble in solutions containing excess chloride and in solutions of cyanide, thiosulfate, and ammonia. Silver chloride is insoluble in nitric and dilute sulfuric acid. Treatment with concentrated sulfuric acid gives silver sulfate. 

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