Alkali with ammonia

A similar decomposition is produced by the action of alkalies. With ammonia, ammonium thiocyanate is formed. The alkali sulphites react vigorously as follows (Rathke) ... 

Chloroform Reactions.—This ready giving up of its chlorine is also shown by the reactions of chloroform with alkalies, with ammonia and with amines. With alkalies chloroform yields salts of formic acid. This reaction consists in a replacement of all of the chlorine by hydroxyl yielding a tri-hydroxy methane. As we have previously discussed. 

Bucherer reaction Bucherer discovered that the interconversion of 2-naphthol and 2-naphthylamine through the action of alkali and ammonia could be facilitated if the reaction was carried out in the presence of (HSO3]" at about 150 C. This reaction is exceptional for the ease with which an aromatic C —OH bond is broken. It is not of general application, it is probable that the reaction depends upon the addition of [HSO3]" to the normally unstable keto-form of 2-naphthol, and subsequent displacement of —OH by —NH2. 

The nitrochlorobenzenes are valuable dyestufTs intermediates. The presence of the nitro-groups makes the chlorine atom very reactive and easily replaceable. Treatment with ammonia or dilute alkalis substitutes an amino- or hydroxy-group for the chlorine atom and gives a series of nilroanilines and nilrophenols. 

The chemical resistance of PTFE is almost universal It resists attack by aqua regia, hot fummg nitnc acid, hot caustic, chlorine, chlorosulfonic acid, and all solvents. Despite this broad chemical resistance, PTFE is attacked by molten alkali metals, ammonia solutions of such metals, chlorine trifluoride, and gaseous fluonne at elevated temperature and pressure PTFE swells or dissolves m certam highly fluonnated oils near its melting point. Specific lists of chemicals compatible with PTFE are available [/.8]... 

The 3-amino-8-oxo derivative of 1,2,4,5,7-pentaazanaphthalene (475) is known as well as various 3-substituted derivatives of the 6,8-dioxo compound. The 3-methylthio- and 3-ethylthio-6,8-dioxo derivatives and their 7-methyl and 5,7-dimethyl analogs were prepared by ring-closure. 3-Ethylthiopyrimido[4,5-e]-as-triazine-6,8-dione was 3-substituted with alkali 2N, 100°, > 30 min) or acid 2N, 100°, < 2 hr, 70% yield) and with ammonia, aniline, piperidine, or monoalkylamines (in pyridine, 115°, 4 hr, 75-85% yield). ... 

With aldehydes some diaziridines condense under the conditions of preparation. The formation of a fused triazolidine ring occurs regularly if aldehydes are treated with ammonia and chloramine to give diaziri-dines [Eq. (39)]. If, however, chloral is added previously to the reaction mixture, the 3-aIkyl-diaziridines (45) arc caught as their chloral adducts. By the alkali fission of these chloral adducts, 3-alkyl-diaziridines, e.g. (45), can be prepared. 

The product is relatively stable towards water and aqueous alkalies in which it proves to be insoluble even after dwelling therein several hours at room temperature. It reacts, better if at elevated temperature, with lower alcohols with which it forms the corresponding esters, and with ammonia under suitable conditions for forming the amide (melting point 219°C to 221°C). 

Nitric acid is a strong, monobasic acid. It reacts readily with alkalies, oxides, and basic materials, forming salts. The reaction with ammonia, forming ammonium nitrate, for use as a fertilizer, is by far the largest single industrial outlet for nitric acid... 

The treatment of sulfonyl chlorides with ammonia or amines is the usual way of preparing sulfonamides. Primary amines give N-alkyl sulfonamides, and secondary amines give N,N-dialkyl sulfonamides. The reaction is the basis of the Hinsberg test for distinguishing between primary, secondary, and tertiary amines. N-Alkyl sulfonamides, having an acidic hydrogen, are soluble in alkali, while N,N-dialkyl sulfon-... 

During preparation of an oxidising agent on a larger scale than described [1], addition of warm sodium hydroxide solution to warm ammoniacal silver nitrate with stirring caused immediate precipitation of black silver nitride which exploded [2], Similar incidents had been reported previously [3], including one where explosion appeared to be initiated by addition of Devarda s alloy (Al—Cu—Zn) [4], The explosive species separates at pH values above 12.9, only produced when alkali is added to ammoniacal silver solutions, or when silver oxide is dissolved with ammonia [5], The Sommer Market reagent mixture used to identify cellulose derivatives led to a severe explosion [6],... 

Freeder, B. G. et al., J. Loss Prev. Process Ind., 1988, 1, 164-168 Accidental contamination of a 90 kg cylinder of ethylene oxide with a little sodium hydroxide solution led to explosive failure of the cylinder over 8 hours later [1], Based on later studies of the kinetics and heat release of the poly condensation reaction, it was estimated that after 8 hours and 1 min, some 12.7% of the oxide had condensed with an increase in temperature from 20 to 100°C. At this point the heat release rate was calculated to be 2.1 MJ/min, and 100 s later the temperature and heat release rate would be 160° and 1.67 MJ/s respectively, with 28% condensation. Complete reaction would have been attained some 16 s later at a temperature of 700°C [2], Precautions designed to prevent explosive polymerisation of ethylene oxide are discussed, including rigid exclusion of acids covalent halides, such as aluminium chloride, iron(III) chloride, tin(IV) chloride basic materials like alkali hydroxides, ammonia, amines, metallic potassium and catalytically active solids such as aluminium oxide, iron oxide, or rust [1] A comparative study of the runaway exothermic polymerisation of ethylene oxide and of propylene oxide by 10 wt% of solutions of sodium hydroxide of various concentrations has been done using ARC. Results below show onset temperatures/corrected adiabatic exotherm/maximum pressure attained and heat of polymerisation for the least (0.125 M) and most (1 M) concentrated alkali solutions used as catalysts. 

Thorpe s Dictionary of Applied Chemistry London, 1940, IV, 477 Dinitrophenol forms explosive (ad-quinonoid ) salts with alkalies or ammonia, and should not be heated with them in closed vessels [1]. Dinitrophenol forms explosive salts with most metals [2],... 

There is a strong fixation of ammonia at higher temperatures. Hofmann and Ohlerich 28) found that the fixed ammonia was resistant to hydrolysis and that it formed no salts with hydrochloric acid as would be expected of amino groups. The formation of amides was not excluded. Studebaker 86) investigated the reaction of carbon blacks with ammonia. He observed also that the nitrogen became completely unreactive after heating, towards acids as well as towards alkali. 

In the pyridine V-oxide series a C-N exchange rearrangement was also observed when 3-aminocarbonyl-l-methoxypyridinium salt (131) reacts with ammonia or alkali, 3-methoxyiminomethylpyridin-2(l//)-one (132) being obtained (74T4055). This conversion takes place via the ANRORC pathway the ring opening occurs between N-1 and C-6 after initial addition of the hydroxide ion at C-6 (Scheme IV.50). 

The presence of three nitro groups on the aromatic ring of picryl chloride makes the chloro group extremely reactive towards nucleophiles. Picryl chloride (87) is hydrolyzed to picric acid (4) in the presence of hot water or aqueous sodium hydroxide. Aminolysis of picryl chloride in the presence of primary and secondary amines is complete in minutes at room temperature. Picryl chloride is therefore a very useful starting material for the synthesis of a range of other picryl derivatives. The reaction of picryl chloride (87) with ammonia can be used to synthesize 2,4,6-trinitroaniline (53) (picramide). Treatment of picryl chloride with alcohols under reflux forms picric acid and the alkyl chloride of the corresponding alcohol, whereas the same reaction in the presence of alkali metal hydroxides, or the alkoxide anion of... 

Acetyluracil — Ethyl 2-hydroxy-4-methyl-5-pyrimidinecarboxylate (XXXVI), which is prepared by the cyclization of the ureidomethylene derivative of aceto-acetic ester, can be caused to rearrange into 5-acetyluracil (XXXVII) in dilute alkali [304]. Compound (XXXVII) can also be prepared from diketene and ethyl carbamate, followed by treatment with ethyl orthoformate and cyclization with ammonia [305]. 

The mechanism of this reaction was explained by Erlenmeyer and Kunlin in 1899. Just as benzoyl-a-amidocinnamic acid is converted by alkali into phenylpyruvic acid and benzamide, so also does this reaction take place with ammonia the phenylpyruvic acid then reacts with ammonia giving a body of the composition,... 

In general, amino-1,2,4-thiadiazoles are resistant to the action of acids under mild conditions. Prolonged treatment with hot mineral acids, however, can result in decomposition with liberation of sulfur <65AHC(5)119>. 5-Amino-1,2,4-thiadiazoles are decomposed by hot alkalis, with evolution of ammonia, the rate of degradation depending on the nature of the substituent in position 3. The corresponding 3-amino isomers are much more stable to alkali <84CHEC-I(6)463>. 

Alternatively, the compound can be prepared by heating boric oxide or boric acid with ammonium chloride or an alkali metal cyanide. Purified product can be obtained by high temperature reaction of boron halide with ammonia ... 

Chromium metal reacts at 600 to 700°C with sulfur dioxide and caustic alkalis. It combines with phosphorus at 800°C. Reaction with ammonia at... 

Although there have been few new developments in the period since 1993, halogenopyrazines 42 have been convenient precursors for a variety of pyrazine derivatives. For example, the halogenopyrazines 42 are cyanated by palladium-catalyzed cross-coupling with alkali cyanide or by treatment with copper cyanide in refluxing picoline, to yield cyanopyrazines 48. Alkoxypyrazines 49 are produced by treatment with alkoxide-alcohol, and aminopyrazines 50 are prepared by amination with ammonia or appropriate amines. The nucleophilic substitution of chloropyrazine with sodium alkoxide, phenoxide, alkyl- or arylthiolate is efficiently effected under focused microwave irradiation <2002T887>. 

Coupling of allylic or piopargylic halides and terminal acetylenes can also be realized under completely catalytic conditions [204,205]. The reactions are carried out in aqueous medium in the presence of catalytic amounts of cqpper(I)halide. The hydrogen halide liberated in the reaction is neutralized with ammonia, an amine or alkali hydroxide. In many cases both the 1,1- and the 1,3-coupling product is obtained ... 

---