Ammonium hydroxide, reaction with

SOLUTION TO 10a Although an amine cannot undergo an elimination reaction, a quaternary ammonium hydroxide can. The amine, therefore, must first be converted into a quaternary ammonium hydroxide. Reaction with excess methyl iodide converts the amine into a quaternary ammonium iodide, and treatment with aqueous silver oxide forms the quaternary ammonium hydroxide. Heat is required for the elimination reaction. 

Figure 1.4 also shows two other reactions. In reaction 2, ammonia reacts with water to form ammonium hydroxide. Reaction 3 shows that ammonia can also be oxidized to form nitric acid from which all forms of nitrates can be produced. All three forms of nitrogen (ammonia, ammonium hydroxide, and nitrates in various forms) are commonly found in soil and can be added to soil to supply nitrogen to plants (see also Figure 6.5). This process thus opened up an inexpensive method of producing nitrogen compounds that would be used as fertilizers.

Directions (a) Saturate 10 c.c. of ammonium hydroxide solution with sodium chloride in a large test tube by adding an excess of the salt, shaking the mixture vigorously, and then filtering out the undissolved remainder. Set up a generator for carbon dioxide as in Experiment 38 6, and pass the gas into the solution until a heavy precipitate is obtained. Filter out the precipitate and dry it by pressing it between sheets of filter paper. (1) What is this substance (2) Write two equations for the reactions which takes place and cause the formation of the precipitated substance. (3) What caused the second reaction to take place (4) Why is not a solution of ammonium acid carbonate used to produce this reaction with a solution of sodium chloride ... 

Challenge Write the equation for the reaction that occurs in a titration of ammonium hydroxide (NFI4OFI) with hydrogen bromide (FIBr). Will the pFI at the equivalence point be greater or less than 7 ... 

The pyridine-1-oxide XI-117 was synthesized by treating compound W-116 with ammonium hydroxide. Reaction of the sulfonamide XI-118 with... 

Figure 2-9. The pH and conductivity of the gelation reaction. This data was collected on a dispersion of42 wt c silica with 0.2 mM (solution phase concentration) tetraethyl ammonium hydroxide andgelled with an equal molar concentration ofmethylformate. The arrow indicates the gel point.

Now, contrary to popular opinions, this method need not be conducted in a sealed pipe bomb. Secondary amination by substitution is as much a reaction of opportunity as it is of brute force and heat. In fact, heating can tend to cause the reformation of safrole and isosafrole. So the simplest way to do this would be to use 500mL of ammonium hydroxide or alcoholic ammonia or, for those wishing to make MDMA or meth, 40% aqueous methylamine or alcoholic methylamine (to tell you the truth, methylamine is preferable in this method because it is more reactive that ammonia so yield will increase). This 500mL is placed in a flask and into it is poured a solution of 35g bromosafrole (30g phenylisopropyl-bromide) mixed with 50mL methanol. The flask is stoppered and stirred at room temperature for anywhere from 3 to 7 days. The chemist could also reflux the same mixture for 6-12 hours or she could throw the whole mix into a sealed pipe bomb (see How to Make section) and cook it for 5 hours in a 120-130°C oil bath. 

Amidation. Heating of the diammonium salt or reaction of the dimethyl ester with concentrated ammonium hydroxide gives adipamide [628-94-4] mp 228°C, which is relatively insoluble in cold water. Substituted amides are readily formed when amines are used. The most industrially significant reaction of adipic acid is its reaction with diamines, specifically 1,6-hexanediamine. A water-soluble polymeric salt is formed initially upon mixing solutions of the two materials then hea ting with removal of water produces the polyamide, nylon-6,6. This reaction has been studied extensively, and the hterature contains hundreds of references to it and to polyamide product properties (31). 

This carbon dioxide-free solution is usually treated in an external, weU-agitated liming tank called a "prelimer." Then the ammonium chloride reacts with milk of lime and the resultant ammonia gas is vented back to the distiller. Hot calcium chloride solution, containing residual ammonia in the form of ammonium hydroxide, flows back to a lower section of the distiller. Low pressure steam sweeps practically all of the ammonia out of the limed solution. The final solution, known as "distiller waste," contains calcium chloride, unreacted sodium chloride, and excess lime. It is diluted by the condensed steam and the water in which the lime was conveyed to the reaction. Distiller waste also contains inert soHds brought in with the lime. In some plants, calcium chloride [10045-52-4], CaCl, is recovered from part of this solution. Close control of the distillation process is requited in order to thoroughly strip carbon dioxide, avoid waste of lime, and achieve nearly complete ammonia recovery. The hot (56°C) mixture of wet ammonia and carbon dioxide leaving the top of the distiller is cooled to remove water vapor before being sent back to the ammonia absorber. 

Ammonia—Gas-Cured Flame Retardants. The first flame-retardant process based on curing with ammonia gas, ie, THPC—amide—NH, consisted of padding cotton with a solution containing THPC, TMM, and urea. The fabric was dried and then cured with either gaseous ammonia or ammonium hydroxide (96). There was Httle or no reaction with cellulose. A very stable polymer was deposited in situ in the cellulose matrix. Because the fire-retardant finish did not actually react with the cellulose matrix, there was generally Httle loss in fabric strength. However, the finish was very effective and quite durable to laundering. 

The MauIg Color Reaction. The procedure for this test consists basically of three sequential treatments of lignified material with 1% potassium permanganate, 3% hydrochloric acid, and concentrated ammonium hydroxide. A red-purple color develops for hardwoods and a brown color... 

Acidic Properties. As a typical acid, it reacts readily with alkaUes, basic oxides, and carbonates to form salts. The largest iadustrial appHcation of nitric acid is the reaction with ammonia to produce ammonium nitrate. However, because of its oxidising nature, nitric acid does not always behave as a typical acid. Bases having metallic radicals ia a reduced state (eg, ferrous and staimous hydroxide becoming ferric and stannic salts) are oxidized by nitric acid. Except for magnesium and manganese ia very dilute acid, nitric acid does not Hberate hydrogen upon reaction with metals. 

The nitro alcohols available in commercial quantities are manufactured by the condensation of nitroparaffins with formaldehyde [50-00-0]. These condensations are equiUbrium reactions, and potential exists for the formation of polymeric materials. Therefore, reaction conditions, eg, reaction time, temperature, mole ratio of the reactants, catalyst level, and catalyst removal, must be carefully controlled in order to obtain the desired nitro alcohol in good yield (6). Paraformaldehyde can be used in place of aqueous formaldehyde. A wide variety of basic catalysts, including amines, quaternary ammonium hydroxides, and inorganic hydroxides and carbonates, can be used. After completion of the reaction, the reaction mixture must be made acidic, either by addition of mineral acid or by removal of base by an ion-exchange resin in order to prevent reversal of the reaction during the isolation of the nitro alcohol (see Ion exchange). 

Some fabrication processes, such as continuous panel processes, are mn at elevated temperatures to improve productivity. Dual-catalyst systems are commonly used to initiate a controlled rapid gel and then a fast cure to complete the cross-linking reaction. Cumene hydroperoxide initiated at 50°C with benzyl trimethyl ammonium hydroxide and copper naphthenate in combination with tert-huty octoate are preferred for panel products. Other heat-initiated catalysts, such as lauroyl peroxide and tert-huty perbenzoate, are optional systems. Eor higher temperature mol ding processes such as pultmsion or matched metal die mol ding at temperatures of 150°C, dual-catalyst systems are usually employed based on /-butyl perbenzoate and 2,5-dimethyl-2,5-di-2-ethyIhexanoylperoxy-hexane (Table 6). 

Qualitative. The classic method for the quaUtative determination of silver ia solution is precipitation as silver chloride with dilute nitric acid and chloride ion. The silver chloride can be differentiated from lead or mercurous chlorides, which also may precipitate, by the fact that lead chloride is soluble ia hot water but not ia ammonium hydroxide, whereas mercurous chloride turns black ia ammonium hydroxide. Silver chloride dissolves ia ammonium hydroxide because of the formation of soluble silver—ammonia complexes. A number of selective spot tests (24) iaclude reactions with /)-dimethy1amino-henz1idenerhodanine, ceric ammonium nitrate, or bromopyrogaHol red [16574-43-9]. Silver is detected by x-ray fluorescence and arc-emission spectrometry. Two sensitive arc-emission lines for silver occur at 328.1 and 338.3 nm. 

Sulfamic acid readily forms various metal sulfamates by reaction with the metal or the respective carbonates, oxides, or hydroxides. The ammonium salt is formed by neutralizing the acid with ammonium hydroxide ... 

Dilution with water reverses the reaction, and heating the solution Hberates sulfur dioxide. Upon being added to a solution of teUurides, teUurium forms colored polyteUurides. Unlike selenium, teUurium is not soluble in aqueous sodium sulfite. This difference offers a method of separating the two elements. Like selenium, teUurium is soluble in hot alkaline solutions except for ammonium hydroxide solutions. Cooling reverses the reaction. Because teUurium forms solutions of anions, Te , and cations, Te" ", teUurium films can be deposited on inert electrodes of either sign. 

OC-Hydroxycarboxylic Acid Complexes. Water-soluble titanium lactate complexes can be prepared by reactions of an aqueous solution of a titanium salt, such as TiCl, titanyl sulfate, or titanyl nitrate, with calcium, strontium, or barium lactate. The insoluble metal sulfate is filtered off and the filtrate neutralized using an alkaline metal hydroxide or carbonate, ammonium hydroxide, amine, or alkanolamine (78,79). Similar solutions of titanium lactate, malate, tartrate, and citrate can be produced by hydrolyzation of titanium salts, such as TiCl, in strongly (>pH 10) alkaline water isolation of the... 

Reactions of the Side Chain. Benzyl chloride is hydrolyzed slowly by boiling water and more rapidly at elevated temperature and pressure in the presence of alkaHes (11). Reaction with aqueous sodium cyanide, preferably in the presence of a quaternary ammonium chloride, produces phenylacetonitrile [140-29-4] in high yield (12). The presence of a lower molecular-weight alcohol gives faster rates and higher yields. In the presence of suitable catalysts benzyl chloride reacts with carbon monoxide to produce phenylacetic acid [103-82-2] (13—15). With different catalyst systems in the presence of calcium hydroxide, double carbonylation to phenylpymvic acid [156-06-9] occurs (16). Benzyl esters are formed by heating benzyl chloride with the sodium salts of acids benzyl ethers by reaction with sodium alkoxides. The ease of ether formation is improved by the use of phase-transfer catalysts (17) (see Catalysis, phase-thansfer). 

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