Amines Form Alkaline Solutions

Diethyl ether is the systematic name for the ether historically used as an anesthetic. 

Low-formula-mass amines like these tend to have an offensive odor. 

Ethylamine acts as a base and accepts a hydrogen ion from water to become the eth-ylammonium ion. This reaction generates a hydroxide ion, which increases the pH of the solution. 

Caffeine, free-base form (water-insoluble) Phosphoric acid Caffeine-phosphoric acid salt (water-soluble)  

All alkaloids are bases that react with acids to form salts. An example is the alkaloid caffeine, shown here reacting with phosphoric acid. 

Why do most caffeinated soft drinks also contain phosphoric acid  

---

Method 1. Treat 2 0 g. of the mixture of amines with 40 ml. of 10 per cent, sodium hydroxide solution and add 4 g. (3 ml.) of benzenesulphonyl chloi de (or 4 g. of p-toluenesulphonyl chloride) in small portions. Warm on a water bath to complete the reaction. Acidify the alkaline solution with dilute hydrochloric acid when the sulphonamides of the primary and secondary amines are precipitated. Filter off the solid and wash it with a little cold water the tertiary amine will be present in the filtrate. To convert any disulphOnamide that may have been formed from the primary amine into the sulphonamide, boil the solid under reflux with 2 0 g. of sodium dissolved in 40 ml. of absolute ethyl alcohol for 30 minutes. Dilute with a little water and distil off the alcohol filter off the precipitate of the sulphonamide of the secondary amine. Acidify the filtrate with dilute hydrochloric acid to precipitate the derivative of the primary amine. Recrystallise the respective derivatives from alcohol or from dilute alcohol, and identify them inter alia by a determination of the m.p. 

The reduction of the nitro group to yield aniline is the most commercially important reaction of nitrobenzene. Usually the reaction is carried out by the catalytic hydrogenation of nitrobenzene, either in the gas phase or in solution, or by using iron borings and dilute hydrochloric acid (the Bechamp process). Depending on the conditions, the reduction of nitrobenzene can lead to a variety of products. The series of reduction products is shown in Figure 1 (see Amines byreduction). Nitrosobenzene, /V-pbenylbydroxylamine, and aniline are primary reduction products. Azoxybenzene is formed by the condensation of nitrosobenzene and /V-pbenylbydroxylamine in alkaline solutions, and azoxybenzene can be reduced to form azobenzene and hydrazobenzene. The reduction products of nitrobenzene under various conditions ate given in Table 2. 

Amine oxides show either nonionic or cationic behavior in aqueous solution depending on pH. In acid solution the cationic form (R2N" OH) is observed (2) while in neutral and alkaline solution the nonionic form predorninates as the hydrate R NO H2O. The formation of an ionic species in the acidic pH range stabilizes the form generated by the most studied commercial amine oxide, dimethyldodecylamine oxide (6). 

In the reduction of nitro compounds to amines, several of the iatermediate species are stable and under the right conditions, it is possible to stop the reduction at these iatermediate stages and isolate the products (see Figure 1, where R = CgH ). Nitrosoben2ene [586-96-9] C H NO, can be obtained by electrochemical reduction of nitrobenzene [98-95-3]. Phenylhydroxylamine, C H NHOH, is obtained when nitrobenzene reacts with ziac dust and calcium chloride ia an alcohoHc solution. When a similar reaction is carried out with iron or ziac ia an acidic solution, aniline is the reduction product. Hydrazobenzene [122-66-7] formed when nitrobenzene reacts with ziac dust ia an alkaline solution. Azoxybenzene [495-48-7], C22H2QN2O, is... 

Activated tertiary amines such as triethanolamine (TEA) and methyl diethanolamine (MDEA) have gained wide acceptance for CO2 removal. These materials require very low regeneration energy because of weak CO2 amine adduct formation, and do not form carbamates or other corrosive compounds (53). Hybrid CO2 removal systems, such as MDEA —sulfolane—water and DIPA—sulfolane—water, where DIPA is diisopropylamine, are aqueous alkaline solutions in a nonaqueous solvent, and are normally used in tandem with other systems for residual clean-up. Extensive data on the solubiUty of acid gases in amine solutions are available (55,56). 

To minimize the formation of fuhninating silver, these complexes should not be prepared from strongly basic suspensions of silver oxide. Highly explosive fuhninating silver, beheved to consist of either silver nitride or silver imide, may detonate spontaneously when silver oxide is heated with ammonia or when alkaline solutions of a silver—amine complex are stored. Addition of appropriate amounts of HCl to a solution of fuhninating silver renders it harmless. Stable silver complexes are also formed from many ahphatic and aromatic amines, eg, ethylamine, aniline, and pyridine. 

Chloroform reacts with aniline and other aromatic and aliphatic primary amines in alcohoHc alkaline solution to form isonitnles, ie, isocyanides, carbylamines, as shown ... 

Nickel peroxide is a solid, insoluble oxidant prepared by reaction of nickel (II) salts with hypochlorite or ozone in aqueous alkaline solution. This reagent when used in nonpolar medium is similar to, but more reactive than, activated manganese dioxide in selectively oxidizing allylic or acetylenic alcohols. It also reacts rapidly with amines, phenols, hydrazones and sulfides so that selective oxidation of allylic alcohols in the presence of these functionalities may not be possible. In basic media the oxidizing power of nickel peroxide is increased and saturated primary alcohols can be oxidized directly to carboxylic acids. In the presence of ammonia at —20°, primary allylic alcohols give amides while at elevated temperatures nitriles are formed. At elevated temperatures efficient cleavage of a-glycols, a-ketols... 

The reaction mixture was then dissolved in methylene chloride, the amine was removed by shaking with dilute hydrochloric acid, the reaction product was extracted from the organic phase by means of dilute sodium hydroxide solution and the alkaline solution was acidified with acetic acid to a pH value of 6. The 1 -hvdroxv-4-methyl-6-cvclohexvl-2-pyridone precipitated in crystalline form. It was filtered off with suction, washed with water and dried. The yield was 1.05 g (49% of theory) melting point 143°C. 

Based on observations by Bamberger, Bucherer, and Wolff at the turn of the century, Matrka et al. (1967) described experiments which show that alkaline solutions (pH 8.5-9.2) of substituted benzenediazonium chlorides form nitrite ions and triazenes. The latter is obviously the reaction product of the amine formed in a retro-diazotization with the diazonium ion that is still present. The yield of nitrite formed was between 0.5% (benzenediazonium ion) and 50.2% (2-nitrobenzenediazonium ion). 

A layer of poly (vinyl alcohol) forms a gel when treated with aqueous alkaline solutions of acylacetamides of aromatic amines which have an unsubstituted methylene group between the two carbonyl groups 29). Several examples are illustrated in Figure 5. 

Post-combustion capture using chemical absorption by aqueous alkaline amine solutions has been used for C02 and H2S removal from gas-treating plants for decades [6]. Amines react rapidly, selectively and reversibly with C02 and can be applied at low C02 partial pressure conditions. Amines are volatile, cheap and safe in handling. They show several disadvantages as they are also corrosive and require the use of resistant materials. Furthermore, amines form stable salts in the presence of O2, SOx and other impurities such as particles, HC1, HF and organic and inorganic Fig trace compounds that extremely constrain the content of those compounds in the treated gas. 

Figure 3.11 Woodward s reagent K undergoes a rearrangement in alkaline solution to form a reactive ketoket-enimine. This active species can react with a carboxylate group to create another active group, an enol ester derivative. In the presence of amine nucleophiles, amide bond formation takes place.

Subsequent treatment with alkali provides a free base solution in excess amine, which can be separated from the aqueous/alkaline aluminate layer. The thus prepared product is precipitated with acid, possibly converted into the free base with aqueous alkaline solution, and isolated. The dried base or its salt is then sulfonated with concentrated sulfuric acid to form the monosulfonic acid 121. 

Technetium dissolves in dilute or concentrated nitric acid to form nitrate, Tc(N03)2. Reaction with concentrated sulfuric acid yields the sulfate TCSO4. Technetium is oxidized by hydrogen peroxide in alkaline solution to form soluble pertechnetate, Tc04 anion. Such pertechnatate anion forms complexes with tertiary or quarternary amines, pyridine and its methyl-substituted derivatives. 

The present authors studied the extraction of aromatic amines into ILs. As is seen from experimental data for [C4CiIm][PFg] (Figure 9.2), aniline, napthylamine, and o-toluidine are efficiently extracted from the alkaline aqueous solution. Thus, as in the case of phenols, neutral (molecular) forms of solutes were extracted. Another example of the same behavior is given by many polyfunctional compounds, for example, 8-hydroxyquinoline (Figure 9.3 presents a comparison of extraction pH-profile with the distribution diagram for ionic forms of the solute). 

JV-Nitraminopyridines are reducible both in acid and alkali. In hydrochloric acid the main product from 2-nitraminopyridine was the hydrazino-pyridine, formed in a six-electron reduction, but 2-aminopyridine and 2-chloropyridine were side products, the latter possibly through reaction by an intermediate diazonium compound with chloride. Contrary to nitramines of most primary amines, 2-nitraminopyridine431 is reducible in alkaline solution uptake of the first two electrons forms the 2-pyridyl-N-nitrosamine, which is further reduced to 2-aminopyridine. 

Solutions of alkali metals in ammonia have been the best studied, but other metals and other solvents give similar results. The alkaline earth metals except- beryllium form similar solutions readily, but upon evaporation a solid ammoniste. M(NHJ)jr, is formed. Lanthanide elements with stable +2 oxidation states (europium, ytterbium) also form solutions. Cathodic reduction of solutions of aluminum iodide, beryllium chloride, and teUraalkybmmonium halides yields blue solutions, presumably containing AP+, 3e Be2, 2e and R4N, e respectively. Other solvents such as various amines, ethers, and hexameihytphosphoramide have been investigated and show some propensity to form this type of solution. Although none does so as readily as ammonia, stabilization of the cation by complexation results in typical blue solutions... 

The add is slowly hydrolysed by water at 25°Cj rapidly at higher temperatures. Warm alkaline solutions decompose the material to form sulfates and unstable imine organic aromatic compounds. Aqueous acids cause reversion... 

---