Amides reaction with water

By the action of concentrate aqueous ammonia solution upon esters. This process is spoken of as ammonolysls of the ester, by analogy with hydrolysis applied to a similar reaction with water. If the amide is soluble in water, e.g., acetamide, it may be isolated by distillation, for example ... 

The zwitterion (6) can react with protic solvents to produce a variety of products. Reaction with water yields a transient hydroperoxy alcohol (10) that can dehydrate to a carboxyUc acid or spHt out H2O2 to form a carbonyl compound (aldehyde or ketone, R2CO). In alcohoHc media, the product is an isolable hydroperoxy ether (11) that can be hydrolyzed or reduced (with (CH O) or (CH2)2S) to a carbonyl compound. Reductive amination of (11) over Raney nickel produces amides and amines (64). Reaction of the zwitterion with a carboxyUc acid to form a hydroperoxy ester (12) is commercially important because it can be oxidized to other acids, RCOOH and R COOH. Reaction of zwitterion with HCN produces a-hydroxy nitriles that can be hydrolyzed to a-hydroxy carboxyUc acids. Carboxylates are obtained with H2O2/OH (65). The zwitterion can be reduced during the course of the reaction by tetracyanoethylene to produce its epoxide (66). 

The ketocarbene 4 that is generated by loss of Na from the a-diazo ketone, and that has an electron-sextet, rearranges to the more stable ketene 2 by a nucleophilic 1,2-shift of substituent R. The ketene thus formed corresponds to the isocyanate product of the related Curtius reaction. The ketene can further react with nucleophilic agents, that add to the C=0-double bond. For example by reaction with water a carboxylic acid 3 is formed, while from reaction with an alcohol R -OH an ester 5 is obtained directly. The reaction with ammonia or an amine R -NHa leads to formation of a carboxylic amide 6 or 7 ... 

Reaction with water to yield a carboxylic acid Reaction with an alcohol to yield an ester Reaction with ammonia or an amine to yield an amide Reaction with a hydride reducing agent to yield an aldehyde or an alcohol... 

It can also be done by in situ generation of other types of electrophiles. For example, good yields of /V-acyl a-amino acids are formed in a process in which an amide and aldehyde combine to generate a carbinolamide and, presumably, an acyliminium ion. The organopalladium intermediate is then carbonylated prior to reaction with water.254... 

When heated rapidly, the amide may explode. Reaction with water is violent. See other /V-METAL DERIVATIVES... 

The hydrochloric acid is removed by the strong tertiary base, methyldibutylamine, which has a soluble hydrochloride. In B.P. s 631,549 and 652,981 it was shown that compound (II) could be prepared by the action of dimethylamine on P0C13 in chloroform containing an excess of methylbutylamine. The further reaction with water is very conveniently carried out in the same system by adding an excess of aqueous sodium hydroxide solution. The chloroform layer contains the tertiary amine and (I). The solvent and amine are stripped off leaving the product. Side reactions take place, and the commercial product also contains some triphosphoric pentadimethylamide (I A) and smaller amounts of other phosphoric amides. The compound (I A) is itself also a valuable systemic insecticide. 

Both esters and amides undergo hydrolysis reactions. In a hydrolysis reaction, the ester or amide bond is cleaved, or split in two, to form two products. As mentioned earlier, the hydrolysis of an ester produces a carboxylic acid and an alcohol. The hydrolysis of an amide produces a carboxylic acid and an amine. There are two methods of hydrolysis acidic hydrolysis and basic hydrolysis. Both methods are shown in Figure 2.9. Hydrolysis usually requires heat. In acidic hydrolysis, the ester or amide reacts with water in the presence of an acid, such as H2SO4. In basic hydrolysis, the ester or amide reacts with the OH ion, from NaOH or water, in the presence of a base. Soap is made by the basic hydrolysis of ester bonds in vegetable oils or animal fats. 

Amides undergo an acid- or base-catalyzed hydrolysis reaction with water in the same way that esters do. Just as an ester yields a carboxylic acid and an alcohol, an amide yields a carboxylic acid and an amine (or ammonia). The net effect is a substitution of -N by -OH. This hydrolysis of amides is the key process that occurs in the stomach during digestion of proteins. 

DOT CLASSIFICATION 4.3 Label Dangerous When Wet SAFETY PROFILE Poison by ingestion, inhalation, skin contact, intravenous, and intraperitoneal routes. Moderately toxic to humans by ingestion. Questionable carcinogen with experimental tumorigenic data. Mutation data reported. The fatal dose, by ingestion, is probably around 20 to 30 g for an adult. It does not have a cyanide effect. Calcium cyanamide is not believed to have a cumulative action. Flammable. Reaction with water forms the explosive acetylene gas. When heated to decomposition it emits toxic fumes of NOx and CN". See also CALCIUM COMPOUNDS, AMIDES, and CYANIDE. 

Anhydrides can t be used to make acid chlorides, because RCOO is a stronger base and therefore a poorer leaving group than d . Anhydrides can be used to make all other acyl derivatives, however. Reaction with water and alcohols yields carboxylic adds and esters, respectively. Reaction with two equivalents of NH3 or amines forms 1°, 2°, and 3° amides. A molecule of carboxylic acid (or a carboxylate salt) is always formed as a by-product. 

Perfluoromethylenecyclopropane is extremely reactive towards nucleophiles most alcohols, amines, and water undergo exothermal addition at 0°C with the exocyclic carbon acting as the electrophilic center.The reaction of water with perfluoromethylenecyclopropane gave 2,2,3,3-tetrafluorocyclopropanecarboxylic acid (5). The primary addition products of amines formed the respective amides 4 upon subsequent reaction with water. 

In all forms of digestion (whether of proteins, carbohydrates, or fats), larger molecules are broken down into smaller molecules by a reaction with water in which a water molecule is split in two, each part joining a different product molecule. This type of reaction is called hydrolysis. Remember that proteins are long chains of amino acids linked together by amide functional groups called peptide bonds. When protein molecules are digested, a series of hydrolysis reactions convert them into separate amino acids. 

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