Ammonia, addition carboxylation

Hydrolysis of cyanohydrins 6-16 Reaction between aldehydes, ammonia. and carboxylic acids or esters 6-50 Addition of cyanide and ammonium ions to aldehydes or ketones, followed by hydrolysis (Strecker)... 

Oil Repellent. Fluorochemicals are the only class of material that can provide oil repeUency without altering the porosity of the paper or paperboard. Physical barriers to oil penetration are used primarily for their moisture- or gas-barrier properties, with retarded oil penetration as a secondary benefit. The most common od-repeUent additives are long-chain perfluoroalkyl phosphate salts of ammonia or diethanol amine. Commercial sources include Scotchban (3M), Zonyl (DuPont), and Lodyne (Ciba Specialties). There are also a fluorochemical carboxylate salt, Lodyne (Ciba Specialties), and fluorochemical copolymers, eg, Scotchban (3M). The widest range of oily fluid holdout is provided by the fluorochemical copolymers. 

Conversion of Amides into Carboxylic Acids Hydrolysis Amides undergo hydrolysis to yield carboxylic acids plus ammonia or an amine on heating in either aqueous acid or aqueous base. The conditions required for amide hydrolysis are more severe than those required for the hydrolysis of add chlorides or esters but the mechanisms are similar. Acidic hydrolysis reaction occurs by nucleophilic addition of water to the protonated amide, followed by transfer of a proton from oxygen to nitrogen to make the nitrogen a better leaving group and subsequent elimination. The steps are reversible, with the equilibrium shifted toward product by protonation of NH3 in the final step. 

The addition of ammonia to the variety of acids derivable from either the breakdown of glucose, glycolysis, or of the pentose shunt reaction products, ribose and NADPH, and from the citrate cycle, gives the amino acids (see Table 4.7 and Figure 4.4) Polymerisation of amino acids in cells gives proteins. In some of the amino acids sulfur and selenium can be incorporated easily. We assume NH3 was present. (Note that Se is in a coded amino acid not in Table 4.7.) Some selective metal-binding properties can be seen in Table 4.7, but amino acid carboxylates can bind all. 

Replacement of the hydroxyl group on the phenyl ring with a carboxyl group forms a molecule of benzoic acid. Addition of a hydroxyl at the 2-position on a benzoic acid molecule forms 2-hydroxybenzoic acid or salicylic acid. The slightly more complex phenylpropanoid skeleton contains a linear three-carbon chain (the propanoic group) added to the benzene ring (the phenyl group). Addition of ammonia to carbon 2 of this three-carbon side chain yields the amino acid phenylalanine (Fig. 3.3). Phenylalanine... 

The nucleophilic addition of alcohols [130, 204-207], phenols [130], carboxylates [208], ammonia [130, 209], primary and secondary amines [41, 130, 205, 210, 211] and thiols [211-213] was used very early to convert several acceptor-substituted allenes 155 to products of type 158 and 159 (Scheme 7.25, Nu = OR, OAr, 02CR, NH2, NHR, NRR and SR). While the addition of alcohols, phenols and thiols is generally carried out in the presence of an auxiliary base, the reaction of allenyl ketones to give vinyl ethers of type 159 (Nu = OMe) is successful also by irradiation in pure methanol [214], Using widely varying reaction conditions, the addition of hydrogen halides (Nu= Cl, Br, I) to the allenes 155 leads to reaction products of type 158 [130, 215-220], Therefore, this transformation was also classified as a nucleophilic addition. Finally, the nucleophiles hydride (such as lithium aluminum hydride-aluminum trichloride) [211] and azide [221] could also be added to allenic esters to yield products of type 159. 

When the reaction with substituted benzaldehydes is conducted in the presence of ammonia, the a-amino carboxylic acids are formed [11], The corresponding reaction involving bromoform is less effective and, for optimum yields, the addition of lithium chloride, which enhances the activity of the carbonyl group, is required. In its absence, the overall yields are halved. The reaction of dichlorocarbene with ketones or aryl aldehydes in the presence of secondary amines produces a-aminoacetamides [12, 13] (see Section 7.6). 

Ammonia lyases catalyze the enantioselective addition of ammonia to an activated double bond. A one-pot, three-step protocol was developed for the enantioselective synthesis of L-arylalanines 50 using phenylalanine ammonia lyase (PAL) in the key step (Scheme 2.20). After formation of the unsaturated esters 48 in situ via a Wittig reaction from the corresponding aldehydes, addition of porcine Ever esterase and basification of the reaction mixture resulted in hydrolysis to the carboxylic acids 49. Once this reaction had gone to completion, introduction of PAL and further addition of ammonia generated the amino acids 50 in good yield and excellent optical purity [22]. 

Addition of a 2-alkynoic acid to alkali amide in liquid ammonia initially gives a solution of the alkali salt of the carboxylic acid. If an excess of alkali amide is present, the weakly basic salt is further deprotonated at a position next to the triple bond 183], This double deprotonation which may be compared with the formation of di-anions from 1,3-diketones and alkali amides [71], is essentially complete. The high kinetic stability of the alkynoic acid-dianion may be explained on the basis of resonance stabilization ... 

Nucleophilic addition to C=0 (contd.) ammonia derivs., 219 base catalysis, 204, 207, 212, 216, 226 benzoin condensation, 231 bisulphite anion, 207, 213 Cannizzaro reaction, 216 carbanions, 221-234 Claisen ester condensation, 229 Claisen-Schmidt reaction, 226 conjugate, 200, 213 cyanide ion, 212 Dieckmann reaction, 230 electronic effects in, 205, 208, 226 electrons, 217 Grignard reagents, 221, 235 halide ion, 214 hydration, 207 hydride ion, 214 hydrogen bonding in, 204, 209 in carboxylic derivs., 236-244 intermediates in, 50, 219 intramolecular, 217, 232 irreversible, 215, 222 Knoevenagel reaction, 228 Lewis acids in, 204, 222 Meerwein-Ponndorf reaction, 215 MejSiCN, 213 nitroalkanes, 226 Perkin reaction, 227 pH and, 204, 208, 219 protection, 211... 

In addition to carboxyl groups, amino acids have a second functional group, the amine group (NH2). Amines are related to ammonia (NH3). 

The stoichiometric composition of the halogenoborane complexes is 1 1, as a rule. However, in some cases, 2 1 and 4 1 complexes are also obtained (Table 4). In the latter instances additional ligands are bonded to the 1 1 complex through hydrogen bonds.2,11 55 With ammonia only the 1 1 complex is stable, whereas (H20)2-BF3 is more stable than H20-BF3. BF3 produces 2 1 complexes of similar stability with alcohols and carboxylic acids.2,55,57 At low temperatures some tertiary amines give complexes with halogenoboranes and complexes of... 

Carboxylic acids often have been identified by means of paper chromatography Clarke and Bazill (10) have extracted plasticizers from polyvinyl chloride first with ether and then with methanol. Subsequently the extracts were saponified with alcoholic potassium hydroxide, and the precipitated potassium salts were isolated and converted into free acids. These, in alcoholic solution, were then applied to paper and chromatographed ascendingly with a mixture of butanol, pyridine, water, and ammonia the migration period was about six hours. A number of additional color tests facilitated identification of unknown acids. 

Pyridine is not polarographically reducible in aqueous solvents but in aprotic media, such as acetonitrile,211 DMF,212 or liquid ammonia,213 it is reduced at rather negative potentials to the anion-radical, which then dimerizes. Some electron-attracting substituents, notably carboxyl derivatives, render the nucleus reducible even in aqueous solvents. Quaternary derivatives are generally reducible. JV-Alkylpyridinium ions thus give a free radical, which dimerizes rapidly the radical was trapped by a-phenyl-Af-tert-butylnitrone.214 1,3-Dimethylpyridinium ion is reduced in buffered aqueous medium to a 4,4 -dimer, which undergoes further chemical reaction, possibly an addition of water to one of the double bonds of the 1,4-dihydropyridine rings.215... 

Ring opening is common in the alkali metal and liquid ammonia reduction of furans unless an anion stabilizing group is present, so most work has been done with derivatives of furancarboxylic acids. Treatment of furan-2-carboxylic acid with lithium and ammonia at -78 °C followed by rapid addition of ammonium chloride affords 2,5-dihydrofuran-2-carboxylic acid (80%). Reductive alkylation similarly gives 2-alkyl-2,5-dihydrofuran-2-carboxylic acids. This method has been used in a synthesis of rosefuran, the intermediate dihydrofuran (66) being converted into the product (67) by oxidative decarboxylation with... 

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