Amine section

The experimental technique is similar to that given under Aromatic Amines, Section IV,100,2. The following alternative method may also be used. Mix together 0 -5-0 - 8 ml. of the polyhydroxy compound, 5 ml. of pyridine and 2 -5 ml. of redistilled benzoyl chloride in a 50 ml. flask. 

Benzenesulphonyl or p-toluenesulphonyl derivatives. These are generally very satisfactory. For experimental details, see under Aromatic Amines, Section IV,100,d. 

Those reactions which are common to both aliphatic and aromatic amines and have been described under Aliphatic Amines (Section 111,123) will not be repeated in this Section except where differences in experimental technique occur. 

Picrates. Experimental details will be found under Aliphatic Amines, Section 111,123, 3. 

Acetates. The acetates of monohydric phenols are usually liquids, but those of di and tri-hydric phenols and also of many substituted phenols are frequently crystaUine sohds. They may be prepared with acetic anhydride as detailed under Amines, Section IV,100,7. 

The Schotten - Baumann method of benzoylation with benzoyl chloride in the presence of aqueous sodium hydroxide may be used. Full details are given under Amines Section IV.lOO, 2. 

The carbylamine or taocyanide test for primary amines Section IV,100,(i) is so extremely delicate that it will detect traces of primary amines in secondary and tertiary amines it must therefore be applied with due regard to this factor. 

Reaction with primary amines (Section 17 10) Isolated product is an imine (Schiff s base) A carbinolamine inter mediate is formed which undergoes de hydration to an imine... 

The first stage of the mechanism is exactly the same as for nucleophilic addition to the carbonyl group of an aldehyde or ketone Many of the same nucleophiles that add to aldehydes and ketones—water (Section 17 6) alcohols (Section 17 8) amines (Sections 17 10-17 11)—add to the carbonyl groups of carboxylic acid derivatives... 

Reaction with ammonia and amines (Section 20 14) Acid an hydrides react with ammonia and amines to form amides Two molar equivalents of amine are required In the example shown only one acyl group of acetic anhydride becomes incor porated into the amide the other becomes the acyl group of the amine salt of acetic acid... 

N Nitroso amine (Section 22 15) A compound of the type R2N—N=0 R may be alkyl or aryl groups which may be the same or different N Nitroso amines are formed by ni trosation of secondary amines... 

Primary amine (Section 22 1) An amine with a single alkyl or aryl substituent and two hydrogens an amine of the type RNH2 (pnmary alkylamine) or ArNH2 (primary aryl amine)... 

Tertiary amine (Section 22 1) Amine of the type R3N with any combination of three alkyl or aryl substituents on nitrogen Tertiary carbon (Section 2 13) A carbon that is directly at tached to three other carbons... 

Reaction with secondary amines (Section 17.11) Isolated product is an en-amine. Carbinolamine intermediate cannot dehydrate to a stable imine. 

Reaction with ammonia and amines (Section 20.14) Acid anhydrides react with ammonia and amines to form amides. 

Reductive amination (Section 22.10) Reaction of ammonia or an amine with an aldehyde or a ketone in the presence of a reducing agent is an effective method for the preparation of primary, secondary, or tertiary amines. The reducing agent may be either hydrogen in the presence of a metal catalyst or sodium cyanoborohy-dride. R, R, and R" may be either alkyl or aryl. 

The 20 fflnino acids listed in Table 27.1 are biosynthesized by a number of different pathways, and we will touch on only a few of them in an introductory way. We will examine the biosynthesis of glutamic acid first because it illustrates a biochemical process analogous to a reaction we discussed earlier in the context of amine synthesis, reductive amination (Section 22.10). 

Reductive amination (Section 22.10) Method for the preparation of amines in which an aldehyde or a ketone is treated with ammonia or an amine under conditions of catalytic hydrogenation. 

Amides are usually prepared by reaction of an acid chloride with an amine (Section 21.4). Ammonia monosubstituted amineS and disubstituted amines all undergo the reaction. 

Flippin. L.A. Carter, D.S. Dubree, HJ.P. Tetrahedron Lett., 1993, 34, 3255 Related Methods Ketones from Amines (Section 172)... 

Section 315 (Carboxylic Acid - Amide) Section 316 (Carboxylic Acid - Amine) Section 351 (Amine - Ester)... 

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