Naming the Amines

Amines are derivatives of ammonia, in which one, two, or three of the hydrogens have been replaced by aUcyl or aryl groups. Therefore, amines are related to ammonia in the same sense as ethers and alcohols are related to water. Note, however, that the designations primary, secondary, and tertiary (see below) are used in a different way. In alcohols, ROH, the nature of the R group defines this designation in amines, the number of R substituents on nitrogen determines the amine classification. 

The system for naming amines is confused by the variety of conunon names in the literamre. Probably the best way to name aliphatic amines is that used by Chemical Abstracts— that is, as alkanamines, in which the name of the alkane stem is modified by replacing the ending -e by -amine. The position of the functional group is indicated by a prefix designating the carbon atom to which it is attached, as in the alcohols (Section 8-1). 

Substances with two amine functions are diamines, two examples of which are 1,4-butanediamine and 1,5-pentanediamine. Their contribution to the smell of dead fish and rotting flesh leads to their descriptive common names, putrescine and cadaverine, respectively. 

The aromatic amines, or anilines, are called benzenamines (Section 15-1). For secondary and tertiary anunes, the largest alkyl substituent on nitrogen is chosen as the alkanamine stem, and the other groups are named by using the letter N-, followed by the name of the additional substituent(s). 

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Nomenclature.—A definite system of nomenclature has been adopted for metal-ammines, and the old names derived from the colour of the compounds have, in the main, been abandoned, as they lead to confusion. The system adopted is that suggested by Werner. Ammonia molecules present in the complex are indicated by the terms monam-mino, diammino, triammino, tetrammino, pentammino, hexammino, the word ammino, written with a double m, having been adopted to show the relationship with ammonia and to distinguish from the ammonium salts and the substituted ammonia compounds, namely, the amines. 

Name the amines represented by the condensed formulas below. (23.2)... 

Further studies of the photochemically induced conversion of JV-methyl-diphenylamine into N-methylcarbazole have been reported.28 Two successive intermediates have been detected, namely the amine triplet and iV-methyl-4a,4b-dihydrocarbazole. Oxygen appears to participate in the overall reaction in two ways, viz. by dehydrogenation of the dihydrocarbazole intermediate to carbazole and by quenching the amine triplet. Non-oxidative cyclization of 5-(iV-methyl-anilino)- and 5-(iV-acetylanilino)-l,3-dimethyluracil (26) similarly gives the trans-dihydropyrimido[5,4-6]indoles (27) in high yield.24 Orbital symmetry arguments... 

Name the amine from which the amine salt is derived. 

Name the amine used to bring about Step 2, and propose a mechanism for this step. 

There also exists an acidregioselective condensation of the aldol type, namely the Mannich reaction (B. Reichert, 1959 H. Hellmann, 1960 see also p. 291f.). The condensation of secondary amines with aldehydes yields Immonium salts, which react with ketones to give 3-amino ketones (=Mannich bases). Ketones with two enolizable CHj-groupings may form 1,5-diamino-3-pentanones, but monosubstitution products can always be obtained in high yield. Unsymmetrical ketones react preferentially at the most highly substituted carbon atom. Sterical hindrance can reverse this regioselectivity. Thermal elimination of amines leads to the a,)3-unsaturated ketone. Another efficient pathway to vinyl ketones starts with the addition of terminal alkynes to immonium salts. On mercury(ll) catalyzed hydration the product is converted to the Mannich base (H. Smith, 1964). 

Alkylamines are named m two ways One method adds the ending amine to the name of the alkyl group The other applies the principles of sub stitutive nomenclature by replacing the e ending of an alkane name by amine and uses appropriate locants to identify the position of the ammo group Arylammes are named as derivatives of aniline... 

Wnte structural formulas or build molecular models for all the amines of molecular formula C4H11N Give an acceptable name for each one and classify it as a pnmary secondary or terti ary amine... 

The amine, under the name N,N,N, N -tetramethyl-methylenediamine, may be purchased from Ames Laboratories, South Norwalk, Connecticut. The checkers prepared it by the following procedure. A solution of 60.7 g. (0.75 mole) of 37% aqueous formaldehyde solution is placed in an 800-ml. beaker equipped with a mechanical stirrer and thermometer, and cooled in an ice bath. Two hundred seventy-one grams (1.50 moles) of a 25% aqueous solution of dimethylamine is added to this solution at a rate such that the reaction temperature is kept below 15°. The solution is stirred for 30 minutes after the addition is complete, and potassium hydroxide pellets (approximately 150 g.) are added in portions until the reaction mixture separates into two layers. The upper layer is separated, dried over potassium hydroxide pellets overnight, and distilled to give 59 -64 g. (77-83%) of bis(dimcthylamin())mclliane, b.p. 83 84°. ... 

The amines are a group of compounds with the general formula R-NHj, and all the common amines are hazardous. As a class the amines pose more than one hazard, being flammable, toxic, and, in some cases, corrosive. The amines are an analogous series of compounds and follow the naming pattern of the alkyl halides and the alcohols that is, the simplest amine is methyl amine, with the molecular formula of CH NHj. Methyl amine is a colorless gas with an ammonia-like odor and an ignition temperature of 806°F. It is a tissue irritant and toxic, and it is used as an intermediate in the manufacture of many chemicals. Ethyl amine is next in the series, followed by propyl amine, isopropyl amine, butyl amine and its isomers, and so on. 

The prototype of the antihistamines based on benzhydrol, diphenhydramine (3), is familiar to many today under the trade name Benadryl . Light-induced bromination of diphenylmethane affords benzhydryl bromide (2). This is then allowed to react with dimethylaminoethanol to give the desired ether. Although no mechanistic studies have been reported, it is not unlikely that I he bromine undergoes SNi solvolysis in the reaction medium the carbonitjm ion then simply picks up the alcohol. It might be noted in passing that the theophyline salt of 4 is familiar to many Iravelers as a motion sickness remedy under the trade name Oram amine . 

Heterocyclic amines—compounds in which the nitrogen atom occurs as part of a ring—are also common, and each different heterocyclic ring system has its own parent name. The heterocyclic nitrogen atom is always numbered as position 1. 

Name the following amines, and identify each as primary, secondary, or tertiary ... 

Name the following amine, including R,S stereochemistry, and draw the product of its reaction with excess iodomethane followed by heating with Ag20 (Hofmann elimination). Is the stereochemistry of the alkene product Z or E Explain. 

The ending caine stems from cocaine, the first clinically employed local anaesthetic. Procaine and tetracaine are ester-linked substances, the others are amides. Amide bonded local anaesthetics usually contain two i s in their name, ester-bonded only one. In the structure drawings, the lipophilic portion of the molecule is depicted at the left, the amine at the right. The asterisk marks the chiral centre of the stereoisomeric drugs. Lipid solubility is given as the logarithm of the water octanol partition coefficient, log(P). 

In addition to the Ross-Schiessler process, utilising p-CH20 and AN, the synthesis of RDX/ HMX mixts has also been reported starting with other smail molecules (Ref 7), namely, methyl-amine nitrate methylene diamine dinitrate and nitramine (NH2N02) in combination with CH20. In these reactions, the intermediate formation of Hexamine or a cyclic analog, is not necessarily established... 

The tetracyano derivative of 2.49, 5-diazo-l,2,3,4-tetracyanocyclopentadiene (2.52), and its heterocyclic analogue, 2-diazo-4,5-dicyano-imidazole (2.53) can be obtained by diazotization of the corresponding amines, namely the (anionic) 1-amino-... 

Although Hammett convincingly explained the nitrosation of aliphatic amines and the diazotization of aniline under the conditions employed by Schmid and others, one unsatisfactory point remained namely the second-order kinetic equation obtained by Hantzsch and the workers who followed him for diazotization in a more weakly acidic medium. Comparison of experimental details shows that at concentrations of free mineral acid below 0.05 m the reaction is apparently second-order, but it becomes third-order at higher concentrations of acid. 

Two investigations on coupling reactions with aromatic amines to yield N- and C-coupling products have been carried out, namely the 7V-couplings with aniline (Beranek and Vecera, 1970) and with 7V-methylaniline (Beranek et al., 1972). ... 

There are actually three reactions called by the name Schmidt reaction, involving the addition of hydrazoic acid to carboxylic acids, aldehydes and ketones, and alcohols and alkenes. The most common is the reaction with carboxylic acids, illustrated above.Sulfuric acid is the most common catalyst, but Lewis acids have also been used. Good results are obtained for aliphatic R, especially for long chains. When R is aryl, the yields are variable, being best for sterically hindered compounds like mesi-toic acid. This method has the advantage over 18-13 and 18-14 that it is just one laboratory step from the acid to the amine, but conditions are more drastic. Under the acid conditions employed, the isocyanate is virtually never isolated. 

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