Nomenclature of Organic Compounds

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23 Amines and Imines

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An

amine may be defined as a derivative of ammonia ( N H ) in which one or more hydrogen atoms have been replaced by non-acyl organic groups linked to the nitrogen atom through carbon. In addition, the subclassifying terms primary, secondary, and tertiary are used to distinguish among amines conceptually derived by the replacement of one, two, or three such hydrogen atoms, respectively. Compounds in which two hydrogen atoms of NH have been replaced by a group attached through a single carbon atom with formation of a double bond are called imines; when the remaining hydrogen atom is replaced by a non-acyl organic group the structure may be regarded as either a substituted imine or a substituted amine. When a nitrogen atom replaces carbon in an organic ring system, the resulting structure is named as a heterocyclic compound (see Chapter 6); for nomenclature purposes it is not formally classed as an amine or imine. 3

3

Recommended Nomenclature Practice Primary monoamines are preferably named substitutively by adding the suffix amine to the name of the chain or ring system to which the NH group is attached, with elision of the terminal e in names wherein it occurs. 2

2-Pentanamine

Cyclohexanamine

l,5-Diazaanthracen-3-amine

Primary polyamines are best named substitutively, by using the suffixes diamine, triamine, tetramine, pentamine, etc. 180 In Nomenclature of Organic Compounds; Fletcher, J., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1974.

23.

181

Amines and Imines CH

I

3

1,3-Butanediamine

H NCH CH CHNH 2

2

2

2

1,4,5,8-Naphthalenetetramine

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NH

NH

2

2

Secondary and tertiary acyclic amines having no more than two N H or N R groups within a single straight chain otherwise composed of carbon atoms are preferably named substitutively as derivatives of the highestranking primary amine structure present. The parent primary amine is selected by applying the following criteria in the order listed: (1) largest number o f amine groups expressed in the suffix, (2) largest number of unsaturated linkages, (3) longest parent chain, and (4) lowest locants for amine groups expressed in the suffix. The locants N , N , IV , etc. (or IV and IV' when no ambiguity would result) are used to designate substituents attached to N H groups o f the parent structure. 1

2

3

2

CH CH CH NHCH 3

2

2

N-Methyl- 1-propanamine

3

CH CH CH NHCH CHCH NHCH NHCH 3

2

2

2

2

2

3

| CH ==CHCH NCH C=CH 2

2

3

N -Dimethyl-iV -propyl-1,2,3propanetriamine

3

N-Methyl-iV-(2-propynyl)-2-propen-l-amirie

2

A s alternatives to alkanamine-type names for symmetrical acyclic second­ ary and tertiary monoamines, substitutive names based on amine, denoting the parent compound N H , are acceptable. 3

CH CH NHCH CH 3

2

2

(C1CH CH ) N 2

2

3

3

N-Ethylethanamine Diethylamine 2-Chloro-N,N-bis(2-chloroethyl)ethanamine Tris(2-chloroethyl)amine

In Nomenclature of Organic Compounds; Fletcher, J., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1974.

182

NOMENCLATURE OF ORGANIC COMPOUNDS

Acyclic polyamines having more than two N H or N R groups within a single straight chain are best named by using replacement nomenclature (see Chapter 7). CH I CH NHCH CH NCH CH NHCH 3

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3

2

2

2

2

5-Methyl-2,5,8-triazanonane 7

3

Cyclic amines in which one or more nitrogen atoms are each directly connected to two or more ring systems are preferably named substitutive­ ly as derivatives of the highest-ranking primary amine structure present. The parent primary amine is selected by applying the following criteria in the order listed: (1) largest number of amine groups expressed in the suffix, and (2) seniority of parent ring system as specified by I U P A C Rule C-14.1 or the Introduction to the Subject Index, Chem. Abstr. (1967) 66, H 29-33 and (3) largest number of N-substituents. In the ranks o f ring systems, all heterocycles are preferred to all carbocycles, and nitrogencontaining heterocycles are preferred to those not containing nitrogen; consideration is next given to (a) number of rings, (b) type of ring fusion, in the order spiro, bridged, and non-bridged, and (c) total number of atoms in the ring system. A s recommended above for acyclic secondary and tertiary amines, the locants N ,N ,N , etc. are used when necessary to avoid ambiguity. l

l

2

3

4

N -(4-Aminophenyl)-AT-phenyl-1,4- benzenediamine

N-Cyclohexylazacyclobutan-2-amine

For symmetrical cyclic secondary and tertiary monoamines the commonly used substitutive names ending in amine are acceptable alternatives to the preferred names in which a primary amine is the parent compound.

// (/

\

// \\_ -( NH

\ J

N-Phenylbenzenamine Diphenylamine

In Nomenclature of Organic Compounds; Fletcher, J., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1974.

23.

183

Amines and 1mines iV,iV-Dicyclopentylqrclopentanamine Tricyclopentylamine

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Cyclic-acyclic amines are best named substitutively as derivatives of the senior primary amine structure present. In selecting the parent amine, the chain or ring system carrying the most amine groups is preferred; if there is a further choice, all heterocyclic systems are preferred to all cyclic and acyclic hydrocarbon systems; otherwise, the largest hydrocarbon is chosen. Additional seniority criteria are provided in the Introduction to the Subject Index, Cbem. Abstr. (1967) 66, f 29-33. NH

2

—NHCH CH NH 2

2

2

iV -(2-Aminoethyl)-l,2-naphthalenediamine

2

CH CH CH CH CH N-