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Chapter 20
Amines
21
Chemistry
Undergraduate 4
05/02/2011

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Term
Amine
Definition
A molecule containing an amino group, -NH2 , -NHR, or -NR2 , obtained by removing one or more hydrogen atoms from ammonia, with the general formula RNH2 , RNHR, or RNR2 . A primary amine has one R group attached to the N atom, a secondary amine has two R groups attached to the N atom, and a tertiary amine has three R groups attached to the N atom
Term
Alkylamine
Definition
An amine that has one or more alkyl groups attached to the amine nitrogen, such as RNH2
Term
Amino group
Definition
The -NH2 group; if alky1ated, it becomes an alkylamino group -NHR, or a dialkylamino group -NR2
Term
Arylamine
Definition
An amine that has one or more aromatic groups attached to the amine nitrogen, such as ArNH2
Term
Ammonium salt
Definition
A derivative of an amine with a positively charged nitrogen atom having four bonds; an amine is protonated by an acid to give an ammonium salt: RNH2 + HA → RN+H3 A- ; a quaternary ammonium salt has a positively charged nitrogen atom bonded to four alkyl (or aryl) groups: R4N+ . Also called aminium salt, or amine salt
Term
Azide
Definition
A compound having the azido group, -N3
Term
Gabriel amine synthesis
Definition
of primary amines by alkylation of the potassium salt of phthalimide, followed by displacement of the amine by hydrazine
Term
Reductive amination
Definition
The reduction of an imine or oxime derivative of a ketone or aldehyde to an amine
Term
Hofmann rearrangement
Definition
Conversion of a primary carboxylic amide to a primary amine, with one fewer carbon atom, by treatment with bromine in aqueous NaOH, via an isocyanate intermediate. Also called Hofmann reaction
Term
Curtius rearrangement
Definition
Conversion of a carboxylic acid to an amine having one fewer carbon atoms, which proceeds via thermal decomposition of an acyl azide into an isocyanate. Also called Curtius reaction
Term
Diazotization of an amine
Definition
The reaction of a primary aromatic amine with nitrous acid, HNO2 , which forms a diazonium ion, R-N+≡N: and can be used to prepare aryl halides, phenols, and aryl cyanides, or to deaminate the amine
Term
Diazonium ion
Definition
Ion of the type R-N+≡N: Aryl diazonium ions are formed by treatment of primary aromatic amines with nitrous acid, HNO2 , which can be used to prepare aryl halides, phenols, and aryl cyanides, or to deaminate the amine
Term
Nitrosoamine
Definition
An amine with a nitroso group -N=O bonded to the amine nitrogen atom; the reaction of secondary amines with nitrous acid gives secondary nitrosoamines
Term
Sandmeyer reaction
Definition
Replacement of the -N≡N group in an arenediazonium salt by a cuprous salt; usually cuprous chloride, bromide, or cyanide
Term
Diazo coupling
Definition
The use of an electrophilic diazonium salt in electrophilic aromatic substitution, such as the reaction of an aryl diazonium salt with an arene, which forms a compound of the type ArN=NAr'. The arene must be strongly activated toward electrophilic aromatic substitution; that is, it must bear a powerful electron-releasing substituent such as -OH or -NR2
Term
Sulfonamide
Definition
An amide of a sulfonic acid, which is the nitrogen analogue of a sulfonate ester
Term
Hinsberg test
Definition
The reaction of an amine with benzenesulfonyl chloride to form a benzenesulfonamide, in order to determine whether it is a primary, secondary, or tertiary amine
Term
Hofmann elimination
Definition
Elimination of a quaternary ammonium hydroxide by pyrolysis into an alkene and a tertiary amine, which usually gives the least-substituted alkene (Hofmann product). Also called Hofmann degradation
Term
Hofmann rule
Definition
The major product of an elimination reaction that uses a large, bulky base will be the less stable alkene, which has the less substituted double bond.
Term
Cope elimination
Definition
Pyrolysis of a tertiary amine oxide into an alkene and a hydroxylamine
Term
Alkaloid
Definition
An amine that occurs naturally in many plants, fungi and bacteria, and has profound physiological effects on animals, often toxic; the name derives from the word alkaline, since these compounds are weak bases with a bitter taste
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