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F324

Amines

Amines
Basicity of amines explain the basicity of amines in terms of proton acceptance by the nitrogen lone pair describe the reactions of amines with acids to form salts Comparison of basicity of different amines not required. Preparation of amines describe the preparation of: (i) aliphatic amines by substitution of halogenoalkanes with excess ethanolic ammonia (ii) aromatic amines by reduction of nitroarenes using tin and concentrated hydrochloric acid Synthesis of azo dyes describe the synthesis of an azo dye by reaction of an aromatic amine with nitrous acid (<10 C), with formation of a diazonium ion, followed by coupling with a phenol under alkaline conditions. Nitrous acid is generated in situ from NaNO2/HCl. state the use of this reaction in the formation of dyestuffs.

About amines: Amines can be considered as derivatives of ammonia, NH3, with one or more of the H atoms replaced by an alkyl group. They are noted for their unpleasant, often fishy odours. Like alcohols, amines can be described as primary, secondary or tertiary depending on how many carbons are bonded to the N atom. Common naturally-occuring amines include amphetamine (used to treat daytime drowsiness and chronic fatigue syndrome), phenylephrine (decongestant in LemSip) and adrenalin. Naming amines:

The N- in the naming simply refers to the alkyl group being bonded to the nitrogen atom rather than one of the carbons in the chain. The longest alkyl group gains the 'amine' suffix, and the other alkyl groups are added as prefixes.

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F324

Amines

Amines as bases A base is defined as a proton acceptor. The nitrogen atom in an ammonia molecule can do this since its lone pair can accept a proton forming a dative bond and becoming an NH4+ ammonium ion. Amines can behave in exactly the same way, and are therefore weak bases.

Reactions of amines as bases Since amines are weak bases they will react with acids to form salts. e.g. CH2CH2NH2(aq) + HCl(aq) CH3CH2NH3+Cl-(aq) ethylamine ethylammonium chloride

Alkylammonium salts are named based on the acid from which they are formed, just like metal salts and ammonium salts. Aromatic amines react in exactly the same way: e.g.

Making aliphatic amines Starting material: Conditions: Type of reaction: Equation: e.g. halogenoalkane gently warm with excess ammonia using ethanol as solvent nucleophilic substitution (see AS mechanism for halogenoalkanes) CH3CH2CH2Cl + NH3 CH3CH2CH2NH2 + HCl 1-chloropropane propylamine The HCl formed reacts with the excess ammonia, neutralising it: HCl + NH3 NH4+ClNotes: Ammonia has a lone pair of electrons on the nitrogen which allows it to act as a nucleophile, attacking the + carbon in the C-X bond.

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F324

Amines The product amine ALSO has a lone pair on the nitrogen, so it is equally able to act as a nucleophile, attacking another halogenoalkane molecule and becoming a secondary amine. CH3CH2CH2NH2 + CH3CH2CH2Cl (CH3CH2CH2)2NH + HCl An excess of ammonia is used to minimise this further substitution (the more ammonia there is, the greater the probability of reaction of the nearest nucleophile being NH3 not the amine).

Making aromatic amines Starting material: Conditions: Type of reaction: Nitroarenes (nitro group on a benzene ring) Heat under reflux with mixture of tin and conc. hydrochloric acid, then neutralise the acid when reaction is complete Reduction. The mixture of tin and HCl acts as a reducing agent which we can show as[H] for simplicity.

Notes:

Remember, if there are other groups present, that you are only reducing the nitro- group. Aldehydes, ketones etc. unaffected.

The role of amines in dye-making The history of synthetic dyes is linked to amines. The first synthetic purple dye, mauveine, was made by Sir W.H. Perkin in 1856. This was the first example of an "aniline dye" (aniline is the trivial name for phenylamine). Another family of dyes are the "azo dyes" and these are also made from aromatic amines. Synthesis of azo-dyes Stage 1: diazotisastion When a mixture of phenylamine and nitrous acid (HNO2) is reacted below 10C, a diazonium salt is formed. The diazonium salt is unstable and decomposes if allowed to warm above 10CC. Nitrous acid is generated in-situ by reacting sodium nitrite (NaNO2) with hydrochloric acid:

NaNO2 + HCl HNO2 + NaCl


The cold nitrous acid then reacts with an aromatic amine such as phenylamime to form a salt containing the diazonium ion:

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F324

Amines

Stage 2: coupling reaction A coupling reaction occurs when the diazonium salt, e.g. benzene diazonium chloride is reacted with a phenol, or another aromatic compound such as an amine, under alkaline conditions. The temperature must remain below 10C or the diazonium salt decomposes.

The two benzene rings become linked through an azo functional group, -N=NThe azo link is generally formed opposite the OH or NH2 group, although you may see examples where it has been formed elsewhere on the ring. The product is a brightly coloured compound used as an azo dye. We may, however, see other aromatic amines used to form the diazonium salt, and other aromatic amines or phenols used in the coupling reaction. Many different colours can be produced by varying the structure of the azo compound

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