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Haloalkanes

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U2 mod 1chem. Halogenoalkanes

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Introduction Halogenoalkanes or alkyl halides are derivatives of alkanes. General formula = CnH2n+1X or simply R—X where R represents an alkyl group They can be classified as primary, secondary or tertiary alkyl halides. Primary alkyl halides have either 1 or no alkyl groups attached to the central carbon atom.

Secondary alkyl halides have 2 alkyl groups (circled) attached to the central carbon atom.

Tertiary alkyl halides have 3 alkyl groups (circled) attached to the central carbon atom

Aryl halides are compounds in which the halogen atom is attached directly to the aromatic ring.

U2 mod 1chem. Halogenoalkanes

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Reactions of alkyl halides The point of attack would be the electron deficient carbon atom (due to the difference in electronegativity in the C-X bond) attached to the halogen atom , thus the attacking species would be a nucleophile. All reactions need the present of heat i.e. reflux 1. Alcohol formation (R represents any hydrocarbon chain) R—X + OH-  R—OH + XPrimary and secondary alkyl halides undergo alkaline hydrolysis to the alcohol while tertiary alkyl halides can be hydrolysed by water. Aryl halides do not undergo hydrolysis except under VERY SEVERE conditions. Industrially chlorobenzene is reacted with NaOH(aq) at 360 °C at a high pressure then adding dilute HCl. 2. Amine formation R—X + NH3(alc) heat in a sealed tube R—NH2 + HX Note (alc) means an alcoholic solution as opposed to an aqueous solution. Further substitution can occur to give a secondary or even a tertiary amine. However if an excess of ammonia is used, a better yield of the primary amine can be obtained. 3. Nitrile (cyanide) formation R—X + CN- aqueous alcohol R—CN + XAqueous alcohol is used as the solvent, the alcohol dissolves the organic compound while the water dissolves the sodium cyanide (source of cyanide ions) Please note, this reaction allows for the lengthening of the carbon chain. Checkpoint A 1. State what type of alkyl halides (primary “P”, secondary “S” or tertiary “T”), the following compounds are a) 2-chloropropane ………………. b) chloroethane………………

c) 2-chloro-2-methylpropane…………………..

U2 mod 1chem. Halogenoalkanes

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2. Complete the word equations for the following reactions a) chloromethane + sodium hydroxide  …………………….................................................................................

3. Write the chemical equations for the word equations completed in question 2 a) …………………………………………………………………..

. Halogenoalkanes undergo nucleophilic substitution mechanisms Primary alkyl halides undergo SN2 reaction (S= substitution, N = nucleophilic, 2 = bimolecular i.e. 2 species involved in forming the intermediate) Tertiary alkyl halides undergo SN1 (S= substitution, N = nucleophilic, 1 = unimolecular i.e. 1 species involved in forming the intermediate) Secondary alkyl halides undergo a mixture of the two mechanisms S N1

The intermediate is the carbocation above

S N2

U2 mod 1chem. Halogenoalkanes

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In SN1, the nucleophile (hydroxide ion) approaches the partially positive carbon atom from the opposite side as where the halogen atom is attached (least steric hindrance) and as it forms a bond between itself and the carbon atom, the C-X bond breaks. The alcohol has a configuration which is the opposite of that of the alkyl halide and this is called inversion of configuration. Note: if alkyl halides are reacted with an alcoholic solution of sodium hydroxide, the corresponding alkene is formed and NOT the alcohol.

Worksheet
1. Theoretically methane can be converted into ethanoic acid via the following steps CH4 I CH3Cl II CH3CN III CH3COOH

State the reagents and conditions for steps I and II Step I …………………………………………………………………………………… Step II ...............................……………………………………………………………… 2. Show the displayed formula of the product formed if 1-chloropropane is reacted with an alcoholic solution of sodium hydroxide.

3. Show the displayed formula of the product formed if 2-chloropropane is reacted with an aqueous solution of sodium hydroxide.

4. The difference in bond strength influences the reactivity of the alkyl halide. The lower the bond strength, the more reactive the compound. Arrange the list C –Cl, C- F, C- I, C- Br in DECREASING reactivity. Give a reason for your answer. …………………………………………………................................................................. ...............................................................................................................…………………..

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