Topics 1.7 and 2.

10: Organic chemistry

Organic reactions for Edexcel AS Chemistry

Alkanes (CnH2n+2)
Combustion e.g. C3H8 + 5O2 3CO2 + 4H2O Exothermic, non-toxic products, hence use as fuel [up to C4H10 are gases at r.t.p; C5H12 C12H26 are liquids] Halogenation e.g. C6H14 + Br2
UV UV

C6H13Br + HBr

C6H13Br + Br2 C6H12Br2 + HBr , etc. Free radical mechanism, mixture of products, little control over isomers or degree of substitution

Alkenes (CnH2n)
Combustion e.g. C3H6 + 4 O2 3CO2 + 3H2O Exothermic, smoky flame (incomplete combustion), hence not commonly used as fuel Electrophilic addition CH2 + Br2 BrCH2CH2Br (dibromoalkane) a) Bromination e.g. H2C Proceeds in the dark (c.f. alkanes); A related reaction is used as test for alkenes (alkene decolourises bromine water on shaking but forms a bromoalcohol) CH2 + Br2 + H2O e.g H2C BrH2CCH2OH + HBr (bromoalcohol) b) Hydrobromination CH2 + HBr H3CCH H3CCH(Br)CH3 H3CCH2CH2Br H3CCH3 H3CCH2OH (major product) (minor product)

Markovnikovs Rule (H goes to C with most H) Catalytic addition a) Hydrogenation b) Hydration Oxidative addition CH2 + [O] + H2O H2C
+

CH2 + H2 H2C CH2(g) + H2O(g) H2C

Pt High T and P
H 3 PO 4 High P, 300C

(reduction reaction) (ethanol manufacture)

KMnO 4 , H / OH

HOH2CCH2OH
2+ 2-

(diol)

Used as test for alkenes [purple KMnO4/H is decolourised (Mn ); KMnO4/OH goes green (MnO4 ) on shaking] Addition polymerisation

H H
CH2 n H2C
catalyst pressure

C C H H n

poly(ethene)

Free radical mechanism: initiation, propagation, termination Ziegler-Natta catalyst to control stereochemistry of product for unsymmetrical alkenes

Halogenoalkanes (CnH2n+1X)
Nucleophilic substitution a) With hydroxide ion R-X + OH
-

aqueous KOH warm

ROH + X

Substitution favoured in aqueous solution (see also elimination). Test for R-X: neutralise xs OH with HNO3; add AgNO3(aq); ppt white R-Cl; cream R-Br; yellow R-I Rate: R-I > R-Br > R-Cl; 3 > 2 > 1 b) With ammonia R-X + NH3
closed vessel xs NH 3 , pressure

RNH2 + HX

(primary amine) (secondary amine)

An additional mole of ammonia is required to react with the HX formed competing reaction RX + RNH2 R2NH + HX Elimination

H X
With hydroxide ion

C C

+ OH

KOH ethanol

C C

+ H 2O + X

(alkene)

Elimination favoured in ethanolic solution Base-catalysed elimination of HX to form an alkene; mixture of alkenes from unsymmetrical haloalkanes
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Alcohols (CnH2n+1OH)
Reaction with sodium e.g. 2C3H7OH + 2Na Similar to reaction of Na with water, though less vigorous
c H 2 SO 4

2C3H7O Na + H2

(sodium propoxide)

CH2 + H2O H3CHC Dehydration e.g. C3H7OH Can also be achieved by passing alcohol vapour over heated aluminium oxide Halogenation a) Phosphorus trihalides 3C3H7OH + PCl3 3C3H7OH + P + 1 Br2 3C3H7OH + P + 1 I2 b) Phosphorus pentachloride
heat under reflux heat under reflux

(alkene)

3C3H7Cl + H3PO3 3C3H7Br + H3PO3 3C3H7I + H3PO3

C3H7OH + PCl5 C3H7Cl + POCl3 + HCl Test for compounds containing OH group; exothermic reaction - steamy fumes which turn damp litmus red c) Thionyl chloride C3H7OH + SOCl2 C3H7Cl + SO2(g) + HCl(g) Non-organic products are gaseous hence organic product is easily purified d) Hydrogen halides (CH3)3COH + HCl C3H7OH + HBr C3H7OH + HI
c HCl NaBr, c H 2 SO 4 distil off product KI, c H 3 PO 4 distil off product

C3H7Cl + H2O C3H7Br + H2O C 3 H 7 I + H2 O

(only effective for 3 alcohols)

HBr and HI produced in situ; H2SO4 not appropriate for producing HI as it oxidises HI to I2 Oxidation a) Primary alcohols RCH2OH
K 2 Cr 2 O 7 , H
+

O R C H O R C OH O R C R
(ketone) (carboxylic acid) (aldehyde)

distil off product

RCH2OH

K 2 Cr 2 O 7 , H

boil under reflux

Orange dichromate(VI) reduced to green chromium(III) b) Secondary alcohols No further oxidation possible c) Tertiary alcohols No oxidation possible, hence dichromate(VI) remains orange R2CHOH
K 2 Cr 2 O 7 , H
+

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