Topic 4.

5: Organic chemistry II

Additional organic reactions for Edexcel A2 Chemistry (Unit 4)

Grignard reagents (R-Mg-X)
Preparation e.g. C3H7Br + Mg
dry ether, I2 catalyst reflux

C3H7MgBr

2+ With water e.g. C3H7MgBr + H2O C3H8 + Mg + Br + OH Simple hydrolysis to form an alkane not a synthetically useful reaction

With CO2

e.g.

C3H7MgBr + CO2
+

dry ether
aq

O)OMgBr C3H7C(
2+ -

O)OMgBr + H C3H7C( C3H7COOH + Mg + Br Nucleophilic attack by Grignard on C in CO2; followed by acidic hydrolysis to give carboxylic acid (1 extra C) With aldehydes e.g. C3H7MgBr + CH3CHO
+
dry ether
aq

C3H7CH(CH3)OMgBr
2+ -

C3H7CH(CH3)OMgBr + H C3H7CH(CH3)OH + Mg + Br Nucleophilic attack by Grignard on C in carbonyl; followed by acidic hydrolysis to give secondary alcohol With ketones e.g. C3H7MgBr + CH3COCH3
+
dry ether
aq

C3H7C(CH3)2OMgBr
2+ -

C3H7CH(CH3)2OMgBr + H C3H7C(CH3)2OH + Mg + Br Nucleophilic attack by Grignard on C in carbonyl; followed by acidic hydrolysis to give tertiary alcohol

Carboxylic acids (RCOOH)

reflux Preparation e.g. C3H7CH2OH + 2[O] C3H7COOH + H2O Oxidation of primary alcohol (or aldehyde) by heating under reflux to ensure complete oxidation K2Cr2O7/H2SO4(aq)

Typical reactions of acids a) With alkalis e.g. C3H7COOH + NaOH b) With metals e.g. 2 C3H7COOH + Mg c) With Na2CO3 e.g. 2 C3H7COOH + Na2CO3 d) With NaHCO3 e.g. C3H7COOH + NaHCO3

C3H7COONa + H2O (C3H7COO)2Mg + H2 2 C3H7COONa + CO2 + H2O C3H7COONa + CO2 + H2O

O
Esterification e.g. C3H7OH + H3C

O
c H 2 SO 4 , warm H or OH , reflux
+ -

H3C

+ H2O

(ester)

O C3H7 Forward reaction catalysed by conc. H2SO4 which removes water; reverse reaction catalysed by dilute acid/alkali. Esters are generally insoluble in water and typically smell sweet and sickly (e.g. glue, pear drops)
LiAlH4 dry ether Reduction e.g. C3H7COOH + 4[H] + Initial nucleophilic attack by H in AlH4 on C in carbonyl

OH

C3H7CH2OH + H2O

Halogenation e.g. C3H7COOH + PCl5 room temp C3H7COCl + POCl3 + HCl Test for compounds containing OH group; exothermic reaction - steamy fumes which turn damp litmus red; separate products by fractional distillation

Acid chlorides (RCOCl)

Preparation see halogenation of carboxylic acids With water e.g. C3H7COCl + H2O C3H7COOH + HCl Simple hydrolysis to form carboxylic acid not a synthetically useful reaction (nucleophilic attack by H2O:) With alcohols e.g. C3H7COCl + CH3OH C3H7COOCH3 + HCl Irreversible formation of ester; condensation reaction; nucleophilic addition followed by elimination With ammonia e.g. C3H7COCl + H3N C3H7CONH2 + HCl Formation of amide similar mechanism to hydrolysis (i.e. nucleophilic addition - elimination) C3H7CONHCH3 + HCl With amines e.g. C3H7COCl + H2NCH3 Formation of N-substituted amide c.f. reaction with ammonia

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 Polymer formation a) diacid chloride with diol condensation polymerisation to form polyester

Cl n O C C

Cl HO O OH C O C O

O + n n HCl

b) diacid chloride with diamine condensation polymerisation to form polyamide

Cl n O C C

Cl H2N O NH2 C O C O

NH

NH + n n HCl

Esters (RCOOR)
Preparation see carboxylic acids (esterification) and acid chlorides with alcohols
HCl(aq)

With dilute acid, e.g.

C3H7COOCH3 + H2O

heat

C3H7COOH + CH3OH
+

Hydrolysis to form carboxylic acid and alcohol (nucleophilic attack by H2O:) catalysed by H
NaOH(aq)

With dilute alkali, e.g. C3H7COOCH3 + NaOH

heat

C3H7COONa + CH3OH
-

Hydrolysis to form carboxylate ion and alcohol (nucleophilic attack by OH )

Aldehydes (RCHO)
distil Preparation e.g. C3H7CH2OH + [O] C3H7CHO + H2O Oxidation of primary alcohol with distillation of (lower b.p.) product
K2Cr2O7/H2SO4(aq)

Reduction a) Tollens reagent ammoniacal silver nitrate Addition of Tollens reagent with gentle heating gives a silver mirror on the inside of the test tube Used as a test to distinguish aldehydes from ketones 2+ b) Fehlings (or Benedicts) solution alkaline solution containing complexed Cu ions Addition of Fehlings solution with gentle heating gives a red precipitate of copper(I) oxide Used as a test to distinguish aldehydes from ketones
LiAlH4 in dry ether

c) Reduction d) Hydrogenation

CH3CHO + 2[H] CH3CHO + H2

or NaBH4(aq) Ni or Pt catalyst

CH3CH2OH CH3CH2OH

(primary alcohol) (primary alcohol)

distil With 2,4-DNP e.g. C3H7CH2OH + [O] C3H7CHO + H2O Oxidation of primary alcohol with distillation of (lower b.p.) product

K2Cr2O7/H2SO4(aq)

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 Electrophilic addition CH2 + Br2 a) Bromination e.g. H2C BrCH2CH2Br (dibromoalkane) Proceeds in the dark (c.f. alkanes); used as test for alkenes (alkene decolourises bromine water on shaking) CH2 + HBr b) Hydrobromination H3CCH H3CCH(Br)CH3 (major product) Markovnikovs Rule (H goes to C with most H) Catalytic addition a) Hydrogenation b) Hydration Oxidative addition CH2 + [O] + H2O H2C
+

H3CCH2CH2Br H3CCH3 H3CCH2OH

(minor product)

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

Haloalkanes (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) (nitrile)

An additional mole of ammonia is required to react with the HX formed competing reaction RX + RNH2 R2NH + HX c) With cyanide ion R-X + CN
-

KCN in ethanol heat under reflux

RCN + X

Useful reaction for increasing the carbon chain length 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

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 ethanoate)

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

(alkene)

3C3H7Cl + H3PO3 3C3H7Br + H3PO3

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3C3H7OH + P + 1 I2 b) Phosphorus pentachloride

heat under reflux

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

O
Esterification e.g. C3H7OH + H3C

O
c H 2 SO 4 , warm H or OH , reflux
+ -

H3C

+ H2O

(ester)

O C3H7 Forward reaction catalysed by conc. H2SO4 which removes water; reverse reaction catalysed by dilute acid/alkali. Esters are generally insoluble in water and typically smell sweet and sickly (e.g. glue, pear drops)
Oxidation a) Primary alcohols RCH2OH
K 2 Cr 2 O 7 , H
+

OH

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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