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Organic Reactions

1) Grignard reagents (R-Mg-X) react with carbon dioxide to form carboxylic acids, with aldehydes to form secondary alcohols, and with ketones to form tertiary alcohols. 2) Carboxylic acids undergo esterification reactions with alcohols catalyzed by sulfuric acid. They also react with alkoxides, metals, carbonates, and bicarbonates. 3) Aldehydes can be oxidized to carboxylic acids, reduced to primary alcohols, and undergo addition reactions like bromination. They are also tested for using Tollens' reagent and Fehling's solution.

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Organic Reactions

1) Grignard reagents (R-Mg-X) react with carbon dioxide to form carboxylic acids, with aldehydes to form secondary alcohols, and with ketones to form tertiary alcohols. 2) Carboxylic acids undergo esterification reactions with alcohols catalyzed by sulfuric acid. They also react with alkoxides, metals, carbonates, and bicarbonates. 3) Aldehydes can be oxidized to carboxylic acids, reduced to primary alcohols, and undergo addition reactions like bromination. They are also tested for using Tollens' reagent and Fehling's solution.

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Robbing_Hood
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© Attribution Non-Commercial (BY-NC)
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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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