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April 24, 2014

Edexcel A-Level Organic Chemistry

AS Unit 1 Reactions
Technically chemistry is the study of matter, but I prefer to see it as the study of
change. It is growth, then decay, then transformation.
- Walter White
1. Combustion of alkanes (incomplete also forms C & CO)
CH4 + 2 O2
2 H2 O + CO2
2. Subsitution of chlorine in alkanes
Overall: CH4 + Cl2
CH3 Cl + HCl
UV

Free Radical Mechanism

Initiation: Cl

Cl

Propagation: Cl + CH4
CH3 + Cl2
Termination: Cl + Cl

2Cl.

UV

CH3 + HCl
CH3 Cl + Cl
Cl2

etc.

etc.

3. Addition of hydrogen to alkenes

H2 + C 2 H4
C 2 H6
Ni

4. Addition of halogens to alkenes (electrophilic addition, see 5.)

X2 + C2H4
CH2XCH2X
5. Addition of hydrogen halides to alkenes
overall HX + C2H4
CH3CH2X
Electrophilic Addition Mechanism for Propene
CH3
C
H

CH3

C H3
C+

CH2
H

Br

CH3
Br

CH3

Br

6. Addition of bromine water t o alkenes: Test f or C=C

C2H4 + Br2 + H2O
CH2OHCH2Br + HBr
7. Oxidation of alkenes to diols
KMnO4
C2 H4 + [O]
CH2 OHCH2 OH
Trivial additional polymerisation is also in unit 1.
See specific examples in 42.

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Edexcel A-Level Organic Chemistry

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AS Unit 2 Reactions
It is the destiny of glucose to be oxidized; it is the destiny of alcohol to be drunk.
- Primo Levi
8. Alcohol with sodium
2 CH3 OH + 2 Na
2 CH3 O Na+ + H2
9. Substitution of halides in alcohols
(a) Chlorine
(CH3 )3 COH + HCl

c.HCl

(b) or Chlorine
CH3 OH + PCl5

(CH3 )3 CCl + H2 O

CH3 Cl + POCl3 + HCl

(c) Bromine
CH3 OH + HBr

NaBr

CH3 Br + H2 O

c.H2SO4

(d) Iodine
CH3 OH + HI

NaI
c.H3PO4

CH3 I + H2 O

(e) or Bromine / Iodine

3 CH3 OH + PBr3

P+Br2

3 CH3 Br + H3 PO3

10. Oxidation of alcohols

(a) Primary alcohols partially
CH3 CH2 OH + [O]
CH3 CHO
(b) Primary alcohols fully
CH3 CH2 OH + [O]
CH3 COOH
(c) Secondary alcohols
(CH3 )2 CHOH + [O]

(CH3 )2 CHO

11. Haloalkanes with aqueous alkali (nucleophilic substitution)

(a) Primary / Secondary haloalkanes
Overall: CH3 CH2 Br + KOH
CH3 CH2 OH + KBr
Nucleophilic Substitution - SN 2 Mechanism
CH3

C H3
OH +

C
H

Br

HO

H + Br-

Cont.

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Edexcel A-Level Organic Chemistry

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(b) Tertiary / Secondary haloalkanes

Overall: CH3 CH2 Br + KOH
CH3 CH2 OH + KBr
Nucleophilic Substitution - SN 1 Mechanism
CH3
H3 C

CH3
Br

slow

C+

H3 C

CH3

CH3
CH3

CH3
H3 C

fast

OH

C+

+ Br

H3 C

OH

CH3

CH3

12. Haloalkanes with alcholic alkalis (elimination)

(CH3 )3 Br + KOH
CH2 CHCH3 + KBr + H2 O
13. Haloalknes with water with silver nitrate
CH3 CH2 OH + HNO3 + AgX
CH3 CH2 X + H2 O + AgNO3
14. Haloalkanes with alcoholic ammonia

CH3 CH2 Br + NH3

CH3 CH2 NH+
3 Br

CH3 CH2 NH+

3 Br + NH3

CH3 CH2 NH2 + NH+

3 Br

15. Depletion of ozone by CFCs in atmosphere

Overall: O3 + O
2 O2
UV

Free Radical Mechanism

Cl
Initiation: F

Cl

CClF.2 + Cl.

UV

F
Propagation: O3 + Cl
ClO + O
Termination: Cl + Cl

O2 + ClO
Cl + O2
Cl2

etc.
etc.

Cont.

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Edexcel A-Level Organic Chemistry

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A2 Unit 4 Reactions
When thinking through a chemical problem, I would often ask myself, What would
I do if I were an electron?
- Jacques Monod

16. Oxidation of Carbonyls

General: CH3 CH2 CHO + H2 O

CH3 CH2 COOH + 2 H+ + 2 e

(a) Fehlings / Benedicts solution: Test for aldeehyde

Cu2+ + e
Cu+
Blue
Red-Brown
(b) Tollens reagent: Test for aldeehyde

2 Ag+
2 Ag(s)
(aq) + 2 e
Colourless

Silver Mirror

(c) Acidified Potassium Dichromate (VI): Tests for aldeehyde or alcohol

+

Cr2 O2
7 + 14 H + 6 e
Orange

2 Cr3+ + 7 H2 O
Green

17. Reduction of Carbonyl or Carboxylic Acid

CH3 CHO + 2 [H]

LiAlH4

CH3 CH2 OH

DryEther

18. STEP up of carbonyls

Overall: (CH3 )2 CO + HCN

(CH3 )2 COHCN

Nucleophilic Addition Mechanism

CH3

H3 C
N

C +

H3 C

cold alkali

NC

CH3
O

CN

NC

CH3

CH3

19. Carbonyl with Iodine: Test for methylcarbonyl group

RCOCH3 + 3 I2 + 4 NaOH

RCOO Na+ + 3 NaI + 3 H2 O + CHI3(s)

Yellow ppt. & antiseptic smell

20. Addition of 2,4 DNP to Carbonyl: Test for Carbonyl group

Orange ppt. forms
21. Carboxylic acids react with metals, hydroxides and carbonates like any acid, forming ionic
salts (e.g. RCOO Na+ ) and H2 , H2 O or CO2 respectively.
Cont.

OH

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Edexcel A-Level Organic Chemistry

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22. Carboxylic acids with phosphorus (V) chloride

2 CH3 COOH + PCl5

2 CH3 COCl + POCl + 2 HCl

Misty fumes

23. Carboxylic acids with alcohols

CH3 COOCH3 + H2 O
CH3 OH + CH3 COOH
H2SO4

24. Substitutions of acyl chlorides

(a) with water
RCOCl + H2 O

RCOOH + HCl

(b) with conc. ammonia

RCOCl + NH3
RCONH2 + HCl
(c) with amines
RCOCl + CH3 NH2

RCONHCH3 + HCl

(d) with alcohol

RCOCl + CH3 OH

RCOOCH3 + HCl

25. Hydrolysis of esters

(a) with an acid
RCOOCH3 + H2 O

H2SO4

(b) with a base

RCOOCH3 + NaOH

RCOO Na+ + CH3 OH

26. Transesterification of esters

(C17 H35 COOCH2 )3 + 3 CH3 OH
Fat

RCOOH + CH3 OH

NaOH

3 C17 H35 COOCH3 + CHOH(CH2 OH)2

Methanol

Biodiesel

Glycerol

27. Condensation of di-ol and di-carboxylic acid

O
HO

R1

OH + HO

R2

OH

O
O
O

R1

R2

+ H2 O

Cont.

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Edexcel A-Level Organic Chemistry

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A2 Unit 5 Reactions
Let us learn to dream, gentlemen, and then perhaps we shall learn the truth.
- Friedrich August Kekule

28. Combustion of benzene to smoky flame

C6 H6 + 72 O2
3 H2 O + 6 CO2
29. Addition of halogens to benzene
C6 H6 + 3 Br2
C6 Br6 H6
UV

30. Addition of hydrogen to benzene

C6 H6 + 3 H2
C6 H12
Ni

31. Nitration of benzene (electrophilic substitution)

Overall: C6H6 + HNO3
C6H5NO2 + H2O
H2SO4

+
NO+
2 + 2 HSO4 + H3 O

Forming electrophile: HNO3 + 2 H2 SO4

Electrophilic Subsitution Mechanism
+
NO2

NO2
+

NO2

H
HSO
4

H2 SO4

32. Sulfonation of benzene (electrophilic substitution)

Overall: C6 H6 + H2 SO4 (fuming)
Forming electrophile: H2 SO4

C6 H5 SO3 H + H2 O
SO3 + H2 O

Electrophilic Substitution Mechanism

O
S

O
SO
3

O
+

SO2 OH

Cont.

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Edexcel A-Level Organic Chemistry

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33. Friedel-Crafts r eactions ( electrophilic substitution, s ee 31.)

(a) Halogenation of benzene
Overall: C6 H6 + Cl2

AlCl3

C6 H5 Cl + HCl
Cl + AlCl4

Forming electrophile: Cl2 + AlCl3

(b) Alkylation of benzene
Overall: C6 H6 + CH3 Cl

AlCl3

C6 H5 CH3 + HCl
CH3 + AlCl4

Forming electrophile: CH3 Cl + AlCl3

(c) Acylation of benzene
Overall: C6 H6 + CH3 COCl

AlCl3

C6 H5 COCH3 + HCl

Forming electrophile: CH3 COCl + AlCl3

COCH3 + AlCl4

34. Phenol with bromine water and dil. nitric acid (activation of ring)
OH
OH
Br

Br

+ 3Br2

+ 3HBr

Br

35. Alkalinity of Amines

CH3 NH2 + H2 O
CH3 NH+
3 + OH
36. Amines with haloalkanes
(a) Ammonia to Primary amine: Lab Preparation of Amine
NH3 + CH3 Br
CH3 NH2 + HBr
(b) Primary amine to Secondary
NH(CH3 )2 + HBr
CH3 NH2 + CH3 Br
(c) Secondary amine to Tertiary
CH3 NHCH3 + CH3 Br
N(CH3 )3 + HBr
(d) Tertiary amine to Quaternary Salt
N(CH3 )3 + CH3 Br
[N(CH3 )4 ]+ Br

Cont.

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Edexcel A-Level Organic Chemistry

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37. Amines with acyl chlorides: Preparation of Amides, also see 24(c)
CH3 NH2 + CH3 COCl
CH3 CONHCH3 + HCl
38. Reduction of Nitrile: Preparation of Amine
CH3 CN + 4 [H]

LiAlH4
DryEther

CH3 CH2 NH2

39. Reduction of Nitrobenzene: Preparation of Phenylamine

C6 H5 NO2 + 6 [H]

Sn+conc.HCl

C6 H5 NH2 + 2 H2 O

40. Coupling reaction to form a dye

NH2

N2 + Cl

phenylamine

diazonium ion

HNO2 + HCl

OH
OH

azo group forms

+ NaOH

phenol
41. Condensation polymerisation see 27. for actual reaction
(a) Polyester - Terylene
H

(b) Polyamide - Kevlar

O
O

CH2

CH2

O
(c) Polyamide - nylon
O
O

R1

R2

O
Cont.

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Edexcel A-Level Organic Chemistry

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42. Addition polymerisation

OH

H
(a) Poly(ethanol) n . C

OH

H
n

(b) Poly(propenamide) n . C

C
n

NH2

NH2

43. Amino acids with formation of zwitterions

H
H2 N

+ H+

COOH

H3 N+

CH3

CH3

H
H2 N

COOH

+ OH-

COOH

H2 N

CH3

COO

CH3

zwitterion forms when pH is just right and both reactions occur

44. Adding ninydrin to an amino acid forms a colour which distinguishes it in chromatography
45. Condensation polymerisation of amino acids (forming peptide bonds)

H
N

OH +

O
H
N

OH

O
H

C
O

C
O

The End.