piguy Edexcel A-Level Organic Chemistry April 24, 2014

1 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 2Cl.
UV

Propagation: Cl + CH4 CH3 + HCl

CH3 + Cl2 CH3 Cl + Cl etc.

Termination: Cl + Cl Cl2 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
CH3 C H3
C CH2 C+ CH3 H C CH3
H H Br H Br 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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2 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 (CH3 )3 CCl + H2 O
c.HCl

(b) or Chlorine
CH3 OH + PCl5 CH3 Cl + POCl3 + HCl

(c) Bromine
NaBr
CH3 OH + HBr CH3 Br + H2 O
c.H2SO4

(d) Iodine
NaI
CH3 OH + HI CH3 I + H2 O
c.H3PO4

(e) or Bromine / Iodine

P+Br2
3 CH3 OH + PBr3 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

C H3 CH3

OH + C Br HO C H + Br-
H
H H

Cont.
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(b) Tertiary / Secondary haloalkanes

Overall: CH3 CH2 Br + KOH CH3 CH2 OH + KBr

Nucleophilic Substitution - SN 1 Mechanism

CH3 CH3
slow
H3 C C Br H3 C C+ + Br

CH3 CH3

CH3 CH3
fast
H3 C C+ OH H3 C 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 X + H2 O + AgNO3 CH3 CH2 OH + HNO3 + AgX

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 C Cl CClF.2 + Cl.

UV

Propagation: O3 + Cl O2 + ClO
ClO + O Cl + O2 etc.

Termination: Cl + Cl Cl2 etc.

Cont.
piguy Edexcel A-Level Organic Chemistry Page 4 of 9

3 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+
(aq) + 2 e
2 Ag(s)
Colourless Silver Mirror

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

Cr2 O2 +
7 + 14 H + 6 e
2 Cr3+ + 7 H2 O
Orange Green

17. Reduction of Carbonyl or Carboxylic Acid

LiAlH4
CH3 CHO + 2 [H] CH3 CH2 OH
DryEther

18. STEP up of carbonyls

Overall: (CH3 )2 CO + HCN (CH3 )2 COHCN

Nucleophilic Addition Mechanism

CH3 CH3
H3 C
N C + C O NC C O H CN NC C OH
cold alkali
H3 C
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.
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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 OH + CH3 COOH CH3 COOCH3 + H2 O
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

H2SO4
RCOOCH3 + H2 O RCOOH + CH3 OH

(b) with a base

RCOOCH3 + NaOH RCOO Na+ + CH3 OH

26. Transesterification of esters

NaOH
(C17 H35 COOCH2 )3 + 3 CH3 OH 3 C17 H35 COOCH3 + CHOH(CH2 OH)2
Fat Methanol Biodiesel Glycerol

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

HO C R1 C OH + HO R2 OH

O C R1 C O R2 O + H2 O

Cont.
piguy Edexcel A-Level Organic Chemistry Page 6 of 9

4 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

Forming electrophile: HNO3 + 2 H2 SO4 NO+

2 + 2 HSO4 + H3 O
+

Electrophilic Subsitution Mechanism

+
NO2 NO2
NO2

+ H
HSO
4 H2 SO4

32. Sulfonation of benzene (electrophilic substitution)

Overall: C6 H6 + H2 SO4 (fuming) C6 H5 SO3 H + H2 O
Forming electrophile: H2 SO4 SO3 + H2 O

Electrophilic Substitution Mechanism

S O
SO
3
O SO2 OH

+ H

Cont.
piguy Edexcel A-Level Organic Chemistry Page 7 of 9

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

(a) Halogenation of benzene

Overall: C6 H6 + Cl2 C6 H5 Cl + HCl
AlCl3

Forming electrophile: Cl2 + AlCl3 Cl + AlCl4

(b) Alkylation of benzene

Overall: C6 H6 + CH3 Cl C6 H5 CH3 + HCl
AlCl3

Forming electrophile: CH3 Cl + AlCl3 CH3 + AlCl4

(c) Acylation of benzene

Overall: C6 H6 + CH3 COCl C6 H5 COCH3 + HCl
AlCl3

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

CH3 NH2 + CH3 Br NH(CH3 )2 + HBr

(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.
piguy Edexcel A-Level Organic Chemistry Page 8 of 9

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

LiAlH4
CH3 CN + 4 [H] CH3 CH2 NH2
DryEther

39. Reduction of Nitrobenzene: Preparation of Phenylamine

Sn+conc.HCl
C6 H5 NO2 + 6 [H] C6 H5 NH2 + 2 H2 O

40. Coupling reaction to form a dye

NH2

N2 + Cl
phenylamine

N N
HNO2 + HCl diazonium ion

OH
OH
azo group forms
+ NaOH

phenol

41. Condensation polymerisation see 27. for actual reaction

(a) Polyester - Terylene

H H

N N C C
O O
(b) Polyamide - Kevlar

O
O C C O CH2 CH2

O
(c) Polyamide - nylon

O
O C R1 C O R2 O

Cont.
piguy Edexcel A-Level Organic Chemistry Page 9 of 9

42. Addition polymerisation

H OH H OH


(a) Poly(ethanol) n . C C C
C


H H H H
n

H H H H


(b) Poly(propenamide) n . C C C
C


H C H C
n
NH2 NH2

43. Amino acids with formation of zwitterions

H H
H2 N C COOH + H+ H3 N+ C COOH

CH3 CH3

H H

H2 N C COOH + OH- H2 N C COO

CH3 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 H
N R C OH + N R C OH
H H
O O

H H
N R C N R C
O O

The End.