F324: Rings, Polymers and Analysis

Reactions to learn

Arenes c.H SO 1. Benzene + c. Nitric Acid Nitrobenzene (50-55oC)

2

eg C6H6 + HNO3
FeCl 2. Benzene + Halogen Hydrogen Halide
3

C6H5NO2 + H2O Halobenzene +

FeCl3 *

eg C6H6 + Cl2
halide

C6H5Cl + HCl *

can use Fe, or any iron halide and aluminium

3. Phenol + Base eg. C6H5OH + NaOH

Salt + Water C6H5O-Na+ + H2O sodium phenoxide Sodium Phenoxide +

4. Phenol + Sodium Hydrogen eg 2C6H5OH + 2Na

2C6H5O-Na+ + H2

5. Phenol + Bromine hydrogen bromide (RT)

OH Br

2,4,6-tribromophenol +

OH Br

+ 3Br2

3HBr

Br

Carbonyl Compounds 1. Reduction reducing agents NaBH4 or AlLiH4 use [H] in equations Aldehyde + 2[H] Primary Alcohol Eg CH3CHO + 2[H] ethanol Ketone + 2[H] CH3CH2OH ethanal Secondary Alcohol CH3CH(OH)CH3 propan-2-ol

Eg CH3COCH3 + 2[H] propanone

2.Oxidation used to distinguish between aldehydes & ketones; aldehydes oxidised to carboxylic acids whilst ketones will not react. a) Tollens Reagent (ammoniacal silver nitrate)

O C H

[Ag(NH3)]2+
O C OH

+ Ag

+ 2NH3

Benzaldehyde silver mirror

benzoic acid

b) Fehlings Solution (complex ion of Cu2+ )

H

Cu2+ complex ion

C H O

H C HO O

Cu2O

(blue); warm

methanol red/brown ppt

methanoic acid

3.Condensation (not expected to memorise but to be familiar with) used to identify the presence of a carbonyl compound using 2,4-dinitrophenylhydrazine.
H H2N N NO2 H3C H3C C H3C O2N O H3C O2N C H N NO2

H2O

2,4-dinitrophenylhydrazine

yellow/orange ppt

Carboxylic Acids 1. Carboxylic Acid + Alkali Water eg C2H5COOH + KOH H2O Salt + C2H5COOK +

propanoic acid propanoate 2. Carboxylic Acid + Metal Hydrogen eg C3H7COOH + Mg + H2 butanoic acid butanoate

potassium Salt + (C3H7COO)2Mg magnesium

3. Esterification mineral Carboxylic Acid + Alcohol acid + Water

O CH2CH3C OH

Ester
O

c. H2SO4 C2H5OH
CH2CH3C

+
OC2H5

H2O

propanoic acid

ethyl propanoate

Esters 1. Hydrolysis (acid catalyst) mineral Ester + Water acid Alcohol c.H SO
2

Carboxylic Acid +
4

+
O

H2O
OH

OH

ethyl ethanoate ethanol

ethanoic acid

2. Hydrolysis (alkali catalyst) alkali Ester + Water Alcohol

Carboxylic Acid Salt +

O C OC2H5

NaOH + H2O
C

+
ONa

C2H5OH

ethyl benzoate

sodium benzoate

Amines 1. Preparation a) Halogenoalkane + Ammonia Hydrogen halide

(ethanolic soln)

Amine +

eg CH3CH2CH2Cl + NH3 + HCl 1-chloropropane b) Nitrobenzene + Tin + c.HCl Phenylamine + Water

Sn/c.HCl
NO2

CH3CH2CH2NH2 propylamine

6[H]

NH2

2H2O

2. Salt Formation Primary Amine + Acid eg C2H5NH2(aq) + HCl(aq)

ethylamine chloride

Salt C2H5NH3+(aq) + Cl-(aq)

ethylammonium

3. Diazotisation Phenylamine reacts with nitrous acid (formed in situ , < 10oC) eg. Nitrous acid formation a) NaNO2 + HCl HNO2 + NaCl
nitrous acid

NH2

HNO2

+ HCl

N.Cl-

2H2O

phenylamine chloride

benzenediazonium

b) Coupling Reaction the diazonium salt can take part in a coupling reaction with phenols (alkali conditions) to form azo dyes. eg
+

N.Cl-

OH

N N

F324: Rings, Polymers and Analysis

OH

+ HCl

Mechanisms to learn

1. Electrophilic Substitution Benzene H2SO4 + HNO3 H2NO3+

:NO2+ +
NO2

HSO4- + H2NO3+ H2O + NO2+

H NO2

+ H+

H+

HSO4-

H2SO4

2. Nucleophilic Addition Aldehydes or Ketones

H3C C H H3C H H C OH H O H CH3 C H OH

+ OH-

H-

(AS Mechanisms you will be expected to know these as well)

3. Nucleophilic Substitution Halogenoalkanes

H H H C H Cl H H HO H H C C Cl H H H HO H C C H H H

+ Cl-

OH-

4. Electrophilic Addition Alkenes

H H C H H C H H H C H C H H H H C H H C Br H

Br-

Br -

5. Free Radical Substitution Alkanes i) Initiation

Cl2 UV Light Cl + Cl

ii) Propegation
CH4 CH3 + + Cl Cl2 CH3 CH3Cl + + HCl Cl

iii) Termination
CH3 CH3 + + Cl CH3 CH3Cl CH3CH3