ALKYL HALIDES

-Compounds where the halogen is bonded to Alkyl group

e.g
R-X where R = Alkyl group, X = F, Cl, Br or I
Alkyl halides can be divided into three groups
(i) Primary alkyl halide: the halogen is bonded to a primary carbon atom
(ii)Secondary alkyl halide: the halogen is bonded to a secondary carbon atom
(iii)Tertiary alkyl halide: the halogen is bonded to a tertiary carbon atom
CH2CH3
CH3CH Br
CH3CH2 Br CH3C Cl
CH2CH3 tertiary alkyl halide
primary alkyl halide CH(CH3)2
secondary alkyl halide
 Nomenclature

 Naming of alkyl halides follow the rules of alkane and alkene

 Halogens are treated as substituent groups
 The halogen substituents are flouro, chloro, bromo and Iodo CH2CH3

CH3CH
CH3CH2 Cl CH3CH CHCH2CH2Cl
Br
chloroethane Cl CHCH2CH2CH3
5-chloro-2-pentene
bromocyclohexane 4-chloro-methylheptane

CH3CH CHCH3

Br F 2-bromo-3-flourobutane
 Physical properties of alkyl halides
Most alkyl halides are polar molecules due to electronegativity of halogens
For example
H3C Cl
 
 The boiling points increases with increasing in molecular weights.
Therefore, the boiling points increases in the order F<Cl<Br<I. The alkyl
group should remain the same i.e CH3F, CH3Cl, CH3Br and CH3I
 BP also increases for “straight” chain isomers. Greater branching = lower
BP.
 All organic halides are insoluble in water and soluble in common organic
solvents
 Preparation of alkyl halides
(i). Halogenation of alkanes and alkenes
Alkanes are halogenated in the presence of UV light or heat to form alky halide

CH4 + Cl2 CH3Cl + HCl

Alkenes react with halogens at room temperature to form dihalides

+ Br2 Br
Br
(ii) Hydrohalogenation of alkenes and alkynes
+ HBr markonikov's product
Br

peroxide
+ HBr Br anti-markonikov's product
 Br Br
CH3C CH + 2HBr markonikov's product

Br
peroxide
CH3C CH + 2HBr Br anti-markonikov's product

(iii) Reaction of alcohol with HX, SOCl2, PCl3, PCl5

H2SO4
CH3(CH2)2CH2 OH + HBr CH3(CH2)2CH2 Br + H2O
heat

CH3 CH3
H2SO4 + H2O
H3C C OH + HBr H3C C Br
heat
CH3 CH3

CH3(CH2)6CH2 OH + SOCl2 CH3(CH2)6CH2 Cl + SO2 + H2O

 Reactions of alkyl halides

Dehydohalogenation
 The removal of halogen together with hydrogen from the adjacent carbon atom
 The reaction takes place in the presence of a base like sodium ethoxide
CH3
CH3
C2H5ONa
H 3C C Br CH2 + NaBr
H 3C C
C2H5OH
CH3
 The reaction can also be regioselective (saytzev rule) is followed to determine the
major product
C2H5ONa
CH3CH2CHCH3 CH3CH2CH CH2 + CH3CH CHCH3
C2H5OH
Cl
 Uses of alkyl halide
 Used as organic solvents in industrial and house hold cleaners e.g. dichloromethane and chloroform
(CHCl3)
 Used as refrigirants like Freons and CFC’s
 Propellants in aerosol products
 Used as insecticides e.g. DDT
 Halogen containing alkenes serves as monomers for synthesis of polymers e.g PVC, Teflon
 Use as anesthetic e.g. chloroform Cl
n H2C CHCl
CH2CH
n
vinyl chloride polyvinyl chloride
F F
n F2C CF2
C C
tetraflouroethene F n
F
teflon
 Aldehydes and ketones
 Compounds having carbonyl group as the functional group
C O C O
 Aldehydes have at least one hydrogen attached to carbonyl carbon.
a carbonyl bond polar  Ketones have two alkyl groups attached to carbonyl carbon
Nomenclature of aldehydes
 Names end with a suffix ‘al’ and a prefix used to indicate number of
O O
carbon atoms
C C  Check the longest chain with aldehyde group e.g.
R H R R

aldehydes ketones
O O O
C C C
H3C H H3CH2C H H H
ethanal propanal methanal
 In numbering the carbon chain an aldehyde carbonyl group receives number 1
O Br O
CH3CH2CHCH CH3CHCHCH

CH3 CH3
2-methylbutanal 3-bromo-2-methylbutanal

Nomenclature for ketones

 Names end with ‘one’
 Number the longest chain in such away that the carbonyl group is given the lowest number

O O
CH3CCH3 CH3CH2CH2CCH3
O
propanone 2-pentanone
2,4-dimethyl-3-pentanone
Exercise on nomenclature of aldehydes and ketones
1. Give the structures of the following compounds:
a) 4- methyl-2-pentanone
b) 3,5 – dimethyl-2-heptanone
c) 3 – hydroxyl- 2 – butanone
d) 3,4-dichloro-2-methylbutanal

2. Write IUPAC names for each of the following compounds

(i) CH3CH2CH2CH2CHO (ii) CH3CH2COCH2CH2CH3

O
Br
(iii) CH3CH2CHCH2CHO (iv)
 Physical properties of aldehydes and ketones

 Are polar molecules because the C=O bond has a dipole moment
 Polarity makes aldehydes and ketones have a higher boiling points than
alkenes/alkanes of similar molecular weight
 Aldehydes and ketones do not form hydrogen bonds therefore, they have a
lower boiling points than alcohols of similar molecular weight
 Form hydrogen bonds with water molecule therefore they are soluble in water
 Lower aldehydes like methanal and ethanal have sharp smell
 Synthesis of aldehydes and ketones
1. Oxidation of alcohols
[O]
 Primary alcohols are oxidized to aldehydes RCH2OH RCHO
[O]
 Secondary alcohols oxidized to ketones R2CHOH RCOR'

Examples
OH O
Na2Cr2O7
CH3CHCH2CH2CH2CH3 CH3CCH2CH2CH2CH3
H2SO4

CrO3 CH3CH2CHCHO
CH3CH2CHCH2OH
CH3 pyridine CH3
 Primary alcohols react with K2Cr2O7 reagent to form aldehydes which can further be
oxidized to carboxylic acid
 Chromium (vi) in the presence of pyridine is used for laboratory preparation of
aldehydes
 Tertiary alcohols are not readily oxidized under usual conditions

(ii) Reduction of carboxylic acid

Carboxylic acid are reduced to alcohol using LiAlH4

O LiAlH4
LiAlH4 OH
RCOOH RCH2OH OH OH-
OH-
 Reactions of aldehydes and ketones

Ketones are less reactive than aldehydes because of:

 Steric hindrance: the alkyl groups attached to carbonyl carbon are bulky
making the reactive site in accessible thus reactive
 Indutive effect: the alkyl groups donate electrons inductively to the carbonyl
carbon making it less positive hence less reactive

O O
R C R R C H
 Oxidation reactions
 Aldehydes are easily oxidised to acids as they have a hydrogen atom attached to the carbonyl carbon.
 Oxidation involves abstraction of the hydrogen atom.
 Most reagents that oxidize an alcohol also oxidise an aldehyde (KMnO 4, Cr(VI) reagents and nitric acid).

O
CH3(CH2)4C H
KMnO4 H3O+ CH3(CH2)4COOH
H2O , NaOH

 Ketones are not easily oxidized. Oxidation involves breaking the carbon-carbon bonds.
 They are resistant to mild oxidation
 Mild oxidizing agents can be used to differentiate between aldehydes and ketones
 Mild oxidising agents e.g. Ag+ or Cu2+
(i) Fehlings and Benedicts solutions
 both contain the cupric ion, Cu2+.
 Adding certain compounds with the aldehyde groups to either of these clear solutions causes
a precipitate of cuprous oxide, Cu2O.
 Benedicts solution contains sodium citrate to keep the cupric ion in solution, while Fehlings
solution contains sodium tartrate and does not store as well.
 Simple sugars contain an aldehyde group and will reduce cupric ions (Cu 2+) to cuprous (Cu+).
 Cuprous ions then form cuprous oxide, Cu2O, an insoluble red precipitate.

CH3CH2CH2CHO + Cu2+ CH3CH2CH2COOH + Cu2O

 (ii) Tollen’s Reagent - Ammonical silver nitrate solution (colourless solution).

 Oxidation by silver ions require alkaline conditions to prevent the precipitation of

insoluble silver oxide, so a complexing agent, NH3 , is added.
 Aldehydes are oxidized to acids and silver ions (Ag+) are reduced to silver metal (Ag)
 Positive test formation of a silver mirror on the wall of a test tube is observed.

CH3CH2CH2CHO + Ag(NH3)2+OH- CH3CH2CH2COOH + Ag(s)

silver mirror
 Haloform reaction (Iodoform test)
 This is a characteristic reaction of compounds with a terminal methyl group bonded to a
carbonyl group, like methyl ketones.
 The methyl is iodinated stepwise until the yellow solid of iodoform (CHI3) is formed.
 The reaction is used for identification of such compound.
O OH-, H2O O
OH-
C CH3 + 3I2 C CI3

Cyclohexyl methyl Cyclohexyl triiodomethyl

ketone ketone
(unstable intermediate)
O
C O- + CHI3

Cyclohexyl- Iodoform
carboxylate ion (yellow solid)

Note: Chlorine and bromine also react the same way as iodine but the resulting haloform products are non-
distinctive clear liquids. For that reason, they are not useful for test purposes.
Methanal
 Formalin acts as a disinfectant (a germicide).
 Is used in embalming fluid.
 Is used as a preservative of various tissues i.e. hardens tissues.
 Formaldehydes gas and the polymer paraformaldehyde are used extensively as insecticides,
fumigating agents and antiseptics.
 Large quantities are used in the manufacture of synthetic (lightweight) resins (e.g. bakelite
foam)
 syntheses of other organic compounds.
Ethanal
 is used in the production of ethanoic acid (acetic acid, vinegar), ethyl acetate, synthetic
rubber, etc.
 Paraldehyde, (mp 125 0C; polymer of ethanol) an acetal (cyclic ether), is more stable than
ethanol and serves as a source of the latter compound when heated. When three molecules
of ethanal is heated with a trace of acid paraldehyde is formed.
Propanone
• Used as an organic solvent
• Used in paints and vanishes
• Used in nail polish removers