METHODS OF PREPARATION

From alkenes

H2 in the presence of Pd/Ni/Pt

Reduction Ni version is called Sabatier Senderens reaction

Hydroboration Reacting alkene with BH3 followed by CH3COOH

converts alkene to alkane

Wurtz reaction

Alkyl halide and sodium in dry ether

Drawbacks
CH4 can not be prepared
1,3 dihalides give cyclised products
unsymmetrical alkanes can not be prepared

ALKANES
From alkyl halides

From alcohols

Alkyl halids are reduced to alkanes using

HI/Red P(also reduces alcohols,
aldehydes,ketones and carboxylic acids)
LAH
Na/Ethanol
Zn-Cu couple ethanol.
Ni/Pd/Pt

Alcohols are reduced to alkanes using HI/RedP

From carboxylic acids

Decarboxylation

Sodium carboxylates are heated with Sodalime to get alkanes

RCOOH gives RH
Kolbe electrolysis Sodium salt of carboxylic acid is electrolysed.

Alkanes form at anode,NaOH forms at cathode.

RCOOH gives R-R

From ketones

Carbonyl compounds react with Zn-Hg/HCl

to give alkanes-Clemmensen reduction
Wolf Kishner reduction Carbonyl compounds react withNH2NH2/KOH to give alkanes-Wolf Kishner
reduction
Clemmensen reduction

From carbides

Action of water on Al4C3and Be2C give methane

METHODS OF PREPARATION
From Elimination reactions
elimination of H2O-reagents-H2SO4,H3PO4,KHSO4,Alumina. Zaitzef
rule followed
elimination of HX-reagents-Bulky and strong bases like NaOEt.
Zaitzef rule followed
elimination of X2-reagents-Zn
Hoffmann elimination-Quaternary ammonium salts reacted with Ag2O+H2O mixture.Least
substituted alkene results.
Cope elimination-Quaternary amine oxides are heate.Least substituted alkene results.

ALKENES

Pyrolysis reaction
Heating esters at high temperatur yield alkenes
Heating halides at high temperatur yield alkenes
Wittig reaction-Carbonyl compounds are reacted with alkyl halides in the presence of Ph3P
and NaNH2
From Alkynes
Lindlar catalyst, H2 in the presence of Pd on BaSO4 converts alkyne to cis alkene
Na in liq ammonia converts alkyne to trans alkene

METHODS OF PREPARATION OF ALKYNES

Dehydrohalogenation of dihylides- Both vic and geminal dihalides can be dehalogenated
by heating with NaNH2

Dehalogenation of tetrahalides-Tetrahalides can be dehalogenated using Zn to get

alkynes

ALKYNES

From calcium carbide-Action water on calcium carbide gives acetylene.

From iodoform- Heating iodoform with Ag gives alkynes.
From Kolbes electrolysis-Sodium fumarate when electrolysed gives acetylene

REACTIONS OF ALKENES
Bromination-Alkenes give vic dihalides when reacted with Br2 in CCl4.Addition is anti.cis
alkene give threose compound as racemic mixture.trans alkene gives mesocompound
Reduction-Alkenes give alkanes when reacted with H2 in presence of Pd,Pt and Ni
Addition of haloacids-HX adds to alkene according to markonikof rule.X adds to highly
substituted carbon of alkene and H adds to least substituted carbon of alkene
Addition of HBr to alkene in the presence of peroxide results in antimarkonikof addition.

Acid catalysed hydration- converts alkene into alcohol.Markonikof rule is followed.There will
be rearrangement of carbocation.
Hydroboration oxidation- Reacting alkene with BH3 followed by H2O2 and OH-gives antiMarkonikof alcohol
Oxymercuration-Demercuration-reacting alkene with Hg(OCOCH3) and H2O followed by
NaBH4 gives markonikof alcohol.No rearrangement takes place

ALKENES

Ozonolysis - Oxidative ozonolysis in the presence of O3 followed by H2O2 converts

alkene into carboxylic acid or ketone depending on substitution.Reductive ozonolysis
converts alkene into carbonyl compounds.
Addition of KMnO4-Addition of KMnO4 under cold condition to alkene results in formation
of vic diols.cis alkene gives mesocompound and the trans gives threose as racemic mixture.
Addition of KMnO4 under hot condition converts CH2 of double bond into CO2and H2O,CH of
double bond into carboxylic acid and C of double bond into ketone
OsO4 and RuO4 give diol with alkene.
Epoxidation- Alkenes react with peracids like peracetic acid to give epoxides
Diels Alder reaction-Alkenes react with dienes to give cyclised products under heating

Addition of HOBr- HOBr adds to alkene in the same way as unsymmetrical reagents,OH
adding to highly substituted carbon and Cl adding to least substituted carbon.
Hydroboration-Alkenes react with BH3 followed by CH3COOH to give alkanes
Alkoxymercuration_Demercuration_reacting alkene with Hg(OCOCH3) andROH followed
by NaBH4 gives ethers according to Markonikof alcohol.

REACTIONS OF ALKYNES
Bromination-1 mole of bromine converts alkyne into vic alkene dihalide. 2 moles
convert into tetrahalide.
Hydrogenation- Lindlar catalyst converts alkyne into cis alkene.Birch reagent converts alkyne
into trans alkene
Ozonolysis-Ozonolysis converts alkyne into carboxylic acids
Cold KMnO4- Alkynes give tetrahydroxyl compounds which eliminate 2 molecules of
water to give diketones
Hot KMnO4 converts alkyne into carboxylic acids
ALKYNES

Diels-Alder reaction-Alkynes undergo D-A reaction with dienes to give cyclic compounds

Addition of HBr- Alkynes add 1 mole of HBr to give alkene halides according to
Markonikof rule,when 2 moles are added the second bromine goes to the same carbon
whre first bromine is attached
Addition of HBr in the presence of peroxide gives products according to antimarkonikof rule
Polymerisation- Alkynes undergo polymerisation when passed through red hot tube. 3
moles of acetylene give benzene,3 moles of propyne give mesitylene,4 moles of acetylene
give cyclooctatetraene.
Reactions of Sodium acetylide-Terminal alkynes react with sodamide(NaNH2) to give
sodium acetylides which are powerful nucleophiles react similar to Grignard reagents.
Acid catalysed hydration_ Alkynes react with H2O in the presence of acid and HgSO4 to
give ketones
Hydroboration -oxidation_ Terminal alkynes react with BH3 followed by H2O2 to give
aldehydes

Addition of hypohalous acid_ Addition of 2 moles of HOCl to alkynes give alpha dichloro
ketones

REACTIONS OF ALKANES
Free radical substitution-Alkanes undergo free radical substitution under the influence of
heat or sunlight to give akyl halides.Rate with respect to Hs is 30>20>10.Rate with resect
to halogens F2>Cl2.Br>I2.Chlorination is less selective than bromination with relative rate
of abstraction of hydrogens 5:3.8:1 and 1600:82:1 respectively.

ALKANES

Isomeristion_ Alkanes undergo isomerisation in the presence of AlCl3 to give branched

alkanes
Aromatisation_Hexane undergoes aromatisatin in the [presence of Fe2O3,Cr2O3at high
temperature to give benzene

H2/Pd
Br2,CCl4

Hg(OCOCH3)/H2O
NaBH4
HOBr
H2O/H+
BH3/H2O2
O3/Zn
BH3/CH3COOH
O3/H2O2

Heat
cold KMnO4
hot KMnO4

OsO4
CH3COOOH

H2/Pd

2 moles Br2,CCl4
Hg(OCOCH3)/H2O
NaBH4
2 moles HOBr
H2O/H+
BH3/H2O2
H3C

CH

O3/H2O
BH3/CH3COOH

H2/Pd on BaSO4

Heat
cold KMnO4
hot KMnO4

OsO4
Na in liq NH3

AROMATIC HYDROCARBONS-BENZENE
1. Benzene is characterized by following factors

Substitution in preference to addition

Single mono-substituted products
Three di-substituted product
Low heats of combustion and hydrogenation
Identical CC bond lengths

2. Methods of preparation.
Benzene can be prepared by
Heating phenol with Zn dust
Aromatizing hexane
Passing acetylene through red hot tube
Desulphonation of benzene sulfonic acid
Heating benzene diazonium chloride with H3PO2
Heating sodium benzoate with sodalime

3. Reactions of benzene. Benzene undergoes electrophilic substitution

reactions majorly.
Electrophilic substitution reaction ob benzene involves 3 steps
Step1-Generation of electrophile
Step2-Attack of electrophile on benzene
Step3-Regeneration of aromaticity
Reaction
Halogenation
Nitration
F-C alkylation
F-C acylation

Reagent
X2/AlX3
HNO3/H2SO4
R-X/AlCl3
RCOCl/AlCl3

Electrophile
X+
NO2+
R+
RCO+

Sulphonation

H2SO4

SO3

Product
Halobenzene
Nitrobenzene
Alkyl benzene
Acyl
benzene(Keton
e)
Benzene
sulfonic acid