Organic Chemistry: Haloalkane and Haloarene

ORGANIC CHEMISTRY
HALOALKANE AND HALOARENE

REACTIONS OF HALOALKANE
 NUCLEOPHILIC SUBSTITUTION
 ELIMINATION REACTIION
 REACTION WITH METALS
NUCLEOPHILIC SUBSTITUTION
REACTIONS
 What is a nucleophile? Where does it attack?
 What is nucleophilic substitution reaction?
 Here the substrate is haloalkane,a nucleophile reacts with haloalkane having a partial positive
charge on the carbon atom bonded to halogen.A substitution reaction takes place and halogen
atom called leaving group departs as halide ion.Since it is initiated by a nucleophile it is called
nucleophilic reaction.
 AMBIDENT NUCLEOPHILES ex:cyanide and nitrites,having two nucleophilic centre.
 Alkyl cyanide,isocyanide
 Alkyl nitrites,nitroalkanes
 Haloalkane react with KCN to form alkyl cyanides as main product while AgCN form
isocyanide as chief product explain?
MECHANISM
 SUBSTITUTION NUCLEOPHILIC BIMOLECULAR(SN2)

 The reaction between methyl chloride and hydroxide ion yield methanol and chloride ion
 Second order kinectics
 Rate depends upon the concentration of both the reactants.
 Single step,no intermediate.
 The incoming nucleophile interacts with alkyl halide causing the carbon-halide bond to
break and a new bond is formed between C and the attacking nucleophile.Here it is C-O
bond formed between C and –OH .These two processes take place simultaneously in a
single step and no intermediate is formed.
Explanation
 As the reaction progresses and the bond between the incoming nucleophile and the carbon atom starts
forming,the bond between carbon atom and the leaving group weakens.
 As this happens,the three carbon-hydrogen bonds of the substrate start moving away from the attacking
nucleophile.In the transition state all the three C-H bonds are in the same plane and the attacking and
leaving nucleophile are partially attached to the carbon.As the attacking nucleophile approches closer
to the carbon.C-H bonds still keep on moving in the same direction till the attacking nucleophile
approaches closer to the carbon.As a result configuration is inverted,same way as an umberalla caught
in a strong wind.INVERSION OF CONFIGURATION.In the transition state carbon is
simultaneously bonded to incoming nucleophile and outgoing leaving hgroup.such structures are
unstable and cannot be isolated.carbon is bonded to 5 atoms in this state.
 CONFIGURATION :Spacial arrangement of fuctional goups around carbon is called configuration.
 Presence of bulky substituents on or near the carbon atom produces inhibiting effect.
 Primary>Secondary>Teritiary.
SUBSTITUTION NUCLEOPHILIC
UNIMOLECULAR(SN1)
 Generally carried out in polar protic solvents(water, alcohol etc)
 Reaction between tert-butyl bromide and hydroxide ion yield tert-butyl alcohol.
 First order kinectics,Rate depends on the concentration of only one reactant.
 2 step reaction . In step 1_ the polarized C-Br bond undergoes slow cleavage to produce carbocation and a
bromide ion.The carbocation thus formed is attacked by nucleophile in step 2.
 Step 1 is slowest and reversible .It involves the C-Br bond breaking for which energy is obtained through
solvation of halide ion with the proton of protic solvent.Rate depend on the slowest step,depends on the
concentration of alkyl halide
 Greater the stability of carbocation faster the rate of reaction
 Teritiary>Secondary>primary
 Allylic and benzylic halides have high reactivity in SN1
 In both R-I>R-Br>R-Cl>R-F
STEREOCHEMICAL ASPECTS OF
NUCLEOPHILIC SUBSTITUTION
REACTION
 OPTICAL ACTIVITY
 MOLECULAR ASSYMETRY, CHIRALITY,ENANTIOMERS
 RETENTION
 INVERSION,RACEMISATION
OPTICAL ACTIVITY
ILLUSTRATION
EXPLANATION
 Plane of plane polarized light produced by passing ordinary light through nicol prism is
rotated when it is passed through the solution of certain compounds are called
opticallyactive compounds
 The angle by which the plane polarized light is rotated is measured by an instrument
called polarimeter.
 If the compound rotates the plane polarized light to the right (clockwise direction).It is
called dextro rotatory or the d form(+)
 If the compound rotates the light towards left it is leavorotatory,l form(-)
 Such + and- isomers of a compound are called optical isomers and the phenomenom is
termed as optical isomerism.
MOLECULAR ASSYMETRY
 AYSMMETRIC CARBON:If all the substituents attached to the carbon are different,the
mirror image is non superimposable –asymmetric carbon or stereocentre.
 Asymmetry +nonsuperimposability=>optical activity
ENANTIOMERS AND RACEMICATION
 The stereoisomers related to each other as nonsuperimposable mirror images are called
enantiomers
 Enantiomers possess identical physical properties namely meting and boiling
point,refractive index,They only differ with respect to the rotation of plane polarized
light.If one of the enantiomer is dextrorotatory the other will be laevo rotatory
 A mixture containing two enantiomers in equal proportion will have zero optical rotation
,as the rotation due to one isomer will be cancelled by the rotation due to the other
isomer.=>Racemic mixture dl mixture
QUESTION

Organic Chemistry: Haloalkane and Haloarene

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ORGANIC CHEMISTRY

HALOALKANE AND HALOARENE

 SUBSTITUTION NUCLEOPHILIC BIMOLECULAR(SN2)

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