3 ORGANIC CHEMISTRY
HALOALKANES AND HALOARENES
by Dr. M.K. JAIN (HOD- CHEMISTRY)
ALKYL HALIDES (HALOALKANES)
(i) Monohalides : (b) From alkenes (Hydrohalogenation) :
(ii) Dihalides :
(c) From alcohols :
(i) By action of dry H-X (Grove's process)
(ii) By action of PCl3 :
(iii) Trihalides :
(iv) Tetrahalides :
(iii) By action of PCl5 :
MONOHALIDES OR MONOHALOALKANES
(iv) Action of Thionyl chloride (Darzen's Process) :
0
(a) Primary or 1 alkyl halide :
0
(b) Secondary or 2 alkyl halide :
(d) From silver salt of carboxylic acids :
(Borodine-Hunsdiecker reation) :
(c) Tertiary halide or 30 alkyl halide :
Preparation of Monohalides
(a) From alkanes (Halogenation) :
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CHEMISTRY HALOALKANES AND HALOARENES
(c) By halogen exchange
With NaI (Finkelstein Reaction) :
reactions lead to Walden inversion
With AgF (Swarts Reaction) :
By reaction of alkene with sulphuryl chloride (Allylic
chlorination) :
(i) Hydrolysis :
(a) With aqueous KOH :
Physical Properties
(b) Using moist Ag2O :
(a) Reaction with NaOR
Chemical Properties
(A) Nucleophilic substitution reactions : (b) Using dry Ag2O
(1) SN1 Reaction (Substitution Nucleophilic Unimolecular)
(iii) Reaction with Na2S
(iv) Reaction with KSH :
Mechanism L
(v) Reaction with KCN :
(2) SN2 Reactions (Substitution Nucleophilic Bimolecular)
(vi) Reaction with AgCN :
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CHEMISTRY HALOALKANES AND HALOARENES
(vii) Reaction with KNO2 : (v) With Na - lead alloy :
(viii) Reaction with AgNO2 :
(ix) Reaction with Na2SO3 : Uses :
(x) Reaction with silver acetate (Esterification) :
DIHALIDES OR DIHALOALKANES
(xi) Reaction with benzene (Friedel-Craft reaction) :
(a) Gem dihalides or Alkylidene halides
(B) Elimination reactions
(i) With alcoholic KOH :
(b) Vicinal dihalides or Alkylene halides
(ii) Action of heat :
(c) Reduction :
(D) Reaction with metals :
(i) With Na : (Wurtz reaction)
(ii) With Mg : (Grignard reaction) Preparation of Dihalides
(a) Gem dihalides
(i) From alkynes (By hydrohalogenation) :
(iii) With Zn dust : (Frankland reaction)
(iv) With Li :
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CHEMISTRY HALOALKANES AND HALOARENES
(ii) From carbonyl compounds :
(ii) From vicinal glycol :
Physical Properties
(b) Vicinal dihalides
(i) From alkene (By halogenation)
Chemical Properties
S.No. Property Alkylidene halides (Gem dihalide) Alkylene halides (Vicinal dihalide)
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CHEMISTRY HALOALKANES AND HALOARENES
TRIHALIDES OR TRIHALOALKANES
Preparation of CHCl3
(i) Haloform reaction :
2. Reaction :
3. Reaction with Alcoholic KOH :
(ii) Preparation of pure chloroform :
(iii) From carbon tetrachloride (Pyrene)
4. Reaction with Alcoholic KOH :
(iv) From methane :
Chemical Properties
(i) Oxidation :
5. Reaction with Acetone :
Precautions :
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CHEMISTRY HALOALKANES AND HALOARENES
6. Reaction with silver powder (Dehalogenation) : Preparations
(i) From methane (CH4) :
7. Reaction with Primary amine :
(ii) From carbon disulphide (CS2) :
8. Reaction with Phenol :
(iii) From CHCl3
(iv) From propane :
PHYSICAL PROPERTIES
9. Reaction with 2-Butene :
CHEMICAL PROPERTIES
(i) Oxidation :
(ii) Hydrolysis :
(iii) Reduction :
Uses
(v) Reaction with benzene :
IODOFORM (TRIIODOMETYHANE) CHI3
TETRA HALIDES OR TETRAHALOALKANES
Uses :
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CHEMISTRY HALOALKANES AND HALOARENES
OTHER USEFUL HALOGEN DERIVATIVES (C) Westron (Acetylene Tetrachloride) : (Cl2CH-CHCl2)
(A) Freons or CFC's (Chlorofluoro Carbons) :
(i) Preparation of freons : (i) Preparation :
(ii) Properties :
(ii) Properties
Uses :
(iii) Uses of Freons :
(D) Westrosol : (Trichloro Ethylene)
(iv) Nomenclature of Freons : (i) Preparation :
(ii) Properties :
Example : (iii) Uses :
HALOARENES ( ARYL HALIDES)
Preparation
(B) Teflon
(i) Preparation : (i) By direction chlorination of benzene :
(ii) By Sandmeyer's reaction :
(ii) Properties :
(iii) Uses :
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CHEMISTRY HALOALKANES AND HALOARENES
(i) Replacement by-OH group:
(ii) Replacement by-NH2 group:
(iii) Replacement by-CN :
(iii) By Hunsdiecker reaction :
2. Reduction :
(iv) Rasching process :
PHYSICAL PROPERTIES
3. Wurtz-Fittig reaction :
CHEMICAL PROPERTIES
1. Nucleophilic substitution
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CHEMISTRY HALOALKANES AND HALOARENES
(b) Nitration :
4. Ullmann Reaction :
(c) Sulphonation :
5. Formation of Grignard's reagents :
(d) Friedel -Crafts reaction :
6. Reaction with chloral
8. Elimination addition reaction :
7. Reactions due to the benzene ring :
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CHEMISTRY HALOALKANES AND HALOARENES
IMPORTANT POINTS
1. Elimination Reactions :
(a) a-Elimination reactions:
(b) b
-Elimination reactions:
2. Analysis of Alkyl and Ary Halides :
(i) Beilstein test :
(ii) Lassaigne's test :
(a) Ionic halogen
(b) Labile halogen
(c) Inert halogen
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CHEMISTRY HALOALKANES AND HALOARENES
MISCELLANEOUS SOLVED EXAMPLES
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Daily Practice Problems
TARGET : IIT-JEE / NEET
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CHEMISTRY HALOALKANES AND HALOARENES
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CHEMISTRY HALOALKANES AND HALOARENES
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SOLUTION
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CHEMISTRY HALOALKANES AND HALOARENES
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