NEET Full Course Halogen Derivatives of Organic Compounds Halogen Derivatives Of Organic Compounds Revision Notes PDF 2026-27

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Halogen Derivatives Of Organic Compounds Summary & Notes for Full Course Halogen Derivatives of Organic Compounds

Halogen Derivatives of Organic Compounds

Organic Compounds Containing Halogens can be divided into two groups:

• Alkyl Halides: Aliphatic carbon chain with halogen atom(s) as substitution.

Example: Chlorobutane.

• Aryl Halides: Aromatic carbon ring with halogen atom(s) as substitution on ring.

Example: Chlorobenzene.

Methods of Preparation of Alkyl Halides:

Grove’s process: Replacement of “OH” group in primary and secondary alcohols with an “X’ atom in presence of Zinc chloride.

NEET Chemistry Halogen Derivatives of Organic Compounds Revision Notes

The reaction follows S_N2 mechanism when the concentration of zinc chloride is low.

Darzen Process: Reaction of thionyl chloride with straight-chain primary alcohols without presence or absence of pyridine.

In presence of pyridine:

ROH + SOCl₂ → HCl + ROSOCl

HCl+C₅H₅N →C₅H₅NH++Cl^-

ROSOCl + Cl^– →RCl + SO₂ (SN₂)

• Action of a phosphorus halide on the alcohol: ROH + PCl₅ → RCl + HCl + POCl₃.

• By addition of Halogen to an alefins: R-CH=CH₂ +Br₂+CCl₄ →R-CH(Br)CH₂Br

• Photohalogenation: CH₄ + Cl₂ +hv → CH₃Cl + HCl

• Displacement of one halogen atom by another:RCl + NaI →RI + NaCl

• Bonodine – Hünsdiecker Reaction: RCO₂Ag + Br₂→RBr + CO₂ + AgBr

• Hydrohalogenation of unsaturated hydrocarbons:

• In absence of peroxide: RCH=CH₂ +HBr→RCH(Br)CH₃

• In presence of peroxide: RCH=CH₂ +HBr + Peroxide →RCH₂CH_2Br

Methods of Preparation of aryl halides

• Halogenation: Ar-H + X2 +Lewis Base → Ar-x + HX

• From diazonium salts:

• C₆H₅N₂Cl + HBF₄ →C₆H₅F (Schiemann Reaction)

• C₆H₅N₂Cl + CuCl →C₆H₅Cl (Sandmeyer Reaction)

• C₆H₅N₂Cl + Cu powder →C₆H₅Cl (Gatterman Reaction)

S_N1 and S_N2 mechanism:

Reactions of Alkyl Halides:

• Hydrolysis: : RX + OH^– → ROH + X^–

• Williamson Synthasis: R-ONa +R'X → R-R' + NaX

• Reaction with dry silver oxide: 2R-X + Ag₂O → R-O-R

• Reaction with sodio-Alkynides: R-C≡C-Na +X-R→ R-C=C-R +NaX

• Reaction with potassium-cyanide: KCN+X-R→ RCN +KX

• Reaction with silver-cyanide: AgCN+X-R→ RNC +AgX

• Reaction with silver-nitrite: AgNO₂+X-R→ RNO₂ +AgX

• Reaction with potassium-nitrite: KNO₂+X-R→ R-O-N=O +KX

• Fridal Craft Reaction: R-X + C₆H₆ + AlCl₃→C₆H₅-R

• Malonic Ester Synthasis: R-X + ^-CH(CO₂C₂H₅)₂ →R-CH(CO₂C₂H₅)₂ +HX

• Acetoacetic Ester Synthasis: R-X +^-CH(CO₂CH₃)₂ →R-CH(CO₂CH₃)₂ +HX

• Reaction with Ammonia: R-X +NH₃→ R-NH₂ +HX

• Wurtz Reaction: 2R-I+ 2Na →R—R + 2NaI

• Dehydrohalogenation: CH₃.CH₂.CH₂Br + alco.KOH → CH₃–CH = CH₂ + KBr + H₂O

• Reaction with alcoholic AgNO₃: R-X +AgNO₃ → R+ + AgX↓+HNO₃

Substitution Versus Elimination:

Haloform(Tri halide):

• Preparation: It can be prepared from any alcohol having –CH(OH)CH₃ group or from the aldehydes and ketones formed from above type of alcohols i.e, from a carbonyl compound

having three a - hydrogen atoms by the action of X₂and an alkali or Na₂CO₃.

• Laboratory Preparation of CHCl₃:

• Physical properties of CHCl₃: colourless liquid with sweet smell and test. It is heavier than water and insoluble in it but soluble in alcohol and ether.

Chemical Reactions of CHCl3:

• Oxidation: CHCl₃ + 1/2 O₂ → HCl + COCl₂ (phosgene)

• Hydrolysis: CHCl₃ + 4NaOH → HCOONa + 3NaCl + 2H₂O

• Carbyl amine reactions: CHCl₃ + CH3NH2 + 3NaOH →CH₃N≡C +3NaCl +3H

5. Hydroboration-Oxidation:

6. Halogen Addition in Non-polar Solvent:

NEET Chemistry Halogen Derivatives of Organic Compounds Revision Notes-5

7. Halogen Addition in Aqueous Medium:

8. Syn – Hydroxylation: Formation of di-oles.

9. Ozonolysis of Alkenes:

Alkyne

• Saturated open chain hydrocarbon with general formula (C_nH_2n-2).

• At least one -c≡c- (triple bond) group i.e. sp hybridisation, is present throughout the chain.

• Physical properties of alkynes are similar to those of the corresponding alkenes

Preparation

1. Dehydrohalogenation of vic-Dihalides or gem-Dihalides

NEET Chemistry Halogen Derivatives of Organic Compounds Revision Notes-9

2. Dehalogenation of vic-Tetrahalogen Compounds

3. Alkyl Substitution in Acetylene; Acidity of º C-H

4. From Calcium Carbide:

CaC₂ +2H₂O → Ca(OH)₂+ C₂H₂

5. Kolbe’s Electrolysis:

Chemical Properties

1. Hydrogenation: RC ≡ CCH₂CH₃ + 2H₂ → CH₃CH₂CH₂CH₂CH₃

2. Hydro-halogenation:

Markovnikov addition: RC≡CH +HBr → RCBr=CH₂ +HBr→ RCBr₂-CH₃

Anti-markovnikov addition: RC≡CH +HBr +peroxide → RCH=CHBr

NEET Chemistry Halogen Derivatives of Organic Compounds Revision Notes-13

Aromatic Hydrocarbons:

For being aromatic a hydrocarbon should

• be a cyclic compounds.

• have planarity in geometry.

• have complete delocalization of electrons over ring.

• follow Huckel Rule i.e. number of ?? electrons in ring = (4n+2).

NEET Chemistry Halogen Derivatives of Organic Compounds Revision Notes-14

Benzene (C₆H₆)

1. Structure:

NEET Chemistry Halogen Derivatives of Organic Compounds Revision Notes-15

2. Chemical Reactions of Benzene:

Anti-aromatic Hydrocarbons:

Highly unstable compounds.

Number of π electrons in ring = 4n.

Example:

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