Haloalkanes and haloarenes

Organic compounds in which halogen atom is directly linked with carbon atom.
Haloalkanes are also called as alkyl halides.
General formula of haloalkanes is CnH2n+1X, (X = F, Br, Cl, I).
The carbon that bears functional group (halogen atom) is sp3 hybridised in alkyl halides.
In these compounds, geometry of carbon is tetrahedral.
Central carbon atom has a bond angle of 109°28’.

On the basis of number of halogen atom(s), haloalkanes are:

(i) Monohalides – They possess only one halogen atom; e.g., CH3Cl, CH3CH2Br, etc.
(ii) Dihalides – They possess two halogen atoms. These are of following three types:
geminal dihalide, vicinal dihalide, and a, w or terminal dihalide.
(iii) Trihalides – They possess three halogen atoms; e.g., CHCl3, CHI3, etc.
(iv) Tetrahalides – They possess four halogen atoms; e.g., CCl4, etc.

Alkyl halide shows chain and position isomerism. If unsymmetrical or chiral carbon is
present, then it shows optical isomerism also.
Alkyl halides do not show functional isomerism, metamerism, tautomerism, and geometrical
isomerism.

PHYSICAL PROPERTIES Haloaikanes

• Colourless with sweet smelling oily liquid. However, CH3F, CH3Cl, CH3Br,
CH3CH2F, CH3CH2Cl are gaseous in nature.
• Although carbon–halogen bond is polar in nature, alkyl halides are partially soluble in H2O.
• Alkyl halides are completely soluble in organic solvents.
• Boiling point μ molecular weight

• Chloroform is colourless and pleasant smelling liquid while iodoform is yellow crystalline solid.
• Chloroform is used as an anaesthetic agent.
• Iodoform is more reactive than chloroform due to large size of iodine atom.
CHI3 + AgNO3 Æ AgI (yellow ppt)

CHCl3 + AgNO3 → No white ppt of AgCl

• Carbon tetrachloride is colourless liquid and used as fire extinguisher under the trade name pyrene.
• Chloroform is kept in dark coloured bottles to avoid the following oxidation reaction.
• Polarity order is RF > RCl > RBr > RI
• Reactivity order is RI > RBr > RCl > RF
• For same halide group, the reactivity order is 3∞ halide > 2∞ halide > 1∞ halide
• Fluorides and chlorides are lighter than water whereas bromides and iodides are heavier than H2O due to
more
density of bromine than oxygen. CH2I2 is heavier liquid after Hg.
• All haloalkanes burn on copper wire with green flame (BELESTEIN TEST for halogens)

Aliphatic nucleophilic substitution