Haloalkanes and Haloarenes

Chlorine

Bromine

Either can be first

Depends on position

2-chloro-3-methylbutane

3-chloro-2-methylbutane

2-methyl-3-chlorobutane

Isopentyl chloride

n-butyl bromide

Isobutyl bromide

sec-butyl bromide

tert-butyl bromide

1-chloropentane

2-chloropentane

Chlorobutane

1-chlorohexane

2-Bromo-3-methylbut-3-ene

3-Bromo-2-methylbut-1-ene

2-Methyl-3-bromobut-1-ene

4-Bromo-3-methylbut-2-ene

1-Chloro-2-phenylethane

2-Chloro-1-phenylethane

Benzyl methyl chloride

Phenylethyl chloride

1,1-Dichloroethane

1,2-Dichloroethane

1,1-Dichloropropane

Chloroethane

1,3-Dichloro-2,2-bis(chloromethyl)propane

Pentaerythrityl tetrachloride

Tetrakis(chloromethyl)methane

1,1,1,1-Tetrachloromethylmethane

Allylic halides

Vinylic halides

Benzylic halides

Aryl halides

3-Chloro-1-iodo-2-methylpentane

3-Chloro-5-iodo-4-methylpentane

1-Iodo-2-methyl-3-chloropentane

2-Methyl-1-iodo-3-chloropentane

$p$-orbital

$s$-orbital

$sp^{3}$ hybrid orbital

$sp^{2}$ hybrid orbital

Only the nature of alkyl group

Only the nature of halogen group

Both the nature of alkyl and halogen groups

Atmospheric pressure

$I$

$Br$

$Cl$

$F$

$sp^{3}$ hybridization of carbon

Resonance and $sp^{2}$ hybridization

Inductive effect of methyl group

Van der Waals forces

$C-F < C-Cl < C-Br < C-I$

$C-I < C-Br < C-Cl < C-F$

$C-Cl < C-F < C-Br < C-I$

$C-F < C-Br < C-Cl < C-I$

In benzyl chloride, the carbon is $sp^2$ hybridized.

In benzyl chloride, there is no resonance effect directly involving the $C-Cl$ bond.

In benzyl chloride, the chlorine is less electronegative.

In chlorobenzene, the carbon is $sp^3$ hybridized.

Fluorine

Chlorine

Bromine

Iodine

C-I

C-Br

C-Cl

C-F

The ortho-isomer, due to its higher dipole moment and stronger dipole-dipole interactions.

The para-isomer, due to its symmetry and better packing in the crystal lattice.

The meta-isomer, due to its intermediate polarity.

All isomers have the same boiling point as they are structural isomers.

The halogen atom is electron-deficient.

The carbon atom is electron-deficient due to the polarity of the bond.

The bond is non-polar, allowing for radical attack.

The halogen atom is a strong nucleophile itself.

Carbon-1

Carbon-2

Carbon-3

Carbon-4

Ethyl chloride is formed

Ethyl bromide is formed

Ethane is formed

Ethene is the only product

Due to their different chemical reactivities

Due to large difference in their melting points

Due to their different colors

Due to their different smells

1,1-Dibromopropane

2,2-Dibromopropane

1,2-Dibromopropane

1,3-Dibromopropane

$PCl_{5}$

$SOCl_{2}$

$HCl/ZnCl_{2}$

All of these

Fluorine is too unreactive.

The reaction is highly exothermic and explosive.

Fluorine reacts with the glass apparatus.

The $C-F$ bond is very weak.

2-Bromobutane

1-Bromobutane

1,2-Dibromobutane

2,2-Dibromobutane

Oxygen reacts with methyl radicals to form less reactive peroxy radicals

Oxygen reacts with chlorine radicals to form $ClO_2$

Oxygen acts as a catalyst for the reverse reaction

Oxygen inhibits the light absorption process

Reaction with $PI_3$ generated in situ from red $P$ and $I_2$

Reaction with $HI$ and $ZnCl_2$

Reaction with $KI$ and $H_2SO_4$

Direct reaction with $I_2$ gas

2-chloro-1-iodopropane

1-chloro-2-iodopropane

1,2-dichloro-1-iodopropane

2-chloro-2-iodopropane

Chloroform

Bromoform

Iodoform

Freon

Alkyl halide only

Nucleophile only

Both alkyl halide and nucleophile

Solvent only

Wurtz reaction

Fittig reaction

Sandmeyer reaction

Gattermann reaction

Nitroalkane

Alkyl nitrite

Alkyl cyanide

Alkyl isocyanide

Ethyl tert-butyl ether

2-Methylprop-1-ene

2-Methylpropan-2-ol

But-2-ene

$(CH_3)_3C-F$

$(CH_3)_3C-Cl$

$(CH_3)_3C-Br$

$(CH_3)_3C-I$

$HI > HBr > HCl > HF$

$HF > HCl > HBr > HI$

$HCl > HBr > HI > HF$

$HI > HCl > HBr > HF$

Phenol

Chlorobenzene

Benzene

Aniline

1-bromobutane

1-bromo-3-methylbutane

1-bromo-2-methylbutane

1-bromo-2,2-dimethylpropane

Ethane only

Propane only

Ethane, Propane, and Butane

Methane, Ethane, and Propane

$CH_3F$

$CH_3Cl$

$CH_3Br$

$CH_3I$

A stable carbocation

A primary alkyl halide

A tertiary alkyl halide

A polar protic solvent

$C-Nu$ forms, $C-X$ breaks

$C-X$ forms, $C-Nu$ breaks

$C-H$ forms, $C-X$ breaks

$C-X$ breaks, $X-Nu$ forms

Zero order

First order

Second order

Third order

It is the preferred mechanism for primary alkyl halides to minimize steric repulsion.

It proceeds via a concerted transition state with no discrete intermediate.

It involves the formation of a planar $sp^2$ hybridized carbocation intermediate in the slow step.

The rate of the reaction will increase four-fold if the concentration of the nucleophile is doubled.

Fluorine is more electronegative.

The C-I bond is weaker and breaks more easily than the C-F bond.

The iodide ion is a stronger base than the fluoride ion.

Methyl iodide is more polar than methyl fluoride.

Protonation followed by loss of water.

Nucleophilic attack followed by loss of bromide.

Loss of bromide ion followed by nucleophilic attack of water.

Simultaneous loss of bromide and attack of water.

The crown ether acts as a Lewis acid, coordinating with the chlorine atom to facilitate its departure as a leaving group.

The crown ether increases the solvent's polarity, thereby stabilizing the transition state of the substitution reaction.

The crown ether sequesters the $K^+$ cation, thereby minimizing ion-pairing and liberating the $F^-$ ion as a highly reactive 'naked' nucleophile.

The crown ether reacts with the alkyl halide to form a stable carbocation intermediate, allowing the reaction to proceed via an $S_N1$ mechanism.

If the reaction mechanism shifts to $S_N1$.

If the solvent is changed to a very non-polar one.

If the temperature is lowered significantly.

If a very bulky nucleophile is used in an $S_N2$ process.

Triple

Increase by 1.5 times

Decrease by half

Stay the same

Dichloromethane

Chloroform

Chloromethane

Iodoform

$90^{\circ}$

$120^{\circ}$

$109.5^{\circ}$

$180^{\circ}$

Oxygen

None, it is a non-volatile solid

Helium

Hydrogen

Reduction

Dehydration

Nitration

Hydrogenation

Chlorine

Iodine

Oxygen

Nitrogen

BHC

DDT

Lindane

Gammexane

$COCl$

$CCl_{3}CHO$

$COCl_{2}$

$CCl_{3}NO_{2}$

Dechlorination; $sp^3$ to $sp^2$

Dehydrochlorination; $sp^2$ to $sp^3$

Dehydrochlorination; $sp^3$ to $sp^2$

Dehydrogenation; $sp^3$ to $sp^2$

$d$-orbital resonance stabilization of the $CCl_3^-$ carbanion

The $+I$ effect of Fluorine

Higher electronegativity of Chlorine

Larger size of the Fluorine atom

Benzene hexachloride

Hexachlorobenzene

1,1,1-trichloroethane

Tetrachloromethane