Chemical properties of haloalkanes

The alkyl halides are highly reactive, the order of reactivity is,

Iodide > Bromide > Chloride (Nature of the halogen atom)

Tertiary > Secondary > Primary (Type of the halogen atom)

Amongst the primary alkyl halide, the order of reactivity is : CH3X > C2H5X > C3H7X, etc.

The high reactivity of alkyl halides can be explained in terms of the nature of C — X bond which is highly polarised covalent bond due to large difference in the electronegativities of carbon and halogen atoms. The halogen is far more electronegative than carbon and tends to pull the electrons away from carbon, i.e.,halogen acquires a small negative charge and carbon a small positive charge.

δ+ δ
— C — X

This polarity is responsible for reactions,

(i) Nucleophilic substitution reactions (ii) Elimination reactions

Example 1: Alkyl halides can be converted into Grignard reagents by

(a) Boiling them with Mg ribbon in alcoholic solution

(b) Warming them with magnesium powder in dry ether

(c) Refluxing them with MgCl2 solution

(d) Warming them with MgCl2

Ans: b

Example 2: Which is not present in Grignard reagent

(a) Methyl group (b) Magnesium

(c) Halogen (d) —COOH group

Ans: d

Example 3: The reactivity of ethyl chloride is

(a) More or less equal to that of benzyl chloride

(b) More than that of benzyl chloride

(c) More or less equal to that of chlorobenzene

(d) Less than that of chlorobenzene

Ans: b

Nucleophilic substitution (SN) reactions

The Cδ+ site is susceptible to attack by nucleophiles (An electron rich species).

Nu + R – X ————> Nu – R + X

–X Nu
R – X ————> R+ ————> R – Nu (SN1 reaction)
Slow Fast

Slow Fast
Nu + R — X ————> Nu ...... R ...... X ————> Nu – R + X
Transtition state

Example 1: Aryl halide is less reactive than alkyl halide towards nucleophilic substitution because

(a) Less stable carbonium ion

(b) Due to large C — Cl bond energy

(c) Inductive effect

(d) Resonance stabilization and sp2 - hybridisation of C attached to halide

Ans: d

Example 2:R — X + NaOH ————> ROH + NaX

The above reaction is classified as

(a) Nucleophilic substitution

(b) Electrophilic substitution

(c) Reduction

(d) Oxidation

Ans: a


Reactions of Alkyl Halide

(a) Reaction with alkoxides or dry silver oxide :

Heat
RX + NaOR' —————> ROR' + NaX
Unsym ether

2 RX + Ag2O —————> R — O — R + 2 AgX
Sym. ether

(b) Reaction with sodium or potassium hydrogen sulphide :

RX + NaSH ————> RSH + NaX
Sodium hydrogen Thioalcohol
sulphide or Alkanethiol
or Alkyl mercaptan

(c) Reaction with alcoholic potassium cyanide and silver cyanide :

Alcohol
RX + KCN —————> RCN + KX
Alkycyanide or
Alkane nitrile

(d) Reaction with potassium nitrite or silver nitrite :

triangle.JPG
RX + K — O — N = O ————> R — O — N = O + KX

potassium nitrite or silver nitrite.JPG

(e) Reaction with ammonia :

C2H5 + H — NH2 ———> C2H5NH2 + HBr
Ethylamine (p.)

C2H5NH2 + BrC2H5 ———> C2H5NHC2H5+ HBr
Diethylamine (sec.)

(C2H5)2NH + BrC2H5 ———> (C2H5)3N + HBr
Triethylamine (tert.)

+ –
(C2H5)3N + BrC2H5 ———> (C2H5)4 NBr
Tertraethyl ammonium
bromide (Qu. aternary)

Elimination reactions of Alkyl Halides

The positive charge on carbon is propagated to the neighbouring carbon atoms by inductive effect. When approached by a strongest base (B), it tends to lose a proton usually from the β-carbon atom. Such reactions are termed elimination reactions. They are also E1 and E2 reactions.

E1 reaction : E1 reaction E1 reaction.JPG

E2Reaction : E2 Reaction.JPG

As the above reactions involve leaving of X-, the reactivity of alkyl halides (Same alkyl group, different halogens) should be limited with C - X bond strength.

Type of bond C - I C - Br C - CI

Bond strength (kcal/mol) 45.5 54 66.5
——
Bond strength increases

The breaking of the bond becomes more and more difficult and thus, the reactivity decrease.

The order of reactivity (Tertiary > Secondary > Primary) is due to +I effect of the alkyl groups which increases the polarity of C - X bond.

Elimination reactions of Alkyl Halides.JPG

The primary alkyl halides undergo reactions either by SN2 or E2 mechanisms which involve the formation of transition state. The bulky groups cause steric hinderance in the formation of transition state. Therefore, higher homologues are less reactive than lower homologues. CH3 X > C2H5X > C3H7X , etc.

Examples of elimination reaction

(a) Dehydrohalogenation :

Cn H2n+1 X + KOH ——→ Cn H2n + KX + H2O
(Alcoholic) Alkene

In this reactions, ether is a by-product as potassium ethoxide is always present in small quantity.

C2H5 Br + KOC2H5 ——→ C2H5 - O - C2H5 + KBr

(b) Action of heat :

300oc
RCH2 CH2 X ——→ RCH = CH2 + HX
Alkene
300oC
C2H5Br ———→ CH2 = CH2 + HBr
Ethene

The decomposition follows the following order,

Iodide > Bromide > Chloride (When same alkyl group is present) and

Tertiary > Secondary > Primary (When same halogen is present).

Light
Example 1: C3H8 + Cl2 ——→ C3 H7 CI + HCI is an example of which of the following types of reactions

(a) Substitution (b) Elimination

(c) Addition (d) Rearrangement

Ans: b

Wurtz reaction

An ether solution of an alkyl halide (Preferably bromide or iodide) gives an alkane when heated with metallic sodium.

2RX + 2Na ——→ R - R + 2NaX

Example 1: Reaction C2 H5I + C5H11I + 2Na → C2H5 - C5H11 + 2NaI is called

(a) Hoffmann's reaction

(b) Dow's reaction

(c) Wurtz's reaction

(d) Riemer-Tiemann's reaction

Ans: c

Example 2: In Wurtz reaction alkyl halide react with

(a) Sodium in ether (b) Sodium in dry ether
(c) Sodium only (d) Alkyl halide in ether
Ans: c

Reactions Of Alkyl Halides

Reaction with magnesium

Alkyl halides form Grignard reagent when treated with dry magnesium powder in dry ether.

Dryether
RX + Mg ———→ R - Mg - x
( Powder) Grignard reagent

Grignard reagents are used for making a very large number of organic compounds.

Reaction with other metals : Organometallic compounds are formed.

  • When heated with zinc powder in ether, alkyl halides form dialkyl zinc compounds. These are called Frankland reagents.
Ether
2C2H5 Br + 2Zn ———→ ( C2H5 )2 Zn + ZnBr2
Heat

  • When heated with lead-sodium alloy, ethyl bromide gives tetra ethyl lead which is used an antiknock compound in petrol.

4C2H5Br + 4 Pb ( Na) ———→ ( C2H5)4 Pb + 4 NaBr + 3Pb

  • Reaction with lithium : Alkyl halides react with lithium in dry ether to form alkyl lithiums.
Ether
RX + 2Li ———→ R - Li + LiX ;

C2H5Br + 2Li ———→ C2H5 - Li + LiBr
Ethylbromide

Alkyl lithiums are similar in properties with Grignard reagents. These are reactive reagents also.


Friedel-Craft's reaction :

AlCl3
C6H6 + RCl ————→ C6H5R + HCl
Benzene Alkylbenzene

AIBr3
C6H6 + C2H5Br ———→ C6H5C2H5 + HBr

Substitution (Halogenation) : Alkyl halides undergo further halogenation in presence of sunlight, heat energy or peroxide.

Br2 Br2
C2H5Br ——→ C2H4Br2 ——→ C2H3Br3......
hv hv

Example 1: A new carbon-carbon bond formation is possible in

(a) Cannizzaro reaction (b) Friedel-Craft's alkylation

(c) Clemmensen reduction (d) Reimer-Tiemann reaction

Ans: b,d