Reasoning on

Haloalkanes and haloarenes

(1) Haloarenes are chemically less reactive than haloalkanes .

(1) Haloarenes are chemically less reactive because of resonance . resonating structures impart a partial double
bond character to C-Cl bond ,which also results in shortening of bond length and this imparts stability to aryl
halide and thus bond cleavage becomes difficult . Therefore ,aryl halides are less reactive than alkyl halides.

(2) Vinyl chloride is less reactive than C2H5Cl .

(2) In vinyl chloride ,the lone pair of electrons on Cl atom conjugate with π – electron pair of double bond.

CH2 = CH – Cl → CH2 - – CH = Cl +

There is partial double bond character in C – Cl and its bond strength increases. As a result it is difficult to break
C-Cl bond in vinyl chloride as compared to C- Cl single bond in ethyl chloride.

(3) Chloroform is stored in dark coloured bottles.

(3) Chloroform is stored in dark coloured bottles so as to cut off sunlight. It reacts with oxygen in presence of
sunlight to form phosgene (COCl2) gas which is poisonous.

2CHCl3 + O2 → 2COCl2 + 2HCl

Phosgene

(4) A small amount of ethyl alcohol is added to chloroform bottles.

(4) Alcohol retards the oxidation of chloroform to phosgene and it converts phosgene if formed to harmless
ethyl carbonate.
2C2H5OH + COCl2 → (C2H5)2CO3 + 2 HCl

(5) Alkyl halides though polar are immiscible with water.

(5) Alkyl halides though polar are immiscible with water as they cannot form H-bond with water and cannot
break H- bond between water molecules, therefore they are insoluble in water.

(6) Although chlorine is an electron- withdrawing group, yet it is o- and p- directing in electrophilic substitution
reactions.
(6) Chlorobenzene shows resonance. Since there is –ive charge at o- and p- positions, therefore electrophilic
substitution reaction will take place at o- and p- positions due to +R effect inspite of –I effect of halogen. +R
effect is dominating over –I effect.

(7) The treatment of alkyl chlorides with aqueous KOH leads to the formation of alcohols but in the presence of
alcoholic KOH , alkenes are the major products.
(7) In aqueous state KOH, is almost completely ionized to give OH – ions. These being strong nucleophiles result
into substitution reaction on alkyl chlorides to form alcohols . Moreover, in aqueous solution, the OH- ions are
highly hydrated (solvated) . The hydration reduces the basic character of OH- ions which therefore , fails to
abstract a hydrogen from the β – carbon of the alkyl chloride to form an alkene.
On the other hand , an alcoholic solution of KOH contains alkoxide (RO- ) ions which being stronger base than
OH- ions preferentially eliminates a molecule of HCl from an alkyl halide to form alkenes.

(8) Gridnard’s reagent should be prepared under anhydrous conditions.

(8) Gridnard reagents are very reactive. They react with moisture present in the apparatus or the starting material.
They should be prepared under anhydrous conditions because if water is present then it will convert Gridnard
reagents to alkane.
R-Mg -X + HOH → R-H + Mg(OH)X

(9) Haloalkanes react with KCN to give alkyl cyanide as main product while with AgCN, they form isocyanide
as main product.
(9) Cyanide ion is a resonance hybrid of following two resonating structures:
-
:C ≡ N: ↔ :C = ¨ N: -

It can attack the nucleophile site through C as well as through N. Such a nucleophile which is capable of
attacking through more than one site is called ambident nucleophile. Thus , CN- behaves as an ambident
nucleophile.
KCN is predominantly , ionic and therefore , both C and N atoms is available for the electron donation but the
reaction occurs through carbon as C-C bonds are stronger than C- N bond, therefore the attack occurs through
the carbon atom of the cyanide group forming alkyl cyanides as the main product.
On the other hand ,AgCN is predominantly covalent in nature and nitrogen is free to donate electron pair
forming isocyanides as the main product.

(10) Thionyl chloride method is preferred for preparing alkyl chlorides from alcohols.
(10) The by poroducts of the reaction i.e. SO2 and HCl are gases and escape into the atmosphere leaving behind
alkyl chlorides in almost pure form.

CH3CH2-OH + SOCl2 → CH3CH2-Cl + SO2 ↑ + HCl ↑

(11) Iodoform gives a precipitate with silver nitrate on heating while chloroform does not.
(11) Carbon –iodide bond is quite weak as compared to carbon – chlorine bond .Therefore ,when
Iodoform is heated with AgNO3 solution ,C-I bond gets cleaved easily and iodide ions react with AgNO3 to give
precipitate of AgI. On the other hand ,C-Cl bond does not get cleaved.

(12) Alkyl halides are generally not prepared in the laboratory by free radical halogenation of alkanes.
(12) Free radical halogenation of alkanes is not suitable method for the preparation of alkyl halides because of
the following reasons:
(i) presence of different types of hydrogen atom in in alkanes give a mixture of isomeric monohalogenated
products whose b.p. are so close that they cannot be easily separated in the laboratory.
(ii) Substitution of more than one hydrogen atom yields polyhalogen compounds making the mixture more
complex and hence difficult to separate.