Class Notes:
Haloalkanes(R-X)
and
Haloarenes(Ar-X)
Date: 3/05/2021
The replacement of hydrogen atom(s) in a
hydrocarbon, aliphatic or aromatic, by halogen
atom(s) results in the formation of alkyl halide
(haloalkane) and aryl halide (haloarene),
respectively. Haloalkanes contain halogen
atom(s) attached to the sp3 hybridised carbon atom
of an alkyl group whereas haloarenes contain
halogen atom(s) attached to sp2 hybridised carbon
atom(s) of an aryl group.
Eg- Chlorine containing antibiotic, chloramphenicol, produced by soil
microorganisms is very effective for the treatment of typhoid fever.
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Our body produces iodine containing hormone, thyroxine, the
deficiency of which causes a disease called goiter. Synthetic halogen
compounds, viz. chloroquine is used for the treatment of malaria;
halothane is used as an anaesthetic during surgery. Certain fully
fluorinated compounds are being considered as potential blood
substitutes in surger
Classification-(1.)On the Basis of Number of
Halogen Atoms-Haloalkanes and haloarenes may be
classified as mono, di, or polyhalogen (tri-,tetra-, etc.)
compounds depending on whether they contain one, two or
more halogen atoms in their structures.
(2.) Compounds Containing sp3 C—X Bond -
(a) Alkyl halides or haloalkanes (R—X)- In alkyl
halides, the halogen atom is bonded to an alkyl group (R). They
form a homologous series represented by CnH2n+1X.
They are further classified as primary, secondary or tertiary
according to the nature of carbon to which halogen is attached.
(b) Allylic halides These are the compounds in which the
halogen atom is bonded to an sp3 -hybridised carbon atom
next to carbon-carbon double bond (C=C) i.e. to an allylic
carbon.
(c) Benzylic halides -These are the compounds in which the
halogen atom is bonded to an sp3-hybridised carbon atom
next to an aromatic ring.
(d) Vinylic halides- These are the compounds in which the
halogen atom is bonded to an sp2-hybridised carbon atom of
a carbon-carbon double bond.
(e) Aryl halides -These are the compounds in which the
halogen atom is bonded to the sp2 -hybridised carbon atom of
an aromatic ring.
HOME-WORK
10.1 Write structures of the following compounds-
(i) 2-Chloro-3-methylpentane
(ii) 1-Chloro-4-ethylcyclohexane
(iii) 4-tert. Butyl-3-iodoheptane
(iv) 1,4-Dibromobut-2-ene
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(v) 1-Bromo-4-sec. butyl-2-methylbenzene.
NATURE OF C-X BOND- The carbon halogen bond of alkyl halide is polarised;
the carbon atom bears a partial positive charge whereas the halogen atom bears a
partial negative charge. Since the size of halogen atom increases as we go down
the group in the periodic table, fluorine atom is the smallest and iodine atom, the
largest. Consequently the carbon-halogen bond length also increases from C—F
to C—I.
Methods of PREPARATION of ALKYL HALIDE -
Alkyl halides are best prepared from alcohols, which are easily accessible. The hydroxyl
group of an alcohol is replaced by halogen in reaction with concentrated halogen acids,
phosphorus halides or thionyl chloride. Thionyl chloride is preferred because the other
two products are escapable gases
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HALOGEN EXCHANGE REACTIONS
Alkyl iodides are often prepared by the reaction of alkyl chlorides/ bromides with
NaI in dry acetone. This reaction is known as Finkelstein reaction. NaCl or NaBr
thus formed is precipitated in dry acetone. It facilitates the forward reaction according to
Le Chatelier’s Principle.
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The synthesis of alkyl fluorides is best accomplished by heating an alkyl
chloride/bromide in the presence of a metallic fluoride such as AgF, Hg2F2 , CoF2 or
SbF3. The reaction is termed as Swarts reaction.
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Physical Properties Properties of alkyl halides
1.COLOUR- Alkyl halides are colourless when pure. However, bromides and iodides
develop colour when exposed to light.
2.Alkyl halides are colourless when pure. However, bromides and iodides develop colour
when exposed to light.
3 M.P. & B.P..For the same alkyl group, the boiling points of alkyl halides decrease in the
order: RI> RBr> RCl> RF. This is because with the increase in size and mass of halogen
atom, the magnitude of van der Waal forces increases.
4.The boiling points of isomeric haloalkanes decrease with increase in branching (Unit
12, Class XI). For example, 2-bromo-2-methylpropane has the lowest boiling point among
the three isomers.
5.Boiling points of isomeric dihalobenzenes are very nearly the same. However, the
para-isomers are high melting as compared to their orthoand meta-isomers. It is due to
symmetry of para-isomers that fits in crystal lattice better as compared to ortho- and
meta-isomers.
6. Density -Bromo, iodo and polychloro derivatives of hydrocarbons are heavier than
water. The density increases with increase in number of carbon atoms.
7. Solubility The haloalkanes are only very slightly soluble in water.
8. However, haloalkanes tend to dissolve in organic solvents because the new
intermolecular attractions between haloalkanes and solvent molecules have much the
same strength as the ones being broken in the separate haloalkane and solvent
molecules.
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CHEMICAL PROPERTIES (REACTIONS)
The reactions of haloalkanes may be divided into the following
categories:-
(i) Nucleophilic substitution
(ii) Elimination reactions
(iii) Reaction with metals.
(i) Nucleophilic substitution reactions- In this type of reaction, a
nucleophile reacts with haloalkane (the substrate) having a partial
positive charge on the carbon atom bonded to halogen.
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2. Elimination reactions- When a haloalkane with β-hydrogen atom
is heated with alcoholic solution of potassium hydroxide, there is elimination of
hydrogen atom from β-carbon and a halogen atom from the α-carbon atom. As a result,
an alkene is formed as a product. Since β-hydrogen atom is involved in elimination, it is
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often called β-elimination. E.g.- Dehydrohalogenation reactions.
Saytzeff- RULE-“in dehydrohalogenation reactions, the preferred product is
that alkene which has the greater number of alkyl groups attached to the
doubly bonded carbon atoms.”
Thus, 2-bromopentane gives pent-2-ene as the major product on reaction
with alc.KOH SOLUTIONS.
Reaction with metals - Most organic chlorides, bromides and
iodides react with certain metals to give compounds containing carbon-metal
bonds. Such compounds are known as organo-metallic compounds. An important
class of organo-metallic compounds discovered by Victor Grignard in 1900 is
alkyl magnesium halide, RMgX, referred as Grignard Reagents. These reagents
are obtained by the reaction of haloalkanes with magnesium metal in dry ether.
In the Grignard reagent, the carbon-magnesium bond is covalent
but highly polar, with carbon pulling electrons from electropositive magnesium;
the magnesium halogen bond is essentially ionic. Grignard reagents are highly
reactive and react with any source of proton to give hydrocarbons. Even water,
alcohols, amines are sufficiently acidic to convert them to corresponding
hydrocarbons. It is therefore necessary to avoid even traces of moisture from a
Grignard reagent. On the other hand, this could be considered as one of the
methods for converting halides to hydrocarbons.
Wurtz reaction- Alkyl halides react with sodium in dry ether to give
hydrocarbons containing double the number of carbon atoms present in the
halide. This reaction is known as Wurtz reaction. (Unit 13, Class XI).
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SKT_CHEMISTRY/Date: 03/05/20XI___TO BE
CONTINUE…..
Science
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