& HALOARENES SYLLABUS ★ General methods of preparation, properties, and reactions ★ Nature of C-X bond; Mechanisms of substitution reactions ★ Uses; Environmental effects of chloroform, iodoform freons, and DDT HALOALKANES ➢ Series of compound that is obtained by the replacement of one or more H atom of Hydrocarbon by halogen atom
1.From alkanes ⇒ Cl2/UV light Or heat CH3CH2CH2CH3 CH3CH2CH2CH2CI + CH3CH2CHClCH3 Addition of Hydrogen halide
C=C + HX C-C
2. From alkenes H X CH3CH=CH2+HI CH3CH2CH2I +CH3CHICH3 (Minor) (Major) Addition of Halogen CCl4 C=C + Br2 Br-CH2-CH2-Br
(vic-dibromide) 3. HALO EXCHANGE
1. Finkelstein reaction
R-X + NaI Dry acetone R-I + NaX
( X = Cl, Br)
2. Swart’s reaction
CH3-Br + AgF H3C-F + AgBr
● Reaction takes place in the presence of
Metallic fluorides such as AgF, Hg2F2 CoF2 or SbF3 . PHYSICAL PROPERTIES ❏ Alkyl halides are colourless when pure. ❏ Bromides and iodides develop colour when exposed to light. ❏ Many volatile halogen compounds have sweet smell.
❏ MELTING AND BOILING POINT
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.
Boiling points of isomeric dihalobenzenes are very nearly
the same They having same molecular formula why they have different boiling points ?
The boiling points of isomeric haloalkanes decrease with increase in
branching CH3 | CH3CH2CH2CH2Br CH3CH2CHCH3 H3C-C-CH3 | | Br Br B.P 375K 364K 346K ❏ DENSITY The density increases with increase in number of carbon atoms,
halogen atoms and atomic mass of the halogen atoms
❏ SOLUBILITY
● The haloalkanes are very slightly soluble in water
● energy is required to overcome the attractions between the
haloalkane molecules and break the hydrogen bonds between water molecules
● Less energy is released when new attractions are set up
between the haloalkane and the water molecules as these are not as strong as the original hydrogen bonds in water. CHEMICAL REACTION
❏ Nucleophilic substitution
❏ Elimination reactions
❏ Reaction with metals.
1.NUCLEOPHILIC SUBSTITUTION REACTION
Nu- = nucleophile X = halogen
❏ Nucleophilic substitution of alkyl halides
R-x + Nu- R-Nu + x-
Eg : CH3Cl + NaOH CH3OH + NaCl
OH- = Nucleophile CH3OH = Substitution product of R-Nu- ❏ Groups like cyanides and nitrites possess two nucleophilic centres and are called ambident nucleophiles
CYANIDE [-C ≡ N ↔ :C=N-]
● Linking through carbon atom resulting in alkyl cyanides
& through nitrogen atom leading to isocyanides
.. – NITRITES [ O— N =O]
● The linkage through oxygen results in alkyl nitrites
through nitrogen atom, it leads to nitroalkanes NUCLEOPHILIC SUBSTITUTION REACTION MECHANISM
SUBSTITUTION REACTION SUBSTITUTION REACTION
BIMOLECULAR SN2 UNIMOLECULAR SN1 ● 2nd order reaction ● 1st order reaction ● One step mechanism ● Two step mechanism ● Product formation takes place by ● Product formation takes place by transition state carbocation intermediate ● No carbon rearrangement ● Carbocation rearrangement ● Inversion of stereochemistry ● Product can be a racemic mixture happens all the time since stereochemistry retention or inversion can happen ● Reaction is favoured by polar aprotic solvents ● Reaction is favoured by polar protic solvents SN2 MECHANISM
Nu - Nucleophile L - Leaving group Nu- will attack the opposite side of the leaving group x,y,z - Alkyl groups ➔ The order of reactivity of alkyl halide to SN2 reaction CH3 CH3 | CH3-Br > CH3- CH2- Br > CH-Br > H3C - C - Br CH3 | CH3
❏ elimination of hydrogen atom from β-carbon and a halogen atom from the α-carbon called β-elimination ( on heated with alcoholic potassium hydroxide)
B = Base X = Leaving group 3.REACTION WITH METALS
❏ Alkyl magnesium halide, RMgX, referred as Grignard Reagents
❏ Are obtained by the reaction of haloalkanes with magnesium
metal in dry ether
Dry ether CH3CH2Br + Mg CH3CH2MgBr
❏ Wurtz reaction Alkyl halides react with sodium in dry ether to give hydrocarbons containing double the number of carbon atoms present in the Halide
2RX + 2Na RR + 2NaX
HALOARENES ➢ Halogen atom is attached to sp2 hybridised C atom
❏ PREPARATIONS ❏ PHYSICAL PROPERTIES ❏ CHEMICAL REACTIONS PREPARATIONS
1. FROM HYDROCARBON 2. SANDMEYER’S REACTION 3. GATTERMANN REACTION PREPARATIONS
1. FROM HYDROCARBON BY ELECTROPHILIC SUBSTITUTION
CH3 Fe dark + X2 +
p-Halo toluene o -Halo toluene
CH3 catalysts : iron or iron(III) chloride
Fluoro compounds are not prepared by this method due to high reactivity of fluorine 2.FROM AMINES BY SANDMEYER’S REACTION
NaNO2+HX
273 - 278 K
Primary aromatic Benzene diazonium
amine halide
Mixing the solution of freshly prepared diazonium salt with cuprous chloride or cuprous bromide results in the replacement of the diazonium group X
Cu2X2 + N2 (Sandmeyers Reaction)
Aryl halide X = Cl, Br
I Diazonium salt
KI + N2
Replacement of the diazonium group by iodine does not require the presence of cuprous halide and is done simply by shaking the diazonium salt with potassium iodide 3.GATTERMANN REACTION Cl
Cu/HCl + N2
Chlorobenzene
Br Diazonium salt
Cu/HBr + N2
Bromobenzene PHYSICAL PROPERTIES 1. MELTING POINT
❏ The para-isomers are high melting as compared to their
ortho and meta-isomers.
❏ It is due to symmetry of para-isomers that fits in crystal
lattice better as compared to ortho- and meta-isomers
Cl Cl Cl Cl
Cl b.p = 448 K b.p = 453K b.p = 446 K m.p = 256K m.p = 249 K m.p = 323 K Cl CHEMICAL REACTION
➔ Allylic and benzylic halides show high reactivity towards the SN1 reaction.
➔ The carbocation thus formed gets stabilised through resonance
+ CH2＝C -C+H2 CH2- C＝ CH2 H H
➔ For a given alkyl group, the reactivity of the halide, R-X, follows the same order in both the SN1 and SN2 mechanisms
R–I > R–Br > R–Cl >> R–F
NUCLEOPHILIC SUBSTITUTION REACTION
❏ Aryl halides are extremely less reactive towards nucleophilic
substitution reactions due to the following reasons
1.Resonance Effect 2.Difference in hybridisation of carbon atom in C—X bond 3.Instability of phenyl cation
4.Because of the possible repulsion, it is less likely for the electron
rich nucleophile to approach electron rich arenes 1.RESONANCE EFFECT
In haloarenes, the electron pairs on halogen atom are in conjugation
with p-electrons of the ring
● C—Cl bond acquires a partial double bond character due to resonance
● The bond cleavage in haloarene is difficult than haloalkane ● So they are less reactive towards nucleophilic substitution reaction 2.DIFFERENCE IN HYBRIDISATION OF CARBON ATOM IN C-X BOND
X H 2 SP Hybrid Carbon SP3 Hybrid Carbon C R X H
Haloarenes are less reactive than Haloalkanes towards nucleophilic substitution reaction Why this Haloarenes are less reactive than Haloalkanes towards nucleophilic substitution reaction? ★ The sp2 hybridised carbon with a greater s-character is more electronegative and can hold the electron pair of C—X bond more tightly than sp3 -hybridised carbon in haloalkane with less s-character ★ Thus, C—Cl bond length in haloalkane is 177pm while in haloarene is 169 pm. Since it is difficult to break a shorter bond than a longer bond 3.INSTABILITY OF PHENYL CATION
★ In haloarenes, the phenyl cation formed as a result of
self-ionisation will not be stabilised by resonance and therefore, SN1 mechanism is ruled out 4.ELECTRONIC REPULSION
★ Because of the possible repulsion, it is less likely for the electron
rich nucleophile to approach electron rich arenes REPLACEMENT OF HYDROXYL GROUP
Cl OH
1. NaOH, 632K, 300 atm
2. H+
Chlorobenzene Phenol
Reactant: Chlorobenzene Product: Phenol Condition: temp - 632k Pressure - 300 atm ★ The presence of an electron withdrawing group (-NO2 ) at ortho- and para-positions increases the reactivity of haloarenes
Cl OH 1. NaOH, 443K
2. H+
NO2 NO2 Cl Cl NO2 NO2 1. NaOH, 368K
2. H+
NO2 NO2 Cl OH NO2 NO2 NO2 NO2 Warm
H2O
NO2 NO2
No effect on reactivity of haloarenes is observed by the presence of electron
withdrawing group at meta-position Then why not at meta position ? ELECTROPHILIC SUBSTITUTION REACTION
★ Due to resonance, the electron density increases more at ortho- and
para-positions than at meta-positions
★ Halogen atom because of its –I effect has some tendency to withdraw
electrons from the benzene ring
★ The ring gets somewhat deactivated as compared to benzene
★ So the electrophilic substitution reactions in haloarenes occur slowly and
require more drastic conditions as compared to those in benzene
1) production of the freon 1) Depresses the central nervous
refrigerant R-22 system 2) general anaesthetic in surgery 2) Breathing short time - dizziness, 3) Metal cleaning and finishing fatigue, and headache. solvent 3) damage to the liver( CCl4 to Phosgene.
2 CHCl3 + O2 2 COCl2 + 2HCl
Phosgene TRIIODOMETHANE (IODOFORM)
USES
➢ It was used earlier as an antiseptic but the antiseptic properties are due to the liberation of free iodine and not due to iodoform itself FREONS
● Extremely stable, unreactive, non-toxic, non-corrosive and easily liquefiable gases
● Produced for aerosol propellants, refrigeration and air conditioning purposes ● In stratosphere, freon is able to initiate radical chain reactions that can upset the natural ozone balance
Cl F
Cl C Cl Cl C Cl
F F Freon - 12 Freon - 11 Dichlorodiphenyltrichloroethane(DDT)
USES DRAWBACKS
1. first chlorinated organic insecticides 1) insects developed resistance to DDT
2. World War II - against the mosquito 2) DDT is not metabolised very rapidly by that spreads malaria animals; instead, it is deposited and stored in the fatty tissues
