HALOALKANES AND HALOARENES

 They persist in the environment due to resistance to breakdown by soil bacteria

 Great importance in medicine and healthcare
E.g. - Chlorine-containing antibiotic chloramphenicol produced by soil microorganisms is
effective in treatment of typhoid
Body produces iodine-containing hormone thyroxine, whose deficiency causes goiter
 Synthetic halogen compounds
E.g. - Chloroquine for treatment of malaria
Halothane (CF3CHClBr) used as anesthetic

Classification

1) On the basis of number of halogen atoms

 Depends on number of halogen atoms (X) in structure
 May be Mono Tetra
Di Penta
Tri

2) On the basis of nature of Carbon of C-X Bond

a) sp3 C-X Bond

 Alkyl halides: X is bonded to an alkyl group
Form homologous series with formula Cn H2n+1 X
Classified into 1°, 2°, 3° depending on nature of C-atom to which X is attached

 Allylic halides: X is bonded to sp3 hybridized C-atom next to carbon C==C (allylic carbon)

 Benzyl halides: X is bonded to sp3 hybridized carbon atom next to an aromatic ring (benzylic
carbon)

b) sp2 C-X Bond

 Vinylic halides: X is bonded to sp2 hybridized C-atom of C==C (vinylic carbon)
 Aryl halides: X is bonded to sp2 hybridized C-atom of aromatic ring

Isomerism

 Chain isomerism
 4+ C-atoms
 Make branched or straight chain compounds

 Positional isomerism
 3+ C-atoms
 Have halogen atoms at different carbon number
Nomenclature

1) Mono-substituted Haloalkane

Common/ trivial name: Alkyl halide

IUPAC name: Haloalkane

2) Di-substituted Haloalkane

IUPAC name: Dihaloalkane

Trivial name:
 Geminal halides: X present on same C-atom
Alkylidene halide
 Vicinal halides: X present on adjacent C-atoms
Alkylene dihalide

3) Haloarene
Prefix ‘halo’ before name of aromatic hydrocarbon
Prefixes o-, m-, p- are used in common system

Nature of C-X Bond

 Electronegativity of X is greater than that of C-atom, due to which shared pair of electrons in C-X
Bond lies closer to X. As a result, X bears partial negative charge and C-atom bears partial
positive charge

 Down the group, size of X increases. F is smallest and I is largest. Consequently, bond length
increases from C-F to C-I

 F to I, electronegativity decreases; therefore, polarity of C-X bond decreases

 In haloarenes, sp2 hybridized C of benzene is bonded to X. C-X is polar due to high

electronegativity of X. Lone pair of e.- of X is involved in resonance with benzene ring. So, C-X
bond acquires partial double bond character

 C-X bond of haloarenes is less polar than C-X bond of haloalkanes as dipole moment is lower

 C-X bond is shorter in haloarenes as they are more electron rich, due to presence of double bond,
than haloalkanes. The benzene ring as a whole, due to resonance, is strongly attracted towards
electronegative X

 Haloarenes are more stable than haloalkanes because C-atom in former is sp2 hybridized, while in
latter it is sp3 hybridized. sp2 C-atom is more electronegative due to more s-character; hence, it is
more stable

*situ- synthesis tube

Physical Properties

 Physical State
a) Alkyl halides are colorless when pure
b) Bromides, iodides develop color when exposed to light
c) Methyl chloride/ bromide, ethyl chloride some chlorofluoromethanes are gases at room temp
d) Higher members are liquids or solids
e) Many volatile halogen compounds have sweet smell

 Melting and Boiling Points

a) Generally polar. Due to greater polarity and higher molecular mass compared to parent
hydrocarbon, intermolecular f.o.a (dipole- dipole and Van der Waals) between molecules are
stronger in halogen derivatives

b) As molecular mass increases, m.p. and b.p. increases as attractions get stronger, as molecules get
bigger in size and have more electrons

c) For same alkyl group, b.p. of alkyl halides decreases in order

RI > RBr > RCl > RF

because with increase in size and mass of X, magnitude of Van der Waals’ forces increases

d) As size of alkyl group decreases, b.p. decreases for same X

CH3CH2CH2X > CH3CH2X > CH3X

For isomeric alkyl halides, b.p. decreases as branching increases, because with increase in
branching, surface area of alkyl halide decreases and hence, magnitude of Van der Waals’ f.o.a.
decreases

e) B.p. of chloro, bromo, iodo compounds increases as number of X increases

f) B.p. of isomeric dihalobenzenes are nearly same. However, p- isomers have high m.p. as
compared to o- and m- isomers, as due to symmetry of p- isomers it fits in crystal lattice better

 Density
Fluoro and chloro alkanes are lighter than water, while bromo, iodo and polychloro derivatives
are heavier than water. With increase in number of C-atoms and X, and atomic mass of X, density
increases

 Solubility
a) For haloalkanes to dissolve in water, E is required to overcome attractions between haloalkane
molecules and hydrogen bonds between water molecules. Less E is released when new attractions
are set up between haloalkanes and water molecules, as these are not as strong as original
hydrogen bonds in water. As a result, solubility of haloalkanes in water is low
b) They are soluble in organic solvents as new intermolecular attraction between haloalkanes and
solvent molecules are of same strength as the ones being broken

 Stability decreases as strength of C-X bond decreases

RF > RCl > RBr > RI
 Dipole Moment
As electronegativity of X decreases from Cl to I, dipole moment also decreases, whereas fluorides
have lower dipole moment than chlorides because of very small size of F, which outweighs effect of
greater electronegativity

CH3Cl > CH3F > CH3Br > CH3I

Stereochemistry

 A beam of ordinary light consists of EM waves vibrating in all planes of space. When light is
passed through a Nicol prism, it becomes plane polarized light, which vibrates only in one plane

 When solutions of certain organic compounds are placing in path of PPL, they rotate path of light
either to left or right. Such a substance is called optically active substance

 Right rotating- dextrorotatory/ d-form/ + / clockwise

Left rotating- laevorotatory/ l-form/ - / anticlockwise

 D- and l-forms of compound are called optical isomers and this phenomenon called optical
isomerism

 Angle through which PPL is rotated is measured by instrument called polarimeter

 Asymmetric C-atom/ Stereocenter- All atoms/ groups attached to C-atom are different
Resulting molecule would lack symmetry; called asymmetric molecule. This asymmetry is
responsible for optical activity

 An object/ molecule which is not superimposable on its mirror image; called chiral. This property
called chirality
An object which is superimposable on mirror image; called achiral

 Enantiomers: Optical isomers which are non-superimposable mirror images of each other.
Phenomenon called enantiomerism. Enantiomers have identical physical and chemical properties,
but differ w.r.t. rotation of PPL

 Racemic mixture: Equimolar mixture containing 2 enantiomers, having zero optical rotation, as
rotation due to one isomer will be cancelled by rotation due to the other isomer. Represented as
dl- / ± form and will be optically inactive
 Racemization- Process of converting d- or l- form of an optically-active compound into racemic
form (dl)

 Chiral/ Optical Resolution: Process of separating racemic mixture into its enantiomers

 When relative spatial arrangement of bonds to asymmetric center in chiral molecule remains
same before and after reaction, reaction is said to occur with retention of configuration

 Meso compound: Compounds which have many stereocenters, but are optically inactive as plane
of symmetry lies within. Cannot be resolved due to internal symmetry
*dl- form under absolute configuration
Poly Halogen Compounds
Carbon compounds with more than one X

I. Dichloromethane (Methylene chloride- CH2Cl2)

 Colorless, sweet-smelling, volatile liquid
 Low b.p.- 313 K
 Prepared industrially by direct chlorination of methane in presence of diffused sunlight
ℎ𝜐
𝐶𝐻4 + 2 𝐶𝑙2 → 𝐶𝐻2 𝐶𝑙2 + 2 𝐻𝐶𝑙

 Uses:
i. Solvent
ii. Paint remover
iii. Propellant in aerosols
iv. Metal cleaning and finishing solvent
v. Solvent in manufacture of drugs
vi. Refrigerant
vii. Dewaxing agent

 Harmful Effects:
i. Harms human CNS
ii. Exposure to low levels leads to impaired hearing and vision
iii. Exposure to high levels causes dizziness, nausea, tingling and numbness in
fingers and toes
iv. Direct contact with skin causes intense burning and mild redness of the skin
v. Direct contact with eyes can burn the cornea

II. Trichloromethane (Chloroform- CHCl3)

 Colorless, oily liquid, peculiar smell and a burning taste
 Slowly oxidized by air in presence of light to extremely poisonous gas carbonyl chloride
or phosgene (COCl2). Therefore, stored in dark-colored bottles, to avoid oxidation. These
bottles are completely filled with chloroform up to the brim and properly stoppered to
keep the air out. 1% ethanol is added so as to convert phosgene gas to diethyl carbonate,
which is non-volatile and non-toxic
𝑆𝑢𝑛𝑙𝑖𝑔ℎ𝑡
2 𝐶𝐻𝐶𝑙3 + 𝑂2 → 2 𝐶𝑂𝐶𝑙2 + 2 𝐻𝐶𝑙

𝐶𝑂𝐶𝑙2 + 2 𝐶2 𝐻5 𝑂𝐻 → (𝐶2 𝐻5 )2 𝐶𝑂3 + 2 𝐻𝐶𝑙

 Uses:
i. Lab reagent
ii. Medicines
iii. In preparation of chloropicrin
iv. Production of freon refrigerant, R-22
v. Anesthetic (earlier)
vi. Solvent for fats, alkaloids, iodine, etc.

 Harmful Effects:
i. Affects CNS. Inhaling 900 PPM in air for a short time causes dizziness, fatigue,
headache
ii. Chronic exposure damages liver, kidney due to formation of phosgene in body
 iii. Skin develops sore if immersed directly into chloroformed

III. Triiodomethane (Iodoform- CHI3)

 Yellow- colored crystalline solid, characteristic unpleasant odor
 Uses:
i. Antiseptic (earlier- replaced by other formulations due to unpleasant smell), due
to liberation of free iodine
∆
4 𝐶𝐻𝐼3 + 5𝑂2 → 6𝐼2 + 4𝐶𝑂2 + 2 𝐻2 𝑂

ii. Manufacture of pharmaceuticals

IV. Tetrachloromethane (Carbon tetrachloride- CCl4)

 Colorless, oily liquids with smell
 B.p.- 350 K
ℎ𝜈
𝐶𝐻𝐶𝑙3 + 𝐶𝑙2 → 𝐶𝐶𝑙4 + 𝐻𝐶𝑙

 Uses:
i. Manufacture of refrigerants and propellants (large quantities)
ii. Feedstock in synthesis of CFCs and other chemicals
iii. Fire extinguisher
iv. Cleaning fluid, degreasing agent, spot remover

 Harmful Effects:
i. Exposure causes liver cancer in humans
ii. Most common effects are dizziness, lightheadedness, nausea, vomiting, which
can cause permanent damage to nerve cells, and in severe cases, can lead to
coma, unconsciousness or death
iii. Exposure to vapors can make heartbeat irregular or stop it
iv. When brought in contact with eyes, may cause irritation
v. Harmful to environment. When released in air, it rises in atmosphere and
depletes ozone layer, which causes increased human exposure to UV rays

V. Freons (chlorofluorocarbon compounds of methane and ethane)

 Extremely stable, non-toxic, non-corrosive, easily liquefiable gases
 Freon- 12 (dichlorodifluoromethane- CCl2F2) is one of the most common freons in
industrial use. Manufactured from CCl4 by Swarts reaction
3 𝐶𝐶𝑙4 + 2 𝑆𝑏𝐹3 → 2 𝑆𝑏𝐶𝑙3 + 3 𝐶𝐶𝑙2 𝐹2

 Uses:
i. Refrigerant in fridge and AC
ii. Propellants for aerosols and foams to spray out deodorants, cleansers, shaving
creams
 Harmful Effects
Most freons make their way into the atmosphere, where they undergo photochemical
decomposition, initiate radical chain reactions for depletion of ozone layer

VI. p, p- Dichlorodiphenyltrichloroethane (DDT)

 First chlorinated organic insecticide
 1873- Paul Muller- Nobel Prize
  White powder, insoluble in water, soluble in oil
 Uses:
i. Cheap powerful insecticide
ii. Effective against anopheles mosquito (malaria) and lice carrying typhus

 Harmful Effects
i. Non-biodegradable, extremely stable compound, which acts as water pollutant
and kills aquatic animals
ii. When higher animals feed on dead fish killed by DDT, it enters food chain
iii. DDT gets stored in fat issues of animals and increases in amount over time.
Research shows that deposition in long run may cause cancer and other harmful
diseases
# Nitro Bromo Succinimide
Reagent which undergoes allylic/ benzylic substitution and ESR

𝑁𝐵𝑆
→
𝑁𝐵𝑆
CH3 – CH = CH2 → Br – CH2 – CH = CH2
 HALOALKANES

Preparation

 From Alcohols
 Most convenient method
 By action of halogen acids
 R- OH + H-X  RX + H2O
 R.o.R. depends on nature of alcohol and halogen acid
 Reaction of 1°, 2° alcohols with halogen acids require presence of catalyst ZnCl2 (Lewis
acid), which helps in cleavage of C-O bond

Stability of C+ ∝ Benzylic > Allylic > 3° > 2° > 1°

 Groove’s Process: Chloro alkanes prepared by reaction of Lucas reagent (HCl + anhyd.
ZnCl2) with 1°, 2° alcohols
 3° alcohols are very reactive, so reactions conducted by simply shaking concentrated HCl
at room temp, even in absence of ZnCl2

HCl + ZnCl2  Zn-Cl3 + H+

R-OH + H+  R+ + H2O
R + Zn-Cl3  R-Cl + ZnCl2
+

3° is most stable, thus RCl forms fastest. Hence, turbidity forms immediately

 Bromo alkanes prepared by heating alcohol with constant boiling HBr (48%) in presence
of conc. H2SO4
HBr (unstable due to size) can also be generated in situ by action of conc. H2SO4 on KBr
/ NaBr
∆
ROH + KBr + H2SO4 → RBr + KHSO4 + H2O

 Iodo alkanes prepared by heating alcohol with constant boiling HI (57%)

HI (unstable due to size) can be generated in situ by action of 95% phosphoric acid on KI
∆
ROH + KI + H3PO4 → RI + KH2PO4 + H2O

 2°, 3° bromides and iodides cannot be prepared from respective alcohols in presence of
conc. H2SO4 as they undergo dehydration to form alkenes
 H2SO4 is used in case of bromine and H3PO4 is used in case of iodine as former is a
strong oxidizing agent, which oxidizes HI to I2. Hence, mild oxidizing agent is used

 Order of reactivity of alcohols with given halo acid (Inductive Effect)

3° > 2° > 1°
 Order of reactivity of halogen acid with alcohol
HI > HBr > HCl > HF

 By action of phosphorus halides

 Chloro alkanes are obtained by action of PCl5 or PCl3 on alcohols
 2 R-OH + PCl5  2 R-Cl + POCl3 + H2O
3 R-OH + PCl3  3 R-Cl + H3PO3
3 R-OH + POCl3  3 R-Cl + H3PO4

Phosphoryl chloride (POCl3)

Phosphorus acid (H3PO4)

 Bromo and iodo alkanes are prepared by reaction of PBr3 and PI3 with alcohol
They can be generated in situ by reaction of red phosphorus with bromine and iodine
𝑅𝑒𝑑 𝑃/ 𝑋2
𝑅 − 𝑂𝐻 → 𝑅 − 𝑋

 By action of thionyl chloride

 Chloro alkanes are prepared by refluxing alcohol with SOCl2 in presence of pyridine

𝑃𝑦𝑟𝑖𝑑𝑖𝑛𝑒
𝐶𝐻3 𝐶𝐻2 𝑂𝐻 + 𝑆𝑂𝐶𝑙2 → 𝐶𝐻3 𝐶𝐻2 𝐶𝑙 + 𝑆𝑂2 + 𝐻𝐶𝑙

By-products (SO2, HCl) are gases. Hence, preferred method

 Above 3 methods not applicable for preparation of aryl halides as C-O bond in phenol is
a partial double bond; so, difficult to break

 From Hydrocarbons
 By free radical halogenation
 Alkanes react with Cl2 and Br2 in presence of UV light to form haloalkanes
 Reaction proceeds through free radical mechanism
 Gives complex mixture of isomeric mono and poly haloalkanes which are difficult to separate
 Allylic Halogenation: When alkene is chlorinated with heat, Cl2 breaks and attaches to allylic
C-atom
 When Br2 is added in presence of CS2 to alkene, Br2 breaks and attaches to C=C (both)
 For ease of substitution,
3° > 2° > 1°

o From alkenes
 Addition of hydrogen halides:
C == C + HX  H – C – C - X

In case of addition to unsymmetrical alkenes, Markovnikov Rule is followed: Br goes to

carbon with less hydrogen atoms

In presence of peroxide, addition of HBr to unsymmetrical alkene proceeds contrary to

Markovnikov Rule. This effect is known as Kharasch Effect or Peroxide Effect: Br goes
to carbon with more hydrogen atoms

 Addition of halogens: Addition of bromine to alkene in CCl4 results in discharge of

reddish brown color of bromine. Imp method for detection of double bond. Addition
results in synthesis of vic-dibromides which are colorless
 𝐶𝐶𝑙4
𝐻2 𝐶 = 𝐶𝐻2 + 𝐵𝑟2 → 𝐵𝑟𝐶𝐻2 𝐶𝐻2 𝐵𝑟

 Halogen Exchange
o Finkelstein Reaction- Alkyl iodides prepared by reaction of alkyl chloride/ bromide with NaI in
dry acetone
𝐴𝑐𝑒𝑡𝑜𝑛𝑒
𝑅 − 𝑋 + 𝑁𝑎𝐼 → 𝑅 − 𝐼 + 𝑁𝑎𝑋

NaBr/ NaCl formed gets precipitated in acetone, which facilitates forward reaction

o Swarts Reaction- Fluoro alkanes prepared by treating alkyl chloride/ bromide in presence of
metallic fluoride such as AgF/ Hg2F2/ CoF2/ SbF3,to give products RF and MX

 From Silver Salts of Acids

Borodine- Hunsdiecker Reaction- Bromo alkanes prepared by refluxing silver salt of acids with
bromine in CCl4
𝐶𝐶𝑙4
𝐶𝐻3 𝐶𝑂𝑂𝐴𝑔 + 𝐵𝑟2 → 𝐶𝐻3 𝐵𝑟 + 𝐶𝑂2 + 𝐴𝑔𝐵𝑟

Chemical Reactions

 NSR
When nucleophile stronger than halide reacts with haloalkane having partial positive charge on C-
atom bonded to X, substitution reaction takes place and X (called leaving group) departs as halide ion.
Since substitution reaction is initiated by nucleophile, called NSR

 Ambident nucleophile: Nucleophile with 2 nucleophilic centers, but can attack only through one
center at a time

When cyanide links through C-atom, results in formation of alkyl cyanide/nitrile

N-atom, results in formation of alkyl isocyanides

When nitrite ion links through O, alkyl nitrites

N, nitro alkanes

 Among alkyl halides, iodide ion is best leaving group, and hence, iodo alkanes undergo NSR at
fastest rate; compared to fluoride ion
  KCN is predominantly ionic and provides cyanide ions in solution. Although both C and N are
in position to donate electron pairs, attack takes place mainly through C since C-C bond is more
stable than C-N bond. However, AgCN is mainly covalent in nature. Only electron pair of
nitrogen is available for bond formation; as a result, alkyl isocyanide is chief product
 KNO2 is predominantly ionic and one of the O has negative charge. Nucleophilic attack through
this negatively charged O on alkyl halide mainly gives alkyl nitrites. In contrast, AgNO2 is
covalent and both O and N carry lone pair of electrons. Since N is less electronegative than O,
lone pair of electrons of N is more easily available for bond formation. As a result, nitro alkane
is chief product

o Bimolecular Nucleophilic Substitution- SN2

(i) 2 molecules take part in determining R.o.R.

(ii) Rate depends on conc. of both reactants

(iii) Incoming nucleophile approaches RX and starts interacting with it, due to which C-X
bond starts breaking and new C-Nu bond starts forming. These 2 processes take place
simultaneously in single step, transition step, and no intermediate is formed
(iv) In transition state, C is simultaneously bonded to incoming nucleophile and outgoing
leaving group, i.e. C is bonded to 5 atoms. This state is unstable, results in formation of
product

(v) Inversion of Configuration/ Walden Inversion: Attack of Nu occurs from backside while
leaving group leaves from front. As this happens, configuration of C-atom under attack
inverts

(vi) Presence of bulky alkyl groups blocks approach of Nu to C due to steric hindrance, which
is why simple alkyl halides, methyl halides and primary alkyl halides react predominantly
by SN2 mechanism
Tertiary halides are least reactive due to presence of bulky groups
Non-polar solvents favor SN2 mechanism

Methyl halide > 1° halide > 2° halide > 3° halide

o Unimolecular Nucleophilic Substitution- SN1

a) Only 1 molecule involved in determining R.o.R.
b) Carried out in polar protic solvents as they stabilize carbocation by solvation
 *Polar protic solvent has H bonded to F, O, N; they readily donate proton (H+); dissolve
both anion and cation

c) Formation of carbocation takes place due to heterolytic cleavage of C-X bond. This is a
slow and reversible step (rate-determining) and involves only one reactant, and therefore,
depends only on concentration of RX
d) Nu attacks carbocation formed in step 1

e) Greater the stability of carbocation, greater will be its ease of formation from RX and
faster will be R.o.R.
3° halide > 2° halide > 1° halide > Methyl halide

f) Allylic and benzylic halides show high reactivity towards SN1 reaction as carbocation
formed gets stabilized through resonance
g) For given alkyl group, reactivity of halide follows same order in both mechanisms
RI > RBr > RCl > RF

h) In SN1 reactions, if alkyl halide is optically active, product obtained is racemic mixture.
Intermediate carbocation formed in slow step being sp2 hybridized is planar species
(achiral). Therefore, attack of nucleophile can occur from both faces with equal ease of
forming a mixture of two enantiomers

o Ammonolysis
Whenever RX is allowed to react with alc. NH3, alkyl amine is formed
RX + H – NH2 (alc.)  R - NH2 + HX [1°]

Lone pair of N attacks R; hence, partial positive charge develops on N. Thus, H and X break and
form HX
a) 2° : R - NH2 + RX  R2 - NH + HX

b) 3° : R2 - NH + RX  R3 - N + HX

c) 4° : R3 - N + RX  R4 – N+ + X-  R4NX

 Elimination Reaction
o Dehydrohalogenation
When haloalkanes with β-hydrogen atom is heated with alc. KOH solution, then alkene is formed.
In this reaction, H is eliminated from β-carbon and X is lost from α-carbon. As a result, alkene is
formed as product. Due to involvement of elimination of β-hydrogen and α-halogen, process is
also called αβ-elimination

*Aq. KOH gives OH- as Nu, while alc. KOH gives OH- as base
 Alkene is formed acc. to Saytzeff Rule: In dehydrohalogenation reactions, preferred product is
that alkene which has greater number of alkyl groups attached to doubly-bonded carbon atoms

*Elimination vs Substitution
i. Nature of alkyl halide: 1° alkyl halide will prefer SN2 reaction. 2° alkyl halide can undergo
substitution or elimination depending on strength of Nu. 3° alkyl halide will undergo substitution
or elimination depending upon stability of carbocation or more substituted alkene
ii. Strength and size of Nu/ base: Bulkier Nu will carry out elimination more easily than substitution
as it prefers to act as a base and abstract a proton rather than approach a tetravalent C-atom, due
to stearic reasons, and vice versa. Stronger Nu like C2H5O- will bring out elimination, whereas
Nu like OH- will bring out substitution
iii. Conditions of reaction like temp, pressure

 Reactions with Metals

o Organometallic Compounds: Most organic compounds react with certain metals to give
compounds containing carbon-metal bonds
o Action with Mg- Formation of Grignard reagent
 Victor Grignard- 1900
 R-MgX commonly called Grignard reagent
𝐷𝑟𝑦 𝐸𝑡ℎ𝑒𝑟
𝐶𝐻3 𝐶𝐻2 𝐵𝑟 + 𝑀𝑔 → 𝐶𝐻3 𝐶𝐻2 𝑀𝑔𝐵𝑟

 C-Mg bond is covalent but highly polar, with carbon pulling electrons from
electropositive Mg, Mg-X bond is essentially ionic

 They are highly reactive and react with any source of proton to give hydrocarbons. Even
alcohols, amines and water are sufficiently acidic to convert them to corresponding
hydrocarbons
𝑅𝑀𝑔𝑋 + 𝐻2 𝑂 → 𝑅𝐻 + 𝑀𝑔(𝑂𝐻)𝑋
 Due to high reactivity, necessary to avoid even traces of moisture from Grignard reagent

o Action with Na- Wurtz Reaction

 Alkyl halides react with Na in presence of dry ether to form hydrocarbons containing
double the number of carbon atoms present in halide

𝐷𝑟𝑦 𝐸𝑡ℎ𝑒𝑟
2 𝑅𝑋 + 2 𝑁𝑎 → 2 𝑅 + 2 𝑁𝑎𝑋

# Esters
RX + RCOOAg  RCOOR + AgX

# Sodium Alkoxide
RX + RONa  ROR +NaX

# Sodium Ethyne
RX +  NaX + R -

# KSH
RX + KSH  R – SH + KX
RSH- Thionol

# Carbyl Amine/ Alkyl Isocyanide Test

Mixture of primary amine and CHCl3 is boiled with alc. KOH (CHCl3: KOH = 1:3) to give bad- smelling
compound, alkyl isocyanide/ carbyl amine
 HALOARENES

Preparation

 Electrophilic Aromatic Substitution

 Aryl chlorides/ bromides are easily prepared by EAS of arenes with chlorine/ bromine in
the dark at ordinary temp, in presence of Lewis acid catalysts like FeCl3, FeBr3, and
AlCl3. Lewis acid used to generate electrophile, Cl+ / Br+

𝐹𝑒, 𝐷𝑎𝑟𝑘
+ 𝐶𝑙2 → +

 o- and p- isomers easily separated due to large difference in m.p.

 Reaction with iodine is reversible and requires presence of oxidizing agent (HNO3, HIO4)
to oxidize HI formed during iodination
 Reaction with fluorine violent, uncontrollable; hence, cannot be prepared by direct
fluorination

 From Diazonium Salts

 Sandmeyer's Reaction:
Diazonium salt prepared by treating aniline dissolved in cold aqueous mineral acid with
aq. solution of sodium nitrite at low temp (0°-5° C.)

𝑁𝑎𝑁𝑂2 +𝐻𝐶𝑙 (273−278 𝐾)

→

 Bromo/ chloro arenes prepared by treating freshly prepared diazonium salt solution with
cuprous bromide/ chloride

𝐶𝑢2 𝐶𝑙2
→ + N2 (↑)

 Iodine prepared by simply shaking diazonium salt with KI

 Gatterman’s Reaction: Sandmeyer's reaction modified by using copper powder in place
of cuprous halide

𝐶𝑢, 𝐻𝐶𝑙
→ + N2 (↑)

 Balz- Schiemann Reaction: Diazonium group is replaced using fluoroboric acid

Chemical Reactions

 NSR

o Only under drastic conditions as haloarenes are chemically less reactive towards NSR than
haloalkanes. Reasons-
I. Resonance Effect: In haloarenes, lone pair of electrons on X are in conjugation with π-
electrons of ring and hence, these are localized on benzene ring. As a result of resonance,
C-X bond acquires partial double bond character. Thus bond cleavages is difficult
II. Difference in hybridization of C-atom in C-X bond: In haloalkanes, C-atoms attached to
X is sp3 hybridized, while in haloarenes, it is sp2 hybridized. sp2 hybridized C-atom with
greater s-character is more electronegative. It can hold electron pair of bond more tightly
than sp3 hybridized C-atom, with less s-character. As a result, C-X bond in haloarenes is
shorter than haloalkanes and more difficult to break
III. Instability of phenyl cation: In haloarenes, phenyl cation formed as a result of self-
ionization will not be stabilized by resonance, hence SN1 mechanism cannot occur
IV. Repulsion between electron rich attacking nucleophiles and electron rich arenes

o Replacement by hydroxyl group

Chlorobenzene when heated in aq. solution of NaOH at temp of 623 K, pressure of 300 ATM,
forms phenol

Presence of electron withdrawing groups like –NO2 and -CN at o-, p- positions of haloarenes w.r.t
X greatly activates benzene ring towards NSR. Further, greater the number of such groups at o-,
p- positions, more reactive is the halo arene

NO2 group at m- position has no effect on reactivity as there is no such structure in which
negative charge is present on C-atom bearing NO2 group. Therefore, presence of nitro group at
m- position does not stabilize negative charge
 ESR
o Stronger electrophile replaces weaker electrophile
o Occurs slowly and requires more drastic conditions, due to ortho para directing influence of X
attached to benzene ring
o Due to resonance, electron density increases more at o-, p- positions than at m- position. Hence,
electrophilic reactions occur at o- and p- positions. X has tendency to withdraw electrons due to
which electron density on benzene ring decreases (-I effect) and ring gets deactivated. Hence,
ESR in halo arene occurs at slower rate

o Halogenation: Reacting haloarenes with halogens in presence of ferric salt

o Nitration: Heating halo arene with conc. HNO3 in presence of conc. H2SO4

o Sulphonation: Heating halo arene with conc. H2SO4

o Benzylation:

Anhyd. AlCl3

o Friedel- Crafts Reactions: Treating haloarenes with alkyl chloride or acyl chloride in presence of
anhyd. AlCl3
 Reaction with Metals

o Wurtz- Fittig Reaction: Aryl halide is heated with alkyl halide in presence of Na in dry ether. X is
replaced by alkyl group and alkyl arene is formed

o Fittig Reaction: Haloarenes react with Na in presence of dry ether to form diphenyl

o Reaction with Mg: Grignard reagent is formed

o Reaction with Li: Bromo/ iodo arenes react with Li in presence of ether to form corresponding
organometallic compounds

𝐷𝑟𝑦 𝐸𝑡ℎ𝑒𝑟
+ Li →

o Ullmann Reaction: Iodo benzene is heated with Cu powder in sealed tube to form diphenyl

∆
2 + 2 Cu → + Cu2I2

 Reduction
*Drastic Conditions-
o High temp
o High pressure
o Strong electron-withdrawing group on ring

*All compounds with double bond are meta-directing

*Aniline undergoes reactions because it is a Lewis base. It reacts with FeCl3, AlCl3 to form salt and
hence, becomes electron- deactivating/ withdrawing group

#Relative Configuration
o Cahn-Ingold-Prelog Rule

o R/ S does not necessarily mean +/ -

o R- Rectus
S- Siniski