Chemistry

Lecture 3 By: Syed Ali Shan

Alkyl Halides, Alcohols, Phenol

Outline:

Alkyl Halides/Halogenoalkanes:

Importance of Halogenoalkanes
Reactions of Alkyl Halides
Nucleophilic substitution reactions and mechanisms

Alcohols:

Primary, secondary and tertiary alcohols

Preparation of Ethanol
Reactions of alcohols

Phenol:

Reactions of phenol
Acidity of water, ethanol and phenol

Alkyl Halides/Halogenoalkanes(Haloalkanes)

 General formula CnH2n+1X (for one halogen atom)

 Most methyl halides are gases at room temperature
 Alkyl fluorides and alkyl chlorides mostly are lighter than water
 Alkyl bromides and alkyl iodides are heavier than water
 Alkyl halides prefer nucleophilic substitution reactions
 They are prepared from alcohols directly except iodide which are prepared using NaI/KI with
RCl/RBr
 Best method of preparation is from SOCl2/pyridine as the products are gases

Types:

 Primary Alkyl Halides: If carbon to which halogen atom is attached is further directly attached
with one or no carbon atom.
 Secondary Alkyl Halides: If carbon to which halogen atom is attached is further directly
attached with two carbon atoms.
 Tertiary Alkyl Halides: If carbon to which halogen atom is attached is further directly attached
with three carbon atoms.
 Importance of Halogenoalkanes

Carbon
Chlorofluorocarbons Halothane Teflon (CF2-CF2)n Chloroform tetrachloride
(CFC’S) (CHCl3) (CCl4)
2-bromo-2-chloro- Polymer of the Used to create
CCl2F2, CClF3 1,1,1- tetrafluoro- Used as solvent inert atmosphere
trifluoroethane ethylene
Used as refrigerants Used as Used in corrosion As the cleansing As the fire
anesthetic proof parts of solvent extinguisher
machinery
Used as the aerosol Non stick coating As a preservative Used as solvent in
propellants of cooking pans for anatomical halogenation of
specimen alkene/alkyne

Used for coating As anesthetic

of electrical
wiring

Reactivity:

 On basis of bond energy

R-I > R-Br > R-Cl > R-F
 On basis of bond polarity
R-F > R-Cl > R-Br > R-I
 On basis of experiments
R-I > R-Br > R-Cl > R-F

Nucleophile and Electrophile (In lecture 1)

Leaving Group: An atom or group of atoms which departs with unshaired pair of electrons when
nucleophile attacks on substrate.

 Good Leaving Groups: HSO4-, Cl-, Br-, I- (Good L.G and Nucleophile, also best L.G among them)
 Poor Leaving Groups: OH-, OR-, NH2-

Good L.G ∝ Polarizability Good L.G ∝

Reactions of Alkyl Halides and Mechansims

Nucleophilic Substitution Reactions (SN): Reactions in which halogen atom is replaced by another atom.
Occurs in presence of aqueous KOH.
 SN1 SN2

Two step mechanism One step mechanism

Nucleophile can attack from either side of carbocation Nucleophile attacks from opposite side of L.G
50 % inversion, 50 % retention in configuration 100% inversion in configuration
1st step is slow and rate determining Only step involved gives rate
Rate = k [Alkyl halide] Rate = k [Alkyl halide][OH-]
Molecularity = 1 Order = 1 Molecularity = 2 Order = 2
Favoured by polar solvent Favoured by non polar solvent
Tertiary give SN1 Primary give SN2
Secondary in polar solvents Secondary in non polar solvents
Reactivity order; 30 > 20 > 10 > CH3-X(Never
(Never give SN1) Reactivity order; CH3-X > 10 > 20 > 30
Not depend on nature of attacking nucleophile Strong nucleophile is required
Require good leaving group Require good leaving group

Examples of SN Reactions:

 With NH3:

CH3-CH2-Br
Br + NH3 → CH3-CH2-NH2(primary amine) + HBr

CH3-CH2-Br
Br + CH3-CH2-NH2 → (CH3-CH2-)2NH(sec. amine) + HBr

CH3-CH2-Br
Br + (CH3-CH2-)2NH → (CH3-CH2-)3N(tert. amine) + HBr

Br + (CH3-CH2-)3N → (CH3-CH2-)4N+Br- (Quart. amine)

CH3-CH2-Br

 With KCN:

CH3-CH2-Br
Br + KCN → CH3-CH2-CN(propane nitrile) + KBr

CH3-CH2-CN + HCl + H2O → CH3-CH2-COOH + NH4Cl

  Which alkyl halides will produce ethane nitrile?
 Which acid can be produced from 1-chloro
1 butane?

β-Elimination Reactions (E): Reactions in which β-hydrogen

hydrogen along with halogen is removed in the form
of HX by the attack of nucleophile. Occurs in presence of alcoholic KOH

E1 E2

Two step mechanism One step mechanism

Nucleophile can attack from either side of carbocation Nucleophile attacks from opposite side of L.G
1st step is slow and rate determining Only step involved gives rate
Rate = k [Alkyl halide] Rate = k [Alkyl halide][OH-]
Molecularity = 1 Order = 1 Molecularity = 2 Order = 2
Favoured by polar solvent Favoured by non polar solvent
Tertiary give E1 Primary give E2
Secondary in polar solvents Secondary in non polar solvents
Reactivity order; 30 > 20 > 10 > CH3-X(never
(never give SN1) Reactivity order; CH3-X > 10 > 20 > 30
Strong base (relatively weaker than E2) Strong base
Require good leaving group Require good leaving group

Comparison between SN and E reactions:

SN Reactions E Reactions
At low temperature At high temperature
More polar conditions Less polar conditions
Normally in aqueous conditions Normally in alcoholic conditions
Steric hinderance does not favour Steric hinderance favours
Both SN1 and E1 have 1st steps same

Some other Reactions of Alkyl Halides:

 Wurtz Synthesis:
  To prepare symmetrical alkanes
 Double no. of carbons in alkane produced than respective alkyl halide

2CH3-Cl + 2Na ⎯⎯ CH3-CH3 + 2NaCl

 Reduction of Alkyl Halides:

 To prepare alkanes
 Reduced with Zn dust in aqueous acid
 Same no. of carbons in alkane produced as of respective alkyl halide

CH3-CH2-Cl + Zn + H+ + Cl- → CH3-CH3 + ZnCl2

 Reaction with Sodium Lead Alloy (Na4Pb):

 To prepare anti knocking agents i.e. tetramethyl lead and tetraethyl lead

4CH3-Cl + Na4Pb → (CH3)4Pb + 4NaCl

4CH3-CH2-Cl + Na4Pb → (C2H5)4Pb + 4NaCl

Alcohols

 General formula is CnH2n+2O or CnH2n+1OH

Types:

 Monohydric Alcohols: Alcohols having only one –OH group

 Dihydric Alcohols: Alcohols having two –OH group
 Polyhydric Alcohols: Alcohols having more than two –OH group

Types of Monohydric Alcohols:

 Primary Alcohols: If carbon to which –OH group is attached is further directly attached with one
or no carbon atom.
 Secondary Alcohols: If carbon to which –OH group is attached is further directly attached with
two carbon atoms.
 Tertiary Alcohols: If carbon to which –OH group is attached is further directly attached with
three carbon atoms.

Preparation of Ethanol

 By Fermentation (a biochemical process occurs in presence of enzymes)

 Necessary condition are:
 Optimum temperature (25-350C)
 Proper aeration
 Dilution of solution
 Absence of any preservative
  In Pakistan prepared from molasses, starch, grains, and fruit juices.

From Molasses:

 Residue after crystallization of sugar from sugar juice

 So it is sucrose
 Sucrose on hydrolysis in presence of Invertase breaks into glucose and fructose
 Glucose further decomposes in presence of Zymase to give ethanol

C12H22O11 + H2O ⎯⎯⎯⎯⎯ C6H12O6 + C6H12O6

C6H12O6 ⎯⎯⎯⎯ 2C2H5OH + 2CO2

From Starch:

 Starch on hydrolysis in presence of Diastase breaks into maltose

 Maltose on hydrolysis in presence of Maltase breaks into glucose units
 Glucose further decomposes in presence of Zymase to give ethanol

2(C6H10O5) + nH2O ⎯⎯⎯⎯ n C12H22O11

C12H22O11 + H2O ⎯⎯⎯⎯ C6H12O6 + C6H12O6

C6H12O6 ⎯⎯⎯⎯ 2C2H5OH + 2CO2

 Ethanol never exceeds 12-14 % as beyond this limit enzyme becomes inactive
 Distillation gives Rectified spirit (95 %)
 Distillation in presence of CaO gives Absolute alcohol (100 %)
 10 % methanol is added in ethanol to avoid its drinking (denaturing)
 Pyridine or acetone can be used

Reactions of Alcohol

1.When O-H bond to is be broken 2.When C-O bond is to be broken

Act as nucleophile except as acid with only Na
Attack of electrophile on it
Show electrophilic substitution reactions except
with Na gives acid base reaction
Reactivity/Acidity; Methyl alcohol > 10 > 20 > 30
2C2H5OH + 2Na ⎯⎯ 2C2H5ONa + H2
C2H5OH + CH3MgI ⎯⎯ CH4 + Mg(I)(OC2H5)
C2H5OH + CH3COOH ⇌ CH3COOC2H5 + H2O
Act as electrophile
Attack of nucleophile on it
Show nucleophilic substitution reactions
Reactivity; 30 > 20 > 10 > Methyl alcohol
C2H5OH + SOCl2 ⎯⎯⎯⎯⎯ C2H5Cl + SO2 + HCl
C2H5OH + HCl ⎯⎯ C2H5Cl + H2O
C2H5OH + NH3 ⎯⎯ C2H5 NH2 + H2O
C2H5OH + PCl3 → C2H5Cl + H3PO3
 C2H5OH + PCl5 → C2H5Cl + POCl3+ HCl

3. Oxidation Reactions:

 KMnO4/H2SO4 ⇒ Pink colour of KMnO4 disappears

 K2Cr2O7/H2SO4 ⇒ Colour turns green due to reduction of dichromate ion (Cr+6) to
chromate ion (Cr+3)
 Primary alcohols on oxidation give aldehydes which in same conditions further oxidize to
carboxylic acids.
 Secondary alcohols on oxidation give ketones which do not oxidize further in such conditions
 Tertiary alcohols don’t oxidize rather undergo elimination reaction to give alkene
[ ] [ ]
C2H5OH (wine) CH3CHO CH3COOH (vinegar)

[ ]
CH3-CH(OH)-CH3 (CH3)2CO (acetone)

(CH3)3C-OH → CH2=C(CH3)2 + H2O

4. Dehydration:
.
C2H5OH ⎯⎯⎯⎯⎯⎯⎯ CH2=CH2 + H2O

.
2C2H5OH ⎯⎯⎯⎯⎯⎯⎯ C2H5O C2H5 + H2O

5. Lucas Test:

 Alcohols form oily layer of respective alkyl halide with HCl in presence of ZnCl2
 Primary alcohols form oily layer on heating
 Secondary alcohols form oily layer in 5-10 min.
 Tertiary alcohols form oily layer immediately

6. Iodoform Test (I2/NaOH):

 Yellow ppts. of iodoform (CHI3) forms

 Only ethanol gives iodoform test among primary alcohols
 Those secondary alcohols give iodoform test in which at least one -CH3 group is attached with α-
carbon
 Tertiary alcohols don’t give iodoform test

Phenol

 Carbolic acid
 Deliquescent
 Anesthetic
  Poisonous
 Used to prepare pharmaceutical drugs
 As disinfectant in hospitals and washrooms
 More acidic than alcohol and water due to stability of phenoxide ion
 Phenoxide ion has 5 resonating structures (reason for stability)
 Acidity order Carboxylic acid > Phenol > Water > Alcohol

Reactions of Phenol

(a) Involving Benzene Ring:

 With Br2:
 Test to distinguish phenol from rest
 White ppts. of 2,4,6-Tribromophenol
 Nitration:

 Sulphonation:
 Phenol reacts with conc. H2SO4 to form ortho, para hydroxy benzene sulphonic acid.

 Hydrogenation:
 On hydrogenation, phenol gives cyclohexanol
  Reaction with Formaldehyde:
 Phenol + formaldehyde in presence of alkali/acid produce ortho, para hydroxyl benzyl
alcohol
 This hydroxyl benzyl alcohol further react with phenol molecule to form Bakelite
(polymer).

(b) Involving –OH group:

 Salt Formation: Phenol reacts with alkalies to form salts

 Ester Formation: Phenol reacts with acetyl chloride in presence of base to form ester

 Reduction with Zn: Phenol reduces with Zn to give benzene