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Session - 2013-14
ORGANIC CHEMISTRY
TOPIC
Reduction, Oxidation & Hydrolysis
CONTENTS :
1 Reduction.
2 Oxidation
3. Hydrolysis
Reduction of alkene, Alkyne, Alcohol, Aldehyde, Ketone, Acid, Acid halide, Ester, Amide & Anhy-
dride.
Oxidation of Alkene, Alkyne, Alcohol, Aldehyde, Ketone, Acid, Acid halide, Ester, Amide & Anhy-
dride.
Hydrolysis reaction of Acid halide, Ester, Amide & Anhydride, Cyanide, Ether etc.
Reduction, Oxidation & Hydrolysis
LECTURE PLAN
Note : (If H2 and D2 mixture is used with a Pt catalyst, the two isotopes quickly scramble to produce a random
mixture of HD, H2 and D2. (No scrambling occurs in the absence of the catalyst.) The product has both D and
H atoms).
RESONANCE 2
Catalytic Hydrogenation : [H2/Pd (C)] Raney nickel (Ni), Palladium on charcol (Pd/C), Platinum metal or
its oxide are commonly used for catalytic hydrogenation.
They reduced the organic functional groups as given in the table.
Catalytic Reduction of Functional Groups Using H2/Pd(C).
Ni or Pd
R –CH = CH – R + H2 R – CH2 – CH2 – R + heat
Note : Stereochemistry of catalytic hydrogenation : The above reaction is syn addition (addition takes place
from the same face of alkene or alkyne).
(ii) Homogeneous catalysis : (catalysts soluble in the reaction medium). It uses reactants and catalyst
in the same phase. Both hydrogen atoms usually add from the same side of the molecule. Common
example : Use of Wilkinsion catalyst.
(iii) Lindlar’s catalyst : [H2/Pd (CaCO3, quinoline)]
It is a poisoned palladium catalyst. It is composed of powdered calcium carbonate coated with palladium and
poisoned with quinoline. It carry out partial reduction of alkyne to alkene and acid chloride to aldehyde.
Stereochemistry : Syn addition.
(a) CH3–CC–CH3
H2 / Pd BaSO 4
(b) CH3 – CHO
Note : Nickel boride Ni2B (P-2 catalyst) (made from sodium acetate and sodium borohidride) is an excellent alternative
catalyst for the conversion of alkyne into alkene. Stereochemistry : Syn addition.
RESONANCE 3
A-3 Metal/proton (acid) reduction :
Reduction by dissolving metals is based on the fact that the metal acts as a source of electrons.
Step -1 : Metals give electrons to the electrophilic species and form anion
Step-2 : Proton is abstracted from the acidic source.
–
e – – H
A + B : or A : + B
A – B A + B – H
–
e H
: A – B or A – B :
A = B A – BH
Na / NH 3
R – C C – R (anti addition)
Na / NH
3
Presence of nitro, cyano, carboxylic or aldehyded group reduces the benzene ring at ipso position.
Na / NH
3
CH3CHO CH3CH2OH
Acetaldehyde Ethanol
RESONANCE 4
(iii) Stephen’s Reductions : [SnCl2/HCl]
When reduction of compounds is carried out with acidified stannous chloride (SnCl2/HCl) at room temperature,
imine hydrochloride is obtained which on subsequent hydrolysis with boiling water gives aldehyde. This
specific type of reduction of nitrile is called stephen’s reduction.
Zn Hg / conc . HCl
(a) R – CHO
RCH3 + H2O
O
|| Zn Hg / conc . HCl
(b) R C R RCH2R + H2O
Note : Clemmensen reduction is not used for compounds which have acid sensitive group.
[Like Alcohol, Alkene, Alkyne, Ether, Ester, Amides & Cyanides].
RESONANCE 5
REDUCTION-2 (L-2)
A-4 Metal hydrides reduction
Certain complex metal and boron hydrides, are important reagents for reduction.
Reactant Aldehyde Ketone Acid Acidanhydride Acid chloride Ester Cyanide Amide Isocyanide Nitro
Product 1º alcohol 2º alcohol 1º alcohol 1º alcohol 1º alcohol 1º alcohol 1º amine 1º amine 2º amine 1º amine
Note : Alkene, alkyne, benzene rings are not reduced by LiAlH4 in ether but it is reported that
(*) double bond can be reduced by LiAlH4 / THF in cinnamic system.
LiAlH 4
LiAlH THF
4 Ph–CH –CH –CH OH + C H OH
(a) Ph–CH=CH—COOC2H5 2 2 2 2 5
H2O
Ph–CH=CH—CH2OH
(b) By DIBAL at ordinary temperature esters are reduced to alcohols but at low temperature esters are
reduced to aldehyde.
RESONANCE 6
O
|| DIBAL
C6H5– C –OCH3 C6H5CH2OH
toluene 25 ºC
C6H5CHO
(c) LAH reduce RCN to amine but DIBAL is found to be reduce it to aldehyde.
LiAlH THF
4 CH –CH –NH
CH3–CN 3 2 2
H2O
CH3–CHO
A-5 Miscellaneous Reductions :
(i) Wolff-kishner reduction [NH2NH2 / KOH] :
Used to prepane alkane from carbonyl compounds
NH2NH2 / KOH
; RCHO RCH3
Note : Wolff-kishner reduction is not used for compounds which have base sensitive groups used to reduce carbonyl
& carbonyl group. [Halogens, Acid halide, Esters, Anhydride, Cyanide]
Red P & HI Red P & HI Red P & HI Red P & HI Red P & HI Red P & HI
Re d P HI Re d P HI
(a) R – CH3 (b) R – CH3
Re d P HI Re d P HI
(c) R – CH3 (d) R – CH – R
2
Re d P HI Red P HI
CH CH CH
(e) CH3CH=O CH3CH3 (f) 3 2 3
eg. + +
RESONANCE 7
(B). Oxidation-1 (L-3)
B-1. INTRODUCTION
1. oxidation is defined as the addition of oxygen (electronegative) element to a substance or removal of
hydrogen (electropositive) element from a substance.
or
2. Oxidation of an organic molecule usually corresponds to increasing its oxygen content or decreasing
its hydrogen content.
3. Oxidation of an organic compound may be more broadly defined as a reaction that increases its
content of any element more electronegative than carbon.
Replacing hydrogen atoms by chlorine atoms is an oxidation
When organic compound is oxidised, something else the oxidising agent is reduced. When an
organic compound is reduced, something else - the reducing agent must be oxidized.
(i) Chemical oxidation with KMnO4 or K2Cr2O7 : Alkanes are usually not affected by oxidising
agents like KMnO4 or K2Cr2O7. However, alkanes having tertiary hydrogen are oxidised by these oxidising
agents to an alcohol.
KMnO 4
(CH3)3CH (CH3)3COH
(Isobutane) (Tertiary butyl alcohol)
RESONANCE 8
¯ OH
Ex.1
+ MnO2 + H2O
H2O
Ex.-3 RC C – R [
O]
2RCOOH
O OH
KMnO4
Ex.4 + C
Warm O
conc.
KMnO4
Ex.5 + CO2 + H2O
Warm COOH
COOH
conc.
O
RESONANCE 9
O O
|| ||
(1) KMnO 4 , NaOH,
Ex.6 CH3 – C C – CH2CH3 CH3 C OH + HO C CH2CH3
( 2 ) H
O
(1) KMnO 4 , NaOH, ||
Ex.7 CH3CH2CH2 – C CH CH3 CH2CH2 C OH + CO2 + H2O
(2) H
O O
|| ||
General Reaction C=C +R– C –O– –H + R – C – O – H (acid)
The epoxidation of an alkene is clearly an oxidation, since in oxidation, an oxygen atom is added. Peroxyacids
are highly selective oxidizing agents. Some simple peroxyacids (sometimes called peracids) are shown
below :
CO H
– 3
= MCPBA (Metachloro perbenzoic acid)
–
Cl
CF3CO3H = TFPAA (Trifluoro peracetic acid)
Stereochemistry : anti addition in diol formation.
H , H O
2
General Reaction
RESONANCE 10
Note : The more highly substituted olifinic bond is more nucleophilic and therefore reacts faster with the peroxyacid
than the less susbstituted double bond.
HCO3H
–HCO2H
O3/ Zn, H2O O3/ Zn, H2O O3/ Zn, H2O O3/ Zn, H2O O3/ Zn, H2O O3/ Zn, H2O
Ex.16 O 3 , H2 O
C8H10 (A) Acid (B) Identify (A) and (B) in the above reaction
Ex.17 A certain hydrocarbon has the formula C16H26. Ozonolysis followed by hydrolysis gives CH3(CH2)4CO2H and
succinic acid as the only product. What is hydrocarbon
Sol. DU = 4
Molecular structure must be :
CH3(CH2)4CC–CH2–CH2–CC(CH2)4–CH3
RESONANCE 11
Oxidation-2 (L-4)
*MnO2 (Selectively oxidised allylic and benzylic alcohol into aldehyde and ketone).
**Oppenaur's oxidation
Base + Ketone (solvent)
2–
Cr2 O 7 H
+ [O] CH3COOH + CO2 + H2O
or KMnO4 H
In case of mixed or unsymmetrical ketones the >C = O group remains with the smaller alkyl group.
(Popoff’s rule)
RESONANCE 12
Mechanism (with Cr+6 oxidising agents) :
H O
–H2 O rds
(ii) R – C – OH + H – O – Cr – OH R – C = O + H2CrO3
H O H
.. OH OH O
H2O H2 CrO 4 rds
– –
–
H H H O OH
Gemdiol Acid
unstable
Remarks :
(1) Primary alcohol forms a chromate ester with chromic acid.
(2) The chromate ester decomposes in 2nd slow step with the elimination of -hydrogen. So the first
oxidation product, an aldehyde is obtained.
(3) In aqueous medium, aldehyde forms a gemdiol (hydrated aldehyde). It is further oxidised to an
acid by similar mechanism.
(4) The following reactivity orders can be explained by this mechanism :
Rate of Oxidation
(a) RCH2OH > R2CHOH > R3C – OH (inert)
Aldehydes reduce Tollen’s reagent to Ag and appears in the form of silver mirror is called silver-mirror test.
It is given by all aldehydes and reducing sugars.
RCHO + 2[Ag(NH3)2+ ] + 3OH– RCOO– + 2Ag + 4NH3 + 2H2O
(iii) With Fehling Solution :
Aldehydes (except benzaldehyde) reduce Fehling’s solution (Cu2+ reduced to Cu+) which is an alkaline
solution of cupric (Cu2+) ion complexed with tartrate ion.
RCHO + 2Cu2+ + 3OH– RCOO– + Cu2O + 2H2O
red ppt.
Aldehydes also reduce Benedict’s solution (Cu2+ complexed with citrate ion) to Cu+
RESONANCE 13
B-5 Oxidation reaction of diols
R R
| |
RC + CR
|| ||
O18 18 O
2H O
2
Remarks
(1) HIO4 (periodic acid) oxidises vicinal diols (1, 2-diols).
(2) It brings about oxidative cleavage of vicinal diol.
(3) It can also oxidise -hydroxy carbonyl compound, -dicarbonyl compound and -hydroxy acid.
(4) HIO4 forms a cyclic periodate ester as an intermediate. So the two – OH groups should have syn-
conformation.
(5) In cyclic diols only cis-vicinal diols are oxidised. Trans isomers are not oxidised.
RESONANCE 14
Oxidation Product of 1º, 2º and 3º alcohol
OH
(X)
O
K 2 Cr2 O 7
X CH3 – C – OH + HOOC – C – CH2 – C – OH
(1) H 2SO 4
O O
PCC
X
CH – CH = CH – C – CH – CHO
( 2) 3 2
O
Oppenau er oxidation
X
CH3 – CH = CH – C – CH2 – CHO
(3)
O
CrO3 / aq.
X ( CH – CH = CH – C – CH – COOH
4) acetone 3 2
O
MnO 2
X CH3 CH CH C CH2 CH2 OH
(5 )
||
O
RESONANCE 15
Common Oxidising Agents In Organic Chemistry
RESONANCE 16
(C). HYDROLYSIS (L-5)
(i) Introduction :
Hydrolysis is a chemical reaction or process in which a molecule splits into two parts by reacting with a
molecule of water,(H2O). One of the parts gets OH- from the water molecule and the other part gets H+ from
the water.Such reactions are endothermic.
This is distinct from a hydration reaction, in which water molecules are added to a substance, but no
fragmentation of molecule/species occurs.Such a process is exothermic.
+ HCl
+ NH3
RESONANCE 17
(vi) Hydrolysis of cyanides :
Cyanides has 30 nitrogen bonded with SP carbon.On hydrolysis C-N bond dissociates to produce ammonia
and carboxylc acids.It is carried out in acidic medium.
+ NH3
+ RNH2
RESONANCE 18
HYDROLYSIS OF COMMON FUNCTIONAL GROUPS
Functional Groups Reactant Bond Products Products Catalysis
Broken
Alkyl Halides C-Hal R OH + H Cl Alcohol and Basic
R Cl Hydrogen Halides
1
basic
1
R O R R OH HO R
Nitriles/Cyanides HC N O Acids and Acidic
R C N Ammonia
R C + NH3
OH
Esters O C-O O Acids and Alcohols Acidic or
basic
1 R 1 H H R
R O R O + O
Amides O C-N Acids and Strong
Amides and N- O Ammonia or Acidic
1 R
substituted
R NH H + H NH Amines
1
R O R
Isonitriles/isocyanid HC N Formic acid and Acidic
es + - O Primary amines
R N C
R NH2 + H
HO
Metal Alkyl Halides M-C R—H Hydrocarbons H 2O
R Mg Br
and Metal
Hydroxides
Metal Alkyls M-C R—H Hydrocarbons H 2O
R Li and Metal
Hydroxides
RESONANCE 19