Reduction, Oxidation - Hydrolysis Theory PDF

Reduction, Oxidation & Hydrolysis
Reactions
Section (A) : Reduction-1

Introduction :
Reduction covers both the addition of hydrogen (or deuterium) to a double bond and the replacement of
an atom or group by hydrogen (or deuterium). In other words, reduction means hydrogenation or
hydrogenolysis.
Reduction can be carried out in following ways:
(a) Catalytic hydrogenation (b) Metal/proton (acid) reduction
(c) Metal hydrides reduction (d) Miscellaneous Reductions
1.1 Catalytic hydrogenation :
Hydrogenation using H2(g) on metal surface or other suitable catalyst is called catalytic hydrogenation.
A catalyst provides a new pathway for the reaction that involves lower free energy of activation.
Heterogeneous hydrogenation catalysts typically involve finely divided platinum.

The catalysts used can be divided into two broad classes, (a) Heterogeneous catalysts (b)
Homogeneous catalysts. Both of which mainly consist of transition metals and their compounds :
(i) Heterogeneous catalysts : (catalysts insoluble in the reaction medium)
In heterogeneous catalytic hydrogenation catalysts are used in powdered form. Raney nickel (Ni),
Palladium on charcol (Pd/C), Platinum metal or its oxide are common heterogeneous catalysts.
Facts of catalysis :
(i) Substrate molecules are assumed to undergo homolysis into atoms at the surface of the catalyst.
(ii) The substrate is chemisorbed on the surface of the catalyst and hydrogenation takes place.
(iii) The process is exothermic.
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).
Catalytic Reduction of Functional Groups Using H2/Pd(C) or H2/Pt or H2/Ni
Ni or Pd
R–CH=CH–R + H2  R–CH2–CH2–R + heat
Substrate Product
RCOCl RCH2OH
RNO2 RNH2
RCCR RCH2CH2R
RCHO RCH2OH
RCH=CHR RCH2CH2R
RCOR RCHOHR
RCN RCH2NH2
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Reactions
Note : (i) Generally RCOOH, RCOOR, RCONH2 groups are not reduced by catalytic hydrogenation.
(ii) Stereochemistry of catalytic hydrogenation: The above reaction is syn addition (addition takes
place from the same side 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 Rh [(C6H5)3P]3Cl.
(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 is used to carry out partial reduction of alkyne to alkene and
acid chloride to aldehyde.
Stereochemistry : Syn addition.
H Lindlar ' s catalyst

CH3–CH2–CC–CH3 
2
 (syn addition)
or Ni2B
Note : Nickel boride Ni2B (P-2 catalyst) (made from Nickel acetate and sodium borohydride) is an excellent
alternative catalyst for the conversion of alkyne into alkene. Stereochemistry : Syn addition.
NaBH
Ni(OCOCH3)2 
4
 Ni2B.
C2H5OH
(iv) Rosenmund catalyst : [H2/Pd, BaSO4, quinoline] Hydrogenation in presence of H2/Pd/BaSO4

is called Rosenmund Reduction. It reduces alkyne to alkene and acid halide to aldehyde. It is
poisoned palladium catalyst, composed of powdered barium sulphate coated with palladium, poisoned
with quinoline or sulphur.
Stereochemistry : Syn addition.
(a) CH3–CC–CH3
(b) CH3–CHO
1.2 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  A + B : or A : + B   A+ B–H
–  
e
A=B  : A– B or A – B : A–BH
(i) Birch reduction [Na or Li/NH3(liq.) or (ethyl alcohol)] :

Alkyne and Aromatic Compounds are reduced by Na or Li/NH3.
Alkynes are reduced to trans alkene. Stereochemistry : anti addition.
Na / NH
R–CC–R 
3
 (anti addition)
Benzene ring is reduced at 1, 4-position.

Typical example of reduction for aromatic system :
Presence of alkyl, alkoxy, amines reduces the benzene ring at ortho position.
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Reactions
Na / NH

3

Presence of nitro, cyano, carboxylic, keto or aldehyded group reduces the benzene ring at ipso
position.
Na / NH

3

(ii) Bouvealt-Blanc reduction [Na/C2H5OH] :

Reduction of aldehydes, ketones, acidhalides, esters or cyanide by means of excess of Na/C2H5OH is
called Bouvealt-Blanc reduction.
Na + C2H5OH is mild reducing agent.
Reagent Na/C2H5OH Na/C2H5OH Na/C2H5OH Na/C2H5OH Na/C2H5OH
Reactant Aldehyde Ketone Cyanide Ester acid halide
Product 1° alcohol 2° alcohol 1° amine 1° alchol 1° alchol
CH3CHO CH3CH2OH
Acetaldehyde Ethanol
(iii) Stephen’s Reductions : [SnCl2/HCl]

When reduction of cyanide is carried out with acidified stannous chloride (SnCl 2/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.
(iv) Clemmensen’s Reduction : [Zn-Hg/Conc. HCl]

It is used to prepare alkanes from carbonyl compounds (Aldehyde and ketones in absence of acid
sensitive groups).
Conc.
Zn – Hg / HCl
Mechanism :


O
Zn  Hg / conc. HCl
|| Zn  Hg / conc. HCl
(a) R – CHO 
 RCH3 + H2O (b) R  C  R   RCH2R + H2O
 
Note : Clemmensen reduction is avoid to use for compounds which have acid sensitive group.
[Like: Alcohol, Alkene, Alkyne, Ether].
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Reactions
Section (B) : Reduction-2
1.3 Metal hydrides reduction
Certain complex metal and boron hydrides, are important reagents for reduction.
(i) LiAlH4 (LAH) Lithium aluminium hydride [LiAlH4 / Ether or THF] :

LAH is most common and versatile reagent. It is sensitive to protic solvent and therefore used in ether.
Reagent LiAlH4 LiAlH4 LiAlH4/Excess LiAlH4/Excess LiAlH4 LiAlH4 LiAlH4 LiAlH4 LiAlH4 LiAlH4
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 few cases like :
(i) LiAlH4  THF
Ph–CH=CH–CHO   Ph–CH2–CH2–CH2OH
(ii) H2O
[Cinnamaldehyde]
(ii) Sodium borohydride [NaBH4 / C2H5OH or Ether] :
It is more specific than LAH as a reducing agent. It reduces ketones and aldehydes to the
corresponding alcohols without affecting other functional groups, reduces acid chlorides to 1º alcohols.
It does not reduce any other derivative of acid. It is effective even in protic solvent like alcohol.
Reagent NaBH4 NaBH4 NaBH4
Reactant Aldehyde Ketone Acid chloride
Product 1º alcohol 2º alcohol 1º alcohol
NaBH

4

(iii) Diisobutyl Aluminium Hydride [DIBAL-H / Inert solvent] :

Diisobutyl aluminium hydride is parallel to LAH (Lithium aluminium hydride) as a reducing agent but it is
more selective.
Reagent DiBAL-H/(–78ºC) DiBAL-H
Reactant Ester Cyanide
Product Aldehyde Aldehyde
(a)
(b) By DIBAL at ordinary temperature esters are reduced to alcohols but at low temperature esters
are reduced to aldehyde.
(c) LAH reduce RCN to amine but DIBAL is found to be reduce it to aldehyde.
CH3–CN
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Reactions
1.4 Miscellaneous reductions :
(i) By Red P & HI :
Used to prepare alkane from carbonyl compounds and alcohols generally.
Red P  HI
(a)  R–CH2–R

Red P  HI
(b) CH3CH=O  CH3CH3

Red P  HI
(c) R–CH2OH  R–CH3

Red P  HI
(d) CH3 – CH – CH3  CH3CH2CH3
| 
OH
(ii) Meerwein-Pondorf-Verley reduction (MPV reduction) (Reduction by isopropyl

alcohol and aluminium isopropoxide): It is selective reduction of ketones to alcohol, even in
presence of other functional groups using Aluminium isopropoxide in isopropyl alcohol.
eg. + +
(iii) Wolff-kishner reduction [NH2NH2 / KOH] :
Used to prepane alkane from carbonyl compounds

NH2NH2 / KOH
; RCHO   RCH3

Mechanism :
Note : Wolff-kishner reduction is avoid to use for compounds which have base sensitive groups. [Like :
Halogens, Acid halide, Esters, Anhydride]
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Reactions
Section (C) : Oxidation-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
Ar–CH3 ArCH2Cl ArCHCl2 ArCCl3
When organic compound is oxidised, oxidising agent used is reduced. When an organic compound is
reduced, the reducing agent used must be oxidized.
2.1 Oxidation of alkanes
Different products are formed by the use of different oxidising agents or different reaction conditions.
(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.
KMnO4
(CH3)3CH   (CH3)3COH
(Isobutane) (Tertiary butyl alcohol)
Cu / 523K /1000atm
Ex. (i) 2CH4  O2   2CH3OH (methanol)
9: 1
Mo O
(ii) CH4 + O2 
2 3
 HCHO + H2O

(CH COO )Mn
(iii) 2CH3–CH3 + 3O2 
3 2
 2CH3COOH + 2H2O

Burn
(iv) CH4  O2  C + 2H2O
limited carbon
black
2.2 Oxidation of alkenes and alkynes

(i) Baeyer reagent [cold diluted to 1% alkaline KMnO4 solution] :
Baeyer Reagent Baeyer Reagent Baeyer Reagent
Reactant Alkene Alkyne
Product Vicinal diol Diketone
Stereochemistry : syn addition.
Both-OH groups are add from same stereochemical side.
General Reaction
Stereochemistry : syn addition.
¯OH
Ex. 
 
 + MnO2  + H2O
H2O
O O HO OH
Mn diol
O O¯
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(ii) Reactions
Osmium tetraoxide in alkaline medium [OsO4 / NaHSO3] :
Similar to Baeyer's reagent.
OsO4 /NaHSO3 OsO4 /NaHSO3 OsO4 /NaHSO3
Reactant Alkene Alkyne
Product Vicinal diol Diketone
OH
OsO4 , H2O2
Ex. 
OH
Cyclohexene
(iii) Oxidation with peroxyacids

An alkene is converted to an epoxide by a peroxyacid.
[a carboxylic acid that has an extra oxygen atom in a –O–O– (peroxy) linkage].
O O
|| ||
General Reaction C=C + R – C – O– –H + R – C – O – H (acid)
Some simple peroxyacids (sometimes called peracids) are shown below :
(a) (b)
(c) (d)
Peroxyformic acid
Cl Metachloro perbenzoic acid
(MCPBA)
H , H O
General Reaction 
2 
Stereochemistry : anti addition in diol formation.

OH
(i) per acid



Ex. (ii) H3O
OH
Cyclohexene trans-
Ex. + Enantiomer
Ex.
Note : The more highly substituted olifinic bond is more nucleophilic and therefore reacts faster with the
peroxyacid than the less susbstituted double bond.
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Reactions
HCO3H
 
–HCO2H
(iv) Oxidation with acidic KMnO4 [KMnO4/H+] : Stereochemistry : syn addition.

When alkene & alkyne heated with KMnO4 in acidic or in alkaline medium; following changes takes
place.
KMnO4/H+ KMnO4/H+ KMnO4/H+ KMnO4/H+ KMnO4/H+ KMnO4/H+
Reactant .= CH2 group .= CH R group .= CR1R2 group . CH group . CR group
Product CO2 RCOOH O.= CR1R2 group CO2 RCOOH
Carbon dioxide Carboxylic acid Ketone Carbon dioxide Carboxylic acid
[O]
Ex. RCH=CH2   CO2 + H2O + RCOOH
[O]
Ex. RCCH   CO2 + H2O + RCOOH
[O]
Ex. RCC–R   2RCOOH
w
KMnO4
COOH
Ex. Warm COOH + CO2 + H2O
conc. O
O O
||
(1) KMnO4 , NaOH,  ||
Ex. CH3–CC–CH2CH3 

 CH3  C  OH + HO  C  CH2CH3
(2) H
O
(1) KMnO4 , NaOH, ||
Ex. CH3CH2CH2–CCH   CH CH CH  C  OH + CO2 + H2O
(2) H 3 2 2
(v). Oxidation with ozone (ozonolysis) :

Alkene & Alkyne
Like permanganate ozone cleaves double at very low temperature (–78ºC) bonds to give Ketones and
aldehydes. However, ozonolysis is milder, and both Ketones and aldehydes can be recovered without
further oxidation.
Reductive Ozonolysis Products (O3/Zn, H2O)
O3/Zn, H2O O3/Zn, H2O O3/Zn, H2O O3/Zn, H2O O3/Zn, H2O O3/Zn, H2O
Reactant = CH2 group = CH R group = CR1 R2 group  CH group  CR group
O
Product HCHO O = CHR group O = CR1R2 group || diketone
–C – CHO
Formaldehyde Aldehyde Ketone Keto aldehyde diketone
Oxidative Ozonolysis Products
O3/H2O2 O3/H2O2 O3/H2O2 O3/H2O2 O3/H2O2 O3/H2O2
Reactant =CH2 group =CHR group = CR1R2 group CH group CR group
Product CO2 RCOOH O=CR1R2 group CO2 RCOOH
Carbon dioxide Carboxylic acid Ketone Carbon dioxide Carboxylic acid
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Reactions
O3 , H2O
Ex. C8H10 (A)  C4H6O2 Acid (B). Identify (A) and (B) in the above reaction
Sol. (A) C C (B) COOH
Ex. 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)4CC–CH2–CH2–CC(CH2)4–CH3
Section (D) : Oxidation-2

2.3 Oxidation reaction of alcohols :
Oxidation Product of Alcohol-1
Weak oxidising agent Strong oxidising agent
CrO3/Inert CrO3 in water
PCC* PDC** KMnO4/H+ K2Cr2O7/H+
medium or H2CrO4
1º alcohol
Aldehyde Carboxylic acid
or primary alcohol
2º alcohol
Ketone Ketone
or secondary alcohol
3º alcohol
Not oxidised Not oxidised
or tertiary alcohol
(a) Pyridinium Chloro Chromate (PCC)
+ HCl + CrO3 

Non aqueous solvent
 .Cl–.CrO3
(b) Pyridinium dichromate (PDC) = (2C6H5N.CrO3)

(c) Jones reagent = dilute chromic acid + acetone
(d) Collin's Reagent = CrO3 + pyridine, CH2Cl2
(e) MnO2 = It is selectively oxidised reagent & oxidised allylic and benzylic alcohol into aldehyde
and ketone.
Oxidation Product of Alcohol-2
Very-Very Strong oxidising agent Copper & heat
KMnO4/H+/Heat as oxidising agent
1º alcohol or Primary alcohol Carboxylic acid Aldehyde
2º alcohol or Secondary alcohol Mixture of Carboxylic acid Ketone
3º alcohol or tertiary alcohol Mixture of Carboxylic acid Dehydrate to alkene
Oppenaur's oxidation
(i) This reaction involves the oxidation of a secondary alcohol with a ketone and base to the
corresponding ketone.
(ii) Commonly used bases are aluminium tert-butoxide.
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Rate ofReactions
Oxidation :
(a) RCH2OH > R2CHOH > R3C–OH (inert) (b) RCHO > RCH2OH
Ex. Write the product of following reactions.
CH3–CH=CH– CH –CH2–CH2–OH
–
OH
(X)
O
K 2Cr2O7
X  CH3 – C – OH + HOOC– C –CH2– C –OH
(1) H2SO 4
O O
PCC
X 
 CH3–CH=CH– C –CH2–CHO
(2)
O
Oppenauer oxidation
X 
 CH3–CH=CH– C –CH2–CHO
(3 )
O
CrO3 / aq.
X 
 CH3–CH=CH– C –CH2–COOH
( 4) acetone
O
 CH3  CH  CH  C  CH2  CH2  OH
MnO2
X 
(5) ||
O
2.4 Oxidation reaction of carbonyl compound

(i) Acidic KMnO4 & K2Cr2O7 as oxidising agent :
Aldehydes are oxidised to carboxylic acid having same number of C atoms as aldehyde.
HCHO + [O] HCOOH ; RCHO + [O]  RCOOH
Ketones are oxidised with difficulty. They are oxidised only on heating with a strong oxidising agent.
2–
Cr2O7  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)
[O] [O]
CH3COCH2CH3   2CH3COOH ; CH3COCH2CH2CH3   CH3COOH + CH3CH2COOH
Mechanism (with Cr+6 oxidising agents) :
(i) CrO3 + H2O H2CrO4 =
H O
–H2O rds
(ii) R – C – OH + H – O – Cr – OH     R – C = O + H2CrO3
H H
O
.. OH O
OH
– –
H2O H2CrO4 rds

(iii) R – C = O R – C – OH  
R – C – O – Cr – OH   R – C = O + H2CrO3
–
H H OH
Gemdiol H O Acid
unstable
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RemarksReactions
:
(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) R–CH2OH > R–CD2OH (Bond Energy : C–H < C–D ) (b) RCHO > RCDO
(ii) With Tollen's reagent :

RCHO (aldehydes) can be easily oxidised to RCOOH (except HCHO that can be oxidised to CO 2) by
weak oxidising agents like ammonical AgNO 3 (Tollen’s reagent) hence they are better reducing
agents.
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
(Silver mirror )
(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.
 Cu2O 
RCHO + 2Cu2+ + 3OH–   RCOO– + + 2H2O
red ppt.
Aldehydes also reduce Benedict’s solution (Cu2+ complexed with citrate ion) to Cu+
(iv) With Benedict's solution

Sodium citrate + NaOH + NaHCO3 + CuSO4
HO
RCHO + Cu2+ 
2
 +

RCHO + HgCl2 + H2O 


 RCOOH + 2HCl + Hg2Cl2
RCHO + Hg2Cl2 + H2O  RCOOH + 2HCl + 2Hg  grey ppt.
(v) With Schiff's reagent

Schiff's Reagent is aq. solution of following base decolourised by passing SO 2.
Aldehyde restore pink colour of Schiff's reagent.
SO2 RCHO
  Colourless solution (Schiff's Reagent) 
 RCOOH + Pink colour

p-Rosaniline Hydrochloride
Magenta colour (Fuschin)
Ketons are not easy to oxidize so they do not give these 5 tests. These five tests can be used to
distinguish aldehyde and ketones. Both gives 2, 4 DNP test.
ADVROHO - 11
(vi) Reactions
Oxidation by using SeO 2
SeO2 is a selective oxidizing agent with converts –CH2–group adjacent to carbonyl group into carbonyl
group. The reagent, in general, oxidises active methylene and methyl groups to ketonic and aldehydic
groups respectively.
SeO SeO

2
 ; 
2

(vii) Baeyer-villiger oxidation

Baeyer-villiger oxidation is the oxidative cleavage of a carbon-carbon bond adjacent to a carbonyl which
converts ketones to esters and cyclic ketones to lactones.
It can be carried out with peracids such as MCBPA, or with hydrogen peroxide and a lewis acid.
O O
Ph COOOH
 (67 %)
CH2Cl2
O
O
HO

2 2
 O (62%)
BF3
Ether
O
KETONES ARE DIFFICULT TO OXIDIZE :
Ketones can be oxidized from their enolic form at high temperature with very strong oxidizing agent.
Oxidation of ketones is sometimes governed by Popoff's rule. According to this rule carbonyl group
remains with the smaller alkyl group. More electron rich alkene will be easy to oxidized.
[O]
  MeCOOH + CO2 + H2O

2.5 Oxidation reaction of diols

(i) HIO4 oxidation : (Oxidation by lead acetate is similar to HIO4 oxidation)
Mechanism :
R
R
+ |
|
C R
RC
||
||
O
O
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 and -dicarbonyl compound.
(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.
Ex. General reaction
HIO

4
 R – CHO + HCOOH + R–CHO
HIO
Ex. 
4

ADVROHO - 12
Reactions
Section (E) : Hydrolysis
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.
(i) Hydrolysis of an ester :

Hydrolysis of an ester involves breaking off an ester link. It can takes place in
(a) Mild acidic medium : Dilute H2SO4, dilute HCl.

(b) Strong alkaline medium : Aqueous NaOH or KOH and heat.
One hydrolysis product contains a hydroxyl functional group, while the other contains a carboxylic acid
functional group.
(ii) Hydrolysis of an anhydride :

The hydrolysis of acid anhydride produces two carboxylic acids.
+ OH
(iii) Hydrolysis of acid halide :

Hydrolysis of an acid halide results into a carboxylic acid and hydrogenhalide. Only the carboxylic acid
product has a hydroxyl group derived from the water. Hydrohalic acid product gains the remaining
hydrogen ion.
Cl OH + HCl
(iv) Hydrolysis of acid amide :

Hydrolysis of an amide results into a carboxylic acid and an amine product or ammonia, only the
carboxylic acid product has a hydroxyl group derived from the water. The amine product (or ammonia)
gains the remaining hydrogen ion.
NH2
OH + NH
3
(v) Hydrolysis of cyanides :

Cyanide on hydrolysis produce ammonia and carboxylc acids. It is carried out in acidic medium
generally but hydrolyse in basic medium also.
OH+ NH
3
ADVROHO - 13
(vi) Reactions
Hydrolysis of isocyanides :
Isocyanides on hydrolysis produce primary amines and formic acids. It is carried out in acidic medium.
H OH + RNH
2
Note : Alkylisocyanide does not hydrolyse in basic medium.
(vii) Hydrolysis of imine :

H O

3
 R – CHO + NH
3
(viii) Hydrolysis of ethers :

Ethers has R–O–R group. In strong acidic medium (HI or HBr) in hydrolysis to produce 2 equivalent of
alcohols.

C2H5–O–C(CH3)3 
H3O
 C2H5OH + (CH3)3C–OH
(ix) Hydrolysis of Vinyl ether :

H O

3

CH3–CHO + ROH
(x) Hydrolysis of phenyl ether :

H O

3
 Ph–OH + ROH
(xi) Hydrolysis of hemiacetals and acetals :

Hemiacetals and Acetals has R–O–R group.
Hemiacetals are unstable and get hydrolysed to aldehyde/ketones even in aq medium. However
acetals/Ketals are stable and hydrolyse only in strong acidic medium (HI or HBr) to produce 2
equivalent of alcohols and one equivalent of aldehyde/ketone. Acetals are often used as protecting
groups.
HO–H
OR +
H /H2O OR OH
C C ROH + C C=O
OR OR OH
HO–H
Unstable
(xii) Hydrolysis of epoxide :

H O

3

Note : Three and four membered expoxides can also be hydrolysed in basic medium.
ADVROHO - 14

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Reduction, Oxidation & Hydrolysis

Section (A) : Reduction-1

Heterogeneous hydrogenation catalysts typically involve finely divided platinum.

(iii) Lindlar’s catalyst : [H2/Pd, CaCO3, quinoline]

H Lindlar ' s catalyst

(iv) Rosenmund catalyst : [H2/Pd, BaSO4, quinoline] Hydrogenation in presence of H2/Pd/BaSO4

1.2 Metal/proton (acid) reduction :

(i) Birch reduction [Na or Li/NH3(liq.) or (ethyl alcohol)] :

Benzene ring is reduced at 1, 4-position.

(ii) Bouvealt-Blanc reduction [Na/C2H5OH] :

(iii) Stephen’s Reductions : [SnCl2/HCl]

(iv) Clemmensen’s Reduction : [Zn-Hg/Conc. HCl]

(i) LiAlH4 (LAH) Lithium aluminium hydride [LiAlH4 / Ether or THF] :

(iii) Diisobutyl Aluminium Hydride [DIBAL-H / Inert solvent] :

(ii) Meerwein-Pondorf-Verley reduction (MPV reduction) (Reduction by isopropyl

(iii) Wolff-kishner reduction [NH2NH2 / KOH] :

Used to prepane alkane from carbonyl compounds

Ar–CH3 ArCH2Cl ArCHCl2 ArCCl3

2.2 Oxidation of alkenes and alkynes

Stereochemistry : syn addition.

(iii) Oxidation with peroxyacids

Some simple peroxyacids (sometimes called peracids) are shown below :

Stereochemistry : anti addition in diol formation.

(iv) Oxidation with acidic KMnO4 [KMnO4/H+] : Stereochemistry : syn addition.

(v). Oxidation with ozone (ozonolysis) :

Sol. (A) C C (B) COOH

Section (D) : Oxidation-2

(a) Pyridinium Chloro Chromate (PCC)

+ HCl + CrO3 

(b) Pyridinium dichromate (PDC) = (2C6H5N.CrO3)

2.4 Oxidation reaction of carbonyl compound

(i) CrO3 + H2O H2CrO4 =

H2O H2CrO4 rds

(ii) With Tollen's reagent :

(iii) With Fehling solution :

(iv) With Benedict's solution

RCHO + HgCl2 + H2O 

(v) With Schiff's reagent

(vii) Baeyer-villiger oxidation

2.5 Oxidation reaction of diols

(i) Hydrolysis of an ester :

(a) Mild acidic medium : Dilute H2SO4, dilute HCl.

(ii) Hydrolysis of an anhydride :

(iii) Hydrolysis of acid halide :

(iv) Hydrolysis of acid amide :

(v) Hydrolysis of cyanides :

Note : Alkylisocyanide does not hydrolyse in basic medium.

(vii) Hydrolysis of imine :

(viii) Hydrolysis of ethers :

(ix) Hydrolysis of Vinyl ether :

(x) Hydrolysis of phenyl ether :

(xi) Hydrolysis of hemiacetals and acetals :

(xii) Hydrolysis of epoxide :

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