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Oxidation Reduction - Final - MS Sir Add

The document provides an overview of oxidation and reduction processes in organic chemistry, focusing on hydrogenation methods and catalysts such as Raney nickel, platinum, and palladium. It discusses the mechanisms and applications of catalytic hydrogenation for reducing alkenes, alkynes, and aromatic compounds, as well as the use of sodium borohydride in reductions. Additionally, it highlights the importance of catalyst choice based on the substrate and the selectivity of reactions.

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OXIDATION AND REDUCTION

FOR IRP

THEORY - NOTES

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OXIDATION & REDUCTION IN ORGANIC CHEMISTRY
Oxidation : Decreases electron density on carbon by :
forming one of these : C–O, C–N, C–X
or breaking this : C – H
Reduction : Increases electron density on carbon by :
Forming this : C – H
or breaking one of these ; C–O, C–N, C–X

REDUCTION
(A) HETERGENOUS CATALYTIC HYDROGENATION

Ø Transition metals adsorbed H2 onto a solid support

Ø Metal : Pd, Pt, Rh, Ni
Ø Support : Charcoal, Alumina, Silica
Ø Solvents : MeOH, EtOH, EtOAc, AcOH, Et2O, Hexanes

Example :

• Properties :
(i) Reduces olefins & acetylenes to saturated hydrocarbons.
(ii) Sensitive to steric effects & choice of solvents.
(iii) Polar functional groups, like hydroxyl groups can sometimes direct the delivery of H2.
(iv) cis-addition of H2
(v) Catalysts can be poisoned
(viii) Order of solvent reactivity is : Hexane < EtOH < HOAc < HOAc/HCl

Mechanism :

(1) (2)

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Example :

RANEY NICKEL
Raney nikel also called spongy nickel, is a fine-grained solid composed mostly of nickel derived from a
nickel-aluminium alloy. Raney nickel is used as a reagent and as a catalyst in organic chemistry.

Raney nickel include the conversion of :

Ø Nitro compounds to amines Ø Nitriles to amines
Ø Olefins to paraffins Ø Acetylenes to paraffins
Ø Raney nickel is used in organic synthesis for desulfurization for eg. : thioacetals will be reduced to hydrocarbons.

Example of desulfurization of thioacetals using Raney nickel

l Nitriles are also reduced to primary amines by catalytic hydorgenation using Raney nickel, a type of nickel-
aluminium alloy.

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Reduction of Alkenes
Alkenes react with H2 in the presence of a catalyst to yield the corresponding saturated alkane addition
products. The double bond has been hydrogenated, or reduced.

l Platinum and palladium are the most common catalyst for alkene hydrogenations.
l Palladium is normally used as a very fine powder “Supported” on an inert material such as charcoal (Pd/C) to
maximize surface area.
l Platinum is normally used as PtO2, a reagent known as Adams’ catalyst after its discover, Roger Adams.
Hydrogenation usually occurs with syn stereochemistry – both hydrogens add to the double bond
from the same face.

Examples :

Directed Heterogeneous Hydrogenation :

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Catalytic Hydrogenation of Aromatic Rings
Ø Just as aromatic rings are inert to oxidation under most conditions, they're also inert to catalytic hydrogena-
tion under conditions that reduce typical alkene double bond.
As a result, it's possible to selectively reduce an alkene double bond in the presence of an aromatic ring.

To hydrogenate an aromatic ring, it's necessary either to use a platinum/nickel catalyst with hydrogen gas at
several hundred atmospheres pressure or to use a more powerful catalyst such as rhodium on carbon.

4. It is quite possible to hydrogenate double

bonds in the presence of aldehydes.

Reduction of Aryl Alkyl Ketones :

l Aryl and alkyl ketones activates a neighboring carbonyl group toward reduction.
l Thus, an aryl alkyl ketone can be converted into an alkylbenzene by catalytic hydrogenation over a palladium
catalysts.

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l Note that the conversion of a carbonyl group into a methylene group (C=O ® CH2) by catalytic hydrogenation
is limited to aryl alkyl ketones.
l Dialkyl ketones are not reduced under there conditions.
l The catalytic reduction of aryl alkyl ketones is not compatible with the presence of a nitro substituent on the
aromatic ring, because a nitro group is reduced to an amino group under the reaction conditions.

l The catalyst in each of hydrogenation reductions is a different metal.

l Palladium and platinum are the most commonly used metal catalysts for hydrogenation, but hydrogenation
can also work with nickel, rhodium, or ruthenium.
l The choice of catalyst depends on the compound to be reduced.

Substrate Usual choice of metal

benzyl amine or ether Pd
alkene Pd, Pt, or Ni
aromatic ring Pt or Rh, or Ni under high pressure and temperature

**Catalytic hydrogenation is often chosen as a method for reduction because of its chemoselectivity for C=C
double bonds and benzylic C–X bonds over C=O groups.

l It should not surprise you that regioselective reduction of the C=C double bond alone is best done using
catalytic hydrogenation as the C=C bond is weaker than the C=O bond.

Reduction of Alkynes :
Alkynes are easily reduced to alkanes by addition of H2 over a metal catalyst. The reaction occurs in steps
through an alkene intermediate
H
HCº CH ¾¾¾¾ 2
Catalyst
® H2 C = CH2 DH°hydrog = – 176 kJ/mol (– 42 kcal/mol)

H2
H2C = CH2 ¾¾¾¾
Catalyst
® CH3 - CH3 DH°hydrog = – 137 kJ/mol (– 33 cal/mol)
Lindlar's catalyst :
l Complete reduction of alkynes to the alkanes occurs when palladium on carbon (Pd/C) is used as catalyst,
but hydrogenation can be stopped at the alkene if the less active Lindlar catalyst is used.
l The Lindlar catalyst is a finely divided palladium metal that has been precipitated onto a calcium carbonate
support and then deactivated by treatment with lead acetate and quinoline, an aromatic amine.
l The hydrogenation occurs with syn stereochemistry giving a cis alkene product.

2
3 2 8 3

3 2 3 3 3

eg. 1 2

3 2 3 2 3 3

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eg.2

eg. 3

Birch Reduction :
l Another method for the conversion of an alkyne to an alkene uses sodium or lithium metal as the reducing
agent in liquid ammonia as solvent.
l This method is complementary to the Lindlar reduction because it produces trans rather than cis alkenes.

3 2 2 2

3 2 2 2 2 2 2 3
3
2 2 2 3

l Li, Na, K, Ca, in liquid ammonia, Et2NH, EtNH2, ROH, H2O

Partial Reduction of Aromatic Rings (Li/NH3) :

+ +

Electron Donating Substituents :

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Electron Withdrawing Substituents :

Wilkinson's catalyst [(PPh3)3RhCl]

Chlorotris (triphenylphosphine) rhodium (I)
• It is used as a homogenous hydrogenation catalyst.
• It is used in the selective hydrogenation of alkenes & alkynes without affecting the functional
groups like : –C = O, –CN, –NO2, Aryl, –CO2R etc.
• The Rate of hydrogenation decrease with increase in the alkyl group due to steric hinderance
on double bond.
Examples :

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Ø Nitro group reduction :
Near the top of the list of reactivity towards hydrogenation lies the NO2 group and we saw how the sequence
of nitration of aromatic rings followed by reduction was a useful route to aromatic amines. The reduction can
be carried out by Sn/HCl but catalytic hydrogenation is much simpler. The reaction is usually done in ethanol
with a Pd or Pt catalyst and it may be necessary to add a weak acid to prevent the amine produced from
poisoning the catalyst.

WORKSHEET-1
For Raney Ni
Reactants Products
2Ni-H
1. CH2 = CH2 + ¾¾¾¾¾¾®
RoomTemp.

2Ni-H
2. HC º CH + ¾¾¾¾¾¾®
RoomTemp.

Ni-H
2
3. ¾¾¾¾
100°C
®

Ni-H2
4. ¾¾¾¾¾¾®
150°C -200°C

5. Ni- H
¾¾ ¾2 ¾
60 ° C
®

WORKSHEET-2
For Catalytic hydrogenation
Reactants Products

H2
1. ¾¾
Pt
¾
®

H2
2. ¾¾
Pt
¾
®

H2
3. ¾¾¾
Pt/C
®

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Ni
4. ¾¾¾¾¾¾
102atm,120°C
®

Pd/C
5. ¾¾¾ ®

H2
6. ¾¾
Pt
¾
®

Reduction with NaBH4 :

Boron Based Reagents :
Ø NaBH4 Ø NaBH4/CeCl3 Ø NaBH4/NiCl2
Ø LiBH4 Ø Boranes Ø NaCNBH3
Ø Zn(BH4)2 Ø NaB(OAc)3H Ø Me4NB(OAc)3H
Ø Alkyl borohydrides

(i) NaBH4 :
Ø Temperature : 0-25°C
Ø Solvents : EtOH, MeOH, Dimethoxy ethane (DME)
Ø Substrate : RCHO, RCOR, RCOCl, R2C=NR
Mechanism :

The essence of the reaction is the transfer of a hydrogen atom with two electrons (called hydride transfer
though no hydride ion is involved). In addition, the developing negative charge on oxygen gets help from the
alcohol or the sodium ion or both and a molecule of alcohol adds to the boron during or immediately after the
reduction.

Sodium borohydride is white, crystalline solid that can be weighed in the open atmosphere and
used in either water or alcohol solution.
High yields of products are usually obtained.
Aldehyde reduction :

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Ketone reduction :

Examples :

1. (does not reduce –NO2 group)

Luche Reduction :

CeCl3 is a good Lewis acid & highly oxophilic

NaBH4 / NiCl2

Uses :
Ar – NO2 ¾® Ar–NH2
Ar–NO ¾® Ar–NH2
Ar–CH = N–OH ¾® Ar–CH2–NH2
Ø How to reduce unsaturated carbonyl compounds :
l Hydride reducing agents are not good choices for the selective reduction of the C=O bond of unsaturated
carbonyl compounds because they tend to add to the double bond as well, giving first the saturated carbonyl
compound, which is then reduced to the alcohol.
l The way to get regioselective addition directly to the carbonyl group is to add a hard, Lewis-acidic metal salt,
such as CeCl3.

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Borohydride can usually be relied upon to reduce an aldehyde or a ketone in the presence of an ester, while
lithium aluminium hydride will reduce almost any carbonyl group.

Note : Each reduction gives an alcohol, apart from the reduction of an amide with LiAlH4, which gives an amine.
NaBH4 is more selective: it will reduce this nitroketone.

[LiAlH4 will reduce nitro group as well]

Sodium borohydride will reduce only in protic solvents (usually ethanol, methanol, or water) or in
the presence of electrophilic metal cations such as Li+ or Mg2+ (LiBH4 can be used in THF, for
example).
l Reduction of esters to alcohols
Note : LiAlH4 is often the best reagent, and gives alcohols. As a milder alternative (LiAlH4 has caused countless
fires through careless handling), lithium borohydride in alcoholic solution will reduce esters—in fact, it has
useful selectivity for esters over acids or amides that LiAlH4 does not have. Sodium borohydride reduces
most esters only rather slowly.

WORKSHEET-3
For NaBH4
Reactants Products

NaBH4
1. ¾¾¾¾ ®

NaBH4
2. ¾¾¾¾ ®

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NaBH4
3. ¾¾¾¾ ®

NaBH4
4. CH2OH·(CH–OH)4·CHO ¾¾¾¾ ®
Glucose

NaBH4
5. ¾¾¾¾ ®

NaBH4
6. NC–CH2–CH2–CHO ¾¾¾¾ ®

NaBH4
7. ¾¾¾¾ ®

NaBH4
8. ¾¾¾¾ ®

NaBH4
9. ¾¾¾¾ ®

Reduction with LiAlH4 :

Reduction :
Aluminium – based reagents
• LiAlH4 • AlH3 • Li(O-t-Bu)3AlH • DIBAL–H

Lithium Aluminium Hydride (LiAlH4)

l Very powerful reducing reagent
l Available as either powder or pallet
l Used as a suspension in ether or THF
l Reacts violently with water, alcohol
l Reduces nitrile, amide & aryl nitro group to amine
l Reduces C-X bond, opens epoxide

Mechanism :

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Examples :

1. 2.

3. 4.

5. 6.

7. 8.

9. R – OTs ¾® R – H

Aluminium-based reagents Easy

RCHO ¾® RCH2OH
RCOR ¾® RCHOHR
RCOCl ¾® RCH2OH
Lactone ¾® Diol
Epoxide ¾® Alcohol
Ester ¾® Alcohol
Carboxylic acid ¾® Alcohol
Carboxylate salt ¾® Alcohol
Amide ¾® Amine
Nitrile ¾® Amine
Difficult

Lithium aluminium hydride, LiAlH4, is a reducing agent often used for reduction of ketones and aldehydes. A
grayish powder soluble in ether and tetrahydrofuran, LiAlH4 is much more reactive than NaBH4 but also more
dangerous. It reacts violently with water and decomposes explosively when heated above 120°C.

This reaction can be used to make secondary amines, from primary amines and acyl chlorides.

l Large nucleophiles attack equatorially and small nucleophiles attack axially.

l For example, reduction of 4-t-butylcyclohexanone with lithium aluminium hydride in Et2O gives 90% of the
trans alcohol: 90% of the hydride has added axially.
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l AlH4– is quite small as nucleophiles go: to make more o f the cis alcohol we need a larger nucleophile–lithium
tri-sec-butylborohydride, This is so large that it only attacks equatorially, yielding typically 95% of the cis
alcohol.

Reduction of Carboxylic Acids and Esters

l Carboxylic acids and esters are reduced to give primary alcohol :
l NaBH4 reduces esters very slowly and does not reduce carboxylic acid at all.
l Carboxylic acid and ester reductions are therefore usually carried out with the more reactive reducing agent LiAlH4.
All carbonyl groups, including acids, esters, ketones, and aldehydes, are rapidly reduced by LiAlH4.
Ø Carboxylic acid reduction :

+
3
2. 3 2 4 3 2 2

3
3

Mechanism :
Before the reduction itself takes place, LiAlH4, a source of the very strongly basic hydride ion (H:–), reacts
with the acidic hydrogen of the carboxylic acid to give the lithium salt of the carboxylic acid and one equivalent
of hydrogen gas (that is, dihydration).

The reduction occurs in two stages. In the first stage, the AlH3 formed, reduces the carboxylate ion to an
aldehyde. The aldehyde is rapidly reduced further to give, after protonolysis, the primary alcohol.

Ø Ester reduction :
Lithium aluminum hydride reduces all carboxylic acid derivatives, Reduction of esters with this reagent, like
reduction of carboxylic acids, gives primary alcohols.

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Ø Reduction of Amides to Amines :
Amines are formed when amides are reduced with LiAlH4.

Mechanism :
l In the first step of the mechanism, the weakly acidic amide proton reacts with an equivalent of hydride, a
strong base, to give hydrogen gas, AlH3 and the lithium salt of the amide.

l The lithium salt of the amide, a Lewis base, reacts with the Lewis acid AlH3.

l The resulting species is an active hydride reagent, conceptually much like LiAlH4 and it can deliver hydride
to the C = N double bond.

Loss of the carbonyl oxygen occurs because it is converted into a better leaving group then the nitrogen.

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Ø Reduction of Nitriles to Primary Amines :
Nitriles are reduced to primary amines by reaction with LiAlH4, followed by the usual protonolysis step.

Mechanism :

Ø Reduction of Azides :
Azides are easily reduced to primary amines, either by LiAlH4 or by catalytic hydrogenation. Alkyl azides
can be explosive, so they are reduced without purification.

(i)

(ii)

Ø Reduction of Acid Chlorides to Aldehydes :

l A second, more recent, method of converting acid chlorides into aldehydes is the reaction of an acid chloride
at low temperature with a lithium tri(tert-butoxy) aluminium hydride).

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l The hydride reagent used in this reduction is derived by the replacement of three hydrogens of lithium
aluminum hydride by tert-butoxy groups. As the hydrides of LiAlH4 are replaced successively with alkoxy
groups, less reactive reagents are obtained.

Solved Examples : What carbonyl compounds would you reduce to obtain the following alcohol?

(a) (b)

Sol. (a) the target molecule is secondary alcohol, which can only be prepared by reduction of a ketone. Either
NaBH4 or LiAlH4 can be used.

(b) The target molecule is a primary alcohol, which can be prepared by reduction of an aldehyde, an ester, or
a carboxylic acid. LiAlH4 is needed for the ester and carboxylic acid reductions.

Ø Reduction with DIBAL-H (DIBAH or diisobutyl aluminium hydride, i-Bu2AlH)

l Preparing Aldehydes :
The partial reduction of an ester by diisobutylaluminium hydride (DIBAH) is an important laboratory-scale
method of aldehyde synthesis. The reaction is normally carried out at –78°C. (dry-ice temperature) in toluene
solution.

where DIBA-H =

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l DIBAL-H is in some ways like borane—it exists as a bridged dimer, and it becomes a reducing agent only
after it has formed a Lewis acid–base complex, so it too reduces electron-rich carbonyl groups most rapidly.
DIBAL will reduce esters even at –70°C, and at this temperature the tetrahedral intermediate may be stable.

l DIBAL-H is also good for reducing nitriles to aldehydes.

Ø Tris-(tert-butoxy) lithium aluminium hydride [LiAlH(OtBu)3]

l It is an Alternative to Rosenmund reduction :

Practice Problem : Complete the following reactions by giving the principal organic product(s).

RaneyNi
(a) PhCH2C º N + H2 ¾¾¾¾
heat
®

(b)

(c)

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WORKSHEET-4
For LiAlH4
Reactants Products

1. LAH
1. CH3–(CH3)2–CH2–COOH ¾¾¾¾
2. H OÅ
®
3

1. LAH
2. CH3–CH=CH–COOH ¾¾¾¾
2. H OÅ
®
3

1. LAH
3. H2N–CH2–CH2–COOH ¾¾¾¾
2. H OÅ
®
3

1. LAH
4. ¾¾¾¾
2. H OÅ
®
3

1. LAH
5. ¾¾¾¾
2. H OÅ
®
3

1. LAH
6. ¾¾¾¾
2. H OÅ
®
3

1. LAH
7. ¾¾¾¾
2. H OÅ
®
3

LAH
8. ¾¾¾ ®

LAH
9. RN3 ¾¾¾ ®
azide

LAH
10. Ph2C=N–OH ¾¾¾ ®
Oxime

1. LAH
11. R–CN ¾¾¾¾
2. H OÅ
®
3

1. LiAlD 4
12. ¾¾¾¾
2. H OÅ
®
3

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Reduction with BH3 :
Alternatively, borane in tetrahydrofuran (BH3, THF) is a useful reagent for reducing carboxylic acids to primary
alcohols. Reaction of an acid with BH3/THF occurs rapidly at room temperature, and the procedure is often
preferred to reduction with LiAlH4 because of its relative case, safety and specificity.

l Although borane appears superficially similar to borohydride, it is not an ion and that makes all the difference
to its reactivity. Whereas borohydride reacts best with the most electrophilic carbonyl groups, borane’s
reactivity is dominated by its desire to accept an electron pair into its empty p orbital. In the context of
carbonyl group reductions, this means that it reduces electron-rich carbonyl groups fastest. The carbonyl
groups of acyl chlorides and esters are relatively electron-poor (Cl and OR are very electronegative); borane
will not touch acyl chlorides and reduces esters only slowly. But it will reduce amides.

Ø BH3 reduces carboxylic acids to alcohols

l The best reagent for this is borane, BH3.

l Borane is an excellent reagent for reducing carboxylic acids. It reacts with them first of all by forming
triacylborates, with evolution of hydrogen gas. Esters are usually less electrophilic than ketones because of
conjugation between the carbonyl group and the lone pair of the sp3 hybridized oxygen atom—but, in these
boron esters, the oxygen next to the boron has to share its lone pair between the carbonyl group and the
boron’s empty p orbital, so they are considerably more reactive than normal esters, or the lithium carboxy-
lates formed from carboxylic acids and LiAlH4.

l Borane also makes a good alternative to LiAlH4 for reducing amides as the two reagents have slightly
different chemoselectivity—in this example borane reduces an amide in the presence of an ester.

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l Borane is a highly chemoselective reagent for the reduction of carboxylic acids in the presence of other
reducible functional groups such as esters, and even ketones.

Ø Summary :

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EXERCISE
1. Predict the products of the following reactions (the aromatic ring is unreactive in all cases). Indicate
regiochemistry when relevant.

ì(a) ¾¾¾¾¾
H2 /Pd
®?
ï
ï(b) ¾¾¾¾¾
Br2
®?
ï
ï HBr
í(c) ¾¾¾¾¾® ?
ï 1.OsO 4
ï(d) ¾¾¾¾¾
2.NaHSO3
®?
ï
D2 /Pd
ï(e) ¾¾¾¾¾
î ®?

2. Suggest structures for alkenes that give the following reaction products. There may be more than one answer
for some cases.
H /Pd
(a)? ¾¾¾¾¾
2
® 2 - Methylhexane

H /Pd
(b)? ¾¾¾¾¾
2
®1,1 - Dimethylcyclohexane

3. Propose structures for alkynes that gives the following products on oxidative cleavage by KMnO4 :

(a)

(b) 2CH3(CH2)7COOH + HO2C(CH2)7COOH

4. Predict the products of the following reactions :

5. Predict the products from reaction of 5-decyne with the following reagents:
(A) H2, Lindlar catalyst
(B) Li in NH3
(C) Excess H2, Pd/C catalyst

6. Hydrocarbon A has the formula C9H12 and absorbs 3 equivalents of H2 to yield B, C9H18, when hydrogenated
over a Pd/C catalyst. On treatment of A with aqueous H2SO4 in the presence of mercury (II), two isomeric
ketones, C and D, are produced. Oxidation of A with KMnO4 gives a mixture of acetic acid (CH3COOH) and
the tri-carboxylic acid E. Propose structure for compounds A–D, and write the reactions.

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OXIDATION
OXIDIZING AGENTS
(i) Peracids, RCO3H
(ii) Cr(VI) compounds (K2Cr2O7, Na2Cr2O7, CrO3)
(iii) Osmium tetroxide, OsO4
(iv) Mn(VII) compounds (MnO2)
(v) Ozone, O3
(vi) Some high oxidation state Hal, N, or S compounds

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(A) Oxidation with Na2Cr2O7

l For large-scale oxidations, an expensive reagent such as Na2Cr2O7 in aqueous acetic acid is used.
Na2Cr2O7 [O]
1. R–CH2–OH ¾¾¾¾ ® R–CHO ¾¾¾
¾ ® R–COOH

Na2Cr2O7
2. ¾¾¾¾ ¾
®

Mechanism :
Oxidation of isopropyl alcohol to the ketone acetone by chromic acid.
The first steps of the reaction involve an acid-catalyzed displacement of water from chromic acid by the
alcohol to form a chromate ester.

... (i)

After protonation of the chromate ester, it decomposes in a b-elimination reaction.

... (ii)

... (iii)

This last step is much like an E2 reaction. Because Cr(VI) is particularly electronegative, especially when
protonated, the chromium readily accepts an electron pair and is thus reduced. The reaction is so rapid that
the Bronsted base in the reaction can be very weak; notice that water is the base in eq. (iii). In the resulting
H2CrO3 by-product chromium is in a + 4 oxidation state. The ultimate by-product is Cr3+ because, in subse-
quent reactions, Cr(IV) and Cr(VI) react to give two equivalents of a Cr(V) species, which then oxidizes an
additional molecule of alcohol by a similar mechanism.
Cr (IV) + Cr(VI) ¾® 2Cr(V)
Cr(V) + (CH3)2CH – OH ¾® Cr(III) + (CH3)2C = O + 2HÅ

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l Chromic acid is best avoided if acid-sensitive alcohols are to be oxidized, and an alternative reagent for these
is PCC (pyridinium chlorochromate), which can be used in dichloromethane.

l Several forms of Cr(VI) can be used to convert secondary alcohols into ketones. Three of these are chromate
(CrO42–), dichromate (Cr2O72–), and chromic anhydride or chromium trioxide (CrO3). The chromium is typically
reduced to a form of Cr(III) such as Cr3+.
l Aldehydes are further oxidized to carboxylic acids.

l Tertiary alcohols are not oxidized under the usual conditions. Notice that for oxidation of alcohols at the
a -carbon to occur, the a -carbon atom must bear one or more hydrogen atoms. Consider, for example, the
oxidation of isopropyl alcohol to the ketone acetone by chromic acid (H2CrO4).

Practice Problems :

1. Complete each of the following reactions by giving the major organic product.

3 CrO - pyridine
(A) (B) HO—CH2CH2CH2—OH ¾¾¾¾¾¾
CH2 Cl2
®

2. From which alcohol and by what method would each of the following compounds best be prepared by an
oxidation?

(A) (CH3)2CHCH2CH2CH2CO2H (B) 3 2 2 3

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Oxidation with CrO3 :
Chromium trioxide (CrO3) in aqueous acid, oxidize primary alcohols to carboxylic acids. An aldehyde is
involved as an intermediate in this reaction but can’t usually be isolated because it is further oxidized too
rapidly.

Secondary alcohols are oxidized easily and in high yield to give ketones.

Ø Oxidation of Aromatic side Chains

The selective oxidation of alkyl chains attached to an aromatic ring can be carried out with CrO3 in acetic
anhydride. Thus, p-nitrotoluene is converted into p-nitrobenzylidine diacetate, which on hydrolysis in the
presence of acid gives p-nitrobenzaldehyde.

Ø How to oxidize secondary alcohols to ketones :

The combination of CrO3 and sulfuric acid is often referred as Jones reagent, and the oxidation of alcohols
with this reagent in acetone is called Jones oxidation. The reagent is selective as it is useful for the
oxidation of alcohols, which contain carbon-carbon double or triple bonds, allylic or benzylic C–H bonds. The
reaction is carried at 0-20°C to give the corresponding carbonyl compounds.

l Complex between chromium trioxide and two molecules of pyridine in methylene chloride solvent, commonly
known as the Collins reagent :

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(A) Oxidation with PCC
l The best method for preparing an aldehyde from a primary alcohol on a laboratory scale (as opposed to an
industrial scale) is by use of pyridinium chlorochromate (PCC, C5H6HCrO3Cl) in dichloromethane solvent.
l It occurs at low temperatures.

(A)

(B)

(C)

Mechanism :
The first step involves reaction between the alcohol and a Cr(VI) reagent to form a chromate intermediate,
which contains an O-Cr bond.

Practice Problems :
3. What alcohols would give the following products on oxidation ?

(a) (b) (c)

4. What products would you expect from oxidation of the following compounds with CrO3 in aqueous acid ?
With pyridinium chlorochromate ?
(a) 1-Hexanol (b) 2-Hexanol (c) Hexanal

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Pyridinium Dichromate (PDC) Oxidation
l Pyridinium dichromate (PDC), (C5H5NH+)2Cr2O72–, oxidizes alcohols under neutral condition without affecting
other functional groups. Primary alcohols are oxidized to aldehydes with excellent yield.
l Allylic alcohol can be oxidized to ab-unsaturated carbonyl compounds.
l Excellent yields are obtained by the oxidation of secondary alcohols by using trimethyl silyl peroxide and
PDC.
l PDC is less acidic than PCC (pyridinium chlorochromate) and hence is more suitable in the oxidation of acid
sensitive compounds.
l PDC in CH2Cl2 or DMF is also called as Corey-Schmidt reagent.
l It is used for the selective oxidation of allylic alcohols in presence of other alcoholic groups.
l In CH2Cl2, it conveniently oxidizes primary alcohols to aldehydes at room temperature.
l However conjugated alcohols like allylic and benylic primary alcohols, always give aldehydes.

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WORKSHEET-5
For Oxidation
Reactants Products

Na2Cr2O7
1. ¾¾¾¾
H SO
¾®
2 4

Na2Cr2O7
2. ¾¾¾¾
H SO
¾®
2 4

CrO3
3. CH2–CH2–OH ¾¾¾¾
Pyridene
®

PDC
4. ¾¾¾¾
CH Cl
®
2 2

PDC
5. 2 ¾¾¾¾
CH Cl
®
2 2

CrO3 +H 2SO 4
6. ¾¾¾¾¾¾
H O+acetone
®
2

CrO3 +H 2SO 4
7. ¾¾¾¾¾¾
H O+acetone
®
2

K 2Cr2O7 +H 2SO 4
8. ¾¾¾¾¾¾¾
H O+acetone
®
2

K 2Cr2O7 +H 2SO 4
9. ¾¾¾¾¾¾¾
H O +acetone
®
2

(B) Oxidation with HIO4 :

Ø 1,2-Diol Cleavage :
1,2-Diols are oxidatively cleaved by reaction with periodic acid (HHO4) to yield carbonyl compounds, a reaction
similar to the KMnO4 cleavage of alkenes.
Mechanism :

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1.

If the two –OH groups are on an open chain, two carbonyl compounds result. If the two –OH groups are on a
ring, a single, open-chain dicarbonyl compound is formed.

WORKSHEET-6
For HIO4
Reactants Products

1. + HIO4 ¾¾®

2. + HIO4 ¾¾®

3. + HIO4 ¾¾®

4. + HIO4 ¾¾®

5. + HIO4 ¾¾®

6. + HIO4 ¾¾®

7. + HIO4 ¾¾®

8. ¾¾®

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(C) Oxidation of Phenols : Quinones
l Phenols do not undergo oxidation in the same manner that alcohols do because they do not have a hydrogen
atom on the hydroxyl-bearing carbon.
l Reaction of a phenol with any of a number of strong oxidizing agents yields a 2, 5-cyclohexadiene-1,4-dione,
or quinone.
l Fremy’s salt [potassium nitrosodisulfonate, (KSO3)2NO] is now preferred.

(D) Oxidation with OsO4

Ø Oxidation of Alkenes : Hydroxylation and Cleavage :
l Hydroxylation of an alkene — the addition of an –OH group to each of the two alkene carbons — can be
carried out by reaction of the alkene with osmium tetraoxide (OsO4).
l The reaction with syn stereochemistry and yields a 1,2-dialcohol, or diol product (also called a glycol).

Ø Reaction with Alkynes

l Alkynes react with OsO4 in the presence of tertiary amines such as pyridine to give osmium (VI) ester
complexes, which on hydrolysis with sodium sulfite yield the corresponding carbonyl compounds. In the
case of terminal alkynes, carboxylic acids are obtained.

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(E) Oxidation with KMnO4 :
(a) Oxidative cleavage of alkene :
l Potassium permanganate (KMnO4) in neutral or acidic solution cleaves alkenes, giving carbonyl-containing
products in low to moderate yield.
l If hydrogens are present on the double bond, carboxylic acids produced; if terminal alkene is
present then, CO2 is formed.

hot KMnO4
2. CH3 – CH = CH – CH3 ¾¾¾¾¾
H OÅ
® 2CH3COOH
3

Examples :

(b) Oxidative Cleavage of Alkynes :

l Alkynes, like alkenes, can be cleaved by KMnO4.
l A triple bond is generally less reactive than a double bond.
l The product obtained from cleavage of an internal alkyne are carboxylic acids; from a terminal
alkyne, CO2 is formed as one product.

An internal alkyne

A terminal alkyne

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(c) Oxidation of Alkylbenzene Side Chains :
l The benzene ring is inert to strong oxidising agents such a KMnO4 and Na2Cr2O7
l Alkyl side chains are readily attacked by oxidizing agents and are converted into carboxyl groups, –COOH.
l The net effect conversion of an alkylbenzene to a benzoic acid, Ar–R ¾® Ar–COOH.

(has no benzylic hydrogens)

WORKSHEET-7
For KMnO4
Reactants Products

cold KMnO
7. HO–CH2–CH=CH–CH2–OH ¾¾¾¾¾
4
®

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(F) Oxidation of Amines
Amines are easy to oxidize, and oxidation is often a side reaction in amine synthesis.
The following partial structures show some of the bonding and oxidation states of amines :

l Depending on their specific structure, these states are generally more oxidized as you go from left to right
(Note the increasing number of bonds to oxygen.)
l Most amines are oxidized by common oxidants such as H2O2, permanganate, and peroxyacids.
l Primary amines oxidize easily, but complex mixtures of products often result.
l The following sequence shows increasingly oxidized products of a primary amine, as it becomes more
oxidized from left to right. [O] is a generic oxidizing agent.

l Secondary amines are easily oxidized to hydroxylamines.

l Tertiary amines are oxidized to amine oxides, often in good yields. Either H2O2 or peroxyacid may be used
for this oxidation.

(G) Mn(IV) Reagents as an Oxidant

MnO2 is a useful selective oxidizing reagent in organic synthesis. It is commercially available, and it can also
be prepared by the reaction of MnSO4.4H2O with KMnO4 in aqueous NaOH.

Ø Oxidation of Alcohols
MnO2 can selectively oxidize allylic and benzylic alcohols to the corresponding carbonyl compounds. The
advantage of this method is that the reaction takes place under mild and neutral conditions, also carbon-
carbon double and triple bonds are unaffected.

2
1.

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(H) Selenium Dioxide
l Selenium dioxide (SeO2) is a colorless crystalline solid. It is soluble in solvents like dioxane, ethanol, acetic
acid and acetic anhydride. It is extremely poisonous and should be carefully handled while working with it.
However, it is very selective oxidant.
This reagent is used for selective oxidation of

1. Active methylene and methyl groups

SeO2
(a) CH3CHO ¾¾¾® CHO·CHO

SeO2
(b) ¾¾¾®

(activated ring methylene groups)

2. Allylic hydroxilation and oxidation :

The methylene or methyl group µ to the most highly substituted end of the double bond is hydroxylated
according to the order of preference of oxidation CH2 > CH3 > CH groups.

SeO2
(a) ¾¾¾®

SeO2
(b) ¾¾¾®

SeO2
(c) ¾¾¾®

SeO2
(d) CH3–CH2–CH2–CH=CH2 ¾¾¾® CH3–CH2–CH=CH–CH2–OH

Mechanism :
The oxidation is carried out in aqueous acetic acid medium and hence the actual reagent is selenious acid,
H2SeO3. The mechanism is still not clearly known. It is suggested that the reaction proceeds by the attack
of selenious acid on the enol form of the substrate to yield selenate ester which eliminates water and
selenium to give the product.

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WORKSHEET-8
1. Worksheet of SeO2

Reactants Products
SeO
2
1. CH3CHO ¾¾¾¾ ®

SeO
2
2. ¾¾¾¾ ®

SeO
2
3. ¾¾¾¾ ®

SeO
2
4. ¾¾¾¾ ®

SeO
2
5. ¾¾¾¾ ®

SeO
2
6. ¾¾¾¾ ®

SeO
2
7. ¾¾¾¾ ®

SeO
2
8. ¾¾¾¾ ®

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(K) Palladium Catalyzed Reactions
Ø Wacker Oxidation
l Wacker oxidation of alkenes to aldehydes to ketones is one of the most important industrial processes. In
Wacker process, Pd catalyst is used in combination with O2 and copper salt to transform alkenes to aldehydes
or ketones. In these reactions, copper (II) oxidizes the reduced Pd(0) to palladium (II) by oxygen. The oxygen
incorporated in the alkene to give the carbonyl compound is obtained from water.

Oxo Process/Hydroformylation :
Hydroformylation is another commericially important process that involves a transition-metal catalyst, in this
case a tetracarbonylhydricobalt (I) catalyst. Propionaldehyde, for example, is produced by the hydroformylation
of ethylene. (This is sometimes called the oxo process).

Fehling's Test and Fehling's Reagent :

Fehling's Reagent consists of the mixture of two solutions (Fehling Solution A & B). Fehling solution A is
made up of aqueous copper sulfate and Fehling solution B is made up of Rochelle salt or alkaline sodium
potassium tartrate. Prior to the test equal quantity of both the solutions are mixed together.
The reaction requires heating of aldehyde with Fehling's Reagent which will result in the formation of a
reddish-brown colour precipitate. Hence, the reaction results in the formation of carboxylate anion. However,
aromatic aldehydes do not react to Fehling's Test. Moreover, ketones do not undergo this reaction. Thus, we
can differentiate between aldehydes and ketones.
The reaction requires heating of aldehyde with Fehling's Reagent which will result in the formation of a
reddish-brown colour precipitate. Hence, the reaction results in the formation of carboxylate anion. However,
aromatic aldehydes do not react to Fehling's Test. Moreover, ketones do not undergo this reaction. Thus, we
can differentiate between aldehydes and ketones.

Tollens' Test (Silver Mirror Test) :

The ease with which aldehydes undergo oxidation provides a useful test that differentiates aldehydes from
most ketones. Mixing aqueous silver nitrate with aqueous ammonia produces a solution known as Tollens'
regent. The reagent contains the diamminosilver (I) ion, Ag(NH3)2+. Although this ion is a very weak oxidizing
agent, it oxidizes aldehydes to carboxylate anions. As it does this, silver is reduced from the +1 oxidation
state [of Ag(NH3)2+] to metallic silver. If the rate of reaction is slow and the walls of the vessel are clean,
metallic silver deposits on the walls of the test tube as a mirror; if not, it deposits as a gray-to-black precipitate.

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Tollens' reagent gives a negative result with all ketones except a-hydroxy ketones :

Benedict's : Reducing Sugar :

Benedict's reagent (an alkaline solution containing a cupric citrate complex ion) oxidize and thus give positive
tests with aldoses and ketoses. The tests are positive even though aldoses and ketoses exist primarily as
cylic hemiacetals.
Benedict's solution (which contains a cupric tartrate complex ion) give brick-red precipitates of Cu2O when
they oxidize an aldose. [In alkaline solution ketoses are converted to aldoses, which are then oxidized by the
cupric complexes.] Since the solutions of cupric tartrates and citrates are blue, the appearance of a brick-
red precipitate is a vivid and unmistakable indication of a positive test.

Sugars that give positive tests with Benedict's solutions are known as reducing sugars, and all carboydrates
that contain a hemiacetal group give positive tests. In aqueous solution these hemiacetals exist in equilibrium
with relatively small, but not insignificant, concentration of noncyclic aldehydes or a-hydroxy ketones. It is
the latter two that undergo the oxidation, perturbing the equilibrium to produce more aldehyde or a-hydroxy
ketone, which then undergoes oxidation until one reactant is exhausted.
Carbohydrates that contain only acetal groups do not give positive tests with Benedict's and they are called
nonreducing sugars. Acetals do not exist in equilibrium with aldehydes or a-hydroxy ketones in the basic
aqueous media of the test reagents.

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