Oxidation is an important process and has played an important role in

organic synthesis1. Oxidation of various compounds such as alkanes, alkenes,

alkynes, arenes, ethers, alcohols, aldehydes, ketones amines etc. are oxidized by

several oxidizing agents such as KMnO4 , Osmium tetroxide, Ruthenium

tetroxide, Cr(VI) compounds, Palladium (II) and Platinum (II)compounds, Lead

(IV), Hg(II), Thallium (II) compounds, copper (II), Vanadium pentoxide,

Manganese dioxide, Cobalt (III), selenium dioxide, glycol-cleavage agents in the

oxidative scission of carbon-carbon double bonds, peracid, peroxide.

Majority of the oxidation processes employed industrially involve catalysis

by metal and their compounds.

A brief discussion on different reactions related to oxidation of alcohols with

different oxidizing agents has been given below.

II. 1. Oxidation of Alcohols with Different Oxidizing Agents

II. 1. A. Oxidation of alcohols with Potassium permanganate:

Primary and secondary alcohols are readily oxidized by permanganate ion

both in acidic and basic medium.2-5 Permanganate ion is a strong oxidizing agent

and the product obtained from the oxidation of alcohol is mainly corresponding

carboxylic acid 3. (Scheme-1)

CH3 CH 3
KMnO4/1.5 MH2SO4
CH3 CH 2CH(CH2)5 OH CH3 CH 2CH(CH2)4 CO 2H
250C

1 2

23
 KMnO4/ 0.9MNaOH
CHOHCO2H COCO2 H
-200C, 2hr

3 4 (50-67%)

Scheme-1

Under neutral or mild acidic conditions the rate of reaction is very slow;

e.g. the relative rates of oxidation of 2-butanol under alkaline, acid and neutral

conditions are 21:25:1; however, addition of peroxide is known to accelerate the

rate of oxidation in dilute acid.6

7-11
Stewart & Co-Workers reported that the rate acceleration in basic

solution is caused by ionization of the alcohols to give alkoxide ion which readily

transfers electrons to the oxidants. (Scheme-2)

- -
OH - MnO4
R2CHOH R2CHO R2CO

5 6 7

Scheme-2

In general good yields are obtained from alkaline permanganate oxidation

except when the initial product is an enolizable aldehyde or ketone. In such cases

oxidation of the enolic C-C double bond may become a serious side reaction.

Alkaline permanganate has been successfully used in the oxidation of

carbohydrates to monocarboxylic acid derivatives.12, 13

In this procedure all the

hydroxyl except the one undergoing oxidation are first protected by acetoneation

or similar means. For example Link and Sell12 have been describing the

24
conversion of diacetone D-galactose (8) to diacetone D-galacturonic acid (9).

(Scheme-3)

HC O
HC O

O O
H O KMnO4/ 1.7M KOH H O

250C, 24 hr O H
O H

O H O H

H H

CH 2OH CO2H

8 9 (49-65%)

Scheme-3

The base catalysis of these reactions is due to ionization of the alcohols.

However, the observation of acid catalysis is probably due to a change in nature of

the oxidant rather than the substrate, i.e., in acidic solutions manganese (VII)

exists partially in the form of permanganate acid, which is presumably a better

oxidant than the anion.10, 14

MnO4- H+ HMnO4

Since permanganate is a fairly vigorous and non selective oxidant, it does

not readily lend itself to use in organic solvents. However acid permanganate
15
oxidation can be conducted in glacial acetic acid; e.g. Neidig and co-workers

obtained good yields of alkyl phenyl ketones (71-96%) by the oxidation of

alkylphenylcarbinol. A solution of potassium permanganate dissolved in 175ml

water and 400ml of glacial acetic acid was added dropwise to a stirred solution of

25
the alcohol over a period of 3 hr during which time the temperature was

maintained between 25-30 0C .The products then isolated by steam distillation and

purified by conventional methods. Yields were greatly decreased with t-

alkylphenylcarbinols because these compounds readily undergo cleavage to give

benzaldehyde. (Scheme-4)

OH
O O
KMnO4
CHC(CH 3) 3 CC(CH 3) 3 CH
250 C, 3hr

10 11 (34%) 12 (46%)

Scheme-4

Under neutral aqueous conditions 1, 4-diols undergo an oxidative

cyclization to give γ-lactones when treated with permanganate ion.16 (Scheme-5)

OH
KMnO 4/ H2O
O
OH 20C, 8hr

13 14 (71%)

Scheme-5

II. 1.B. Oxidation of alcohols with Manganese Dioxide:

Manganese dioxide occupies an important place as oxidants because of its

considerable selectivity. MnO2 exhibits considerable selectivity and under mild

conditions it is a specific oxidant for α, β-unsaturated alcohols. However in the

26
absence of unsaturation. It will also slowly attack primary and secondary alcohols

to give aldehydes and ketones in good yields. It can be used as a suspension in a

variety of solvents (water, acetic acid, carbon tetrachloride, chloroform,

methylene chloride, hexane, benzene, tetrahydrofuran, isopropyl alcohol,

acetonitrile, ether ethyl acetate, pyridine, DMSO etc. ) to selectively convert α, β-

unsaturated alcohols to α, β- unsaturated carbonyl compounds but other easily

oxidizable functional groups such as carbon-carbon double bonds, saturated

alcohols and vicinal glycols are much less readily attacked by this reagent at room

temperature. These may be understood from following reactions.17-19 (Scheme-6)

OH O
CH3 CH 3
MnO2 / pet ether
HC CC CHCH CH CHCH3 HC CC CHCH CH CCH3
250 C, 30 min

15 16

OH
OH
OH
OH
MnO2/ CHCl3

250 C, 6.25 hr
O
OH

17 18

OH O
OH OH
MnO2
C CCHCH 3 C CCCH 3

19 20

Scheme-6

27
 It is apparent that it makes little difference if the unsaturation is part of an

olefinic, acetylenic, aromatic, and allylic or carbonyl system. α-hydroxy ethers are

also oxidized by MnO2, suggesting that the reaction may be initiated with any

structure that provides an electron-rich source in the position adjacent to the

hydroxyl20. Much evidence has accumulated suggesting that the activity of this

reagent depends on the procedure used in its preparation.17, 21-23

II.1.C. Oxidation of alcohols with Lead Tetraacetate:

Lead Tetraacetate can be used as an alcohol oxidant in a variety of

solvents including acetic acid, benzene, heptane, pyridine, chloroform and

OCH3

(AcO)2Pb

mixtures of these. Isolation of the crystalline ester OCH3 from a wet

methanol solution of lead tetra acetate indicates that the reaction probably

proceeds by way of an esterification mechanism reminiscent of the one previously

discussed for chromic acid oxidations24. In nonpolar solvents these esters can then

undergo decomposition to give carbonyl compounds, cyclic ethers or olefins. All

these products can be formally accounted for by assuming a cyclic transfer of

electrons with concomitant hydrogen abstraction from either the α-, β-, δ- or ε-

carbons.

If hydrogen is abstraction from α-position, the products are carbonyl

compounds.(Scheme-7)

28
 R O
Pb(OAc)2 RCOR' + Pb(OAc)2 + HOAc
R' H
O

Ac

21 22

Scheme-7

With short chain primary aliphatic alcohols almost equal quantities of

25
ether and aldehyde are formed , but with longer chain primary and secondary

alcohols the yield of carbonyl product decreases.26, 27 (Scheme-8)

Pb(OAc)2/heptane
CH3CH2CH2CH2CH 2OH C4H9CHO C5H11OAc C5H 11OH
reflux, 18 hr
O CH 3

23 24(25%) 25(20%) 26(30%) 27(25%)

Scheme-8

Mihailovic and co-workers28 investigated optimum conditions for the

formation of cyclic ethers from aliphatic alcohols and found it best to dissolve

both the alcohol and the oxidant in benzene before starting the reaction by

applications of heat.

The products obtained from oxidations of δ,ε- andγ, δ-unsaturated alcohols

can be satisfactorily accounted for by similar cyclic electron transfers.29, 30

In such cyclic mechanism it is difficult to assign the direction of electron

flow and thus determine if the hydrogen is being transferred as a proton, as a

hydride ion, or as an unchanged atom. Hence the arrows used in the above

29
formulation are illustrative of only one of three possibilities. Current evidence, in
31
fact, indicates that an ionic mechanism predominates in acetic acid and

pyridine26, 28
solutions, with single-electron shifts being more likely in nonpolar

solvents such as benzene and heptanes.32 (Scheme-9)

OAc
O Pb(OAc)2 CH 2O
O
Pb(OAc)2

28 29

O
Pb(OAc)2 O
OAc
+ Pb(OAc)2
OAc

30 31

Scheme-9

For example:

Pb(OAc)2/C 6H6
CH2=CHCH2 CH2OH
reflux
C H2=CHCH2OA c + CH2=CHCH2CH2OCH2C H=CH2

(30%) (13%)
CH2CH=C H2

+ CH2=CHC H2CH2OAc +

(20%) (32%)

Nonpolar solvents would favor the hemolytic process, while polar and

basic solvents such as pyridine would promote carbonyl formation. Thus when

primary and secondary alcohols are oxidized in pyridine, the yield of carbonyl

30
product is generally increased (50-90%) and no cyclic ether is formed. Hence use

of lead tetraacetate in this solvent provides an easy route from primary alcohols to

aldehydes. (Scheme-10)

Pb(OAc)4/ P yridine
CH3CH2CH2CH2OH CH3CH2CH2CHO
ref lux, 18 hr

32 33 (75%)

Scheme-10

II.1.D. Oxidation of alcohols with Copper and Cupric ion:

Primary and secondary alcohols may be dehydrogenated to aldehydes and

ketones, respectively, by passing the vapors at an elevated temperature over

activated copper, copper-chromium or copper-nickel catalysts in the presence of

oxygen.33 Fair yields (46-72%) of aldehydes are obtained by passing primary

alcohol vapors over copper gauze at 5000 C and 80-150 mm of Hg pressure33.

Copper catalysts have also been employed in the commercial preparation of α, β-

unsaturated carbonyl compounds from the corresponding alcohols. Thus

methacrolein can be prepared in good yield (95%) from methallyl alcohol by

passing the vapor along with air 1 atm and about 350 0 C over copper gauze.34

(Scheme-11)

CH 3 Cu, O2 CH 3
CH=C-CH2OH CH 2=CH-CHO
3500C

34 35 (95%)

Scheme-11

31
 Cupric ion can also be used in aqueous acetic acid or pyridine solution to

convert α-ketols into the corresponding α-diketones.35-36 The typical application

of this reactions are found in the conversion of benzoin (36) to benzil35,36 ; the

oxidation of sebacoin (38) to sebacil.35(Scheme-12)

O OH O O
Cu(OAc)2, NH4NO3/HOAc
C CH C C
reflux, 1.5 hr

36 37

C=O
C=O Cu(OAc)2/ AcOH (CH2) 8
(CH2)8
reflux, 1 min. C=O
CHOH

38 39

Scheme-12

Wendler and Coworkers have reported the conversion of α-ketols (40) and

(42) to the corresponding disophenol37 (43) or the glyoxal (41).38 (Scheme-13)

CH 2OH CH(OH) 2

C=O C=O

Cu(OAc)2, O2 / CH3OH

250C, 15 min

40 41

32
 O
O

OH
OH
Cu(OAc)2/ CH3OH
reflux, 1 hr

42 43
Scheme-13

In addition , both liquid and vapor phase dehydrogenation of 1,4-,1,5- and

1,6- diols to the corresponding lactones is accomplished by use of a copper

chromite catalyst.39-41 (Scheme-14)

O
Copper Chromite
HOCH2CH2CH2CH2CH2OH
2100C, 30 min

44 45
Scheme- 14

II.1.E. Oxidation of alcohols with Platinum and Oxygen:

Primary and secondary alcohols are readily oxidized by oxygen in the

presence of platinum.42 The reaction is of particular importance because of its

unique selectively. Primary alcohols are usually oxidized more than secondary

alcohols and with polyhydroxy compounds such as carbohydrates, oxidation of

only the primary hydroxyl can be achived.43-46 Under alkaline conditions (water or

aqueous acetone) primary alcohols are converted, often in quantitative yields, to

the corresponding carboxylic acids. However when the reactions is carried out

under neutral conditions in an organic solvent (heptane, dioxane, ethyl acetate,

33
glacial acetic acid, chloroform, butanone or benzene), the products are

aldehydes.47

Steroids containing two or more hydroxyls, with one being in the 3-

position, undergo selective oxidation at that position.48-52 (Scheme-15)

OH
OH
CO2CH 3
CO 2CH3

Pt, O2/ EtOAc

250C, 16 hr
HO
OH O
OH

46 47 (70%)

Scheme-15

In an investigation of the oxidation of several cyclitols it was observed that

axial hydroxyl were attacked in preference to equatorial hydroxyl groups; i.e.,

myo-inositol (48) underwent oxidation only at the lone axial hydroxyl to give the

corresponding ketone (49) as the product, while scyllo-inositol (50) lacking axial

hydroxyls, was resistant to oxidation42 When two or more axial hydroxyls are

present, only one is oxidized, no diketones have been found in the products.

(Scheme-16)

HO
HO
HO Pt, O2
HO OH
HO OH
HO OH
HO OH

48 49

34
 OH
HO
Pt, O2
HO OH

HO OH

50
Scheme-16

The reagent can also be used in the oxidation of unsaturated alcohols since

it does not readily attack carbon- carbon double bonds.53

II.1.F. Oxidation of alcohols with Ruthenium Tetroxide:

Ruthenium tetroxide is a vigorous oxidant that can be used for the

oxidation of secondary alcohols to ketones. Following reactions indicate the

successful use of RuO4 as an oxidant for different types of alcohols.54-56 (Scheme-

17)

OH O

RuO4/CCl4
10-15 0C

51 52 (93%)

OH
RuO4/CFCl3 O

10C, 1-5 min

53 54 (62%)

Scheme-17

35
 Although benzyl alcohol has been reported to give benzaldehyde in good

yield (90%) when oxidized by RuO4, the yield from other primary alcohols is

much lower.56

II.1.G. Oxidation of alcohols with Bismuth Trioxide:

Bismuth trioxide has been used in the oxidation of acyloins and it appears

to be a specific reagent for this type of compound. Acyloins are easily oxidized to

α-diketones by heating in acetic acid.57 For example, octane-4, 5-dione is obtained

in good yield (84%) from the oxidation of butyroin with bismuth trioxide in acetic

acid for 15 min at 1000C. (Scheme-18)

Bi2 O3 /AcOH
RCOCHOHR RCOCOR

55 56
Scheme-18

Application of this reaction to steroids has been made in the conversion of

α-ketols into diosphenols.58 (Scheme-19)

Bi2O3/AcOH

O
HO
OH
O

57 58

Scheme-19

36
II.1.H.Oxidation of alcohols with Ceric ammonium Nitrate (Ceric
ion):

Ceric ion is a strong oxidant which readily attacks alcohols. However

carbonyl compounds bearing α-hydrogen are also very rapidly degraded by this
59
reagent thus unless a large excess of alcohol is used its synthetic usefulness is

limited to the preparation of aldehydes and ketones which do not bear α-

hydrogen.60-61

For example, benzaldehyde and several substituted benzaldehyde were

prepared in over 90% yield by oxidation of the corresponding benzyl alcohols

with 0.5 M ceric ammonium nitrate in 50% aqueous acetic acid. 62 (Scheme-20)

CAN
CH 3O CH 2OH CH 3O CHO
750C

59 60 (80%)

CAN
CH 2OH CHO
750C

61 62 (64%)

Scheme-20

This is most useful and widespread oxidation, as it encompasses the

alcohols to aldehydes to carboxylic acids sequence that is used so often in

synthesis.

37
II.2. Oxidation with Cr(VI) Compounds:

A great variety of compounds containing Cr (VI) have been proved to be

versatile reagents capable of oxidizing almost every oxidizable organic functional

group.63(a-g) In spite of this wide spectrum of action the reagents may be controlled

to give largely just one single product.64 Chromic acid is the most popular reagent

of this type used in organic chemistry for well over a century.64 In the last two

decades, however, a number of new chromium (VI) containing reagents together

with special reaction conditions have been developed to improve the selectivity of

oxidation and to deal with complex, highly sensitive compounds.64

II.2. Oxidation of Different Substrates with Cr(VI) Compounds:

II.2. A. Oxidation of alkanes:

Chromium (VI) oxidation of saturated hydrocarbons does not represent a

useful synthetic procedure since the reaction lacks selectivity and owing to the

vigorous reaction conditions and considerable second stage oxidation occur. As a

result complex mixtures of products are obtained, e.g. it is difficult to oxidize a

methylene group to secondary alcohols without further oxidation of the alcohol to

ketone and in some cases it is necessary to use condition sufficiently vigorous to

cause carbon-carbon bond cleavage as well. Usually it is possible to convert

tertiary C-H bonds to tertiary alcohols and isolated methylene to ketones.

However, many tertiary alcohols undergo a facile dehydration, making these

compounds difficult to obtain in good yield with reagents such as chromic acid

which require acidic conditions.

38
 In principle it might seem that compound containing Cr(VI) (chromic acid,

chromyl acetate, chromyl chloride, t-butyl-chromate, or dichromate ion ) should

be excellent oxidants for alkanes since they are soluble in a number of non-

aqueous solvents such as acetic acid , acetone and pyridine. However it has been

found difficult to avoid further oxidation of the initial products when chromium

(VI) oxidants are used due to the presence of tertiary C-H bonds, it is usually

possible to oxidize tertiary hydrogens preferentially in the presence of secondary

hydrogens. For example cis-decalin gives as the major products cis 9- decalol

when oxidized by dichromate ions in aqueous acetic acid.65 However, the tertiary

alcohols so produced often dehydrate readily and undergo a facile second stage

oxidation.

The Sager and Bradley 66reported that triethylmethane was easily oxidized

to triethylcarbinol, but unfortunately the product underwent dehydration and

further oxidation to diethyl ketone. The alcohol was obtained in 41% yield only if

the reaction was quenched after an appropriate time interval. Clearly maximum

possible yield for particular compounds will be determined by the relative

oxidation rate for the hydrocarbon and the corresponding alcohols reaction shown

below (Scheme-21):

Na2 Cr2 O7 +
AcOH/H2O
O
H OH

63 64(41%) 65 (36%)

Scheme-21

39
 Wiberg and Foster studied the oxidation of tertiary C-H bonds with

chromic acid predominantly to retention of configuration about the carbon atoms.

Oxidation of (+)-3- methylheptane by dichromate ion in 91% acetic acid gives

(+)-3- methyl -3-heptanol in only about 10% yield, but 70-85% retention of

configuration.67 (Scheme-22)

H OH
CrO3
AcOH

66 67 (7%)
Scheme-22

II.2.B. Oxidation of alkenes:

Chromium (VI) oxidation of C-C double bonds can lead to formation of a

variety of compounds, including epoxides, α-ketol and cleavage products. Since

mixtures of products are usually obtained, the synthetic value of this reaction is

minimized. However, it is possible to obtain respectable yields of some products if

experimental conditions are carefully controlled and if structure of the oxidant is

such possible number of oxidation path is limited.68

II.2.B. (i) oxidation of allylic C-H bonds

Good yields of α, β unsaturated ketones have been obtained from certain

compounds (usually steroidal alkenes) when they are subjected to oxidation by Cr

(VI) in acetic acid solution.

40
 Marshall et. al.69 has reported the introduction of a carbonyl at the C-7

position of pregneolone acetate by use of sodium chromate in an acetic acid –

acetic anhydride solution. (Scheme23)

CH3
CH3
C=O
C=O -2
CrO4 /AcOH

AcO O
AcO

68 69 (79%)
Scheme-23

With ∆8–pregnene derivatives, oxidation of allylic C-H bond is

complicated by the possibility of carbonyl formation at both the C-7 and C-11

position. For example 3β, 21- diacetoxy- 4,4,14 α-trimethyl ∆8-5α-pregnene-20-

one (70) gives the triketone (71) when oxidized by chromium trioxide in acetic

acid.70 (Scheme-24)

CH2OAc CH2OAc

C=O C=O

CrO 3/ AcOH

OAc OAc O

70 71

Scheme24

41
 From other compounds which have two unsubstituted allylic position,

mixture of products has been obtained. Thus both carvotanacetone (73) and

piperitone (74) obtained from carvomenthene (72).71, 72 (Scheme-25)

Cr(VI)

72 73 (25%) 74 (26%)
Scheme-25

The products of these reactions are sometimes contaminated by side

products arising from epoxide formation or double bond migration. For example
Wintersteiner and Moore73 obtained fine products (76-80) in varying yields when
they oxidized α (∆8-14) –cholesteryl acetate (75) with chromium trioxide in acetic
acid. (Scheme-26)

R
R
R

CrO 3 +
O
AcO H
O

O AcO
AcO

Ac O

75 76(16%) 77 (6%)

R
R
R

+
+
OH O
O OH
+ O OH
O O
AcO
O
AcO
AcO

78 (2%) 79 (1%) 80 (1%)

Scheme-26

42
II.2.B. (ii) Formation of epoxide and cleavage products:

Phenyl substituted C-C double bonds often yield epoxides and /or cleavage

products when oxidized by chromium (VI). These reactions are considerable

interest from a mechanistic point of view74 but because of the variety of products

usually obtained and because the epoxides and Cleavage products can be more

easily produced using other above reagents, they have little synthetic value. For

example A synthetically useful cleavage of a double bond by means of chromium

trioxide in acetic acid has been devised by Barbier75 which has first applied for

degradation of bile acid side chains by Wieland.76 The degradation involves

oxidation of trisubstituted olefins obtained by reaction of a carboxylic ester with

Grignard reagent (usually phenyl magnesium bromide or, less frequently methyl

magnesium iodide). Followed by dehydration of the resulting tertiary alcohol.

(Scheme-27)

R' C6H5 R'

C6H5
R'
C6H5MgBr R-CH-C-OH C C
R-CH-COOCH3
C6H5 R C 6H5

CrO3 AcOH

b
a

R-COOH R-C-R'
O

81 82

Scheme-27

43
II.2.C. Oxidation of arenes:

Chromium (VI) is the most versatile reagents for the oxidation of arenas

used in its various forms [ HCrO4-, Cr2O72- ,CrO2Cl2, CrO2(OAC)2] . Under proper

condition it will selectively convert side chain to carboxylic acids, aldehydes,

ketones, and diacetates. Under other conditions it attacks polynuclear arenes and

leaves the side chains intact.

Chromic acid oxidizes the side chain of phenylalkanes to give benzoic acid

derivatives77, 78
but benzene ring is itself attacked only under very vigorous

condition.79 Polynuclear aromatic hydrocarbons, however readily undergo ring

oxidation to yield the corresponding quinine.80 This chemoselectivity is shown in

the Cr (VI) oxide in anhydrous acetic acid (Fieser reagent).

A dichromate ion in neutral aqueous solution does not attack aromatic

systems but instead oxidizes aryl alkanes to the corresponding carboxylic acids or

ketones.81-82 Chromyl chloride converts toluene derivatives to substituted

benzaldehydes and other aryl alkanes primarily to β-phenyl carbonyl products.83

Chromyl acetate reacts with toluene derivatives to give fair yields of the

corresponding benzal diacetates.84

The selectivity that can be achieved with these reagents is indicated by the

reactions on the following pages.78, 82-84 (Scheme-28)

44
 Cr 2O7-2/H2SO4
O2N CO2 H
1000C, 30min

84 (82-86%)

Cr 2O2O7-2/H2O
O2 N CO 2H
2500C, 18hr

85 (94%)
O2 N CH 3

O
83 Cr2O2Cl 2/CCL4
O2 N CH
770C, 10hr

86(26%)

Cr2O7(OAc)2O/ (OAc)2O
O2 N CH(OAc) 2
5-100C, 2 hr

87 (66-67%)

Scheme-28

Chromic acid probably attacks arylalkanes at the C-H bond adjacent to the

ring. Four piece of evidence support this view. (Scheme-29)

(1) Chromic acid will not oxidize side chain such as t-butyl which lack α-

hydrogens.

(2) The oxidation of secondary alkyl chain gives phenyl ketones and a carboxylic

acid from CrO3

CH3 CH3
CH3
CrO3 -H2 O
CH CH2R C CH2R C CHR

OH

88 89 90

45
 CrO3

C CH3
RCOOH +

91

Scheme-29

(3) oxidation of n-alkyl benzene gives benzoic acid and an aliphatic carboxylic

acid with one carbon atom less than the original side chain.85 (Scheme-30)

CrO3 CO2H + RCO2H

CH2CH2R

92 93

Scheme-30

(4) The products obtained from the oxidation of equilenin acetate (94) and similar

compounds obviously result from α attack.86 (Scheme-31)

O O
O O

CrO3

OH
OAc
OAc
OAc

94 95

Scheme-31

46
II.2.D.Oxidation of ethers:

Inorganic oxidants have seldom been used to convert ether to more highly

oxidized compounds. However several reagents are capable of reacting with

methylene groups activated by adjacent oxygen.

Chromic acid converts ethers into esters or lactones by oxidation of α-

methylene groups to carbonyl functions.

87
Henbest and Nicholls obtained a high yield of the (97) from the

corresponding cyclic ether (96). Use of acetic acid as the solvent in a similar

reaction gave a lower yield (54%) of lactone.88 (Scheme-32)

CrO3/acetone-H 2SO4
200 C, 12hr
O O

96 97 (82%)
Scheme-32

Anhydrous chromium trioxide in acetic acid can also be used to convert

methyl ethers (98) into the corresponding (99).89 (Scheme-33)

O
CrO3/AcOH
CH3OR
HCOR

98 99 (50%)

Scheme-33

47
II.2.E. Oxidation of aldehydes:

Dichromate ions readily oxidize aldehydes to the corresponding carboxylic

acids in aqueous solutions. With both reagents however, and particularly under

strongly acidic or basic conditions, enolizable aldehydes suffer C-C bond

cleavage. Hence because of its greater reactivity under neutral conditions,

permanganate ion is probably the more useful oxidant for these compounds.

Furoic (101) for example, has been prepared in good yield from furfural by

use of potassium dichromate in an aqueous sulphuric acid solution.90 (Scheme-34)

O
K2Cr2O 7/9H 2SO 4
CH CO2H
1000C, 45 min.
O O

100 101 (75%)

Scheme-34

Aldehydes hydrates form chromate esters which undergo an acid catalyzed

decomposition with cleavage of the α C-H bond in the rate determining step.

(Scheme-35)

RCHO + H 2O RCH(OH)2

RCH(OH)2 + HCrO4- RCH(OH)OCrO3- + H2O

RCH(OH)OCrO3- + H+ RCOOH + H2O + Cr(IV)

Scheme-35

48
 In contrast to alcohols oxidation however the rate of reaction is not greatly

increased by replacing water with acetic acid as solvent.91 Such a change

suppresses the hydration equilibrium and this reagent is a C-C bond cleavage

initiated by attack at the α position of enolizable aldehydes. Thus oxidation of

normal and isobutylaldehyde results in formation of approximately 30% CO2 by

the following reactions.92 (Scheme-36)

Cr(VI)
(CH 3)2CHCHO (CH 3)2C=CHOH CH3COCH3 + CO2

Cr(VI)
CH3CH2CH2CHO CH3CH2CH=CHOH CH3CH2CO2H + CO2

Scheme-36

II.2.E. (i) Oxidation of aldehydes with heterocyclic halochromate:

Pyridinium Chlorochromate (PCC) is a mild acidic oxidizing agent which

can promote oxidative cationic cyclization of certain unsaturated aldehydes.93

This 2 isobutenylcyclohexan carboxaldehyde is converted to 3-methyl Δ2-

1-octalone in 78% yield in methylene chloride with 3 equivalent of PCC at room

temperature, followed by acidic treatment of the crude cyclization product with p-

toluenesulphonic acid. Formations of intermediate bicyclic alcohols which further

oxidize to the corresponding ketones have also been observed. (Scheme-37)

OH OH

CHO
PCC
CH2Cl 2 +

OH

102 103 104

49
 O O
O

H+
+
CH 2Cl2

OH

107 105 106

Scheme-37

Jameel94 have investigated the oxidation of disubstituted benzaldehyde by

PCC in binary solvent mixture of 50 % (v/v) aqua-acetic acid. The reaction is first

order with respect to [aldehyde], [PCC] and [H+].

Pyridinium dichromate (PDC) is found as an useful oxidant of aldehydes

in aprotic media. Unconjugated aldehydes are readily oxidized to the

corresponding carboxylic acids by PDC in dimethylforamide at 250C95.

Cyclohexene-4-carboxyaldehyde and 4-methyl cyclohexene-4- carboxaldehyde

have been converted under these conditions into the corresponding carboxylic acid

in 90% yield. (Scheme-38)

R R
CHO COOH

PDC
DMF, 250C

108 109

R=H, CH3

Scheme-38

50
 Oxidation of both aliphatic and aromatic aldehydes by PFC has been

reported.96, 97
The kinetics is similar to those observed in the oxidation of

alcohols. Oxidation of deuteriated acetaldehyde and benzaldehyde indicated the

presence of substantial primary kinetic isotope effects. The following

mechanism has been proposed to account for the observed data

(Scheme-39).

- +
O O PyH
R C O Cr
+
O F
H

O O -PyH+
R C O + Cr

H F
O

+ + (HOCrOPyH)-
R C O

RCOOH + CrOFOPyH

Scheme-39

The oxidation of aliphatic aldehyde by BPCC in DMSO has been reported

by Banerji et.al.98. The reaction was found first order with respect to aldehyde and

BPCC. The reaction is catalyzed by hydrogen ion, the hydrogen ion dependence

taking the form kobs = a + b [H+]. The oxidation of deuterated acetaldehyde

indicated the presence of primary isotope effect. A mechanism involving transfer

via a chromate ester has been proposed.

51
 Pandurangan et. al.99 observed that the oxidation of substituted

benzaldehydes by QFC is first order with respect to each of the reductant, QFC

and hydrogen ions. They obtained a reaction constant of 1.16 for the oxidation of

m- and p-substituted benzaldehydes. The authors have suggested a mechanism

involving formation of a chromate ester in a rapid pre-equilibrium step. The

decomposition of the chromate ester, in the rate-determining step, is base-

catalyzed.

Jameel100 studied the kinetics of oxidation of benzaldehyde and several

para and meta substituted benzaldehydes to corresponding carboxylic acid. The

reaction proceeds with the formation of QCC-ester as the intermediate.

II.2.F. Oxidation of ketones:

Oxidation of ketones with dichromate ion usually results in formation of a

carboxylic acid by cleavage of an adjacent C-C bond.

2-acetylfluorene (110) is converted to fluorenone -2-carboxylic acid (111)

in fair yield by treatment with sodium dichromate in acetic acid101. Oxidation of

cyclic ketone gives a dicarboxylic acid as principle product containing the same

number of carbons as the parent compound.102 (Scheme-40)

O Na 2Cr 2O 7/CH 3COOH

C CH3
reflux, 10 hr
CO 2H

110 111 (67-74%)

Scheme-40

52
 Sometimes when glacial acetic acid is used as the solvent, it is found

helpful to add acetic anhydride in the midway of the reaction to remove water

which is produced during the oxidation. At the completion of the reaction excess

chromium (VI) is reduced by addition of a few milliliters of ethanol.

Rocek & Riehl 102, 103 have shown from a kinetic study of the oxidation of

isobutyrophenone and 2-chlorocyclohexanone that the reaction proceeds via an

end intermediate. At high oxidant concentrations the rate of reaction becomes

approximately equal to rate of enolization and independent of the hexavalent

chromium concentration. Oxidation of the enol produce a diketone which can in

104, 105
some cases be isolated but which usually undergo a facile cleavage to give

final products. For example the oxidation of cyclohexanone has been studied in

some details. It has been shown that the first step of the reaction in aqueous

perchloric acid is an α-oxidation leading to 2-hydroxycyclohexanone. Less than

3% of the reaction proceeds by dehydrogenation 2-cyclohexen-l-one, 2-

hydroxycyclohexanone is then oxidized further to 1, 2- cyclohexandione and

cleaved to adipic acid.102 (Scheme-41)

O O O

OH COOH
O COOH
aq. perchloric acid +

112 113 114 115

Scheme-41

53
II.2.G. Oxidation of amines:

Cr(VI) compounds react with amines by abstraction of a hydrogen atom

from the α-position to give either a compound with an oxygen function in that

position or one containing a carbon nitrogen double bond. In the latter case the double

bond is often cleaved to give carbonyl compounds. An example is provided by

reaction of an indole derivative, deoxygajmaline O-acetate, with chromium

trioxide.106 (Scheme-42)

CrO3 /Pyridine +
250 C, 16 hr N
N
N
OH

CH3 CH3

116 117 (19%) 118 (15%)

Scheme-42

The oxidation is affected simply by adding the amine in pyridine to an ice-

cold solution of CrO3 in 30 ml of pyridine and stirring at room temperature for
several hours.

Bottini and Olsen107 have developed a procedure whereby primary and secondary

amines can readily be converted to the corresponding carbonyl compounds. In this

procedure the amine is first reacted with 2, 4-dinitroaniline (119) which can then

be oxidized with hexavalent chromium. (Scheme-43)

O2N O2N

CrO3/12MH2SO4
RR'CHNH NO2 RCOR' + H2N NO2
1250C, 15 min

119 120 (25-95%)

Scheme-43

54
 The greater difficulty with this reaction is the fact that although 2,4-

dinitroaniline is relatively resistant to further oxidation under these conditions, the

carbonyl compounds are not , and lowest yields were observed for those

aldehydes and ketones that are most susceptible to further reaction with chromic

acid.

II.2.H. Oxidation of Alkyl Halides:

The direct conversion of alkyl halide into the corresponding carbonyl

compounds, despite its potential interest for organic synthesis, is seldom referred

to in the literature. Only few examples of the oxidation of benzylic halides with

aqueous acidic chromic acid or with aqueous sodium dichromate and alkali

hydroxides under rather drastic conditions have been reported.108 A preparatively

useful example is the oxidation of α-chlorohydrindene to α- chlorohydrindanone

in 50-60% yield by means of chromic acid in aqueous acetic acid at 400 C.109

(Scheme-44)

Cl Cl

CrO3
H 2O/AcOH

121 122
Scheme-44

Oxidation of steroidal vicinal dibromide to the α-bromoketone by

means of chromic acid in aqueous acetone in the presence of silver chromate at

room temperature forms a key step in an early procedure for the synthesis of

corticoids from bile acids.110 (Scheme-45)

55
 Br
Br
O COOMe
Br COOMe
CrO3

Ag2CrO4
Acetone - H2 O O
O

123 124
Scheme-45

The reaction is performed in hexamethylphosphoramide using a slight

excess of potassium chromate in the presence of one equivalent of dicyclohexyl-

18-crown-6 at1000c. The yields are in the range of 80%.

A remarkable improvement of this reaction which avoids the use of

hexmethylphosphramide and the crown ether has been obtained by using polymer

supported chromic acid as oxidant.111 (Scheme-46)

O
C6H 6
P CH2N+ + RCH=CHCH2-Hal RCH=CHCHO
-
O Cr OH

125 126
Scheme-46

II.2.I. Oxidation of Acetals:

Cyclic methylene or benzylidene acetals of alditols cleaved by chromium

trioxide in glacial acetic acid to give derivatives of ketoses, provided that the

hydroxyl groups are suitably protected, e.g. by acylation. For example, 1, 3, 5-tri-

O-benzylidene-DL-xylitol (127) is oxidized smoothly by the reagent in 1 hr at

56
room temperature to 1, 3, 5-tri-O-acetyl-4-O-benzoyl-keto-DL-thero-pentulose

(128) in 84% yield.112 (Scheme-47)

CH 2OH
CH2 OH
O
CrO3 O
AcO Ph
O AcOH, 250C AcO
OCOPh
CH 2OAc
CH2 OAc

127 128 (84%)

Scheme-47

Unsymmetrical acetals, however, can open at either position of attachment

to yield two products. Thus , 1,3,5,6-tetra-O-acetyl-2,4-O-benzylidene-D-glucitol

(129) is oxidized to yield 1,3,5,6- tetra-O-acetyl-2,4-O-benzoyl-keto-D-fructose

(130) , as the main product, together with small amounts of 5-O-benzoyl-oxyhex-

3-ulose (131).112 (Scheme-48)

CH2 OAc CH2 OAc CH2 OAc

O O OCOPh
Ph
CrO 3
AcO AcOH AcOH
+
O 250C/AcOH OCOPh O

OAc OAc OAc

CH2 OAc CH2 OAc CH2 OAc

129 130 131

Scheme-48

Methylene acetals behave similarly. For example1 3, 4, 6-tetra-O-acetyl-

2,5-O-methylene-D-mannitol (132) under similar conditions affords 1,3,4,6- tetra-

O-acetyl-5-O-formyl-keto-D-fructose (133) in 87% yield.112 (Scheme-49)

57
 CH 2OAc CH2 OAc

AcO AcO

CrO3 O
O
AcOH, 25 0C
CH2
OCHO
O
OAc OAc

CH 2OAc CH2 OAc

132 133
Scheme-49
The oxidation of aromatic acetals by acidic Pyridinium chlorochromate

(PCC) has been studied by P.S. Ramakrishnan 113. The reaction is first order each

in [PCC] and [Acetal]. The reaction does not induce polymerization of

acrylonitrile. The presence of electron withdrawing substituents in the benzene

ring enhances the rate of oxidation. The rate of oxidation depends on the nature of

alkyl group.

II.2. J. Oxidation of sulphides:

Oxidation of Sulphides is oxidized to sulphones by chromic acid under

acidic conditions although the conversion is under acidic medium affected more

efficiently using other oxidants such as potassium permanganate. For example, 2,

2, 4, 4’, 6, 6’-hexanitro-3-methyldiphenyl sulphide (134) is converted to the

corresponding sulphone (135) in 95%yield on treatment with chromium trioxide

in concentrate nitric acid at room temperature.114(Scheme-50)

NO2 O 2N
NO2 O2N

O2 N S NO2
CrO3
HNO 3 conc. O 2N SO2 NO2
20 0C
NO 2 O 2N
NO2 O2N

134 135 (95%)

Scheme-50

58
 Meenakshisundaram et.al.115 studied the oxidation of organic sulphides by

PDC in acetonitrile medium. They observed a first order dependence on PDC and

sulphide but second order in TsOH. In case of aryl methyl sulphides, the order

with respect to TsOH is >1 and < 2, while Michaelis–Menten type kinetics were

observed with respect to the sulphide. A nonlinear Hammett plot was obtained

with both electron donating and electron withdrawing groups slowing down the

rate of reaction. The reaction was retarded by acrylonitrile, thereby indicating a

one electron oxidation giving rise to free radicals.

The oxidation of a number of organic sulphides116 showed by PFC that the

reaction is second order, first in each reactant. The substituent effect was analyzed

using techniques of correlation analysis. Solvent effect showed that the transition

state is more polar than the reactants.

Meenakshisundaram et.al.117 studied the oxidation of sulfides by QFC in

non-aqueous medium. The oxidation kinetics of sulfides was studied under pseudo

first order condition with QFC and second order in catalyst, MeCN α-

MeC6H4SO3H. Sulfide concentration has no effect on the reaction rate. CH2

=CHCN retard the oxidation rate significantly in di-Ph sulfides, indicating the

involvement of free radical cation intermediate in rate determining step. The

Michaelis - Menten dependence each on [sulfide] [α-MeC6H4SO3H] was well

explained by two-pathway mechanism in sulfide oxidation.

The rate of oxidation of dialkyl and alkyl phenyl sulphides by QCC has been

studied in aqueous acetic acid.118 The proposed mechanism envisages oxygen

transfer from QCC, which is in agreement with the earlier observations.

59
II.2.K.Oxidation of Oximes:

Chromic acid in 50% aqueous acetic acid, Jones’ reagent and chromium

trioxide-(pyridine)2 in methylene chloride have been shown to bring about

oxidative deoximation of ketoximes to the corresponding carbonyl compounds

with varying degrees of success.119 (Scheme-51)

OH
N
O
Cr(VI)
R'-C-R" R'-C-R"

136 137
Scheme-51

Palaniappan et.al.120 studied the oxidation of oxime by PDC in 60 % acetic

acid-water (v/v) medium. The order of reaction is first with respect to [oxidant],

second with respect to the [substrate] and zero with respect to [H+].

The use of 2 equivalent of pyridiniunm chlorochromate was in methylene

chloride at room temperature for 12 hrs. It is also effective in converting

ketoximes to the corresponding ketones in yields of 50-85% while benzaldoxime

affords benzaldehyde without further oxidation & oxime ethers are resistant to the

reagent.121 (Scheme-52)

OH
N O

PCC
CH2Cl2

138 139
Scheme-52

60
 The oxidative deoximination of several aldo and ketooximes by

Quinolinium fluorochromate [QFC] in DMSO exhibited a first order dependence

on both the oxime & QFC.122 The oxidation of ketoximes is slower than that of

aldoximes. The oxidation of aldoximes correlated well in term of PAVELICH-

TAFT dual substituent–parameter equation .The low positive value of polar

reaction constant indicated a nucleophillic attack by a chromate-oxygen on the

carbon. The reaction is subject to steric hindrance by alkyl groups. A mechanism

involving the formation of a cyclic intermediate in the rate determining step has

been proposed.

II.3. Oxidation of Alcohols with Cr(VI) Compounds:

The first review pertaining to the use of novel chromium (VI) reagents for

the oxidation of primary and secondary alcohols was published in 1982, which

summarized the salient features of several hexavalent chromium compounds123.

The oxidation of alcohols constitutes the synthetically most important application

of Cr (VI) compounds. It has been largely divided into four sections.

1. Acid catalyzed oxidation with chromium trioxide and chromic acid in

acetone(Jones’s reagent), DMSO and dimethylforamide (DMF)

2. Oxidation promoted by a family of Cr (VI) reagents obtained from chromium

trioxide, chromic acid and halochromic acids heterocyclic bases.

3. Oxidation carried out under neutral or almost neutral conditions

4. Chromium (VI) reagents supported on various insoluble organic and

inorganic matrices.

61
II.3.A. Oxidation of alcohols by Cr(VI) under acid conditions:

Much important chromium (VI) oxidation of alcohols are carried out under

acid condition. Aqueous acidic solution of chromium trioxide as well as chromate

and dichromate salts in the presence of co-solvents like acetic acid or acetone

have been widely used as oxidizing reagents. Oxidations have also been

performed in a two phase system consisting of an aqueous acidic solution of

chromic acid and an organic immiscible solvent like benzene, DCM, or ether or

without a phase transfer catalyst.

In 1859 G.Stadler124 reported that the first description of oxidation of

primary alcohols with potassium dichromate in aqueous sulfuric acid.

3 R-CH2OH 2 CrO3 3 H2SO4 3 R-CHO Cr 2(SO4) 3 6 H2O

Beckmann 125and Kilani126 introduced two standard chromic acid solutions

in aqueous sulfuric acid .The first is made with Na2Cr2O7/K2Cr2O7, and the second

with chromium trioxide. This method seems to be particularly useful for the

preparation of aromatic aldehydes127 even if they are sterically hindered.128

(Scheme-53)

CH 2OH CHO

Na 2Cr 2O7

H2SO4 , H 2O

140 141 (42%)

Scheme-53

62
 Oxidations with aqueous chromic acid in a heterogeneous system have

proved to be useful the direct conversion of low molecular weight primary

alcohols to the corresponding acid. The absence of a co-solvent in this case greatly

facilities the isolation of oxidation products. In respect to reaction conditions best

results were obtained by adding the alcohol to an excess of the oxidizing

mixture.129, 130 (Scheme-54)

CH2FCH2CH2OH K2Cr 2O7 CH2FCH2COOH

H2SO4, H2O

142 143 (80%)

Scheme-54
Unlike primary alcohols; the secondary ones which are sufficiently in

water are generally oxidized in good yield when other oxidation sensitive groups

absent.131 (Scheme-55)

O
OH

Na2Cr 2O7
H 2SO4, H2O

144 145 (90%)

Scheme-55

A common co-solvent with water in chromic acid oxidation of alcohols is

acetic acid. The use of acetic acid not only improves the solubility of the organic

substrates in the oxidizing mixture but also increase the rate of the reaction. The

oxidation rate can be further increased by adding sulfuric acid.

63
 Primary alcohols have been oxidized to aldehydes under these conditions in

moderate yield.132 (Scheme-56)

CrO3/AcOH
CH 2OH CHO
H 2O, 00C

146 147 (33-35%)

Scheme-56

Less hindered primary alcohols may be converted to the corresponding

carboxylic acid under milder conditions. Thus, for example, a variety of

halogenated primary alcohols were oxidized to carboxylic acids in moderate

yields upon overnight-treatment with chromium trioxide in acetic acid at room

temperature.133 (Scheme-57)

CrO3/ AcOH
F COOH
F CH2OH
H2O, 2hr, 50C

148 149 (93%)

Scheme-57
Chromic acid oxidation of secondary alcohols in aqueous acetic acid yields

cleavage products (route A) in addition to the expected ketones (route B).

(Scheme-58)

RCHO + R'OH
A
OH

R R' O

B
R R'

Scheme-58

64
 The cleavage products may then be further oxidized to corresponding acids

and carbonyl compounds or may combine, via the formation and oxidation of the

hemiacetal to the ester. The cleavage reaction becomes more pronounced for

secondary alcohols bearing one or more alkyl group in α position. For example,

the oxidation of n-propyl-t-butylcarbinol with chromium trioxide in aqueous

acetic acid yields 41% of the corresponding ketone, 4% tert-butylcarboxaldehyde

and a corresponding amount of tert-butyl cabinol.

134 (a)
Detailed investigations revealed that Cr (VI) oxidized cyclobutanol

to the “normal” product of cyclobutanone in a C-H bond cleavage reaction,

whereas the intermediate chromium (IV) reacts by carbon-carbon cleavage to give

a free radical CH2 CH2CH3CHO which, upon further oxidation, gives rise to the

hyroxyaldehyde. (Scheme-59)

OH O

CrO3/AcOH CHO
+
H2O
CH 2OH

150 (48%) 151 (31%) 152

Scheme-59

Tertiary alcohols are generally inert toward oxidation by chromic acid.

Expectations have, however been reported.

Several tertiary cyclopropanols 134( a, b) 124,125 bicyclic tertiary alcohols react

quickly135 with chromic acid yielding ketones arising by cleavage products may

be considered to arise from breakage of the C1-C7 or C1-C2 bond. The relative

yields depend on the substituents at C2-C7. (Scheme-60)

65
 O

H2CrO4 COOH

AcOH
HO

153 154 (16%)

Scheme-60

A notable improvement in the oxidation of alcohols was achieved by using

a solution of chromic acid/sulphuric acid in water for which oxygen 8 N (the so

called Jones reagent) using acetone as co-solvent. The procedure involves titration

of alcohol in acetone with the standard chromium trioxide-sulphuric acid solution.

The reaction mixture separates into a green layer of chromium salts with an upper

layer of an acetone solution of the oxidation product

A limitation of the method is the low solubility power of acetone and strong

acidic conditions of the reaction. Primary alcohols are rapidly oxidized by this

reagent to yield good amounts of carboxylic acids, even in the presence of double
136
or triple137 carbon-carbon bonds.

Primary α, β unsaturated alcohols may be converted into high yields of the

corresponding aldehydes under nitrogen at 0 0C. As a matter of fact α, β

unsaturated and aromatic aldehydes seems to be relatively inert towards the

138
normal conditions of the Jones’s oxidation However, a small amount of

isomerization of the double bond occurs in certain cases. (Scheme-61)

66
 Jones reagent

CHO
OH

155 156 (84%)

Scheme-61

Chromium trioxide dissolves in DMF to give solution with very little

oxidation power toward alcohols. Thus cholesterol is recovered unchanged after

three weeks of exposure to the solution and only a 50 % conversion of 5 α-

cholestan-3-ones is observed after heating 5α-cholestan-3 β- ol for 45 hours at

500C. However, the oxidation is strongly catalyzed by adding a few drops of

con.H2SO4 acid. Under these conditions a number of steroidal alcohols have been

converted to ketones at room temperature with 80% yield.139

DMSO acts as an excellent solvent for sodium dichromate dehydrate. The

solution at 70 0C cause only slight oxidation of benzyl alcohol to benzaldehyde,

but the addition of small amount of H2SO4 strongly accelerates the reaction.

Primary and secondary saturated, allylic and benzylic alcohols are oxidized by this

procedure to aldehydes and ketones in 80-90% yield.140

Many modified procedures have been developed to simplify the isolation

process, to achieve certain selectively, and to improve the yield as well as the

purity of products. A simple useful procedure consists in stirring a solution of the

compound to be oxidized in an immiscible solvent stable to chromic acid

(benzene, DCM, ether) with an acidic aqueous solution of the oxidant. The

organic phase protects the carbonyl compound from undesirable side reactions,

67
such as further oxidation or epimerization. In this way sensitive ketones may be

isolated in high yield without appreciable epimerization of adjacent chiral centers.

Benzene and DCM have been widely used as an organic phase. As an

example, 2, 5, 5, - trimethylcyclohex-2-en-1-one has been obtained in a 91% yield

from the corresponding alcohol in a benzene- water two phase system.141

(Scheme-62)

Na2Cr 2O7/H2SO 4
C 6H 6

HO O

157 158 (90%)

Scheme-62

An advantage of the use of water immiscible solvents like hydrocarbon

and chlorinated hydrocarbon lies in the fact that they easily from emulsion which
142(a, b)
hamper the isolation of the product. Ethyl ether has proved to be superior,

oxidation proceeds smoothly as no emulsions are formed. Under these conditions

oxidation of (-) menthol give to (-) menthone in 97% yield along with mere traces

of (+) –isomenthone.

The two phase procedure has recently been modified by adding a phase
143,144
transfer catalyst Under these conditions primary alcohols which were

insoluble in the aqueous phase were oxidized to aldehydes at a higher than 90%

yield. The temperature and concentration of acid in the aqueous phase and that of

the substrate are crucial factors for the reaction.

68
II.4. Oxidation of Alcohols with Compounds of Cr(VI) and

Heterocyclic Bases

Chromium trioxide is capable of reacting as Lewis acid with many

heterocyclic bases leading to a number of addition compounds. Pyridine,

dipyridine, quinolone, 3, 5, dimethyl pyrazole etc. are among the bases which

gives complexes by simple additions of the compounds at room temperature.145

Moreover, chromic acid and chlorochromic acid was found to give a

variety of heterocyclic bases.

146
Such useful reagents are dipyridine-chromium (VI) oxide complex , 1,
147
8-naphthpyridinium chlorochromate and pyrazinium chlorochromate ,

tetrakis(pyridine) silver dichromate 148 , nicotinium dichromate and isonicotinium

dichromate149 quinolinium dichromate150, imidazolinium Fluorochromate151,

imidazolinium dichromate152, tetraalkylammonium chlorochromate153, 2,4-

bipyridinium chlorochromate154, pyridinium dichromate 95

, trimetylsilyl
155 156
chlorochromate , 2,2'-bipyridinium chlorochromate , pyridinium

Fluorochromate157, pyridinium bromo-chromate158 quinolinium chlorochromate

159
, quinolinium Fluorochromate 160, quinolinium bromochromate161, 4-(Dimethyl-

amino) pyridinium chlorochromate162, bis[benzyltrimethyl

ammonium]dichromate163, 3,5-dimethylpyrazole chromium(VI) complexes164,

165 166
benzotriazole trioxide complexes , halosilanes chromium trioxide ,

butylammonium chlorochromate & teramethyl-ammomium fluorochromium

trioxide 167, chromium peroxide etheratem (CPE) and pyridine chromium peroxide
168
(PCP) and 2,2’–bipyridyl chromium peroxide (BPCP) , biphosphonium

69
 169 170
dichromate , butyltriphenyl phosphonium dichromate (BTPPD , ferric
171
dichromate , zinc dichromate trihydrate (ZnCr2O7)172, 1-methylimidazolium

chlorochromate (MCC), imidazolium chlorochromate (ICC) and isoquinolinium

173 174
chlorochromate (IQC) benzyl trimethyl ammonium dichloroiodate have

been reported as mild and selective oxidizing reagent.

Some heteocyclic base and halochromate Cr(VI) reagents were

described in this section.

II.4. A. Oxidation of alcohols with Chromium Trioxide-(Pyridine)2

Complex.

Chromium trioxide in pyridine was introduced as a unique, nonacidic

reagent for alcohol oxidations and has been used extensively to prepare ketones
175
, but has been applied with only limited success to the preparation of aldehydes.

2-Methoxybenzaldehyde was obtained in 89% yield, 4-nitrobenzaldehyde and

heptanal were obtained in 28 % and 10 % yields, respectively176.

Using the performed dipyridine chromium (VI) oxide in DCM, the rate of
177
chromium ester formation and decay to the aldehyde is enhanced at least

twentyfold over the rate observed in pyridine solution.146 Isolation of products is

facile, and aldehydes appear to be relatively stable to excess reagent. The reagent

has been used extensively to prepare acid-sensitive aldehydes, particularly

178
intermediates in the total synthesis of prostaglandins and steroids.179 An 85%

yield was reported for the conversion of 2-vinylcyclopropylcarbinol to the

aldehydes.180 Although excess reagent is required for the oxidations (usually

70
sixfold), the reaction conditions are so mild and isolation of products so easy that

the complex will undoubtedly find broad use as a specialty reagent. Isolation of

complex can be avoided by in situ preparation of the chromium oxide/pyridine

complex.181

II.4.B. Pyridinium Dichromate (PDC)

PDC reagent was prepared from pyridine, CrO3 in water. It is bright

orange solid. It is very soluble in water, DMF, DMSO, dimethylacetamide (DMA)

and it is soluble in DCM, ethanol-free chloroform or acetone and not soluble in

hexane, toluene, ether or ethyl acetate. Although PDC dissolve in acetonitrile, the

solutions are not stable.

This reagent was first used for oxidation of alcohols by J.W.Conforth182

for the oxidation of 2, 4 -dimethyl-4-(3-hyroxy-4-methyl pentyl)-1, 3-dioxane to

the corresponding ketone with a yield of 88%.

The wide applicability of PDC for oxidation of alcohols to aldehydes,

ketones and carboxylic acid has been shown by E.J. Corey.95 The reagent was

used in most cases in the form of DMF solution or a DCM suspension. In DMF

primary and secondary allylic alcohols and secondary saturated ones are rapidly

oxidized to the corresponding carbonyl compounds. Thus, 2-cyclohexen-1-ol,

cinnamyl alcohol and geraniol are converted to high yields to α, β- unsaturated

carbonyl derivatives at 00C in 4-5 hours using only 1.25 equivalent of the reagent.

Oxidation occurs without overoxidation in the case of aldehydes and no E to Z

isomerization for geraniol.95 Saturated primary alcohols are readily converted to

71
carboxylic acids in good yield with 3.5 equivalents of PDC in DMF at 250C in 7-9

hours via the corresponding aldehydes which have been isolated.95, 183

184
B. L. Hiran and J. Choudhary developed a new reagent 4-Methyl

pyridinium dichromate (m. p. 109° C), and they studied oxidation of some

substituted benzhydrols (4-methyl, 2-methyl, 4-chloro, 4, 4-dichlorobenzhydrol

etc.) in acetic acid–water medium and observed first order with respect to

[substrate], [oxidant] and [H+] each. The rate of reaction increases with increase

in hydrogen ion concentration and percentage of acetic acid. Thermodynamic

activation parameters have been computed. A plausible mechanism consistent

with the observed experimental results and suitable rate law has been deduced. In

rate determining step water acts as proton abstracting agent and C-H bond

breaking takes place.

Hiran & Kailash Chand185 studied oxidation of aliphatic alcohols by PDC

in aquo-dioxane medium and observed first order with respect to [substrate],

[oxidant] and [H+] each. The rate of reaction increases with increase in hydrogen

ion concentration. Thermodynamic activation parameters have been computed. A

plausible mechanism consistent with the observed experimental results and

suitable rate law has been deduced. In rate determining step water acts as proton

abstracting agent and C-H bond breaking takes place.

II.4.C. Pyridinium Chlorochromate (PCC)

Corey and Suggs introduced PCC for the oxidation of both primary and

secondary alcohols to carbonyl compounds186 PCC was prepared from pyridine

72
and CrO3 in HCl. This reagent which appears particularly suitable for moderate to

large scale oxidations is normally used in a 1:1.5 molar ratio as a suspension in

DCM at room temperature. More polar solvents, like acetone and acetonitrile in

which the reagent was soluble greatly reduce the reaction times.

The stochiometry of the oxidation of 1-octanol with PCC in DCM has

been studied by H.C. Brown 187 by using varying amounts of reagents. The use of

both 16.5 and 22.5 mmole of reagent for 15 mmole of alcohol affords a

quantitative yield of octanol. It, therefore, seems likely that a substrate: reagent

molar ratio of 1:1.1 should be to perform quantitative oxidation.

The oxidation of secondary hydroxyl groups in sugars has been found to

be very slow with PCC in DCM, even in the presence of a large excess of oxidant

under reflux conditions. Instead, benzene was found to be a good alternative

solvent. Oxidation of sugars, which failed with DMSO- dicyclohexylcarbodimide

and other reagent related to DMSO, was readily accomplished in good yield, also

on a molar scale, simply by heating a benzene solution of the sugar under reflux in

the presence of 1.7 equivalent of PCC.

The reactivity of PCC towards slow reacting alcohols like nucleosides or

sugars may be increased by adding 3A molecular sieve powder to a suspension of

PCC in DCM.188 The attempts to catalyze the reaction by celite, alumina and silica

gel were unsuccessful. Thus, for instance, the oxidation of benzhydrol to

benzophenone with two equivalent of PCC and 0.5 g of molecular sieve powder

leads to a quick and complete in 15 min. The acidic character of PCC (pH of a

73
0.01 M solution=1.75) 170 may be convenient to bring about a one-step conversion

(70%) of citronellol essentially to pulegone.189

Efficient cyclization with PCC is only observed with substrates which

produce tertiary cations as initial cyclic intermediate which then lead to six

membered enones. This process represents a milder and more efficient alternative

in organic synthesis to the two-step cationic cyclization of preparing α, β-

unsaturated enones190. The oxidation of cyclic tertiary allylic alcohols to α, β-

unsaturated cyclic ketones with 2 equivalent of PCC in DCM affords transposed

3-alkyl - α, β- unsaturated in good yields.191 Various tertiary vinylic alcohols of

natural origin have also been transformed into the corresponding unsaturated

aldehydes following the same procedure .A cyclic allylic tertiary alcohols192 also

afford transposed α, β- unsaturated ketones albeit in lower yield. However,

byproducts are frequently observed. For exp. Oxidation of 2-phenyl-3-buten-2-ol

gives a 35 % yield of acetophenone in addition to the transposed aldehyde.

The first report about the kinetics and mechanism of the oxidation of
193,194
alcohol was published in 1978. Banerjee and Venkatsubrumaian et.al195

reported the oxidation of alcohols by PCC in 1:1 (v/v) DCM and nitrobenzene

solution. The reaction was first order with respect to PCC and the alcohol.

Banerjee193, 194
reported the reactions catalyzed by toluene-p-sulphonic acid

(TsOH). The reactions exhibited negative reaction constants. The oxidation of

193
deuteriated benzyl alcohol and ethanol 194 showed the presence of substantial

kinetic isotope effects. This confirmed the cleavage of an α-C-H bond in the rate
196
determining step. The oxidation of cycloalkanols by PCC in chlorobenzene-

74
nitobenzene solvent presented similar kinetics. The author suggested, on the basis

of the reactivity of the cycloalkanol and effect of solvent, that probably a

chromate ester mechanism is operative. Banerjee studied the temperature

dependence of kinetic isotope effect in the oxidation of substituted benzhydrol

197
by PCC in DMSO. An analysis of the temperature- dependence of the kinetic
198
isotope effect by the method of Kwart and Nickle , in the oxidation of

benzhydrol, showed that the hydride-transfer take place via a chromate ester
199
through a symmetrical cyclic transition state. Agarawal et.al studied the

oxidation of 2-pentanol by PCC in chloroform solution. They observed that

kinetically the oxidation is comprised of two reactions. The first one consisted of

the formation of a chromate ester and the second one a decomposition of ester.

They obtained a kinetic isotope effect, kO-H/kO-D =1.30, for the first reaction. In

essence, their data support a hydride-ion transfer via a chromate ester.

II.4.D. Pyridinium Fluorochromate (PFC)

Development of PFC was essential to overcome the practical difficulties

associated with PCC, which was found unfortunately quite unstable. Mihir Kanti

et.al. reported a noble and environmentally cleans process for the preparation of

Pyridinium salt of fluorotrioxochromate (VI) having a chemical formula

C5H5NH[CrO3]200. The compound was prepared by direct reaction of HF acid,

chromium trioxide and pyridine. This complex is soluble in benzene, CCl4,

chloroform and hexane. Unlike PDC, the reagent does not react with acetonitrile

which also may be used as a solvent. The acidity of PFC is less pronounced than

that of PCC which may have advantage of preventing side reactions.

75
 The first preliminary report on the oxidation of alcohols by PFC was

published by Bhattacharjee et.al.201 In this reaction the molar stoichiometry of the

oxidation of n-butanol, isopropanol, benzyl alcohol and cyclohexanol involving

PFC in DCM has been found to be 1:1.5. They obtained Michaelis-Menten type

kinetics with respect to the alcohols and observed that the reactions were

catalyzed by TsOH but could not determine the order with respect to the acid, as

the reactions were very fast. A systematic study of the oxidation of substituted

benzyl alcohol and of aliphatic alcohols by PFC in DMSO was reported by

Banerjee.202, 203 He also observed Michaelis-Menten type kinetics with respect to

alcohols, suggesting the formation of an intermediate in a pre-equilibrium and its

subsequent disproportionation in the rate-determining step. The oxidation of

202
deuteriated ethanol and benzyl alcohol203 exhibited a substantial primary

kinetics isotope effect. This confirmed the α-C-H bond in the rate-determining

step. The oxidation of aliphatic alcohols is susceptible to both the polar and steric

effects of the alkyl group. The polar reaction constants have negative values. The
203
oxidation of benzyl alcohol was studied in nineteen organic solvents. An

analysis of the solvent effect, in term of swains 204 equation, indicated the greater

importance of the cation-solvating power of solvents. In both the cases, the in

analysis of the temperature-dependence of the kinetic isotope effect indicated the

presence of a symmetrical cyclic transition state in the rate –determining step of

the oxidation. The oxidation of vicinal and non-vicinal diols by various

halochromates viz. PFC 205 in DMSO has been studied. The oxidation of vicinal

diols correlated well with the polar and steric substituent constant of the alkyl

group.205-208 Kinetics and mechanism of the oxidation of p-chlorophenol, p-

76
nirophenol and p-cresol in glacial acetic acid as a solvent at 25-450C using PFC as

have been studied and reported by Patil and Coworkers.209 The oxidation of D-

glucose and some other monosaccharaides by PFC210 in aqueous perchloric acid

solution has been reported. The reactions are first order with respect to each of the

oxidant, the sugar and hydrogen ions. The oxidation by PFC210 on the other hand,

yields only formic acid and D-arabinose. In the PFC oxidation, a solvent isotope

effect, k (D2O)/ k (H2O) = 3.1 has been obtained. The author interpreted this in

term of two acid-catalyzed reactions

(i) The acid-catalyzed anomerization of α-D- glucose to β-D-glucose

(ii) A pre-equilibrium protonation of PFC

The author suggested a bimolecular hydride ion transfer in the rate

determining step.

II.4.E. Bypyridinium Chlorochromate (BPCC)

Frank S. Guziec reported the successful use of 2, 2- Bypyridinium

Chlorochromate (BPCC) for the oxidation of 2-isopropyl cyclohexanol in DCM at

room temperature211 2-isopropylcyclohexanone was the main oxidized product.

Percentage yield was as high as 86 %. Kabilan et.al reported the kinetics and

mechanism of the oxidation of cyclopentanol, cyclohexanol, cycloheptanol and

cyclooctanol by BPCC in the presence of H+ ions.212 The oxidation of benzyl

213
alcohol by BPCC was examined in various solvents and greater yield of

benzaldehyde was observed in the solvent with higher dielectric constant such as

chloroform, dichloromethane etc. The oxidation of benzyl alcohol derives by

77
BPCC in DMF was examined and similar product was observed regardless of

substituent. The oxidation rate was dependent linearly on the concentration of acid

and Arrhenius equation indicated that there was a charge transition state.

Kinetics of the oxidation of substituted benzyl alcohol with 4, 4’ BPCC has

also been reported in the literature.212 Treatment of primary and secondary alcohol

in DCM or acetone with 2:1 to 4:1 excess of bipy H+ CrO3Cl- affords aldehydes or

ketone in high yields. The chromium containing byproducts from these reactions

are water soluble crystalline materials which are easily removed by filtration

through a 1 cm celite pad. The bipy H+ CrO3Cl- complex may prove to be

especially useful in oxidation of compounds with acid-sensitive protecting groups,

due to the internal buffering of the 2, 2’- bipyridyl system.

II.4.F. Quinolinium Chlorochromate (QCC)

Quinolinium chlorochromate was first reported in 1986 by Kalsi et. al.159

as effective and mild oxidant for organic substrates under mild condition.

R. Srinivasan, and Coworkers have reported the selective oxidation of 10

alcohols in presence of 2 0 alcohols by mild, stable and efficient QCC. 213, 159
QCC

is prepared by treating a solution of CrO3 in 6M HCl with quinoline at 00C. The

orange red solid compound is stable to ordinary exposure to air, moisture and

light. It efficiently oxidizes 1 0 and 20 alcohols to the corresponding carbonyl

compounds. QCC is soluble in water, DMF and DMSO, sparingly soluble in

DCM and chloroform and insoluble in ether, ethyl acetate, toluene, and heptane.

78
 QCC (1 molar equivalent) oxidizes 1 0 alcohols to the corresponding

aldehydes in refluxing DCM and reasonably oxidizes 20 alcohols to ketones.

Solution of QCC in DMF oxidizes benzoin and benzhydrol to the corresponding

ketones in excellent yields. Mechanism and comparative study with IQCC has

also been reported.214 a

The oxidation of aliphatic primary alcohol215 by QCC has been studied in

aqueous acetic acid medium. The rate shows first order dependence each in

[QCC] and [alcohol]. The linear increase in the oxidation rate of alcohol with

acidity suggest the involvement of protonated Cr(VI) species in the rate

determining step which is confirmed by decrease in the rate of reaction with an

increase in dielectric constant with the change in ionic strength. The reaction does

not induce the polymerization of acrylonitrile. As a result, hydrogen abstraction

mechanism is unlikely. The oxidation of [1, 1-2H2]- ethanol shows the presence of

primary kinetic isotope effect. The observed results suggest a hydride transfer in

the rate determining step. In a concerted sigmatropic reaction a cyclic hydride

transfer takes place.

The oxidation of substituted benzyl alcohols by QCC involves the

decomposition of an initially formed chromate ester via a concerted symmetrical

214b
transition state. It has been found as a more efficient reagent for the oxidation

of aromatic alcohols as compared to the oxidation of aliphatic alcohols.

79
II.4.G. Quinolinium Fluorochromate (QFC)

Chaudhary and coworkers reported the synthesis of quinolinium

fluorochromate (QFC) in 1991Though the details were published in 1994216 in

the meanwhile, Murugesan and Pandurangan also reported the synthesis of

QFC.160 The preparations, reported by the two groups of workers are similar.

Chaudhury et.a.l216observed that QFC was univalent electrolyte and corresponds

to the formula C9H7NH+[FCrO3]-. They characterized the compound by IR and

EPR spectroscopy and SEM techniques. QFC is less acidic as compared to PCC

and PFC.

QFC was prepared from quinoline, 40% HF acid and chromium trioxide in

molar ratio of 1:1.5:1. QFC is soluble in in water, DMF, DMSO and acetone. It is

sparingly soluble in DCM and chloform and insoluble in benzene, 1, 4 dioxane,

heptane, ethyl acetate, toluene, ether.

Further QFC does not react with acetonitrile and nitrobenzene which is a

suitable medium for showing oxidation kinetics and mechanism.1 0 alcohols are

oxidized to aldehydes by QFC in DCM at room temperature. The diverse types of

organic substrates that have been oxidized by it have highlighted the versatile

nature of QFC. Recently Chandrasekhar et al217 reported that QFC in DCM was

able to deprotect and oxidize the 10 alcoholic group, while leaving the protect

secondary 1 0 alcoholic group intact

Most of the workers have explained the hydrogen ion dependence by

assuming the formation of a protonated chromium (VI) species in a pre-

80
equilibrium, either both the unprotonated and protonated or only the protonated

form being the reactive species. In the oxidation by QFC218 the rates were

obtained in different organic solvents and the analysis of the solvent effect

indicated the greater importance of the cation-solvating power of the solvents. The

temperature-dependence of reactions indicated a symmetrical transition state in

the rate-determining step of this oxidation. The oxidation of vicinal and non-

vicinal diols by various halochromates, viz QFC in DMSO has been studied.

Kinetics and mechanism of the oxidation of substituted benzyl alcohols by

219
QFC have been reported. Itishri Dave et.al. reported the correlation analysis of

reactivity in the oxidation of substituted benzyl alcohols by QFC. Oxidation of

benzyl alcohol and some ortho, meta, and para-monosubstituted ones by

Quinolinium Fluorochromate in DMSO leads to the formation of corresponding

benzaldehydes. The reaction is first order each in both QFC and alcohol. The

effect of hydrogen ions was studied in the oxidation by QFC. In the oxidation by

QFC, the hydrogen-ion dependence has the form

kobs = a+b [H+]

Oxidation of α, α- dideuteriobenzyl alcohol has exhibited a sustainable

primary kinetic isotope effect. The reaction has been studied in nineteen organic

solvents and the effect of solvent analyzed using Taft’s and swain’s muti-

parametric equations. The rates of oxidation of para and meta substituted benzyl

alcohols have been correlated in terms of Charton’s triparametric LDR equation.

Whereas the oxidation of ortho-substituted benzyl alcohols with tetraparametric

LDRS equation. The oxidation of para-substituted benzyl alcohols is more

81
susceptible to the delocalization effect than that of ortho- and meta substituted

compounds, which display a greater dependence on the field effect. The positive

value of η suggests the presence of an electron-deficient reaction center in the rate

determining step. The reaction is subjected to steric acceleration by the ortho-

substituents.

II.5. Oxidation of Alcohols with Cr(VI) Under Neutral Conditions

The oxidations of particularly sensitive alcohols may require complete

neutral conditions to attain good yields. For this purpose some neutral Cr (VI)

containing reagent and special reactions conditions have been developed.

Chromium trioxide dissolves in tert-butyl alcohol by depolymerization to

give di-tert-butyl chromate which acts an oxidation in a variety of apolar solvents.

di-tert-butyl chromate (DTBC) has been especially used for oxidation of allylic

oxidation of double bonds, it may also be used for oxidation of alcohols. The

reaction is performed in non-polar media such as pet.ether, benzene, or carbon

tetrachloride. The oxidation of primary alcohols in pet.ether or benzene at room

temperature with 1 equivalent of TBC does not appear to be particularly

promising; however, a mixture of the aldehyde, acid and the ester of the acid is

invariably obtained.220 (Scheme-63)

DTBC
CH 2 OH CHO COOH COOCH 2
C6 H6

159 160(40%) 161(28%) 162 (19%)

Scheme-63

82
 In each case a small percentage of starting material was recovered. On the

other hand, oxidation of benzylic primary alcohols gave the aldehyde in good

yields together with small amounts of the corresponding acid, but not the ester.221

(Scheme-64)

CHO COOH
CH 2OH
DTBC

163 164 (90%) 165(7%)

Scheme-64

Better results were obtained by using TBC in situ from chromyl chloride.

This procedure avoids the formation of water which may cause side reaction.222

When chromyl chloride is added to a solution of pyridine/ tert-butyl alcohol in

DCM in a dry ice/ acetone bath and the reaction mixture allowed warming at room

temperature, the solution becomes orange-red and a white precipitate of pyridine

hydrochloride appears. (Scheme-65)

O O
CrO2Cl2 2 Cl
2 OH 2 Cr
- 780 C, then r.t. N
N O O H

Scheme-65
This solution is capable of oxidizing aliphatic, allylic and benzylic

alcohols to aldehydes and ketones in high yield when treated at room temperature

for 2 hours with a ratio of chromyl chloride to substrate of 1.1:1.

83
 Solutions of chromium trioxide in hexamethylphosphoramide (HMPA) are

also capable of converting alcohols to carbonyl compounds under mild conditions.

Chromium trioxide readily dissolves in HMPA at room temperature to give stable,

deep red solutions which have been used on steroids under neutral conditions for

the selective oxidation of certain allylic and benzylic hydroxyl group in the

presence of other unprotected saturated groups.223 ( Scheme-66)

OH O
CrO3

HMPA
OH OH

166 167 (90%)

Scheme-66

Saturated alcohols are oxidized more slowly while aldehydes may,

nevertheless, be obtained in good yields from saturated primary alcohols under

appropriate conditions. The reagent was found useful for performing selective

oxidations of primary alcohols in the presence of unprotected secondary ones for

example; strophantidol is slowly converted to strophantidine in about 35 % yield

without ketonic products being formed.224

Chromate salt of tetraalkylammonium ions is soluble in aprotic solvents,

as e.g. benzene (orange benzene), resulting in solutions which show interesting

oxidizing properties. The use tetraalkylammonium salts to facilitate the solubility

of inorganic ions in organic solvents of low solvating ability has recently called

increasing attention.225 It was eventually found that a liquid commercial mixture

of methyl trialkyl ammonium chlorides, facilitates the solubilization of potassium

84
dichromate in several apolar organic solvents as DCM, CHCl3, tetachloromethane,

and benzene; a 2:1 adogen to dichromate molar ratio is used. The organic solution

of the dichromate can be formed without priorly dissolving the salt in water,

simply by vigorously stirring the crushed salt in the desired solvent containing two

equivalents of adogen.226 The resulting orange solutions are fairly stable at room

temperature but slowly darken after several days. Dichromate anions in orange

benzene reveal to be a very mild oxidizing reagent which discriminately oxidizes

alcohols to the corresponding carbonyl compounds. In fact, α, β unsaturated

alcohols are oxidized to corresponding carbonyl compounds at 550C in good yield

while saturated alcohols only give poor yields under acidic conditions. This

procedure may, therefore be useful for neutral oxidations of activated alcohols

where acidic or basic conditions must be avoided.

II.6. Oxidation of Alcohols with Oxochromium(VI) Supported on

Polymers.

Literature survey 227 reveals that through a good number of oxochromium

(VI) reagents have been developed for the oxidation of alcohols but their

commercial uses are still restrict mainly due to long reaction time, low selectivity,

non-catalyzed nature and above all the difficulty in product isolation.

The concept of supporting Cr (VI) reagents onto inert inorganic and

organic polymeric matrices may be circumvented some of the problems associated

with the soluble Cr (VI) reagents.228 It has been found that Cr (VI) derivatives

supported on an insoluble organic or inorganic matrix are particularly convenient

in organic synthesis. The insoluble support provides a particular environment

85
capable of enhancing and modifying the reactivity of the bound reagent.229The use

of polymeric reagents facilitates the purification of final product. In order to

increase the industrial applicability of soluble Cr (VI) compound significant

230-231
attempts have been made to anchor the soluble reagent to both organic
232-235
inorganic polymers. The polymer supported reagent often exhibits higher

thermal stability and better selectivity.

Reported polymer supported Cr (VI) reagents may be broadly classified as follow:

230, 231, 236(a, b)

(i) Polymeric analogue of heterocyclic halochromate.

237(a-i)
(ii) Chromium trioxide supported on inert inorganic supports.

(iii) Heterocyclic halochromate supported on inert inorganic supports. 238 ( a-d)

230
Poly (vinylpyridine) was used as an organic polymer support for PCC and

PDC231. Both the reagents were found moderately effective towards the oxidation

of different types of allylic, benzylic primary and secondary alcohols. (Scheme-

67)

OH CHO
PVPCC

168 169 (94%)

CH 2OH CHO
PVPDC

170 171 (99%)

Scheme-67

86
 The main disadvantage associated with these organic polymers were

their very low accessibility requiring a two to five fold excess of the reagent.

Literature survey reveals that in many occasions chromium trioxide

were supported on inert inorganic polymers such as silica gel, α-alumina, γ-

alumina, ZSM-5 etc233-235, 239.

Chromium acid adsorbed on silica gel was found suitable for the oxidation

of alcohols to the corresponding carbonyl compounds 237( b) This reagent prepared

by addition of silica gel to an aqueous solution of chromic anhydride subsequently

evaporated to dryness. The yellow resultant solid was then kept overnight at

1000C and stored under vacuum in the dark.

Pyridinium chromate on silica gel was obtained by treating chromic acid

adsorbed on silica gel with pyridine and was used for the oxidation of alcohols

containing acid-labile functions 237 c Chromyl chloride was supported onto silica –

alumina 240 and the reagent was used for the oxidation of primary and secondary

alcohols to respective aldehydes and ketones. (Scheme-68 )

CrO2Cl2 on
CHO
OH
silica-alumina

172 173

OH O

CrO2Cl2 on

silica-alumina

174 175
Scheme-68

87
 237(g)
B. Khadikar and coworkers prepared silica gel supported chromium

trioxide by co-grinding anhydrous CrO3 with silica gel. This reagent was used in

equimolar quantity to oxide alcohols to carbonyl compounds with good yields. γ-

Alumina, which is frequently used as a solid support consists of very high area.

Dispersion of CrO3 and wet alumina in hexane afforded the alumina-supported

chromium reagents may be used for the chemo selective oxidation of a wide range

of alcohols. Thus 2-cyclohexen-1-ol in hexane afforded 94% 2-cyclohexenone on

treatment with alumina-supported chromium (VI) reagents237(h). Masao Hirano

et.al. 241 reported the oxidation of alcohols with chromium trioxide in the presence

of wet alumina oxide in aprotic solvents.

In some cases the bulk of a high surface area material serves as catalyst.

Such material is called a uniform catalyst. One such example of uniform catalyst

is ZSM-5. It has three dimensional, network built from AlO4 and SiO4

tetrahedral.242 Zeolites are used as catalyst in various synthetic organic

transformations much more effectively and selectively than the Lewis acid

catalysts. Thus the use of heterogeneous catalysis in different areas of organic

synthesis has now reached to significant level not only because it enables

environmentally begin synthesis, but also due to the good yields, accompanied by

excellent selectivities. These properties of ZSM-5 may allow it to act as a highly

effective solid support for oxochromium (VI) reagents and may lead the hybrid

reagents highly effective and catalytic towards the oxidation of primary and

secondary alcohols.

88
 A variety of alcohols were oxidized to the corresponding carbonyl

compounds in excellent yields by chromium trioxide / ZSM-5 in DCM at room

temperature.243 The oxidation of alcohols to the corresponding carbonyl

compounds using zeolites has been reported by a number of researchers.243-245

Attempts were also made to have solution of some the problems associated

with the soluble heterocyclic halochromate by immobilizing the same with inert

inorganic supports.246, 247, 237(a-d )

Frederick A. Luzzio et.al. reported a facile oxidation of cis, trans-4 – tert-

butyl cyclohexanol to 4- tert-butyl cyclohexanone and d,l menthol to dl menthone

using PCC on silica gel. It was used in conjunction with silica gel to facilitate

removal of reduced chromium byproduct and to provide anhydrous conditions that

would otherwise lead to unwanted side reaction with decreased yields.246

M. M. Heravi and coworkers247 were reported a simple and efficient

method for oxidation of alcohols to carbonyl compounds under non-aqueous

conditions employing 3-carboxypyridinium Chlorochromate (CPCC) adsorbed on

alumina. CPCC adsorbed on alumina was prepared by adding alumina to a

solution of CPCC in DCM and evaporating to dryness. The yellow orange solid

was then kept in vacuum at room temperature and stored in the dark before use.

Mohammed M. Hasmi and coworkers248 were introduced silica gel

supported 4-aminopyridinium Chlorochromate. It was prepared from reaction of

4-aminopyridine with activated silica gel which was then reacted with a solution

of chromium trioxide in hydrochloric acid. The oxidation of alcohols is performed

in DCM as solvent and work up was simply by separation of the heterogeneous

89
supported oxidant by filtration and purification by column chromatography led to

aldehydes and ketones in high yields. Mild reaction conditions, easy work up,

high yield and reusability of the supported reagent are the most significant aspect
238 d
of this method. Quinolinium fluochromate (QFC) supported on alumina

prepared by a new method oxidizes selectively aliphatic 1 0 and 2 0 alcohols,

substituted benzylic alcohols and allylic alcohols to their corresponding carbonyl

compounds in good yields. The effect of solvent in the oxidation reaction was

evaluated by carrying out the oxidation in a series of solvents with varying

polarity. The period for maximum conversion was found to be minimum in

hexane. Although the oxidation reactions proceed smoothly in DCM, hexane was

chosen as the solvent for the entire oxidation process keeping in view of the

environmental hazards associated with chlorinated hydrocarbon. A comparative

237c
study of the oxidation by this reagent and the one already reported (prepared

by a different method) was carried out with a series of aliphatic 1 0 alcohols, benzyl

alcohol, furfurol, cyclohexanol and benzoin. Studies revealed that the present

reagent is a better one in terms of reaction period and percentage yield.

A new selective method of QFC-supported silica gel for the oxidation of a

wide variety of alcohols to the corresponding carbonyl compounds in good yield

has been reported.249 The maximum conversion of benzyl alcohol to

benzaldehyde occurred in a shorter reaction period in hexane and DCM. The

oxidation of a series of aliphatic 10 alcohols with QFC-silica gel revealed that the

lower homologues up to 1-octanol are readily converted to the corresponding

aldehydes at room temperature while the higher homologues such as 1-nonanol

and 1-decanol require reflux conditions. It was interesting to note that the

90
oxidation of 10 alcohols with alkyl group at C-2 position such as 2-ethyl 1-hexanol

and neopentyl alcohols proceeds smoothly at a faster rate than 1-hexanol and 1-

pentanol. It was observed that the oxidation of 2 0 alcohols with QFC-silica gel

proceeds smoothly only under reflux conditions resulting in high conversion of

alcohols to the corresponding ketones. The reagent selectively oxidizes 10

hydroxyl group in the presence of secondary hydroxyl group. The selectivity is

also exhibited in the oxidation of axial hydroxy group of the cis-t-butyl

cyclohexanol in preference to equatorial hydroxyl group. Oxidation of steroidal

homoallyilc alcohols is a crucial step in the synthesis of most of the steroidal

hormones; oxidation of 3-β-chloestanol with QFC-silica gel gave chloestanone

with 60% yield. These reactions clearly indicate the potential utility of QFC-silica

gel in biosynthesis. QFC-silica gel is quite effective for the oxidation of

heterocyclic alcohols also. On the other hand the oxidation 3-pyridyl methanol

afforded 3-pyridyl carboxaldehyde with 65 % along with 20 % quinoline. ESR

spectral analysis of the reduced product of the QFC-silica gel showed a single

band with a g value of 1.982 and this value shows the presence of d2 Cr (IV)

species.

Synthesis organic chemist has wide variety of technique and method in

this repertoire to tailor an elegant synthesis but today any new development in

synthesis has to take into consideration of ecological aspect, toxic waste

generation, and formation of unwanted byproducts and cost of manufacture, no

matter how innovative chemistry is employed in the process. Therefore, the

demand today is for a synthesis which (a) is environmentally begin (b) minimizes

or eliminates waste generation (c) uses chemicals which do not need for special

91
methods of preparation (d) avoids the use of environmentally unfriendly solvents

(e) is stereoselective or regioselective for the desired enantiomers or isomers and

(f) a number of steps into a single operation. Microwave assisted organic synthesis

is the outcome of these progressive thoughts.

II.7. Microwave Technology

Since the appearance of the first article on the uses of microwave for
250,
chemical reactions the approach has blossomed into a useful technique for a

variety of applications in organic synthesis and functional group

transformations.251 Microwave technique has a great potential and can be utilized

as a highly innovative synthetic tool for the generation of highly functionalized

products.

The practical utility of MW assisted green protocol has been realized in

several synthetic operations such as protection/deprotection, condensation,

oxidation, reduction, rearrangement reaction and in the synthesis of various

heterocyclic systems. The reviews on this subject illustrate clearly the ingenuity

and imaginative breath in this area by presenting a showcase of research over the

past ten year.252-256

With easy availability of ultrasound and microwaves, their use in

chemistry has gained momentum recently.257 Microwave heating emerged as a

powerful technique to promote a variety of chemical reactions.

250
Microwave was first reported by the group of Gedye and Giguere

Majetich 258 in 1986, but the use of microwave in organic synthesis was initially

92
hampered by a lack of understanding of basic principles of MW dielectric

microwave ovens. Today over 2000 articles have been published in the area of

MW assisted organic synthesis, including several reviews.259-265

II.7.A. Application of Microwave for the oxidation of alcohols

Balogh and Coworkers266 have introduced a facile method for the

oxidation of alcohols to carbonyl compounds with yields wherein clayfen [ Iron

(III) nitrate] was used under microwave irradiation in solvent free condition

(Scheme-69)

R2 Clayfen R2
CH OH C O
MW, 15-60 Sec.
R1 R1

176 177 (87-96%)

R1=Ph, p-MeC6H4, p-MeOC6H4 ; R2=H

R1=Ph; R2=Et, PhCO

R1= p-MeOC6H4 R2= p-MeOC6H4CO

Scheme-69

R.S.Varma and Coworkers267have developed a new reagent manganese

dioxide-silica for the oxidation of alcohols to carbonyl compounds under

microwave irradiation. Benzyl alcohol were selectively oxidized to carbonyl

compounds using 35% MnO2 ‘doped’ silica under MW irradiations (Scheme-70)

93
 R2 MnO2 - Silica R2
CH OH C O
MW, 20-60 Sec.
R1 R1

178 179(67-96%)

R1=Ph, p-MeC6H4, p-MeOC6H4, PhCH=CH ; R2=H

R1=Ph; R2=Et, PhCO

R1= p-MeOC6H4 ; R2= p-MeOC6H4CO

Scheme-70

R.S. Varma and coworkers268have studied the facile oxidation of alcohols

to carbonyl compounds with alumina supported iodobenzene diacetate (IBD)

under solvent free condition in microwave irradiation with quantitative yields. The

advantage of using alumina as a support was apparent in marked improvement in

yields obtained with the alumina-IBD system as compared to neat IBD. (Scheme-

71)

R MW, 1-3 min R

CH OH C O
IBD/ Neutral alumina
R1 R1

180 181
Scheme-71

R.S. Varma and coworkers269 were used chromium trioxide impregnated

pre-moistened alumina for the oxidation of benzyl alcohol at room temperature.

The reactions were observed clean with no tar formation. No over oxidation to

carboxylic acid was observed (Scheme-72).

94
 R Wet CrO3-Al 2O 3 R
CH OH C O
MW, 40 Sec.
R1 R1

182 183 (68-90%)

R=Ph, p-MeC6H4, p-MeOC6H4, p-NO2C6H4; R1=H

R=Ph; R1=Et, PhCO

Scheme-72

R.S.Varma and coworkers270 have studied the oxidation of symmetrical

and unsymmetrical benzoin to benzil by copper (II) sulfate-alumina or oxone-wet

alumina under microwave heating (Scheme-73).

O
OH
CuSO4-Al2O3 or Oxone -Al2O3 R1
R1 R
R MW, 2-3.5 min
O
O

184 185

R=R1=C6H5, p-MeC6H4, p-MeOC6H4, p-ClC6 H4

R=C6H5; R1= p-MeC6H4, p-MeOC6H4

R= Me; R1=C6H5

Scheme-73

M. M. Heravi and coworkers271 reported a facile and selective oxidation of

alcohols to carbonyl compounds using ammonium chlorochromate on

95
montmorillonite k-10 under solvent free conditions that was accelerated in most

cases by exposure to microwaves. Primary alcohols were oxid oxidized to the

corresponding aldehydes and the oxidation of aldehydes to the corresponding acid

derivative was not observed even after prolonged irradiation and with excess of

supported chromium reagent.

M. M. Heravi and coworkers272reported oxidation of various alcohols to the

corresponding carbonyl compounds in excellent yields by chromium trioxide –

HZSM-5 zeolite under microwave irradiation in a solventless system. Two

equivalent of CrO3 and a weight equivalent of HZSM-5 zeolite per mol of benzyl

alcohol was used and exposed to microwave irradiation for 30 sec. which led to

the formation of benzaldehyde almost quantitatively, no trace of benzoic acid was

observed showing that no overoxidation occurs. Cinnamyl alcohol (186) was

converted to cinnamylaldehyde (187) in 90 % yield. (Scheme-74).

HZSM-5 Zeolite, CrO3

OH O
MW

186 187
Scheme-74

M. M. Heravi and coworkers273 reported the selective oxidation of alcohols

by silica-gel supported ammonium Chlorochromate in solvent less system. The

oxidation reaction is conducted by mixing finely ground reagent with alcohols.

This procedure was found a rapid, economic, manipulatively, simple, selective

and environmentally benign protocol when compared to the conventional solution

phase reaction.

96
 274
M.M. Heravi and coworkers used CrO3/wet silica gel for oxidation of

alcohols to corresponding carbonyl compounds under microwave irradiation in

solvent free conditions. The oxidation of cinnamyl alcohol (188) with this method

gave a moderate yield of cinnamaldehyde (189) (70%) and benzaldehyde (190)

(30 %) showing the carbon-carbon bonds are prone to cleavage by this procedure.

(Scheme-75).

O
CrO 3- Silica gel
OH O +
MW

188 189 190

Scheme-75

N. Noroozi –Pesyan and Coworkers275have used the alumina or silica gel as

catalysts for a solvent-free oxidation of benzoins to the corresponding benzils.

These catalysts were easily recovered after completion of the reactions.

Comparison of the results obtained with both catalysts indicates that all the

reactants were oxidized faster on alumina than on silica under these conditions.

Scheme-76)

OH O
Alumina or Silica gel

Ar' Ar Microwave or Heat Ar' Ar

191 192

Ar' = C6H5 , Ar =C6H5 -CO

Ar' = C6H5 , Ar = 4-Me2 NC6H4-CO

Ar' = 4-MeOC6H4 , Ar = 4-MeOC6 H4-CO

Ar' = C6H5 , Ar =4-MeOC6H4-CO

Ar' = Ar = C6H5

Ar' = C6H5 , Ar = H

Scheme-76

97
 Jitender M. Khurana and Coworkers276 have reported the simple and

efficient protocol for microwave-assisted solvent-free oxidation of hydrobenzoins

to benzoins or benzils, benzoins to benzils, and alcohols to the corresponding

aldehydes or ketones, using N-bromosuccinimide – neutral alumina.

Amit Sahu and coworkers277have been studied chromium based oxidants

like PCC, BIFC, PFC ACC etc. supported on alumina for oxidation of benzoin

under MW irradiation. Alumina was acted both as a catalyst as well as a solid

support in the reaction and increases the yield of product (Scheme-77).

O Acidic Alumina O
I. PCC
II. BIFC
III. ACC O
OH IV. PFC

193 194
Scheme-77

98
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