HYDROGEN PEROXIDE

1

Hydrogen Peroxide

1

HOOH

[7722-84-1]

H

2

O

2

(MW 34.02)

InChI = 1/H2O2/c1-2/h1-2H
InChIKey = MHAJPDPJQMAIIY-UHFFFAOYAL

(nucleophilic reagent capable of effecting substitution reactions

2

and epoxidation of electron-deficient alkenes;

3

weak electrophile

whose activity is enhanced in combination with transition metal
oxides

4

and Lewis acids;

5

strong nonpolluting oxidant which can

oxidize hydrogen halides

6

)

Physical Data:

95% H

2

O

2

: mp −0.41

◦

C; bp 150.2

◦

C; d 1.4425

g cm

−

3

(at 25

◦

C). 90% H

2

O

2

: mp −11.5

◦

C; bp 141.3

◦

C; d

1.3867 g cm

−

3

. 30% H

2

O

2

: mp −25.7

◦

C; bp 106.2

◦

C; d 1.108

g cm

−

3

.

Solubility:

sol ethanol, methanol, 1,4-dioxane, acetonitrile, THF,

acetic acid.

Form Supplied in:

clear colorless liquid widely available as a

30% aqueous solution and 50% aqueous solution; 70% and
90% H

2

O

2

are not widely available.

Analysis of Reagent Purity:

titration with KMnO

4

or cerium(IV)

sulfate.

7

Purification:

95% H

2

O

2

(caution!) can be prepared from 50%

solution by distilling off water in a vacuum at rt.

8

Handling, Storage, and Precautions:

H

2

O

2

having a concen-

tration of 50% or more is very hazardous and can explode
violently, particularly in the presence of certain inorganic salts
and easily oxidizable organic material. A safety shield should
be used when handling this reagent.

9

After the reaction is

complete, excess H

2

O

2

should be destroyed by treatment with

MnO

2

or Na

2

SO

3

soln. Before solvent evaporation, ensure ab-

sence of peroxides. The use of acetone as solvent should be
avoided.

10

The reagent should be stored in aluminum drums in

a cool place away from oxidizable substances.

Synthesis of Peroxides via Perhydrolysis. H

2

O

2

and the hy-

droperoxy anion are excellent nucleophiles which react with alkyl
halides and other substrates having good leaving groups to fur-
nish hydroperoxides. The hydroperoxide (2) has been prepared
employing 98% H

2

O

2

(eq 1).

11

To a stirred mixture of THF (50

mL), Silver(I) Trifluoromethanesulfonate (0.04 mol), and pyri-
dine (0.02 mol) kept at 6

◦

C under argon and protected from light

is gradually added 98% H

2

O

2

(0.32 mol). The chloride (1) (0.02

mol) dissolved in THF (10 mL) is next added dropwise with cool-
ing (6

◦

C). The reaction mixture is kept at rt for 24 h; the or-

ganic layer is separated by gravity filtration, diluted with ether,
and washed with saturated aq NaHCO

3

at 0

◦

C. The organic layer

is dried. The solvent as well as traces of pyridine and starting ma-
terial are distilled out at rt under vacuum. The residual material

(1)

Cl

OOH

H

2

O

2

, AgOSO

2

CF

3

py, THF

rt, 24 h

(1)

(2)

83%

is the hydroperoxide (2) which has been distilled in high vacuum
using a bath maintained at 40

◦

C. The hydroperoxide (3) has been

prepared in a similar fashion employing 30% H

2

O

2

(eq 2).

12

(2)

30% H

2

O

2

MeOH, KOH

rt, 48 h

(3)

t

-Bu

Br

t

-Bu

OOH

42%

Tertiary alcohols R

1

R

2

R

3

COH and other alcohols which can

readily furnish carbenium ion intermediates are solvolyzed by
90% H

2

O

2

in the presence of acid catalysts to yield hydroper-

oxides R

1

R

2

R

3

COOH.

13

Trimeric hydroperoxides having a nine-

membered oxa heterocyclic ring have been prepared from ketones
and hydrogen peroxide in the presence of acid catalysts.

14

N

-Alkyl-N

′

-tosyl hydrazides are oxidized by H

2

O

2

and Na

2

O

2

in THF at rt to the corresponding hydroperoxides; by employing
this procedure, cyclohexyl hydroperoxide has been obtained in
92% yield.

15

Several gem hydroperoxides have been prepared from acetals

(eq 3).

16

(3)

30% H

2

O

2

THF, H

2

WO

4

0 °C, 48 h

O

O

OOH

OOH

86%

The prostaglandin PGG

2

(5) has been synthesized from the

dibromide (4) (eq 4).

17

Br

Br

Cl

CO

2

H

90% H

2

O

2

, Ag

+

O

OOH

(4)

CO

2

H

O

(4)

(5)

15–20%

Perhydrolysis of acid anhydrides furnishes the corresponding

peroxy acids (for an example, see Trifluoroperacetic Acid). Per-
hydrolysis of acid chlorides also furnishes peroxy acids.

18

When

an organic acid is mixed with H

2

O

2

an equilibrium reaction is

established, as shown in eq 5.

18

Methanesulfonic Acid has been

used to accelerate the reaction and also to function as solvent (see
preparation of Perbenzoic Acid).

RCO

2

H

+

H

2

O

2

RCO

3

H

+

H

2

O

(5)

H

+

A number of diacyl peroxides have been prepared in 90–95%

yield by reacting the acid chloride (for example, phenylacetyl
chloride) (1 equiv) with 30% H

2

O

2

(0.55 equiv) in ether in the

presence of pyridine (2 equiv) at 0

◦

C for 2 h.

19

Reactions with Amides, Aldehydes, and Ketones. The oxa-

zolidinone (6) is deacylated regioselectively on treatment with

Avoid Skin Contact with All Reagents

2

HYDROGEN PEROXIDE

Lithium Hydroperoxide (eq 6).

20

For another example, see

Evans.

21

(6)

O

N

O

Ph

O

OH

Ph

HO

Ph

O

OH

O

NH

Ph

O

+

30% H

2

O

2

LiOH, THF, H

2

O

rt, 1 h

(6)

100%

Aromatic aldehydes can be transformed to phenols by oxidizing

with H

2

O

2

in acidic methanol (eq 7).

22

Dilute alkaline H

2

O

2

can

convert only aldehydes having an hydroxyl in the ortho or para po-
sition to the corresponding phenols (Dakin reaction).

1b

m

-CPBA

is not useful for the preparation of phenol (8) from (7).

22

31% H

2

O

2

MeOH, KHSO

4

rt, 4 h

(7)

CHO

OMe

O

OH

OMe

O

(7)

(8)

80%

Alkyl and aryl aldehydes are oxidized to the corresponding

carboxylic acids in high yields via oxidation with H

2

O

2

in the

presence of Benzeneseleninic Acid as catalyst.

23

Cyclobutanones

and other strained ketones undergo Baeyer–Villiger oxidation
with H

2

O

2

. The cyclobutanone (9) has thus been oxidized to the

γ

-lactone (10) (eq 8).

24

Baeyer–Villiger oxidation of some cy-

clobutanones proceeds under very mild conditions (−78

◦

C).

25

Baeyer–Villiger reaction of ketones having isolated double bonds
can be carried out with H

2

O

2

without reaction at the double bond;

however, when organic peroxy acids are used, the alkene often is
oxidized.

26

30% H

2

O

2

glacial AcOH
5–10 °C, 16 h

(9)

(8)

O

OMe

OMe

O

O

(10)

>90%

Epoxidation of α,β-Unsaturated Ketones and Acids. α,β-

Unsaturated ketones furnish the corresponding α,β-epoxy ketones
in high yields on treatment with H

2

O

2

in the presence of a base.

3

In the cyclopentenone (11), approach to the β-face is sterically
hindered. Epoxidation of (11) at −40

◦

C furnishes quantitatively

a 94:6 mixture of α- and β-epoxides; the selectivity is less when the
reaction is carried out at higher temperatures (eq 9).

27

Optically

active epoxy ketones (about 99%) have been prepared with high ee
by carrying out the epoxidation in the presence of a chiral catalyst
such as polymer-supported poly(

L

-leucine).

28

O

C

5

H

11

CO

2

H

O

Si(CH

2

C

6

H

4

Me)

3

O

C

5

H

11

CO

2

H

(11)

3

O

Si(CH

2

C

6

H

4

Me)

3

(9)

30% H

2

O

2

MeOH, NaOH

O

3

α:β = 94:6

–45 °C, 12 h

α

,β-Unsaturated acids have been epoxidized with 35% H

2

O

2

using a catalyst prepared from 12-tungstophosphoric acid (WPA)
and cetylpyridinium chloride (CPC) (pH 6–7, 60–65

◦

C); by this

method, crotonic acid furnishes the α,β-epoxy acid in 90% yield.

29

Synthesis of Epoxides, Vicinal Diols, Dichlorides, and Ke-

tones from Alkenes. Terminal alkenes, as well as di- and trisub-
stituted alkenes, have been epoxidized at 25

◦

C using a molyb-

denum blue–Bis(tributyltin) Oxide catalyst system (eq 10).

30

Epoxides have been prepared with 16% H

2

O

2

using a (diperoxo-

tungsto)phosphate catalyst (12) in a biphasic system.

31

(10)

60% H

2

O

2

Mo cat., CHCl

3

3 h

O

88%

[(C

8

H

17

)

3

NMe]

3

+

[PO

4

{W(O)(O

2

)

2

}

4

]

3–

(12)

Asymmetric epoxidation of 1,2-dihydronaphthalene has been

achieved employing a chiral manganese(III) salen complex with
an axial N-donor; even 1% H

2

O

2

can be used as oxidant and the

highest ee observed was 64%.

32

Vicinal diols have been prepared from alkenes by oxidizing

with H

2

O

2

in the presence of Re

2

O

7

catalyst, in dioxane at 90

◦

C

for 16 h; the mole ratio of Re

2

O

7

:alkene:H

2

O

2

is 1:100:120.

The reaction proceeds via epoxidation followed by acid-catalyzed
ring opening. Cyclohexene furnishes trans-cyclohexane-1,2-diol
in 74% yield.

33

Oxidative cleavage of ene–lactams takes place during oxida-

tion with H

2

O

2

in the presence of a selenium catalyst (eq 11).

34

The reaction proceeds under neutral and mild conditions. For the
preparation of macrocyclic ketoimides, Palladium(II) Acetate is
used as the catalyst.

34

N
H

O

O

N
H

O

(11)

HO

2

C

30% aq H

2

O

2

SeO

2

, CH

2

Cl

2

rt, 2 h

82%

Alkenes have been chlorinated with concentrated HCl/30%

H

2

O

2

/CCl

4

in the presence of the phase-transfer catalyst Ben-

zyltriethylammonium Chloride. Side reactions take place when
gaseous chlorine and sulfuryl chloride react with alkenes; under
ionic conditions these side reactions are not favored. The method
has also been applied for the bromination of alkenes.

6

1-Octene

furnishes 1,2-dichlorooctane in 56% yield.

Oxidation of Alcohols and Phenols.

The system H

2

O

2

/

RuCl

3

·

3H

2

O/phase-transfer catalyst (didecyldimethylammonium

A list of General Abbreviations appears on the front Endpapers

HYDROGEN PEROXIDE

3

bromide) oxidizes a variety of alcohols selectively; the require-
ment of ruthenium is very low; ratio of substrate:RuCl

3

= 625:1.

35

By this method, p-methylbenzyl alcohol was oxidized to p-
methyl benzaldehyde in 100% yield.

Vicinal diols are oxidized to α-hydroxy ketones by 35% H

2

O

2

in the presence of peroxotungstophosphate (PCWP; 1.6 mol %)
in a biphasic system using CHCl

3

as solvent. 1,2-Hexanediol has

been oxidized in 93% yield to 1-hydroxy-2-hexanone.

36

When 1,4-dihydroxybenzenes are reacted with stoichiomet-

ric quantities of iodine, the corresponding p-benzoquinones are
formed in poor yields; however, they are oxidized in very good
yields to p-quinones by reaction with 60% H

2

O

2

in methanol or

aq solution at rt in the presence of catalytic quantities of I

2

or

HI. 2-Methyl-1,4-dihydroxynaphthalene has been oxidized to 2-
methyl-1,4-naphthoquinone in 98% yield.

37

Radical Reactions. Homolytic substitutions of pyrrole, in-

dole, and some pyrrole derivatives have been carried out using
electrophilic carbon centered radicals generated in DMSO by
Fe

2+

/H

2

O

2

and ethyl iodoacetate or related iodo compounds; the

substrate is taken in large excess (eq 12).

38

N

Me

O

N

Me

(12)

O

EtO

2

C

35% H

2

O

2

ICH

2

CO

2

Et

FeSO

4

·

7H

2

O

DMSO

90%

N

-Acylpyrrolidines and -piperidines are oxidized by Fe

II

/

hydrogen peroxide in aqueous 95% acetonitrile to the
corresponding pyrrolidin-2-ones and piperidin-2-ones;

39

N

-

phenylcarbamoyl-2-phenylpiperidine was oxidized to the corre-
sponding lactam in 61% yield.

Oxidation of Organoboranes. Oxidative cleavage of the C–B

bond with alkaline H

2

O

2

to convert organoboranes to alcohols is

a standard step in hydroboration reactions. In some procedures,
organoboranes are formed in the presence of 1,4-oxathiane. When
a mixture of tri-n-octylborane and 1,4-oxathiane in THF was
treated initially with NaOH and subsequently with 30% H

2

O

2

, the

organoborane was selectively oxidized to furnish in 98% yield a
mixture (93:7) of octan-1-ol and octan-2-ol.

40

Oxidation of Organosilicon Compounds.

Organosilicon

compounds having at least one heteroatom on silicon undergo
oxidative cleavage of the Si–C bond when treated with H

2

O

2

(eq 13).

41

For additional examples, see Roush

42a

and Andrey.

42b

OH

SiMe

2

(O-i-Pr)

OH

OH

(13)

30% H

2

O

2

KHCO

3

, KF

MeOH, THF

rt, 2 h

77%

Oxidation of Amines. H

2

O

2

in the presence of Na

2

WO

4

has

been used to oxidize (a) 2,4,4-trimethyl-2-pentanamine to the cor-
responding nitroso compound in 52% yield,

43

and (b) a primary

amine (containing β-lactam and phenolic OH) to the correspond-
ing oxime in 72% yield.

44

The secondary amine 2-methylpiperidine (13) has been ox-

idized to the nitrone (14) with H

2

O

2

/Na

2

WO

4

(eq 14);

45

the

oxidation product also contains about 6–15% of the isomeric
2-methyl-2,3,4,5-tetrahydropyridine N-oxide (Selenium(IV) Ox-
ide is also an effective catalyst for this oxidation).

46

1,2,3,4-

Tetrahydroquinoline is oxidized to the 1-hydroxy-3,4-dihydro-
quinolin-2(1H)-one in 84% yield by H

2

O

2

/Na

2

WO

4

.

47

The flavin,

FlEt

+

ClO

4

−

(15) is a good catalyst for the H

2

O

2

oxidation of sec-

ondary amines to nitrones.

48

N
H

(13)

N

O

–

(14)

30% aq H

2

O

2

Na

2

WO

4 ·

2H

2

O

H

2

O, add. 30 min

+

(14)

rt, 3 h

62–70%

(15)

N

N

Me

Et

NMe

N

O

O

+

N

O

–

Me

t

-Bu

+

(16)

trans

:cis = 95:5

ClO

4

–

The tertiary amine N-methylmorpholine has been oxidized to

the N-oxide in 84–89% yield; the reaction is carried out at 75

◦

C

with 30% H

2

O

2

and the reaction time (0.3 mol scale) is about 24

h.

49

The trans-N-oxide (16) has been obtained stereoselectively

(trans:cis = 95:5) by reacting the corresponding N-methylpiperi-
dine with 30% H

2

O

2

in acetone at 25

◦

C.

50

Oxidation of Sulfur-containing Compounds. Oxidation of

di-n-butyl sulfide with H

2

O

2

in the presence of the catalyst

FlEt

+

ClO

4

−

(15) furnished the corresponding sulfoxide in 99%

yield.

48

Sulfides have been oxidized to the corresponding sul-

foxides with H

2

O

2

in CH

2

Cl

2

solution in the presence of the

heterocycle (17); di-n-octyl sulfide yields n-octyl sulfoxide in 96%
yield, and benzylpenicillin methyl ester is oxidized to the (S)-S-
oxide in 90% yield.

51

(17)

N

N

N

N

COMe

The oxidation of sulfides to sulfones proceeds in good yields

when the reaction is catalyzed by tungstic acid; the cyclic sul-
fide thietane is oxidized to the sulfone (thietane 1,1-dioxide) in
89–94% yield.

52

Oxidation of Selenium-containing Compounds. Oxidation

of the phenyl selenide (18) with H

2

O

2

in THF furnishes the alkene

(19) (eq 15);

53

the selenoxide initially formed through oxidation

of (18) undergoes facile syn elimination (see also Grieco

54

).

O

O

SePh

O

O

(15)

30% H

2

O

2

THF

25 °C, 12 h

(18)

(19)

90%

Avoid Skin Contact with All Reagents

4

HYDROGEN PEROXIDE

Hydrogen peroxide has a high (47%) active oxygen content

and low molecular weight. It is cheap and is widely available. Af-
ter delivering oxygen, the byproduct formed in H

2

O

2

oxidations

is the nonpolluting water. Hence the use of H

2

O

2

in industry is

highly favored. This reagent is able to oxidize SeO

2

, WO

3

, MoO

3

,

and several other inorganic oxides efficiently to the correspond-
ing inorganic peroxy acids which are the actual oxidizing agents
in many reactions described above.

4

Use of these oxides in cat-

alytic amounts along with H

2

O

2

as the primary oxidant reduces

the cost of production, simplifies workup and minimizes the efflu-
ent disposal problem. Phase-transfer-catalyzed (PTC) reactions in
a two-phase system are well suited for H

2

O

2

oxidations and are

widely used; epoxides are susceptible to ring opening by water
and the PTC procedure allows the preparation of epoxides even
with 16% aq H

2

O

2

since the epoxide and water are in different

phases.

31

Handling chlorine and bromine poses many problems,

but HCl/H

2

O

2

and HBr/H

2

O

2

systems may be used as substi-

tutes for chlorine and bromine, respectively.

6

The solids Sodium

Perborate, sodium percarbonate, and Hydrogen Peroxide–Urea,
which are prepared from H

2

O

2

, have wide applications since they

release H

2

O

2

readily.

Reactions with Nitriles.

Treatment of nitriles (20) with

NaOH/H

2

O

2

in aqueous ethanol is a standard synthetic proce-

dure for the preparation of amides (21); aromatic nitriles furnish
amides in high yields but aliphatic nitriles give amides in moder-
ate yields (50–60%).

55

It has been suggested

56

that addition of the

hydroperoxy anion to the nitrile (20) furnishes the peroxycarbox-
imidic acid (22) which reacts with H

2

O

2

to give the amide (21)

and molecular oxygen.

R

N

R

O

NH

2

R

NH

OOH

(20)

(21)

(22)

It has been observed

57

that in the reaction of nitriles with 30%

H

2

O

2

in the presence of 20% NaOH there is a significant increase

in the reaction rate when n-tetrabutylammonium hydrogen sulfate
(20 mol %) is used as phase-transfer catalyst. The reaction is car-
ried out at 25

◦

C for 1–2 h employing CH

2

Cl

2

; aromatic as well

as aliphatic amides are obtained in high yields (e.g. eq 16). This
method cannot be used if the nitrile has an electron-withdrawing
substituent on the carbon atom α to the cyano group.

57

(16)

CN

CONH

2

1.6 h

97%

Treating a DMSO solution of a nitrile with an excess of 30%

H

2

O

2

in the presence of a catalytic amount of K

2

CO

3

for 1–30 min

at 25

◦

C furnishes the corresponding amide in high yields

58

(e.g.

eq 17). Under these conditions, esters, amides, and urethanes do
not react. α,β-Unsaturated nitriles furnish α,β-epoxy amides.

58

For other routes for the synthesis of amides from nitriles, see
Cacchi

57

and Katritzky.

58

CN

CONH

2

Cl

Cl

(17)

30% H

2

O

2

DMSO, K

2

CO

3

20 °C, 5 min

85%

Related Reagents. Hydrogen Peroxide–Ammonium Hepta-

molybdate; Hydrogen Peroxide–Boron Trifluoride; Hydrogen
Peroxide–Iron(II) Sulfate; Hydrogen Peroxide–Tellurium Dio-
xide; Hydrogen Peroxide–Tungstic Acid; Hydrogen Pero-
xide–Urea; Iron(III) Acetylacetonate–Hydrogen Peroxide; Per-
benzoic Acid; Peroxyacetimidic Acid; Trifluoroperacetic Acid.

1.

(a) Kirk-Othmer Encyclopedia of Chemical Technology; Wiley: New
York, 1978; Vol. 3, p 944; Vol. 13 p 12; Vol. 2, p 264. (b) Fieser, L. F.;
Fieser, M., Fieser & Fieser 1967, 1, 456.

2.

Swern, D. In Comprehensive Organic Chemistry; Barton, D. H. R., Ed.;
Pergamon: Oxford, 1979; Vol. 1. p 909.

3.

Weitz, E.; Scheffer, A., Chem. Ber. 1921, 54, 2327.

4.

Mimoun, H. In Comprehensive Coordination Chemistry; Wilkinson, G.,
Ed., Pergamon: Oxford, 1987, Vol. 6, p 317.

5.

Olah, G. A.; Fung, A. P.; Keumi, T., J. Org. Chem. 1981, 46, 4305.

6.

Ho, T.-L.; Gupta, B. G. B.; Olah, G. A., Synthesis 1977, 676.

7.

Swern, D. Organic Peroxides; Wiley: New York, 1970; Vol. 1, p 475.

8.

Cofre, P.; Sawyer, D. T., Inorg. Chem. 1986, 25, 2089.

9.

(a) Pagano, A. S.; Emmons, W. D., Org. Synth. 1969, 49, 47.
(b) Hazards in the Chemical Laboratory; Luxon, S. G., Ed.; Royal
Society of Chemistry: Cambridge, 1992.

10.

Organic Peroxides

; Swern, D., Ed.; Wiley: New York, 1970; Vol. 1, p 1.

11.

Frimer, A. A., J. Org. Chem. 1977, 42, 3194.

12.

Bloodworth, A. J.; Curtis, R. J.; Spencer, M. D.; Tallant, N. A.,
Tetrahedron 1993

, 49, 2729.

13.

Davies, A. G.; Foster, R. V.; White, A. M., J. Chem. Soc. 1953, 1541.

14.

Story, P. R.; Lee, B.; Bishop, C. E.; Denson, D. D.; Busch, P., J. Org.
Chem. 1970

, 35, 3059.

15.

Caglioti, L.; Gasparrini, F.; Palmieri, G., Tetrahedron Lett. 1976, 3987.

16.

Jefford, C. W.; Li, Y.; Jaber, A.; Boukouvalas, J., Synth. Commun. 1990,
20

, 2589.

17.

Porter, N. A.; Byers, J. D.; Ali, A. E.; Eling, T. E., J. Am. Chem. Soc.
1980, 102, 1183.

18.

Ogata, Y.; Sawaki, Y., Tetrahedron 1967, 23, 3327.

19.

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A. Somasekar Rao & H. Rama Mohan

Indian Institute of Chemical Technology, Hyderabad, India

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