Sulfamic acid: as a green and reusable homogeneous catalyst for peroxidation of ketones and aldehydes using aqueous 30 % H2O2

Article abstract of DOI:10.1007/s13738-015-0598-8

Abstract Sulfamic acid has been used as an active, low-cost and reusable solid catalyst for conversion of ketones and aldehydes to corresponding gem-dihydroperoxides using 30 % aqueous hydrogen peroxide at room temperature. The reactions proceed with high rates and excellent yields.

Full text of DOI:10.1007/s13738-015-0598-8

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J IRAN CHEM SOC
DOI 10.1007/s13738-015-0598-8
ORIGINAL PAPER
Sulfamic acid: as a green and reusable homogeneous catalyst
for peroxidation of ketones and aldehydes using aqueous 30 %
H2O2
Kaveh Khosravi · Fariba Pirbodaghi · Samira Kazemi ·
Atefe Asgari
Received: 12 July 2014 / Accepted: 17 January 2015
© Iranian Chemical Society 2015
Abstract Sulfamic acid has been used as an active, low-
cost and reusable solid catalyst for conversion of ketones
and aldehydes to corresponding gem-dihydroperoxides using
30 % aqueous hydrogen peroxide at room temperature. The
reactions proceed with high rates and excellent yields.
22, 23], (ii) reaction of ketals with H2O2 in the presence of
tungstic acid [24], or BF3·Et2O [25], and (iv) peroxidation
of ketones using an acidic solvent [26]. However, many
of these methods have certain drawbacks including use of
concentrated H2O2 and excess acid, low yield, limited sub-
strate range and production of mixtures of peroxidic prod-
ucts [27]. Also, poor selectivity and the presence of ozone-
sensitive groups in the substrates are further limitations in
ozonolysis reaction. To avoid such limitations, recently,
reactions of ketones and aldehydes with H2O2 in the pres-
ence of Lewis acids in organic solvents have been reported.
Among the Lewis acids, I2 [28, 29], ceric ammonium
nitrate (CAN) [30], CSA [31], NaHSO4·SiO2 [32], Re2O7
[33], and PMA [34] have been reported as the catalysts in
the synthesis of gem-dihydroperoxides with aqueous H2O2.
In continuation of our efforts to explore new catalysts for
synthesis of gem-dihydroperoxides [35, 36]. Herein, we
wish to introduce the sulfamic acid as a low-cost, green and
effective recoverable solid catalyst in the synthesis of gem-
dihydroperoxides from ketones and aldehydes with 30 %
aqueous H2O2 at room temperature (Scheme 1).
Keywords Gem-dihydroperoxide · Aldehyde · Ketones ·
Sulfamic acid · Hydrogen peroxide
Introduction
Gem-dihydroperoxides (DHPs) are considered as stable
derivatives of ketones and aldehydes [1], which have been
of considerable interest because of their relevance to per-
oxidic antimalarial drugs [2, 3]. Also, these compounds are
important intermediates in synthesis of a number of classes
of peroxides including tetraoxanes [4–6], silateraoxans
[7], spirobisperoxyketals [8, 9], bisperoxyketals [10], and
1,2,4,5-tetraoxacycloalkanes [11, 12]. Gem-dihydroper-
oxides have also been employed as initiators for radical
polymerization reactions [13], as precursors for synthesis
of dicarboxylic acid esters [14], and as reagents for oxida-
tion reactions such epoxidation of α,β-unsaturated ketones
[15, 16], enantioselective oxidation of 2-substituted
1,4-naphtoquinones [17], oxidation of sulfides [18, 19], and
as suitable oxidants in other synthetic organic reactions [15,
20, 21]. Three major methods reported for the synthesis of
gem-dihydroperoxides are: (i) ozonolysis of ketone enol
ethers or α-olefines in the presence of aqueous H2O2 [11,
Sulfamic acid (SA) (NH2SO3H) is commercially avail-
able green heterogeneous catalyst that is solvable in water
and has been used widely as an effective catalyst in organic
synthesis [37, 38].
Experimental
Solvents, reagents, and chemical materials were obtained
from Aldrich and Merck chemical companies and puri-
fied prior to use. Nuclear magnetic resonance spectra were
recorded on JEOL FX 90Q using tetramethylsilane (TMS)
as an internal standard. Infrared spectra were recorded on a
PerkinElmer GX FT IR spectrometer (KBr pellets).
K. Khosravi (*) · F. Pirbodaghi · S. Kazemi · A. Asgari
Department of Chemistry, Faculty of Science, Arak University,
Arak 38156-8-8349, Iran
e-mail: khosravi.kaveh@gmail.com; k-khosravi@araku.ac.ir
1 3

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J IRAN CHEM SOC
extracted with CH2Cl2 (3 × 5 ml). Aqueous layer which
contains SA and organic layer that contains products, was
separated, dried over anhydrous Mg2SO4, and evaporated
under reduced pressure. The residue was purified by silica-
packed column chromatography (hexane–EtOAc) to afford
pure gem-dihydroperoxides (Tables 2, 3, 4). Products were
characterized on the basis of their melting points, elemental
Scheme 1 Peroxidation of aldehydes and ketones catalyzed by sul-
famic acid
1
analysis and IR, H NMR, and 13C NMR spectral analysis
Caution: Although we did not encounter any prob-
lem with gem-dihydroperoxides, peroxides are potentially
explosive and should be handled with precautions; all reac-
tions should be carried out behind a safety shield inside a
fume hood and heating should be avoided Table 1.
and amount of peroxide in products has been determined
by iodometric titration.
Catalyst recovery and reuse
General procedure for synthesis of gem-dihyroperoxides
The reusability potential of the catalyst was examined
in reaction of cyclohexanone with 30 % aqueous H2O2 at
room temperature in the presence of recovered SA (Table 2,
entry 1a). SA was easily solved in water, therefore, after
evaporation of aqueous layer, SA as the residue reused after
washing with CHCl3 and drying at 60 °C.
To a mixture of carbonyl compound (1 mmol) and SA
(0.0097 g, 0.1 mmol) in MeCN (2 ml) 30 % aqueous H2O2
was added (3 ml), and the mixture was stirred at room tem-
perature for an appropriate time (Tables 2, 3, 4). After com-
pletion of reaction as monitored by thin-layer chromatogra-
phy (TLC), the mixture was diluted with water (5 ml) and
The spectrum information for new compounds is
reported in below:
O
H
H
Table 1 Screening of reaction
parameters for formation of
dihydroperoxycyclohexane
OO OO
H
SA
30
%
)
)
2O2
(
cat
(
rt
Entrya
Solvent
SA(mmol)
0.1
Time (min)
Yield (%)b
1
2
Et2O
30
20
60
50
60
10
15
30
8
78
80
40
47
45
98
90
70
92
73
EtOAc
CH2Cl2
CHCl3
CCl4
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
0.1
3
0.1
a
1 mmol cyclohexanon,
4
0.1
5
0.1
amount of H2O2 in all entries
is 3 ml
6
0.1
7
0.08
0.05
0.15
0.2
b
Isolated yields
8
9
10
8
Table 2 Peroxidation of different cyclic ketones
Entry
Ketone
Productb
Time
(min)
10
Yield
Mp (oC)
oil
Ref
36
(%)c
1a
98, 96,95d
H
OO
OO
O
H
1b
15
90
oil
30
H
OO
O
H
OO
H
H
OO
1c
1d
11
14
96
93
oil
oil
30
36
O
OO
H
H
OO
O
OO
1e
1f
1e
20
15
30
91
95
82
64-66
oil
28
8
H
H
OO
OO
O
OOH
OOH
O
OOH
OOH
O
138-140
(decomposed)
28
O
H
OO
1h
14
94
148-150
28
H
OO
a
Conditions: ketone and aldehyde (1 mmol), CH3CN (2 mL), SA (0.1 mmol), 30 % aq. H2O2 (3 mL), reactions are carried out at rt
b
The structures of the products were established from their physical properties and spectral (1H NMR, 13C NMR and IR) analysis and com-
pared with the data reported in the literature and amount the peroxide is determined by Iodometric titration. Isolated Yield. d Yield after third
c
run
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Table 3 Peroxidation of side chain aliphatic ketones and aldehydes
Entry
Ketone
Productb
Time
(min)
12
Yield
(%)c
93
Mp
(oC)
oil
Ref
O
H
OO
H
OO
2a
2b
2c
36
30
28
O
H
H
OO OO
12
13
92
90
oil
HOO
OOH
O
31-33
2d
2e
19
22
89
75
oil
oil
28
28
H
H
O
OO OO
O
O
H
OO
H
OO
O
O
H
H
OO OO
2f
10
10
96
95
oil
oil
36
36
H
H
OO OO
2g
HH
O
H
OO
2h
2i
50
45
94
96
oil
oil
36
36
H
H
H
H
O OO
O
H
a
Conditions: ketone and aldehyde (1 mmol), CH3CN (2 mL), SA (0.1 mmol), 30 % aq. H2O2 (3 mL), reactions are carried out at rt
b
The structures of the products were established from their physical properties and spectral (1H NMR, 13C NMR and IR) analysis and com-
pared with the data reported in the literature and amount the peroxide is determined by Iodometric titration
c
Isolated yield
4-(dihydroperoxymethyl)-N,N-dimethylaniline (Table 4,
entry 3k): sticky brown oil. IR νmax/cm−1 (Nujol mull):
3,400, 3,092, 1,592, 1,425, 1,363, 1,221, 1,111, 979; H
NMR (90 MHz, CDCl3), δH: 3.00 (s, 6H), 6.28 (s, 1H),
7.32–7.42 (d, 2 H), 7.97–8.17 (d, 2 H), 10.47 (br, s, 2
H);13C NMR (22.5 MHz, DMSO-d6), δC: 38.50, 101.00,
127.75, 130.56, 138.06, 143.42; Anal. Calcd for C9H13NO4:
C, 54.26; H, 6.58. Found: C, 54.44; H, 6.83.
1,1-dihydroperoxycyclohexane by the model reaction of
cyclohexanone with 30 % aqueous H2O2 under catalytic
effect of SA and the results are summarized in Table 1.
As seen in this Table, the best result in terms of yield and
reaction time was provided using MeCN as the solvent of
choice at room temperature with 0.1 mmol of catalyst load-
ing (entry 6, Table 1).
1
With optimized conditions in hand [aldehyde or ketones
(1 mmol), aqueous 30 % H2O2 (3 ml), 0.1 mmol catalyst,
MeCN (2 ml, r.t)] we began to study the scope of the reac-
tion using a range of cyclic aliphatic ketones (Table 2),
side chain aliphatic aldehydes and ketones (Table 3) and
aromatic aldehydes and ketones (Table 4). According to
results summarized in these tables, generally, both cyclic
and side-chain aliphatic ketones react faster than the aro-
matic ketones to afford the corresponding gem-dihy-
droperoxides comparatively in higher yields. For cyclic
ketones, cyclohexanone reacts faster than cyclopentanone
in higher yield (Table 2, entries 1a and 1d). Also, interest-
ingly, the aromatic aldehydes and ketones substituted by
power electron-withdrawing substituent were not reacted
at all or reacted in very long time with nearly low yields.
It has been explained by Katja Zmitek and Co-workers
[28]. They reported that the transition state for this reac-
tion has positive charge on carbonyl group. So, this reac-
tion has high negative reaction constant (ρ = −2.76)
that suggests a transition state with a more developed
charge in the rate-determining step [28]. For example, we
observed that 4-N,N-dimethylamino benzaldehyde reacts
faster than 4-chlorobenzaldehyde (Table 4, entry 3k). On
the other hands, 4-nitro benzaldehyde because of pow-
erful electron-withdrawing of NO2 group, converted to
2-(1,1-dihydroperoxyethyl)thiophene (Table 4, entry
°
3m): White solid, m. p: 200–202 C. IR νmax/cm−1 (KBr
pellet): 3,420, 2,922, 2,829, 1,635, 1,558, 1,458, 1,363,
1,271, 987, 721, 599, 435, 353; 1H NMR (90 MHz,
CDCl3), δH: 2.55 (s, 3H), 7.20–7.90 (m, 3 H), 8.21 (br, s,
2 H). 13C NMR (22.5 MHz, DMSO-d6): δC: 31.56, 100.42,
126.75, 129.34, 130.00, 142.79; Anal. Calcd for C6H8O4S:
C, 40.90; H, 4.58; S, 18.20. Found: C, 41.18; H, 4.60, S,
19.12.
4-(dihydroperoxymethyl)benzaldehyde (Table 4, entry
3j): White solid, m.p: 210–212 °C. IR νmax/cm−1 (KBr
pellet): 3,338, 3,085, 2,920, 1,697, 1,612, 1,579, 1,419,
1
1,319, 1,275, 1,203, 1,014, 972, 835, 808, 621; H NMR
(90 MHz, CDCl3), δH: 6.04 (s, 1H), 7.21–8.27 (d, 2 H),
8.04–9.00 (d, 2H), 10.68 (br, s, 3 H, aldehyde and per-
oxides H). 13C NMR (22.5 MHz, DMSO-d6), δC: 110.08,
121.47, 129.71, 132.43, 145.36, 199.50. Anal. Calcd for
C8H8O5: C, 52.18; H, 4.38. Found: C, 52.36; H, 4.65.
Results and discussion
In an effort to establish the reaction conditions, vari-
ous reaction parameters were studied for preparation of
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Productb
Time
(min)
100
Yield
(%)c
73
Mp (oC)
75-77
Ref
36
Table 4 Peroxidation of
aromatic ketones and aldehydes
Entry
3a
Ketone
O
H
OO
H
OO
H
OO
O
H
OO
3b
3c
3d
80
80
80
58
58
58
oil
oil
oil
36
36
36
Me
O
Me
O
O
H
OO
H
OO
Cl
Cl
O
OOH
H
OO
H
C
O
H
OO
3e
3f
3g
3h
3i
40
40
85
88
83
95
15
oil
54-56
36
36
36
36
30
H
OO
H
OO
CHO
CHO
CHO
CHO
H
H
OO
OO
50
72-74
Cl
Me
Cl
H
OO
OO
a
H
Conditions: ketone and
40
oil
O
Me
O
aldehyde (1 mmol), CH3CN
(2 mL), Sulfamic acid
(0.1 mmol), 30 % aq. H2O2
(3 mL), reactions are carried
out at rt
H
H
OO
OO
180
decomposed
O2N
O2N
OHC
H
OO
H
H
OO
3j
3k
3l
360
36
91
70
96
210-212
Sticky oil
oil
new
new
36
H
O
C
CHO
H
C
OO
OO
H
b
N
N
H
O
H
C
C
The structures of the products
H
OO
O
O
HOO
were established from their
physical properties and spectral
(1H NMR, 13C NMR and IR)
analysis and compared with the
data reported in the literature
and amount the peroxide is
determined by Iodometric
titration
50
H
OO
3m
3n
60
85
_
200-202
_
new
_
S
S
H
H
OO OO
O
_
200
c
Isolated Yield
gem-dihydroperoxide very slowly and in very low conver-
sion (15 %) and decomposed after 0.5 h (Table 4, entry
3i). Therefore, we suggest that sulfamic acid activates both
carbonyl group and hydrogen peroxide. Sulfamic acid is a
powerful acid, so generates H+ that activates the carbonyl
group. On the other hands, the nitrogen atom of sulfamic
acid via hydrogen bonding activates hydrogen peroxide
(Scheme 2).
+δ
-δ
-δ
+δ
+δ
-δ
Scheme 2 Suggested mechanism for catalitic effect of sulfamic acid
In Addition, It is interesting that aliphatic aldehydes
react with only one molecule of hydrogen peroxide in car-
bonyl group and 1,1-hydroxyhydroperoxide derivatives
have been formed instead of their expected DHPs (Table 3,
entries 2h and 2i, Scheme 3).
For the first time, terephthalaldehyde has been reacted as
a dialdehyde, but we observed that only one of the aldehyde
groups has been converted to gem-dihydroeperoxide after
360 min (Table 3, entry 3j). Also, we have converted suc-
cessfully 2-methyltheilnyl ketone as a heterocyclic ketone
to corresponding gem-dihydroperoxide without any by-
product (Table 3, entry 3m). Like other our reported works,
benzophenone was recovered unreactive after 200 min
(Table 3, entry 3n).
Scheme 3 Conversion of aliphatic aldehydes to 1,1-hydroxyhydrop-
eroxide derivatives
Finally, this method for peroxidation of cyclohexanone
(entry 1a, Table 2) is compared with other reported meth-
odologies in the Table 5. As shown results, this methodol-
ogy clearly is better. This methodology really improves the
time reaction, yields and reaction condition.
1 3