Journal of Molecular Catalysis A: Chemical 365 (2012) 15–23

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Journal of Molecular Catalysis A: Chemical

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Preparation, characterization and use of 1,3-disulfonic acid imidazolium

hydrogen sulfate as an efficient, halogen-free and reusable ionic liquid catalyst
for the trimethylsilyl protection of hydroxyl groups and deprotection of the
obtained trimethylsilanes
Farhad Shirini ∗ , Nader Ghaffari Khaligh, Somayeh Akbari-Dadamahaleh
Department of Chemistry, College of Sciences, Guilan University, Rasht 41335-19141, Iran

a r t i c l e i n f o a b s t r a c t

Article history: Novel 1,3-disulfonic acid imidazolium hydrogen sulfate, a halogen-free ionic liquid, is a recyclable and
Received 3 June 2012 eco-benign catalyst for the trimethylsilyl protection of hydroxyl groups at room temperature under sol-
Received in revised form 24 July 2012 vent free conditions to afford trimethylsilanes in excellent yields (92–100%) and in very short reaction
Accepted 1 August 2012
times (1–5 min). Deprotection of the resulting trimethylsilanes can also be achieved using the same cata-
Available online 10 August 2012
lyst in methanol. The catalyst was characterized by IR, 1 H NMR, 13 C NMR and MS studies. All the products
were extensively characterized by IR, 1 H NMR, MS, and elemental and melting point analyses. This new
Keywords:
method consistently has the advantages of excellent yields and short reaction times. Further, the cata-
Ionic liquid
1,3-Disulfonic acid imidazolium hydrogen
lyst can be recovered and reused for several times without loss of activity. The work-up of the reaction
sulfate consists of a simple separation, followed by concentration of the crude product and purification.
Trimethylsilylation © 2012 Elsevier B.V. All rights reserved.
Protection
Deprotection

1. Introduction toxicology have appeared in literature [17]. Typical ionic liquids

Nowadays task-specific ionic liquids (TSILs) have received con-
siderable interest as eco-friendly solvents, catalysts and reagents
in green synthesis because of their unique properties, such as low
volatility, nonflammability, high thermal stability, negligible vapor
pressure and ability to dissolve a wide range of materials [1–9].
Among them, Brönsted acidic ionic liquids have designed to replace
solid acids and traditional mineral liquid acids like sulfuric acid and
hydrochloric acid in chemical procedures [10–14]. Introduction of
Brönsted-acidic functional groups into cations or anions of ionic
liquids, especially SO3 H and SO4 H functional groups, obviously
enhances their acidities and water solubility [15,16]. Moreover,
their polar nature makes them useful for use under solvent-free
conditions. An ever-increasing interest has focused on TSILs for
catalytic reactions where catalyst is in one phase and product in
another, which makes product-isolation easy and catalyst-reuse
convenient.
To date, research of some “greener” halogen-free ionic liquids
with phosphate or sulfate anions and the effects of the anion on
∗ Corresponding author. Tel.: +98 131 3233262; fax: +98 131 3233262.
E-mail addresses: shirini@guilan.ac.ir, fshirini@gmail.com (F. Shirini),
ngkhaligh@guilan.ac.ir, ngkhaligh@gmail.com (N.G. Khaligh).
consist of halogen-containing anions (for example [Cl]− , [PF6 ]− ,
[BF4 ]− , [CF3 SO3 ]− , or [(CF3 SO2 )2 N]− ) which to some extent limits
their “greenness” [17,18], therefore, it is necessary to synthesize
novel efficient and halogen-free TSILs.
Transformation of hydroxyl groups to their trimethylsilyl ethers
is of value from different views [19,20]. This conversion enhances
solubility of the compounds in non-polar solvents, increases ther-
mal stability, and used extensively to increase volatility of the
compounds for gas chromatography and mass spectrometry. More-
over, protection of hydroxyl groups and their transformation to
the corresponding silyl ethers is of vital importance in the total
synthesis of complex organic molecules. For these vast appli-
cations of silyl ethers presentation of new methods, using new
catalysts is of demand from industries and academia. Generally,
the formation of silylethers was carried out by the treatment of
alcohols with silylchlorides or silyl triflates under the influence of
basic conditions [21–26]. However, some of these methods fre-
quently suffered from drawbacks such as lack of reactivity and
the difficulty in removing amine salts derived from the reaction
of produced acids and bases during the course of the reaction.
Hexamethyldisilazane (HMDS) is a cheap and commercially avail-
able reagent that can be used for the preparation of trimethylsilyl
ethers from hydroxyl compounds. O-Silylation of alcohols using
HMDS is an attractive alternative, since the only by-product of

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http://dx.doi.org/10.1016/j.molcata.2012.08.002
16 F. Shirini et al. / Journal of Molecular Catalysis A: Chemical 365 (2012) 15–23
the reaction is ammonia which is easily removed from the reac-
tion mixture. However, its main drawback is its poor silylating
power, which needs forceful conditions and long reaction times
[27]. A variety of catalysts have been reported for the activation
of HMDS; of them trichloroisocyanuric acid (TCCA) [28], zirconium
sulfophenyl phosphonate [29], ZnCl2 [30], Envirocat EPZGO [31],
tungstophosphoric acid [32], K-10 montmorillonite [33], iodine
[34], lithium perchlorate [35], cupric sulfate pentahydrate [36],
H-␤ zeolite [37], MgBr2 [38], lithium perchlorate supported on
silica gel [39], sulfonic acid-functionalized silica [40], magnesium
triflate [41], InBr3 [42], zirconium triflate [43], ZrCl4 [44], NBS
[45], iron(III) trifluoroacetate [46], silica supported perchloric acid
[47], Fe3 O4 [48], poly(N-bromobenzene-1,3-disulfonamide) [49],
barbutric acid [50], Al(H2 PO4 )3 [51], V(HSO4 )3 [52], Fe(HSO4 )3
[53], tetrabutylammonium phtalimide-N-oxyl (TBAPINO) [54],
TiCl3 (OTf) [55], Nafion® SAC-13 [56], SaSA [57], SANM [58], SuSA
[59], P(4-VP) [60] and [Msim]HSO4 [61] are examples. Although
the silylation ability of HMDS has been promoted in the pres-
ence of these catalysts, yet some of the presented methods suffer
from long reaction times, low yields, and drastic reaction condi-
tions and sometimes, a tedious workup is required. In addition, in
most of the reported methods, selectivity of the protocols is either
poor or is not reported properly. On the other hand, most of these
methods are not applicable for the silylation of tertiary alcohols.
Consequently, a new procedure that addresses these drawbacks is
desirable.
2. Experimental
2.1. Materials
All chemicals were purchased from Merck or Fluka Chemical
Companies. All yields refer to the isolated products. Products were
characterized by their physical constants and comparison with
authentic samples. The purity determination of the substrates and
reaction monitoring were accompanied by TLC using silica gel SIL
G/UV 254 plates.
2.2. Instrumentation
IR spectra were run on a Perkin Elmer 781 Spectrophotome-
ter. The reaction conversions were measured by GC on a Shimadzu
model GC-16A instrument. The 1 H NMR (300 or 400 MHz) and 13 C
NMR (75 or 100 MHz) were run on a Bruker Avance DRX-300 or
400 spectrometer (ı in ppm). Microanalyses were performed on a
Perkin Elmer 240-B microanalyzer. Melting points were recorded
on a Büchi B-545 apparatus in open capillary tubes.
2.3. Procedure for the preparation of the ionic liquid [Dsim]HSO4
Chlorosulfonic acid (1.400 g, 12.0 mmol) was added dropwise to
a stirred solution of imidazole (0.408 g, 6.0 mmol) in dry CH2 Cl2
(10 mL) over a period of 3 min at ice-bath. After the addition
was completed, the reaction mixture was stirred for 30 min, and
then sulfuric acid 98% (0.588 g, 6.0 mmol) was added dropwise
over a period of 1 min at room temperature. The reaction mix-
ture was stirred for 2 h under pressure of nitrogen (to remove
the produced HCl); heat for 1 h at 50 ◦ C, and then CH2 Cl2 was
decanted. The residue was washed with dry CH2 Cl2 (3 × 10 mL) and
dried under vacuum to give 1,3-disulfonic acid imidazolium hydro-
gen sulfate [Dsim]HSO4 as a viscous pale yellow oil in 98% yield,
1.91 g.
Viscous pale yellow oil: FT-IR (liquid film):  = 3500–2400,
1715, 1587, 1288, 1171, 1073, 1009, 882, 579, 451 cm−1 ;
1 H NMR (400 MHz, DMSO-d ): ı = 7.61 (s, 2H), 8.99 (s, 1H),
6
10.72 (s, 1H), 14.24 (s, 2H) ppm; 13 C NMR (100 MHz, DMSO-
d6 ): ı = 121.1, 131.5 ppm; MS (EI, 70 eV) m/z = 327 [M+ +1], 326
[M+ ], 245 [M+ −SO3 H], 229 [M+ −SO4 H], 164 [M+ −2(SO3 H)], 67
[M+ −2(SO3 H)SO4 H].
2.3.1. Characterization of the catalyst
2.3.1.1. FTIR studies. The corresponding FTIR spectral data of
imidazole and 1,3-disulfonic acid imidazolium hydrogen sulfate
[Dsim]HSO4 have been presented in Fig. 1. The strong absorp-
tions at 1288.22, 1171.74 and 579.84 cm−1 in ionic liquid were
assigned to the asymmetric and symmetric stretching and bend-
ing for S O vibrations of sulfonic acid and sulfate groups, that
were absent in imidazole [62]. The symmetric N S stretching vibra-
tion also appeared at 882.14 cm−1 . These special peaks indicated
that sulfonic groups were successfully introduced in the imidaz-
ole molecule. On the other hand, the presence of two sulfonic
acid groups on the imidazole nitrogen in the [Dsim]HSO4 ionic
liquid increased the number of vibrational modes and brought com-
pletely different FTIR spectra. The strong band at 1705.08 cm−1
arising from the sulfonated imidazole ion was appeared. By com-
parison with SOH bending frequencies in sulfuric acid and other
sulfonic acids, the band at 1073.63 cm−1 were assigned to SOH bend
[63]. The broad and strong band at 2700–3550 cm−1 arise from the
hydroxyl groups in the [Dsim]HSO4 ionic liquid.
2.3.1.2. 1 H NMR and 13 C NMR analysis. 1 H and 13 C NMR spectra
of the [Dsim]HSO4 ionic liquid are presented in Fig. 2. The impor-
tant peaks of 1 H NMR spectrum of ionic liquid were related to the
acidic hydrogen (SO4 H) and (SO3 H) which observed in 10.72 and
14.23 ppm. In order to prove that the ionic liquid was synthesized,
we run the 1 H NMR spectra of H2 SO4 and imidazolium chloride
in DMSO-d6 and also use 1 H NMR of [Dsim]Cl and chlorosulfonic
acid presented in literature [64]. The peaks of the acidic hydro-
gen of H2 SO4 , [Dsim]Cl, ClSO3 H and imidazolium chloride were
observed in 10.32, 13.34, 13.45 and 9.08 ppm, respectively. The dif-
ference between the peaks of the acidic hydrogen confirmed that
the peaks observed in 10.72 and 14.24 ppm of the 1 H NMR spectra
of [Dsim]HSO4 were correctly related to the SO4 H and SO3 H groups
of ionic liquid.
The other case for the mixing of imidazole with ClSO3 H and
H2 SO4 in dry CH2 Cl2 , was formation of a separated phase, “H2 SO4
and ClSO3 H dissolved in imidazole”. To recognize the formation of
a separated phase physical phenomenon, again, we noticed to the
1 H NMR spectral data of the product obtained from the mixing,
with those in imidazole, ClSO3 H, H2 SO4 and the intermediate 1,3-
disulfonic acid imidazolium chloride [Dsim]Cl, separately. The 1 H
NMR spectral data include:
1,3-Disulfonic acid imidazolium hydrogen sulfate: 1 H NMR
(300 MHz, DMSO-d6 , ppm): ı = 7.61 (s, 2H), 8.99 (s, 1H), 10.71 (s,
1H), 14.23 (s, 2H).
1,3-Disulfonic acid imidazolium chloride: 1 H NMR (DMSO-d6 ,
300 MHz, ppm): ı = 7.34 (s, 2H), 8.67 (s, 1H), 13.34 (s, 2H) [64].
Imidazole: 1 H NMR (DMSO-d6 , 300 MHz, ppm): ı = 7.13 (s, 2H),
7.74 (s, 2H).
ClSO3 H: 1 H NMR (DMSO-d6 , 300 MHz, ppm): ı = 13.45 (s, 1H) [64].
H2 SO4 : 1 H NMR (DMSO-d6 , 300 MHz, ppm): ı = 10.32 (s, 1H).
As it can be seen, the 1 H NMR data of the ionic liquid were differ-
ent with those in imidazole, ClSO3 H, H2 SO4 and the intermediate
[Dsim]Cl. Moreover, imidazole and ClSO3 H were easily dissolved in
CH2 Cl2 ; however, the [Dsim]Cl and [Dsim]HSO4 ionic liquids were
insoluble in CH2 Cl2 .
2.3.1.3. MS studies. Mass spectra of the [Dsim]HSO4 ionic liquid
are presented in Fig. 3. The important peaks of MS spectrum
 F. Shirini et al. / Journal of Molecular Catalysis A: Chemical 365 (2012) 15–23 17

Fig. 1. FTIR spectra of imidazole (top), 1,3-disulfonic acid imidazolium chloride [Dsim]Cl and 1,3-disulfonic acid imidazolium hydrogen sulfate [Dsim]HSO4 (bottom).

of the ionic liquid were related to the [M+ +1] = 327, [M+ ] = 326,
[M+ −SO3 H] = 245, [M+ −SO4 H] = 229, [M+ −2(SO3 H)] = 164 and
[M+ −2(SO3 H)SO4 H] = 67.
2.4. General procedure for O-silylation of alcohols and phenols
with HMDS in the presence of [Dsim]HSO4 ionic liquid
under reduced pressure gave the highly pure product without fur-
ther purification. The desired pure products were characterized by
comparison of their IR, NMR and MS data as well as boiling point
with those of known compounds [5,9,10,33,40,51,56–61].
2.5. The spectral data of new products

Ionic liquid [Dsim]HSO4 (6.5 mg, ∼0.02 mmol) was added to
a stirred mixture of alcohol, phenol or naphthol (1.0 mmol) and
HMDS (80 mg, 0.5 mmol) at room temperature under solvent free
conditions. After completion of the reaction (monitored by TLC,
It should be noted that when addition of HMDS is finished stir-
ring of the mixture is stopped after 1 min. TLC showed that in
most of the cases the reaction is completed immediately after the
addition of HMDS), the product was extracted with Et2 O and the
ionic liquid was recovered and was dried at 65 ◦ C under vacuum
to remove moisture, and then reused. Evaporation of the solvent
2.5.1. (1,1-Dimethyl-2-phenyl-ethoxy)-trimethylsilyl ether
IR (neat):  = 2950, 1450, 1255, 1095, 838, 740, 693 cm−1 ; 1 H
NMR (400 MHz, CDCl3 ): ı = 0.148 (s, 9H), 1.292 (s, 6H), 2.802 (s,
2H), 7.272–7.356 (m, 5H) ppm; MS (EI, 70 eV) m/z: 222 [M+ ], 207
[M+ −CH3 ], 133 [M+ −OTMS]; Anal. calcd for C13 H22 OSi: C, 70.27; H,
9.90. Found: C, 70.25; H, 9.87.
2.5.2. (1-Biphenyl-4-yl-1-methyl-ethoxy)-trimethylsilyl ether
IR (neat):  = 3010, 2950, 1690, 1680, 1670, 1600, 1506, 1253,
1180, 1120, 1100, 880, 840, 752 cm−1 ; 1 H NMR (400 MHz, CDCl3 ):
18 F. Shirini et al. / Journal of Molecular Catalysis A: Chemical 365 (2012) 15–23

1
Fig. 2. H NMR (top) and 13 C NMR (bottom) spectra of the 1,3-disulfonic acid imidazolium hydrogen sulfate [Dsim]HSO4 .

ı = 0.296 (s, 9H), 1.777 (s, 6H), 7.461 (t, J = 7.2 Hz, 1H), 7.564 (dd,
J = 7.2 and 8.0 Hz, 2H), 7657–7.715 (m, 4H), 7.749 (d, J = 7.2 Hz, 2H)
ppm; MS (EI, 70 eV) m/z: 284 [M+ ], 269 [M+ −CH3 ], 195 [M+ −OTMS];
Anal. calcd for C18 H24 OSi: C, 76.05; H, 8.45. Found: C, 76.02; H, 8.41.
2.5.3. Trimethyl-trityloxysilyl ether
IR (neat):  = 2970, 2900, 1580, 1480, 1462, 1300, 1253, 1050,
910, 838 cm−1 ; 1 H NMR (400 MHz, CDCl3 ): ı = −0.014 (s, 9H),
7.320 (t, J = 7.2 Hz, 3H), 7.389 (dd, J = 7.2 and 7.6 Hz, 6H), 7.560 (d,
J = 7.2 Hz, 6H) ppm; MS (EI, 70 eV) m/z: 332 [M+ ], 317 [M+ −CH3 ], 243
[M+ −OTMS]; Anal. calcd for C22 H24 OSi: C, 79.52; H, 7.22. Found: C,
79.49; H, 7.20.
2.5.4. tert-Butoxy-trimethylsilyl ether
IR (neat):  = 2960, 2900, 1587, 1440, 1255, 1158, 1022, 850, 750,
688 cm−1 ; 1 H NMR (400 MHz, CDCl3 ): ı = 0.047 (s, 9H), 1.237 (s, 9H)
ppm; MS (EI, 70 eV) m/z: 146 [M+ ], 131 [M+ −CH3 ], 57 [M+ −OTMS];
Anal. calcd for C7 H18 OSi: C, 57.53; H, 12.33. Found: C, 57.49; H,
12.31.
2.6. General procedure for the deprotection of trimethylsilyl
ethers
A mixture of the substrate (1 mmol), ionic liquid [Dsim]HSO4
(6.5 mg, ∼0.02 mmol) in methanol (2 mL) was stirred at room
 F. Shirini et al. / Journal of Molecular Catalysis A: Chemical 365 (2012) 15–23 19

Fig. 3. Mass spectra of 1,3-disulfonic acid imidazolium hydrogen sulfate [Dsim]HSO4 .

Scheme 1. Synthesis of Brönsted acidic ionic liquid [Dsim]HSO4 .

temperature. After completion of the reaction (monitored by TLC),

solvent was evaporated, water (1 mL) was added to the mixture,
and stirred vigorously. Decantation of the mixture gave almost pure
product(s). The products were characterized by comparison of their
IR and NMR data. The ionic liquid was dried at 65 ◦ C under vacuum Scheme 2. The protection of hydroxyl groups with HMDS and deprotection of the
to remove moisture, and then reused. obtained trimethylsilyl ethers in the presence of [Dsim]HSO4 .

3. Results and discussion
Very recently Zolfigol et al. reported the preparation of 1,3-
disulfonic acid imidazolium chloride [Dsim]Cl and its applications
in functional group transformations [64,65]. Based on these studies
we have found that 1,3-disulfonic acid imidazolium chloride can
be easily converted to 1,3-disulfonic acid imidazolium hydrogen
sulfate ([Dsim]HSO4 ), in reaction with H2 SO4 (98%) (Scheme 1).
The structure of [Dsim]HSO4 assured us to accept that this
reagent can act as an efficient catalyst in reactions that need acidic
reagents to speed-up. Our investigations clarified that this predic-
tion is correct and O-trimethylsilylation of alcohols and phenols
and deprotection of the obtained trimethylsilyl ethers can be effi-
ciently promoted in the presence of [Dsim]HSO4 (Scheme 2).
Initially and in order to obtain the best reaction conditions,
we choose 4-chlorobenzyl alcohol and triphenyl methanol as
model substrates and treated them with HMDS in presence of
[Dsim]HSO4 . Optimization of the reaction conditions showed
that the best results were obtained when the reaction was
performed at room temperature under solvent-free conditions,
while the relative ratio of the substrate/HMDS/[Dsim]HSO4 were
1.0 mmol/0.5 mmol/0.02 mmol (6.5 mg), respectively.
To confirm the role of the prepared [Dsim]HSO4 ionic liquid, in
the controlled blank experiments, the protection of 4-chlorobenzyl
alcohol and triphenyl methanol with HMDS under similar reaction
conditions was also carried out in the presence of 0.02 mmol of the
starting materials used for the preparation of the ionic liquid (i.e.
imidazole, ClSO3 H, H2 SO4 ), also imidazolium chloride and inter-
mediate [Dsim]Cl. The catalytic results are presented in Table 1.
It can be seen when the protection was carried out in the pres-
ence of [Dsim]HSO4 , higher yield (100%) at shorter reaction time is
observed.

Table 1
The protection of 4-chlorobenzyl alcohol and triphenyl methanol with HMDS using [Dsim]HSO4 and [Dsim]Cl ionic liquids, chlorosulfonic acid, sulfuric acid, imidazole,
imidazolium chloride.a

Entry Catalyst 4-Chlorobenzyl alcohol Triphenyl methanol

b
Time (min) Yield (%) Time (min) Yield (%)b

1 – 8 (h) N.R. 8 (h) N.R.

2 [Dsim]HSO4 >1 99 4 98
3 [Dsim]Cl 5 98 60 32
4 ClSO3 Hc – N.R. – N.R.
5 H2 SO4 c – N.R. – N.R.
6 Imidazole 20 82 60 N.R.
7 Imidazolium chloride 60 78 60 N.R.
a
The reaction conditions: 4-chlorobenzyl alcohol (1 mmol), HMDS (0.5 mmol), the catalyst (0.02 mmol), room temperature and solvent-free.
b
Isolated and unoptimized yields.
c
Degradation of HMDS.
20 F. Shirini et al. / Journal of Molecular Catalysis A: Chemical 365 (2012) 15–23

Table 2
The protection of alcohols with HMDS and the deprotection obtained trimethylsilanes in the presence of [Dsim]HSO4 at room temperature under solvent-free conditions.a , b

Entry Substrate Product Protection Deprotection

Time (min) Yield (%) Time (min) Yield (%)

1 C6 H5 CH2 OH C6 H5 CH2 OTMS 1 98 5 98

2 2-ClC6 H4 CH2 OH 2-ClC6 H4 CH2 OTMS 1 99 5 99
3 2-BrC6 H4 CH2 OH 2-BrC6 H4 CH2 OTMS 1 98 6 99
4 2-MeC6 H4 CH2 OH 2-MeC6 H4 CH2 OTMS 1 96 4 99
5 2-O2 NC6 H4 CH2 OH 2-O2 NC6 H4 CH2 OTMS 5 92 5 98
6 4-ClC6 H4 CH2 OH 4-ClC6 H4 CH2 OTMS 1 100 4 96
7 4-BrC6 H4 CH2 OH 4-BrC6 H4 CH2 OTMS 1 98 5 98
8 4-O2 NC6 H4 CH2 OH 4-O2 NC6 H4 CH2 OTMS 5 97 7 99
9 4-i-PrC6 H4 CH2 OH 4-i-PrC6 H4 CH2 OTMS 1 97 4 97
10 2-(PhO)C6 H4 CH2 OH 2-(PhO)C6 H4 CH2 OTMS 2 99 5 99
11 3,4-Cl2 C6 H3 CH2 OH 3,4-Cl2 C6 H3 CH2 OTMS 1 98 4 98
12 C6 H5 CH(Me)OH C6 H5 CH(Me)OTMS 2 95 6 98
13 C6 H5 CH(OH)CH(Me)2 C6 H5 CH(OTMS)CH(Me)2 2 95 6 98

14 3 94 5 96

15 (C6 H5 )2 CHOH (C6 H5 )2 CHOTMS 1 98 4 97

16 1 97 4 98

17 C6 H5 CH2 CH2 OH C6 H5 CH2 CH2 OTMS 2 99 5 98

18 C6 H5 CH2 CH2 CH2 OH C6 H5 CH2 CH2 CH2 OTMS 2 97 4 99
19 C6 H5 CH(Me)CH2 OH C6 H5 CH(Me)CH2 OTMS 2 96 4 99
20 C6 H5 CH2 NHCH2 CH2 OH C6 H5 CH2 NHCH2 CH2 OTMS 5 95 4 97

21 2 96 5 99

22 (Me)2 CHOH (Me)2 CHOTMS 2 96 4 97

23 (CH2 )4 CHOH (CH2 )4 CHOTMS 3 94 4 98
24 (CH2 )5 CHOH (CH2 )5 CHOH 3 95 5 98

25 4 93 5 96

26 4 92 5 99

27 6 94 6 99

28 C6 H5 CH2 C(OH)(Me)2 C6 H5 CH2 C(OTMS)(Me)2 5 99 5 98

29 C6 H5 -C6 H4 C(OH)(Me)2 C6 H5 -C6 H4 C(OTMS)(Me)2 5 99 4 98
30 (C6 H5 )3 COH (C6 H5 )3 COTMS 4 98 5 99
31 Me3 COH Me3 COTMS 2 96 5 99
32 C6 H5 CH2 CH(OH)CH2 OH C6 H5 CH2 CH(OTMS)CH2 OTMS 3 91c 4 99
33 C6 H5 (CO)CH(OH)C6 H5 C6 H5 (CO)CH(OTMS)C6 H5 2 98 5 98
34 4-Me-C6 H5 (CO)CH(OH)C6 H5 - 4-Me-C6 H5 (CO)CH(OTMS)C6 H5 - 3 98 5 99
Me-4 Me-4
a
Products were characterized by their physical constants, comparison with authentic samples, and IR, 1 H NMR, 13 C NMR spectroscopy.
b
Isolated yields.
c
HMDS 1.0 mmol is used.

After optimization of the reaction conditions various type electron-donating or electron-withdrawing groups proceeded effi-
of alcohols were subjected to trimethylsilylation with HMDS ciently with high isolated yield (Table 2, entries 1–16). Primary
under the selected conditions. As shown in Table 2, using this and secondary aliphatic alcohols were also efficiently converted to
method, O-Silylation of benzylic alcohols including acid sensitive, their corresponding trimethylsilyl ethers under the same reaction
 F. Shirini et al. / Journal of Molecular Catalysis A: Chemical 365 (2012) 15–23 21

Table 3
The protection of phenols and naphthols with HMDS and the deprotection of the obtained trimethylsilyl ethers in the presence of [Dsim]HSO4 at room temperature under
solvent-free conditions.a , b

Entry Substrate Product Protection Deprotection

Time (min) Yield (%) Time (min) Yield (%)

1 C6 H5 OH C6 H5 OTMS 1 100 4 98
2 4-FC6 H4 OH 4-FC6 H4 OTMS 1 99 4 99
2 4-EtC6 H4 OH 4-EtC6 H4 OTMS 1 99 5 98
3 3-MeC6 H4 OH 3-MeC6 H4 OTMS 1 99 4 98
4 3,4-(Me)2 C6 H3 OH 3,4-(Me)2 C6 H3 OTMS 2 96 5 97
5 2,4-(Me)2 C6 H3 OH 2,4-(Me)2 C6 H3 OTMS 1 97 4 96
6 4-i-PrC6 H4 OH 4-i-PrC6 H4 OTMS 2 98 4 96
7 2-PhC6 H4 OH 2-PhC6 H4 OTMS 4 98 4 99
8 C6 H5 CH2 C6 H4 OH C6 H5 CH2 C6 H4 OTMS 2 98 6 98

9 2 98 4 98

10 2-NH2 C6 H4 OH 2-NH2 C6 H4 OTMS 5 95c 5 98

11 4-NH2 C6 H4 OH 4-NH2 C6 H4 OTMS 2 96c 4 98
12 1,2-(OH)2 C6 H4 1,2-(OTMS)2 C6 H4 4 98c 4 98
13 1,4-(OH)2 C6 H4 1,4-(OTMS)2 C6 H4 4 98c 5 98
14 4-HOC6 H4 -C6 H4 OH-4 4-TMSOC6 H4 -C6 H4 OTMS-4 4 98c 5 97

15 5 98c 6 99

c
16 2-(OH)C6 H4 CH2 OH 2-(OTMS)C6 H4 CH2 OTMS 2 95 4 98

17 15 92d 8 96

18 8 92d 7 98

19 1-Naphthol 1-Naphthyl trimethylsilyl ether 2 95 4 97

20 2-Naphthol 2-Naphthyl trimethylsilyl ether 5 92 9 98
21 C6 H5 CH2 NH2 C6 H5 CH2 NHTMS 120 0 – –
22 C6 H5 CH2 SH C6 H5 CH2 STMS 120 0 – –
23 4-MeC6 H4 CH2 NH2 4-MeC6 H4 CH2 NHTMS 120 0 – –
24 4-MeC6 H4 CH2 SH 4-MeC6 H4 CH2 STMS 120 0 – –
a 1 13
Products were characterized by their physical constants, comparison with authentic samples, and IR, H NMR, C NMR spectroscopy.
b
Isolated yields.
c
HMDS 1.0 mmol is used.
d
HMDS 1.5 mmol is used.

conditions (Table 2, entries 17–21). This method was found to
be very useful for the protection of hindered secondary (Table 2,
entries 22–26) and especially tertiary alcohols (Table 2, entries
27–31). This method was also useful for the silylation of diols and
acyloins (Table 2, entries 32–34). No elimination or rearrangement
by-product was observed during the course of the reaction.
In order to show the generality of the method, we also applied
the optimized conditions for the silylation of the structurally differ-
ent phenols and some naphthols (Table 3). Phenol and substituted
phenols were silylated easily and their corresponding silylethers
were isolated in excellent yields. The change of phenyl to napthyl
group (Table 3, entries 19 and 20) hardly influences the reactivity
and give the excellent comparable yields. We have also applied this
method for the silylation of two amines and thiols. The reactions did
not proceed after a long reaction times and the starting materials
were isolated intact (Table 3, entries 21–24).
To compare the applicability and the efficiency of our catalyst
with the reported catalysts for the protection of the hydroxyl
groups, we have tabulated the results of this catalyst to perform
the silylation of benzhydrol and triphenyl methanol with HMDS
in Table 4. As it is shown in Table 4, the [Dsim]HSO4 ionic liquid
remarkably improved the silylation of benzhydrol and triphenyl
methanol in different terms, for example room temperature,
shorter reaction times, halogen-free and reusability of the ionic
liquid, high to excellent yields, and generality of the substrate
applicability. Obviously these advantages make our system as a
better choice. It is important to note that, although ZrCl4 is a useful
promoter for the silylation of triphenyl methanol (Table 4, entry
5), its applicability is influenced by its moisture sensitivity and
decomposition accompanied by liberation of corrosive HCl fumes
on storing [66].
In order to show the recyclability of the ionic liquid [Dsim]HSO4 ,
the silylation of 4-chlorobenzyl alcohol with HMDS using reagent
was carried out several times. After completion of the reaction
(monitored by TLC), the product was extracted with Et2 O and the
ionic liquid was recovered and was dried at 65 ◦ C under vacuum
to remove moisture, and then reused. The catalytic activity of the
recovered [Dsim]HSO4 was as same as the first one (Fig. 4).
22 F. Shirini et al. / Journal of Molecular Catalysis A: Chemical 365 (2012) 15–23

Table 4
Comparison of the silylation of benzhydrol and triphenyl methanol in the presence of [Dsim]HSO4 with some other catalysts.

Entry Catalyst/solvent/condition Benzhydrol Triphenyl methanol Refs.

Time (min) Yield (%) Time (min) Yield (%)a

1 TCCA (10 mol%)/CH2 Cl2 /r.t. 180 95 – – [28]

2 H3 PW12 O40 (1 mol%)/neat/55–60 ◦ C 48 93 – – [32]
3 LiClO4 SiO2 (100 mg)/CH2 Cl2 /r.t. 50 87 – – [39]
4 Mg(OTf)2 (1 mol%)/neat/r.t. 120 70 – – [41]
5 ZrCl4 (2 mol%)/CH3 CN/r.t. 2 90 8 82 [44]
6 V(HSO4 )3 (3.0 mol%)/CH3 CN/r.t. 5 93 – – [52]
7 Fe(HSO4 )3 (25 mol%)/CH3 CN/r.t. 50 75 – – [53]
8 Fe(HSO4 )3 (25 mol%)/neat/r.t. 42 85 – – [53]
9 TiCl3 (OTf) (1 mol%)/neat/r.t. 2 92 – – [55]
10 SaSA (10 mol%)/CH3 CN/r.t. 10 92 – – [57]
11 SuSA (2 mol%)/CH3 CN/r.t. 1 96 – – [58]
12 SANM (20 mg)/CH3 CN/r.t. 5 87 – – [59]
13 P(4-VP) (10 mg)/CH3 CN/r.t. 50 98 – – [60]
14 [Msim]HSO4 (2 mol%)/neat/r.t. 1 96 – – [61]
15 [Dsim]HSO4 (2 mol%)/neat/r.t. 1 98 4 98 This work
a
Isolated yield.

Fig. 4. Reusability of [Dsim]HSO4 .

4. Conclusion
In conclusion, here we have reported the preparation of 1,3-
disulfonic acid imidazolium hydrogen sulfate and its application
in the promotion of the silylation of alcohols and phenols with
HMDS and deprotection of the obtained trimethylsilanes. Mildness
of the reaction conditions, short reaction times, excellent yields,
easy work-up, halogen-free, recoverability and reusability of the
ionic liquid, and chemoselectivity are noteworthy advantages of
this method.
Acknowledgment
The authors are thankful to the Guilan University Research
Council for the partial support of this work.
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