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Article

Deprotection of Acetals and Ketals by Silica Sulfuric Acid and Wet SiO2

by
BiBi Fathemeh Mirjalili
1,
Mohamad Ali Zolfigol
2,* and
Abdolhamid Bamoniri
3
1
Department of Chemistry, College of Science, Yazd University, Yazd, Iran
2
Department of Chemistry, College of Science, Bu-Ali Sina University, Hamadan 65174, P.O. Box 4135, Iran
3
Department of Chemistry, College of Science, Kashan University, Kashan 51167, Iran
*
Author to whom correspondence should be addressed.
Molecules 2002, 7(10), 751-755; https://doi.org/10.3390/71000751
Submission received: 25 October 2001 / Revised: 13 October 2002 / Accepted: 14 October 2002 / Published: 31 October 2002
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Abstract

:
Neat chlorosulfonic acid reacts with silica gel to give silica sulfuric acid in which sulfuric acid is immobilized on the surface of silica gel via covalent bonds. A combination of silica sulfuric acid and wet SiO2 was used as an effective deacetalizating agent for the conversion of acetals to their corresponding carbonyl derivatives under thermal conditions.

Introduction

Acetals are widely used as protecting groups in organic synthesis and, as a consequence, many methods have been examined for both their formation and removal [1,2]. Typically, deprotection of acetals requires the use of protic [3] or Lewis acids [4], iodotrimethylsilane [5], cobalt or manganese salts in the presence of air or O2 [6] pyridinium tosylate [7], montmorillonite K10 [8], cerium ammonium nitrate(CAN) [9], etc.
On the other hand, any reduction in the amount of sulfuric acid needed and/or any simplification in handling procedures is desirable for risk reduction, economic advantages and environmental protection [10]. In addition, there is current research and general interest in heterogeneous systems because of the importance such systems have in industry and in developing technologies [11]. In continuation of our studies on the application of inorganic acidic salts [12] we have found that silica gel reacts with chlorosulfonic acid to give silica sulfuric acid (I). It is interesting to note that the reaction is easy and clean without any work-up procedure because HCl gas is evolved from the reaction vessel immediately (Scheme 1).
Molecules 07 00751 g001 550
Scheme 1.
Scheme 1.
Molecules 07 00751 g001
We hoped that the silica sulfuric acid (I) would be a superior proton source to all of the reported acidic solid supports or acidic resins such as polystyrene sulfonic acid and Nafion-H [13] for running reactions under heterogeneous conditions. Here we wish to report a convenient method for the deacetalization of acetals by using silica sulfuric acid (I) and wet SiO2 (II) under thermal conditions (Scheme 2).

Results and Discussion

Different types of acetals and ketals (1) were subjected to the deacetalization reaction in the presence of silica sulfuric acid and wet SiO2 (60% w/w) under thermal conditions with quantitative yields. We used toluene as a solvent at 60-70 °C. The results of deacetalization reactions are shown in Table 1.
Molecules 07 00751 g002 550
Scheme 2.
Scheme 2.
Molecules 07 00751 g002

Conclusions

Silica sulfuric acid is an excellent proton source for acetal deprotection reactions in terms of convenience, cheapness, easy production and insolubility to all of organic solvents. The cheapness and availability of the reagents, easy procedure and work-up make this method attractive for large scale operations.
Table
Table 1. Deprotection of Acetals and Ketals in Toluene at 60-70 °C
Table 1. Deprotection of Acetals and Ketals in Toluene at 60-70 °C
EntrySubstrateSubstrate (mmole) / I (g) / II (g)Time (min)Yield (%)Product
1a Molecules 07 00751 i001 0.2 / 0.12 / 0.26095 Molecules 07 00751 i002
1b Molecules 07 00751 i003 0.35 / 0.1 / 0.16094 Molecules 07 00751 i004
1c Molecules 07 00751 i005 0.26 / 0.25 / 0.276098 Molecules 07 00751 i006
1d Molecules 07 00751 i007 0.25 / 0.2 / 0.26093 Molecules 07 00751 i008
1e Molecules 07 00751 i009 0.25 / 0.2 / 0.27594 Molecules 07 00751 i010
1f Molecules 07 00751 i011 0.3 / 0.11 / 0.156097 Molecules 07 00751 i012
1g Molecules 07 00751 i013 0.25 / 0.3 / 0.36098 Molecules 07 00751 i014
1h Molecules 07 00751 i015 0.2 / 0.3 / 0.36097 Molecules 07 00751 i016
1i Molecules 07 00751 i017 0.25 / 0.3 / 0.37595 Molecules 07 00751 i018
1j Molecules 07 00751 i019 0.25 / 0.4 / 0.46098 Molecules 07 00751 i020
1k Molecules 07 00751 i021 0.25 / 0.3 / 0.36096 Molecules 07 00751 i022
1l Molecules 07 00751 i023 0.25 / 0.3 / 0.36098 Molecules 07 00751 i024
1m Molecules 07 00751 i025 0.25 / 0.3 / 0.46097 Molecules 07 00751 i026

Acknowledgments

Financial support for this work by the Office of Research Affairs, Yazd University, Yazd, Iran and also Bu-Ali Sina University, Hamadan, Iran, are gratefully acknowledged.

Experimental

General

Chemicals such as carbonyl compounds, ethylene glycol, chlorosulfonic acid and silica gel were purchased from the Fluka, Merck and Aldrich chemicals companies. Acetals and 5-norbornene-2,2-dimethylol were synthesized according to the our previously reported procedure [1]. The deacetalization products were characterized by comparison of their spectral (IR, 1H-NMR), TLC and physical data with the authentic samples. Silica sulfuric acid was prepared according to our very recently reported procedure as follows [14].

Preparation of silica sulfuric acid

A 500 mL suction flask equipped with a constant-pressure dropping funnel and a gas inlet tube for conducting HCl gas over an adsorbing solution (i. e. water) was used. It was charged with silica gel (60.0 g). Chlorosulfonic acid (23.3 g, 0.2 mol) was added dropwise over a period of 30 min at room temperature. HCl gas evolved from the reaction vessel immediately (Scheme 1). After the addition was complete the mixture was shaken 30 min. A white solid (silica sulfuric acid) 76.0 g was obtained.

Typical procedure for deacetalization of acetals (1) to the corresponding aldehydes (2): Preparation of 4-nitrobenzaldehyde (2g).

A mixture of 1g (0.07 g, 0.25 mmol), silica sulfuric acid (I) (0.3 g) and wet SiO2 (60% w/w, 0.3 g) in toluene (3 mL) was heated at 60-70°C for 60 minutes. Then the solvent was removed under reduced pressure. The product, 4-nitrobenzaldehyde (2g), was obtained in quantitative yield by addition of ethanol and water.

References

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  12. Zolfigol, M.A. Synth. Commun. 2000, 30, 1593.Zolfigol, M.A.; Bagherzadeh, M.; Chehardoli, G.; Mallakpour, S.E. ibid. 2001, 31, 1149.Zolfigol, M.A.; Bagherzadeh, M.; Ghorbani Choghamarani, A.; Keypour, H.; Salehzadeh, S. ibid. 2001, 31, 1661.Zolfigol, M.A.; Sadeghi, M.M.; Mohammadpoor-Baltork, I.; Ghorbani Choghamarani, A.; Taqian-nasab, A. Asian J. Chem. 2001, 13, 887.Zolfigol, M.A.; Bagherzadeh, M.; Madrakian, E.; Ghaemi, E.; Taqian-nasab, A. J. Chem. Res. 2001, 140.Zolfigol, M.A.; Ghaemi, E.; Madrakian, E. Molecules 2001, 6, 614.Zolfigol, M.A.; Ghaemi, E.; Madrakian, E.; Kiany-Borazjani, M. Synth. Commun. 2000, 30, 2057.Zolfigol, M.A.; Madrakian, E.; Ghaemi, E. Indian J. Chem. 2000, 39B, 308.Zolfigol, M.A.; Kiany-Borazjani, M.; Sadeghi, M.M.; Memarian, H.R.; Mohammadpoor-Baltork, I. Synth. Commun. 2000, 30, 2945.Zolfigol, M.A.; Kiany-Borazjani, M.; Mallakpour, S.E.; Nassr-Isfahani, H. ibid. 2000, 30, 2573.Zolfigol, M.A.; Kiany-Borazjani, M.; Sadeghi, M.M.; Mohammadpoor-Baltork, I.; Memarian, H.R. ibid. 2000, 30, 3919.Zolfigol, M.A.; Kiany-Borazjani, M.; Sadeghi, M.M.; Memarian, H.R.; Mohammadpoor-Baltork, I. J. Chem. Res. 2000, 197.Salehi, P.; Khodaie, M.; Zolfigol, M.A.; Keyvan, A. Synth. Commun. 2001, 31, 1947.
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  • Sample Availability: Samples of substrates 1c, 1g-1l and the 3-nitro and 4-cyano analogs of substrate 1g are available from MDPI.

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MDPI and ACS Style

Mirjalili, B.F.; Zolfigol, M.A.; Bamoniri, A. Deprotection of Acetals and Ketals by Silica Sulfuric Acid and Wet SiO2. Molecules 2002, 7, 751-755. https://doi.org/10.3390/71000751

AMA Style

Mirjalili BF, Zolfigol MA, Bamoniri A. Deprotection of Acetals and Ketals by Silica Sulfuric Acid and Wet SiO2. Molecules. 2002; 7(10):751-755. https://doi.org/10.3390/71000751

Chicago/Turabian Style

Mirjalili, BiBi Fathemeh, Mohamad Ali Zolfigol, and Abdolhamid Bamoniri. 2002. "Deprotection of Acetals and Ketals by Silica Sulfuric Acid and Wet SiO2" Molecules 7, no. 10: 751-755. https://doi.org/10.3390/71000751

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