Methane Sulphonic Acid is Green Catalyst in Organic Synthesis

Introduction

Physical properties of Methane Sulphoic Acid

Methane sulphonic acid is a clear colourless liquid available as a 70% solution in water and anhydrous form. The structure of methane sulphonic acid lends itself to many catalytic reactions, due to its high acid strength (pKa= -1.9) and low molecular weight (96.0 g/mol).

Methane Sulphonic Acid is Green Acid Catalysts

1. It is easy to handle methane sulphonic acid as liquid and can be recyclized.
2. It has low LD₅₀ and biodegradable forming sulphate and CO₂.
3. Methane sulphonic acid is considered to be natural product and is part of the natural sulphur.
4. It is less corrosive and toxic than other mineral acids.

Due to these properties methane sulphonic acid making an environmentally benign material [1].

Applications of Methane Sulphonic Acid as Catalyst in Organic Synthesis

1.  H. Naeimi et. al used methane sulphonic acid as catalyst for regioselective route for Direct Ortho-Acylation of Phenols and Naphthols under Microwave condition [2].

Figure1: Direct ortho acylation of Phenol using MSA  Click here to View figure

 

2.  M. Heravi et. al use MSA as catalyst for One-pot synthesis of 2-Amino-4 H-chromenes [3].

Figure2: MSA catalyzed one-pot synthesis of 2-Amino-4H-chromenes  Click here to View figure

 

3.  V. Jhansi Rani et. al use MSA for synthesis of 1-amidoalkyl-2-naphthols [4]

Figure3: Use of MSA for synthesis of 1-amidoalkyl-2-naphthols  Click here to View figure

 

4.  P. Kulkarni et. al use MSA for synthesis of flavanone [5].

Figure4: Synthesis of flavanone using MSA  Click here to View figure

 

5.  H. Sharghi et. al use MSA with Al₂O₃ for synthesis of monoesterification of diols [6].

Figure5: Use of MSA for monoesterification of diols  Click here to View figure

 

6.  Methanesulphonic acid in combination with morpholine used as catalyst for the preparation of ylidenemalononitriles via Knoevenagel condensation of ketones with malononitrile under solvent free condition [7].

Figure6: Use of MSA in Knoevenagel condensation  Click here to View figure

 

7.  Phosphorus pentoxide-Methanesulphonic acid (Eaton’s reagent) used catalyst for an expeditious, one-pot method for the synthesis of 3,4-dihydropyrimidin-2(1H)-ones under solvent free condition[8].

Figure7: Use of P2O5/ MSA in the synthesis of 3, 4-dihydropyrimidin-2(1H)-ones   Click here to View figure

 

8.  Hydrofluoric acid was used as catalyst for synthesis of paracetamol from phenyl acetate but tis acid is toxic and hazardous. A. Commarieua et. al  uses methane sulphonic acid as a catalyst for this reaction to give para-hydroxyacetophenone with high conversion and selectivity (up to 92% of para-isomer and 8% of ortho-isomer at 100 % conversion) [1].

Figure8: Use of MSA in synthesis hydroxyacetophen one  Click here to View figure

 

9.  Methane sulphonic acid used as catalyst for synthesis of 3-amino 2H-pyrazoles prepared by reaction of β-keto nitrile with hydrazine under solvent and solvent free conditions [9].

Figure9: Use of MSA in synthesis of 3-amino-2H-pyrazoles  Click here to View figure

 

10.  Silica-supported methane sulphonic acid used as a solid acid catalyst for three component coupling reactions of indoles and sodiumnitrite to synthesize (E)-2, 3’-bi(3H-indol)-3-one oxime derivatives [10].

Figure10: Use of MSA for synthesis of (E)-2, 3′-bis(3H-indol)-3-one oxime  Click here to View figure

 

11.  Methane sulphonic acid on silica was used as solid support catalyst for Pechmann reaction to synthesize Coumarin [11].

Figure11: Use of MSA for synthesis of Coumarin  Click here to View figure

 

12.  R. Reddy Leleti et. al reported isomerisation of secondary and tertiary allylic alcohols undergo 1,3-isomerization using MSA under simple and efficient conditions  to afford selectively the corresponding primary E-allylic alcohols in excellent yields [12].

Figure12: Isomerization of allylic alcohols using MSA  Click here to View figure

 

13.  M. Heravi et. al MSA used for catalyzes one-pot, three component reaction of an aromatic aldehyde, malonitrile and α or β-naphthol to yield 2-amino-4H-chromenes in very good yields[13].

Figure13: MSA as a catalyst for synthesis of 2-amino-4H-chromenes  Click here to View figure

 

References

1. Commarieua, A. ; Hoelderich, W.;  Laffitte, J.;  Dupont, M. J. Mol. Catalysis A: Chemical 2002,  182-183, 137-141.
2. Naeimi, H.; Raeisi, A.; Moradian, M.  Arabian Journal of Chemistry 2013, doi: http://dx.doi.org/10.1016/j.arabjc.2013.10.017
3. Heravi, M.; Baghernejad, B.; Oskooie, H. Journal of the Chinese Chemical Society, 2008, 55, 659-662.
4. Jhansi Rani, V.;  Suresh, M.;  Lavanya, P.;   Vani, K.; Nagarjuna, B.; Venkata Rao, C.  Der Pharma Chemica, 2010, 2, 224-230
5. Kulkarni, P.;  Wagh, P.;  Zubaidha, P. Chemistry Journal 2012   2 106-110
6. Sharghi, H.;  Sarvari, M. Tetrahedron 2003, 59, 3627-3633
7. Gora, M.; Kozik, B.;  Jamrozy, K.; Luczynski, M.; Brzuzan, P.;  Wozny, M. Green Chemistry 2009, 11, 863-867
8. Borse, A.; Patil, M.; Patil, N.; Shinde, R. ISRN Organic Chemistry 2012, 2012, doi: 10.5402/2012/415645
9. Suryakiran, N. ;  Reddy, T.; Asha Latha, K.; Prabhakar, P.;  Yadagiri, K. Journal of Molecular Catalysis A: Chemical 2006, 258, 371-375.
10. Chang, Q.; Qu, H.; Qin, W.; Liu, L.; Chen, Z. Synthetic Communications 2013, 43, 2926-2935.
11. Joshi, J.; Mishra, M.; Srinivasarao, M. Canadian Journal of Chemistry 2011, 89, 663-670.
12. Reddy Leleti ,R.;  Hu, B.; Prashad, M.; Repic, O. Tetrahedron Letters, 2007, 48, 8505-8507.
13. Heravi, M.; Baghernejad, B.; Oskooie, H. Journal of the Chinese Chemical Society, 2008, 55, 659-662.

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