Synthesis and Characterization of Mikanecic acid Diesters using NaH

 

R.Nandhikumar1,2*, K. Subramani1,3

1R&D Centre, Bharathiar University, Coimbatore, Tamilnadu, India.

2Global Institute of Engineering and Technology, Tamilnadu, India.

3PG & Research Department of Chemistry, Islamiah College, Vaniyambadi, Tamilnadu, India.

*Corresponding Author E-mail: nandhikumar@gmail.com

 

ABSTRACT:

Catalysts are used to make changes easier in the organic synthetic mechanism. Catalysts are involved in the process of chemical changes by reducing time and making it faster to get things done. Catalysts play a vital role in organic synthesis with a novel method for the synthesis of a terpenoid, Mikanecic acid diester. In this research we are using NaH to synthesis Baylis-Hillman adducts (alkyl-3-hydroxy-2-methylenepropanoates reacts with aldehyde with a variety of acrylates catalyzed in presence of TiCl4). Mikanecic acid diesters obtained from 1, 3-butadiene-2-carboxylate of (Diels-Alder type) self-dimerization occur in the presence of different catalysts. The yield which we obtained is in good ratio.

 

KEYWORDS: Baylis-Hillman adducts, Mikanecic acid diester, NaH, THF.

 

 

1. INTRODUCTION:

Synthetic organic chemistry is the paramount developing, expanding and successful branches of Science. During the past years, synthetic organic research has seen massive  growth.1-5 Development of new methods for the synthesis of heterocyclic compound, novel reagents, catalysts, strategies, and transformations is used. In synthetic organic chemistry, the constructions of quaternary carbon center have been one of the demanding and most attractive field due to a number of biologically active natural compounds consisting structural sub-units. 6-9 Terpenoid dicarboxylic acid and Mikanecic acid have attracted our attention due to its special feature of having vinylic quaternary carbon center. In 1936, Manske10 isolated Mikanecic acid from the alkaloid Mikanoidine obtained by base hydrolysis of Senecio mikakioides otto. In literature11 many research papers have been published based on the synthesis and characterization of Mikanecic acid.12 Inorganic catalyzed organic reactions are obtaining importance owing to their low-cost nature and special catalytic attributes in various reactions.

 

In this view, our research is focused to develop environmentally benign protocols. Herein, we report, NaH 13-16 catalyzed synthesis of Mikanecic acid diesters results in fairly good yields. 

 

In past years, many researchers developed the Baylis-Hillman reaction. In literature, DABCO 17 was used to perform this reaction and it resulted with the slow reaction rates. A Lewis acid (TiCl4) reaction of acetaldehyde with appropriate acrylates successfully resulted with Baylis-Hillman adducts 18-19 (1a-1c). Then these adducts on treatment with suitable catalysts yielded with Mikanecic acid diesters (2a-2c) by Diels-Alder type (i.e. self-dimerization of 1, 3-butadiene-2-carboxylate) (Scheme I Table 1). Mikanecic acid diesters on hydrolysis gave Mikanecic acid. (3)

 

2. EXPERIMENTAL:

2.1 Materials and Methods

For this research, the use of chemical, reagents and solvent were bought from the real scientific company, India and used as such. Melting points were found out in an open capillary tube with a Buchi melting point apparatus. Elemental analyses were done by using Perkin-Elmer 240C CHN-analyzer. Perkin Elmer IR spectrophotometer records the 1H- NMR spectra .This was run in (CDCl3) solvent at 200 MHz NMR spectrophotometer. In the same way 13CNMR Spectra records the spectrum at 50 MHz.

 

2.2 Synthesis of Mikanecic Acid using NaH catalyst:

The synthetic procedure is very simple method. As shown in Scheme I. 0.01 Mole Baylis-Hillman adducts with THF in the presence of base catalyst (NaH) were refluxed for 2 hr. Then completion of their action monitored by TLC, common workup and column chromatographic purification (hex/ether, 5:1) gave products, which were characterized by IR, NMR spectral data. The outcomes obtained are very much consistent with literature report. The spectral and analytical data of the compound 2a-c.

IR (neat): 1711, 1640 cm-1; 1H-NMR (200 MHz, CDCl3): δ 1.71-1.92 (1H, m), 2.09-2.14 (1H, m), 2.22-2.44 (3H, m), 2.70-2.90 (1H, m), 3.71 (3H, s), 3.72 (3H,s), 5.10-5.22 (2H, m), 5.73-5.97 (1H, m), 6.91 (1H, m); Anal. Calcd for C12H16O4: C, 64.21; H, 7.14 %.Found: C, 63.34; H, 6.90%.

 

Spectral data for Mikanecic acid: IR (KBr): 1691, 1641 cm-1; 1H-NMR (200 MHz, CDCl3): δ 1.64-2.80(6H, m), 5.02-5.32 (1H, m), 5.72-6.04 (1H, m), 6.83(1H, m), 12.41 (2H, s, br); 13C-NMR (50 MHz,CDCl3): δ 21.53, 29.11, 31.74, 46.53, 114.53, 129.31, 136.73, 140.24, 167.60, 175.20; EI-MS: m/z 196 (M·); Anal. Calcd for C10H12O4: C, 61.20; H, 6.11 %. Found: C, 57.43; H, 6.55 %.

 

Scheme: Synthesis of Mikanecic acid diester using NaH catalyst.

 

 

3. RESULT AND DISCUSSION:

3.1. Synthesis and Characterization:

The synthesis of Mikanecic acid diester from Baylis Hillman adducts using NaH catalyst. In this study first we prepared different Baylis Hillman adducts (1 a-c) by using acetaldehyde with different acrylates (Me, Et and t-Bu) in the presence of TiCl4. Chloroform is used as solvent. Further these different Baylis Hillman adducts react with NaH Mikanecic acid diesters (2a-c) and which on hydrolysis gives Mikanecic acid (3). (Scheme I). All the synthesized compounds were characterized by IR, NMR and mass spectral analysis.

 

Table .1 Synthesis of Mikanecic acid diesters a, b and c (a-Me, b-Et

and c-t-But acrylate).

Substrate

Reaction time/catalyst

Product

Yield (%)

1a

2h /NaH

2a

51

1b

2h /NaH

2b

59

1c

2h /NaH

2c

49

 

Figure.1 Comparison of Different Acrylate with NaH for Synthesis of Mikanecic acid Diester.

 

4. CONCLUSIONS:

As a conclusion, this research describes a facile synthesis of Mikanecic acid diesters from Baylis-Hillman compounds, react with NaH and  gives Mikanecic acid diesters, during Diels-Alder type self-dimerization of adducts (1, 3-Butadiene-2-carboxylate). The process represented was the indirect way of performing the Diels-Alder type method. In this method equal molecule of diene and dienophile react and resulted in Baylis-Hillman molecule.

 

5. ACKNOWLEDGMENT:

We whole heartedly thank the management, Principal of Global Institution of Engineering and Technology and Bharathiar University, R&D Centre for rendering full support for this work.

 

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Received on 26.02.2016         Modified on 07.04.2016

Accepted on 08.04.2016         © AJRC All right reserved

Asian J. Research Chem. 2016; 9(5): 197-199

DOI: 10.5958/0974-4150.2016.00033.X