Sains Malaysiana 46(5)(2017): 725–731

http://dx.doi.org/10.17576/jsm-2017-4605-07

 

Synthesis and Structural Characterization of 6-(N-Methyl-pyridin-2-ylcarbamoyl)-pyridine-2-carboxylic Acid Methyl Ester Isomers

(Sintesis dan Pencirian Struktur Isomer 6-(N-Metil-piridina-2-ylkarbamoil)-piridina-2-karboksilik Asid Metil Ester)

 

MAISARA ABDUL KADIR*, NAFISAH MANSOR & UWAISULQARNI M. OSMAN

 

School of Fundamental Science, Universiti Malaysia Terengganu, 21030 Kuala Terengganu, Terengganu Darul Iman, Malaysia

 

Received: 20 July 2016/Accepted: 24 October 2016

 

ABSTRACT

A series of monoamide isomers have been successfully synthesised and characterised using combination of common spectroscopic techniques such Fourier Transform Infrared (FT-IR), 1H and 13C Nuclear Magnetic Resonance (NMR) and Ultraviolet-visible (UV-vis). The monoamide compounds namely 6-(3-methyl-pyridin-2-ylcarbamoyl)-pyridine-2-carboxylic acid methyl ester (L1), 6-(4-methyl-pyridin-2-ylcarbamoyl)-pyridine-2-carboxylic acid methyl ester (L2), 6-(5-methyl-pyridin-2-ylcarbamoyl)-pyridine-2-carboxylic acid methyl ester (L3) and 6-(6-methyl-pyridin-2-ylcarbamoyl)-pyridine-2-carboxylic acid methyl ester (L4) were prepared from reaction between 6-(methoxycarbonyl)pyridine-2-carboxylic acid with 2-amino-N-methylpyridine (where N = 3, 4, 5 and 6) by using acyl chloride reaction. In this present studies, the synthesis and characterization of these compounds are discussed along with the inductive effects contributed by methyl substituted groups at the pyridine ring.

 

Keywords: Acyl chloride; inductive; isomers; monoamide; pyridine

 

ABSTRAK

Suatu siri isomer baru monoamida telah berjaya disintesis dan dicirikan menggunakan gabungan beberapa teknik spektroskopi seperti Fourier Penukar Inframerah (FTIR), 1H dan 13C Resonans Magnet Nukleus (RMN) dan Ultra-lembayung boleh nampak (UV-vis). Sebatian yang dinamakan sebagai 6-(3-metil-piridin-2-ilkarbamoil)-piridina-2-karboksilik asid metil ester (L1), 6-(4-metil-piridin-2-ilkarbamoil)-piridina-2-karboksilik asid metil ester (L2), 6-(5-metil-piridin-2-ilkarbamoil)-piridina-2-karboksilik asid metil ester (L3) dan 6-(6-metil-piridin-2-ilkarbamoil)-piridina-2-karboksilik asid metil ester (L4) dihasilkan daripada tindak balas antara 6-(metoksikarbonil)piridin-2-karboksilik asid dengan 2-amino-N-metilpiridin (dengan N = 3, 4, 5 dan 6) menggunakan kaedah asil klorida. Dalam kajian ini, kaedah sintesis dan pencirian struktur sebatian berikut akan dibincangkan bersama kesan induktif yang disumbangkan oleh kumpulan penukarganti metil pada gegelang piridin.

 

Kata kunci: Asil klorida; induktif; isomer; monoamida; piridina

REFERENCES

Abdul-Kadir, M., Sumby, C.J. & Hanton, L.R. 2011. Self-assembled metallo-macrocycle based coordination polymers with unsymmetrical amide ligands. Dalton Trans 40: 12374- 12380.

Ardona, H.A.M. & Tovar, J.D. 2015. Peptide π-electron conjugates: Organic electronics for biology. Bioconjugate Chem. 26(12): 2290-2302.

Boon, J.A., Levisky, J.A., Pflug, J.L. & Wilkes, J.S. 1986. Friedel- Crafts reactions in ambient-temperature molten salts. Journal of Organic Chemistry 51: 480-483.

Devi, P., Barry, S.M., Houlihan, K.M., Murphy, M.J., Turner, P., Jensen, P. & Rutledge, P.J. 2015. Synthesis and structural characterisation of amides from picolinic acid and pyridine- 2,6-dicarboxylic acid. Scientific Reports 5: 9950.

Diaz-Alejo, L.A., Menchaca-Campos, E.C., Chavarin, J.U., Sosa-Fonseca, R. & Garcia-Sanchez, M.A. 2013. Effects of the addition of Ortho- and Para-NH2 substituted etraphenylporphyrins on the structure of nylon 66. International Journal of Polymer Science 2013: 14.

Dunetz, J.R., Magano, J. & Weisenburger, G.A. 2016. Large-scale applications of amide coupling reagents for the synthesis of pharmaceuticals. Org. Process Res. Dev. 20(2): 140-177.

Jakob, U., Petersen, T.O. & Bannwarth, W. 2015. Unusual metal complexes of N,N-bis(2-picolyl)amides - A comparative study of structure and reactivity. Journal of Organometallic Chemistry 797: 46-51.

Janeta, M., John, L., Ejfler, J. & Szafert, S. 2014. High-yield synthesis of amido-functionalized polyoctahedral oligomeric silsesquioxanes by using acyl chlorides. Chem. Eur. J. 20: 15966-15974.

Kadir, M.A., Nafisah, M., Yusof, M.S.M. & Sumby, C.J. 2014. Synthesis and crystal structure of N-6-[(4pyridylamino)carbonyl]-pyridine-2- carboxylic acid methyl ester zinc complex. Complex Metals 1: 32-37.

Lanigan, R.M., Starkov, P. & Sheppard, T.D. 2013. Direct synthesis of amides from carboxylic acids and amines using B(OCH2CF3)3. J. Org. Chem. 78: 4512-4523.

Leggio, A., Belsito, E.L., Gioia, L.D., Leotta, V., Romio, E., Siciliano, C. & Liguori, A. 2015. Silver acetate-assisted formation of amide from acyl chlorides. Tetrahedron Letters 56: 199-202.

Lenstra, D.C., Nguyen, D.T. & Mecinovic, J. 2015. Zirconium-catalysts direct amide bond formation between carboxylic esters and amines. Tetrahedron 71: 5547-5553.

Park, J.K., Shin, W.K. & An, D.K. 2013. New and efficient synthesis of amides from acid chlorides using diisobutyl(amino) aluminium. Bull. Korean Chem. Soc. 34: 1592-1594.

Pattabiraman, V.R. & Bode, J.W. 2011. Rethinking amide bond synthesis. Nature 480: 471-479.

Sharma, A., Gupta, V., Mishra, R., Tandon, P., Maeda, S. & Kunimoto, K.K. 2011. Study of vibrational spectra and molecular structure of intermolecular hydrogen bonded 2-thiohydantoin using density functional theory. Journal of Molecular Structure 1004: 237-247.

Wilson, S.O., Tran, N.T. & Franz, A.K. 2012. NMR and X-ray studies of hydrogen bonding for amide-containing silanediols. Organometallics 31: 6715-6718.

Yalcin, S.P., Ceylan, U., Sarioglu, A.O. & Sonmez, M. 2015. Sythesis, structural, spectral (FT-IR, 1H and 13C NMR and Uv-Vis), NBO and first order hyperpolarizability analysis of N-(4-nitrophenyl)-2, 2-dibenzoylacetamide by density functional theory. Journal of Molecular Structure 1098: 400-407.

Zaragoza, F. 2015. Amide compounds show a widely used in the many fields of sciences such as industrial, pharmacological and biological. J. Org. Chem. 80(20): 10370-10374.

Zhang, L., Wang, X.J., Wang, J., Grinberg, N., Krishnamurthy, D. & Senanayake, C.H. 2009. An improved method of amide synthesis using acyl chlorides. Tetrahedron Letters 50: 2964-2966.

Zivec, M., Jakopin, Z. & Gobec, S. 2009. Recent advances in the synthesis and applications of reduced amide pseudopeptides. Curr. Med. Chem. 16(18): 2289-304.

 

 

*Corresponding author; email: maisara@umt.edu.my

 

 

 

previous