International Journal of Scientific & Engineering Research, Volume 5, Issue 1, January-2014 70

ISSN 2229-5518

Transesterification of dimethyl malonate with a

novel catalyst derived from Musa balbisiana colla

Swarnali Pathak and Dibakar Chandra Deka

Abstract— Malonate esters are important synthons that can be transformed into variety of building blocks in organic syntheses. Trunk of Musa balbisiana colla triggered successful transesterification of dimethyl malonate with a series of higher alcohols efficiently. The catalyst is obtained from seedy variety of banana plant Musa balbisiana colla which is popularly known as kolakhar in the Assamese community of the north-eastern region of India and is used as an additive in many traditional cuisines. This work highlights the transesterification of dimethyl malonate with different types of alcohols resulting in the products from moderate to good yields. This newly developed catalyst can be considered as green catalyst as it is heterogeneous, natural, biodegradable, non-toxic, easily obtainable, inexpensive and environmentally safe. We are hopeful that it will contribute a lot in the field of organic synthesis.

Index Terms— Banana plant, Dicarboxylic esters, Dimethyl malonate, Heterogeneous, Kolakhar, Musa balbisiana colla, Transesterification.


—————————— ——————————
n the present scenario, dicarboxylic esters are of great inter- est amongst researchers as they are entirely bio-renewable
plays an important role here as it shows a simple route for the synthesis of more complex products from more easily accessi-


and green chemicals that can replace petroleum based sol-
vents [1]. Due to their rich content of oxygen atoms, many
diesters can be blended with fuels. They can be used as an
additive to enhance the BCN value (blended cetane number)
of the fuel and diminishing the probability of particulate mat-
ter emissions [2]. They can play a vital role as intermediates in
the synthesis of fine chemicals, drugs, plasticizers, food pre-
servatives, pharmaceuticals and cosmetics [1]. Malonic acid
and its derivatives like malonic esters can act like platform
molecules as they possess the potential to be transformed into useful building blocks and serve as a valuable tool for the syn- thesis of various complex compounds and pharmaceutics, plasticizers, perfumes etc. [1], [3], [4], [5]. Malonic ester is also
used for the synthesis of carboxylic acid by malonic ester syn- thesis. Petrochemical based production routes to malonates and malonate derived compounds are dependent on nonre- newable feedstock accompanied by deficiency in oxygen con- tent [6]. Conventional procedures for production of dicarbox- ylic ester involve a stirred batch or continuous reactor in pres- ence of H2 SO4 as a homogeneous catalyst. Due to known dis- advantages of the traditional liquid acids (corrosiveness, sepa- ration problem and short life span), much attention has been focused on the development of easily recoverable, recyclable, non-toxic, inexpensive, environmentally benign solid hetero- geneous catalysts with cleaner operations. Transesterification


Swarnali Pathak is currently pursuing Ph. D., Dept. of Chemistry, Gauhati

University, Guwahati, Assam, India. E-mail:

Dibakar Chandra Deka is Professor and Head, Dept. of Chemistry, Gauhati

University, Guwahati, Assam, India.

ble compounds [7]. A literature survey shows that malonate
esters have been generally synthesized by transesterification
reaction. Transesterification is an important synthetic process
used as an alternative method to synthesize a large variety of
carboxylic esters [8]. It’s a single pot equilibrium reaction
which gets accelerated in presence of a catalyst. Transesterifi-
cation has wide applications in industrial field as well as in
academic research [9], [10], [11], [12]. Transesterification is
more advantageous than esterification owing to the high sta-
bility and solubility of the esters in most organic solvents, whereas carboxylic acids have often low solubility in organic solvents [13]. Transesterification has tremendous application in biodiesel industries [12], [14], [15], [16], [17], [18], paint in-
dustry and is important in the synthesis of biologically active compounds and drugs [7], [19]. It is an essential part for the synthesis of polyethylene terephthalate [8]. Various esters are used for transesterification reactions but rather few generally applicable methods are known about the transesterification reaction carried out with malonic acid esters.
A number of useful transesterification methods have been reported in the literature, catalyzed by tin oxide-modified mesoporous SBA-15 [20], amino functionalized SBA-15 [21], Mg-Al calcined hydrotalcite [22], aluminophosphate and alu- minophosphate modified with different transition metals ( V, Fe, Co, Ni, Cu) [23], zinc perchlorate hexahydrate [24]. Diffi- cult preparation steps and economic consideration limit the applicability of many heterogeneous catalysts. Here, we wish to report the transesterification of dimethyl malonate cata- lyzed by trunk of Musa balbisiana colla which is environmen- tally safe, non-toxic, heterogeneous, economical which comes at almost zero cost. Post harvesting of banana plant is also free of cost. This catalyst has been successfully applied for bio- diesel production from yellow oleander (Thevetia peruviana) seed oil. Fuel properties conform to standards set for ASTM

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International Journal of Scientific & Engineering Research, Volume 5, Issue 1, January-2014 71

ISSN 2229-5518

D6751, EN14214, BSII and BSIII, and in certain aspects it is found to be better [25].

The catalyst is derived from trunk of Musa bulbisiana colla


atalyst 20% wt. of ester O O

locally known as athia kal, the seedy variety of banana plant
which is considered to be the best as far the quality of kolakhar




( )

Ref lux R O O R

is concerned. Kolakhar is obtained from the ash of different parts of banana plant and is a very popular food additive in the north-eastern region. The main objective of this study is to investigate the general applicability of the catalyst for the transesterification of dimethyl malonate with a series of struc- turally varied alcohols.


2.1 Materials

Dimethyl malonate and amyl alcohol were purchased from Loba Chemie and other alcohols viz., methanol, ethanol, buta- nol, heptanol, benzyl alcohol were purchased from Merck Ltd. Alcohols were dried over Na2 SO4 prior to use. The catalyst was also dried in oven at 120 °C for 2 hours as it is hygroscop- ic in nature and presence of moisture can retard the rate of the reaction.

2.2 Catalyst preparation

We followed the traditional procedure for the preparation of

R=Ethyl, Butyl, Amyl, Heptyl, Benzyl

1:20 molar ratio

Fig.1. Transesterification of dimethyl malonate with various alco- hols.



the catalyst known as kolakhar. Parts of banana plant (Musa balbisiana colla) were cut into pieces and air dried under sun for several weeks. The dry material was burnt into ashes and stored in a plastic container. Chemical and spectroscopic in- vestigation of the catalyst shows the presence of chloride, car- bonate. Major components present are K+, CO3 2-, Na+, Cl- along with other metals viz., Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, in trace amount (ppm level)[26].

2.3 General procedure for Transesterification

A 1:20 molar ratio mixture of dimethyl malonate ester and alcohol together with the catalyst derived from trunk of bana- na plant (20% wt. of ester) without a co-solvent were stirred in a two neck round bottomed flask with a magnetic stirrer. Re- actions were carried out under reflux. The progress of the re- action was monitored by TLC. After completion of the reac- tion, the reaction mixture was partitioned between petroleum ether and water. The organic layer was washed with (10%, 10 ml) brine solution and dried over Na2 SO4 . Solvent was re- moved under vacuum and crude product was chromato- graphed on silica gel using light petroleum ether (bp. 40 -60
C) and ethyl acetate as the eluent. Products were identified by IR and NMR. 1H and 13C NMR were recorded in CDCl3 at 300 and 75 MHz, respectively using Bruker Advance III
300MHz/54mm NMR spectrometer. FT-IR spectra were ob- tained on a Perkin Elmer RX I FT –IR spectrometer.


The scheme of the reaction is shown in Fig. 1 and results of various reactions carried out are summarized in Table 1.

All yields are isolated product yields.

1, 3-Diethyl propanedioate (Diethyl malonate): 1H NMR (300 MHz, CDCl3 ): δ 1.255-1.302 (6H, t, CH3 ), 3.358 (2H, s, OOCCH2 COO), 4.169-4.240 (4H, m, -OCH2 -). 13C NMR (75

MHz, CDCl3 ): 14.02, 41.65, 61.47, 166.61. FT-IR (thin film on
KBr, cm-1): 1029.99, 1149.57, 1265.30, 1739.79, 2858.51, 2924.
Dibutyl propanedioate (Dibutyl malonate): 1H NMR (300
MHz, CDCl3 ): δ 0.883-.934 (6H, t, CH3 ), 1.302-1.419 (4H, m, - CH2 -), 1.561-1.653 (4H, m, -CH2 -), 3.345 (2H, s, OOC- CH2 COO), 4.102-4.148 (4H, t, -OCH2 -). 13C NMR (75 MHz, CDCl3 ): 13.61, 18.98, 30.45, 41.66, 65.32, 166.69. FT-IR (thin film
on KBr, cm-1): 1026.13, 1068.56, 1458.18, 1658.78, 1735.93,
2862.36, 2927.94.
Dipentyl propanedioate (Diamyl malonate): 1H NMR (300
MHz, CDCl3 ): δ 0.901 (6H, t, CH3 ), 1.249-1.325 (8H, m, - CH2 CH2 -), 1.625-1.644 (4H, m, -CH2 -), 3.368 (2H, s, OOC- CH2 COO), 4.115-4.157 (4H, t, -OCH2 -). 13C NMR (75 MHz, CDCl3 ): 14.06, 22.21, 27.86, 28.08, 41.65, 65.62, 166.68. FT-IR
(thin film on KBr, cm-1): 1049.28, 1064.71, 1273.02, 1739.79,
2862.36, 2939.52.

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Diheptyl propanedioate (Diheptyl malonate): 1H NMR (300 MHz, CDCl3 ): δ 0.864-.885 (6H, m, CH3 ), 1.287 (12H, m, - CH2 CH2 CH2 -), 1.596-1.639 (8H, m, -CH2 CH2 -), 3.642 (2H, s, OOCCH2 COO), 4.036-4.080 (4H, t, -OCH2 -). 13C NMR (75

MHz, CDCl3 ): 14.04, 22.58, 25.88, 28.91, 29.10, 31.71, 41.64,
65.38, 174.05. FT-IR (thin film on KBr, cm-1): 1045.42, 1065,
1273.02, 1411.89, 1712.19, 2870.08, 2943.37.
Dibenzyl propanedioate (Dibenzyl malonate): 1H NMR
(300 MHz, CDCl3 ): δ 3.669 (2H, s, OOCCH2 COO), 5.377 (4H, s,
-OCH2 -), 7.266-7.909 (10H, m, C6 H5 ). 13C NMR (75 MHz, CDCl3 ): 40.8, 66.65, 126.94, 127.62, 128.96, and 136.02, 166.49.
FT-IR (thin film on KBr, cm-1): 1454.33, 1735.93, 2962.66, and


In this study, the catalytic activity of the catalyst derived from the trunk of Musa balbisiana colla was explored for the trans- esterification of dimethyl malonate with a variety of higher alcohols. The catalyst shows good activity towards transesteri- fication of dicarboxylic ester to its higher esters especially with butanol. However, with the increase in chain length its activity decreases. This will be a very good option for the transesterifi-
cation of dimethyl malonate with lower chain alcohols. This

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