Scalable preparation, characterization, and application of alkali-treated starch as a new organic base catalyst

Article abstract of DOI:10.1016/j.carres.2016.10.014

Preparation, characterization, and application of alkali starch (AS) given by dry co-grinding of starch and alkali is described in this work. Grinding using a mortar (agate) and pestle or, more conveniently, a ball mill has been found to be satisfactory for the preparation of the AS. The AS products were characterized by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) and x-ray fluorescence (XRF) analyses. The base capacities of ASs were 4.25–4.45 mmol/g, respectively. AS is a low cost and easy to handle base catalyst that showed promising catalytic performance in the synthesis of a dihydroquinazoline-based antibacterial drug that involves tandem hydration or decarboxylative amidation, imination, and Aza-Michael reactions.

Full text of DOI:10.1016/j.carres.2016.10.014

Accepted Manuscript
Scalable preparation, characterization, and application of alkali-treated starch as a
new organic base catalyst
Fatemeh Tamaddon, MohammadTaghi KazemiVarnamkhasti
PII:
S0008-6215(16)30313-5
10.1016/j.carres.2016.10.014
CAR 7283
DOI:
Reference:
To appear in: Carbohydrate Research
Received Date: 20 August 2016
Revised Date: 27 October 2016
Accepted Date: 28 October 2016
Please cite this article as: F. Tamaddon, M. KazemiVarnamkhasti, Scalable preparation,
characterization, and application of alkali-treated starch as a new organic base catalyst, Carbohydrate
Research (2016), doi: 10.1016/j.carres.2016.10.014.
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ACCEPTED MANUSCRIPT
Scalable preparation, characterization, and application of alkali-treated
starch as a new organic base catalyst
Author 1: Fatemeh Tamaddon, Department of Chemistry, Yazd University, Yazd 89195-741,
Iran, E-mail: ftamaddon@yazd.ac.ir.
Author 2: MohammadTaghi KazemiVarnamkhasti, Department of Chemistry, Yazd University,
Yazd 89195-741, Iran, E-mail: Marshal67FH@yahoo.com.
1

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Graphical Abstract
2

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Scalable preparation, characterization, and application of alkali-treated
starch as a new organic base catalyst
Fatemeh Tamaddon,* MohammadTaghi KazemiVarnamkhasti
Department of Chemistry, Faculty of Science, Yazd University, Yazd 89195-741, Iran.
_
_________________________________________________
Abstract: Preparation, characterization, and application of alkali starch (AS) given by dry co-
grinding of starch and alkali is described in this work. Grinding using a mortar (agate) and pestle
or, more conveniently, a ball mill has been found to be satisfactory for the preparation of the AS.
The AS products were characterized by scanning electron microscopy (SEM) and Fourier
transform infrared spectroscopy (FTIR) and x-ray fluorescence (XRF) analyses. The base
capacities of ASs were 4.25-4.45 mmol/g, respectively. AS is a low cost and easy to handle base
catalyst that showed promising catalytic performance in the synthesis of a dihydroquinazoline-
based antibacterial drug that involves tandem hydration or decarboxylative amidation, imination,
and Aza-Michael reactions.
Keywords: Alkaline starch; Anionic polymer; Base catalyst; Antibacterial drug.
_
_______________________________________________
*
Corresponding author: Tel.: 00983531232666; fax: 00983538210644; e-mail:
ftamaddon@yazd.ac.ir
3

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1
. Introduction
Natural carbohydrates are among the best alternatives for the manmade polymeric materials,
1
-3
because of their biocompatibility, simple reproduction, and extra active sites. Starch is the
second most abundant polysaccharide composed of cross-linked amylopectin and linear
4
polymers of amylose that helically solubilize in water. Amylose and amylopectin are different in
5
their chain length, degree of cross-linking, and branching, so the percent of these polymers are
6
different in various starches. The amylose/amylopectin ratio determines the average molecular
7
weight (AMW) of starches, so the AMW of amylopectin (>10 g/mol) is greater than amylose-
7
,8
enriched starches. The granules of starch have amylopectin short chains in their semi-
9
crystalline parts and mixture of branched amylopectin and amylose in their amorphous parts.
1 4
Although glycoside linkages in starch is predominantly α-C -C , amylopectin contains shorter
chains of linked α-C -C glucoses that joined to each other by α-C -C glycoside bonds after each
1
4
1
6
1
0
2
5-30 glucose units. However, the physical and chemical properties of starch including AMW,
particle size, morphology, viscosity, and adhesion are dependent to the ratio of
1
1
amylose/amylopectin. Due to the susceptibility of starch to enzymatic, chemical, and physical
treatments, oxidation, etherification, alkalization, esterification, dextrination, cross-linking,
1
2-16
grafting, or partial hydrolysis improves the properties of this natural biopolymer.
Alkali-
treated starch (AS), obtained from the reaction of starch with alcoholic solutions of sodium or
potassium hydroxide, is a kind of anionic starch that used as thickener, stabilizer, and binder of
1
7-19
feed products.
The main problems associated with preparation of AS in aqueous alkaline
solutions are gelatinization of starch, consumption of a large amount of volatile alcohols, and
fewer interaction of NaOH with starch in these hydrogen-bonded solutions. Despite the
recognized features of the value-added AS in food industries, this organic base has not yet been
4

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considered as an anionic catalyst in chemical processes. To overcome the above shortcomings,
development of more efficient methods for preparation of AS and use of this biocompatible
alkali catalyst in green organic transformations has been established in our laboratory.
2
0
21
Grinding by mortar-pestle or ball milling provide dual chemo-mechanical mixing of
starting materials together with local heating and large area of contact between the solids. Co-
grinding of solids by pestle or ball milling is an efficient way to synthesis of supra-molecular
materials that have advantages of short reaction times, high yields, and easy workup of the
2
2
product.
Due to the antibacterial properties of 2-phenyl-2,3-dihydroquinazoline-4(1H)-one (1),
have recently prepared this pharmaceutical and its derivatives using Amberlyst A26-OH as
2
3-26
we
2
5
catalyst. The objective of this work was easier access to AS by simple grinding or ball milling
of starch with NaOH in the absence of organic solvents, characterization of AS, and examination
of the catalytic proficiency of this anionic carbohydrate polymer in the large scale synthesis of
2
6
antibacterial drug 1 (Scheme 1)
5

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Scheme 1. Preparation of alkaline starch and its catalytic use in synthesis of antibacterial compound 1.
2
. Experimental
2
.1. Materials
5
7
Corn starch with approximately 20.7% amylose and 79.3% amylopectin (M =10 -10 ) was
W
purchased from Mahshad Co-operation (Yazd, Iran). The water content was determined by
drying the corn starch in a vacuum oven at 50 °C until constant weight and was found to be
1
1.1%. Sodium hydroxide, Hammet indicators, isatoic anhydride, ammonium acetate, and
benzaldehyde were all purchased from Merck (Darmstadt, Germany).
2
.2. Characterization of catalysts and products
6

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The base capacity of the prepared ASs was determined by either acid-base titration or
Hammet indicators. FT-IR spectra were carried out on a Brucker instrument (Brucker, Karlsrohe,
Germany). The XRF (Brucker, S4 Explorer, Germany) analysis were recorded at room
temperature. The surface morphology of ASs was examined by SEM (Vega3 Tescan, Czech).
The viscosity of corn starch and ASs were measured by viscometer (Ford cup, Biuged, China).
The melting point of AS was determined by a Büchi B-540 apparatus (Germany). The drug
1
13
prepared using AS was characterized by FT-IR, H NMR, C NMR, and melting point
Supporting file).
(
2
.3. Preparation of AS
AS was prepared by finely grinding of corn starch (100 g) with NaOH (38 g) in either an
agate mortar (AS1) or ball milling (AS2) at 25 minutes. To remove the unreacted NaOH from
the prepared AS, it was washed four times with EtOH, until to pH 7 for output EtOH. The given
pale yellowish solid was then dried in a vacuum oven at 70 °C for 2 h.
2
.4. Evaluation of the catalytic activities of ASs in synthesis of 1
To check the catalytic efficiencies of the given ASs in the synthesis of 1, three individual
experiments were performed for each of AS1 and AS2. In the first experiments, a mixture of
AS1 or AS2 (0.5 g), isatoic anhydride (50 mmol), NH OAc (75 mmol), and benzaldehyde (50
4
mmol) was magnetically stirred at 80 °C for 30 min. In the second experiments, a mixture of
AS1 or AS2 (0.5 g), 2-aminobenzamide (50 mmol), and benzaldehyde (50 mmol) was stirred at
8
0 °C for 20 minutes. Alternatively, a mixture of AS1 or AS2 (1 g), benzonitrile (50 mmol),
water (25 mL), and benzaldehyde (50 mmol) was stirred at 80 °C for 1 h.
In each case, after the completion of the reaction (thin layer chromatography monitoring with
hexane:EtOAc (70:30)), 50 mL of EtOAc was added, the catalyst was filtered, and the product
7

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was isolated by evaporation of the solvent. The above three reactions with AS2 yielded product 1
in 96%, 97%, and 93%, respectively. The yields of similar reactions with AS1 were 93, 91, and
8
7%. The purity of the given 1 from AS2-catalyzed reactions was so high that the analytical data
confirmed its structure without further purification.
3
. Results and discussion
3
.1. Preparation of AS by mortar-pestle or ball milling grinding methods
The alkaline starches AS1 and AS2 were respectively prepared by grinding of corn starch
with NaOH using mortar-pestle and ball milling, four times washing of the pale yellowish solids
with EtOH, and drying in vacuum oven. Color changes from white to pale yellow besides to pH
changes from 7 to 12.5 and 12.6 in these processes support the alkoxidiation of some of 2,3,6-
hydroxyl groups of starch and breaking of some of glycoside bonds to give the AS1 and AS2.
These anionic polymers were characterized by acid-base titration, chemical composition, surface
morphology, and FT-IR spectral data.
3
.2. Acid-base analysis of ASs
While corn starch is neutral (pH = 7), the prepared alkaline starches by simple grinding or ball
milling showed pHs of 12.5 and 12.6, respectively. The base capacities of these alkaline starches
were determined by titration of the solution of 1 g AS1 or AS2 in 100 mL of water with 0.1 N
standard solution of HCl. The volume of titrant used for neutralization of the given solutions
from AS1 and AS2 were 42.5 and 44.5 mL, respectively. According to M V = M V at
1
1
2
2
neutralization point, the molarity of solutions of AS1 and AS2 were 0.0425 and 0.0445 mol/Li
-
(
mmol/mL) and the base capacity or mmols of OH in solution of 1 g AS1/100 mL is 4.25
-
mmol/g, whereas 1 g of AS2 is equal to 4.45 mmol/g of OH .
8

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2
7
Alternatively, the base strengths (H-) of the prepared ASs were determined by shaking of a
5
0 mg of AS1 and AS2 sample in methanol solution of various Hammet indicators and left to
equilibrate for 2 h after which no color changes was observed. Nitroaniline (H- = 18.4), 2,4-
dinitroaniline (H- = 15.0), and phenolphthalein (H- = 9.8) are the Hammet indicators used in this
work and the base strengths of both of ASs were found to be H- > 18.4. The acid-base titrations,
pH values of 12.5 and 12.6 as well as H- > 18.4 for ASs confirmed the alkalization of starch to
ASs.
3
.3. FT-IR spectral analysis of ASs
As FT-IR spectra of ASs show (Fig 1.), broadening of O-H stretching at 2000-3500 cm and
-1
-1
CH stretching at ~2930 cm are significant, although the C-O stretching for AS1 and AS2
2
-1
appears sharper than neutral starch at 1021 cm . A similar sharpening of CH bending at 1456
2
-1
cm for ASs supports much polarity and freedom of their CH groups by breaking of some of H-
2
O-CH bonds. The expansion of O-H stretching bands of ASs is also due to the salt formation as
2
+
C-OꢀNa , all these changes are evident from Fig. 1.
9

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Fig 1. The FT-IR spectra of corn starch and ASs.
3
.3. XRF analysis of ASs
The comparative chemical compositions of AS1 and AS2 with corn starch in Table 1 shows
large differences in %C, %O, %Na, C/O, and Na/O that all support the conversion of starch to
AS (Table 1).
Table 1
The chemical composition of corn starch and ASs
Composition Starch AS1
AS2
17.7
Na (%)
Cl (%)
C (%)
O (%)
C/O
0.14
16
0.114 0.131 0.128
27.1
25.3
1.07
21
20.8
44.5
0.47
0.40
43.6
0.48
Na/O
0.005 0.37
1
0

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The Na/O ratio is a good quantity to support the formation and anionic structure of AS. The
4 and 80 times larger amount of Na/O for AS1 and AS2 than starch confirmed the formation of
7
-
+
sodium salt by converting of some OH groups to O Na . Similarly, ~5 times reduced C/O of ASs
is due to increase in their oxygen quantities that maybe due to the cleavage of some of glycoside
bonds to two OH groups.
3
.5. SEM analysis of AS1, AS2, and starch
The compared SEM images of starch, AS1, and AS2 in 5 ꢁm and 100 ꢁm dimensions (Fig. 2.)
showed difference in regular size distribution, morphologies, and porosities of ASs than native
+
starch. These changes are results of the conversion of some OH groups to O
ꢀ
Na and alkaline
hydrolysis of some glycoside bonds. The similarity in surface morphologies and repeated sights
in SEM images of Ass can be attributed to the small differences in mortar-pestle grinding and
ball milling mechanical techniques applied for their preparation. No better uniformity was
obtained by change in the applied conditions for preparation of ASs or extra washing of them by
EtOH.
1
1

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Fig. 2. SEM images in 5 ꢁm (left): starch (A1), AS1 (B1), AS2 (C1) and 100 ꢁm (right): starch (A1), AS1 (B2),
AS2 (C2).
1
2

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While the fine SEM analysis of particle size for AS2 show the irregular particles with
dimension of < 2 ꢁm (Fig. 3), the histogram of size distributions, derived from SEM images of
AS1 and AS2, reveals particles with average diameters of 2-15 ꢁm (Fig. 4).
Fig. 3. SEM micrograph of AS2 in 50 ꢁm dimension.
1
3

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35 35
35
30
25
20
15
10
5
0
3
0
2
5
2
0
1
5
15
1
0
5
3
3
2
2
1
0
0
2
5
10
15
20
30
40
50
Particle size (µm)
AS 1 AS 2
Fig. 4. Histogram of particle size distribution for ASs.
3
.6. Viscosity test of AS and starch
Change in viscosity is demonstrative for structural changes of carbohydrate polymers. Thus,
viscosities of ASs were determined by stirring of the homogeneous solutions of 2 g of each
sample in 75 mL of distilled water at 25 °C for 20 min at controlled pH and temperature. A
similar measurement was applied for starch’s slurry solution, while difference in conditions was
neglected due to the filtering of slurries. The viscosity of the prepared AS1 and AS2 were 5.1%
and 6.5% higher than that initial corn starch.
3
.7. Nitrogen adsorption isotherms of ASs
Based on the results obtained from the nitrogen adsorption isotherms, the surface area of AS2
is slightly higher than AS1 and the surface areas of ASs are significantly larger than starch (Fig.
) .
5
1
4

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Fig. 5. Nitrogen adsorption of ASs at 25 °C.
3
.8. Decomposition point of ASs
The decomposition point of AS1 and AS2 originated with color changes were 221-227 °C and
2
25-230, both lower than that of corn starch (254-260 °C). This trends that is attributed to the
+
lower intermolecular hydrogen-bonding interactions of OꢀNa in ASs show the critical role of
hydrogen bonding in OHs of starch.
3
.9. Catalytic activity of ASs in the synthesis of antibacterial compound 1
To check the activity of ASs in organic transformations, AS-catalyzed synthesis of
2
6
antibacterial drug of 2-phenyl-2,3-dihydroquinazoline-4(1H)-one (1) was considered. Thus,
various ASs were initially prepared by solvent-free ball milling of 10 g of starch with 0.1 mmol
of inorganic bases. To check the effect of base on the catalytic activity of the given ASs in
synthesis of 1, the three-component model reaction of isatoic anhydride (50 mmol),
benzaldehyde (50 mmol), and ammonium acetate (75 mmol) at 80 °C was screened with 0.5 g of
1
5

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these ASs for 30 minutes (Fig. 6). The yield of reactions were calculated after extraction of
product with EtOAc, filtering the remained solid catalyst, and evaporation of solvent.
9
6
96
1
00
90
80
70
60
50
40
30
20
10
0
7
8
6
9
6
5
0
1
2
3
4
5
6
ASs prepared from starch (10 g) and 0.1 mmol of
1
: NaHCO ; 2: Na CO ; 3: Ca(OH) ; 4: NaOH; 5: KOH
3
2
3
2
Fig. 6. Effect of inorganic base on the yield of 1 using AS’s catalysts.
According to the results, higher yields of compound 1 were obtained from AS-catalysts made
by NaOH or KOH, which due to the cheapness of NaOH it was used in further experiments.
In the similar set of trials, seven AS samples were prepared by ball milling of 10 g of corn
starch with various amounts of NaOH. To check the effect of amount of NaOH on the catalytic
behaviors of ASs, synthesis of 1 was followed by running of the model reaction with 0.5 g of
these AS-catalysts (Fig. 7).
1
6

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9
6
96
1
00
91
8
3
90
80
70
60
50
40
30
20
10
0
96
70
5
4
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
5
5.5
NaOH (g)
Fig. 7. Effect of NaOH loading on the efficiency of the given AS from 10 g starch.
As results show, the maximum yield of 1 is due to reaction with 0.5 g of AS made from 10 g
of starch and 3.8 g or 0.095 mmol of NaOH, although a similar control experiment using 0.5 g of
NaOH in place of AS gave 70% yield of 1. Thus, 3.8 g NaOH was selected as the optimum
amount of base for preparation of AS.
Further, AS1 and AS2 were prepared by mortar-pestle grinding or ball milling of 10 g starch
and 3.8 g NaOH. Then, various loadings of these ASs were used in the 50 mmol scale model
reaction. The results of loading of AS1 and AS2 on the yield of 1 was compared with original
starch in Fig. 8.
1
7

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9
9
6
3
96
93
95
1
00
9
1
8
8
8
3
8
8
6
1
9
8
7
6
5
4
3
2
1
0
0
0
0
0
0
0
0
0
0
9
1
88
AS2
AS1
Starch
15
1
5
15
1
0
0
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
Catalyst loading (g)
Fig. 8. Comparison of starch, AS1, and AS2 loadings on the yield of model reaction for synthesis of 1.
The results obviously show the authority of ASs, expressly AS2 in higher yield synthesis of 1.
The higher catalytic performance of AS2 may be due to the higher surface area (Fig. 5) or
smaller particle size of AS2 which is obvious in the SEM results (Figures 2-4).
To optimize the conditions for AS2-catalyzed synthesis of 1, typically the effects of solvent
and temperature were also studied on the reaction yield. Thus, three-component model reaction
of isatoic anhydride (50 mmol), benzaldehyde (50 mmol), and ammonium acetate (75 mmol) at
8
0 °C was run with 0.5 g of AS2 in different solvents for 30 minutes (Figure 9).
1
8

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9
6
1
00
9
0
8
6
9
8
7
6
5
4
3
2
1
0
0
0
0
0
0
0
0
0
0
7
8
6
5
Water
EtOH
EtOH/Water
Solvent-free
EtOAc
Fig. 9. Effect of solvent on the yield of 1 using 0.5 g of AS2 in model reaction at 80 °C.
According to the results, the maximum 96% yield of product 1 was obtained from the solvent-
free experiment in 50 mmol scale with 0.5 g of AS2 at 80 °C and 0.5 h.
The results of screened solvent-free reactions, at temperatures of 40-90 °C in an oil bath,
showed that 80 °C is the optimum reaction temperature for giving the maximum yield of product
1
from the model reaction.
9
6
1
00
92
8
5
9
8
7
6
5
4
3
2
1
0
0
0
0
0
0
0
0
0
0
71
42
3
0
40
50
60
70
80
90
Temperature (°C)
Fig. 10. Effect of temperature on the yield of 1 by solvent-free reaction using 0.5 g of AS2.
1
9

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The recycling of AS2 was also tested. Hence, after the completion of the solvent-free reaction
of isatoic anhydride (50 mmol), benzaldehyde (50 mmol), and ammonium acetate (75 mmol) at
8
0 °C, EtOAc was added and AS2 was separated by filtration. The given solid was washed with
EtOH, and dried in an oven at 70 °C for 2 h. The SEM image of the recycled AS2 shows no
significant changes in its surface morphology (Fig 11).
Fig. 11. The SEM image of recycled AS2.
This is in agreement with the catalytic activity of the reused AS2 in the second reaction run,
although yield of 1 with four times recycled catalyst was also 94-95% (Fig. 12).
2
0

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9
6
95
94
9
4
100
9
8
7
6
5
4
3
2
1
0
0
0
0
0
0
0
0
0
0
1
2
3
4
Reusability time
Fig. 12. The reusability of AS2 in the solvent-free reaction for synthesis of 1.
To show the superiority of AS-catalysts in the synthesis of 1, the results of this work was
compared with the previously reported methods (Table 2).
Table 2
The catalytic performance of AS in the synthesis of 1
O
O
O
O
H
+
Conditions
NH
4
NH OAc
+
N
H
O
N
H
1
a
Catalyst
g)
AS1 (0.01)
Ga(OTf) (1 mol %)
KAl(SO .12H O (0.15)
Conditions
Time Yield
Entry
(
Solvent/Temp. (°C) (min) (%) (Ref.)
1
2
3
4
5
6
Solvent-free/80
EtOH/Reflux
EtOH/Reflux
30
93 (This work)
28
29
30
31
32
3
55
87
71
80
77
88
4
)
2
2
240
240
300
120
30
Montmorillonite K-10 (0.3) EtOH/Reflux
Copolymer-PTSA (0.03)
Catalyst-free
AS2 (0.01)
EtOH/Reflux
O/Reflux
Solvent-free/80
H
2
7
96 (This work)
a
Isolated yield.
To examine the versatility of AS2, product 1 was obtained in 97% yield by different reaction
of 2-aminobenzamide (50 mmol) and benzaldehyde (50 mmol) using 0.5 g of AS2 at 80 °C and
solvent-free conditions. The adaptability of catalyst AS2 was also confirmed by successful
2
1

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reaction of 2-aminobenzonitrile (50 mmol) with benzaldehyde (50 mmol) and 2.5 mL of H
2
O
using 1 g of AS2 at 100 °C to give product 1 in 93% yield.
Conclusion
In conclusion, the alkali-treated starch (AS) prepared by either ball milling or simple grinding
of corn starch with sodium hydroxide have been characterized by way of base capacity,
viscosity, and decomposition point, although XRF, SEM, and FT-IR techniques also support its
operational features. The adeptness of this bioorganic base catalyst was demonstrated in the
synthesis of antibacterial compound of 2-phenyl-2,3-dihydroquinazoline-4(1H)-one, whereas it
was reusable for three cycles without significant loss of activity. The AS is a low cost and easy
handle catalyst that its applications in organic synthesis is in due course in our laboratory.
Acknowledgement
The authors gratefully acknowledge the Research Council of Yazd University, Pasargad
Polyester Company and Mr MohammadSadegh Daneshian for financial support.
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Grinding by mortar-pestle or ball mill of starch and NaOH gives alkaline starch.
Solvent-free alkalization helps to much interaction of starch with NaOH.
The base capacity of alkaline starch (AS) is high to act as an alkali catalyst.
AS is a handlebar solid, low-cost anionic polymer, and reusable catalyst.
As shows a talented catalytic performance in synthesis of an antibacterial drug.