J. Chil. Chem. Soc., 60, Nº 2 (2015)
APPLICATION OF SBA-15 FUNCTIONALIZED SULFONIC ACID (SBA-Pr-SO H) AS AN EFFICIENT
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NANOREACTOR IN THE ONE-POT SYNTHESIS OF PYRIDO[2,3-d]PYRIMIDINE
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GHODSI MOHAMMADI ZIARANI , PARISA GHOLAMZADEH , ALIREZA BADIEI ,
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SHIMA ASADI , ALI ABOLHASANI SOORKI
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Department of Chemistry, Alzahra University, Vanak Square, P.O. Box 1993893973, Tehran, Iran
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School of Chemistry, College of Science, University of Tehran, Tehran, Iran
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Research Institute of Petroleum, Academic Center of Education, Culture & Research, Shahid Beheshti University, Tehran, Iran.
ABSTRACT
Sulfonic acid functionalized nanoporous silica (SBA-Pr-SO H) with a pore size of 6 nm was synthesized using surface modification of Santa Barbara
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Amorphous (SBA-15). It is a solid acid hexagonally nano-reactor with high surface area and is reusable, high selective, non-corrosiveness which can easily isolate
from the products. An efficient and green one-pot three component reaction was developed for the synthesis of pyrido[2,3-d]pyrimidine derivatives via a simple,
mild and effective solvent free reaction of 4(6)-aminouracil, barbituric acid and aromatic aldehydes in the presence using SBA-Pr-SO H. In this reaction, SBA-Pr-
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SO H was an effective nano-catalyst which gave the products in good to high yields in a shorter reaction time compared to the other published reports. Some of
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the products were strong antibiotics against Bacillus subtilis and Staphylococcus aureus.
Keywords: SBA-Pr-SO H; Pyrido[2,3-d]pyrimidine compound; Green synthesis; Antibiotic.
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INTRODUCTION
Preparation of SBA-15 and SBA-Pr-SO H
The synthesis of SBA-15 and its modification to SBA-Pr-SO H was
carried out in accordance with our earlier reports.
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,
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17-19
Synthesis of MCM-41 by Mobil Corporation scientists in 1992 and
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then SBA-15 by Zhao et al. in 1994 were the first approaches to achieve
General procedure for the preparation of the products
mesoporous molecular sieves. SBA-15 is a hexagonal nanoporous silica
with good accessibility due to its large pore size, high surface area, excellent
chemically and thermally stability. Surface modification of SBA-15 makes it
The SBA-Pr-SO H (0.02 gr) was activated in vacuum at 100 °C and then
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after cooling of catalyst to room temperature, barbituric acid (0.128 g, 1 mmol),
uracil (0.127 g, 1mmol) and aryl aldehydes (1 mmol) were added to it. The
mixture was heated in an oil bath (140 °C) in appropriate time as shown in
Table 2. After completion of the reaction, which was monitored by thin layer
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an effective inorganic-organic hybrid which may be acting as a catalyst; up to
day, different modified SBA-15 has been synthesized, including Ionic liquid
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supported SBA-15 (SBA-IL) , propyl amine functionalized SBA-15 (SBA-
chromatography (TLC), the crude product was dissolved in hot EtOH and H O
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5
Pr-NH ) , propyl thiol functionalized and propyl sulfonic acid functionalized
and then the mixture was filtered for removing the solid catalyst. The cooled
filtrate gave the pure product. The solid acid catalyst subsequently was washed
with a diluted acid solution, distilled water and then acetone, dried under
vacuum that it can be used for several times without loss of significant activity.
Selected Spectral Data
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SBA-15 (SBA-Pr-SH and SBA-Pr-SO H, respectively) and so on. SBA-Pr-
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SO H is prepared by the reaction of silanol groups on the SBA-15 surface
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with 3-mercaptopropyltrimethoxysilane following oxidation of thiol groups.
It maintains as a hexagonal structure after modification and can act as a solid
acid nanoreactor; therefore, it is a heterogeneous, non-corrosiveness and
5-(4-OH)C H -3,5,7,9,10-pentahydro-(1H)-pyrimido[5´,4´:5,6]
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4
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reusable solid acid catalyst, which can isolate from the products easily. SBA-
pyrido[2,3-d]pyrimidine-2,4,6,8-tetrone (1d)
Pr-SO H has been applied as an effective nanoreactor in the multi-component
reactions.
IR (KBr): υmax = 3270, 3191, 2923, 2816, 1718, 1667, 1612, 1530, 1448,
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6-12
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1407 and 1347 cm . H NMR (250 MHz, DMSO): d = 5.21 (s, 1H, CH), 5.81
H
The increase in bacterial strains that are resistant to antibacterial therapies
has prompted the development of drugs to treat bacterial diseases. One of the
usual strategies to address bacterial drug resistance is the synthesis of new
compounds which modify to common antibacterial. Heterocyclic compounds
with pyrimidine skeleton are important class of chemical products since they
have wide variety of potentially biological activities, especially antimicrobial
(s, 1H, OH), 6.6 (m, 2H, ArH), 6.72 (bs, 2H, NH), 6.9 (m, 2H, ArH), 11.2 (d,
3H, NH) ppm. MS (m/e): 341 (M , 1 %), 231 (40 %), 128 (90 %), 107 (90 %),
94 (100 %).
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5-(2-OMe)C H -3,5,7,9,10-pentahydro-(1H)-pyrimido[5´,4´:5,6]
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pyrido[2,3-d]pyrimidine-2,4,6,8-tetrone (1e)
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IR (KBr): υmax = 3389, 3193, 2969, 1711, 1664, 1606, 1456 and 1389 cm .
H NMR (250 MHz, DMSO): d = 3.63 (s, 3H, OCH ), 5.25 (s, 1H, CH), 6.5
13-15
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properties.
In addition, the pyridopyrimidine structure and their derivatives
H
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1
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are famous pharma core in the drug design. In connection with such studies,
(bs, 2H, NH), 6.82 (d, 1H, ArH), 7.1 (t, 3H, ArH), 10.39 (d, 3H, NH) ppm. MS
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the present paper reports the synthesis of pyrimidine-fused heterocycles,
(m/e): 355 (M , 4 %), 353 (10 %), 322 (30 %), 213 (100 %), 170 (95 %), 143
with antibacterial properties in the presence of SBA-Pr-SO H as an efficient
(100 %), 127 (98 %).
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nanoreactor.
5-(3-OMe)C H -3,5,7,9,10-pentahydro-(1H)-pyrimido[5´,4´:5,6]
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pyrido[2,3-d]pyrimidine-2,4,6,8-tetrone (1f)
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EXPERIMENTAL
IR (KBr): υmax = 3310, 3190, 2950, 2850, 1711, 1610, 1466 and 1385 cm .
H NMR (250 MHz, DMSO): d = 3.6 (s, 3H, OCH ), 5.25 (s, 1H, CH), 6.5 (bs,
1
H
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The chemicals employed in this work were obtained from Merck Company
and were used with no purifications. IR spectra were recorded from KBr disk
using a FT-IR Bruker Tensor 27 instrument. Melting points were measured by
2H, NH), 6.8 (d, 2H, ArH), 7.1 (t, 2H, ArH), 10.4 (d, 3H, NH) ppm. MS (m/e):
355 (M , 1 %), 353 (5 %), 213 (100 %), 170 (50 %), 143 (95 %), 127 (50 %).
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5-(2,3-OMe )C H -3,5,7,9,10-pentahydro-(1H)-pyrimido[5´,4´:5,6]
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using the capillary tube method with an electro thermal 9200 apparatus. The H
pyrido[2,3-d]pyrimidine-2,4,6,8-tetrone (1h)
NMR (250 MHz) was run on a Bruker DPX. Mass analysis was performed on a
model: 5973 network Agilent. Weight change curve in nitrogen was measured
on a TA instrument of TGA Q50 V6.3 with maximum heating rate of 20 °C/
min. Nitrogen adsorption and desorption isotherms were measured at -196 °C
using a Japan Belsorb II system after the samples were vacuum dried at 150
IR (KBr): υ = 3305, 3196, 2990, 2850, 1710, 1618, 1472, 1384 and 1053
max
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cm . H NMR (250 MHz, DMSO): d = 3.6 (6H, OCH ), 5.25 (s, 1H, CH), 6.5
H
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(bs, 2H, NH), 6.8 (d, 2H, ArH), 7.1 (t, 1H, ArH), 10.4 (d, 3H, NH) ppm. MS
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(m/e): 385 (M , 1 %), 243 (100 %), 214 (95 %), 142 (70 %), 128 (80 %).
°
C overnight. SEM analysis was performed on a PhilipsXL-30 field-emission
RESULT AND DISCUSSION
scanning electron microscope operated at 16 kV while TEM was carried out on
a Tecnai G F30 at 300 kV.
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In this manuscript, 5-aryl-3,5,7,9,10-pentahydro-(1H)-pyrimido[5´,4´:5,6]
e-mail: gmziarani@hotmail.com
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