DOI: 10.1002/slct.

201700919 Full Papers

1
2 z Catalysis
3
4
5
Synergistic Effect of Bronsted and Lewis Acid Amounts on
6 One-Pot Synthesis of Aminoxazole by Propargylation and
7
8 Cycloisomerization
9
10 Naragalu Javaregowda Venkatesha*[a]
11
12
13 One pot synthesis of aminoxazoles through propargylation and of reaction intermediate to both acid sites within the pore
14 cycloisomerization reaction requires both Bronsted and Lewis giving good selectivity of final product. Among the three
15 acid amounts. The variation in any one of the acid amounts or factors, either the increase or decrease in one of the acid
16 pore volume upon loading of oxometalates or metal chlorides amounts or pore volume alters the product distribution. The
17 on gamma alumina causes alteration in the product distribu- combined effect of B/L ratio and pore volume contributes
18 tion. The synergistic effect of Bronsted to Lewis (B/L) acid better yield of final product aminoxazole. It is also evident that,
19 amounts ratio gives better yield. The combination of pore the better correlation was obtained by volume accessibility
20 characteristics and acidity provides an idea about the approach factors.
21
22 1. Introduction:
mentioned above in a single catalyst. However, heterogeneous
23
Heterocyclic compounds containing nitrogen, sulfur and oxy- catalysts such as metal oxides, zeolites, clays etc. have more
24
gen are major class of organic compounds. Among such benefits than homogeneous catalysts on account of their ease
25
compounds, oxazole[1,3] thiazole[4-6] and their derivatives are of handling, less cost, eco-friendly nature and easy modifica-
26
considered as privileged structural motifs in numerous natural tion.[28-30] In recent times, inorganic solid acid-catalyzed organic
27
and synthetically active products.[7-9] Nucleophilic substitution transformations are gaining much attention due to the
28
and cyclisation reactions are two industrially adopted routes for presence of both types of acidity, simplified product isolation,
29
their syntheses because of wide variety of applications in mild reaction conditions, high selectivity, easy recovery, reuse
30
pharmaceutical and fine chemical industries.[10-12] of catalysts and reduction in the generation of byproducts.[31–34]
31
Generally heterocyclic compounds are prepared by con- In this context, we have been investigating various industrially
32
densation and cyclisation reactions using various carbonyl important organic reactions by aiming at adopting solvent-less
33
compounds, amines and alcohols with homogeneous catalysts single step techniques and replacing toxic, corrosive reagents
34
such as HCl, H2SO4, H3PO4, TFA, p-TSA, BF3, Et3N, Cs2CO3, DBU, with innocuous chemicals in the presence of environmentally
35
acetic acid and pyridine,[3–16] CuI,[17] Cu(OTf)2,[18] InCl3,[19] FeCl3,[20] benign solid acid catalysts.[35]
36
B(C6F5)3/K2CO3[21] and metal complexes [Ir(COD)(SnCl3)Cl(m- The present study is aimed at single step greener synthesis
37
Cl)]2,[22] Yb(OTf)3,[23] [Cp*RuCl(2-SMe)2RuCp*Cl]/AuCl3/NH4BF4,[24] of oxazole and thiazole through propargylation and cyclo-
38
(4-Zn(OTf)2/pRuPPh3 (CH3CN)2PF6,[25] CF3C6H4)PAuNTf2,[26] isomerization reactions, which is an alternative to replace multi
39 [27]
AgBF4. These require more than stoichiometric amounts to stage process in homogeneous catalysts. The involvement of
40
get maximum desired product and it also involves tedious Bronsted to Lewis acid sites ratio and pore characteristics of the
41
process in products extraction from the mixture. This process is catalysts enhances the final product formation. The loading of
42
more useful when both nucleophilic substitution and cyclisa- oxometalates and metal chlorides on gamma alumina support
43
tion reactions are carried in one-pot procedure using heteroge- the increase in B/L aspect ratio by minimal reduction of surface
44
neous catalysts. Propargylation and cycloisomerizations are characteristics. These supported samples are used for the
45
such examples for the above mentioned type of transformation above reactions under solvent free microwave irradiation
46
and these reactions require both Bronsted and Lewis acid sites. conditions.
47
Homogeneous acids do not have both type of characteristics
48
49
[a] Assist. Prof. Dr. N. J. Venkatesha
2. Results and discussion:
50
51 Chemistry Research Center 2.1 Acidity and surface characteristics:
Bangalore Institute of Technology
52 K.R. Road, V.V. Pura The gA (gamma alumina) sample obtained upon calcination
53 Bengaluru-560004 Karnataka, India
showed a surface area 220 m2 g-1 and pore volume 0.522 cm3 g-
54 Phone: + 91 9901003120 1
E-mail: venkatesha.312@gmail.com with moderate ammonia TPD acidity 0.167 mmol g-1. While,
55
Supporting information for this article is available on the WWW under oxometalates loaded samples showed an increased acid
56
https://doi.org/10.1002/slct.201700919 amounts and strength. Table 1 shows the changed surface and
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1 Table 1. Surface and acidity characteristics of alumina and different acidic

substrates loaded samples.
2
3 Samples SA TPV APD TPDA Py FT-IR acidity
4 gA 220 0.522 95.28 0.167 0.154
5 10% MA 186 0.466 88.96 0.329 0.211
6 10% VA 181 0.409 86.45 0.312 0.202
5% AlA 201 0.478 90.87 0.265 0.246
7
10% AlA 173 0.433 89.03 0.281 0.265
8 10% FeA 169 0.429 88.95 0.276 0.186
9 10% ZnA 182 0.441 88.78 0.267 0.178
10 5% WA 208 0.486 91.06 0.284 0.189
10% WA 189 0.461 87.58 0.394 0.221
11
15% WA 165 0.436 83.21 0.416 0.257
12 20% WA 132 0.392 72.04 0.383 0.314
13 25% WA 101 0.308 66.04 0.342 0.353
14 30% WA 78 0.244 48.32 0.294 0.332
15 SA- surface area; m2g-1, TPV- total pore volume; cm3g-1, APD- average pore
16 diameter; Å, TPDA-TPD ammonia acidity; mmol g-1, Py FT-IR acidity-sum of Figure 2. Pyridine adsorbed FT-IR patterns of (a) MA (b)WA (c) VA and (d) gA.
17 Bronsted and Lewis acidity in mmolg-1. VA –vanadate loaded on gA, MA-
molybdate loaded on gA and WA-tungstate loaded on gA.
18
19
evident by X-ray pattern (Figure 3). These pronated species are
20
more Bronsted acidic than any other forms. The gA gives TPD
21
acidity characteristics of the different oxometalates and metal
22
chlorides loaded on gA. Equal amount (10%) each was loaded
23
on the gA showed the decreased surface area. It could be seen
24
from adsorption-desorption isotherms and pore volumes (Fig-
25
ure 1), and pyridine adsorbed FT-IR patterns (Figure 2) showed
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41 Figure 3. XRD patterns of gA and 10% individual oxometalates loaded
42 samples (*- gamma alumina phase, $ - HVO3 phase, - H2W2O7 phase and #-
43 H2MoO4).
44 Figure 1. Nitrogen adsorption-desorption isotherms of samples.
45
46
ammonia acidity of 0.167 mmol g-1. The loading of equal
47
increased Bronsted acid amounts, which is attributed to the amounts of different oxometalates like V, Mo and W individually
48
protons attached to oxometalates. It is to be noted that the on gA support showed increased acidity in addition to the
49
metal chloride loaded samples (AlCl3 on gA) AlA, (FeCl3 on gA) acidity of gA. The TPD NH3 patterns and Table 2 showed an
50
FeA and (ZnCl2 on gA) ZnA also showed decreased surface area increased acidity from V to W. It may be due to stability of
51
and pore volumes with increased acid amounts. oxyanions. Among the three oxyanins, WOn-(x + y) is more stable.
52
All the metal oxoacids can show remarkably different behavior
53
over different support. The bonding, morphology and exposed
54 2.2 Role of different oxometalates and metal chlorides:
surface facets also are an important for many reaction systems.
55
The ammonium form of oxometalates gives protonated species The nature of the metal-oxygen-metal and metal-oxygen-
56
HxVOx + y, HxMoOx + y and HxWOx + y upon calcination; this was support bonds, isolated oxides and optimal support are begin
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1 Table 2. Acidity characteristics of alumina and different substrates loaded samples and their catalytic activity.
2 Samples B+L B L % yield % yield %PA conversion
3 of AXZ of NPU
4 gA 0.154 0.093 0.061 28 30 58
5 10% MA 0.232 0.174 0.058 42 29 71
6 10% WA 0.22 0.177 0.043 61 29 90
10% VA 0.205 0.157 0.048 36 47 83
7
10% AlA 0.254 0.076 0.178 35 18 53
8 10% FeA 0.251 0.089 0.162 33 16 49
9 10% ZnA 0.238 0.093 0.145 32 14 46
10
B- Bronsted, L-Lewis, B + L- sum of Bronsted and Lewis acidity in mmol g-1, AXZ-aminoxazole, NPU- N-Propynyl urea. Reaction conditions: Reaction time, 60
11 min; Catalyst amount, 0.5 g; reaction temperature, 120 8C; reactants molar ratio PA:Urea, 1:2.
12
13
14
to control the surface acidity of respective metals. Also
15
structure and electronic properties of the oxides can control its
16
catalytic behavior. The HxVOx + y species having V-O bond is
17
covalent character and V-O-V does not show acidic character
18
only terminal hydroxyl groups show acidity, Mo-O bond is more
19
stabilized by the strong overlap of O 2p and Mo d orbitals,
20
hence both HxVOx + y and HxMoOx + y showed less acidity. And Hx
21
WOx + y more acidic nature by the delocalization of electrons
22
lead to bridging hydrogen, terminal hydroxyl groups and with
23
high electronegativity.[36,37] Further, the acid sites strength of V
24
and Mo are almost similar to gA, while W showed two
25
distinguishable peaks, one at lower temperature range
26
between 90-220 8C and another at 300-430 8C. Higher temper-
27
ature acid amounts are more compared to lower acid amounts
28
and could be seen by peak areas in Figure 4. Figure 5. Pyridine adsorbed FT-IR patterns of (a) gA (b)AlA (c) FeA and (d)
29
ZnA.
30
31
32
masking of the Bronsted acid sites of gA. Among the different
33
metal chlorides, Al belongs to the group 13 and it needs one
34
pair of electron to accommodate to fill vacant orbitals, whereas
35
Fe and Zn belongs transitional elements of the group 8 and
36
12th respectively, these needs more than one pair of electrons
37
to fill outer shell orbitals and also fajan’s rule states that the
38
more the charge to radius ratio of the element will show more
39
acidic nature. So AlCl3 contributes more Lewis acidity compared
40
FeCl3 and ZnCl2 and it follows order Al > Fe > Zn.[38-40]
41
42
43 2.3 Loading Optimization:
44
The various oxometalates loaded samples (V, Mo and W)
45
showed similar surface area and pore volumes, but the
46
variation in acidity was observed between three samples.
47
Figure 4. TPD-NH3 profile of gA and 10% loaded samples. Table 1 show that the total acidity of the samples increased
48
from V to W (10%) and the strength of acid sites was different
49
for W, whereas V and Mo showed the similar trend as gA.
50
Loading of higher amounts more than 15% showed a drastic
51
Loading of three different metal chlorides such as AlCl3, decrease in the surface area, pore volume and slight decreased
52
FeCl3 and ZnCl2 individually on gA showed the increase of acid acidity with increased particle size.
53
amounts, but they are weaker compared to oxometalates. It The loading of Lewis acids such as ZnCl2, FeCl3 and AlCl3
54
could be seen from the pyridine FT-IR patterns (Figure 5). The increases the Lewis acid sites, which are showed lower strength
55
increase in peak area for Lewis acids at 1455 cm-1 and slight than Bronsted acid sites and also cause decreased surface area
56
decrease of peak areas of Bronsted acids at 1545 cm-1 is due to and pore volume. The loading of metal chloride was optimized
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by increasing the amounts from 5 to 20%. The 5% loaded
1 2.4.2 Effect of temperature:
samples showed more acidity with minimal reduction in surface
2
area. Further increase in the amount to 10%, 15% and 20%, Figure 7 shows that the temperature has substantial effect on
3
showed decrease in the acidity, surface area and pore volume. the conversion of PA and selectivity of products. It was
4
5
6 2.4 Oxazole synthesis by propargylation of urea:
7
Reaction parameters were optimized by varying the catalyst
8
amount (10%WA), time, temperature and reactants mole ratio
9
for the propargylation and cycloisomerization of PA (Propargyl
10
alcohol) with urea to get maximum conversion and yield of
11
desired product. Under optimized experimental conditions
12
diffusional limitations were calculated by interphase and inter-
13
particle heat, mass transfer using Mear, Koros-Novak and Weisz-
14
Prater criteria were negligible.
15
16
17 2.4.1 Effect of reaction time:
18
The effect of reaction time on the oxazole synthesis through
19
propargylation and cycloisomerization reaction was studied in
20
the range of 5 to 180 min. Figure 6 shows an increased PA
21
22
23
Figure 7. Effect of temperature on the propargylation and cycloisomerization
24 of PA and urea. Reaction conditions: reaction time, 30 min; catalyst amount
25 0.5g; reactants molar ratio PA:Urea, 1:2.
26
27
28
observed that, when the temperature was raised from 60 to
29
160 8C, the conversion of PA increased from 31 to 92% with
30
changed product selectivity. At lower temperatures of 60 to
31
100 8C, PA conversions were selective towards the condensa-
32
tion product N-Propynylurea 22 to 35% and with further
33
increase in temperature towards higher range of 100-160 8C,
34
the selectivity trend changed from primary product N-Propyny-
35
lurea to cycloisomerized secondary product aminoxazole. This
36
observation is due to initial dehydration of alcohol taking place
37
in the presence of active sites, and as the temperature
38
increases, dehydration becomes rapid leading to form primary
39
product, which reached thermodynamic equilibrium and then
40 Figure 6. Effect of reaction time on the propargylation and cycloisomeriza- get converted into aminoxazole through cycloisomerization.
41 tion of PA and urea. Reaction conditions: reaction temperature, 120 8C;
42 catalyst amount, 0.5g; reactants molar ratio PA:Urea, 1:2.
43 2.4.3 Effect of Catalyst amount:
44
No reaction between PA and urea was observed in the absence
45
conversion from 5 to 50 min. With further increase in reaction of catalyst. In the presence of catalytic amount upto 0.5g of
46
time, the conversion remains unchanged from 60 to 180 min, catalyst, the reaction proceeded slowly and conversion of PA
47
but the product distribution was observed to be different. It is reached maximum of 88 % and further increase in catalyst
48
observed that, in the beginning from 5 to 20 min, the primarily amount did not alter the conversion much and stabilized to 95
49
formed propargylated product (N-Propynylurea) was higher %. The selectivity trend of products got changed as observed
50
with lower amounts of secondary cycloisomerized product in Figure 8. At lower amounts of catalyst from 0.1 to 0.3 g,
51
(aminoxazole). After 20 min, yield of aminoxazole increased by more (27 %) primary product (N-Propynylurea) was formed
52
the cycloisomerization of N-Propynylurea and reached a with lower amounts (14%) of secondary product (aminoxazole).
53
maximum of 62% at 60 min and further increase in time from Also, more than 0.4 g of catalyst N-Propynylurea was equili-
54
60 to 180 min does not cause any change in the selectivity and brated (32 %) and got rapidly cycloisomerized to form
55
conversion. secondary product (aminoxazole) 52 % at 0.5 g. With further
56
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to improve the Bronsted acid amounts and AlCl3 for Lewis acids
1
on alumina to optimize the B/L ratio have been done. An
2
increased loading from 5% to 30% showed an increased
3
conversion upto 15% and the extent of addition more than
4
15% showed decrease in conversion and selectivity due to
5
reduced pore volume, surface area and acidity by masking one
6
over the other molecule as observed in Figure 9. Lower
7
amounts (5%) of HxWOx + y showed an increased conversion
8
from 58 to 72%, but a slight increased selectivity of primary
9
(8%) and secondary (6%) product. Whereas 10% loaded sample
10
showed 90% conversion along with decreased selectivity of 9%
11
primary product and increased selectivity of 27% secondary
12
product. However 15% loaded sample showed 92% conversion
13
with 68% and 24% selectivity of secondary and primary
14
products respectively. It reveals the change in selectivity trend
15
by decreasing primary product due to cycloisomerization.
16
17
The incremental loading of AlCl3 from 5 to 10% showed a
18 Figure 8. Effect of catalyst amount on the propargylation and cycloisomeriza-
tion of PA and urea. Reaction conditions: reaction time, 30 min; reaction moderate conversion with more secondary product selectivity,
19
temperature, 120 8C; reactants molar ratio PA:Urea, 1:2. whereas the more than 10% loaded samples showed a
20
21
22
Table 3. Pore volume and acidity characteristics of alumina and different amounts of substrates loaded samples and their catalytic activity.
23
24 Samples TPV Py FT-IR acidity B L % yield AXZ % yield NPU % conversion PA B/L

25 gA 0.512 0.154 0.085 0.068 28 30 58 1.257

26 5% WA 0.486 0.189 0.126 0.062 34 38 72 2.517
27 10% WA 0.461 0.221 0.177 0.043 66 24 90 4.876
15% WA 0.436 0.257 0.226 0.030 62 30 92 9.345
28 20% WA 0.392 0.314 0.275 0.038 57 37 93 8.092
29 25% WA 0.308 0.353 0.309 0.043 44 46 90 6.568
30 30% WA 0.244 0.332 0.305 0.026 36 42 78 8.18
31 5% AlA 0.478 0.246 0.073 0.172 28 20 48 0.534
10% AlA 0.448 0.265 0.061 0.203 36 17 53 0.356
32 r 0.188 0.356 0.595 0.558 0.766
33
TPV- total pore volume; cm3g-1, B- Bronsted; L-Lewis;Py FT-IR acidity-sum of Bronsted and Lewis acidity; mmol g-1, AXZ-aminoxazole, NPU- N-Propynylurea, PA-
34
Propargylalcohol. Reaction conditions: Reaction time, 60 min; catalyst amount, 0.5 g; reaction temperature, 120 8C; reactants molar ratio PA:Urea, 1:2. r*
35 -correlation coefficient.
36
37
38
increase in the catalyst amounts up to 1.0 g, a slight increase in decreased conversion and selectivity of product. The increased
39
aminoxazole with decreased N-Propynylurea was noticed. loading causes masking of Bronsted acid sites on gA. The
40
combined loading of 5% AlCl3 and 10% HxWOx + y showed
41
maximum of 73% secondary product, where as 10% AlCl3 and
42 2.5 Role of acid amounts (B/L) ratio:
10% HxWOx + y sample showed higher acidity than other
43
To understand the role of B/L ratio, the Bronsted and Lewis acid oxometalate and metal chlorides loaded samples. But the
44
amounts are varied by loading of oxometalates and metal conversion and selectivity dropped, which may possibly due to
45
chlorides on the gA support. The gA itself showed both reduced pore volume and surface area. Both the pore and
46
Bronsted and Lewis acidity with maximum pore volume with acidity characteristics have an important role in the formation
47
lower acid amounts and strength. It showed catalytic activity of major secondary product.
48
(Table 3) of PA conversion (58%) with the primary product
49
selectivity of 30% and secondary product selectivity of 28%.
50 2.6 Improvement of cycloisomerized product by active site
The improvement of conversion and selectivity of product was
51 accessibility:
made by loading oxometalates, which dominate in Bronsted
52
acid sites. The Bronsted acid sites help in dehydration of PA for The variation in acidity and pore volume directly affect the
53
generating more of primary product N-Propynylurea. Further, product distribution. The correlations were made between
54
the primary product requires both Bronsted and Lewis acid product selectivity with surface and acidity characteristics
55
sites to convert it into secondary product through cyclo- individually to know effect of those factors on the reaction. The
56
isomerization reaction. Different amounts of HxWOx + y loading correlations were made between total pore volumes and yield
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22
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Figure 9. SEM images of (a) 10%WA, (b) 25%WA and (c) EDXA spectra of 10%WA sample.
29
30
31
Table 4. Correlation between volume accessibility factors and yields of
32 oxazole for the different catalyst samples
of products, but they showed very poor value of r = 0.188. To
33
check whether acidity alone is responsible for the reaction, the Samples Volume accessibility (mmol cm3 g-1) AXZ
34 B 3 TPV L 3 TPV B/L 3 TPV B + L 3 TPV
acidities of different acid loaded samples were correlated with
35
selectivity of aminoxazole. However, lower r values of 0.356, gA 0.044 0.035 0.644 0.079 28
36
0.602 and 0.558 for total, Bronsted and Lewis acidity respec- 5% WA 0.061 0.031 1.223 0.092 34
37 10% WA 0.082 0.020 2.248 0.102 66
tively were obtained. This confirms that acidity alone is not
38 15% WA 0.099 0.013 4.074 0.112 62
influencing on the selectivity of product. Also, the ratio of
39 20% WA 0.108 0.015 3.172 0.123 57
Bronsted to Lewis acidity showed improved r value with the 25% WA 0.095 0.014 2.023 0.109 44
40
enhanced selectivity of aminoxazole. The combination of two 30% WA 0.074 0.006 1.996 0.081 36
41 5% AlA 0.035 0.083 0.255 0.118 28
characteristics by multiplying pore volume and acidities
42 10% AlA 0.028 0.091 0.159 0.119 36
(volume accessibility) correlated with yield and selectivity of
43 Correl 0.863 0.576 0.912 0.441
aminoxazole and r values are given in Table 4. From the table, it
44 B- Bronsted, L-Lewis, B + L- sum of Bronsted and Lewis acidity; mmol g-1,
is clear that the improved r values for the appropriate
45 AXZ-aminoxazole, Reaction conditions: Reaction time, 60 min; catalyst
combination of B/L and pore volume showed r value 0.912 due amount, 0.5 g; reaction temperature, 120 8C; reactants molar ratio PA:Urea,
46
to higher pore volume and optimized B/L ratio. Even though 15 1:2.
47
and 20% WA loaded samples had more B/L value, their yield
48
and selectivity decreased due to coverage of pore. Hence the
49
orientation of primary product takes place in such way that in
50
both Lewis and Bronsted acid sites, exposure within the pore is
51 2.7 Reaction mechanism and different amide reactants:
hindered. However 10% WA loaded sample showed optimized
52
B/L and pore volume, which provides a better molecular The synthesis of aminoxazole using PA and amides involves
53
orientation in such a way that the intermediate molecule two steps. The first step is condensation between alcohol and
54
(primary product) gets easy access to both Bronsted and Lewis amide group called propargylation and the second is cyclisa-
55
acid sites within the pore to get cycloisomerize leading to tion of N-Propynylurea to aminoxazole called cycloisomeriza-
56
aminoxazole. tion. The propargylation step is favored in the presence of both
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Scheme 1. Plausible reactionmechanism for synthesis of aminoxazole by propragylation and cycloisomerization.
17
18
19
B and L acid sites. This incremental effect of either B or L on the substrates thiourea and urea showed maximum conversion and
20
reaction has been observed previously.[35,41,42] The catalysts used selectivity products, which is attributed to more nucleophilic
21
in this work have both B and L sites, which showed activity for nature of two nitrogen atoms lying beside carbonyl and
22
the conversion and selectivity of products. Plausible reaction sulfonyl group in urea and thiourea respectively. However,
23
mechanism in the Scheme 1 involves the protonation of amide substrates such as formamide, acetamide and benza-
24
alcohol leading to dehydration and immediate attack of amine mides showed lower conversion and selectivity compared
25
group of the amide to form N-propynylurea. On the other hand diamide substrates. It is due to less nucleophilic nitrogen in
26
cycloisomerization requires an optimum B/L ratio. The cyclo- amide functional group. Among the amides used benzamide
27
isomerization mechanism involves both B and L in close showed maximum conversion and yield of oxazole due to the
28
proximity in such a way that the availability of both acid sites presence of benzene ring causing electron donation, whereas
29
can be observed in the catalyst loaded with lower amounts the other two have less electron donating character. Hence
30
having access to both sites through the pore. The orientation acetamide and formamide showed almost similar conversion
31
of N-propynylurea in such prospect is superior in the optimized and selectivity but lesser than former diamides.
32
B/L and pore volume. The augmentation of one acid site over
33
the other at higher loading reduced the cycloisomerization due
34 2.8 Reusability and deactivation:
to the fact that the availability of B & L in close proximity is not
35
fulfilled. The reaction conditions were optimized to get The reusability and deactivation of catalyst samples were
36
maximum yield of oxazole and under similar conditions various performed repeatedly in the reaction under optimized con-
37
amide substrates were used with PA. Table 5 indicates that the ditions. After the completion of reaction, the catalyst was
38
separated by filtration after each use. The separated catalyst
39
was washed with ethanol (4ml) by stirring for 5 minutes to
40 Table 5. Comparison of conversion of different amide substrates and yield dissolve the reactant and product molecules adsorbed on
41 of aminoxazole through propargylation and cycloisomerization.
surface of catalyst. This was dried at 120 8C for 1.5 hours and
42 Reactant % Conver- % Yield % Yield of Product name used for 2nd cycle. The catalyst characteristics such as surface
43 sion of secondary
primary product
area and acidity do not alter much after fifth use and also
44
product conversion and selectivity of products remain unchanged
45
(Table 6). This system showed stable deactivation free catalytic
46 Formamide 62 14 48 5-methyl-1,3-oxa-
zole
activity up to 12th cycle, after that slight decreased activity of
47
Acetamide 64 13 51 2,5-dimethyl-1,3- dropdown to 52%, next 14th and 15th still decrease order of
48
oxazole activity. And activity decrease due to the loss of active site not
49 Benzamide 72 16 56 5-methyl-2- due to the adsorption of intermediate and coke.
50 phenyl-1,3-oxa-
51 zole
Urea 90 24 66 5-methyl-1,3-oxa-
52
zol-2-amine
3. Conclusions
53 Thiourea 91 23 68 5-methyl-1,3-thia- The optimized loading of oxometalates and metal chlorides
54 zol-2-amine
enhance the acidity with decreased surface characteristics of
55 Reaction conditions: Reaction time, 60 min; catalyst amount, 0.5 g; reaction gamma alumina. Among the different oxometalates, W pro-
56 temperature, 120 8C; reactants molar ratio PA:Urea, 1:2.
vides good activity by maintaining better Bronsted to Lewis
57

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 Full Papers

Table 6. Catalytic activity of used catalysts samples Keywords: Aminoxazole · Gamma alumina · N-Propynylurea ·
1
Oxometalates.
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50 Conflict of Interest
51
The authors declare no conflict of interest. Submitted: May 1, 2017
52
Accepted: July 10, 2017
53
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55
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57

ChemistrySelect 2017, 2, 6062 – 6069 6069  2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Wiley VCH
1721 / 95311
Montag, 24.07.2017
[S. 6069/6069] 1