Iron-based metal-organic framework, Fe(BTC): An effective dual-functional catalyst for oxidative cyclization of bisnaphthols and tandem synthesis of quinazolin-4(3H)-ones

Article abstract of DOI:10.1039/c5ra19013d

An iron-based metal-organic framework [Fe(BTC) (BTC: 1,3,5-benzenetricarboxylate)] has been shown to be an active and heterogeneous catalyst for both oxidative cyclization of methylenebisnaphthols and a modern tandem process (an in situ oxidation-aminal formation-oxidation sequence). Such a potential catalytic utility of Fe(BTC) makes it quite attractive for sustainable industrial chemistry.

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Iron-based Metal-Organic Framework, Fe(BTC): An Effective Two-
Function Catalyst for Oxidative Cyclization of Bisnaphthols and Tandem
Synthesis of Quinazolin-4(3H)-ones
Ali Reza Oveisi, Ahmad Khorramabadiꢀzad,* and Saba Daliran
Faculty of Chemistry, BuꢀAli Sina University, Hamedan, Iran
*Corresponding author: P.O. Box: 6517838683; Phone: +989188130018; Fax: +98(81)38257407; Eꢀmail address:
khoram@gmail.com (Ahmad Khorramabadiꢀzad)
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Abstract
Ironꢀbased metalꢀorganic framework [Fe(BTC) (BTC: 1,3,5ꢀbenzenetricarboxylate)] have
been shown to be an active and heterogeneous catalyst for both oxidative cyclization of
methylenebisnaphthols and a modern tandem process (an in situ oxidationꢀaminal formationꢀ
oxidation sequence). Such a potential catalytic utility of Fe(BTC) make it quite attractive for
sustainable industrial chemistry.
Introduction
Calixarenes are synthetic macrocyclic compounds consisting of methylenebisnaphthol or
bisphenol skeletons interconnected by methylene bridges.1 Oxidation of calixarenes can afford
bis(spirodienone) derivatives, which are attractive intermediates in forming functionalized
calixarenes.2 Although, several efforts for the oxidation of methylenebisnaphthols to the
corresponding spirodienones have been performed in the presence of different reagents such as
DDQ,3a phenyltrimethylammonium tribromide (PTMATB) or Br2,3b (diacetoxyiodo)benzene in
benzene,3c Ph3Bi,3d ChloramineꢀT or Nꢀchlorosuccinimide,3e Nꢀhydroxyimides3f and magnetic
coreꢀsell nanoparticleꢀsupported TEMPO (2,2,6,6ꢀtetramethylpiperidineꢀoxyl),3g the use of
environmentally benign, inexpensive reagents, milder reaction conditions, and decrease of
byproducts are highly demanded.
Quinazolinones and their derivatives have been investigated as biologically active molecules
exhibiting a wide range of pharmacological and biological activities such as antitumor,
anticonvulsant, antidiabetic and other anticipated activities.4 Recently, several synthetic
methodologies employing different types of catalysts such as I2,5a iridium,5b ruthenium,5c and αꢀ
5d₸
MnO2 have been reported for the preparation of quinazolinꢀ4(3H)ꢀones. These methods have
2

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some drawbacks such as the use of toxic and/or expensive catalysts or reaction media, not easily
available reagents, additives, tedious procedure, and timeꢀconsuming.
In recent years, a new class of porous materials such as metalꢀorganic frameworks (MOFs) and
porous organic polymers (POPs) have been deeply attracted due to their potential in applications
such as chemical catalysis,6 gas adsorption,7 sensing,8 conductivity9 and light harvesting sensitizer
in solar cells.10 Metalꢀorganic frameworks are porous crystalline hybrid materials, which are
constructed from organic struts and inorganic vertices (metal ions or clusters).6c, 11 Ironꢀbased
metalꢀorganic framework Fe(BTC) also known as Basolite F300, produced by BASF, has a semiꢀ
amorphous structure, a BrunauerꢀEmmettꢀTeller (BET) surface area of 1300ꢀ1600 m2/g with the
same chemical composition of MILꢀ100(Fe).12 The latter is comprised of BTC ligands coordinated
to iron octahedra [(Fe3ꢀꢁ3O) sharing a common vertex ꢁ3O]; this iron octahedra contain
coordinatively unsaturated metal sites (CUSs) participating in catalytic activities. However, it is
reasonable to expect that both Fe(BTC) and MIL(100)ꢀFe frameworks, have probably the same
building units, which can serve to activate substrates for chemical catalysis.12a Ironꢀbased MOF
particularly Fe(BTC) have been used for some reactions such as Friedel–Crafts type reactions,12b
ringꢀopening of styrene oxide with methanol and aniline,13a Knoevenagel condensation,13b
hydroxyalkylation reaction,13b aerobic oxidation of thiols to disulfides,13c and synthesis of
nitriles.13d
Although, many studies have been conducted on catalytic activity of metalꢀorganic
frameworks,12a, 13ꢀ14 only a small number of reports have explored their application in oxidative
cyclization and tandem reactions.6d, 15
Our interest in oxidative cyclization of bisnaphthols,3dꢀg quinazolinones6a,16 synthesis and porous
materials,6a motivated us to assay further the catalytic potential of metalꢀorganic framework
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Fe(BTC) for the oxidative cyclization of methylenebisnaphthols to the corresponding
spirodienones and a tandem process (an in situ oxidationꢀaminal formationꢀoxidation sequence)
for the conversion of benzyl alcohols to quinazolinꢀ4(3H)ꢀones.
Results and discussion
Initial studies were carried out using Fe(BTC) as catalyst for the oxidative cyclization of
bis(2ꢀhydroxyꢀ1ꢀnaphthyl)methane, as a model reaction, in different oxidation conditions (Table
1). It should be noted that Fe(BTC) was activated at 150 °C for 3 h prior to performing these
reactions. The oxidation cyclization reaction did not proceed in the presence and absence of
Fe(BTC) and 2,2,6,6ꢀtetramethylpiperidineꢀ1ꢀoxyl (TEMPO, a stable free nitroxyl radical)17
(Table 1, Entries 1ꢀ3). As indicated in Table 1, the best oxidant was proven to be hydrogen
peroxide (Entries 4ꢀ8). The optimum amount of catalyst was found to be 15 mg (3.75 mg of iron
from inductively coupled plasma (ICP) analysis. 0.067 mmol of Fe) (Table 1, Entry 6). Carrying
out the reaction at room temperature yielded the desired product in 30% after 12 h (Table 1, Entry
7). We have also investigated the effect of solvent (ethanol, acetonitrile, dichloromethane and
ethanol/water) and hence, acetonitrile was chosen as the best one (Table 2), affording the highest
yield (82%) of the product with less timeꢀconsuming than that ethanol and ethanol/water ones,
probably because it is relatively inert toward oxidation in the course of oxidation reactions. Also it
should be noted that acetonitrile is relatively a green solvent as compared with dichloromethane.
Table 1
Table 2
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Having completed the optimization conditions, we were encouraged to examine the oxidative
cyclization reaction on a range of bis(2ꢀhydroxyꢀ1ꢀnaphtyl)methane derivatives (Table 3). As
shown in Table 3, spirodienone derivatives bearing electronꢀwithdrawing and electronꢀdonating
substituents were obtained in reasonable yields. Each product was comprised of two sets of
diastereomers in nearly equal amounts, assigned by their 1H NMR spectra because of the different
anisotropic shielding effect of the ꢀꢀphenyl ring on vinylic Hꢀ3′ of two diastereomers; 1 and
2.3d,3e,3g
Table 3
A test for reusability of Fe(BTC) catalyst was then performed using oxidative cyclization of bis(2ꢀ
hydroxyꢀ1ꢀnaphtyl)methane, as a model reaction. After each run, the catalyst was removed by
centrifugation and washed with acetonitrile, ethyl acetate, and then acetone followed by drying at
150 °C. Fe(BTC) was reused for three cycles with a little loss in its efficiency (a yield of 76% and
68% of product was obtained after the second and third cycles, respectively), due to some blocked
sites by chemicals or partially damage of Fe(BTC) network (Table S1). Atomic absorption
spectroscopy (AAS) analysis of supernatant, at the end of reaction, showed 0.3 ppm Fe leaching
out which is less than 0.01% of the initial Fe present in the catalyst (0.13 and 0.17 ppm for the
second and the third cycles, respectively). Hence, hotꢀfiltration based leaching test was carried out
to understand the nature of active species of catalyst in the reaction. Therefore, Fe(BTC) catalyst
was removed from the reaction mixture after 4 h, while the supernatant ran further under the same
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conditions. There was almost no further yield of spirodienone, even after 8 h in the absence of
catalyst (See Table S1 in Electronic Supplementary Material (ESI)). Thus, the results confirmed
heterogeneity of the participated catalyst.
Powder Xꢀray diffraction (PXRD) patterns of the Fe(BTC) exhibit semiꢀamorphous nature of the
matter, resulting in relatively broad or overlapping peaks because of the small size of crystals and
its disordered structure (Fig. 1); its characterization by XRD being therefore limited, and no
crystal structural data of Fe(BTC) have yet been reported.
To get further information, we compare the PXRD patterns of fresh Fe(BTC) with the simulated
crystalline MILꢀ100(Fe) one (Fig. S1 & S2). As illustrated in Fig 1 and reported in literature,12a,
12b, 18
Fe(BTC) shows a broad diffraction peak at low angle, 2θ ~ 3.6° with d spacing of 21.9 Å.
The value is in agreement with the 220, 311 and 222 reflections observed in MILꢀ100(Fe),
suggesting the presence of some mesopores cages in the Fe(BTC) [Strong peaks at low angle (2θ
= 2ꢀ4°)19 XRD patterns manifest the presence of mesoporous structure], consistent with pore
diameter 21 Å obtained from nitrogen adsorption measurements.12a,13 Moreover, no diffraction
peak appeared in PXRD pattern of Fe(BTC) with d spacing of 42.3 Å, 2θ ~ 2.0°, corresponding to
the 111 reflection, characteristic of the largest mesopores cages (the largest d spacing of the
structure, pore diameter of 29 Å) in MILꢀ100(Fe). However, the XRD patterns indicate that
Fe(BTC) contain just the smallest mesopores cages established in the MILꢀ100(Fe). Also, a broad
peak (2θ ~ 10.6°) shown in the PXRD patterns of Fe(BTC) correlates with the 822, 840 and 911
reflections of observed in MILꢀ100(Fe).
Comparison of the PXRD of the fresh and the reused catalyst indicates some decrease in the peak
intensity of the reused Fe(BTC), suggesting an increase of disordering in the structure or a change
in the mesopores content (poreꢀfilling effect) (as shown in Fig. 1, fresh and reused Fe(BTC)ꢀB).
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Also Fig.1 shows a slight shift of the main peak positions of the XRD, after reusing, to lower 2θ
values (larger dꢀspacing), suggesting that there is an expansion of the framework in response to
the chemicals. It might be attributed to the strain effect of the framework upon strong coordination
of reactants or products within the MOF during the reaction. This is consistent with breathing
effect in MOFs.20
As scanning electron microscopy (SEM) images shows (Fig. 2), the morphology of the Fe(BTC)
was retained under the reaction conditions. SEM images of Fe(BTC) showed agglomerates of
spheroid particles, with particleꢀsize ranging from 45 to 105 nm.
A comparison of the FTꢀIR (See Fig. S3 & S4) of the fresh and reused (the first and the last
cycles) catalyst indicated a slightly higher relative intensity of C=O band about 1710 cmꢀ1 for the
latter, which may be attributed to small amount of spirodienones or impurity along with the free
carboxylic groups, is in agreement with the observed changes in powder XRD patterns.
Fig. 1
Fig. 2
When TEMPO was used as a radical scavenger combined with Fe(BTC) and H2O2, significant
decrease was observed in yield of spirodienone (Table 1, Entry 8). This reveals that the reaction
proceeds through the formation of radical species.12c, 21 Based on literature survey3g, 12a, 12c and this
observation, we proposed a mechanism for the oxidative cyclization of methylenebisnaphthols as
shown in Scheme 1. At first, hydrogen peroxide molecules coordinate to those Fe(III) sites which
are not saturated with the framework carboxylate groups, to give Fe(III)ꢀOOH complexes (I).
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Then the homolytic cleavage of the peroxidic OꢀO bond in intermediate (I) produces the active
species
(HOꢀO·, II) followed by abstracting a hydrogenꢀatom from methylenbisnaphthol to afford radical
intermediate (III). Abstraction of another hydrogen atom from (III) result in formation of a
diradical intermediate formation (IV), which proceed to give the product. Subsequently, Fe(II) is
reꢀoxidized to Fe(III) active sites via an electron transfer to hydrogen peroxide.
Scheme 1
We next examined the potential catalytic activity of this metalꢀorganic framework for a modern
tandem process: quinazolinꢀ4(3H)ꢀones synthesis by the reaction of benzyl alcohols and oꢀ
aminobenzamide in the presence of oxidant (Table 4 and 5). Owing to optimization conditions, at
the outset, benzyl alcohol reacted with oꢀaminobenzamide as a model reaction, which afforded 2ꢀ
phenylquinazolinꢀ4(3H)ꢀone (Table 4). As indicated in Table 4, the use of TBHP (tertꢀbutyl
hydroperoxide), as an oxidant, gave a higher yield with respect to hydrogen peroxide (Table 4,
Entries 1 and 2). It might be due to instability of H2O2 compared with that of TBHP in catalytic
reaction conditions. The best results were obtained with DMSO (dimethyl sulfoxide) as solvent
(Table 4, Entries 5ꢀ8), affording the highest yield (81%) of the product as compared with the other
solvents. It should be noted that DMSO could act as a mild oxidant, in addition its solvent role.
The amount of Fe(BTC) was optimized to be 15 mg (0.067 mmol Fe) in order to reduce the
consumed catalyst and to increase the product yield (Table 4, Entry 5). The effect of temperature
on this reaction was also investigated, which showed that the reaction should be performed at 60
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°C to get a high yield (Table 4, Entry 5). As indicated in Table 4, the reaction did not proceed by
DMSO without TBHP (Table 4, Entry 9).
Table 4
In the next step, the optimal condition for the preparation of quinazolinꢀ4(3H)ꢀone derivatives was
evaluated. The results showed good versatility of this method for neutral, electron rich and
electron deficient groups such as H, Me, OMe, Cl, and NO2 (Table 5). An additional test was also
carried out to examine the reusability of the catalyst, using a model reaction of benzyl alcohol with
oꢀaminobenzamide. The Fe(BTC) was found to be an efficient and reusable catalyst, with a slight
decrease in its activity (Table 5, Entry 1). AAS analysis of supernatant, at the end of reaction,
showed 0.7 ppm Fe leaching out for the reaction, attributing to 0.02% of the initial Fe present in
the catalyst. Some decrease in the peak intensity of PXRD pattern of the reused Fe(BTC) was
observed as compared with that of fresh Fe(BTC) one (see Fig. 1), suggesting an increase of
disordering in the structure or a change in the mesopores content (poreꢀfilling effect).
Table 5
According to literature survey, the catalyst sites are the weak Brønsted acid sites (demonstrated by
IR pyridine adsorption,12a, 22 which may be contributed to unknown impurities or uncoordinated BTC
carboxylic groups), the redoxꢀactive12c and Lewis acid13a iron sites. So, this catalyst can act usefully
both as acid and redox active sites platform.
Based on literature survey and the above agrument, we introduce a mechanism for the tandem
process as follows (Scheme 2). At first, the coordination of tꢀBuOOH to the Fe(III) sites afford
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tꢀBuꢀOOꢀFe(III) species (A) which subsequently produces the active species (tꢀBuꢀOꢀO·, II).
Then, abstraction of a hydrogenꢀatom from benzyl alcohol gives a radical intermediate (C). As the
proposed mechanism shows, three the pathways: (1), (2) and (3) give the aldehyde product (E).
The pathway (1) passes through the carbocation formation with the concomitant reduction of
Fe(III) to Fe(II). The pathway (2) proceeds via a gemꢀdiolꢀlike structure formation, and
dehydration. The other pathway involves a hydrogenꢀatom abstraction from (C) by the tꢀBuOO
·
and tꢀBuO radicals. After that, activated aldehyde reacts with oꢀaminobenzamide to give (G),
·
which in turn, afford aminal intermediate. Finally, oxidation of aminal intermediate results in
quinazolinꢀ4(3H)ꢀone formation followed by oxidation of Fe(II) to Fe(III) accomplishes with an
electron transfer to tꢀBuOOH.
Scheme 2
Conclusion
We have further developed the application of porous ironꢀbased MOF as a heterogeneous and
catalytically active species for the oxidative cyclization of methylenebisnaphthols, leading to the
corresponding two diastereomers in nearly equal amounts (isomers 1 and 2), as well as a modern
tandem process (an in situ oxidationꢀaminal formationꢀoxidation sequence) for the conversion of
benzyl alcohols to quinazolinꢀ4(3H)ꢀones. The catalyst can usefully act as both acid and redox
active sites platform. This work consistently has the advantages such as availability of MOF,
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inexpensive catalyst, mild reaction conditions, reasonable yields, and simple experimental
procedures.
Acknowledgment
The authors gratefully acknowledge the financial support for this work from the BuꢀAli Sina
University, Hamedan, Iran.
Notes and references
₸During the preparation of this work Wang and et al. published a paper related to quinazolinones
synthesis using αꢀMnO2 as a catalyst.5d
1
(a) P. E. Georghiou, M. Ashram, H. J. Clase and J. N. Bridson, J. Org. Chem., 1998, 63, 1819ꢀ1826; (b) S.
Chowdhury and P. E. Georghiou, J. Org. Chem., 2002, 67, 6808ꢀ6811; (c) F. Davis and S. Higson, in
Macrocycles: Construction, Chemistry and Nanotechnology Applications, John Wiley & Sons, Ltd, Chichester,
UK, 2011, ch. 5, pp. 126ꢀ189.
2
3
(a) S. E. Biali, Synlett, 2003, 1, 0001ꢀ0011; (b) R. L. Varma, V. B. Ganga and E. Suresh, J. Org. Chem., 2007, 72,
1017ꢀ1019; (c) S. B. Nimse and T. Kim, Chem. Soc. Rev., 2013, 42, 366ꢀ386.
(a) T. R. Kasturi, B. Rajasekhar, G. J. Raju, G. M. Reddy, R. Sivaramakrishnan, N. Ramasubbu and K.
Venkatesan, J. Chem. Soc., Perkin Trans. 1, 1984, 2375ꢀ2382; (b) P. E. Georghiou, M. Ashram, H. J. Clase and J.
N. Bridson, J. Org. Chem., 1998, 63, 1819ꢀ1826; (c) D. J. Bennett, F. M. Dean, G. A. Herbin, D. A. Matkin, A. W.
Price and M. L. Robinson, J. Chem. Soc., Perkin Trans. 1, 1980, 1978ꢀ1985; (d) A. Khoramabadiꢀzad, I. Yavari,
A. Shiri and A. Bani, J. Heterocycl. Chem., 2008, 45, 1351ꢀ1358; (e) A. Khoramabadiꢀzad, A. Shiri, F.
DerakhshanꢀPanah and Z. Salimi, Mol. Diversity, 2010, 14, 829ꢀ832; (f) A. Khoramabadiꢀzad, S. Mohammadi and
M. Azadmanesh, Z. Naturforsch. B, 2014, 69, 444ꢀ450; (g) A. Khorramabadiꢀzad, S. Daliran and A. R. Oveisi, C.
R. Chim., 2013, 16, 972ꢀ976.
4
(a) S. Eguchi, in Bioactive heterocycles I, , ed. S. Eguchi, SpringerꢀVerlag, BerlinꢀHeidelberg, Germany, 2006,
vol. 6, ch. 2, pp. 113ꢀ156; (b) V. Sridharan, P. A. Suryavanshi and J. C. Menéndez, Chem. Rev., 2011, 111, 7157ꢀ
7259.
11

RSC Advances
Page 12 of 22
View Article Online
DOI: 10.1039/C5RA19013D
5
6
(a) W. Ge, X. Zhu and Y. Wei, RSC Adv., 2013, 3, 10817ꢀ10822; (b) J. Zhou and J. Fang, J. Org. Chem., 2011, 76,
7730ꢀ7736; (c) A. J. A. Watson, A. C. Maxwell and J. M. J. Williams, Org. Biomol. Chem., 2012, 10, 240ꢀ243; (d)
Z. Zhang, M. Wang, C. Zhang, Z. Zhang, J. Lu and F. Wang, Chem. Commun., 2015, 51, 9205ꢀ9207.
(a) A. R. Oveisi, K. Zhang, A. Khorramabadiꢀzad, O. K. Farha and J. T. Hupp, Sci. Rep., 2015, 5, 10621ꢀ10628; (b)
J. Lee, O. K. Farha, J. Roberts, K. A. Scheidt, S. T. Nguyen and J. T. Hupp, Chem. Soc. Rev., 2009, 38, 1450ꢀ1459;
(c) A. Dhakshinamoorthy and H. Garcia, Chem. Soc. Rev., 2014, 43, 5750ꢀ5765; (d) M. H. Beyzavi, N. A.
Vermeulen, A. J. Howarth, S. Tussupbayev, A. B. League, N. M. Schweitzer, J. R. Gallagher, A. E. PlateroꢀPrats,
N. Hafezi, A. A. Sarjeant, J. T. Miller, K. W. Chapman, J. F. Stoddart, C. J. Cramer, J. T. Hupp and O. K. Farha, J.
Am. Chem. Soc., 2015, 137, 13624ꢀ13631; (e) P. Kaur, J. T. Hupp and S. T. Nguyen, ACS Catal., 2011, 1, 819ꢀ835.
(a) A. M. Fracaroli, H. Furukawa, M. Suzuki, M. Dodd, S. Okajima, F. Gándara, J. A. Reimer and O. M. Yaghi, J.
Am. Chem. Soc., 2014, 136, 8863ꢀ8866; (b) X. Zhang, Y.ꢀZ. Zhang, D.ꢀS. Zhang, B. Zhu and J.ꢀR. Li, Dalton
Trans., 2015, 44, 15697ꢀ15702; (c) N. Nijem, H. Bluhm, M. L. Ng, M. Kunz, S. R. Leone and M. K. Gilles, Chem.
Commun., 2014, 50, 10144ꢀ10147; (d) J. A. Mason, M. Veenstra and J. R. Long, Chem. Sci., 2014, 5, 32ꢀ51.
(a) X. Zhu, H. Zheng, X. Wei, Z. Lin, L. Guo, B. Qiu and G. Chen, Chem. Commun., 2013, 49, 1276ꢀ1278; (b) Z.
Hu, B. J. Deibert and J. Li, Chem. Soc. Rev., 2014, 43, 5815ꢀ5840.
7
8
9
(a) Y. Shen, X.ꢀF. Yang, H.ꢀB. Zhu, Y. Zhao and W.ꢀS. Li, Dalton Trans., 2015, 44, 14741ꢀ14746; (b) P.
Ramaswamy, N. E. Wong and G. K. H. Shimizu, Chem. Soc. Rev., 2014, 43, 5913ꢀ5932.
10 (a) D. Y. Lee, E.ꢀK. Kim, C. Y. Shin, D. V. Shinde, W. Lee, N. K. Shrestha, J. K. Lee and S.ꢀH. Han, RSC Adv.,
2014, 4, 12037ꢀ12042; (b) D. Y. Lee, I. Lim, C. Y. Shin, S. A. Patil, W. Lee, N. K. Shrestha, J. K. Lee and S.ꢀH.
Han, J. Mater. Chem. A, 2015, 3, 22669ꢀ22676; (c) H.ꢀJ. Son, S. Jin, S. Patwardhan, S. J. Wezenberg, N. C. Jeong,
M. So, C. E. Wilmer, A. A. Sarjeant, G. C. Schatz, R. Q. Snurr, O. K. Farha, G. P. Wiederrecht and J. T. Hupp, J.
Am. Chem. Soc., 2013, 135, 862ꢀ869.
11 J. Liu, L. Chen, H. Cui, J. Zhang, L. Zhang and C.ꢀY. Su, Chem. Soc. Rev., 2014, 43, 6011ꢀ6061.
12 (a) A. Dhakshinamoorthy, M. Alvaro, P. Horcajada, E. Gibson, M. Vishnuvarthan, A. Vimont, J.ꢀM. Grenèche, C.
Serre, M. Daturi and H. Garcia, ACS Catal., 2012, 2, 2060ꢀ2065; (b) P. Horcajada, S. Surble, C. Serre, D.ꢀY. Hong,
Y.ꢀK. Seo, J.ꢀS. Chang, J.ꢀM. Greneche, I. Margiolaki and G. Ferey, Chem. Commun., 2007, 2820ꢀ2822; (c) A.
Dhakshinamoorthy, M. Alvaro and H. Garcia, J. Catal., 2012, 289, 259ꢀ265.
13 (a) A. Dhakshinamoorthy, M. Alvaro and H. Garcia, Chem Eur. J., 2010, 16, 8530ꢀ8536; (b) M. Opanasenko, A.
Dhakshinamoorthy, J. Čejka and H. Garcia, ChemCatChem, 2013, 5, 1553ꢀ1561; (c) A. Dhakshinamoorthy, M.
Alvaro and H. Garcia, Chem. Commun., 2010, 46, 6476ꢀ6478; (d) A. Rapeyko, M. J. Climent, A. Corma, P.
Concepción and S. Iborra, ChemSusChem, 2015, 8, 3270ꢀ3282.
14 (a) M. H. Beyzavi, R. C. Klet, S. Tussupbayev, J. Borycz, N. A. Vermeulen, C. J. Cramer, J. F. Stoddart, J. T. Hupp
and O. K. Farha, J. Am. Chem. Soc., 2014, 136, 15861ꢀ15864; (b) J. E. Mondloch, M. J. Katz, W. C. Isley Iii, P.
Ghosh, P. Liao, W. Bury, G. W. Wagner, M. G. Hall, J. B. DeCoste, G. W. Peterson, R. Q. Snurr, C. J. Cramer, J. T.
Hupp and O. K. Farha, Nature Mater., 2015, 14, 512ꢀ516.
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DOI: 10.1039/C5RA19013D
15 (a) A. Dhakshinamoorthy and H. Garcia, ChemSusChem, 2014, 7, 2392ꢀ2410; (b) Y. Zhang, B. Li and S. Ma, Chem.
Commun., 2014, 50, 8507ꢀ8510; (c) G. H. Dang, Y. T. H. Vu, Q. A. Dong, D. T. Le, T. Truong and N. T. S. Phan,
Appl. Catal., A, 2015, 491, 189ꢀ195.
16 (a) H. R. Shaterian and A. R. Oveisi, Chin. J. Chem., 2009, 27, 2418ꢀ2422; (b) H. R. Shaterian, A. R. Oveisi and M.
Honarmand, Synth. Commun., 2010, 40, 1231ꢀ1242.
17 Q. Cao, L. M. Dornan, L. Rogan, N. L. Hughes and M. J. Muldoon, Chem. Commun., 2014, 50, 4524ꢀ4543.
18 G. Majano, O. Ingold, M. Yulikov, G. Jeschke and J. PerezꢀRamirez, CrystEngComm, 2013, 15, 9885ꢀ9892.
19 (a) G. Férey, C. MellotꢀDraznieks, C. Serre, F. Millange, J. Dutour, S. Surblé and I. Margiolaki, Science, 2005, 309,
2040ꢀ2042; (b) H.ꢀj. Zhang, S.ꢀd. Qi, X.ꢀy. Niu, J. Hu, C.ꢀl. Ren, H.ꢀl. Chen and X.ꢀg. Chen, Catal. Sci. Technol.,
2014, 4, 3013ꢀ3024.
20 (a) F. Millange, C. Serre, N. Guillou, G. Férey and R. I. Walton, Angew. Chem. Int. Ed., 2008, 47, 4100ꢀ4105; (b)
M. H. Alkordi, Y. Liu, R. W. Larsen, J. F. Eubank and M. Eddaoudi, J. Am. Chem. Soc., 2008, 130, 12639ꢀ12641;
(c) G. Ferey and C. Serre, Chem. Soc. Rev., 2009, 38, 1380ꢀ1399.
21 M. O. Ratnikov and M. P. Doyle, J. Am. Chem. Soc., 2013, 135, 1549ꢀ1557.
22 C. Volkringer, H. Leclerc, J.ꢀC. Lavalley, T. Loiseau, G. Férey, M. Daturi and A. Vimont, J. Phys. Chem. C, 2012,
116, 5710ꢀ5719.
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Schemes, Figures, and Tables captions
Table 1 The oxidative cyclization of bis(2ꢀhydroxyꢀ1ꢀnaphtyl)methane using Fe(BTC) as
heterogonous catalyst
Tabl 2 The oxidative cyclization of bis(2ꢀhydroxyꢀ1ꢀnaphthyl)methane using different types of
solvent in the presence of Fe(BTC)
Table 3 The oxidative cyclization of bisnaphthols using Fe(BTC)
Fig. 1 PXRD patterns of a) fresh (activated at 150 °C), b), and d) reused Fe(BTC) in the oxidative
cyclization of bis(2ꢀhydroxyꢀ1ꢀnaphthyl)methanes (reused Fe(BTC)ꢀB, green) and the
quinazoineꢀ4(3H)ꢀones synthesis (reused Fe(BTC)ꢀQ, blue), respectively.
Fig. 2 SEM images of a) fresh and b) reused Fe(BTC)
Scheme 1 Proposed mechanism for the oxidative cyclization of bisnaphthols in the presence of
Fe(BTC)
Table 4 Tandem catalytic synthesis of 2ꢀphenylquinazolinꢀ4(3H)ꢀone using Fe(BTC)
Table 5 Tandem catalytic synthesis of quinazolinꢀ4(3H)ꢀone derivatives using Fe(BTC)
Scheme 2 Proposed mechanism for the quinazolineꢀ4(3H)ꢀones from benzyl alcohols in the
presence of Fe(BTC)
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Table 1 The oxidative cyclization of bis(2-hydroxy-1-naphthyl)methane using Fe(BTC) as a heterogonous catalysta
Entry
Fe(BTC)b
Fe (mol%)
Oxidant
Time (h)
Yield
(%)c
-
(mg)
15
15
-
1
2
13
13
-
-
12
12
12
8
TEMPO
H2O2
H2O2
H2O2
H2O2
H2O2
H2O2
-
3
trace
55
4
8
7
5
25
15
15
15
22
13
13
13
7
78
6
8
82
7d
8e
12
12
30
30
a Reaction conditions: C21H16O2 (0.5 mmol), Fe(BTC) as catalyst, oxidant (1.6 mmol, 3.2 eq.), and acetonitrile (5 ml) at 40 °C.
b Fe(BTC) is contain of 25% of Fe.
c Total yield (purified by column chromatography).
d Reaction was carried out in room temperature.
e 1.5 equiv. of TEMPO was used
.
Table 2 The oxidative cyclization of bis(2-hydroxy-1-naphthyl)methane
using different types of solvent in the presence of Fe(BTC)
Entry
Solvent
EtOH
Time (h)
Yield (%)
1
2
10
10
22
31
EtOH/H2O
(30:70)
3
4
CH2Cl2
CH3CN
8
8
76
82
a Reaction conditions: C21H16O2 (0.5 mmol), Fe(BTC) (15 mg, 0.067 mmol Fe),
H2O2 (1.6 mmol), and solvent (5 ml) at 40 °C.
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Table 3 The oxidative cyclization of bisnaphthols using Fe(BTC)a
Entry
X
Time
(h)
Yield
(%)b
M.p. (°C)
Diastereomeric
ratio (%)c
Found
Lit [10-13]
170-171
1
2
1
2
1
2
1
2
3
4
5
6
7
8
H
8
82
80
76
81
78
85
80
78
170-171
-
-
C6H5
8
209-211
199-201
187-189
228-231
208-209
214-216
219-221
264-266
210-211
198-200
187-188
229-230
204-206
214-215
218-223
263-264
227-229
225-227
194-196
195-197
145-146
146-148
75
50
50
55
55
50
55
25
50
50
45
45
50
45
4-CH3C6H4
3-CH3C6H4
2-CH3OC6H4
2,4-Cl2C6H3
4-FC6H4
8
228-230
225-227
194-196
195-197
145-146
147-149
10
7
9
10
8
2-BrC6H4
a Reaction conditions: bisnaphthol (0.5 mmol), Fe(BTC) (15 mg, 0.067 mmol Fe), H2O2 (1.6 mmol, 3.2 eq.), and acetonitrile (5 ml) at
40 °C.
b Yield refer to the isolated pure products (isomer 1 + isomer 2).
c The ratio of the two diastereomers (isomer 1 and isomer 2) is distinguished by 1H NMR
.
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Fig. 1 PXRD patterns of a) fresh (activated at 150 °C, red), b), and d) reused Fe(BTC) in the oxidative
cyclization of bis(2-hydroxy-1-naphthyl)methanes (reused Fe(BTC)-B, green) and the quinazoine-4(3H)-
ones synthesis (reused Fe(BTC)-Q, blue), respectively.
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Fig. 2 SEM images of a) fresh and b) reused Fe(BTC)
HO-O
OH
OH
X
II
O
H
Fe(III)
Fe(III)
O
Fe(II)
I
H2O2
H
O
HO
H2O
X
OH
III
H2O2
Fe(II)
HO
O
O
X
H2O
O
O
IV
X
:
Fe(III)
Fe(BTC)
X: H, Ar
Product
Scheme 1 Proposed mechanism for the oxidative cyclization of bisnaphthols in the presence of Fe(BTC)
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Table 4 Tandem catalytic synthesis of 2-phenylquinazolin-4(3H)-one using Fe(BTC)a
Entry
Fe(BTC)b
(mg)
Fe
(mo%)
Oxidant
T (oC)
Solvent
Time
(h)
Yield
(%)c
1
2
3
4
5
6
7
8
9
15
15
15
15
15
15
10
22
15
13
13
13
13
13
13
9
H2O2
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
-
40
40
60
60
60
85
60
60
60
CH3CN
CH3CN
CH3CN
Xylene
DMSO
DMSO
DMSO
DMSO
DMSO
14
14
14
14
14
14
14
14
14
21
39
47
30
81
78
75
82
-
20
13
a Reaction conditions: benzyl alcohol (1.5 mmol), o-aminobenzamide (0.5 mmol), oxidant (2 mmol), solvent (3-5 ml),
Fe(BTC) (10-22 mg).
b 15 mg Fe(BTC) is equal to 3.75 mg Fe (0.067 mmol Fe).
c Yield refer to the isolated pure products.
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Table 5 Tandem catalytic synthesis of quinazolin-4(3H)-
one derivatives using Fe(BTC)a
Entry
X
Time (h)
Yield (%)
1
2
3
4
5
H
14
15
15
14
12
81, 70b
74
Me
MeO
NO2
Cl
70
68
61
a Reaction conditions: o-aminobenzamide (0.5 mmol)benzyl
alcohol (1.5 mmol), TBHP (2 mmol), DMSO (3 ml), Fe(BTC) (15
mg, 0.067 mmol), at 60 °C.
b Reusability of Fe(BTC) in the second run.
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Scheme 2 Proposed mechanism for the quinazoline-4(3H)-ones from benzyl alcohols in the presence of
Fe(BTC)
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Fe(BTC) Catalyzed Synthesis of Spirodienones and Quinazolin-4(3H)-ones
41x23mm (300 x 300 DPI)