Next Article in Journal
Current Trends in the Synthesis of Practically Important Five-Membered Boracarbocycles by Transmetalation of Aluminacarbocycles with Boron Halides
Previous Article in Journal
New Photochemical Properties of Azidoaniline and Ciprofloxacin
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Chemistry Proceedings
Volume 12
Issue 1
10.3390/ecsoc-26-13645
chemproc-logo
Submit to this Journal
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Proceeding Paper

Chemo-Selective Protection of Aldehydes Functional Group Catalyzed by MOFs †

by
Sakineh Mahdian
,
Leila Panahi
and
Mohammad Reza Naimi-Jamal
*
Department of Chemistry, Research Laboratory of Green Organic Synthesis & Polymers, Iran University of Science and Technology, Tehran 16846-13114, Iran
*
Author to whom correspondence should be addressed.
†
Presented at the 26th International Electronic Conference on Synthetic Organic Chemistry, 15–30 November 2022; Available online: https://sciforum.net/event/ecsoc-26.
Chem. Proc. 2022, 12(1), 68; https://doi.org/10.3390/ecsoc-26-13645
Published: 16 November 2022
(This article belongs to the Proceedings of The 26th International Electronic Conference on Synthetic Organic Chemistry)
Browse Figure
Versions Notes

Abstract

A metal-organic framework Zn2(BDC)2(DABCO) was employed as a reusable heterogeneous acidic catalyst in the acylation reaction of various benzaldehydes with acetic anhydride under microwave irradiation. The outstanding features of this efficient solvent-free method are short reaction time, ease of product separation, greatest yields, and the ability to reuse the catalyst several times.

1. Introduction

In order to carry out the selective reactions in the desired position during multi-step procedures, it is necessary to protect parts of the molecules with various functional groups so that they do not participate in the main reaction and also prevent the production of side products [1]. Compounds containing aldehydic carbonyl groups are commonly protected by transforming them into acetals, dithioacetal, oxathioacetals, and diacetate (acylal) [2]. The characteristic of stability in neutral environments, the comfort of preparation, and multiple applications, including as initiating materials for the Diels–Alder reaction, intermediates in industrial processes, and geminal diacetates (acylals), have been highlighted among the various protection approaches of aldehydes [2,3]. Ethanethiol, acetic anhydride, and alcohol are some of the reagents used to protect aldehydes [4]. The use of protic or Lewis acid catalysts such as AC-N-SO4H [5], magnetic Fe3O4@C-600-SO3H microspheres [6], SiO2-NaHSO4 [7], STO/Al-P [8], poly(p-hydroxybenzaldehyde-co-p-phenol sulfonate) [9], tungstosulfonic acid (TSA) [3], hexabromoacetone (HBA) [1], (MNPs-PSA) [2], and 5,10,15,20-tetrakis(pentafluorphenylporphyrin) iron (III) chloride (Fe5F) [10] play an essential role in the better progress of the chemo-selective reactions. Heterogeneous acid catalysts have advantages over their homogeneous types, such as simple separation via straightforward filtration, possible reuse, and convenient provision, which make them an ideal choice for catalyzing synthesis reactions [4]. Metal–organic frameworks (MOFs) are a new type of hybrid material composed of metal nodes and organic ligands [11,12]. Since ligands and constituent metals are available in a wide variety, these versatile and adjustable crystalline structures can be used for a variety of applications [13], including gas absorption and storage [14,15], hydrocarbon separation [16], luminescence [17,18], sensors [19,20], drug delivery [21,22], energy storage [23], enzyme encapsulation [24,25], and catalysts [26]. In recent years, many studies have discussed the application of MOFs as heterogeneous catalysts in multi-step synthesis reactions, especially in the liquid phase. It has been found that the stability of the structure of MOFs in different chemical conditions, the presence of positive metal ions, high porosity, and high surface-to-volume ratio, and the various preparation methods significantly contribute to the appropriate catalytic performance of the MOFs [27]. Continuing our efforts to investigate the catalytic performance of MOFs, we report a simple and efficient approach for protecting the carbonyl group in a range of benzaldehyde compounds using M2(BDC)2(DABCO) as a Lewis acid catalyst under microwave irradiation conditions (Scheme 1). To investigate the catalytic performance of transition metals, such as Ni, Cu, Co, and Zn in M2(BDC)2(DABCO) structures such as Lewis acid catalysts, we investigated benzaldehyde acylation in the presence of Ni2(BDC)2(DABCO), Cu2(BDC)2(DABCO), Co2(BDC)2(DABCO), and Zn2(BDC)2(DABCO).

2. Materials and Methods

For the protection of benzaldehydes with acetic anhydride under microwave irradiation, the general procedure was as follows: 3 mmol acetic anhydrides, 1 mmol benzaldehyde, and 0.03 g M2(BDC)2(DABCO) (M = Ni, Cu, Co, and Zn) catalyst were added into a flask and then exposed to microwave irradiation. The progress of the reaction was observed by GC. After the ending of the reaction, dichloromethane (3 × 5 mL) was added to the reaction mixture and the catalyst was separated via filtration. The organic phase was washed with saturated KHCO3 solution (15 mL), dried over anhydrous MgSO4, and concentrated under reduced pressure in a rotary evaporator to afford the crude product. The yields were isolated and calculated as mmol of purified product with respect to mmol of initial benzaldehydes.

3. Results and Discussion

To determine which catalyst is the best for the acylation of benzaldehyde, 1 mmol benzaldehyde was examined with 3 mmol acetic anhydrides in the presence of 10 mg MOFs such as Ni2(BDC)2(DABCO), Cu2(BDC)2(DABCO), Co2(BDC)2(DABCO), and Zn2(BDC)2(DABCO), under both room temperature and microwave conditions (Table 1).
With respect to the time and reaction yield, Zn2(BDC)2(DABCO) was the best among the others under microwave irradiation conditions. In addition, the reaction in solvent-free conditions and ambient temperature in the presence of different amounts of Zn2(BDC)2(DABCO) catalyst, including 10, 20, 30, and 40 mg, and various quantities of acetic anhydride, including 1, 2, 3, and 4 mmol, was investigated. The results indicated that the optimum amounts of catalyst and acetic anhydride are 30 mg and 3 mmol, respectively. To assess the solvent effect, acylation of benzaldehyde (1 mmol) with acetic anhydride (3 mmol) in the presence of 30 mg of Zn2(BDC)2(DABCO) catalyst was analyzed as a model reaction under different environmental conditions (Table 2).
In terms of time and reaction yield, the best conditions were found in entry 7. The reaction was completed in just 7 min under microwave irradiation and in the solvent-free condition with 30 mg of Zn2(BDC)2(DABCO) used as the catalyst. Inspired by our introductory results, we subjected numerous amounts of benzaldehydes to acylation under the optimized conditions with the Zn2(BDC)2(DABCO) catalyst as summarized in Table 3.

4. Conclusions

In summary, it was found that the catalytic activity of the organic metal framework Zn2(BDC)2(DABCO) under solvent-free conditions and microwave irradiation is significant in the protection reactions of benzaldehydes. The unique advantages of this protocol include short reaction time, ability to recover and reuse the catalyst, solvent-free conditions, high efficiency, and simple method.

Author Contributions

Conceptualization, S.M.; methodology, S.M. and L.P.; software, S.M. and L.P.; validation, L.P. and M.R.N.-J.; formal analysis, S.M.; investigation, S.M.; resources, S.M.; data curation, S.M. and L.P.; writing—original draft preparation, S.M.; writing—review and editing, S.M., L.P., and M.R.N.-J.; visualization, L.P.; supervision, M.R.N.-J.; project administration, M.R.N.-J.; funding acquisition, M.R.N.-J. All authors have read and agreed to the published version of the manuscript.

Funding

This work has received partial support from Iran University of Science and Technology.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Data is contained within the article.

Acknowledgments

The authors gratefully acknowledge Iran University of Science and Technology (IUST) for partial financial support of this work.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Chaiseeda, K.; Chantharadet, L.; Chavasiri, W. Utilization of hexabromoacetone for protection of alcohols and aldehydes and deprotection of acetals, ketals, and oximes under UV irradiation. Res. Chem. Intermed. 2017, 44, 1305–1323. [Google Scholar] [CrossRef]
  2. Sajjadifar, S.; Nasri, P. N-Propylsulfamic acid supported onto magnetic Fe3O4 nanoparticles (MNPs-PSA) as a green and reusable heterogeneous nanocatalyst for the chemoselective preparation and deprotection of acylals. Res. Chem. Intermed. 2017, 43, 6677–6689. [Google Scholar] [CrossRef]
  3. Kalla, R.M.N.; Kim, M.R.; Kim, Y.N.; Kim, I. Tungstosulfonic acid as an efficient solid acid catalyst for acylal synthesis for the protection of the aldehydic carbonyl group. New J. Chem. 2016, 40, 687–693. [Google Scholar] [CrossRef]
  4. Rezayati, S.; Ramazani, A. Metal-based Lewis acid catalysts for conversion of a variety of aldehydes with acetic anhydride to gem 1,1-diacetates. Res. Chem. Intermed. 2020, 46, 3757–3799. [Google Scholar] [CrossRef]
  5. Liu, W.; Guo, R.; Peng, G.; Yin, D. Sulfuric Acid Immobilized on Activated Carbon Aminated with Ethylenediamine: An Efficient Reusable Catalyst for the Synthesis of Acetals (Ketals). Nanomaterials 2022, 12, 1462. [Google Scholar] [CrossRef]
  6. Yuan, C.; Wang, X.; Yang, X.; Alghamdi, A.A.; Alharthi, F.A.; Cheng, X.; Deng, Y. Sulfonic acid-functionalized core-shell Fe3O4@carbon microspheres as magnetically recyclable solid acid catalysts. Chin. Chem. Lett. 2021, 32, 2079–2085. [Google Scholar] [CrossRef]
  7. Azarifar, D.; Forghaniha, A. A Novel Chemoselective Reaction of Aldehydes with 2-Mercaptoethanol Catalyzed by SiO2-NaHSO4 under Solvent-free Condition. J. Chin. Chem. Soc. 2006, 53, 1189–1192. [Google Scholar] [CrossRef]
  8. Sowmiya, M.; Sharma, A.; Parsodkar, S.; Mishra, B.G.; Dubey, A. Nanosized sulfated SnO2 dispersed in the micropores of Al-pillared clay as an efficient catalyst for the synthesis of some biologically important molecules. Appl. Catal. A Gen. 2007, 333, 272–280. [Google Scholar] [CrossRef]
  9. Lv, S.; Li, D.; Ju, H.; Ma, Y.; Qiu, C.; Zhang, G. Synthesis of a phenol copolymer with horseradish peroxidase and the study of its structure-property relations. J. Appl. Polym. Sci. 2013, 128, 523–529. [Google Scholar] [CrossRef]
  10. Ferreira, G.; Carvalho, C.; Nakagaki, S. Studies of the Catalytic Activity of Iron (III) Porphyrins for the Protection of Carbonyl Groups in Homogeneous Media. Catalysts 2019, 9, 334. [Google Scholar] [CrossRef]
  11. Wei, Y.S.; Zhang, M.; Zou, R.; Xu, Q. Metal-Organic Framework-Based Catalysts with Single Metal Sites. Chem. Rev. 2020, 120, 12089–12174. [Google Scholar] [CrossRef]
  12. Li, H.Y.; Zhao, S.N.; Zang, S.Q.; Li, J. Functional metal-organic frameworks as effective sensors of gases and volatile compounds. Chem. Soc. Rev. 2020, 49, 6364–6401. [Google Scholar] [CrossRef] [PubMed]
  13. Xiao, J.D.; Jiang, H.L. Metal-Organic Frameworks for Photocatalysis and Photothermal Catalysis. Acc. Chem. Res. 2019, 52, 356–366. [Google Scholar] [CrossRef]
  14. Choi, J.; Yoo, K.S.; Kim, D.; Kim, J.; Othman, M.R. Microporous Mo-UiO-66 Metal–Organic Framework Nanoparticles as Gas Adsorbents. ACS Appl. Nano Mater. 2021, 4, 4895–4901. [Google Scholar] [CrossRef]
  15. Almáši, M.; Sharma, A.; Zelenka, T. Anionic zinc(II) metal-organic framework post-synthetically modified by alkali-ion exchange: Synthesis, characterization and hydrogen adsorption properties. Inorg. Chim. Acta 2021, 526, 120505. [Google Scholar] [CrossRef]
  16. Haque, E.; Jun, J.W.; Jhung, S.H. Adsorptive removal of methyl orange and methylene blue from aqueous solution with a metal-organic framework material, iron terephthalate (MOF-235). J. Hazard. Mater. 2011, 185, 507–511. [Google Scholar] [CrossRef]
  17. Wu, N.; Guo, H.; Wang, X.; Sun, L.; Zhang, T.; Peng, L.; Yang, W. A water-stable lanthanide-MOF as a highly sensitive and selective luminescence sensor for detection of Fe3+ and benzaldehyde. Colloids Surf. A Physicochem. Eng. Asp. 2021, 616, 126093. [Google Scholar] [CrossRef]
  18. Liu, J.; Yang, L.Y.; Luo, F. A new Zn-triazole MOF showing very long-lived luminescence up to 3 s. J. Solid State Chem. 2021, 301, 122369. [Google Scholar] [CrossRef]
  19. Yu, Y.; Pan, D.; Qiu, S.; Ren, L.; Huang, S.; Liu, R.; Wang, L.; Wang, H. Polyphenylene sulfide paper-based sensor modified by Eu-MOF for efficient detection of Fe3+. React. Funct. Polym. 2021, 165, 104954. [Google Scholar] [CrossRef]
  20. Ming, S.S.; Gowthaman, N.S.K.; Lim, H.N.; Arul, P.; Narayanamoorthi, E.; Ibrahim, I.; Jaafar, H.; John, S.A. Aluminium MOF fabricated electrochemical sensor for the ultra-sensitive detection of hydroquinone in water samples. J. Electroanal. Chem. 2021, 883, 115067. [Google Scholar] [CrossRef]
  21. Hasan, M.N.; Bera, A.; Maji, T.K.; Pal, S.K. Sensitization of nontoxic MOF for their potential drug delivery application against microbial infection. Inorg. Chim. Acta 2021, 523, 120381. [Google Scholar] [CrossRef]
  22. Arabbaghi, E.K.; Mokhtari, J.; Naimi-Jamal, M.R.; Khosravi, A. Zn-MOF: An efficient drug delivery platform for the encapsulation and releasing of Imatinib Mesylate. J. Porous Mater. 2021, 28, 641–649. [Google Scholar] [CrossRef]
  23. Du, R.; Wu, Y.; Yang, Y.; Zhai, T.; Zhou, T.; Shang, Q.; Zhu, L.; Shang, C.; Guo, Z. Porosity Engineering of MOF-Based Materials for Electrochemical Energy Storage. Adv. Energy Mater. 2021, 11, 2100154. [Google Scholar] [CrossRef]
  24. Huang, S.; Kou, X.; Shen, J.; Chen, G.; Ouyang, G. “Armor-Plating” Enzymes with Metal-Organic Frameworks (MOFs). Angew. Chem. Int. Ed. Engl. 2020, 59, 8786–8798. [Google Scholar] [CrossRef]
  25. Drout, R.J.; Robison, L.; Farha, O.K. Catalytic applications of enzymes encapsulated in metal–organic frameworks. Coord. Chem. Rev. 2019, 381, 151–160. [Google Scholar] [CrossRef]
  26. Hao, M.; Qiu, M.; Yang, H.; Hu, B.; Wang, X. Recent advances on preparation and environmental applications of MOF-derived carbons in catalysis. Sci Total Env. 2021, 760, 143333. [Google Scholar] [CrossRef]
  27. Dhakshinamoorthy, A.; Santiago-Portillo, A.; Asiri, A.M.; Garcia, H. Engineering UiO-66 Metal Organic Framework for Heterogeneous Catalysis. ChemCatChem 2019, 11, 899–923. [Google Scholar] [CrossRef]
Chemproc 12 00068 sch001
Scheme 1. Acylation of benzaldehyde employing MOFs under microwave conditions.
Scheme 1. Acylation of benzaldehyde employing MOFs under microwave conditions.
Chemproc 12 00068 sch001
Table 1. Investigating the performance of the MOFs for the acylation reaction a.
Table 1. Investigating the performance of the MOFs for the acylation reaction a.
EntryCatalystRoom Temperature/MicrowaveTime (h/min)Yield (%) b
1Ni2(BDC)2(DABCO)R.T24 h100
MW19 min93
2Cu2(BDC)2(DABCO)R.T33 h94
MW20 min90
3Co2(BDC)2(DABCO)R.T30 h97
MW25 min92
4Zn2(BDC)2(DABCO)R.T10 h100
MW13 min100
a At room temperature and solvent-free condition. b Yields were determined by GC.
Table 2. Investigation of acylation of benzaldehyde with acetic anhydride a.
Table 2. Investigation of acylation of benzaldehyde with acetic anhydride a.
Chemproc 12 00068 i001
EntrySolventConditionTime (h)Yield (%) b
1EtOHr.t16.554
2n-Hexaner.t2273
3EtOAcr.t2057
4CH3CNr.t1852
5Solvent-freer.t6100
6Solvent-freeball-milling, r.t393
7Solvent-freeMW7 min100
a Benzaldehyde (1.0 mmol), acetic anhydride (3.0 mmol), and Zn2(BDC)2(DABCO) (30 mg) were used as catalysts. b The conversion was determined via GC analysis of the crude product.
Table 3. Acylated derivatives of benzaldehydes in the presence of MOF a.
Table 3. Acylated derivatives of benzaldehydes in the presence of MOF a.
EntrySubstrateProductTime (min)Yield (%) b
1Chemproc 12 00068 i002Chemproc 12 00068 i003792
2Chemproc 12 00068 i004Chemproc 12 00068 i005696
3Chemproc 12 00068 i006Chemproc 12 00068 i007794
4Chemproc 12 00068 i008Chemproc 12 00068 i0091091
5Chemproc 12 00068 i010Chemproc 12 00068 i011891
6Chemproc 12 00068 i012Chemproc 12 00068 i013985
7Chemproc 12 00068 i014Chemproc 12 00068 i015890
a Benzaldehyde (1.0 mmol), acetic anhydride (3.0 mmol), and Zn2(BDC)2(DABCO) (30 mg) were used as catalysts under microwave irradiation. b The conversion yield was determined via GC analysis of the crude product.
Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to people or property resulting from any ideas, methods, instructions or products referred to in the content.

Share and Cite

MDPI and ACS Style

Mahdian, S.; Panahi, L.; Naimi-Jamal, M.R. Chemo-Selective Protection of Aldehydes Functional Group Catalyzed by MOFs. Chem. Proc. 2022, 12, 68. https://doi.org/10.3390/ecsoc-26-13645

AMA Style

Mahdian S, Panahi L, Naimi-Jamal MR. Chemo-Selective Protection of Aldehydes Functional Group Catalyzed by MOFs. Chemistry Proceedings. 2022; 12(1):68. https://doi.org/10.3390/ecsoc-26-13645

Chicago/Turabian Style

Mahdian, Sakineh, Leila Panahi, and Mohammad Reza Naimi-Jamal. 2022. "Chemo-Selective Protection of Aldehydes Functional Group Catalyzed by MOFs" Chemistry Proceedings 12, no. 1: 68. https://doi.org/10.3390/ecsoc-26-13645

APA Style

Mahdian, S., Panahi, L., & Naimi-Jamal, M. R. (2022). Chemo-Selective Protection of Aldehydes Functional Group Catalyzed by MOFs. Chemistry Proceedings, 12(1), 68. https://doi.org/10.3390/ecsoc-26-13645

Article Metrics

Back to TopTop