NiCo2O4-Nanoparticle-Catalyzed Microwave-Assisted Dehydrogenative Direct Oxidation of Primary Alcohols to Carboxylic Acids under Oxidant-Free Conditions

Kumari Anchal; Ashok R. Patel; Subhash Banerjee

doi:10.1055/a-2384-6371

Synlett, Inhaltsverzeichnis

Synlett 2024; 35(20): 2409-2416
DOI: 10.1055/a-2384-6371

letter

Special Issue to Celebrate the 75th Birthday of Prof. B. C. Ranu

NiCo₂O₄-Nanoparticle-Catalyzed Microwave-Assisted Dehydrogenative Direct Oxidation of Primary Alcohols to Carboxylic Acids under Oxidant-Free Conditions

Kumari Anchal

,

Ashok R. Patel

,

Subhash Banerjee ∗

Abstract

Alle Artikel dieser Rubrik

Dedicated to the honorable Prof. Brindaban C. Ranu

Abstract

Here, we report the NiCo₂O₄-nanoparticle-catalyzed dehydrogenative direct oxidation of primary alcohols to carboxylic acid in the presence of KOH under microwave irradiation in the absence of any oxidant in good to excellent yields (75–99%) within a short reaction time (5–10 min). The polycrystalline cubic spinel phase of NiCo₂O₄ nanoparticles (NPs) with an average size of 25 nm were synthesized by the co-precipitation method and analyzed properly by using powder X-ray diffraction, field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, and transmission electron microscopy measurements. The NiCo₂O₄ NPs were stable under the reaction conditions and reused for up to eight cycles without appreciable loss in the yield of benzoic acid. According to mechanistic insight, the KOH acts as a second oxygen source and is essential for the synthesis of carboxylic acid from alcohols. The hydrogen gas was found to be the only byproduct of this method detected by chemical reactions.

Keywords

nano-NiCo₂O₄ - dehydrogenative oxidation - direct oxidation of primary alcohols - carboxylic acids - green synthesis - recyclability

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Referenzen

References

1a Modern Oxidation Methods. Bäckwall JE. Wiley-VCH; Weinheim: 2004
1b Ley SV. In Comprehensive Organic Synthesis, 3rd ed. Trost BM, Fleming I. Pergamon Press; Oxford: 1999
1c Arends IW. C. E, Sheldon RA. Modern Oxidation of Alcohols Using Environmentally Benign Oxidants. In Modern Oxidation Methods, 2nd ed. Bäckvall J.-E. Wiley-VCH; Weinheim: 2004
1d Gehrmann S, Tenhumberg N. Chem. Ing. Tech. 2020; 92: 1444

2a Ogliaruso MA, Wolfe JF. Synthesis of Carboxylic Acids, Esters and Their Derivatives: The Chemistry of Functional Groups. Patai S. Wiley; Hoboken: 1991
2b Smith MB. Compendium of Organic Synthetic Methods. Wiley; Hoboken: 2000
2c Larock RC. Comprehensive Organic Transformations, A Guide to Functional Group Preparations, 2nd ed. J. Wiley and Sons; Hoboken: 1999

3a Tojo G, Fernández MI. Oxidation of Primary Alcohols to Carboxylic Acids: A Guide to Current Common Practice. Springer; New York: 2007
3b Tojo G, Fernández M. Oxidation of Primary Alcohols to Carboxylic Acids. In Basic Reactions in Organic Synthesis. Springer; New York: 2010

4 Zhao M, Li J, Song Z, Desmond R, Tschaen DM, Grabowski EJ. J, Reider PJ. Tetrahedron Lett. 1998; 39: 5323
5 Mahmood A, Robinson GE, Powell L. Org. Process Res. Dev. 1999; 3: 363
6 George MV, Balachandran KS. Chem. Rev. 1975; 75: 491
7 Uyanik M, Akakura M, Ishihara K. J. Am. Chem. Soc. 2009; 131: 251

8a Jiang X, Zhang J, Ma S. J. Am. Chem. Soc. 2016; 138: 8344
8b Tan WY, Lu Y, Zhao JF, Chen W, Zhang H. Org. Lett. 2021; 23: 6648

9 Ganji N, Karimi B, Derikvandi SN, Vali H. RSC Adv. 2020; 10: 13616

10a Liu H.-M, Jian L, Li C, Zhang C, Fu H.-y, Zheng X.-L, Chen H, Li R.-X. J. Org. Chem. 2019; 84: 9151
10b Santilli C, Makarov IS, Fristrup P, Madsen R. J. Org. Chem. 2016; 81: 9931

11 Annen S, Zweifel T, Ricatto F, Grützmacher H. ChemCatChem 2010; 2: 1286
12 Cherepakhin V, Williams TJ. ACS Catal. 2018; 8: 3754
13 Selivanova NV, Berdnikova PV, Pai ZP. Catal. Ind. 2021; 13: 111
14 Mannam S, Sekar G. Tetrahedron Lett. 2008; 49: 2457
15 Han L, Xing P, Jiang B. Org. Lett. 2014; 16: 3428
16 Cui X, Huang Z, van Muyden AP, Fei Z, Wang T, Dyson PJ. Sci. Adv. 2020; 6: eabb3831

17a Whitesides GM, Hackett M, Brainard RL, Lavalleye JP. P, Sowinski AF, Izumi AN, Moore SS, Brown DW, Staudt EM. Organometallics 1985; 4: 1819
17b Donze C, Korovchenko P, Gallezot P, Besson M. Appl. Catal., B 2007; 70: 621

18a Nguyen DH, Morin Y, Zhang L, Trivelli X, Capet F, Paul S, Desset S, Dumeignil F, Gauvin RM. ChemCatChem 2017; 9: 2652
18b Jiang X, Zhang J, Ma S. J. Am. Chem. Soc. 2016; 138: 8344

19 Shao Z, Wang Y, Liu Y, Wang Q, Fu X, Liu Q. Org. Chem. Front. 2018; 5: 1248
20 Monda F, Madsen R. Chem. Eur. J. 2018; 24: 17832
21 Balaraman E, Khaskin E, Leitus G, Milstein D. Nat. Chem. 2013; 5: 122
22 Sawama Y, Morita K, Asai S, Kozawa M, Tadokoro S, Nakajima J, Monguchi Y, Sajiki H. Adv. Synth. Catal 2015; 357: 1205

23a Choi JH, Heim LE, Ahrens M, Prechtl MH. G. Dalton Trans. 2014; 43: 17248
23b Santilli C, Makarov IS, Fristrup P, Madsen R. J. Org. Chem. 2016; 81: 9931
23c Espinosa DV, Vicent C, Baya M, Mata JA. Catal. Sci. Technol. 2016; 6: 8024
23d Zhang L, Nguyen DH, Raffa G, Trivelli X, Capet F, Desset S, Paul S, Dumeignil F, Gauvin RM. ChemSusChem 2016; 9: 1413
23e Choi JH, Heim LE, Ahrens M, Prechtl MH. Dalton Trans. 2014; 43: 17248
23f Dai Z, Luo Q, Meng X, Li R, Zhang J, Peng T. J. Organomet. Chem. 2017; 830: 11
23g Tincado M, Grutzmacher H, Bianchini C. Chem. Eur. J. 2010; 16: 2751
23h Sarbajna A, Dutta I, Daw P, Dinda S, Rahaman SW, Sarkar A, Bera JK. ACS Catal. 2017; 7: 2786
23i Rezayati S, Morsali A. Inorg. Chem. 2024; 63: 6051
23j Kalantari F, Rezayati S, Moghadam MM, Ramazani A. Inorg. Chem. Commun. 2024; 164: 112371
23k Rezayati S, Moghadam MM, Naserifar Z, Ramazani A. Inorg. Chem. 2024; 63: 1652
23l Rezayati S, Haghighat H, Ramazani A. Silicon 2023; 15: 2679
23m Partovi M, Rezayati S, Ramazani A, Ahmadi Y, Taherkhani H. RSC Adv. 2023; 13: 33566

24a Gu S, Lou Z, Ma X, Shen G. ChemElectroChem 2015; 2: 1042
24b Serov A, Andersen NI, Roy AJ, Matanovic I, Artyushkova K, Atanassov P. J. Electrochem. Soc. 2015; 162: 449
24c Anke S, Bendt G, Sinev I, Hajiyani H, Antoni H, Zegkinoglou I, Hyosang J, Pentcheva R, Cuenya BR, Schulz S, Muhler M. ACS Catal. 2019; 9: 5974
24d Patel AR, Sereda G, Banerjee S. Curr. Pharm. Biotechnol. 2021; 22: 773

25a Yuan C, Li J, Hou L, Zhang X, Shen L, Lou XW. D. Adv. Funct. Mater. 2012; 22: 4592
25b Wang H, Gao Q, Jiang L. Small 2011; 7: 2454
25c Wang Q, Liu B, Wang X, Ran S, Wang L, Chen D, Hen G. J. Mater. Chem. 2012; 22: 21647
25d Wei TY, Chen CH, Chien HC, Lu SY, Hu CC. Adv. Mater. 2010; 22: 347
25e Zou R, Xu K, Wang T, He G, Liu Q, Liu X, Zhang Z, Hu J. J. Mater. Chem. A 2013; 1: 8560
25f Jiang H, Ma J, Li C. Chem. Commun. 2012; 48: 4465
25g Patel AR, Bhagat S, Neha Neha, Patel G, Maity G, Turpu GR, Singh AK, Banerjee S. Int. J. Hydrogen Energy 2024; 51C: 561

26a Banerjee S, Saha A. New J. Chem. 2013; 37: 4170
26b Banerjee S, Payra S, Saha A, Sereda G. Tetrahedron Lett. 2014; 55: 5515
26c Saha A, Payra S, Banerjee S. Green Chem. 2015; 17: 2859
26d Payra S, Saha A, Banerjee S. RSC Adv. 2016; 6: 12402
26e Payra S, Saha A, Guchhait S, Banerjee S. RSC Adv. 2016; 6: 33462
26f Payra S, Saha A, Banerjee S. RSC Adv. 2016; 6: 52495
26g Payra S, Saha A, Banerjee S. ChemistrySelect 2018; 3: 7535
26h Saha A, Payra S, Selvaratnam B, Bhattacharya S, Pal S, Koodali RT, Banerjee S. ACS Sustainable Chem. Eng. 2018; 6: 11345
26i Patel AR, Asatkar A, Patel G, Banerjee S. ChemistrySelect 2019; 4: 5577
26j Patel AR, Patel G, Banerjee S. ACS Omega 2019; 4: 22445
26k Patel G, Patel AR, Lambat TL, Mahmood SH, Banerjee S. FlatChem 2020; 21: 100163
26l Patel G, Patel AR, Lambat TL, Banerjee S. Curr. Res. Green Sustainable Chem. 2021; 4: 100149

27a Patel AR, Patel G, Maity G, Patel SP, Bhattacharya S, Putta A, Banerjee S. ACS Omega 2020; 5: 30416
27b Patel G, Patel AR, Maity G, Das S, Patel Shiv P, Banerjee S. Curr. Res. Green Sustainable Chem. 2022; 5: 100258

28 Yin H, Zhu J, Chen J, Gong J, Nie Q. J. Mater. Sci. 2018; 53: 11951
29 Mahata A, Rai RK, Choudhuri I, SinghS K, Pathak B. Phys. Chem. Chem. Phys. 2014; 16: 26365

30a Dai Z, Luo Q, Jiang H, Li H, Zhang J, Peng T. Catal. Sci. Technol. 2017; 7: 2506
30b Pradhan DR, Pattanaik S, Kishore J, Gunanathan C. Org. Lett. 2020; 22: 1852

31 General Experimental Procedure for NiCo₂O₄-NPs-Catalyzed Dehydrogenative Oxidation of Alcohol to Acid A round-bottomed flask (50 mL) was charged with a mixture of benzyl alcohol (1.0 mmol), potassium hydroxide (2.0 equiv.), catalyst (30 mg), and toluene (2.0 mL) heated under microwave conditions (120 °C, 100 W) for 10 min. The formation of the product was checked by TLC. Next, the catalyst was separated by centrifugation at 600 rpm, and then the product was extracted with ethyl acetate (5 mL), washed with HCl (1 M) and then distilled water, and purified by column chromatography over silica gel (60–120 mesh) using ethyl acetate and petroleum ether (1:9) as an eluting solvent to obtain the pure product benzoic acid as a white solid. The formation of the benzoic acid was confirmed by its melting point determination and ¹H NMR and ¹³C NMR spectroscopic studies. The solid part was washed with water and ethanol and dried in an oven at 80 °C for 6 h and recycled for subsequent runs. Analytical Data of Compounds
Benzoic Acid (2a) ¹H NMR (500 MHz, CDCl₃): δ = 8.18–8.15 (d, J = 10.0 Hz, 2 H), 7.67–7.65 (t, J = 10.0 Hz, 1 H) 7.64–7.49 (t, J = 10.0 Hz, 2 H). ¹³C NMR (125 MHz, CDCl₃): δ = 172.54, 133.81, 130.24, 129.47, 128.51. 2-Methyl Benzoic Acid (2c) ¹H NMR (500 MHz, CDCl₃) δ = 12.44 (s, 1 H), 8.13–8.10 (d, J = 10.0 Hz, 2 H), 7.51–7.48 (m, 1 H) 7.47–7.30 (t, J = 10.0 Hz, 2 H), 2.70 (s, 3 H). ¹³C NMR (125 MHz, CDCl₃): δ = 173.55, 141.42, 133.01, 131.97, 131.64, 128.34, 125.90, 22.19. Anthracene-9-carboxylic acid (2f) ¹H NMR (500 MHz, CDCl₃): δ = 8.64 (s, 1 H), 8.38 (d, J = 10.0 Hz, 2 H), 8.09 (d, J = 10.0 Hz, 2 H), 7.67–7.63 (m, 2 H), 7.58–7.54 (m, 2 H). ¹³C NMR (125 MHz, CDCl₃): δ = 130.97, 130.47, 128.76, 127.42, 125.96, 125.62, 125.14. 4-Chloro Benzoic Acid (2j) ¹H NMR (500 MHz, CDCl₃): δ = 8.07 (d, J = 10.0 Hz, 1 H), 7.48 (d, J = 10.0, 1 H). ¹³C NMR (125 MHz, CDCl₃): δ = 131.60, 128.93. 4-Amino Benzoic Acid (2m) ¹H NMR (500 MHz, CDCl₃): δ = 7.94 (d, J = 10.0 Hz, 1 H), 6.69 (d, J = 10.0, 1 H). ¹³C NMR (125 MHz, CDCl₃): δ = 151.49, 132.41, 118.54, 113.80. Cinnamic Acid (2q) ¹H NMR (500 MHz, CDCl₃); δ = 7.84 (d, J = 10.00 Hz, 1 H), 7.61–7.57 (m, 2 H), 7.46–7.42 (m, 3 H), 6.50 (d, J = 10.00 Hz, 1 H). ¹³C NMR (125 MHz, CDCl₃): δ = 172.64, 147.14, 134.075, 133.78, 130.787, 128.99, 128.41, 117.37.

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