Vol.:(0123456789)1 3

Journal of the Iranian Chemical Society (2021) 18:1199–1209 https://doi.org/10.1007/s13738-020-02102-x

ORIGINAL PAPER

Magnetic spent coffee ground as an efficient and green catalyst for aerobic oxidation of alcohols and tandem oxidative Groebke–Blackburn–Bienaymé reaction

Hassan Farhid1 · Ahmad Shaabani1

Received: 21 August 2020 / Accepted: 14 October 2020 / Published online: 5 November 2020 © Iranian Chemical Society 2020

Abstract In this work, magnetic spent coffee ground as a green, inexpensive, and abundant material was synthesized and characterized by a variety of techniques, including X-ray diffraction pattern, thermal gravimetric analysis, scanning electron microscopy, energy-dispersive spectroscopy, inductively coupled plasma optical emission spectrometry, and Fourier transform infrared spectroscopy. The magnetic spent coffee ground was successfully utilized as a catalyst in aerobic oxidation of primary and secondary benzylic alcohols and tandem oxidative Groebke–Blackburn–Bienaymé reaction.

Graphic abstract

Keywords Spent coffee grounds · Aerobic oxidation · Tandem oxidation process · Magnetic materials · GBB reaction · Lignocellulose

Electronic supplementary material The online version of this article (https ://doi.org/10.1007/s1373 8-020-02102 -x) contains supplementary material, which is available to authorized users.

Extended author information available on the last page of the article

1200 Journal of the Iranian Chemical Society (2021) 18:1199–1209

1 3

Introduction

Coffee is one of the most popular beverages in the world and one of the superlative vital ingredients in daily human life. This has caused coffee comes second as the world’s most important commodity after fossil fuel [1]. According to the International Coffee Organization (ICO), about 9.1 million tons of coffee production was consumed in 2016 and is esti-mated that 1.6 billion cups of coffee were spent every day by people around the world [2, 3]. Spent coffee ground (SCG) refers to the waste material generated after preparation of the coffee beverage or manufacturing of instant coffee. Uni-versally, 550–670 kg of SCG is produced from 1 ton of cof-fee bean; thus, over 5.8 million tons of SCG has generated annually [4]. This enormous waste directly discards in land-fills and causing environmental problems due to the pres-ence of various organic compounds like caffeine, tannins, and polyphenols [5]. The re-use of these wastes rather than simple disposal is important from both environmental and commercial aspects [6]. Therefore, researchers have found various applications to utilize these wastes such as biodiesel [7], and bioethanol [8] production, catalyst [9], composting [10], activated carbon synthesis [11], sugar production [12], mushroom growth [13], and heavy metals adsorbent [14]. However, due to the high volume of this waste, there is still need to find a solution to utilize these natural wastes [15]. SCG consists of 74.2 wt% carbohydrate (that predominantly is lignocellulose), 13.3 wt% protein, 10.3 wt% oil, and 2.2 wt% ash [16].

Catalytic aerobic oxidation of alcohols is a significant organic transformation from both laboratory and industrial chemistry points of view [17–20]. The tandem oxidation process (TOP) is an inventive and well-organized syn-thetic protocol, which combines in situ generated aldehyde or ketone from oxidation of alcohols with nucleophiles [21–23]. Although the extensive research protocols have been reported for the development of TOP, its applica-tion in some chemical process, especially multicomponent reactions (MCRs), is less considered [24]. This is probably because of the inherent complexity of MCRs mechanism and multiple functionalities of these processes [25, 26].

Fe3O4 nanoparticles (NPs) are prominent and green mate-rials and are widely used as a support for significant homo-geneous catalytically active metals due to easier separation operation [27, 28]. Moreover, these NPs can efficiently cata-lyze various transformations such as oxidation reactions [29] or act as a Lewis acid in acid-catalyzed reactions [30].

According to these points and in order to develop an appropriate utilization for SCG that has causes environ-mental problems, herein, we investigate the catalytic activ-ity of magnetic SCG in aerobic oxidation of alcohols and the tandem oxidative GBB reaction.

Materials and methods

Materials

SCG used was provided by local coffee shops. All reagents were purchased from Sigma-Aldrich and used without fur-ther purification. The FT-IR spectra were recorded on a Thermo Nicolet NEXUS 470 FT-IR spectrometer. The amounts of metals were measured using an inductively coupled plasma optical emission spectrometer (ICP-OES; Varian Vista PRO Radial). Products of oxidation of alco-hols were analyzed using a Varian 3900 GC. The X-ray powder diffraction (XRD) patterns were recorded on an STOE diffractometer with Cu-Kα radiation (λ = 1.5418 Å). Thermogravimetric analysis (TGA) was carried out using STA 1500 instrument at a heating rate of 10 °C min-1 in the air. Scanning electron microscopy (SEM)

Fig. 1 XRD patterns of SCG and SCG@Fe3O4

Fig. 2 TGA curves of SCG and SCG@Fe3O4

1201Journal of the Iranian Chemical Society (2021) 18:1199–1209

1 3

observations were carried out on an electron microscopy Philips XL-30 ESEM. All samples were sputtered with gold before observation. Melting points were measured with an Electrothermal 9200 apparatus. 1H NMR spectra were recorded on a BRUKER DRX-300 AVANCE spec-trometer at 300.13 MHz. NMR spectra were obtained in DMSO-d6.

Preparation of SCG

SCG was washed with boiling water several times until the color of solvent was remained almost colorless and then dried at 100 °C for 8 h. The washed SCG (10 g) is weighed into a thimble in the Soxhlet extractor and fitted to a coni-cal flask. Coffee oil is extracted with 250 mL n-hexane under reflux for 1 h. Then, the sample was washed with n-hexane several times and dried at 100 °C for 8 h.

Fig. 3 SEM images of SCG (a, b) and SCG@Fe3O4 (c, d)

Fig. 4 EDS result for SCG@Fe3O4

Fig. 5 FT-IR spectra of SCG and SCG@Fe3O4

1202 Journal of the Iranian Chemical Society (2021) 18:1199–1209

1 3

Synthesis of SCG@Fe3O4

The prepared SCG (1.00  g) was mixed with 25  mL of deionized water and was stirred for 5  min. Then, FeCl2·4H2O (aq)/FeCl3·6H2O (aq) (1:2) (0.37 g/1.00 g) which was dissolved in 2  mL of deionized water was added while the temperature of the mixture was increased to 80 °C for 1 h. Ammonia solution (25 wt%) was added dropwise to adjust the pH of the solution to 10 and then continuously stirred for 1 h at 80 °C. Subsequently, the reaction mixture was cooled to room temperature and the solution was neutralized with 0.5 M hydrochloric acid solution. After 1 h, magnetic SCG was separated using an external magnet and washed with deionized water and ethanol several times, and then, it was dried at 100 °C for 8 h to afford SCG@Fe3O4.

General procedure for oxidation of alcohols using SCG@Fe3O4

An alcohol (1.00  mmol) was added to a two-necked flask containing SCG@Fe3O4 (0.05 g), KOH (0.028 g, 0.50 mmol), and toluene (4.00 mL). The reaction was heated at 80 °C with continuous bubbling of air with a flow rate of 15 mL min−1 for indicated times as given in

Table 2. The progress of the reaction was followed by TLC. Upon completion, the reaction mixture was filtered and the filtrate was analyzed by GC.

General procedure for tandem oxidative GBB reaction using SCG@Fe3O4

An alcohol (1.00  mmol) was added to a two-necked flask containing SCG@Fe3O4 (0.05 g), KOH (0.028 g, 0.50  mmol) and toluene (4.00  mL). The reaction was heated at 80 °C with continuous bubbling of air with a flow rate of 15 mL min−1 for 5 h. Afterward, the reaction mixture was cooled to room temperature and a 2-amino heterocycle (1.00 mmol) and an isocyanide (1.00 mmol) were added to the reaction mixture and stirred at 80 °C for 3 h. After completion of the reaction (monitored by TLC), the reaction mixture was cooled to the room tem-perature and the crude of the reaction was filtered. The crude product was separated from the catalyst with hot ethanol and recrystallized with deionized water to afford the corresponding pure product.

Spectral data

N‑(tert‑butyl)‑2‑phenylimidazo[1,2‑a]pyridin‑3‑amine (Table 4, Entry 1)

White solid (80%): mp 161 °C. 1H NMR (300.13 MHz, DMSO-d6) δ: 8.39 (d, J = 6.9  Hz, 1H, Harom), 8.16 (d, J = 7.6 Hz, 2H, Harom), 7.47–7.14 (m, 5H, Harom), 6.86 (t, J = 6.8 Hz, 1H, Harom), 4.62 (br s, 1H, NH), 0.99 (s, 9H, Haliphatic). Anal. Calcd for C17H19N3: C, 76.95; H, 7.22; N, 15.84; found C, 77.03; H, 7.20; N, 15.75.

N‑cyclohexyl‑2‑phenylimidazo[1,2‑a]pyridin‑3‑amine (Table 4, Entry 2)

White solid (81%): mp 176–178 °C. 1H NMR (300.13 MHz, DMSO-d6) δ: 8.30 (d, J = 7.0  Hz, 1H, Harom), 8.21 (d, J = 7.7 Hz, 2H, Harom), 7.47–7.14 (m, 5H, Harom), 6.87 (t, J = 6.8 Hz, 1H, Harom), 4.79 (d, J = 5.8 Hz, 1H, NH), 2.82 (br s, 1H, HCN), 1.72–1.48 (m, 5H, Haliphatic), 1.28–1.08 (m, 5H, Haliphatic). Anal. Calcd for C19H21N3: C, 78.32; H, 7.26; N, 14.42; found C, 78.64; H, 7.32; N, 14.04.

2‑(4‑Bromophenyl)‑N‑cyclohexylimidazo[1,2‑a]pyridin‑3‑amine (Table 4, Entry 3)

White solid (73%): mp 175–176 °C. 1H NMR (300.13 MHz, DMSO-d6) δ: 8.31 (d, J = 6.9  Hz, 1H, Harom), 8.19 (d,

Table 1 Optimization of reaction conditions for aerobic oxidation for benzyl alcohol by SCG@Fe3O4

Conditions: benzyl alcohol (1.00  mmol), solvent (4  mL), base (0.50 mmol), air oxidant, 80 °C, 5 ha Yield determined by GC analysisb 50 °Cc 25 °Cd Reflux

Entry Catalyst Amount of catalyst (g)

Solvent Base Yield (%)a

1 – – Toluene KOH 222 SCG 0.05 Toluene KOH 243 SCG@Fe3O4 0.03 Toluene KOH 754 SCG@Fe3O4 0.05 Toluene KOH 945 SCG@Fe3O4 0.05 Toluene K2CO3 186 SCG@Fe3O4 0.05 Toluene NaOH 597b SCG@Fe3O4 0.05 Toluene KOH 408c SCG@Fe3O4 0.05 Toluene KOH 339 SCG@Fe3O4 0.05 p-xylene KOH 9710 SCG@Fe3O4 0.05 DMF KOH 1011d SCG@Fe3O4 0.05 n-hexane KOH Trace12d SCG@Fe3O4 0.05 EtOH KOH N.R.13d SCG@Fe3O4 0.05 H2O KOH N.R.14d SCG@Fe3O4 0.05 CH3CN KOH Trace

1203Journal of the Iranian Chemical Society (2021) 18:1199–1209

1 3

Table 2 Aerobic oxidation of various alcohols to the corresponding carbonyl compounds by SCG@Fe3O4

Entry Alcohol Product Time (h) Yield (%)a

1 5 94

2 5 96

3 5 87

4 5 85

5 5 95

6 5 88

7 5 78

8 5 83

9 1.5 95

10 4 94

11 1.5 99

12 4 81

13 4 90

14 1.5 97

15 4 84

16 5 83

17 8 Trace

18 8 Trace

1204 Journal of the Iranian Chemical Society (2021) 18:1199–1209

1 3

J = 8.2  Hz, 2H, Harom), 7.63–7.16 (m, 4H, Harom), 6.89 (t, J = 6.8 Hz, 1H, Harom), 4.84 (d, J = 5.9 Hz, 1H, NH), 2.82–2.78 (m, 1H, HCN), 1.73–1.50 (m, 5H, Haliphatic), 1.28–1.09 (m, 5H, Haliphatic). Anal. Calcd for C19H20BrN3: C, 61.63; H, 5.44; N, 11.35; found C, 61.82; H, 5.21; N, 11.47.

N‑cyclohexyl‑2‑phenylimidazo[1,2‑a]pyrimidin‑3‑amine (Table 4, Entry 4)

Brown solid (70%): mp 161–162 °C. 1H NMR (300.13 MHz, DMSO-d6) δ: 8.74 (d, J = 6.8 Hz, 1H, Harom), 8.47–8.45 (m, 1H, Harom), 8.25–8.20 (m, 2H, Harom), 7.55–7.28 (m, 3H, Harom), 7.05–6.52 (m, 1H, Harom), 4.90 (d, J = 6.1 Hz, 1H, NH), 2.84 (br s, 1H, HCN), 1.82–1.63 (m, 6H, Haliphatic), 1.50–1.10 (m, 4H, Haliphatic). Anal. Calcd for C18H20N4: C, 73.94; H, 6.89; N, 19.16; found C, 73.59; H, 7.03; N, 19.40.

N‑(tert‑butyl)‑2‑(4‑chlorophenyl)imidazo[1,2‑a]pyridin‑3‑amine (Table 4, Entry 5)

White solid (79%): mp 147 °C. 1H NMR (300.13 MHz, DMSO-d6) δ: 8.40 (d, J = 7.1  Hz, 1H, Harom), 8.21 (d, J = 7.8 Hz, 2H, Harom), 7.48–7.17 (m, 4H, Harom), 6.89 (t, J = 7.0 Hz, 1H, Harom), 4.69 (br s, 1H, NH), 1.01 (s, 9H, Haliphatic). Anal. Calcd for C17H18ClN3: C, 68.11; H, 6.05; N, 14.02; found C, 68.37; H, 5.95; N, 14.12.

Result and discussion

At first, SCG was magnetized through co-precipitation method and characterized by XRD, TGA, SEM, EDS, ICP-OES analysis, and FT-IR. The XRD patterns of SCG and SCG@Fe3O4 were employed to exhibit the structure of the synthetic catalyst (Fig. 1). The diffraction peaks of SCG were appeared as two broad peaks at 2θ values of around 16° and 22° that correspond to the XRD pattern of cellu-lose [31]. In the XRD pattern of SCG@Fe3O4, in addition to the diffractions mentioned for SCG, the diffractions at 2θ values of around 30.3, 35.7, 43.4, 53.7, 57.3, and 62.9° were observed, which are related to the Fe3O4 NPs [29] and confirmed the synthesis of Fe3O4 NPs on SCG.

TGA was performed for SCG and SCG@Fe3O4 in the air to examine the thermal stability, and the results are illustrated in Fig. 2. Up to around 170 °C, approximately 14% of the SCG weight was reduced, which is related to the moisture content, and this value is less for SCG@Fe3O4. Up to around 600 °C, almost about 51% and 18% weight loss was observed for SCG and SCG@Fe3O4, respectively, due to the decomposition of the lignocellu-lose moiety [32]. This 33% difference between residual weights was attributed to the Fe3O4 NPs. It is noteworthy that the thermal stability of SCG@Fe3O4 is about 275 °C.

Conditions: alcohol (1.00 mmol), SCG@Fe3O4 (0.05 g), toluene (4 mL), KOH (0.50 mmol), air oxidant, 80 °C, 5 ha Yield determined by GC analysis

Table 2 (continued)

Table 3 Comparison of the catalytic efficiency of SCG@Fe3O4 with the reported catalysts for aerobic oxidation of benzyl alcohol

a Under UV irradiation

Entry Catalyst Solvent Temperature Oxidant Additive Time (h) Yield (%) References

1 Pd@SBA-15 Toluene 80 °C Air K2CO3 5.5 > 99 [33]2 Au/Hydrotalcite Toluene 40 °C Air – 24 78 [34]3 Fe3O4/CuBDC/GO Acetonitrile 60 °C O2 TEMPO 8 > 98 [35]4 Fe3O4/Cys-Pd – 50 °C O2 – 1.5 85 [36]5 Fe3O4/C/MnO2 Toluene 100 °C O2 – 4 78 [37]6 Ru(OH)x/Fe3O4 Toluene 105 °C O2 – 1 > 99 [38]7 SiO2@Fe3O4-Pro-Pd Toluene 90 °C O2 K2CO3 10 94 [39]8 Fe3O4@SiO2@PEI@Ru(OH)x Toluene 110 °C O2 – 10 91.4 [40]9 Fe3O4@SiO2-Au Toluene 100 °C O2 K2CO3 6 84.3 [41]10 Fe3O4@C – 140 °C O2 – 5 42.5 [42]11 Fe3O4/C Toluene 80 °C Air – 8 93.6 [29]12 MnO2/Cellulose o-xylene r.t. Air K2CO3 7 99 [43]13 Porous chitosan–MnO2 p-xylene 80 °C Air – 0.5 90 [44]14 Co-natural hydroxyapatite p-xylene 80 °C Air KOH 4 95 [45]15a Fe3O4@SiO2@mTiO2-

HN(CH2CH2NH2)2/PdToluene 80 °C O2 – 0.75 99 [46]

16 SCG@Fe3O4 Toluene 80 °C Air KOH 5 94 This work

1205Journal of the Iranian Chemical Society (2021) 18:1199–1209

1 3

Table 4 Tandem oxidative GBB reaction by SCG@Fe3O4

Yield (%)a

Melting pointProductIsocyanide2-Amino heterocycleAlcoholEntry

FoundReported

80161160-

162

[47]

1

81176-

178

176-

178

[47]

2

73175-

176

175-

177

[48]

3

70161-

162

162-

163

[47]

4

79147148-

150

[49]

5

7877-

80

75-80

[50]

6

76200-

205

201-

210

[51]

7

70166-

167

166-

169

[49]

8

68151-

153

150-

152

[52]

9

83206207-

208

[53]

10

1206 Journal of the Iranian Chemical Society (2021) 18:1199–1209

1 3

The SEM analysis was done to represent the structure and morphology of the SCG and SCG@Fe3O4. SCG has porous morphology and did not fundamentally change dur-ing magnetization (Fig. 3). The EDS analysis was carried out to determine the chemical composition of the SCG@Fe3O4. The results showed that the iron is present in the catalyst (Fig. 4). Furthermore, to determine the amount of Fe3O4 NPs, ICP-OES analysis was performed and results revealed a 1.43 mmol/g Fe3O4 is loaded in the catalyst.

Also, comparing FT-IR spectra of SCG and SCG@Fe3O4 illustrates the structure of the SCG did not change after mag-netization (Fig. 5).

In the next step, the catalytic activity of SCG@Fe3O4 was examined in aerobic oxidation of alcohols. In order to optimization of the reaction conditions, aerobic oxida-tion of benzyl alcohol was chosen as a model reaction and the effects of the solvent, temperature, and the amount of catalyst were investigated (Table 1). As shown in Table 1, nonpolar solvents such as toluene and xylene and alkaline bases are more effective for this transformation (Entries 4, 6, and 9). Also, the reaction yield depends on the amount of catalyst (Table 1, Entries 3 and 4). The reaction was carried out in the presence of 0.05 g of catalyst in toluene at 80 °C as the suitable conditions (Entry 4).

Oxidation of different alcohols was examined to inves-tigate the substrates scope. As indicated in Table 2, the catalyst efficiency for the aerobic oxidation of secondary benzylic alcohols is higher than for primary benzylic alco-hols. Various primary benzylic alcohols containing elec-tron-donating as well as electron-withdrawing groups and halogen substitutions were used, and in all cases high yields were achieved. Unfortunately, this catalytic system failed to transform the aliphatic alcohols to their corresponding carbonyl compounds.

A comparison of the catalytic efficiency of SCG@Fe3O4 with the reported catalysts for aerobic oxidation of benzyl alcohol is presented in Table 3. In most cases of magnetic catalysts that were used for aerobic oxidation of alcohols, iron oxides act as vehicles for supporting expensive cata-lytically active transition metals. There are far fewer reports which in Fe3O4 NPs operate as a catalytic active site [29]. Accordingly, utilizing of Fe3O4 NPs as a catalytic active site and SCG as a green support can be significant from green chemistry point of view.

Conditions: alcohol (1.00  mmol), 2-Amino heterocycle (1.00  mmol), isocyanide (1.00  mmol), SCG@Fe3O4 (0.05 g), toluene (4 mL), KOH (0.50 mmol), air oxidant, 80 °C, 8 ha Isolated yield

Table 4 (continued)

Table 5 Investigation of the catalytic activity of SCG@Fe3O4 in GBB reaction

Conditions: benzaldehyde (1.00  mmol), 2-aminopyridine (1.00  mmol), cyclohexyl isocyanide (1.00  mmol), catalyst (0.05  g), toluene (4 mL), 80 °Ca Isolated yield

Entry Catalyst Time (h) Yield (%)a

1 – 3 10 >2 SCG@Fe3O4 3 94

Scheme 1 Plausible mechanism for the formation of product 5

Fig. 6 Recyclability of SCG@Fe3O4 for five cycles using aerobic oxidation of benzyl alcohol and tandem oxidative GBB reaction

1207Journal of the Iranian Chemical Society (2021) 18:1199–1209

1 3

In the following, according to the promising results obtained for aerobic oxidation of primary benzylic alcohols, the tandem oxidative GBB reaction was investigated in a one-pot, two-step sequential strategy. The first step is the oxidation of alcohol in the optimized conditions to afford the corresponding aldehyde as an intermediate. Then, an isocya-nide and a 2-amino heterocycle were added to the reaction mixture and the reaction continued at the same condition without bubbling of air. As indicated in Table 4, various derivatives of benzyl alcohols, 2-amino heterocycles, and isocyanides were employed and in all cases the correspond-ing 3-aminoimidazo-fused heterocycles were synthesized in good yields.

To clarify the role of SCG@Fe3O4 in the GBB reaction, two control experiments were performed. The reaction of benzaldehyde, cyclohexyl isocyanide, and 2-aminopyri-dine was examined in the presence and absence of SCG@Fe3O4 in toluene at 80 °C. As shown in Table 5, the reaction yield in the absence of catalyst was less than 10%, but in the

presence of the catalyst, the reaction proceeded efficiently and the desired product was achieved in 94% yield. These results revealed that SCG@Fe3O4 is an efficient catalyst for the GBB reaction in addition to oxidation transformation.

According to the control experiments and based on the literature reports [54], a plausible mechanism for the GBB reaction is proposed in Scheme 1. Firstly, 2-amino heterocy-cle 3 reacts with aldehyde 2 in the presence of SCG@Fe3O4 to generate imine 6. Nucleophilic attack of isocyanide 4 to activated imine 6 results in the formation of intermediate 7 followed by 1, 3-H shift to afford the desired product.

The heterogeneous character of the catalyst was verified using a filtration test and atomic absorption spectroscopy. A filtration test was accomplished after ~ 50% completion of the model oxidation reaction of benzyl alcohol to control whether the catalyst is working in a heterogeneous fashion or catalyst is merely a reservoir for more active soluble iron species. The filtrates were then transferred to another flask under the same initial reaction conditions. Upon further stir-ring of the catalyst-free solution for 5 h, no significant pro-gress was detected. Furthermore, using atomic absorption spectroscopy of the same reaction solution at the midpoint of completion showed that no significant quantities of iron are lost.

For reusability examination, SCG@Fe3O4 was sur-veyed to five consecutive cycles for the model reactions in the oxidation of benzyl alcohol and tandem oxidative GBB reaction using benzyl alcohol, 2-aminopyridine and cyclohexyl isocyanide. After completion of the reaction, the catalyst was separated from the reaction mixture, washed with water, ethanol and acetone, dried, and reused in the next run. The recycled catalyst was employed in the next four sequential runs without significant loss of catalytic potential as shown in Fig. 6.

XRD pattern of the recovered catalyst for the tandem process was recorded and compared with the XRD pat-tern of the fresh catalyst. Result confirmed the stability of

Fig. 7 XRD patterns of SCG@Fe3O4 before (a), after using (b) for the tandem process

Table 6 Comparison of the catalytic efficiency of SCG@Fe3O4 with the reported Lewis acid catalysts for the reaction of benzaldehyde, 2-aminopyridine, and cyclohexyl isocyanide

a An example of heterogeneous Brønsted acid catalystb 2-Amino-6-bromopyridine was used instead of 2-aminopyridine

Entry Catalyst Solvent Temperature Time (h) Yield (%) References

1 AgOAc Ethylene glycol 90 °C 2 88 [55]2 Fe3O4@mPMF EtOH 60 °C 2.5 94 [56]3 RuCl3·3H2O – 40 °C 1 89 [51]4 NH2-MIL-53(Al) – 65 °C 3 95 [57]5 ZnCl2 1,4-Dioxane MW 1 78 [58]6 Nano-LaMnO3 – 35 °C 1.5 96 [59]7 Cellulose@Fe2O3 MeOH Reflux 3 89 [52]8 LaCl3·7H2O – 60 °C 0.33 95 [60]9 Silica sulfuric acida MeOH r.t. 3 98b [61]10 SCG@Fe3O4 Toluene 80 °C 3 94 This work

1208 Journal of the Iranian Chemical Society (2021) 18:1199–1209

1 3

SCG@Fe3O4 during the process. As indicated in Fig. 7, no significant changes are observable and some trivial differ-ences between the reflection intensities can be attributed to the variation in the orientation of powder samples during XRD patterns recording.

A comparison between catalytic ability of SCG@Fe3O4 with the reported Lewis acid catalysts for the reaction of benzaldehyde, 2-aminopyridine, and cyclohexyl isocya-nide is demonstrated in Table 6. The use of Fe3O4 sup-ported on SCG, as an inexpensive and abundant material that has causes environmental problems, in the tandem oxidation process is the advantages of this protocol.

Conclusions

In summary, SGG as an enormous waste material has been investigated in the field of catalyst. SCG was magnetized through co-precipitation method and successfully used as an efficient catalyst in the aerobic oxidation of alcohols and tandem oxidative GBB reaction. It is demonstrated that this green material has dual catalytic role in the tan-dem process: (i) As a reusable catalyst in the oxidation transformations and (ii) As an acidic heterogeneous cata-lyst in the GBB MCR. As well, high yield, reusability of the catalyst, simple and cheap starting materials, and mild reaction conditions are the other advantages of this work.

Acknowledgements We gratefully acknowledge financial support from the Research Council of Shahid Beheshti University.

Compliance with ethical standards

Conflict of interest All authors declare that they have no conflict of interest.

References

1. T.-A. Kua, M.A. Imteaz, A. Arulrajah, S. Horpibulsuk, Int. J. Sustain. Eng. 12, 223 (2019)

2. Z. Hao, B. Yang, D. Jahng, Water Res. 138, 250 (2018) 3. A. González, M. Plaza, J. Pis, F. Rubiera, C. Pevida, Energy

Procedia 37, 134 (2013) 4. J. Park, B. Kim, J.W. Lee, Bioresour. Technol. 221, 55 (2016) 5. C.T. Primaz, T. Schena, E. Lazzari, E.B. Caramão, R.A.

Jacques, Fuel 232, 572 (2018) 6. H.D. Utomo, K. Hunter, Environ. Technol. 27, 25 (2006) 7. D.R. Vardon, B.R. Moser, W. Zheng, K. Witkin, R.L. Evan-

gelista, T.J. Strathmann, K. Rajagopalan, B.K. Sharma, ACS Sustain. Chem. Eng. 1, 1286 (2013)

8. E.E. Kwon, H. Yi, Y.J. Jeon, Bioresour. Technol. 136, 475 (2013)

9. D. Rodríguez-Padrón, M.J. Muñoz-Batista, H. Li, K. Shih, A.M. Balu, A. Pineda, R. Luque, ACS Sustain. Chem. Eng. 7, 17030 (2019)

10. R. Hachicha, O. Rekik, S. Hachicha, M. Ferchichi, S. Woodward, N. Moncef, J. Cegarra, T. Mechichi, Chemosphere 88, 677 (2012)

11. Y.S. Yun, M.H. Park, S.J. Hong, M.E. Lee, Y.W. Park, H.-J. Jin, ACS Appl. Mater. 7, 3684 (2015)

12. S.I. Mussatto, L.M. Carneiro, J.P. Silva, I.C. Roberto, J.A. Teix-eira, Carbohydr. Polym. 83, 368 (2011)

13. F. Leifa, A. Pandey, C.R. Soccol, Braz. Arch. Biol. Technol. 44, 205 (2001)

14. N.M.M. Alvarez, J.M. Pastrana, Y. Lagos, J.J. Lozada, Sustain. Chem. Pharm. 10, 60 (2018)

15. P.S. Murthy, M.M. Naidu, Resour. Conserv. Recycl. 66, 45 (2012) 16. N. Zarrinbakhsh, T. Wang, A. Rodriguez-Uribe, M. Misra, A.K.

Mohanty, BioResources 11, 7637 (2016) 17. M. Mahyari, M.S. Laeini, A. Shaabani, Chem. Commun. 50,

7855 (2014) 18. A. Shaabani, S. Keshipour, M. Hamidzad, S. Shaabani, J. Mol.

Catal. A: Chem. 395, 494 (2014) 19. A. Shaabani, R. Mohammadian, H. Farhid, M.K. Alavijeh, M.M.

Amini, Catal. Lett. 149, 1237 (2019) 20. A. Shaabani, Z. Hezarkhani, Cellulose 22, 3027 (2015) 21. R.J. Taylor, M. Reid, J. Foot, S.A. Raw, Acc. Chem. Res. 38, 851

(2005) 22. A. Shaabani, A. Maleki, Chem. Pharm. Bull. 56, 79 (2008) 23. A. Shaabani, A. Maleki, M. Behnam, Synth. Commun. 39, 102

(2008) 24. A. Shaabani, R. Mohammadian, A. Hashemzadeh, R. Afshari,

M.M. Amini, New J. Chem. 42, 4167 (2018) 25. M.T. Nazeri, R. Mohammadian, H. Farhid, A. Shaabani, B.

Notash, Tetrahedron Lett. 61, 151408 (2020) 26. M.T. Nazeri, H. Farhid, R. Mohammadian, A. Shaabani, ACS

Comb. Sci. 22, 361 (2020) 27. M.B. Gawande, P.S. Branco, R.S. Varma, Chem. Soc. Rev. 42,

3371 (2013) 28. A. Maleki, V. Eskandarpour, J. Iran. Chem. Soc. 16, 1459 (2019) 29. L. Geng, B. Zheng, X. Wang, W. Zhang, S. Wu, M. Jia, W. Yan,

G. Liu, ChemCatChem 8, 805 (2016) 30. Z.-H. Zhang, H.-Y. Lü, S.-H. Yang, J.-W. Gao, J. Comb. Chem.

12, 643 (2010) 31. L. Zhou, J. He, J. Zhang, Z. He, Y. Hu, C. Zhang, H. He, J. Phys.

Chem. C 115, 16873 (2011) 32. B. Dang, Y. Chen, X. Shen, C. Jin, Q. Sun, X. Li, Cellulose 26,

5455 (2019) 33. B. Karimi, S. Abedi, J.H. Clark, V. Budarin, Angew. Chem. Int.

Ed. 45, 4776 (2006) 34. T. Mitsudome, A. Noujima, T. Mizugaki, K. Jitsukawa, K.

Kaneda, Adv. Synth. Catal. 351, 1890 (2009) 35. H. Alamgholiloo, S. Rostamnia, K. Zhang, T.H. Lee, Y.-S. Lee,

R.S. Varma, H.W. Jang, M. Shokouhimehr, ACS Omega 5, 5182 (2020)

36. F. Zamani, S.M. Hosseini, Catal. Commun. 43, 164 (2014) 37. E. Prathibha, R. Rangasamy, A. Sridhar, K. Lakshmi, Chemis-

trySelect 5, 988 (2020) 38. M. Kotani, T. Koike, K. Yamaguchi, N. Mizuno, Green Chem. 8,

735 (2006) 39. L. Zhang, P. Li, J. Yang, M. Wang, L. Wang, ChemPlusChem 79,

217 (2014) 40. H. Yan, H.-Y. Zhang, L. Wang, Y. Zhang, J. Zhao, React. Kinet.

Mech. Catal. 125, 789 (2018) 41. R.L. Oliveira, P.K. Kiyohara, L.M. Rossi, Green Chem. 12, 144

(2010) 42. L. Sun, W. Zhan, J. Shang, G. Chen, S. Wang, Y. Chen, Z. Long,

React. Kinet. Mech. Catal. 126, 1055 (2019) 43. A. Shaabani, Z. Hezarkhani, S. Shaabani, RSC Adv. 4, 64419

(2014) 44. A. Shaabani, M. BorjianBoroujeni, M.S. Laeini, Appl. Orga-

nomet. Chem. 30, 154 (2016)

1209Journal of the Iranian Chemical Society (2021) 18:1199–1209

1 3

Affiliations

Hassan Farhid1 · Ahmad Shaabani1

* Ahmad Shaabani a-shaabani@sbu.ac.ir

1 Faculty of Chemistry, Shahid Beheshti University, G.C., P.O. Box 19396-4716, Tehran, Iran

45. A. Shaabani, S. Shaabani, H. Afaridoun, RSC Adv. 6, 48396 (2016)

46. A. Maleki, T. Kari, Catal. Lett. 148, 2929 (2018) 47. S. Vidyacharan, A.H. Shinde, B. Satpathi, D.S. Sharada, Green

Chem. 16, 1168 (2014) 48. A. Habibi, Z. Tarameshloo, S. Rostamizadeh, A.M. Amani, Lett.

Org. Chem. 9, 155 (2012) 49. M. Adib, E. Sheikhi, N. Rezaei, Tetrahedron Lett. 52, 3191 (2011) 50. K.N. Shivhare, M.K. Jaiswal, A. Srivastava, S.K. Tiwari, I. Sid-

diqui, New J. Chem. 42, 16591 (2018) 51. S. Rostamnia, A. Hassankhani, RSC Adv. 3, 18626 (2013) 52. A. Shaabani, H. Nosrati, M. Seyyedhamzeh, Res. Chem. Intermed.

41, 3719 (2015) 53. A. Shaabani, E. Soleimani, A. Maleki, Tetrahedron Lett. 47, 3031

(2006) 54. A. Boltjes, A. Dömling, Eur. J. Org. Chem. 2019, 7007 (2019)

55. M. Hussain, J. Liu, L. Fu, M. Hasan, J. Heterocycl. Chem. 57, 955 (2020)

56. M. Heydari, N. Azizi, Z. Mirjafari, M.M. Hashemi, J. Iran. Chem. Soc. 16, 2357 (2019)

57. S. Rostamnia, M. Jafari, Appl. Organomet. Chem. 31, e3584 (2017)

58. A.L. Rousseau, P. Matlaba, C.J. Parkinson, Tetrahedron Lett. 48, 4079 (2007)

59. T. Sanaeishoar, H. Tavakkoli, F. Mohave, Appl. Catal. A-Gen. 470, 56 (2014)

60. A.H. Shinde, M. Srilaxmi, B. Satpathi, D.S. Sharada, Tetrahedron Lett. 55, 5915 (2014)

61. A. Shaabani, E. Soleimani, A. Maleki, Monatsh. Chem. 138, 73 (2007)