Plan
Comptes Rendus
no. 6

Efficient and convenient oxidation of alcohols to aldehydes and ketones with molecular oxygen mediated by In(NO3)3 in ionic liquid [C12mim][FeBr4]
Yu Lin Hu1  ; Dong Fang2
1 College of Materials and Chemical Engineering, China Three Gorges University, Yancheng 443002, PR China
2 College of Chemistry and Chemical Engineering, Yancheng Teachers University, Yancheng 224002, PR China
Comptes Rendus. Chimie, Volume 18 (2015) no. 6, pp. 614-618.

Résumé

A simple, efficient, and ecofriendly procedure for the aerobic oxidation of alcohols to aldehydes and ketones in the presence of In(NO3)3/[C12mim][FeBr4] in aqueous media has been developed. The oxidation reactions afford the target products in good to high yields and no over-oxidation was observed. The products can be separated by a simple extraction with dichloromethane, and the system can be recycled and reused without loss of activity.

Métadonnées
Reçu le :
Accepté le :
Publié le :
DOI : 10.1016/j.crci.2014.11.002
Mots clés : Oxidation, Alcohol, Molecular oxygen, In(NO3)3, Ionic liquid
Yu Lin Hu 1 ; Dong Fang 2

1 College of Materials and Chemical Engineering, China Three Gorges University, Yancheng 443002, PR China
2 College of Chemistry and Chemical Engineering, Yancheng Teachers University, Yancheng 224002, PR China 
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     author = {Yu Lin Hu and Dong Fang},
     title = {Efficient and convenient oxidation of alcohols to aldehydes and ketones with molecular oxygen mediated by {In(NO\protect\textsubscript{3})\protect\textsubscript{3}} in ionic liquid {[C\protect\textsubscript{12}mim][FeBr\protect\textsubscript{4}]}},
     journal = {Comptes Rendus. Chimie},
     pages = {614--618},
     publisher = {Elsevier},
     volume = {18},
     number = {6},
     year = {2015},
     doi = {10.1016/j.crci.2014.11.002},
     language = {en},
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JO  - Comptes Rendus. Chimie
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%0 Journal Article
%A Yu Lin Hu
%A Dong Fang
%T Efficient and convenient oxidation of alcohols to aldehydes and ketones with molecular oxygen mediated by In(NO3)3 in ionic liquid [C12mim][FeBr4]
%J Comptes Rendus. Chimie
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Yu Lin Hu; Dong Fang. Efficient and convenient oxidation of alcohols to aldehydes and ketones with molecular oxygen mediated by In(NO3)3 in ionic liquid [C12mim][FeBr4]. Comptes Rendus. Chimie, Volume 18 (2015) no. 6, pp. 614-618. doi : 10.1016/j.crci.2014.11.002. https://comptes-rendus.academie-sciences.fr/chimie/articles/10.1016/j.crci.2014.11.002/

Version originale du texte intégral

1 Introduction

Aldehydes and ketones are important classes of chemicals that have been used extensively as synthetic intermediates in the preparation of a variety of fine or special chemicals, such as drugs, vitamins, fragrances, etc. [1]. Up to now, many publications in the open literature have been found related to the synthesis of these types of compounds, and a well-known method for such a synthesis is the oxidation of alcohols [2]. Traditional methods for performing such a transformation generally involve the use of stoichiometric amounts of strong oxidizing reagents (e.g., MnO2, SeO2, CrO3, and RuO4) [2–4], and suffer from considerable drawbacks, such as high cost, low yield, harsh or delicate reaction conditions, and a large amount of waste by-products. Oxidation with ceric ammonium nitrate [5], H5IO6 [6], diaziridinone [7], tert-butyl hydroperoxide [8], trichloroisocyanuric acid [9,10], H2O2 [11–13], and other reagents [14–16] have also been developed for this conversion. However, some of the procedures are often associated with one or more disadvantages, such as long reaction times, high temperatures, difficulties in work-up, use of expensive, toxic and moisture-sensitive reagents, and difficulties in recycling the catalyst.

Molecular oxygen has recently been utilized as an attractive oxidant for the oxidation of alcohols for the production of these compounds due to cheap price and environmental friendly nature. Therefore, molecular oxygen-based protocols are powerful methods for oxidation of alcohols and attract a great attention, which make the reactions of choice in large- and industrial-scale applications. A variety of catalytic systems, such as nanopalladium [17], Pd(OAc)2/DMSO[18], Ru(TPFPP)(CO) [19], PI Ru/TEMPO [20], CeO3/RuCl3 [21] VOPO4/TEMPO [22], VO(acac)2/DABCO [23], [copper(II)-(N ligand)n]/TEMPO [24], gold [25], OsHCl(CO)(PiPr3)2 [26], and other systems [27–29], have been developed for this conversion. However, these procedures are invariably associated with one or more disadvantages, such as long reaction times, expensive metals, low yields, use of toxic compounds, difficulties in work-up, harmfulness toward the environment, etc. Consequently, the search for new and environmentally benign synthetic methodologies for the oxidation of alcohols that address these drawbacks remains of value and interest.

Ionic liquids (ILs) have attracted considerable attention during the past few years due, in some cases, to their favourable properties, such as very low vapour pressure, wide liquid temperature range, good ionic conductivity, excellent electrochemical properties, and strong ability to dissolve many chemicals [30–33]. Therefore, ILs have recently gained recognition from scholars from various fields, such as analytical and separation science [34], chemical synthesis [35,36], biocatalytic transformations [37], electrochemistry [38], and catalysis [39–41]. In continuation of our interest in exploring green oxidation reactions in ionic liquids, we report herein a new, efficient and environmentally friendly protocol for the selective aerobic oxidation of alcohols to the aldehydes and ketones mediated by indium nitrate (In(NO3)3) in ionic liquid 1-dodecyl-3-methylimidazolium iron bromide ([C12mim][FeBr4]) under mild conditions (Scheme 1). Furthermore, we demonstrate that the catalytic system can be recycled and reused without any significant loss of activity.

Scheme 1

Aerobic oxidation of alcohols to aldehydes and ketones.

2 Experimental

2.1 General

All the chemicals were from commercial sources without any pre-treatment. All reagents were of analytical grade. The ionic liquids were synthesized according to the literature procedure [33]. 1H NMR spectra were recorded on a Bruker 500-MHz spectrometer using CDCl3 as the solvent with tetramethylsilane (TMS) as an internal standard. High-performance liquid chromatography (HPLC) experiments were performed on a liquid chromatograph (Dionex Softron GmbH, America), consisting of a pump (P680) and ultraviolet-visible light detector (UVD) system (170U). The experiments were performed on Diacovery C18 column, ø 4.6 × 250 mm. Elemental analysis was performed on a Vario EL III instrument (Elmentar Anlalysensy Teme GmbH, Germany).

2.2 General procedure for oxidation reactions

All the three-necked flasks were loaded with alcohol (0.1 mol), In(NO3)3 (0.3 mol), [C12mim][FeBr4] (30 mL), and H2O (10 mL). O2 gas was bubbled into the flask at the flow rate of 60 mL/min. The reaction mixture was stirred at 40 °C for an appropriate time (Table 3), the reaction progress was monitored by HPLC. The mixture was then cooled to room temperature and the organic phase was extracted with dichloromethane (3 × 20 mL). The dichloromethane solution was washed with 5% NaHCO3 (2 × 20 mL) and water (3 × 20 mL), and then dried over anhydrous Na2SO4. The solvent was removed and the residue was distilled under vacuum to give the desired pure product. The rest of the ionic liquid and In(NO3)3 was recovered. Fresh substrates were then recharged to the recovered catalytic system and then recycled under identical reaction conditions. The target substrates were characterized by elemental analysis, 1H NMR spectra or compared with their authentic samples. Spectroscopic data for selected products is as follows.

Table 3

Oxidation of alcohols to aldehydes and ketonesa.

EntrySubstrateProductTime (h)Conversion (%) bYield (%) c
1610092
2610094
3610095
4610093
5610096
6109689
7109586
8810090
9810091
10610095
11610093
12248475d
13248167d

a Unless otherwise specified, the reactions were carried out with alcohol (0.1 mol), In(NO3)3 (0.3 mol), [C12mim][FeBr4] (30 mL), and H2O (10 mL) with O2 gas bubbling (60 mL/min) at 40 °C.

b Isolated conversion.

c Isolated yield.

d The reaction was carried out at 60 °C.

2.2.1 4-Tert-butylbenzaldehyde

Colourless oil. 1H NMR: δ = 1.31 (s, CH3, 9H), 7.51–7.72 (m, Ar–H, 4H), 9.94 (s, CHO, 1H). Anal. calcd. for C11H14O: C, 81.39; H, 8.68; O, 9.84. Found: C, 81.44; H, 8.70; O, 9.86 (Table 3, entry 4).

2.2.2 2,4,6-Trimethylbenzaldehyde

Colourless oil. 1H NMR: δ = 2.15 (s, CH3, 3H), 2.39 (s, CH3, 6H), 7.21 (s, Ar–H, 2H), 9.89 (s, CHO, 1H). Anal. calcd. for C10H12O: C, 81.03; H, 8.14; O, 10.76. Found: C, 81.02; H, 8.16; O, 10.78 (Table 3, entry 5).

2.2.3 4-Acetylbenzaldehyde

White solid, mp: 35–37 °C. 1H NMR: δ = 2.63 (s, CH3, 3H), 7.91–7.96 (m, Ar–H, 2H), 8.17–8.22 (m, Ar–H, 2H), 9.96 (s, CHO, 1H). Anal. calcd for C9H8O2: C, 72.91; H, 5.42; O, 21.57. Found: C, 72.96; H, 5.44; O, 21.60 (Table 3, entry 6).

2.2.4 trans-Cinnamaldehyde

Colourless oil. 1H NMR: δ = 6.65 (d, J = 16.5 Hz, CH, 1H), 6.67 (dd, J = 6.5, 16.5 Hz, CH, 1H), 7.34–7.47 (m, Ar–H, 5H), 9.69 (d, J = 6.5 Hz, CHO, 1H). Anal. calcd for C9H8O: C, 81.79; H, 6.10; O, 12.11. Found: C, 81.79; H, 6.10; O, 12.11 (Table 3, entry 10).

2.2.5 3,7-Dimethyl-2,6-octadienal

Colourless liquid. 1H NMR: δ = 1.59 (s, CH3, 3H), 1.93(s, CH3, 3H), 2.21 (s, CH3, 3H), 2.58 (m, CH2CH2, 4H), 5.07 (s, CH, 1H), 5.87 (d, J = 7.0 Hz, CH, 1H), 9.85 (d, J = 7.0 Hz, CHO, 1H). Anal. calcd for C10H16O: C, 78.87; H, 10.59; O, 10.52. Found: C, 78.90; H, 10.59; O, 10.51 (Table 3, entry 11).

3 Results and discussion

A preliminary survey of the reaction conditions (Table 1) used benzyl alcohol (0.1 mol) as the model substrate in the presence of ionic liquid [C12mim][FeBr4] and In(NO3)3. In the absence of ionic liquid and In(NO3)3, no product was detected (Table 1, entry 1). When the reaction was performed in the presence of ionic liquid [C12mim][FeBr4] (10 mL) or catalyst In(NO3)3 (1.0 equiv), the product could be obtained in a higher yield 28% (Table 1, entry 2) or 23% in a shorter time (12 h) (Table 1, entry 3) under the same conditions. The yield can be greatly improved with the combined use of [C12mim][FeBr4] and In(NO3)3 (Table 1, entries 4–11), and it reached its maximum value (92%) within a shorter time (6 h) when the addition of [C12mim][FeBr4] (30 mL) and In(NO3)3 (3.0 equiv.) (Table 1, entry 10). However, upon further addition of [C12mim][FeBr4] (Table 1, entry 7) or In(NO3)3 (Table 1, entry 11) under the same conditions, the yield was not enhanced significantly. These experiments revealed that In(NO3)3 and ionic liquid [C12mim][FeBr4] are crucial for the oxidation, and the lack of any component can lead to a much lower yield. Therefore, the optimal reaction conditions were observed in Table 1, entry 10.

Table 1

[C12mim][FeBr4]/In(NO3)3 catalysed the oxidation of benzyl alcohol with molecular oxygena.

Entry[C12mim][FeBr4] (mL)In(NO3)3 (equiv.)Time (h)Yield (%) b
1––240
210–1228
3–1.01223
4201.0852
5281.0864
6301.0867
7321.0867
8302.0881
9302.8690
10303.0692
11303.2692

a The reactions were carried out with benzyl alcohol (0.1 mol), In(NO3)3 (0.3 mol), [C12mim][FeBr4] (30 mL), and H2O (10 mL) with the bubbling of O2 gas (60 mL/min) at 40 °C.

b Isolated yield of benzaldehyde.

The effects of different ionic liquids, such as [C8mim][FeBr4], [C12mim][FeBr4], [C12mim][FeCl4], [C12mim][OTf], [C12mim][BF4], and [C12mim]Br, were tested with In(NO3)3 as a catalyst in the reaction (Table 2, entries 1–6), and it was observed that [C12mim][FeBr4] demonstrated the best performance (Table 2, entry 2). The different catalytic effects of ILs may be attributed to their different abilities to stabilize and dissolve O2, the catalyst and the substrate. Under our reaction conditions, O2 may be more soluble in [C12mim][FeBr4], leading to a higher effective concentration of the oxidant, which increases the encounter probabilities between the substrate and the reactive species, and so the higher rate and yield of the reaction were observed. Furthermore, besides In(NO3)3, other types of catalysts were also tested in this model reaction (Table 2, entries 7–11). The results showed that In(NO3)3 demonstrated the best performance. In addition, no over-oxidized product (benzoic acid) was detected by 1H NMR analysis of the crude reaction mixtures in all the cases. Therefore, the combination of [C12mim][FeBr4] and In(NO3)3 was chosen as the optimal conditions for further exploration.

Table 2

Optimization of the conditions for oxidation of benzyl alcohol with molecular oxygena.

EntryIonic liquidCatalystTime (h)Yield (%) b
1[C8mim][FeBr4]In(NO3)3689
2[C12mim][FeBr4]In(NO3)3692
3[C12mim][FeCl4]In(NO3)3685
4[C12mim][OTf]In(NO3)3641
5[C12mim][BF4]In(NO3)3656
6[C12mim]BrIn(NO3)3678
7[C12mim][FeBr4]Cu(NO3)2666
8[C12mim][FeBr4]Fe(NO3)3670
9[C12mim][FeBr4]AgNO3678
10[C12mim][FeBr4]MnO2845
11[C12mim][FeBr4]Ba(NO3)2661

a The reactions were carried out with benzyl alcohol (0.1 mol), catalyst (0.3 mol), IL (30 mL), and H2O (10 mL) with the bubbling of O2 gas (60 mL/min) at 40 °C.

b Isolated yield of benzaldehyde.

In addition, the catalytic system could be typically recovered and reused for subsequent reactions with no appreciable decrease in yields and reaction rates (Fig. 1). The recycling process involved the removal of the upper layer of product, by a simple extraction with organic solvent. Fresh substrates were then recharged to the under-layer of catalytic system and the mixture was heated to react once again.

Fig. 1

Repeated reactions using recovered Ln(NO3)3.

With these results in hand, the catalytic system was then applied to various alcohols as summarized in Table 3. It is clear that various types of benzylic and allylic alcohols, both primary and secondary, have been successfully oxidized to the corresponding aldehydes and ketones in good to high conversions and yields (Table 3, entries 1–11), whereas the aliphatic alcohols were less reactive, and the reactions proceeded more slowly, and even under more drastic reaction conditions, the reactions were still incomplete (Table 3, entries 12 and 13). Surprisingly, the oxidation of primary alcohols to the corresponding carbonyl compounds is faster and more efficient than that of secondary alcohols (Table 3, entries 8 and 9). In addition, it was also observed that the electronic nature of the substituents on the aromatic ring has some impact on the reaction rate. Benzylic alcohols, especially those with electron-donating substituents (Table 3, entries 2–5), were more reactive than those with electron-withdrawing substituents (Table 3, entries 6 and 7), providing excellent yields.

4 Conclusions

In conclusion, a new efficient oxidation reaction system using [C12mim][FeBr4] in combination with In(NO3)3 has been developed, which is capable of converting alcohols into the corresponding aldehydes and ketones in good to excellent isolated yield. Mild reaction conditions, simplicity of operation, high yields, stability, easy isolation of products, and the excellent recyclability of the catalytic system are the attractive features of this methodology. The scope, definition of the mechanism and synthetic application of this reaction are currently under study in our laboratory.

Acknowledgements

We thank the Natural Science Foundation of Jiangsu Province (No. BK20140460 and BK20141257) and the University Science Research Project of Jiangsu Province (No. 14KJD150010) for supporting this research.

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