Startseite Hydrocyanation of 2-arylmethyleneindan-1,3-diones using potassium hexacyanoferrate(II) as a nontoxic cyanating agent
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Hydrocyanation of 2-arylmethyleneindan-1,3-diones using potassium hexacyanoferrate(II) as a nontoxic cyanating agent

  • Zheng Li EMAIL logo , Yan Du , Hao Lu , Aizhen Yang und Jingya Yang
Veröffentlicht/Copyright: 21. April 2018
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Abstract

The hydrocyanation of 2-arylmethyleneindan-1,3-diones with potassium hexacyanoferrate(II) as a nontoxic cyanating agent to synthesize 2-(1,3-dioxoindan-2-yl)-2-arylacetonitriles in the presence of benzoyl chloride as a promoter and potassium carbonate as a base by a one-pot procedure is described. The use of nontoxic and inexpensive cyanide source, high yield and simple workup procedures are the advantages of this protocol.

Keywords: 2-arylmethyleneindan-1,3-dione; hydrocyanation; nontoxic cyanating agent; potassium hexacyanoferrate(II)

1 Introduction

The conjugate addition of various cyanating agents as nucleophiles to Michael acceptors is an important method for the formation of C-CN bonds in organic synthesis [1], [2], [3], [4], [5]. The produced β-cyano ketones can be widely used in organic synthesis [6], [7], [8], and cyano unit can be readily converted into different groups including amides, amines, carboxylic acids, tetrazoles and amidines [9], [10]. However, the reported reactions generally use various strong toxic or unstable chemicals, such as HCN [11], LiCN [12], NaCN [13], KCN [14], [15], diethylaluminum cyanide [16], [17], trimethylsilyl cyanide [18], [19], [20], [21], [22], [23], [24], [25], [26], [27], [28], [29], [30], [31] and acetone cyanohydrin [32], [33], [34], as cyanating agents. Therefore, it is still necessary to explore a nontoxic cyanating agent for the cyanation reaction.

Potassium hexacyanoferrate(II), K4[Fe(CN)6], as a nontoxic and abundant inorganic chemical has been used in the food industry. Recently, it has been used as a nontoxic cyanating agent to synthesize benzonitriles [35], [36], [37], [38], [39], [40], [41], [42], [43], [44], [45], [46], [47], [48], [49], [50], [51], [52], [53], aroyl cyanides [54], sulfonyl cyanides [55], benzyl cyanides [56], [57] and cinnamonitriles [58] by substitution reactions. Our research work currently focused on the addition reactions for unsaturated substances using K4[Fe(CN)6] as a nontoxic cyanating agent [59], [60], [61], [62], [63], [64], [65], [66], [67], [68], [69], [70], [71], [72], [73], [74], [75].

Indan-1,3-dione scaffolds are essential in medicinal chemistry as they can be used as anticancer agents [76], and in material chemistry as they can be used as optoelectronic additives [77]. Therefore, the exploration for synthetic methods for diverse compounds bearing indan-1,3-dione moiety has potential benefits for the future.

In this work, we report the hydrocyanation of 2-arylmethyleneindan-1,3-diones using K4[Fe(CN)6] as a nontoxic cyanating agent to synthesize a series of β-cyano ketones bearing indan-1,3-dione moiety.

2 Materials and methods

1H nuclear magnetic resonance (NMR) and 13C NMR spectra were obtained with the Mercury-400 MB or Mercury-600 MB instrument using CDCl3 as solvent. Elemental analyses were conducted on a Vario El Elemental Analysis instrument. 2-Arylmethyleneindan-1,3-diones were synthesized using methods from the literature [78], [79].

2.1 The general procedure for the hydrocyanation of 2-arylmethyleneindan-1,3-diones

The mixture of potassium hexacyanoferrate(II) (0.2 mmol, 0.08 g) and benzoyl chloride (1.2 mmol, 0.17 g) was stirred at 160°C for 3 h. Then, the resulting mixture was cooled to room temperature, and 2-arylmethleneindan-1,3-dione (1 mmol, 1a: 0.26 g, 1b: 0.28 g, 1c: 0.28 g, 1d: 0.28 g, 1e: 0.29 g, 1f: 0.28 g, 1g: 0.28 g, 1h: 0.30 g, 1i: 0.34 g, 1j: 0.34 g, 1k: 0.34 g, 1l: 0.31 g, 1m: 0.33 g, 1n: 0.27 g, 1o: 0.25 g, 1p: 0.29 g, 1q: 0.23 g), potassium carbonate (0.2 mmol, 0.03 g) and water (2 mmol, 0.04 g) in 5 ml of DMF were added, and the system was stirred at room temperature for another 4 h. After the completion of the reaction, the solids were removed by filtration. The solution was evaporated under reduced pressure, and the residue was separated by column chromatography using ethyl acetate and petroleum ether (1:2) as eluent to obtain pure product. The analytical data for products are shown below and for the NMR spectra see Supplementary material.

2.1.1 2-(1,3-Dioxoindan-2-yl)-2-phenylacetonitrile (2a):

Yellow liquid; 1H NMR (600 MHz, CDCl3) δ 7.93–7.91 (m, 2H, ArH), 7.82–7.79 (m, 2H, ArH), 7.37–7.36 (d, J=6.9 Hz, 2H, ArH), 7.28–7.21 (m, 3H, ArH), 4.75–4.74 (d, J=3.2 Hz, 1H, CH), 3.61–3.60 (d, J=3.2 Hz, 1H, CH). 13C NMR (150 MHz, CDCl3) δ 195.37 (CO), 195.26 (CO), 136.24 (Ar), 136.15 (Ar), 128.94 (Ar), 128.72 (Ar), 128.50 (Ar), 123.57 (Ar), 123.54 (Ar), 118.03 (CN), 55.89 (CH), 34.06 (CH). Anal. Calcd. for C17H11NO2: C, 78.15; H, 4.24; N, 5.36. Found: C, 78.01; H, 4.26; N, 5.38.

2.1.2 2-(1,3-Dioxoindan-2-yl)-2-(o-tolyl)acetonitrile (2b):

Yellow liquid; 1H NMR (600 MHz, CDCl3) δ 8.06–8.02 (m, 1H, ArH), 7.98–7.97 (m, 1H, ArH), 7.90–7.86 (m, 2H, ArH), 7.68–7.67 (d, J=7.0 Hz, 1H, ArH), 7.26–7.22 (m, 2H, ArH), 7.18–7.17 (d, J=6.8 Hz, 1H, ArH), 4.89–4.88 (d, J=3.2 Hz, 1H, CH), 3.44–3.43 (d, J=3.2 Hz, 1H, CH), 2.43 (s, 3H, CH3). 13C NMR (150 MHz, CDCl3) δ 195.98 (CO), 195.17 (CO), 142.32 (Ar), 141.80 (Ar), 136.42 (Ar), 136.25 (Ar), 135.05 (Ar), 131.01 (Ar), 130.91 (Ar), 129.28 (Ar), 128.86 (Ar), 126.74 (Ar), 123.73 (Ar), 123.70 (Ar), 117.69 (CN), 54.72 (CH), 31.14 (CH), 19.11 (CH3). Anal. Calcd. for C18H13NO2: C, 78.53; H, 4.76; N, 5.09. Found: C, 78.64; H, 4.74; N, 5.06.

2.1.3 2-(1,3-Dioxoindan-2-yl)-2-(m-tolyl)acetonitrile (2c):

Yellow liquid; 1H NMR (600 MHz, CDCl3) δ 7.93–7.91 (m, 2H, ArH), 7.82–7.79 (m, 2H, ArH), 7.18 (s, 1H, ArH), 7.15–7.12 (m, 2H, ArH), 7.03–7.02 (d, J=4.1 Hz, 1H, ArH), 4.71–4.70 (d, J=3.3 Hz, 1H, CH), 3.59–3.57 (d, J=3.2 Hz, 1H, CH), 2.27 (s, 3H, CH3). 13C NMR (150 MHz, CDCl3) δ 195.39 (CO), 195.33 (CO), 142.22 (Ar), 142.06 (Ar), 138.80 (Ar), 136.19 (Ar), 136.13 (Ar), 131.30 (Ar), 129.45 (Ar), 129.10 (Ar), 128.78 (Ar), 125.49 (Ar), 123.54 (Ar), 123.51 (Ar), 118.10 (CN), 55.92 (CH), 34.01 (CH), 21.26 (CH3). Anal. Calcd. for C18H13NO2: C, 78.53; H, 4.76; N, 5.09. Found: C, 78.48; H, 4.75; N, 5.11.

2.1.4 2-(1,3-Dioxoindan-2-yl)-2-(p-tolyl)acetonitrile (2d):

Yellow liquid; 1H NMR (400 MHz, CDCl3) δ 7.97–7.90 (m, 2H, ArH), 7.84–7.79 (m, 2H, ArH), 7.25–7.23 (d, J=8.1 Hz, 2H, ArH), 7.07–7.04 (d, J=8.3 Hz, 2H, ArH), 4.73–4.72 (d, J=3.2 Hz, 1H, CH), 3.60–3.59 (d, J=3.2 Hz, 1H, CH), 2.24 (s, 3H, CH3). 13C NMR (150 MHz, CDCl3) δ 195.51 (CO), 195.41 (CO), 142.26 (Ar), 142.03 (Ar), 138.62 (Ar), 136.22 (Ar), 136.13 (Ar), 129.60 (Ar), 128.46 (Ar), 128.36 (Ar), 123.57 (Ar), 123.54 (Ar), 118.26 (CN), 55.95 (CH), 33.70 (CH), 20.99 (CH3). Anal. Calcd. for C18H13NO2: C, 78.53; H, 4.76; N, 5.09. Found: C, 78.53; H, 4.76; N, 5.09.

2.1.5 2-(1,3-Dioxoindan-2-yl)-2-(4-methoxyphenyl)acetonitrile (2e):

Yellow liquid; 1H NMR (600 MHz, CDCl3) δ 7.93–7.90 (m, 2H, ArH), 7.82–7.78 (m, 2H, ArH), 7.26–7.25 (d, J=7.6 Hz, 2H, ArH), 6.76–6.74 (d, J=7.5 Hz, 2H, ArH), 4.70–4.69 (d, J=3.3 Hz, 1H, CH), 3.71 (s, 3H, OCH3), 3.57–3.56 (d, J=3.2 Hz, 1H, CH). 13C NMR (150 MHz, CDCl3) δ 195.62 (CO), 195.47 (CO), 159.66 (Ar), 142.33 (Ar), 142.04 (Ar), 136.24 (Ar), 136.13 (Ar), 129.80 (Ar), 123.55 (Ar), 123.52 (Ar), 123.15 (Ar), 118.39 (CN), 114.25 (Ar), 56.00 (CH), 55.18 (OCH3), 33.32 (CH). Anal. Calcd. for C18H13NO3: C, 74.22; H, 4.50; N, 4.81. Found: C, 74.09; H, 4.52; N, 4.85.

2.1.6 2-(1,3-Dioxoindan-2-yl)-2-(4-hydroxyphenyl)acetonitrile (2f):

Yellow liquid; 1H NMR (600 MHz, CDCl3) δ 7.92–7.90 (m, 2H, ArH), 7.82–7.80 (m, 2H, ArH), 7.20–7.18 (dd, J=8.6, 2.2 Hz, 2H, ArH), 6.69–6.67 (dd, J=8.6, 2.1 Hz, 2H, ArH), 5.42 (s, 1H, OH), 4.68–4.67 (d, J=5.0 Hz, 1H, CH), 3.58–3.57 (d, J=5.0 Hz, 1H, CH). 13C NMR (150 MHz, CDCl3) δ 195.75 (CO), 195.63 (CO), 156.02 (Ar), 142.31 (Ar), 142.02 (Ar), 136.36 (Ar), 136.24 (Ar), 130.00 (Ar), 123.59 (Ar), 123.55 (Ar), 123.04 (Ar), 118.42 (CN), 115.83 (Ar), 55.97 (CH), 33.33 (CH). Anal. Calcd. for C17H11NO3: C, 73.64; H, 4.00; N, 5.05. Found: C, 73.71; H, 3.99; N, 5.03.

2.1.7 2-(1,3-Dioxoindan-2-yl)-2-(2-fluorophenyl)acetonitrile (2g):

Yellow liquid; 1H NMR (600 MHz, CDCl3) δ 8.03–8.01 (m, 1H, ArH), 7.99–7.95 (m, 1H, ArH), 7.89–7.86 (m, 2H, ArH), 7.70–7.67 (td, J=7.7, 1.6 Hz, 1H, ArH), 7.37–7.32 (m, 1H, ArH), 7.25–7.20 (t, J=7.6 Hz, 1H, ArH), 7.09–7.04 (m, 1H, ArH), 5.02–5.01 (d, J=3.7 Hz, 1H, CH), 3.58–3.57 (d, J=3.7 Hz, 1H, CH). 13C NMR (150 MHz, CDCl3) δ 195.24 (CO), 194.95 (CO), 160.29 (Ar), 158.64 (Ar), 142.00 (d, J=64.9 Hz, Ar), 136.40 (d, J=14.8 Hz, Ar), 133.69 (Ar), 130.81 (d, J=8.1 Hz, Ar), 130.63 (d, J=2.4 Hz, Ar), 130.15 (Ar), 128.46 (Ar), 124.71 (d, J=3.9 Hz, Ar), 123.72 (d, J=9.2 Hz, Ar), 119.48 (d, J=13.5 Hz, CN), 116.69 (Ar), 115.68 (d, J=20.8 Hz, Ar), 54.32 (CH), 28.45 (d, J=4.0 Hz, CH). Anal. Calcd. for C17H10FNO2: C, 73.11; H, 3.61; N, 6.80. Found: C, 73.03; H, 3.60; N, 6.84.

2.1.8 2-(4-Chlorophenyl)-2-(1,3-dioxoindan-2-yl)acetonitrile (2h):

Yellow liquid; 1H NMR (600 MHz, CDCl3) δ 7.93 (ddd, J=4.6, 3.1, 1.6 Hz, 2H, ArH), 7.85–7.82 (m, 2H, ArH), 7.33–7.29 (m, 2H, ArH), 7.26–7.22 (m, 2H, ArH), 4.73–4.72 (d, J=1.5 Hz, 1H, CH), 3.61–3.60 (dd, J=3.0, 1.5 Hz, 1H, CH). 13C NMR (150 MHz, CDCl3) δ 195.14 (CO), 194.95 (CO), 142.14 (Ar), 141.90 (Ar), 136.44 (Ar), 136.34 (Ar), 134.94 (Ar), 129.95 (Ar), 129.87 (Ar), 129.18 (Ar), 123.67 (Ar), 123.64 (Ar), 117.69 (CN), 55.81 (CH), 33.34 (CH). Anal. Calcd. for C17H10ClNO2: C, 69.05; H, 3.41; N, 4.74. Found: C, 69.11; H, 3.40; N, 4.72.

2.1.9 2-(2-Bromophenyl)-2-(1,3-dioxoindan-2-yl)acetonitrile (2i):

Yellow liquid; 1H NMR (600 MHz, CDCl3) δ 8.08–8.04 (m, 1H, ArH), 8.01–7.98 (m, 1H, ArH), 7.92–7.88 (m, 2H, ArH), 7.63–7.61 (d, J=7.9 Hz, 1H, ArH), 7.48–7.45 (q, J=7.4 Hz, 2H, ArH), 7.29–7.27 (t, J=7.7 Hz, 1H, ArH), 5.16–5.15 (d, J=3.0 Hz, 1H, CH), 3.68–3.67 (dd, J=3.4, 1.2 Hz, 1H, CH). 13C NMR (150 MHz, CDCl3) δ 195.25 (CO), 195.20 (CO), 142.38 (Ar), 141.59 (Ar), 136.47 (Ar), 136.33 (Ar), 133.20 (Ar), 131.66 (Ar), 131.36 (Ar), 130.48 (Ar), 127.98 (Ar), 123.82 (Ar), 123.70 (Ar), 122.68 (Ar), 116.70 (CN), 53.81 (CH), 34.80 (CH). Anal. Calcd. for C17H10BrNO2: C, 60.02; H, 2.96; N, 4.12. Found: C, 59.94; H, 2.98; N, 4.13.

2.1.10 2-(3-Bromophenyl)-2-(1,3-dioxoindan-2-yl)acetonitrile (2j):

Yellow liquid; 1H NMR (600 MHz, CDCl3) δ 7.97–7.93 (m, 2H, ArH), 7.86–7.82 (m, 2H, ArH), 7.54–7.53 (t, J=1.9 Hz, 1H, ArH), 7.39–7.38 (d, J=8.1 Hz, 1H, ArH), 7.35–7.34 (d, J=8.0 Hz, 1H, ArH), 7.17–7.14 (t, J=7.9 Hz, 1H, ArH), 4.71–4.70 (d, J=3.2 Hz, 1H, CH), 3.61–3.60 (d, J=3.2 Hz, 1H, CH). 13C NMR (150 MHz, CDCl3) δ 194.97 (CO), 194.87 (CO), 142.03 (Ar), 141.91 (Ar), 136.46 (Ar), 136.40 (Ar), 133.60 (Ar), 132.05 (Ar), 131.51 (Ar), 130.48 (Ar), 127.24 (Ar), 123.73 (Ar), 123.71 (Ar), 122.91 (Ar), 117.39 (CN), 55.79 (CH), 33.45 (CH). Anal. Calcd. for C17H10BrNO2: C, 60.02; H, 2.96; N, 4.12. Found: C, 60.08; H, 2.94; N, 4.15.

2.1.11 2-(4-Bromophenyl)-2-(1,3-dioxoindan-2-yl)acetonitrile (2k):

Yellow liquid; 1H NMR (600 MHz, CDCl3) δ 7.95–7.93 (m, 2H, ArH), 7.86–7.81 (m, 2H, ArH), 7.40–7.39 (d, J=7.1 Hz, 2H, ArH), 7.27–7.24 (m, 2H, ArH), 4.71–4.70 (d, J=2.8 Hz, 1H, CH), 3.62–3.61 (dd, J=3.3, 1.3 Hz, 1H, CH). 13C NMR (150 MHz, CDCl3) δ 195.15 (CO), 194.95 (CO), 142.12 (Ar), 141.87 (Ar), 136.48 (Ar), 136.38 (Ar), 132.15 (Ar), 130.25 (Ar), 130.17 (Ar), 128.46 (Ar), 123.71 (Ar), 123.66 (Ar), 117.65 (CN), 55.75 (CH), 33.39 (CH). Anal. Calcd. for C17H10BrNO2: C, 60.02; H, 2.96; N, 4.12. Found: C, 60.06; H, 2.96; N, 4.10.

2.1.12 2-(1,3-Dioxoindan-2-yl)-2-(3-nitrophenyl)acetonitrile (2l):

Yellow liquid; 1H NMR (600 MHz, CDCl3) δ 8.27–8.26 (t, J=2.1 Hz, 1H, ArH), 8.17–8.15 (dd, J=8.2, 2.2 Hz, 1H, ArH), 7.99–7.96 (m, 2H, ArH), 7.88–7.85 (m, 2H, ArH), 7.84–7.83 (d, J=7.8 Hz, 1H, ArH), 7.56–7.53 (t, J=8.0 Hz, 1H, ArH), 4.87–4.86 (d, J=3.3 Hz, 1H, CH), 3.68–3.67 (d, J=3.2 Hz, 1H, CH). 13C NMR (150 MHz, CDCl3) δ 194.63 (CO), 194.48 (CO), 146.86 (Ar), 141.87 (Ar), 141.82 (Ar), 136.66 (Ar), 136.63 (Ar), 134.64 (Ar), 130.18 (Ar), 128.79 (Ar), 123.90 (Ar), 123.87 (Ar), 123.86 (Ar), 123.58 (Ar), 116.81 (CN), 55.73 (CH), 33.51 (CH). Anal. Calcd. for C17H10N2O4: C, 66.67; H, 3.29; N, 9.15. Found: C, 66.75; H, 3.28; N, 9.11.

2.1.13 2-(1,3-Dioxoindan-2-yl)-2-(4-(trifluoromethyl)phenyl)acetonitrile (2m):

Yellow liquid; 1H NMR (400 MHz, CDCl3) δ 7.98–7.93 (m, 2H, ArH), 7.88–7.83 (m, 2H, ArH), 7.5–7.53 (d, J=1.7 Hz, 4H, ArH), 4.82–4.81 (d, J=3.2 Hz, 1H, CH), 3.67–3.66 (d, J=3.1 Hz, 1H, CH). 13C NMR (150 MHz, CDCl3) δ 194.90 (CO), 194.73 (CO), 141.99 (Ar), 141.82 (Ar), 136.55 (Ar), 136.48 (Ar), 129.09 (Ar), 125.99 (q, J=3.6 Hz, Ar), 123.77 (Ar), 123.73 (Ar), 117.33 (CN), 55.80 (CH), 33.61 (CH). Anal. Calcd. for C18H10F3NO2: C, 65.66; H, 3.06; N, 4.25. Found: C, 65.66; H, 3.06; N, 4.25.

2.1.14 2-(1,3-Dioxoindan-2-yl)-2-(thiophen-2-yl)acetonitrile (2n):

Yellow liquid; 1H NMR (600 MHz, CDCl3) δ 7.98–7.95 (m, 2H, ArH), 7.85–7.83 (dd, J=5.7, 3.0 Hz, 2H, ArH), 7.15–7.12 (m, 2H, ThH), 6.87–6.85 (dd, J=5.1, 3.6 Hz, 1H, ThH), 5.00–4.99 (d, J=3.2 Hz, 1H, CH), 3.63–3.62 (d, J=3.2 Hz, 1H, CH). 13C NMR (150 MHz, CDCl3) δ 195.03 (CO), 194.84 (CO), 142.35 (Ar), 142.05 (Ar), 136.35 (Ar), 136.25 (Ar), 132.17 (Th), 128.81 (Th), 127.10 (Th), 126.59 (Th), 123.68 (Ar), 123.66 (Ar), 117.29 (CN), 55.92 (CH), 29.25 (CH). Anal. Calcd. for C15H9NO2S: C, 67.40; H, 3.39; N, 5.24. Found: C, 67.34; H,3.40; N, 5.27.

2.1.15 2-(1,3-Dioxoindan-2-yl)-2-(furan-2-yl)acetonitrile (2o):

Yellow liquid; 1H NMR (600 MHz, CDCl3) δ 8.01–7.99 (m, 2H, ArH), 7.88–7.86 (dd, J=5.7, 3.0 Hz, 2H, ArH), 7.20–7.19 (d, J=1.8 Hz, 1H, FuH), 6.44–6.43 (d, J=4.2 Hz, 1H, FuH), 6.28–6.27 (dd, J=3.4, 1.9 Hz, 1H, FuH), 4.85–4.84 (d, J=3.4 Hz, 1H, CH), 3.65–3.64 (d, J=3.3 Hz, 1H, CH). 13C NMR (150 MHz, CDCl3) δ 194.72 (CO), 194.57 (CO), 143.26 (Fu), 142.01 (Ar), 141.89 (Ar), 136.27 (Ar), 136.25 (Ar), 130.11 (Ar), 128.44 (Ar), 123.70 (Fu), 115.82 (CN), 110.91 (Fu) 109.85 (Fu), 53.47 (CH), 28.19 (CH). Anal. Calcd. for C15H9NO3: C, 71.71; H, 3.61; N, 5.58. Found: C, 71.63; H, 3.63; N, 5.60.

2.1.16 (E)-2-(1,3-Dioxoindan-2-yl)-4-phenylbut-3-enenitrile (2p):

Yellow liquid; 1H NMR (600 MHz, CDCl3) δ 8.12–8.10 (m, 1H, ArH), 8.04–7.99 (m, 2H, ArH), 7.89–7.87 (m, 2H, ArH), 7.31–7.26 (m, 4H, ArH), 6.81–6.78 (dd, J=15.7, 1.1 Hz, 1H, =CH), 6.11–6.07 (dd, J=15.7, 7.4 Hz, 1H, =CH), 4.31–4.29 (ddd, J=7.4, 3.5, 1.2 Hz, 1H, CH), 3.48–3.47 (d, J=3.5 Hz, 1H, CH). 13C NMR (150 MHz, CDCl3) δ 195.48 (CO), 195.36 (CO), 142.25 (Ar), 142.12 (Ar), 136.49 (Ar), 136.43 (Ar), 136.36 (Ar), 135.02 (Ar), 133.70 (Ar), 130.16 (Ar), 128.65 (Ar), 128.63 (Ar), 128.46 (=CH), 126.79 (=CH), 123.76 (Ar), 123.71 (Ar), 118.15 (CN), 54.59 (CH), 31.73 (CH). Anal. Calcd. for C19H13NO2: C, 79.43; H, 4.56; N, 4.88. Found: C, 79.51; H, 4.53; N, 4.85.

2.1.17 2-(1,3-Dioxoindan-2-yl)-3-methylbutanenitrile (2q):

Yellow liquid; 1H NMR (600 MHz, CDCl3) δ 8.04–8.00 (m, 2H, ArH), 7.91–7.87 (m, 2H, ArH), 3.31–3.30 (d, J=3.8 Hz, 1H, CH), 3.07–3.04 (dd, J=9.3, 3.8 Hz, 1H, CH), 2.53–2.47 (m, 1H, CH), 1.21–1.19 (d, J=6.7 Hz, 3H, CH3), 1.08–1.07 (d, J=6.7 Hz, 3H, CH3). 13C NMR (150 MHz, CDCl3) δ 196.89 (CO), 196.19 (CO), 142.09 (Ar), 141.83 (Ar), 136.35 (Ar), 136.22 (Ar), 123.71 (Ar), 123.64 (Ar), 118.22 (CN), 51.77 (CH), 37.03 (CH), 28.49 (CH), 21.09 (CH3), 20.54 (CH3). Anal. Calcd. for C14H13NO2: C, 73.99; H, 5.77; N, 6.16. Found: C, 74.07; H, 5.75; N, 6.19.

3 Results and discussion

Initially, 2-benzylideneindan-1,3-dione (1a) was used as a substrate to examine hydrocyanation by using K4[Fe(CN)6] as a nontoxic cyanating agent. In our previous work on the hydrocyanation of α,β-unsaturated ketones, benzoyl chloride was used to promote the reaction through the formation of an intermediate, benzoyl cyanide [80]. In this reaction, benzoyl chloride was also used as a promoter. It was found that the hydrocyanation of 1a could take place in the presence of an appropriate base to give 2-(1,3-dioxoindan-2-yl)-2-phenylacetonitrile (2a). Meanwhile, for 1 equiv. of 1a, 0.2 equiv. of K4[Fe(CN)6] was required. That implied six CN− of K4[Fe(CN)6] could be fully used for this reaction.

In order to optimize the reaction conditions, we took the bases and solvents into consideration (Table 1). It was found that the reaction could not be conducted in the absence of a base (Table 1, entry 1). Inorganic bases, such as KOH, K2CO3, Cs2CO3 and NaHCO3, could be efficiently advantageous to the formation of product 2a (Table 1, entries 2–5), with K2CO3 affording the best yield (Table 1, entry 3). In contrast, organic bases, such as DBU, DABCO, Et3N and t-BuOK, exhibited a poor effect on the reaction, and only a mediate yield of 2a was afforded (Table 1, entries 6–9).

Table 1:

Condition optimization for reaction of 1a with K4[Fe(CN)6]a.

EntryBaseSolventYield (%)b
1–DMF0
2KOHDMF71
3K2CO3DMF87
4Cs2CO3DMF84
5NaHCO3DMF78
6DBUDMF30
7DABCODMF47
8Et3NDMF38
9t-BuOKDMF57
10K2CO3CH2Cl20
11K2CO3PhMe0
12K2CO31,4-Dioxane0
13K2CO3DMSO70
14K2CO3EtOH47
15K2CO3MeCN23

  1. aReaction conditions: K4[Fe(CN)6] (0.2 mmol) and benzoyl chloride (1.2 mmol) were stirred at 160oC for 3 h, then 1a (1 mmol), base (0.2 mmol) and H2O (2 mmol) in 5 ml of solvent were added, and the mixture was stirred at room temperature for 4 h. bIsolated yields.

The solvent also had a significant effect on the reaction. Reaction in CH2Cl2, PhMe and 1,4-dioxane could not give any product (Table 1, entries 10–12). In contrast, reaction in DMSO, EtOH and MeCN could produce the corresponding product in medium to high yield (Table 1, entries 13–15). However, DMF exhibited the best effect on the reaction, giving 2a in 87% of yield (Table 1, entry 3).

With the optimal conditions on hand, we turned our focus to unearth the generality of the method to access hydrocyanation of 2-arylmethyleneindan-1,3-diones with K4[Fe(CN)6] using benzoyl chloride as a promoter and potassium carbonate as a base in DMF, and the results are shown in Table 2. It was found that the reactions could tolerate a wide range of functional groups including electron-donating and electron-withdrawing groups on aromatic rings. 2-Arylmethyleneindan-1,3-diones bearing electron-donating groups (Me, MeO and OH) on aromatic rings afforded the corresponding products in higher yield (Table 2, 2b–2f). In contrast, 2-arylmethyleneindan-1,3-diones bearing electron-withdrawing groups (F, Cl, Br, NO2 and CF3) on aromatic rings afforded a slightly lower yield (Table 2, 2g–2m). Gratifyingly, substrates containing heteroaryl, such as thienyl and furyl, were also transformed into the desired products in high yield (Table 2, 2n, 2o). In addition, the substrates including conjugate diene bonds could regioselectively conduct 1,4-addition to give the corresponding product in good yield (Table 2, 2p). The reaction could also extend to the substrate bearing aliphatic moiety to give the corresponding product in good yield (Table 2, 2q).

Table 2:

The scope of 2-arylmethyleneindan-1,3-diones for the hydrocyanation.a

CompoundRYield (%)b
2aC6H587
2b2-CH3C6H489
2c3-CH3C6H493
2d4-CH3C6H495
2e4-CH3OC6H486
2f4-OHC6H468
2g2-FC6H457
2h4-ClC6H473
2i2-BrC6H476
2j3-BrC6H484
2k4-BrC6H480
2l3-O2NC6H449
2m4-CF3C6H489
2n
76
2o
87
2p
61
2q
66

  1. aReaction conditions: K4[Fe(CN)6] (0.2 mmol) and benzoyl chloride (1.2 mmol) were stirred at 160°C for 3 h, then substrate 1a–q (1 mmol), K2CO3 (0.2 mmol) and H2O (2 mmol) in 5 ml of DMF were added, and the mixture was stirred at room temperature for 4 h. bIsolated yields.

A plausible mechanism for the hydrocyanation of 1a using K4[Fe(CN) 6] as a nontoxic cyanating agent is shown in Scheme 1. First, K4[Fe(CN)6] reacts with benzoyl chloride to produce benzoyl cyanide (A) as an intermediate, which can be isolated and characterized [80]. Then, A is attacked by water under the condition of potassium carbonate as a base to afford cyanide ion in situ, which further reacts with 1a by Michael addition to form intermediate B. The protonation of B by water yields the final product 2a.

Scheme 1: The mechanism for the hydrocyanation of 1a with K4[Fe(CN)6].
Scheme 1:

The mechanism for the hydrocyanation of 1a with K4[Fe(CN)6].

4 Conclusions

In conclusion, an efficient method for the hydrocyanation of 2-arylmethyleneindan-1,3-diones using K4[Fe(CN)6] as a nontoxic cyanating agent by a one-pot procedure has been developed. The use of nontoxic and inexpensive cyanating agent, high yield and simple workup procedures are the features of this protocol. The products synthesized because of the inclusion of cyano groups, and indan-1,3-dione scaffolds will find potential applications in important organic synthesis and medicinal and material chemistry.

Acknowledgements

The authors thank the National Natural Science Foundation of China (21462038) for the financial support of this work.

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Supplementary Material

The online version of this article offers supplementary material (https://doi.org/10.1515/greenps-2018-0017).

Received: 2018-01-19
Accepted: 2018-02-12
Published Online: 2018-04-21
Published in Print: 2019-01-28

©2019 Walter de Gruyter GmbH, Berlin/Boston

This work is licensed under the Creative Commons Attribution 4.0 Public License.

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  94. Green production of AgNPs and their phytostimulatory impact
  95. Photocatalytic activity of Ag/Ni bi-metallic nanoparticles on textile dye removal
  96. Topical Issue: Green Process Engineering / Guest Editors: Martine Poux, Patrick Cognet
  97. Modelling and optimisation of oxidative desulphurisation of tyre-derived oil via central composite design approach
  98. CO2 sequestration by carbonation of olivine: a new process for optimal separation of the solids produced
  99. Organic carbonates synthesis improved by pervaporation for CO2 utilisation
  100. Production of starch nanoparticles through solvent-antisolvent precipitation in a spinning disc reactor
  101. A kinetic study of Zn halide/TBAB-catalysed fixation of CO2 with styrene oxide in propylene carbonate
  102. Topical on Green Process Engineering
https://doi.org/10.1515/gps-2018-0017
Schlagwörter für diesen Artikel
2-arylmethyleneindan-1,3-dione; hydrocyanation; nontoxic cyanating agent; potassium hexacyanoferrate(II)
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Artikel in diesem Heft

  1. Regular Articles
  2. Studies on the preparation and properties of biodegradable polyester from soybean oil
  3. Flow-mode biodiesel production from palm oil using a pressurized microwave reactor
  4. Reduction of free fatty acids in waste oil for biodiesel production by glycerolysis: investigation and optimization of process parameters
  5. Saccharin: a cheap and mild acidic agent for the synthesis of azo dyes via telescoped dediazotization
  6. Optimization of lipase-catalyzed synthesis of polyethylene glycol stearate in a solvent-free system
  7. Green synthesis of iron oxide nanoparticles using Platanus orientalis leaf extract for antifungal activity
  8. Ultrasound assisted chemical activation of peanut husk for copper removal
  9. Room temperature silanization of Fe3O4 for the preparation of phenyl functionalized magnetic adsorbent for dispersive solid phase extraction for the extraction of phthalates in water
  10. Evaluation of the saponin green extraction from Ziziphus spina-christi leaves using hydrothermal, microwave and Bain-Marie water bath heating methods
  11. Oxidation of dibenzothiophene using the heterogeneous catalyst of tungsten-based carbon nanotubes
  12. Calcined sodium silicate as an efficient and benign heterogeneous catalyst for the transesterification of natural lecithin to L-α-glycerophosphocholine
  13. Synergistic effect between CO2 and H2O2 on ethylbenzene oxidation catalyzed by carbon supported heteropolyanion catalysts
  14. Hydrocyanation of 2-arylmethyleneindan-1,3-diones using potassium hexacyanoferrate(II) as a nontoxic cyanating agent
  15. Green synthesis of hydratropic aldehyde from α-methylstyrene catalyzed by Al2O3-supported metal phthalocyanines
  16. Environmentally benign chemical recycling of polycarbonate wastes: comparison of micro- and nano-TiO2 solid support efficiencies
  17. Medicago polymorpha-mediated antibacterial silver nanoparticles in the reduction of methyl orange
  18. Production of value-added chemicals from esterification of waste glycerol over MCM-41 supported catalysts
  19. Green synthesis of zerovalent copper nanoparticles for efficient reduction of toxic azo dyes congo red and methyl orange
  20. Optimization of the biological synthesis of silver nanoparticles using Penicillium oxalicum GRS-1 and their antimicrobial effects against common food-borne pathogens
  21. Optimization of submerged fermentation conditions to overproduce bioethanol using two industrial and traditional Saccharomyces cerevisiae strains
  22. Extraction of In3+ and Fe3+ from sulfate solutions by using a 3D-printed “Y”-shaped microreactor
  23. Foliar-mediated Ag:ZnO nanophotocatalysts: green synthesis, characterization, pollutants degradation, and in vitro biocidal activity
  24. Green cyclic acetals production by glycerol etherification reaction with benzaldehyde using cationic acidic resin
  25. Biosynthesis, characterization and antimicrobial activities assessment of fabricated selenium nanoparticles using Pelargonium zonale leaf extract
  26. Synthesis of high surface area magnesia by using walnut shell as a template
  27. Controllable biosynthesis of silver nanoparticles using actinobacterial strains
  28. Green vegetation: a promising source of color dyes
  29. Mechano-chemical synthesis of ammonia and acetic acid from inorganic materials in water
  30. Green synthesis and structural characterization of novel N1-substituted 3,4-dihydropyrimidin-2(1H)-ones
  31. Biodiesel production from cotton oil using heterogeneous CaO catalysts from eggshells prepared at different calcination temperatures
  32. Regeneration of spent mercury catalyst for the treatment of dye wastewater by the microwave and ultrasonic spray-assisted method
  33. Green synthesis of the innovative super paramagnetic nanoparticles from the leaves extract of Fraxinus chinensis Roxb and their application for the decolourisation of toxic dyes
  34. Biogenic ZnO nanoparticles: a study of blueshift of optical band gap and photocatalytic degradation of reactive yellow 186 dye under direct sunlight
  35. Leached compounds from the extracts of pomegranate peel, green coconut shell, and karuvelam wood for the removal of hexavalent chromium
  36. Enhancement of molecular weight reduction of natural rubber in triphasic CO2/toluene/H2O systems with hydrogen peroxide for preparation of biobased polyurethanes
  37. An efficient green synthesis of novel 1H-imidazo[1,2-a]imidazole-3-amine and imidazo[2,1-c][1,2,4]triazole-5-amine derivatives via Strecker reaction under controlled microwave heating
  38. Evaluation of three different green fabrication methods for the synthesis of crystalline ZnO nanoparticles using Pelargonium zonale leaf extract
  39. A highly efficient and multifunctional biomass supporting Ag, Ni, and Cu nanoparticles through wetness impregnation for environmental remediation
  40. Simple one-pot green method for large-scale production of mesalamine, an anti-inflammatory agent
  41. Relationships between step and cumulative PMI and E-factors: implications on estimating material efficiency with respect to charting synthesis optimization strategies
  42. A comparative sorption study of Cr3+ and Cr6+ using mango peels: kinetic, equilibrium and thermodynamic
  43. Effects of acid hydrolysis waste liquid recycle on preparation of microcrystalline cellulose
  44. Use of deep eutectic solvents as catalyst: A mini-review
  45. Microwave-assisted synthesis of pyrrolidinone derivatives using 1,1’-butylenebis(3-sulfo-3H-imidazol-1-ium) chloride in ethylene glycol
  46. Green and eco-friendly synthesis of Co3O4 and Ag-Co3O4: Characterization and photo-catalytic activity
  47. Adsorption optimized of the coal-based material and application for cyanide wastewater treatment
  48. Aloe vera leaf extract mediated green synthesis of selenium nanoparticles and assessment of their In vitro antimicrobial activity against spoilage fungi and pathogenic bacteria strains
  49. Waste phenolic resin derived activated carbon by microwave-assisted KOH activation and application to dye wastewater treatment
  50. Direct ethanol production from cellulose by consortium of Trichoderma reesei and Candida molischiana
  51. Agricultural waste biomass-assisted nanostructures: Synthesis and application
  52. Biodiesel production from rubber seed oil using calcium oxide derived from eggshell as catalyst – optimization and modeling studies
  53. Study of fabrication of fully aqueous solution processed SnS quantum dot-sensitized solar cell
  54. Assessment of aqueous extract of Gypsophila aretioides for inhibitory effects on calcium carbonate formation
  55. An environmentally friendly acylation reaction of 2-methylnaphthalene in solvent-free condition in a micro-channel reactor
  56. Aegle marmelos phytochemical stabilized synthesis and characterization of ZnO nanoparticles and their role against agriculture and food pathogen
  57. A reactive coupling process for co-production of solketal and biodiesel
  58. Optimization of the asymmetric synthesis of (S)-1-phenylethanol using Ispir bean as whole-cell biocatalyst
  59. Synthesis of pyrazolopyridine and pyrazoloquinoline derivatives by one-pot, three-component reactions of arylglyoxals, 3-methyl-1-aryl-1H-pyrazol-5-amines and cyclic 1,3-dicarbonyl compounds in the presence of tetrapropylammonium bromide
  60. Preconcentration of morphine in urine sample using a green and solvent-free microextraction method
  61. Extraction of glycyrrhizic acid by aqueous two-phase system formed by PEG and two environmentally friendly organic acid salts - sodium citrate and sodium tartrate
  62. Green synthesis of copper oxide nanoparticles using Juglans regia leaf extract and assessment of their physico-chemical and biological properties
  63. Deep eutectic solvents (DESs) as powerful and recyclable catalysts and solvents for the synthesis of 3,4-dihydropyrimidin-2(1H)-ones/thiones
  64. Biosynthesis, characterization and anti-microbial activity of silver nanoparticle based gel hand wash
  65. Efficient and selective microwave-assisted O-methylation of phenolic compounds using tetramethylammonium hydroxide (TMAH)
  66. Anticoagulant, thrombolytic and antibacterial activities of Euphorbia acruensis latex-mediated bioengineered silver nanoparticles
  67. Volcanic ash as reusable catalyst in the green synthesis of 3H-1,5-benzodiazepines
  68. Green synthesis, anionic polymerization of 1,4-bis(methacryloyl)piperazine using Algerian clay as catalyst
  69. Selenium supplementation during fermentation with sugar beet molasses and Saccharomyces cerevisiae to increase bioethanol production
  70. Biosynthetic potential assessment of four food pathogenic bacteria in hydrothermally silver nanoparticles fabrication
  71. Investigating the effectiveness of classical and eco-friendly approaches for synthesis of dialdehydes from organic dihalides
  72. Pyrolysis of palm oil using zeolite catalyst and characterization of the boil-oil
  73. Azadirachta indica leaves extract assisted green synthesis of Ag-TiO2 for degradation of Methylene blue and Rhodamine B dyes in aqueous medium
  74. Synthesis of vitamin E succinate catalyzed by nano-SiO2 immobilized DMAP derivative in mixed solvent system
  75. Extraction of phytosterols from melon (Cucumis melo) seeds by supercritical CO2 as a clean technology
  76. Production of uronic acids by hydrothermolysis of pectin as a model substance for plant biomass waste
  77. Biofabrication of highly pure copper oxide nanoparticles using wheat seed extract and their catalytic activity: A mechanistic approach
  78. Intelligent modeling and optimization of emulsion aggregation method for producing green printing ink
  79. Improved removal of methylene blue on modified hierarchical zeolite Y: Achieved by a “destructive-constructive” method
  80. Two different facile and efficient approaches for the synthesis of various N-arylacetamides via N-acetylation of arylamines and straightforward one-pot reductive acetylation of nitroarenes promoted by recyclable CuFe2O4 nanoparticles in water
  81. Optimization of acid catalyzed esterification and mixed metal oxide catalyzed transesterification for biodiesel production from Moringa oleifera oil
  82. Kinetics and the fluidity of the stearic acid esters with different carbon backbones
  83. Aiming for a standardized protocol for preparing a process green synthesis report and for ranking multiple synthesis plans to a common target product
  84. Microstructure and luminescence of VO2 (B) nanoparticle synthesis by hydrothermal method
  85. Optimization of uranium removal from uranium plant wastewater by response surface methodology (RSM)
  86. Microwave drying of nickel-containing residue: dielectric properties, kinetics, and energy aspects
  87. Simple and convenient two step synthesis of 5-bromo-2,3-dimethoxy-6-methyl-1,4-benzoquinone
  88. Biodiesel production from waste cooking oil
  89. The effect of activation temperature on structure and properties of blue coke-based activated carbon by CO2 activation
  90. Optimization of reaction parameters for the green synthesis of zero valent iron nanoparticles using pine tree needles
  91. Microwave-assisted protocol for squalene isolation and conversion from oil-deodoriser distillates
  92. Denitrification performance of rare earth tailings-based catalysts
  93. Facile synthesis of silver nanoparticles using Averrhoa bilimbi L and Plum extracts and investigation on the synergistic bioactivity using in vitro models
  94. Green production of AgNPs and their phytostimulatory impact
  95. Photocatalytic activity of Ag/Ni bi-metallic nanoparticles on textile dye removal
  96. Topical Issue: Green Process Engineering / Guest Editors: Martine Poux, Patrick Cognet
  97. Modelling and optimisation of oxidative desulphurisation of tyre-derived oil via central composite design approach
  98. CO2 sequestration by carbonation of olivine: a new process for optimal separation of the solids produced
  99. Organic carbonates synthesis improved by pervaporation for CO2 utilisation
  100. Production of starch nanoparticles through solvent-antisolvent precipitation in a spinning disc reactor
  101. A kinetic study of Zn halide/TBAB-catalysed fixation of CO2 with styrene oxide in propylene carbonate
  102. Topical on Green Process Engineering
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Heruntergeladen am 18.9.2025 von https://www.degruyterbrill.com/document/doi/10.1515/gps-2018-0017/html
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