Lewis Acid Rather than Brønsted Acid Sites of Montmorillonite K10 Act as a Powerful and Reusable Green Heterogeneous Catalyst for Rapid Cyanosilylation of Ketones

Abstract

A practical green protocol was developed for highly efficient cyanosilylation of various ketones catalyzed by commercial montmorillonite K10, with excellent isolated yields (91–99%). The catalyst can be used as received, and its catalytic strength can be easily restored without loss of activity. Investigations of catalyst recycling and of the active catalytic sites indicated that Lewis acid sites were mainly responsible for the cyanosilylation of ketones.

Key words

montmorillonite - heterogeneous catalysis - cyanosilylation - ketones - green chemistry

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• 22 2-Phenyl-2-(trimethylsiloxy)propanenitrile (2a); Typical Procedure A test tube was charged with PhCOMe (1a; 120 mg, 1.0 mmol), MMT K10 (20 mg), and PhMe (0.5 mL). TMSCN (190 μL, 1.5 mmol) was added dropwise with stirring at r.t. After 6 min, TLC indicated that the reaction was complete, and the mixture was filtered, washed with PhMe, and concentrated under reduced pressure to afford 2a as a colourless oil; yield: 218 mg (99%). ¹H NMR (400 MHz, CDCl₃, TMS): δ = 0.18 (s, 9 H), 1.87 (s, 3 H), 7.33–7.40 (m, 3 H), 7.53–7.57 (m, 2 H). ¹³C NMR (100 MHz, CDCl₃, TMS): δ = 1.1, 33.6, 71.6, 121.6, 124.6, 128.5, 128.6, 141.6. 1,3,3-Trimethyl-2-(trimethylsiloxy)bicyclo[2.2.1]heptane-2-carbonitrile (2o) colorless oil; yield: 250 mg (99%). ¹H NMR (300 MHz, CDCl₃, TMS): δ = 0.26 (s, 9 H), 0.91 (s, 3 H), 0.99 (s, 3 H), 1.02 (s, 3 H), 1.12–1.25 (m, 1 H), 1.60–1.88 (m, 4 H), 2.06 (d, J = 14.1 Hz, 1 H), 2.23 (ddd, J = 14.1, 3.4, 3.0 Hz, 1 H). ¹³C NMR (75 MHz, CDCl₃, TMS): δ = 1.0, 10.5, 20.4, 21.1, 26.5, 31.7, 45.1, 47.8, 48.8, 54.1, 78.4, 121.8. 2,2-Diphenyl-2-(trimethylsiloxy)acetonitrile (2p) colourless oil; yield: 281 mg (99%). ¹H NMR (300 MHz, CDCl₃,TMS): δ = 0.12 (s, 9 H), 7.31–7.39 (m, 6 H), 7.47–7.51 (m, 4 H). ¹³C NMR (75 MHz, CDCl₃ , TMS): δ = 1.0, 76.2, 120.5, 125.7, 128.3, 128.5, 141.7.
• 23 Rapid Colorimetric Ninhydrin Detection of Cyanide (see also ref. 18) MMT K10 (100 mg) was treated with TMSCN (400 μL) for 6 h, collected by filtration, washed thoroughly with PhMe, and suction-dried under air for a few minutes. The filtrate was discarded. The resulting catalyst was washed slowly with anhyd MeOH (10 mL), while the filtrate was trapped simultaneously in 1 M aq NaOH (5 mL). Active charcoal (100 mg) was added to the resulting solution, and the mixture was agitated for 10 min then filtered. To the filtrate was added 1 wt% aq ninhydrin solution (1 mL) with stirring. The color of the solution gradually became blue within 2 min, indicating the presence of cyanide anion. The MeOH-washed catalyst was further rinsed thoroughly with an additional 20 mL of anhydrous MeOH to ensure a negative response to ninhydrin (the resulting catalyst was used in Table 2, entry 24, after washing with PhMe and suction-drying under air). The catalyst was washed again with 5 mL of dilute HCl solution, prepared by adding 1 volume of concd HCl to 20 volumes of MeOH, and the filtrate was trapped in 2 M aq NaOH (5 mL). Active charcoal (100 mg) was added to the resulting solution, and the mixture was agitated for 10 min then filtered. The final filtrate was subjected to colorimetric ninhydrin cyanide detection, as described above. The positive blue color obtained within 2 min proved that cyanide anion was present in this solution, showing that cyanide anions had been coordinated by Lewis sites and washed off with the dilute HCl.