Copper-Catalyzed Oxidation of Hydrosilanes: A New Method for the Synthesis of Alkyl- and Siloxysilanols

Abstract

A simple method for the preparation of silanols from the corresponding hydrosilanes is reported. The method employs a commercially available oxidizing system based on CuCO₃/t-BuOOH_(aq) under relatively mild conditions (80 °C, atmospheric pressure) with acetonitrile as the solvent. Furthermore, we present a method that permits the Si−H group to be oxidized to a Si−OH group not only in triethylsilane, but also in bis(trimethylsiloxy)methylsilane, a siloxy derivative of hydrosilane. The products were isolated in gram amounts in yields of 61–73%.

Key words

silanols - peroxides - oxidation - copper catalysis - hydrosilanes - silanes

• References and Notes

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• 14 Triethylsilanol (2a) Silane 1a (2 g, 17.199 mmol, 1 equiv), 70% aq t-BuOOH (4.44 g, 34.39 mmol, 2 equiv), CuCO₃ (0.0106 g, 0.086 mmol, 0.005 equiv), and MeCN (20 mL) were stirred in 50 mL round-­bottomed flask at 80 °C for 9 h. The yield of 2a was determined by GLC (90%). The solvent was then evaporated (150-200 mbar, Т_bath = 40 °C), and the residue was dissolved in hexane (60-80 mL). The solution was filtered through a short pad of Celite 545 (0.4–0.5 cm) and the hexane was then evaporated (250-300 mbar, Т_bath = 40 °C). Distillation at reduced pressure to give a ­colorless liquid; yield: 1.66 mg (73%); bp 60 °C (23 mbar). ¹H NMR (400 MHz, CDCl₃): δ = 0.57 (q, J = 7.96 Hz, 6 H); 0.94 (t, J = 8.0 Hz, 9 H); 2.69–2.9 (br s, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 5.73; 6.47. ²⁹Si NMR (80 MHz, CDCl₃): δ = 18.97. 1,1,1,3,5,5,5-Heptamethyltrisiloxan-3-ol (2b) Silane 1b (1.91 g, 8.59 mmol, 1 equiv), 70% aq t-BuOOH (2.21 g, 17.19 mmol, 2 equiv), CuCO₃ (0.0053 g, 0.043 mmol, 0.005 equiv), and MeCN (10 mL) were stirred in 50 mL round-­bottomed flask at 80 °C for 12 h. The yield of 2b was determined by GLC (67%). Another portion of 70% aq t- BuOOH (1.11 g, 8.59 mmol, 1 equiv) was added, and mixture was stirred for a further 6 h at 80 °C. The yield of 2b was again determined by GLC (80%). The solvent was evaporated (150 – 200 mbar, Т_bath = 40 °C) and the residue was dissolved in hexane (40–50 mL). The solution was filtered through a short pad of Celite 545 (0.4–0.5 cm) and then the hexane was evaporated (250 – 300 mbar, Т_bath = 40 °C). Distillation under reduced pressure gave a colorless liquid; yield: 1.25 g (61%); bp 34 °C (1 mbar). IR (thin film): 3373, 2960, 1256, 1060 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 0.07 (s, 3 H); δ = 0.11 (s, 18 H); 2.50 – 2.74 (br s, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = –2.98, 1.60. ²⁹Si NMR (80 MHz, CDCl₃): δ = –54.73; 8.55. HRMS (ESI): m/z [M – H]^– calcd for C₇H₂₁O₃Si₃: 237.0793; found: 237.0813; [M + Na]⁺ calcd for C₇H₂₂NaO₃Si₃: 261.0769; found: 261.0765; [M + NH₄]⁺ calcd for C₇H₂₆NO₃Si₃, 256.1215; found: 256.1209.