Sulfuryl Fluoride Promoted Thiocyanation of Alcohols: A Practical Method for Preparing Thiocyanates

Abstract

A novel SO₂F₂-promoted thiocyanation method for the one-step synthesis of thiocyanates through C–O bond cleavage of readily available alcohols with ammonium thiocyanate as the thiocyanating agent was developed. The method avoids the use of additional catalyst, and a variety of (hetero)arene, alkene and aliphatic alcohols reacted with high efficiency in ethyl acetate under mild conditions to afford the corresponding thiocyanates in excellent to quantitative yields with broad functional-group compatibility.

Key words

sulfuryl fluoride catalysis - alcohols - thiocyanation - ammonium thiocyanate - thiocyanates

• References and Notes

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• 15 4-Methylbenzyl Thiocyanate (2b); Typical Procedure 4-Methylbenzyl alcohol (1b; 1.0 mmol, 1.0 equiv), NH₄SCN (1.0 mmol, 1.0 equiv), Na₂CO₃ (4.0 mmol, 4.0 equiv), and EtOAc (2.0 mL, 0.5 M) were added sequentially to an oven-dried 30 mL reaction tube equipped with a stirrer bar. The tube was sealed with a plastic stopper and SO₂F₂ gas was introduced into the stirred mixture by slow bubbling from an SO₂F₂-filled balloon at r.t. for 5 h. The mixture was then diluted with H₂O and extracted with EtOAc (3 × 25 mL). The combined organic layers were washed with brine, dried (Na₂SO₄), and concentrated to dryness. The residue was purified by chromatography (silica gel, EtOAc–PE) to give a yellow oil; yield: 158 mg (97%). ¹H NMR (500 MHz, CDCl₃): δ = 7.31–7.21 (m, 2 H), 7.18 (d, J = 7.9 Hz, 2 H), 4.13 (s, 2 H), 2.35 (s, 3 H). ¹³C NMR (125 MHz, CDCl₃): δ = 138.9, 131.3, 129.8, 128.9, 112.1, 38.3, 21.2. HRMS (EI): m/z [M⁺] calcd for C₉H₉NS: 163.0456; found: 163.0458.
• 16 4-(Thiocyanatomethyl)phenyl Fluoridosulfate (2m) 4-(Hydroxymethyl)phenol (1m; 1.0 mmol, 1.0 equiv), NH₄SCN (1.0 mmol, 1.0 equiv), Et₃N (4.0 mmol, 4.0 equiv), and EtOAc (2.0 mL, 0.5 M) were added sequentially to an oven-dried 30 mL reaction tube equipped with a stirrer bar. The tube was sealed with a plastic stopper and SO₂F₂ gas was introduced into the stirred mixture by slow bubbling from an SO₂F₂-filled balloon at r.t. for 5 h. Workup as described above gave a colorless oil; yield: 193 mg (78%). ¹H NMR (500 MHz, CDCl₃): δ = 7.50 (d, J = 8.7 Hz, 2 H), 7.38 (d, J = 8.5 Hz, 2 H), 4.16 (s, 2 H). ¹³C NMR (125 MHz, CDCl₃): δ = 150.1, 135.5, 131.1, 121.8, 111.2, 37.1. HRMS (EI): m/z [M⁺] calcd for C₈H₆FNO₃S₂: 246.9773; found: 246.9796.