Synlett 2014; 25(10): 1409-1412
DOI: 10.1055/s-0033-1338634
letter
© Georg Thieme Verlag Stuttgart · New York

Continuous-Flow Hydroxylation of Aryl Iodides Promoted by Copper Tubing

Patrick Cyr
Centre in Green Chemistry and Catalysis, Faculty of Arts and Sciences, Department of Chemistry, Université de Montréal, P.O. Box 6128 Station Downtown, Montréal, Québec, H3C 3J7, Canada   Email: andre.charette@umontreal.ca
,
André B. Charette*
Centre in Green Chemistry and Catalysis, Faculty of Arts and Sciences, Department of Chemistry, Université de Montréal, P.O. Box 6128 Station Downtown, Montréal, Québec, H3C 3J7, Canada   Email: andre.charette@umontreal.ca
› Author Affiliations
Further Information

Publication History

Received: 21 February 2014

Accepted after revision: 28 March 2014

Publication Date:
08 May 2014 (eFirst)

Abstract

A simple and ligand-free synthesis of phenols from the corresponding aryl iodides in a continuous-flow system is described. The reaction is complete in only 4 to 20 minutes when heated between 150 to 165 °C in a reactor consisting of a commercially available copper coil. An example of trapping of the phenoxide in situ is also shown.

Supporting Information

 
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  • 22 Phenol Synthesis; General Procedure: A solution of the aryl iodide (4.83 mmol) in a mixture of aq n-Bu4NOH (1.5 M, 19.3 mL) and DMSO (19.3 mL, for an overall 0.125 M solution vs. aryl iodide) was prepared. The reaction solution (37 mL) was injected by using direct injection mode and the reagent stream was pumped into the 10-mL copper reactor (1.0 mm i.d.) at the desired temperature for the needed residence time, then 48 mL of the crude reaction solution was collected, acidified to pH 1 with 2 M HCl. H2O (150 mL) was added and the mixture was extracted with Et2O (3 × 150 mL). The combined organic layers were dried over anhydrous MgSO4, filtered, and concentrated under vacuum. The crude mixture was purified by flash chromatography (CH2Cl2–hexanes gradient) to afford the desired product (see the Supporting Information for more details).
  • 23 Benzyl-3-chlorophenyl Ether (3); Typical Procedure: A first solution (A) of 1-chloro-3-iodobenzene (1b; 0.50 g, 2.10 mmol) in a mixture of aq n-Bu4NOH (1.5 M, 8.4 mL) and DMSO (8.4 mL; for an overall 0.125 M solution vs. 1-chloro-3-iodobenzene) was prepared. A second solution (B) consisting of benzyl bromide (0.62 mL, 6.30 mmol) in DMSO (8 mL) was prepared. Solution A was injected using the direct injection mode and the reagent stream was pumped into the first reactor (10 mL copper coil of 1.0 mm i.d.) at 165 °C. Then, solution B was injected by using the direct injection mode and mixed in a T-mixer with solution A after the latter had passed the first reactor. The mixture then passed the second reactor (5 mL PFA coil of 1.0 mm i.d.) at 150 °C. 23 mL of the crude reaction solution was then collected, diluted with H2O (100 mL) and extracted with Et2O (3 × 100 mL). The combined organic layers were dried over anhydrous MgSO4, filtered, and concentrated under vacuum. The crude mixture was purified by flash chromatography (CH2Cl2–hexanes, 0–30%) to afford 3 (385 mg, 84% yield) as a yellow solid (see the Supporting Information for more details).