A New Synthesis of trans-2,3-Diaryloxiranes and 2-(1H-Benzo[d][1,2,3]-
triazol-1-yl)-1-arylethanols via the Reactions of 1-Benzyl-3-methylbenzo-
triazolium Ylide with Aryl Aldehydes

Abstract

1-Benzyl-3-methylbenzotriazolium ylide was formed by the reaction of 1-benzyl-3-methylbenzotriazolium iodide with t-BuOK. Subsequently it reacted with various aryl aldehydes to give the corresponding trans-2,3-diaryloxiranes and 2-(1H-benzo-[d][1,2,3]triazol-1-yl)-1-arylethanols in moderate to high yields.

ammonium ylide - 2,3-diaryloxirane - benzotriazole - Darzens reaction - 2-(1H-benzo[d][1,2,3]triazol-1-yl)-1-arylethanol

References and Notes

<A NAME="RW16611ST-1A">1a</A> Li A.-H. Dai L.-X. Aggarwal VK. Chem. Rev.  1997,  97:  234 

<A NAME="RW16611ST-1B">1b</A> Aggarwal VK. Ford JG. Fonquerna S. Adams H. Jones RVH. Fieldhouse R. J. Am. Chem. Soc.  1998,  120:  8328 

<A NAME="RW16611ST-1C">1c</A> Aggarwal VK. Winn CL. Acc. Chem. Res.  2004,  37:  611 

<A NAME="RW16611ST-1D">1d</A> McGarrigle EM. Myers EL. Illa O. Shaw MA. Riches SL. Aggarwal VK. Chem. Rev.  2007,  107:  5841 

<A NAME="RW16611ST-1E">1e</A> Illa O. Arshad M. Ros A. McGarrigle EM. Aggarwal VK. J. Am. Chem. Soc.  2010,  132:  1828 

<A NAME="RW16611ST-2A">2a</A> Jonczyk A. Konarska A. Synlett  1999,  1085 

<A NAME="RW16611ST-2B">2b</A> Kowalkowska A. Sucholbiak D. Jonczyk A. Eur. J. Org. Chem.  2005,  5:  925 

<A NAME="RW16611ST-2C">2c</A> Kimachi T. Kinoshita H. Kusaka K. Takeuchi Y. Aoe M. Ju-ichi M. Synlett  2005,  842 

<A NAME="RW16611ST-2D">2d</A> Robiette R. Conza M. Aggarwal VK. Org. Biomol. Chem.  2006,  4:  621 

<A NAME="RW16611ST-2E">2e</A> Alex A. Larmanjat B. Marrot J. Couty F. David O. Chem. Commun.  2007,  2500 

<A NAME="RW16611ST-2F">2f</A> Kinoshita H. Ihoriya A. Ju-ichi M. Kimachi T. Synlett  2010,  2330 

<A NAME="RW16611ST-2G">2g</A> Waser M. Herchl R. Mueller N. Chem. Commun.  2011,  47:  2170 

<A NAME="RW16611ST-3">3</A> Hunter EPL. Lias SG. J. Phys. Chem. Ref. Data  1998,  27:  413 

<A NAME="RW16611ST-4">4</A> Xiao X.-H. Lin D.-Q. Tong S.-T. Luo H. He Y.-F. Mo H.-L. Synlett  2011,  1731 

<A NAME="RW16611ST-5">5</A>

Process A: BMeBt iodide (1; 3 mmol), benzaldehyde (2a; 3 mmol), t-BuOK (3 mmol) and solvent (10 mL) were mixed together and stirred at r.t. After the purple color of the solution had faded, H₂O (25 mL) was added and the products were extracted with EtOAc (3 × 25 mL). The combined organic phases were washed with brine (2 × 25 mL) and H₂O (25 mL), and then were dried over anhyd Na₂SO₄, filtered and concentrated in vacuo. The residue was separated by column chromatography.

<A NAME="RW16611ST-6">6</A>

Process B: A solution of BMeBt iodide (1; 3 mmol) and aryl aldehyde 2 (6 mmol) in DMSO (5 mL) was added dropwise to the stirred solution of t-BuOK (6 mmol) in t-BuOH (5 mL) at r.t. After the purple color of the solution had faded, H₂O (25 mL) was added and the products were extracted with EtOAc (3 × 25 mL). The combined organic phases were washed with brine (2 × 25 mL) and H₂O (25 mL), and then were dried over anhyd Na₂SO₄, filtered and concentrated in vacuo. The residue was separated by column chromatog-raphy to afford the corresponding trans-2,3-diaryloxiranes 3 and 2-(1H-benzo[d][1,2,3]triazol-1-yl)-1-arylethanol 4.

<A NAME="RW16611ST-7">7</A> Katritzky AR. Wu J. Kuzmierkiewicz W. Rachwal S. Liebigs Ann. Chem.  1994,  1