Synlett 2015; 26(11): 1501-1504
DOI: 10.1055/s-0034-1380417
letter
© Georg Thieme Verlag Stuttgart · New York

A Convenient Route to 2-Bromo-3-chloronorbornadiene and 2,3-Dibromonorbornadiene

Anders Lennartson, Maria Quant, Kasper Moth-Poulsen*
Further Information

Publication History

Received: 05 March 2015

Accepted after revision: 15 April 2015

Publication Date:
27 May 2015 (eFirst)

This paper is dedicated to Prof. K. P. C. Vollhardt on occasion of his 69th birthday. Thank you for inspirational leadership and enlightening supervision.

Abstract

Substituted norbornadienes are useful in a wide range of applications, including molecular solar-thermal (MOST) energy storage systems. An important precursor for 2,3-substituted norbornadienes is 2-bromo-3-chloronorbornadiene, where the two halogen atoms can be substituted selectively through two consecutive Suzuki cross-coupling reactions. Previous routes to 2-bromo-3-chloronorbornadiene have used 1,2-dibromoethane as a brominating agent, a substance known to be carcinogenic and the use of which is restricted in certain countries. Herein is reported a one-pot route to 2-bromo-3-chloronorbornadiene in 50% yield using p-toluenesulfonyl bromide as a bromine source. In addition, the procedure has been adapted to allow synthesis of 2,3-dibromonorbornadiene in 37% yield.

 
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  • 21 2-Bromo-3-chloronorbornadiene (3) Potassium tert-butoxide (11.2 g, 0.10 mol) was dissolved in THF (200 mL), and the solution was cooled to –84 °C. Norbornadiene (12.2 mL, 0.12 mol) was added, followed by n-BuLi (2.5 M in hexanes, 40 mL, 0.10 mol) over 60 min. The yellow solution was stirred for 5 min at –84 °C and 60 min at –41 °C. The solution was cooled again to –84 °C, and p-toluenesulfonyl chloride (19.0 g, 0.10 mol) was added. The mixture was stirred for 30 min and n-BuLi (2.5 M in hexanes, 40 mL, 0.10 mol) was added over 60 min. The mixture was stirred for 5 min at –84 °C and 60 min at –41 °C. The solution was cooled to –84 °C, and p-toluenesulfonyl bromide (23.4 g, 0.10 mol) was added. The mixture was stirred for 15 min and was then heated to ambient temperature on a room-tempered water bath. The reaction mixture was quenched with H2O (50 mL), the phases were separated, and the aqueous phase was extracted with Et2O (3 × 20 mL). The solvents from the combined organic phases were slowly removed on a rotary evaporator (40 °C, 300 mbar). The residue was dissolved in pentane (50 ml), washed with H2O (10 × 10 mL), brine (20 mL), and dried over Na2SO4. The solvent was removed in vacuo (40 °C, 300 mbar) and the product distilled (2 × 10–2 mbar) using a short Vigreux column, collecting the main fraction at 25–27 °C. This afforded 3 as a colorless liquid; yield 10.24 g (50%). Analytical data were consistent with previous reports.14 The product was stored at –20 °C and should be used within a few weeks to avoid decomposition.
  • 22 2,3-Dibromonorbornadiene (8) Potassium tert-butoxide (11.2 g, 0.10 mol) was dissolved in THF (200 mL), and the solution was cooled to –84 °C. Norbornadiene (12.2 mL, 0.12 mol) was added followed by n-BuLi (2.5 M in hexanes, 40 mL, 0.10 mol) under 60 min. The yellow solution was stirred for 5 min at –84 °C and 60 min at –41 °C. The solution was cooled again to –84 °C, and p-toluenesulfonyl bromide (11.7 g, 0.050 mol) was added. The mixture was stirred for 15 min at –84 °C and 60 min at –41 °C. The solution was cooled to –84 °C, and p-toluenesulfonyl bromide (11.7 g, 0.05 mol) was added. The mixture was stirred for 15 min and was then heated to ambient temperature on a room-tempered water bath. The reaction mixture was quenched with H2O (50 mL), the phases were separated, and the aqueous phase was extracted with Et2O (3 × 20 mL). The solvents from the combined organic phases were slowly removed on a rotary evaporator (40 °C, 300 mbar). The residue was dissolved in pentane (50 mL), washed with H2O (10 × 10 mL), brine (20 mL), and dried over Na2SO4. The solvent was removed in vacuo (40 °C, 300 mbar) and the product distilled (5 × 10–2 mbar) using a short Vigreux column, collecting the main fraction at 29–31 °C. This afforded 8 as a colorless liquid; yield 4.63 g (37%). Analytical data were consistent with previous reports.14 The product was stored at –20 °C and should be used within a few weeks to avoid decomposition.