Tribromoisocyanuric Acid: A New Reagent for Regioselective Cobromination of Alkenes

Abstract

A simple one-step method for the preparation of tri­bromoisocyanuric acid in good yield (87%) has been developed. The reaction of tribromoisocyanuric acid with alkenes in presence of nucleophilic solvents (MeOH, i-PrOH, AcOH and a mixture of H₂O-acetone, 1:5) led to the corresponding β-bromoethers, β-bromoacetates and bromohydrins, in high regioselectivity and good yields (73-98%).

Key words

alkenes - cohalogenation - Oxone^® - tribromoisocyanuric acid

References and Notes

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• 1b De Souza SPL. Da Silva JFM. De Mattos MCS. J. Braz. Chem. Soc.  2003,  14:  832 ; available at http://jbcs.sbq.org.br
• 2 De La Mare PB. Electrophilic Halogenation   Cambridge University Press; Cambridge: 1976.  Chap. 5 and 7.
• 3a Da Silva FM. Jones J. De Mattos MCS. Curr. Org. Synth.  2005,  2:  393 
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11

CP-MAS ¹³C NMR: δ = 151.8 (C=O) ppm. FT-IR: ν = 1741, 1724, 1660, 1652, 1481, 1404, 1396, 1331, 1196, 1144, 1051, 736, 717 cm^-1.

12

¹H NMR (CDCl₃): δ = 1.24-1.37 (m, 3 H), 1.67-1.86 (m, 3 H), 2.10-2.20 (m, 1 H), 2.25-2.60 (m, 2 H), 3.50-3.70 (m, 1 H) 3.90 (ddd, 1 H, J ₁ = 11.68 Hz, J ₂ = 9.57 Hz, J ₃ = 4.35 Hz) ppm. ¹³C NMR (CDCl₃): δ = 24.1, 26.6, 33.5, 36.2, 61.8, 75.30 ppm. MS (70 eV): m/z (%) = 180 [M⁺ + 2], 178 [M⁺], 99, 81 (100), 57, 41.

13

¹H NMR (CDCl₃): δ = 1.20-1.40 (m, 3 H), 1.64-1.88 (m, 3 H), 2.15-2.34 (m, 2 H), 3.17-3.28 (m, 1 H), 3.42 (ddd, 1 H, J ₁ = 9.56 Hz, J ₂ = 8.53 Hz, J ₃ = 4.44 Hz) ppm. ¹³C NMR (CDCl₃): δ = 23.1, 25.3, 29.9, 35.4, 55.2, 57.1, 83.1 ppm. MS (70 eV): m/z (%) = 194 [M⁺ + 2], 192 [M⁺], 113, 81, 71 (100), 41.

14

¹H NMR (CDCl₃): δ = 1.13-1.43 (m, 9 H), 1.62-1.90 (m, 3 H), 2.02-2.11 (m, 1 H), 2.30-2.37 (m, 1 H), 3.33-3.40 (m, 1 H), 3.78 (sept, 1 H, J = 6.15 Hz), 3.90 (ddd, 1 H, J ₁ = 9.76 Hz, J ₂ = 8.93 Hz, J ₃ = 4.43 Hz) ppm. ¹³C NMR (CDCl₃): δ = 27.5, 23.0, 23.5, 25.5, 32.5, 35.8, 56.6, 71.2, 79.7 ppm. MS (70 eV): m/z (%) = 222 [M⁺ + 2], 220 [M⁺], 178, 180, 99, 81 (100), 57, 43.

15

¹H NMR (CDCl₃): δ = 1.27-1.47 (m, 3 H), 1.74-1.96 (m, 3 H), 2.08 (s, 3 H), 2.13 (m, 1 H), 2.32-2.39 (m, 1 H), 3.96 (ddd, 1 H, J ₁ = 10.45 Hz, J ₂ = 9.29 Hz, J ₃ = 4.26 Hz), 4.84-4.93 (m, 1 H) ppm. ¹³C NMR (CDCl₃): δ = 21.0, 23.3, 25.6, 35.7, 52.8, 75.8, 170.0 ppm. MS (70 eV): m/z (%) = 222 [M⁺ + 2], 220 [M⁺], 160, 162, 81, 43 (100).

16

¹H NMR (CDCl₃): δ = 1.25-1.48 (m, 5 H), 1.68-2.05 (m, 4 H), 2.15 (br s, 1 H), 2.21-2.27 (m, 1 H), 4.15 (dd, 1 H, J ₁ = 11.52 Hz, J ₂ = 4.10 Hz) ppm. ¹³C NMR (CDCl₃): δ = 22.8, 23.2, 26.3, 34.7, 38.2, 66.0, 72.5 ppm. MS (70 eV): m/z (%) = 194 [M⁺ + 2], 192 [M⁺], 177, 179, 113, 95, 71 (100), 43.

17

¹H NMR (CDCl₃): δ = 2.81 (d, 1 H, J = 2.73 Hz) 3.48-3.64 (m, 2 H), 4.89-4.94 (m, 1 H), 7.37 (s, 5 H) ppm. ¹³C NMR (CDCl₃): δ = 40.1, 73.7, 125.9, 128.4, 128.6, 140.3 ppm. MS (70 eV): m/z (%) = 202 [M⁺ + 2], 200 [M⁺], 107 (100), 79, 77, 51.

18

¹H NMR (CDCl₃): δ = 3.31 (s, 3 H), 3.42-3.59 (m, 2 H), 4.39 (dd, 1 H, J ₁ = 7.86 Hz, J ₂ = 4.44 Hz), 7.34-7.43 (m, 5 H) ppm. ¹³C NMR (CDCl₃): δ = 36.2, 57.2, 83.4, 126.7, 128.6, 139.0 ppm. MS (70 eV): m/z (%) = 216 [M⁺ + 2], 214 [M⁺], 121 (100), 91, 77, 51.

19

¹H NMR (CDCl₃): δ = 1.12 (d, 3 H, J = 6.15 Hz), 1.23 (d, 3 H, J = 6.14 Hz), 3.38-3.48 (m, 2 H), 3.57 (sept, 1 H, J = 6.14 Hz), 4.58 (dd, 1 H, J ₁ = 7.86 Hz, J ₂ = 4.78 Hz), 7.35 (s, 5 H) ppm.¹³C NMR (CDCl₃): δ = 21.2, 23.1, 37.0, 70.4, 79.3, 126.7, 128.2, 128.5, 140.6 ppm. MS (70 eV): m/z (%) = 185, 183, 149, 107 (100), 79, 43.

20

¹H NMR (CDCl₃): δ = 2.13 (s, 3 H), 3.54 (m, 2 H), 5.98 (dd, 1 H, J ₁ = 7.41 Hz, J ₂ = 5.12 Hz), 7.36 (s, 5 H) ppm. ¹³C NMR (CDCl₃): δ = 20.9, 34.2, 74.8, 126.5, 128.6, 137.6, 169.8 ppm. MS (70 eV): m/z (%) = 244 [M⁺ + 2], 242 [M⁺], 162, 121, 120, 103, 77, 43 (100).

21

¹H NMR (CDCl₃): δ = 1.68 (s, 3 H), 2.63 (s, 1 H), 3.73 (dd, 2 H, J ₁ = 12.45 Hz, J ₂ = 10.20 Hz), 7.25-7.49 (m, 5 H) ppm. ¹³C NMR (CDCl₃): δ = 28.0, 46.2, 73.1, 124.8, 127.5, 128.4, 144.2 ppm. MS (70 eV): m/z (%) = 216 [M⁺ + 2], 214 [M⁺], 199, 201, 121 (100), 77, 43.

22

(a) 1-Bromo-2-octanol: ¹³C NMR (CDCl₃): δ = 14.09, 22.62, 25.63, 29.20, 31.76, 35.19, 40.56, 71.16 ppm. MS (70 eV): m/z (%) = 128, 125, 123, 115, 97, 69, 55 (100), 43.
(b) 2-Bromo-1-octanol: ¹³C NMR (CDCl₃): δ = 14.09, 22.62, 27.45, 28.72, 31.65, 34.95, 60.12, 67.34 ppm. MS (70 eV): m/z (%) = 137, 135, 111, 69 (100), 55.

23

(a) 1-Bromo-2-methoxyoctane: ¹³C NMR (CDCl₃): δ = 13.99, 22.52, 25.08, 29.21, 31.69, 32.81, 34.53, 57.27, 80.27 ppm. MS (70 eV): m/z (%) = 139, 137, 129, 97, 69, 55 (100), 41.
(b) 2-Bromo-1-methoxyoctane: ¹³C NMR (CDCl₃): δ = 13.99, 22.52, 27.16, 28.64, 31.58, 35.26, 53.53, 58.87, 76.93 ppm. MS (70 eV): m/z (%) = 143, 135, 137, 111, 69, 45 (100), 41.