Water → 5-(2-Bromovinyl)-2-methylpyridine

HRID 2176087Notes

Reaction equation

HRID 2176087 reaction equation
[CH3:1][C:2]1[CH:7]=[CH:6][C:5](/[CH:8]=[CH:9]/B2OC(C)(C)C(C)(C)O2)=[CH:4][N:3]=1.[Br:19]N1C(=O)CCC1=O.C(N(CC)CC)C.O>C(#N)C>[Br:19][CH:9]=[CH:8][C:5]1[CH:6]=[CH:7][C:2]([CH3:1])=[N:3][CH:4]=1

Participants

6

Reactant 4

HCID 962WaterHCID 8471TriethylamineHCID 67184N-bromobutanimideHCID 57416208(e)-2-Methyl-5-(2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)vinyl)pyridine

Product 1

HCID 722566695-(2-Bromovinyl)-2-methylpyridine

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

A solution of (E)-2-methyl-5-(2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)vinyl)-pyridine (1.0 g, 4.08 mmol; Example 23B) in acetonitrile (10 mL) was treated with N-bromosuccinimide (0.346 mL, 4.08 mmol; Aldrich) and triethylamine (0.625 mL, 4.49 mmol; Aldrich) and stirred at room temperature for 16 hours. Water was added and the mixture was extracted several times with ethyl acetate. The combined organic extracts were concentrated, and the resulting material was purified by flash chromatography (silica gel, hexane/ethyl acetate, 3:1) to afford the title compound as a 1.2:1 Z/E mixture: 1H NMR (300 MHz, CDCl3) δ ppm 2.54 (s, 3H), 2.57 (s, 3.6H), 6.52 (d, J=14 Hz, 1.2H), 6.75-6.85 (d, J=14 Hz, 1H), 7.01-7.22 (m, 4.4H), 7.52 (dd, J=8, 2 Hz, 1H), 8.07 (dd, J=8, 2 Hz, 1.2H), 8.43 (d, J=2 Hz, 1H), 8.66 (d, J=2 Hz, 1.2H); MS (DCI/NH3) m/z 198/200 (M+H)+.

Workup

  1. extractionthe mixture was extracted several times with ethyl acetate
  2. concentrationThe combined organic extracts were concentrated
  3. customthe resulting material was purified by flash chromatography (silica gel, hexane/ethyl acetate, 3:1)

Sources & evidence

ORD record
ord-364b3651b86448148781e30cfb4b8f42
Source dataset
uspto-grants-2015_06
Patent number
US09063126B2

Reaction notes

Loading…