Water → HCID 43560401, compound

HRID 921059Notes

Reaction equation

HRID 921059 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]([OH:10])=[C:6]([CH:9]=1)[CH:7]=[O:8].C([O-])([O-])=O.[K+].[K+].Br[CH2:18][CH:19]1[CH2:21][CH2:20]1.O>C1COCC1.C(Cl)(Cl)Cl>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([O:10][CH2:18][CH:19]2[CH2:21][CH2:20]2)=[C:6]([CH:9]=1)[CH:7]=[O:8]

Participants

7

Reactant 4

HCID 962WaterHCID 11430Potassium CarbonateHCID 728635-BromosalicylaldehydeHCID 81503Bromomethylcyclopropane

Product 1

HCID 43560401HCID 43560401, compoundYield 83%

Reagents, catalysts & solvents 2

HCID 6212ChloroformSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
70 °C

Procedure

To 5-bromo-2-hydroxybenzaldehyde (1.00 g, 4.97 mmol, 1.00 equiv) and K2CO3 (3.44 g, 24.9 mmol, 5.00 equiv) in THF (10 mL) in an oven-dried round-bottom flask fitted with a reflux condenser under a N2 atmosphere at 23 ° C. was added (bromomethyl)cyclopropane (1.01 g, 0.724 mL, 7.46 mmol, 1.50 equiv). The reaction mixture was warmed in an oil heating bath at a temperature of 70 ° C. and heated at reflux with vigorous stirring for 40 hours. The reaction mixture was cooled to 23 ° C. and poured into H2O (30 mL) in a separatory funnel. CHCl3 (30 mL) was added, the funnel was shaken and the organic phase collected. The aqueous phase was then extracted with CHCl3 (2×30 mL). The combined organic phases were washed with brine (30 mL), dried with Na2SO4, and concentrated in vacuo. The residue was purified by chromatography on silica gel, eluting with 2-7% EtOAc in hexanes (v/v) to afford 1.05 g of the title compound as a colorless solid (83% yield). Rf=0.30 (hexanes/EtOAc 19:1 (v/v)). NMR Spectroscopy: 1H NMR (600 MHz, CDCl3, 23 ° C., δ): 10.45 (s, 1H), 7.91 (d, J=2.5 Hz, 1H), 7.58 (dd, J=8.9, 2.6 Hz, 1H), 6.84 (d, J=8.9 Hz, 1H), 3.91 (d, J=7.2 Hz, 2H), 1.32-1.26 (m, 1H), 0.71-0.63 (m, 2H), 0.41-0.34 (m, 2H). 13C NMR (125 MHz, CDCl3, 23 ° C., δ): 188.7, 160.5, 138.3, 130.9, 126.5, 115.0, 113.5, 73.9, 10.1, 3.4. HRMS-FIA (m/z): calcd for C11H11BrNaO2[M+Na]+, 276.9840; found, 276.9820.

Workup

  1. temperatureThe reaction mixture was warmed in an oil
  2. temperatureheated
  3. temperatureat reflux
  4. temperatureThe reaction mixture was cooled to 23 ° C.
  5. stirringthe funnel was shaken
  6. customthe organic phase collected
  7. extractionThe aqueous phase was then extracted with CHCl3 (2×30 mL)
  8. washThe combined organic phases were washed with brine (30 mL)
  9. dry with materialdried with Na2SO4
  10. concentrationconcentrated in vacuo
  11. customThe residue was purified by chromatography on silica gel
  12. washeluting with 2-7% EtOAc in hexanes (v/v)

Sources & evidence

ORD record
ord-243f449c937a468f9b1c6edfd4e66fa6
Source dataset
uspto-grants-2016_03
Patent number
US09273083B2

Reaction notes

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