Bromine → Ethyl 2-(4-methoxybenzyloxy)-2-(4-bromo-1-hydroxy-3-methylnaphthalen-2-yl)acetate

HRID 514120Notes

Reaction equation

HRID 514120 reaction equation
[CH3:1][O:2][C:3]1[CH:28]=[CH:27][C:6]([CH2:7][O:8][CH:9]([C:15]2[C:24]([CH3:25])=[CH:23][C:22]3[C:17](=[CH:18][CH:19]=[CH:20][CH:21]=3)[C:16]=2[OH:26])[C:10]([O:12][CH2:13][CH3:14])=[O:11])=[CH:5][CH:4]=1.C([O-])(O)=O.[Na+].[Br:34]Br.[O-]S([O-])(=S)=O.[Na+].[Na+]>C(Cl)(Cl)Cl>[CH3:1][O:2][C:3]1[CH:4]=[CH:5][C:6]([CH2:7][O:8][CH:9]([C:15]2[C:24]([CH3:25])=[C:23]([Br:34])[C:22]3[C:17](=[CH:18][CH:19]=[CH:20][CH:21]=3)[C:16]=2[OH:26])[C:10]([O:12][CH2:13][CH3:14])=[O:11])=[CH:27][CH:28]=1

Participants

6

Reactant 4

HCID 24408BromineHCID 24477Sodium ThiosulfateHCID 516892Sodium BicarbonateHCID 67126181Ethyl 2-(4-methoxybenzyloxy)-2-(1-hydroxy-3-methylnaphthalen-2-yl)acetate

Product 1

HCID 67126193Ethyl 2-(4-methoxybenzyloxy)-2-(4-bromo-1-hydroxy-3-methylnaphthalen-2-yl)acetateYield 67.4%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent2×

Procedure

A solution of ethyl 2-(4-methoxybenzyloxy)-2-(1-hydroxy-3-methylnaphthalen-2-yl)acetate (102 mg, 0.268 mmol) in CHCl3 (5.0 mL) was treated with solid NaHCO3 (46 mg, 0.281 mmol). Br2 (45 mg) in CHCl3 (1.0 mL) was added dropwise over 5 min at 23° C. After 15 min, 10% Na2S2O3 (10 mL) was added. The reaction was extracted two times with CHCl3. Combined organic phases were dried (Na2SO4), filtered, and concentrated. The residue was dissolved in DCM. The solution was wet-loaded onto a 12 g “gold” ISCO silica gel column and purified by flash chromatography (ethyl acetate/hexanes) giving the desired product (83 mg, 67%). 1H NMR (400 MHz, CDCl3) δ 8.69 (s, 1H), 8.29 (d, J=8.2 Hz, 1H), 8.22 (d, J=8.6 Hz, 1H), 7.59 (dd, J=7.4, 7.4 Hz, 1H), 7.47 (dd, J=7.8, 7.8 Hz, 1H), 7.26 (d, J=8.2 Hz, 2H), 6.91 (d, J=8.6 Hz, 2H), 5.47 (s, 1H), 4.67-4.56 (m, 2H), 4.26-4.08 (m, 2H), 3.81 (s, 3H), 2.60 (s, 3H), 1.20 (t, J=7.1 Hz, 3H).

Workup

  1. extractionThe reaction was extracted two times with CHCl3
  2. dry with materialCombined organic phases were dried (Na2SO4)
  3. filtrationfiltered
  4. concentrationconcentrated
  5. dissolutionThe residue was dissolved in DCM
  6. custompurified by flash chromatography (ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-c5d509d3e921468ca9bfe6d46ed86d47
Source dataset
uspto-grants-2015_08
Patent number
US09102614B2

Reaction notes

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