2-Hydroxy-5-methoxybenzaldehyde → 2-Hydroxy-3-iodo-5-methoxy-benzaldehyde

HRID 1794471Notes

Reaction equation

HRID 1794471 reaction equation
[OH:1][C:2]1[CH:9]=[CH:8][C:7]([O:10][CH3:11])=[CH:6][C:3]=1[CH:4]=[O:5].C(O[I:16](OC(=O)C)([O-])(=O)=O)(=O)C.C([N+](CC)(CC)CC)C>ClCCl>[OH:1][C:2]1[C:9]([I:16])=[CH:8][C:7]([O:10][CH3:11])=[CH:6][C:3]=1[CH:4]=[O:5]

Participants

4

Reactant 2

HCID 956952-Hydroxy-5-methoxybenzaldehydeHCID 86589546Tetraethylammonium diacetoxyiodate2×

Product 1

HCID 222215902-Hydroxy-3-iodo-5-methoxy-benzaldehydeYield 11.9%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of 2-hydroxy-5-methoxy-benzaldehyde (15.97 g, 104.9 mmole) in 375 mL dichloromethane at −15° C. was added tetraethylammonium diacetoxyiodate (48.06 g, 128.1 mmole) over 15 minutes. After stirring overnight, an additional amount of tetraethylammonium diacetoxyiodate (46.93 g, 125.1 mmole) was added over 15 minutes. The reaction was stirred for an additional 12 hours, concentrated, and added to 2N HCl. The mixture was extracted into ethyl acetate and the combined organic phases were washed with saturated sodium bicarbonate, water, brine, and dried with magnesium sulfate. The organic phases were concentrated in vacuo and the residue was loaded on to silica gel and chromatographed with silica gel (hexanes:ethyl acetate, 9:1) to afford 3.47 g (11.9%) of iodide as a yellow solid: Mp=103–105° C.; 1H NMR (DMSO-d6) δ 11.3 (s, 1H), 9.73 (s, 1H), 7.60 (d, 1 H, J=3.0 Hz,), 7.07 (d, 1 H, J=3.1 Hz), 3.83 (s, 3H).

Workup

  1. stirringThe reaction was stirred for an additional 12 hours
  2. concentrationconcentrated
  3. additionadded to 2N HCl
  4. extractionThe mixture was extracted into ethyl acetate
  5. washthe combined organic phases were washed with saturated sodium bicarbonate, water, brine
  6. dry with materialdried with magnesium sulfate
  7. concentrationThe organic phases were concentrated in vacuo
  8. customchromatographed with silica gel (hexanes:ethyl acetate, 9:1)

Sources & evidence

ORD record
ord-0ae6938e7f1042578912258f6edf0c62
Source dataset
uspto-grants-2006_04
Patent number
US07022733B2

Reaction notes

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