Iodine → Ethyl 4'-hydroxy-3'-iodo-1,1'-biphenyl-3-carboxylate

HRID 494868Notes

Reaction equation

HRID 494868 reaction equation
[OH:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:13]=[CH:12][CH:11]=[C:10]([C:14]([O:16][CH2:17][CH3:18])=[O:15])[CH:9]=2)=[CH:4][CH:3]=1.CN(C)C=O.[I-:24].[K+].II>N.O>[OH:1][C:2]1[CH:3]=[CH:4][C:5]([C:8]2[CH:13]=[CH:12][CH:11]=[C:10]([C:14]([O:16][CH2:17][CH3:18])=[O:15])[CH:9]=2)=[CH:6][C:7]=1[I:24]

Participants

7

Reactant 4

HCID 807IodineHCID 4875Potassium IodideHCID 6228DimethylformamideHCID 41569924'-Hydroxy-biphenyl-3-carboxylic acid ethyl ester

Product 1

HCID 11462768Ethyl 4'-hydroxy-3'-iodo-1,1'-biphenyl-3-carboxylate

Reagents, catalysts & solvents 2

HCID 222AmmoniaSolventHCID 962WaterSolvent

Procedure

The product from Example 143A (7.71 g, 31.8 mmol) was dissolved into N,N-dimethylformamide (30 mL), diluted with concentrated aqueous ammonia (320 mL), and treated with a solution of potassium iodide (27.72 g, 167 mmol) and iodine (8.48 g, 33.4 mmol) in water (100 mL) all at once. After the mixture was stirred for one hour, the ammonia was removed under reduced pressure on a rotary evaporator. The remaining solution was neutralized to pH 7 with aqueous hydrochloric acid, diluted with EtOAc (200 mL), worked up as usual, dried (Na2SO4), concentrated, and chromatographed on silica with a 33 to 100% gradient of CH2Cl2/hexanes to provide the title compound as a white microcrystalline solid (37% yield). 1HNMR (300 MHz, d6-DMSO) δ 1.35 (t, 3H), 4.35 (q, 2H), 7.00 (d, 1H), 7.53-7.60 (m, 2H), 7.84-7.91 (m, 2H), 7.97 (d, 1H), 8.08 (dd, 1H), 10.55 (bs, 1H).

Workup

  1. customthe ammonia was removed under reduced pressure on a rotary evaporator
  2. additiondiluted with EtOAc (200 mL)
  3. dry with materialdried (Na2SO4)
  4. concentrationconcentrated
  5. customchromatographed on silica with a 33 to 100% gradient of CH2Cl2/hexanes

Sources & evidence

ORD record
ord-ec8f63e13e92443195bdcff82ba0bb99
Source dataset
uspto-grants-2009_05
Patent number
US07538138B2

Reaction notes

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