Iodine → Ethyl 3-bromo-4-hydroxy-5-iodobenzoate

HRID 1743407노트

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HRID 1743407 반응식
[CH2:1]([O:3][C:4](=[O:13])[C:5]1[CH:10]=[CH:9][C:8]([OH:11])=[C:7]([Br:12])[CH:6]=1)[CH3:2].C1COCC1.C1(O)C=CC=CC=1.[I:26]I>C(=O)([O-])[O-].[K+].[K+]>[CH2:1]([O:3][C:4](=[O:13])[C:5]1[CH:10]=[C:9]([I:26])[C:8]([OH:11])=[C:7]([Br:12])[CH:6]=1)[CH3:2]

참가 물질

6

반응물 4

HCID 807Iodine2회HCID 996PhenolHCID 8028TetrahydrofuranHCID 4778964Ethyl 3-bromo-4-hydroxybenzoate

생성물 1

HCID 54064945Ethyl 3-bromo-4-hydroxy-5-iodobenzoate수율 90.4%

시약·촉매·용매 1

HCID 11430Potassium Carbonate용매

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온도
0 °C

실험 절차

To a mixture of 3-bromo-4-hydroxybenzoic acid ethyl ester (69.2 g, 282 mmol) in 2N aqueous potassium carbonate (423 mL) was added sufficient THF to completely dissolve the phenol and make the solution clear (˜300 to 500 mL). The solution was cooled to 0° C. and I2 (158 g, 621 mmol) was added portionwise at such a rate as not to accumulate a large amount of solid I2 on the bottom of the flask. After addition was complete, the ice bath was removed, and the solution was allowed to warm to room temperature. The reaction was complete in 2 h. Worked up by adding (slowly with caution) solid sodium bisulfite at a rate so excess foaming doesn't occur. Sodium bisulfite was added until nearly decolorized. The mixture was acidified with concentrated hydrochloric acid, extracted several times with ethyl acetate, the organic layers combined, washed with brine, dried over anhydrous sodium sulfate, decanted, and concentrated in vacuo to give 3-bromo-4-hydroxy-5-iodobenzoic acid ethyl ester (94.6 g, 90%) as a pale yellow solid. NMR indicated it was suitable for use in the next step without further purification. 1H NMR (300 MHz, CDCl3) δ 1.39 (t, J=6.8 Hz, 3H, —CO2CH2CH3), 4.32 (t, J=6.8 Hz, 2H, —CO2CH2CH3), 8.14 (d, 1H, arom), 8.32 (d, 1H, arom).

후처리

  1. additionAfter addition
  2. customthe ice bath was removed
  3. temperatureto warm to room temperature
  4. additionby adding (slowly with caution) solid sodium bisulfite at a rate so excess foaming doesn't
  5. additionSodium bisulfite was added
  6. extractionextracted several times with ethyl acetate
  7. washwashed with brine
  8. dry with materialdried over anhydrous sodium sulfate
  9. customdecanted
  10. concentrationconcentrated in vacuo

출처 및 근거

ORD 기록
ord-1fd4ed9002594ccaa87ca7679982b0f6
출처 데이터셋
uspto-grants-2006_03
특허 번호
US07008636B2

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