Methyl iodide → Methyl 4-iodo-2-nitrobenzoate

HRID 551996

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HRID 551996 반응식
N[C:2]1C=C(I)C=CC=1C(OC)=O.[I:13][C:14]1[CH:22]=[CH:21][C:17]([C:18]([OH:20])=[O:19])=[C:16]([N+:23]([O-:25])=[O:24])[CH:15]=1.C1CCN2C(=NCCC2)CC1.IC>CN(C=O)C.O>[I:13][C:14]1[CH:22]=[CH:21][C:17]([C:18]([O:20][CH3:2])=[O:19])=[C:16]([N+:23]([O-:25])=[O:24])[CH:15]=1

참가 물질

7

반응물 4

HCID 6328Methyl iodideHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 189198834-Iodo-2-nitrobenzoic acidHCID 18929930Methyl 2-amino-4-iodobenzoate

생성물 1

HCID 58476577Methyl 4-iodo-2-nitrobenzoate수율 95%

시약·촉매·용매 2

HCID 962Water용매HCID 6228Dimethylformamide용매

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온도
0 °C

실험 절차

Methyl 2-amino-4-iodobenzoate. To a stirred solution of 4-iodo-2-nitrobenzoic acid (2.3 g, 7.9 mmol) in DMF (30 mL) at 0° C. was added DBU (2.4 mL, 16 mmol) followed by iodomethane (1.5 mL, 24 mmol). The reaction mixture was stirred 15 min at 0° C., then was allowed to warm to room temperature and was stirred overnight. The mixture was poured into H2O and extracted with EtOAc (2×). The combined organic extracts were washed with H2O (2×), dried (MgSO4), and concentrated in vacuo. The residue was purified by flash chromatography (hexanes/EtOAc) to afford methyl 4-iodo-2-nitrobenzoate as a pale yellow solid (2.30 g, 95%). To a solution of the nitrobenzoate (2.3 g, 7.4 mmol) in 1:1 EtOAc/DCM (10 mL) at room temperature was added SnCl2.2H2O (8.3 g, 37 mmol). The reaction mixture was allowed to stir overnight. The solvents were evaporated in vacuo, and the residue was partitioned between satd. aq. NaHCO3 and DCM. The layers were separated, and the aqueous layer was further extracted with DCM (2×). The combined organic layers were dried (MgSO4) and concentrated in vacuo to provide the pure aminobenzoate as a yellow solid (1.87 g, 91%). 1H NMR (500 MHz, CDCl3): 7.52 (d, J=8.5 Hz, 1H), 7.07 (d, J=1.6 Hz, 1H), 6.96 (dd, J=8.5, 1.6 Hz, 1H), 5.72 (br s, 2H), 3.86 (s, 3H).

후처리

  1. temperatureto warm to room temperature
  2. stirringwas stirred overnight
  3. extractionextracted with EtOAc (2×)
  4. washThe combined organic extracts were washed with H2O (2×)
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated in vacuo
  7. customThe residue was purified by flash chromatography (hexanes/EtOAc)

출처 및 근거

ORD 기록
ord-85808cfa7c844806ac4517b6d1389f34
출처 데이터셋
uspto-grants-2011_05
특허 번호
US07947833B2

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