Diisopropylethylamine → 4-fluoro-2-hydroxy-N-(3-nitro-benzyl)-benzamide

HRID 457952

반응식

HRID 457952 반응식
[F:1][C:2]1[CH:3]=[C:4]([OH:11])[C:5](=[CH:9][CH:10]=1)[C:6](Cl)=[O:7].C(N(CC)C(C)C)(C)C.Cl.[N+:22]([C:25]1[CH:26]=[C:27]([CH:30]=[CH:31][CH:32]=1)[CH2:28][NH2:29])([O-:24])=[O:23]>ClCCl>[F:1][C:2]1[CH:10]=[CH:9][C:5]([C:6]([NH:29][CH2:28][C:27]2[CH:30]=[CH:31][CH:32]=[C:25]([N+:22]([O-:24])=[O:23])[CH:26]=2)=[O:7])=[C:4]([OH:11])[CH:3]=1

참가 물질

5

반응물 3

HCID 81531DiisopropylethylamineHCID 2724030Benzenemethanamine, 3-nitro-, hydrochloride (1:1)HCID 184681274-Fluoro-2-hydroxybenzoyl chloride

생성물 1

HCID 184681804-fluoro-2-hydroxy-N-(3-nitro-benzyl)-benzamide수율 67.1%

시약·촉매·용매 1

HCID 6344Dichloromethane용매

실험 절차

A solution of 4-fluoro salicylic acid chloride (12.3 g, 70.3 mmol) in dichloromethane (140 mL) was cooled to 0° C., and treated with N,N-diisopropylethylamine (31.0 mL, 175 mmol) and 3-nitrobenzylamine hydrochloride (16 g, 84.6 mmol). After stirring at room temperature for 24 h, the solution was concentrated in vacuo and diluted with ethyl acetate. The organic layer was washed successively with aq 2 N HCl and saturated aq NaCl, dried over MgSO4, filtered and concentrated. Purification by MPLC (10–100% ethyl acetate in heptane, 23 mL/min, 75 min) provided 4-fluoro-2-hydroxy-N-(3-nitro-benzyl)-benzamide as a yellow solid (13.7 g, 67%): 1H NMR (DMSO-d6 300 MHz) δ 12.75 (s, 1 H), 9.43 (t, J=6.0 Hz, 1 H), 8.11 (ddd, J, =8.3, J2=2.1 Hz, J3=1.2 Hz, 1 H), 8.18 (t, J=1.5 Hz, 1 H), 7.94 (dd, J1=8.9 Hz, J2=6.5 Hz, 1 H), 7.78 (td, J1=7.8 Hz, J2=1.4 Hz, 1 H), 7.63 (t, J=8.0 Hz, 1 H), 6.81–6.72 (m, 2 H), 4.61 (d, J=5.7 Hz, 2 H).

후처리

  1. concentrationthe solution was concentrated in vacuo
  2. additiondiluted with ethyl acetate
  3. washThe organic layer was washed successively with aq 2 N HCl and saturated aq NaCl
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customPurification by MPLC (10–100% ethyl acetate in heptane, 23 mL/min, 75 min)

출처 및 근거

ORD 기록
ord-38414f88160f43a6a8c3b49f271ca38b
출처 데이터셋
uspto-grants-2007_03
특허 번호
US07189749B2

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