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

HRID 457952

反応式

HRID 457952 の反応式
[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

参加物

5

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

実験手順

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).

後処理

  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)

出典と根拠

ORDレコード
ord-38414f88160f43a6a8c3b49f271ca38b
出典データセット
uspto-grants-2007_03
特許番号
US07189749B2

関連ノート

読み込み中…