Methyl iodide → N-(2-methylamino-5-iodobenzoyl)-b-alanine benzyl ester

HRID 1655687ノート

反応式

HRID 1655687 の反応式
[CH2:1]([O:3][C:4](=[O:18])[CH2:5][CH2:6][NH:7][C:8](=[O:17])[C:9]1[CH:14]=[C:13]([I:15])[CH:12]=[CH:11][C:10]=1[NH2:16])[CH3:2].N1C(C)=[CH:23][CH:22]=[CH:21][C:20]=1[CH3:26].[CH3:27]I>CN(C)C=O>[CH2:1]([O:3][C:4](=[O:18])[CH2:5][CH2:6][NH:7][C:8](=[O:17])[C:9]1[CH:14]=[C:13]([I:15])[CH:12]=[CH:11][C:10]=1[NH:16][CH3:27])[C:2]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:26]=1

参加物

5

反応物 3

HCID 6328Methyl iodideHCID 79372,6-LutidineHCID 10861356N-(2-amino-5-iodobenzoyl)-b-alanine ethyl ester

生成物 1

HCID 22905394N-(2-methylamino-5-iodobenzoyl)-b-alanine benzyl ester収率 35%

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

実験手順

A magnetically stirred solution of 0.848 gram of N-(2-amino-5-iodobenzoyl)-β-alanine ethyl ester (2.0 mmol), 0.35 mL 2,6-lutidine (3.0 mmol), 0.19 mL methyl iodide (3.0 mmol), and 15 mL dimethylformamide was heated to 50° C. for 15 hours. The reaction mixture was allowed to cool to room temperature and concentrated in vacuo. The resulting residue was dissolved in 75 mL ethyl acetate and washed 1×50 mL 10% citric acid, 1×50 mL sat. sodium bicarbonate, 1×50 mL brine, dried over magnesium sulfate, filtered and concentrated in vacuo. The resulting oil was further purified by column chromatography, using silica gel, eluting with a solvent gradient of 35/65 ethyl acetate/hexane to 65/35 ethyl acetate/hexane (TLC, SiO2, 1:1 EtOAc/hexane, Rf =0.84, υν positive) to yield 305 mgs (35%) of N-(2-methylamino-5-iodobenzoyl)-β-alanine benzyl ester. 1H NMR (CDCl3, dTMS) 7.56 (2H, m, Ar--H o,p-CON), 7.43 (1H, bq, 3JHH =5 Hz, NHMe), 7.38-7.32 (5H, s, ArH Ph), 6.62 (1H, bt, 3JHH =6 Hz, CONH), 6.42 (1H, d, 3JHH =9 Hz, Ar--H m-CON), 5.16 (2 H, s, OCH2), 3.64 (2H, q, 3JHH =6 Hz, NCH2), 2.81 (3H, d, 3JHH =5 Hz, NCH3), 2.64 (2H, t, 3JHH =6 Hz, CH2CO2). 13C NMR (CDCl3, δTMS) 172.4, 168.4, 148.8, 141.0, 135.5, 128.7, 128.4, 128.3, 117.3, 113.4, 74.1, 66.7, 35.2, 34.0, 29.6.

後処理

  1. concentrationconcentrated in vacuo
  2. dissolutionThe resulting residue was dissolved in 75 mL ethyl acetate
  3. washwashed 1×50 mL 10% citric acid, 1×50 mL sat. sodium bicarbonate, 1×50 mL brine
  4. dry with materialdried over magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe resulting oil was further purified by column chromatography
  8. washeluting with a solvent gradient of 35/65 ethyl acetate/hexane to 65/35 ethyl acetate/hexane (TLC, SiO2, 1:1 EtOAc/hexane, Rf =0.84, υν positive)

出典と根拠

ORDレコード
ord-82aafb3ed71d4dc6b53bec41bfbfca23
出典データセット
uspto-grants-1993_10
特許番号
US05250679

反応ノート

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