Pyridine → 5-tert-Butyl-3-(3-p-tolyl-ureido)-1H-pyrrole-2-carboxylic acid methyl ester

HRID 1698913

反応式

HRID 1698913 の反応式
[NH2:1][C:2]1[CH:6]=[C:5]([C:7]([CH3:10])([CH3:9])[CH3:8])[NH:4][C:3]=1[C:11]([O:13][CH3:14])=[O:12].N1C=CC=CC=1.[C:21](Cl)(Cl)=[O:22].[NH2:25][C:26]1[CH:31]=[CH:30][C:29]([CH3:32])=[CH:28][CH:27]=1>C1(C)C=CC=CC=1>[C:11]([C:3]1[NH:4][C:5]([C:7]([CH3:10])([CH3:8])[CH3:9])=[CH:6][C:2]=1[NH:1][C:21]([NH:25][C:26]1[CH:31]=[CH:30][C:29]([CH3:32])=[CH:28][CH:27]=1)=[O:22])([O:13][CH3:14])=[O:12]

参加物

6

反応物 4

HCID 1049PyridineHCID 6371PhosgeneHCID 7813p-ToluidineHCID 18322367methyl 3-amino-5-(tert-butyl)-1H-pyrrole-2-carboxylate

生成物 1

HCID 98839395-tert-Butyl-3-(3-p-tolyl-ureido)-1H-pyrrole-2-carboxylic acid methyl ester収率 80%

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒

反応条件

温度
90 °C

実験手順

To a solution of methyl 3-amino-5-tert-butylpyrrole-2-carboxylate (12 mg, 0.062 mmol) and anh. pyridine (0.25 mL, 3.06 mmol, 49.4 equiv) in anh. toluene (1 mL) was rapidly added phosgene (1.93M in toluene, 0.32 mL, 0.62 mmol, 10 equiv). After 30 min, the orange suspension was concentrated under reduced pressure, then successively charged with anh. toluene (1 mL) and concentrated (2×). Finally, toluene (2 mL) was added followed by p-toluidine (10 mg, 0.094 mmol). The mixture was heated at 90° C. for 3 h, then was concentrated under reduced pressure. The residue was purified by preparative TLC (2 plates, 20×20 cm×0.25 mm, 2% MeOH/CH2Cl2). The major UV-active band was isolated and the product was extracted from the silica using 5% MeOH/CH2Cl2 to give N-(2-carbomethoxy-5-tert-butyl-3-pyrrolyl)-N′-(4-methylphenyl)urea as a pale yellow amorphous solid (0.016 g, 80%): 1H NMR (d6-DMSO ) δ1.23 (s, 9H), 2.20 (s, 3H), 3.78 (s, 3H), 6.54 (d, J=3.0 Hz, 1H), 7.04 (d, J=8.5 Hz, 2H), 7.32 (d, J=8.5 Hz, 2H), 8.61 (s, 1H), 9.51 (s, 1H), 10.85 (br d, J=2.2 Hz, 1H); 13C NMR (MeOD, CDCl3, partial spectrum) δ19.7, 29.0 (3C), 31.5, 50.0, 97.4, 105.9, 119.6 (2C), 128.9 (2C), 132.2, 136.2, 147.6, 153.5, 161.9; FTIR (KBr) 3341 (s), 2947 (m), 1676 (s), 1583 (s), 1548 (s), 1456 (s), 1279 (s), 1208 (s), 1094 (s); cm−1; FAB-LRMS m/z (rel abundance) 330 (M+H, 47%).

後処理

  1. concentrationthe orange suspension was concentrated under reduced pressure
  2. additionsuccessively charged with anh. toluene (1 mL)
  3. concentrationconcentrated (2×)
  4. additionFinally, toluene (2 mL) was added
  5. concentrationwas concentrated under reduced pressure
  6. customThe residue was purified by preparative TLC (2 plates, 20×20 cm×0.25 mm, 2% MeOH/CH2Cl2)
  7. customThe major UV-active band was isolated
  8. extractionthe product was extracted from the silica using 5% MeOH/CH2Cl2

出典と根拠

ORDレコード
ord-8f6f18dd68cf4535986f2d10368c5c49
出典データセット
uspto-grants-2002_02
特許番号
US06344476B1

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