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

HRID 1698913

반응식

HRID 1698913 반응식
[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]

참가 물질

6

반응물 4

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

생성물 1

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

시약·촉매·용매 1

HCID 1140Toluene용매

반응 조건

온도
90 °C

실험 절차

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%).

후처리

  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

출처 및 근거

ORD 기록
ord-8f6f18dd68cf4535986f2d10368c5c49
출처 데이터셋
uspto-grants-2002_02
특허 번호
US06344476B1

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