Pyridine → Methyl 5-tert-butyl-3-(3-p-tolylureido)furan-2-carboxylate

HRID 1698902ノート

反応式

HRID 1698902 の反応式
[C:1](Cl)(Cl)=[O:2].[NH2:5][C:6]1[CH:10]=[C:9]([C:11]([CH3:14])([CH3:13])[CH3:12])[O:8][C:7]=1[C:15]([O:17][CH3:18])=[O:16].N1C=CC=CC=1.[NH2:25][C:26]1[CH:31]=[CH:30][C:29]([CH3:32])=[CH:28][CH:27]=1>C1(C)C=CC=CC=1.CCOC(C)=O>[C:15]([C:7]1[O:8][C:9]([C:11]([CH3:14])([CH3:12])[CH3:13])=[CH:10][C:6]=1[NH:5][C:1]([NH:25][C:26]1[CH:31]=[CH:30][C:29]([CH3:32])=[CH:28][CH:27]=1)=[O:2])([O:17][CH3:18])=[O:16]

参加物

7

反応物 4

HCID 1049PyridineHCID 6371PhosgeneHCID 7813p-ToluidineHCID 18322376Methyl 3-amino-5-(tert-butyl)furan-2-carboxylate

生成物 1

HCID 9905562Methyl 5-tert-butyl-3-(3-p-tolylureido)furan-2-carboxylate収率 96.9%

試薬・触媒・溶媒 2

HCID 1140Toluene溶媒HCID 8857Ethyl Acetate溶媒

実験手順

Phosgene (1.93M in toluene, 1.3 mL, 2.5 mmol, 10 equiv) was added rapidly to a solution of methyl 3-amino-5-tert-butylfuran-2-carboxylate (0.050 g, 0.25 mmol) and anh. pyridine (1.0 mL) in anh. toluene (5 mL) at room temp. After 30 min, the orange suspension was concentrated under reduced pressure, then successively charged with dry toluene (1 mL) and concentrated (2×). Finally, anh. toluene (3 mL) was added followed by p-toluidine (0.100 g, 0.93 mmol, 3.7 equiv). The orange mixture was stirred overnight, diluted with EtOAc, washed with a 1M HCl solution and a concentrated NaCl solution, then dried (Na2SO4) and concentrated under reduced pressure. The residue was purified by flash chromatography to give N-(2-carbomethoxy-5-tert-butyl-3-furyl)-N′-(4-methylphenyl)urea (0.080 g, 96%) as a pale yellow oil: 1H NMR (CDCl3) δ1.28 (s, 9H), 2.30 (s, 3H), 3.77 (s, 3H), 7.02 (s, 1H), 7.11 (d, J=8.1 Hz, 2H), 7.27 (d, J=8.1 Hz, 2H), 7.87 (br s, 1H), 8.68 (br s, 1H); 13C NMR (CDCl3) δ20.6, 28.3 (3C), 33.0, 51.0, 100.1, 121.4 (2C), 126.0, 129.5 (2C), 134.0, 134.8, 137.7, 152.5, 160.5, 168.2; FTIR (neat) 3400-3200 (br, m), 2966 (s), 1676 (s), 1622 (s), 1536 (s), 1306 (s), 1097 (m) cm−1.

後処理

  1. concentrationthe orange suspension was concentrated under reduced pressure
  2. additionsuccessively charged with dry toluene (1 mL)
  3. concentrationconcentrated (2×)
  4. additionFinally, anh. toluene (3 mL) was added
  5. washwashed with a 1M HCl solution
  6. dry with materiala concentrated NaCl solution, then dried (Na2SO4)
  7. concentrationconcentrated under reduced pressure
  8. customThe residue was purified by flash chromatography

出典と根拠

ORDレコード
ord-6bf21a4539f34282b9ef3d1e01ab68e0
出典データセット
uspto-grants-2002_02
特許番号
US06344476B1

反応ノート

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