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

HRID 1698902Notes

Reaction equation

HRID 1698902 reaction equation
[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]

Participants

7

Reactant 4

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

Product 1

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

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Procedure

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.

Workup

  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

Sources & evidence

ORD record
ord-6bf21a4539f34282b9ef3d1e01ab68e0
Source dataset
uspto-grants-2002_02
Patent number
US06344476B1

Reaction notes

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