Phenyl isocyanate → HCID 15168531, compound

HRID 484437Notes

Reaction equation

HRID 484437 reaction equation
Cl.[NH2:2][C@@H:3]1[C:12]2[C:7](=[CH:8][C:9]([Cl:14])=[CH:10][C:11]=2[Cl:13])[NH:6][C@@H:5]([C:15]([O:17][CH3:18])=[O:16])[CH2:4]1.C(N(CC)CC)C.[C:26]1([N:32]=[C:33]=[O:34])[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1>ClCCl>[Cl:13][C:11]1[CH:10]=[C:9]([Cl:14])[CH:8]=[C:7]2[C:12]=1[C@@H:3]([NH:2][C:33]([NH:32][C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1)=[O:34])[CH2:4][C@H:5]([C:15]([O:17][CH3:18])=[O:16])[NH:6]2

Participants

5

Reactant 3

HCID 7672Phenyl isocyanateHCID 8471TriethylamineHCID 67690826HCID 67690826, compound

Product 1

HCID 15168531HCID 15168531, compoundYield 73.1%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a suspension of trans-4-amino-5,7-dichloro-2-methoxycarbonyl-1,2,3,4-tetrahydroquinoline hydrochloride (0.200 g, 0.642 mmol) in anhydrous dichloromethane (20 ml) under an atmosphere of nitrogen was added dry triethylamine (0.098 ml, 0.706 mmol) and the mixture was stirred until dissolution was complete. To this solution was then added phenyl isocyanate (0.077 ml, 0.706 mmol) and the resulting mixture was stirred at room temperature for 2 h. The solvent was removed under vacuum and the residue was partitioned between ethyl acetate (150 ml) and 1M aqueous citric acid (75 ml). The organic layer was successively washed with 1M aqueous citric acid (1×75 ml), saturated sodium bicarbonate solution (2×75 ml) and saturated brine (1×75 ml), then dried (MgSO4) and evaporated. The crude product was recrystallised from methanol to give the title compound as colourless crystals (0.185 g), m.p. 228°-229° C. (dec). δ (DMSO, 360 MHz) 1.67 (1H, ddd, J=12.7, 12.4 and 3.5 Hz, CHACHBHCCHD), 2.34 (1H, dm, J=12.7 Hz, CHACHBHCCHD), 3.73 (3H, s, CO2CH3), 4.00 (1H, dd, J=12.4 and 2.9 Hz, CH ACHBHCCHD), 4.94 (1H, m, CHACHBHCCHDNHCO), 6.53 (1H, d, J=6.4 Hz, CHDNHCONAr), 6.72 (1H, d, J=2.0 Hz, 6-H or 8-H), 6.88-6.93 (3H, m, 6-H or 8-H, ArH and ArNH), 7.20-7.25 (2H, m, ArH) 7.39 (2H, d, J=8.0 Hz, ArH), 8.15 (1H, s, CHDNHCONHAr); m/e 393 (M+), 198 (100%, M-NHCONHPh, CO2CH3 and H); Found C, 54.76; H, 4.39; N, 10.48; C18H17Cl2N3O3 requires C, 54.84; H, 4.35; N, 10.66%.

Workup

  1. customThe solvent was removed under vacuum
  2. customthe residue was partitioned between ethyl acetate (150 ml) and 1M aqueous citric acid (75 ml)
  3. washThe organic layer was successively washed with 1M aqueous citric acid (1×75 ml), saturated sodium bicarbonate solution (2×75 ml) and saturated brine (1×75 ml)
  4. dry with materialdried (MgSO4)
  5. customevaporated
  6. customThe crude product was recrystallised from methanol

Sources & evidence

ORD record
ord-19296ef86fe5458da612924f6a47c885
Source dataset
uspto-grants-1993_07
Patent number
US05231102

Reaction notes

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