1,1'-Carbonyldiimidazole → (2-Oxo-1,2,4,5-tetrahydroimidazo[1,5,4-de][1,4]benzoxazin-4-yl)methyl 4-methylbenzenesulfonate

HRID 896011Notes

Reaction equation

HRID 896011 reaction equation
[NH2:1][C:2]1[C:7]2[NH:8][CH:9]([CH2:12][O:13][S:14]([C:17]3[CH:22]=[CH:21][C:20]([CH3:23])=[CH:19][CH:18]=3)(=[O:16])=[O:15])[CH2:10][O:11][C:6]=2[CH:5]=[CH:4][CH:3]=1.C(N(CC)C(C)C)(C)C.[C:33](N1C=CN=C1)(N1C=CN=C1)=[O:34]>C(Cl)Cl>[CH3:23][C:20]1[CH:21]=[CH:22][C:17]([S:14]([O:13][CH2:12][CH:9]2[N:8]3[C:33](=[O:34])[NH:1][C:2]4=[CH:3][CH:4]=[CH:5][C:6](=[C:7]34)[O:11][CH2:10]2)(=[O:16])=[O:15])=[CH:18][CH:19]=1

Participants

5

Reactant 3

HCID 682631,1'-CarbonyldiimidazoleHCID 81531DiisopropylethylamineHCID 20814150Toluene-4-sulfonic acid 5-amino-3,4-dihydro-2H-benzo[1,4]oxazin-3-ylmethyl ester

Product 1

HCID 22349481(2-Oxo-1,2,4,5-tetrahydroimidazo[1,5,4-de][1,4]benzoxazin-4-yl)methyl 4-methylbenzenesulfonateYield 55.5%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

Toluene-4-sulfonic acid 5-amino-3,4-dihydro-2H-benzo[1,4]oxazin-3-ylmethyl ester (6.7 g , ˜10 mmole) was dissolved in methylene chloride (100 mL), N, N-diisopropylethylamine (5.22 mL, 30.0 mmole) was added, followed by carbonyldiimidazole (4.05 g, 25.0 mmole), and the mixture was stirred at room temperature under nitrogen overnight. The mixture was diluted with methylene chloride (100 mL), washed with water (2×200 mL), saturated sodium bicarbonate (200 mL) saturated sodium chloride (200 mL) and dried (Na2SO4). Filtration, evaporation in vacuum and column chromatography on silica gel with 1% methanol/methylene chloride as eluent gave 2.0 g of the title compound as an off white solid, m.p. 140-142° C. 1H NMR (DMSO-d6): δ 10.7 (s, 1H); 7.63 (d, 2H); 7.47 (d, 2H); 6.82 (t, 1H); 6.57 (d, 1H); 6.52 (d, 1H); 4.53 (m, 1H); 4.43 (dd, 1H); 4.34 (dd, 1H); 4.16 (dd, 1H); 4.10 (dd, 1H); 2.38 (s, 3H). MS (ESI) m/z359 ([M−H]−).

Workup

  1. washwashed with water (2×200 mL), saturated sodium bicarbonate (200 mL) saturated sodium chloride (200 mL)
  2. dry with materialdried (Na2SO4)
  3. filtrationFiltration, evaporation in vacuum and column chromatography on silica gel with 1% methanol/methylene chloride as eluent

Sources & evidence

ORD record
ord-d15d4f81679e47ef8362b2c741e9cd7b
Source dataset
uspto-grants-2005_07
Patent number
US06919334B2

Reaction notes

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