Sulfuric Acid → HCID 69672878, compound

HRID 63969Notes

Reaction equation

HRID 63969 reaction equation
C(O[C:5]([CH3:8])([CH3:7])[CH3:6])(=O)C.[CH2:9]([O:11][C:12](=[O:36])[CH:13]([OH:35])[C:14]1[C:15]([CH3:34])=[N:16][C:17]2[S:18][C:19]3[CH2:20][O:21][CH2:22][CH2:23][C:24]=3[C:25]=2[C:26]=1[C:27]1[CH:32]=[CH:31][C:30]([CH3:33])=[CH:29][CH:28]=1)[CH3:10].S(=O)(=O)(O)O.C(=O)(O)[O-].[Na+]>ClCCl>[CH2:9]([O:11][C:12](=[O:36])[CH:13]([O:35][C:5]([CH3:8])([CH3:7])[CH3:6])[C:14]1[C:15]([CH3:34])=[N:16][C:17]2[S:18][C:19]3[CH2:20][O:21][CH2:22][CH2:23][C:24]=3[C:25]=2[C:26]=1[C:27]1[CH:28]=[CH:29][C:30]([CH3:33])=[CH:31][CH:32]=1)[CH3:10]

Participants

6

Reactant 4

HCID 1118Sulfuric AcidHCID 10908tert-Butyl acetateHCID 516892Sodium BicarbonateHCID 69672802hydroxy-(2-methyl-4-p-tolyl-5,8-dihydro-6H-7-oxa-9-thia-1-aza-fluoren-3-yl)-acetic acid ethyl ester

Product 1

HCID 69672878HCID 69672878, compoundYield 45%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Tert-Butyl acetate (0.8 mL) was added to a solution of hydroxy-(2-methyl-4-p-tolyl-5,8-dihydro-6H-7-oxa-9-thia-1-aza-fluoren-3-yl)-acetic acid ethyl ester (100 mg, 0.252 mmol) in dichloromethane (0.8 mL) followed by concentrated sulphuric acid (40 μL) and the reaction stirred at room temperature for 2 hours. Sodium bicarbonate solution (10% aqueous, 2 mL) was added and the reaction evaporated in vacuo until only the aqueous remained. The aqueous was extracted with ethyl acetate (2 mL) and the organic layer washed with brine (1 mL), dried and concentrated in vacuo. The residue was purified by flash chromatography on silica eluting with 0-30% ethyl acetate/heptanes to afford a colourless solid (66 mg, 45%). LCMS (12 min acidic) 7.25 min, ES+/AP+ 454 (MH+) 1HNMR (400 MHz, CDCl3) δ ppm 0.98 (s, 9H), 1.20 (t, 3H), 1.55-1.65 (m, 2H), 2.43 (s, 3H), 2.77 (s, 3H), 3.57-3.61 (m, 1H), 3.78-3.82 (m, 1H), 4.06-4.20 (m, 2H), 4.79-4.82 (m, 2H), 7.16 (d, 2H), 7.32 (d, 2H).

Workup

  1. customthe reaction evaporated in vacuo until only the
  2. extractionThe aqueous was extracted with ethyl acetate (2 mL)
  3. washthe organic layer washed with brine (1 mL)
  4. customdried
  5. concentrationconcentrated in vacuo
  6. customThe residue was purified by flash chromatography on silica eluting with 0-30% ethyl acetate/heptanes

Sources & evidence

ORD record
ord-81574e37816c42409cd7cc37af8a4e15
Source dataset
uspto-grants-2016_09
Patent number
US09447116B2

Reaction notes

Loading…