Methanol → HCID 70094791, compound

HRID 1856830Notes

Reaction equation

HRID 1856830 reaction equation
[H-].[Na+].C([O:5][CH2:6][CH3:7])=O.[CH3:8][C:9]1(C)[CH2:25][C:13]2=[C:14]([C:19]3[CH:24]=[CH:23][CH:22]=[CH:21][N:20]=3)[S:15][C:16]([S:17][CH3:18])=[C:12]2[C:11](=[O:26])[CH2:10]1.CO>C1COCC1>[CH3:8][C:9]1([CH3:10])[CH2:25][C:13]2=[C:14]([C:19]3[CH:24]=[CH:23][CH:22]=[CH:21][N:20]=3)[S:15][C:16]([S:17][CH3:18])=[C:12]2[C:11](=[O:26])[C:7]1=[CH:6][OH:5]

Participants

6

Reactant 4

HCID 887MethanolHCID 8025Ethyl formate2×HCID 24758Sodium hydride2×HCID 10990326HCID 10990326, compound

Product 1

HCID 70094791HCID 70094791, compoundYield 40%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of sodium hydride (108 mg of a 60% dispersion in mineral oil, 2.7 mmol) and ethyl formate (0.55 mL, 6.8 mmol) at 0C in THF (5 mL) was added a solution of 6,6-dimethyl-3-methylthio-1-(pyrid-2-yl)-4,5,6,7-tetrahydrobenzo[c]thiophen-4-one (205 mg, 0.68 mmol) in THF (5 mL). The mixture was stirred at room temperature for 2 h then more sodium hydride (50 mg of a 60% dispersion in mineral oil, 1.3 mmol) and ethyl formate (0.55 mL, 6.8 mmol) were added. The mixture was stirred for a further 2 h before MeOH (0.2 mL) was added and the mixture evaporated in vacuo. The residue was dissolved in water (20 mL) and the undissolved solid filtered off. The mixture was acidified to pH 1 using 1M HCl then neutralised with Na2CO3. The mixture was partitioned between EtOAc (20 mL) and water (10 mL) and the organic layer separated and dried (MgSO4). The solvent was evaporated and the residue triturated with ether to afford the title compound (90 mg, 40%) as a yellow solid. 1H NMR (250 MHz, CDCl3) δ1.21 (6H, s), 2.70 (3H, s), 2.93 (2H, s), 7.16-7.22 (1H, m), 7.4.3 (1H, d, J=8.0 Hz), 7.57 (1H, d, J=10.4 Hz), 7.74 (1H, d of t, J=7.7 and 1.8 Hz), 8.62-8.65 (1H, m), 14.68 (1H, d, J=10.4 Hz). MS (ES+) 332 (M+1).

Workup

  1. additionwas added
  2. customthe mixture evaporated in vacuo
  3. dissolutionThe residue was dissolved in water (20 mL)
  4. filtrationthe undissolved solid filtered off
  5. customThe mixture was partitioned between EtOAc (20 mL) and water (10 mL)
  6. customthe organic layer separated
  7. dry with materialdried (MgSO4)
  8. customThe solvent was evaporated
  9. customthe residue triturated with ether

Sources & evidence

ORD record
ord-d6162100c290456fa836f974dc5024ec
Source dataset
uspto-grants-2000_11
Patent number
US06143773

Reaction notes

Loading…