Dimethyl oxalate → HCID 10804586, compound

HRID 1596163Notes

Reaction equation

HRID 1596163 reaction equation
[CH3:1][O:2][CH2:3][N:4]1[CH:8]=[CH:7][N:6]=[C:5]1[S:9][C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1.[Li]CCCC.[C:21](OC)(=[O:26])[C:22]([O:24][CH3:25])=[O:23].[NH4+].[Cl-]>C1COCC1.CCOCC>[CH3:1][O:2][CH2:3][N:4]1[C:8]([C:21](=[O:26])[C:22]([O:24][CH3:25])=[O:23])=[CH:7][N:6]=[C:5]1[S:9][C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1

Participants

7

Reactant 4

HCID 11120Dimethyl oxalateHCID 25517Ammonium ChlorideHCID 110204141H-Imidazole, 1-(methoxymethyl)-2-(phenylthio)-HCID 178418339Butyllithium

Product 1

HCID 10804586HCID 10804586, compoundYield 66%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

To a cold (−78° C.), stirred solution of 1-methoxymethyl-2phenylthioimidazole (Ohta, S. et al. (1992) Chem. Pharm. Bull. 40:2681) (11) 340 mg, 1.55 mmol) in dry THF (8.0 mL) was added a solution of n-BuLi (1.47 M in hexanes, 1.26 mL, 1.85 mmol) and the mixture was stirred for 1 hour. A solution of dimethyl oxalate (540 mg. 4.58 mmol) in dry THF (2.0 mL) was added and the mixture was stirred at −78° C. for an additional 1.25 hours. The reaction mixture was treated with saturated aqueous NH4Cl (5.0 mL) and Et2O (20 mL). The phases were separated and the aqueous layer was extracted with Et2O (25 mL). The combined organic extracts were washed (brine, 10 mL), dried (MgSO4), and concentrated. Flash chromatography (35 g of silica gel, 1:1 petroleum ether-Et2O) of the crude material afforded 305 mg (66%) of 8 as a beige solid that exhibited mp 59-60° C.; IR (KBr) 1729, 1657, 1305, 1273, 1167, 1114, 784 cm−1; 1H NMR (CDCl3, 400 MHz) δ8.23 (s, 1H), 7.52-7.54 (m. 2H), 7.37-7.38 (m, 3H), 5.81 (s, 2H), 3.91 (s, 3H), 3.36 (s, 3H); 13C NMR (CDCl3, 100 MHz) δ172.2, 161.6, 154.1, 145.4, 145.3, 133.2, 129.5, 129.2, 128.7, 75.8, 56.5, 53.0; HREIMS calcd for C14H14N2O4`S 306.0674, found 306.0674.

Workup

  1. stirringthe mixture was stirred at −78° C. for an additional 1.25 hours
  2. customThe phases were separated
  3. extractionthe aqueous layer was extracted with Et2O (25 mL)
  4. washThe combined organic extracts were washed (brine, 10 mL)
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-817b66d2eca9470a84e0693f1ad8dc4c
Source dataset
uspto-grants-2001_09
Patent number
US06291447B1

Reaction notes

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