Dimethyl Sulfoxide → HCID 178448420, compound

HRID 254675Notes

Reaction equation

HRID 254675 reaction equation
O=[C:2]1[CH2:7][O:6][CH2:5][C:4]([O-:8])=[CH:3]1.[Na+].[CH2:10]([NH:14][C:15]([NH2:17])=[S:16])[CH2:11][CH2:12][CH3:13].CS(C)=O.[Cl:22][C:23]1[CH:24]=[CH:25][C:26]([O:32][CH3:33])=[C:27]([CH:31]=1)[C:28](O)=[O:29].CCN=C=NCCCN(C)C.Cl.ON1C2C=CC=CC=2N=N1.C(N(CC)CC)C>O1CCCC1.C(OCC)(=O)C>[CH2:10]([N:14]1[C:2]2[CH2:7][O:6][CH2:5][C:4](=[O:8])[C:3]=2[S:16]/[C:15]/1=[N:17]\[C:28](=[O:29])[C:27]1[CH:31]=[C:23]([Cl:22])[CH:24]=[CH:25][C:26]=1[O:32][CH3:33])[CH2:11][CH2:12][CH3:13]

Participants

10

Reactant 7

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 757711-HydroxybenzotriazoleHCID 769705-Chloro-o-anisic acidHCID 1551919Thiourea, butyl-HCID 27239391,3-Propanediamine, N'-(ethylcarbonimidoyl)-N,N-dimethyl-, monohydrochlorideHCID 66851893HCID 66851893, compound

Product 1

HCID 178448420HCID 178448420, compoundYield 10.4%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent2×

Conditions

Temperature
40 °C

Procedure

To a mixture of sodium 5-oxo-5,6-dihydro-2H-pyran-3-olate (Li, Wenke; Wayne, Gregory S.; Lallaman, John E.; Wittenberger, Steven J. J. Org. Chem. (2006), 71, 1725-1727) (1.36 g, 10 mmol) and n-butylthiourea (Trans World) (1.32 g, 10 mmol) in tetrahydrofuran (15 mL) was added a mixture of DMSO/12 N HCl (1/1 molar ratio, 4.6 mL, 30 mmol). The reaction mixture was heated at 40° C. for overnight, and then cooled. The mixture was diluted with ethyl acetate and washed with aqueous sodium bicarbonate. The organic extract was dried (MgSO4), filtered and concentrated. The residue was dried under vacuum for 12 h and dissolved in tetrahydrofuran (40 mL). To the solution was added 5-chloro-2-methoxy-benzoic acid (1.86 g, 10.0 mmol), N-(3-dimethylaminopropyl)-N-ethylcarbodimide hydrochloride (1.91 g, 10.0 mmol), 1-hydroxybenzotriazole (1.35 g, 10.0 mmol) and triethylamine (3.5 mL, 3.5 mmol). The mixture was stirred overnight at 80° C. and then cooled at room temperature. The mixture was diluted with ethyl acetate, washed with 1 M aqueous NaHCO3, dried (Na2SO4), filtered and concentrated. The residue was purified by flash chromatography (SiO2, 0-75% ethyl acetate in hexanes) to afford 412 mg of the title compound. MS (ESI+) m/z 395 (M+H)+

Workup

  1. additionwas added
  2. temperaturecooled
  3. washwashed with aqueous sodium bicarbonate
  4. extractionThe organic extract
  5. dry with materialwas dried (MgSO4)
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe residue was dried under vacuum for 12 h
  9. dissolutiondissolved in tetrahydrofuran (40 mL)
  10. temperaturecooled at room temperature
  11. washwashed with 1 M aqueous NaHCO3
  12. dry with materialdried (Na2SO4)
  13. filtrationfiltered
  14. concentrationconcentrated
  15. customThe residue was purified by flash chromatography (SiO2, 0-75% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-65dcdcc8226149488d669d20757654eb
Source dataset
uspto-grants-2011_01
Patent number
US07875640B2

Reaction notes

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