Diethyl Ether → HCID 68183080, compound

HRID 1615483Notes

Reaction equation

HRID 1615483 reaction equation
[CH3:1][C:2]1([CH3:18])[C:16](=[O:17])[C:6]2[CH:7]=[C:8]([C:10]3[CH:15]=[CH:14][N:13]=[CH:12][CH:11]=3)[S:9][C:5]=2[CH2:4][CH2:3]1.[Cl:19][C:20]1[CH:25]=[CH:24][C:23]([Mg]Br)=[CH:22][CH:21]=1.CCOCC>O1CCCC1.[NH4+].[Cl-]>[Cl:19][C:20]1[CH:25]=[CH:24][C:23]([C:16]2([OH:17])[C:6]3[CH:7]=[C:8]([C:10]4[CH:15]=[CH:14][N:13]=[CH:12][CH:11]=4)[S:9][C:5]=3[CH2:4][CH2:3][C:2]2([CH3:18])[CH3:1])=[CH:22][CH:21]=1

Participants

6

Reactant 3

HCID 3283Diethyl Ether3×HCID 68183135HCID 68183135, compoundHCID 178478191HCID 178478191, compound3×

Product 1

HCID 68183080HCID 68183080, compoundYield 97%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 25517Ammonium ChlorideSolvent

Procedure

In a 100 mL round bottomed flask was placed 5,5-dimethyl-2-pyridin-4-yl-6,7-dihydro-1-benzothiophen-4(5H)-one (380 mg, 1.5 mmol) and then dissolved in tetrahydrofuran (30 mL). To the mixture was added 1 M of 4-chlorophenyl magnesiumbromide in ether (3.5 mL, 3.5 mmol) and then stirred for 3 h at rt. To the mixture was added 1 M of 4-chlorophenyl magnesiumbromide in ether (2.5 mL, 2.5 mmol) and then stirred for 16 h at rt. The mixture was stirred for 10 h at 70° C. The mixture was allowed to cool to rt and then 1 M of 4-chlorophenyl magnesiumbromide in ether (5 mL, 5 mmol) was added and the mixture was stirred for 16 h at rt. The mixture was diluted with saturated aqueous solution of NH4Cl (50 mL), which was extracted with EtOAc (50 mL×2). The combined organic phase was dried over anhydrous MgSO4. Insoluble materials were removed by filtration and the filtrate was concentrated under reduced pressure. The residue was purified by pre-packed silica gel (24 g) column chromatography eluted with a 30% to 100% EtOAc/hexane to obtain title compound (530 mg; 97%) as a colorless foam. LCMS: (FA) ES+ 370, 372; 1H NMR (400 MHz, d6-DMSO) δ ppm 8.48 (dd, 2H), 7.45 (dd, 2H), 7.33 (d, 2H), 7.23-7.25 (m, 2H), 5.55 (s, 1H), 2.87-2.91 (m, 2H), 1.84-1.90 (m, 1H), 1.57-1.63 (m, 1H, 0.95 (s, 3H), 0.62 (s, 3H).

Workup

  1. customIn a 100 mL round bottomed flask was placed
  2. stirringstirred for 16 h at rt
  3. stirringThe mixture was stirred for 10 h at 70° C
  4. temperatureto cool to rt
  5. stirringthe mixture was stirred for 16 h at rt
  6. extractionwas extracted with EtOAc (50 mL×2)
  7. dry with materialThe combined organic phase was dried over anhydrous MgSO4
  8. customInsoluble materials were removed by filtration
  9. concentrationthe filtrate was concentrated under reduced pressure
  10. customThe residue was purified by pre-packed silica gel (24 g) column chromatography
  11. washeluted with a 30% to 100% EtOAc/hexane

Sources & evidence

ORD record
ord-7324fbbfb11149b1bcc8cb870c5bbb28
Source dataset
uspto-grants-2014_07
Patent number
US08765746B2

Reaction notes

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