p-Toluenesulfonic acid → (2z)-2-(3-Butyl-1,3-thiazol-2(3h)-ylidene)-1-(5-chloro-2-methoxyphenyl)ethanone

HRID 448086

反応式

HRID 448086 の反応式
[H-].[Na+].[CH3:3][C:4]([C:6]1[CH:11]=[C:10]([Cl:12])[CH:9]=[CH:8][C:7]=1[O:13][CH3:14])=[O:5].[CH2:15]([N:19]=[C:20]=[S:21])[CH2:16][CH2:17][CH3:18].Br[CH2:23][CH:24](OC)OC.C1(C)C=CC(S(O)(=O)=O)=CC=1>CN(C=O)C.[Cl-].[Na+].O>[CH2:15]([N:19]1[CH:24]=[CH:23][S:21]/[C:20]/1=[CH:3]\[C:4]([C:6]1[CH:11]=[C:10]([Cl:12])[CH:9]=[CH:8][C:7]=1[O:13][CH3:14])=[O:5])[CH2:16][CH2:17][CH3:18]

参加物

8

反応物 5

HCID 6101p-Toluenesulfonic acidHCID 11613Butyl IsothiocyanateHCID 24758Sodium hydrideHCID 816722-Bromo-1,1-dimethoxyethaneHCID 2404341-(5-Chloro-2-methoxyphenyl)ethanone

生成物 1

HCID 69166144(2z)-2-(3-Butyl-1,3-thiazol-2(3h)-ylidene)-1-(5-chloro-2-methoxyphenyl)ethanone

試薬・触媒・溶媒 2

HCID 6228Dimethylformamide溶媒2 回HCID 57417360Sodium chloride; water溶媒

実験手順

To a stirred suspension of NaH (60% in mineral oil, 0.04 g, 1 mmol) in anhydrous DMF (3 mL) at 0° C. was added 5-chloro-2-methoxyacetophenone (0.15 g, 1 mmol) followed by subsequent addition of n-butylisothiocyanate (0.24 mL, 2 mmol) in DMF (3 mL). The mixture was stirred at 0° C. for 2 hours after which 2-bromo-1,1-dimethoxyethane was added. The reaction mixture was stirred for 2 hr and then poured into brine, extracted with EtOAc. The organic layer was washed with brine (3×30 mL), dried (MgSO4) and concentrated. The residue was dissolved in toluene (10 mL) then treated with p-toluenesulfonic acid (1.5 mmol) and refluxed for 6 hr. The reaction mixture was concentrated and partitioned between EtOAc and saturated NaHCO3. The organic layer was washed with brine, dried (MgSO4) and concentrated. The residue was purified by flash chromatography eluting with 50% ethyl acetate in hexane to provide the title compound as a yellow solid. (10 mg). 1H NMR (300 MHz, DMSO-d6) δ ppm 0.93 (t, J=7.3 Hz, 3 H), 1.32 (dd, J=15.1, 7.3 Hz, 2 H), 1.72 (t, J=7.3 Hz, 2 H), 3.86 (s, 3 H), 4.01 (t, J=7.1 Hz, 2 H), 6.57 (s, 1 H), 6.81 (d, J=4.4 Hz, 1 H), 7.12 (d, J=8.8 Hz, 1 H), 7.33-7.48 (m, 1 H), 7.34-7.49 (m, 1 H), 7.65 (d, J=3.1 Hz, 1 H). MS (DCI), m/z 324 (M+H)+.

後処理

  1. additionwas added
  2. extractionextracted with EtOAc
  3. washThe organic layer was washed with brine (3×30 mL)
  4. dry with materialdried (MgSO4)
  5. concentrationconcentrated
  6. dissolutionThe residue was dissolved in toluene (10 mL)
  7. temperaturerefluxed for 6 hr
  8. concentrationThe reaction mixture was concentrated
  9. custompartitioned between EtOAc and saturated NaHCO3
  10. washThe organic layer was washed with brine
  11. dry with materialdried (MgSO4)
  12. concentrationconcentrated
  13. customThe residue was purified by flash chromatography
  14. washeluting with 50% ethyl acetate in hexane

出典と根拠

ORDレコード
ord-1b2086c0e35f4cc19c0a3ebae8941d12
出典データセット
uspto-grants-2013_07
特許番号
US08481574B2

関連ノート

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