Butyl Isothiocyanate → (z)-2-(5-Acetyl-3-butyl-4-methylthiazol-2(3h)-ylidene)-1-(5-chloro-2-methoxyphenyl)ethanone

HRID 448023

Reaktionsgleichung

Reaktionsgleichung von HRID 448023
[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].Cl[CH:23]([C:27](=[O:29])[CH3:28])[C:24](=O)[CH3:25]>CN(C=O)C.O>[C:27]([C:23]1[S:21]/[C:20](=[CH:3]\[C:4]([C:6]2[CH:11]=[C:10]([Cl:12])[CH:9]=[CH:8][C:7]=2[O:13][CH3:14])=[O:5])/[N:19]([CH2:15][CH2:16][CH2:17][CH3:18])[C:24]=1[CH3:25])(=[O:29])[CH3:28]

Komponenten

7

Edukt 4

HCID 11613Butyl IsothiocyanateHCID 24758Sodium hydrideHCID 743283-Chloro-2,4-pentanedioneHCID 2404341-(5-Chloro-2-methoxyphenyl)ethanone

Produkt 1

HCID 24953913(z)-2-(5-Acetyl-3-butyl-4-methylthiazol-2(3h)-ylidene)-1-(5-chloro-2-methoxyphenyl)ethanone

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 962WaterLösungsmittelHCID 6228DimethylformamideLösungsmittel2×

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

To a stirred suspension of NaH (60% in mineral oil, 0.08 g, 2 mmol) in anhydrous DMF (3 mL) at 0° C. was added 5-chloro-2-methoxyacetophenone (0.37 g, 2 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 3-chloropentane-2,4-dione (0.23 mL, 2 mmol) was added drop-wise. The mixture was stirred at 0° C. for 2 hours and then heated to 90° C. for 5 hours. The mixture was cooled to ambient temperature, diluted with water (30 mL) and extracted with ethyl acetate (3×35 mL). The combined organic layers were washed sequentially with water, brine, dried with MgSO4, filtered and concentrated in vacuo. The residue was purified by flash chromatography eluting with 50% ethyl acetate in hexane to provide the title compound as a yellow solid. 1H NMR (300 MHz, DMSO-d6) δ ppm 0.96 (t, J=7.3 Hz, 3 H), 1.27-1.55 (m, 2 H), 1.58-1.80 (m, 2 H), 2.45 (s, 3 H), 2.65 (s, 3 H), 3.88 (s, 3 H), 3.94-4.10 (m, 2 H), 6.78 (s, 1 H), 7.16 (d, J=8.8 Hz, 1 H), 7.47 (dd, J=8.8, 2.7 Hz, 1 H), 7.65 (d, J=2.7 Hz, 1 H). MS (DCI) m/z 380 (M+H).+ Anal calcd for C19H22ClNO3S: C, 60.07; H, 5.84; N, 3.69. Found: C, 59.56; H, 5.95; N, 3.68.

Aufarbeitung

  1. additionwas added drop-wise
  2. temperatureheated to 90° C. for 5 hours
  3. temperatureThe mixture was cooled to ambient temperature
  4. extractionextracted with ethyl acetate (3×35 mL)
  5. washThe combined organic layers were washed sequentially with water, brine
  6. dry with materialdried with MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customThe residue was purified by flash chromatography
  10. washeluting with 50% ethyl acetate in hexane

Quellen und Nachweise

ORD-Eintrag
ord-651c13ffceca4145b177a0e947f08322
Quelldatensatz
uspto-grants-2013_07
Patentnummer
US08481574B2

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