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

HRID 448023노트

반응식

HRID 448023 반응식
[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]

참가 물질

7

반응물 4

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

생성물 1

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

시약·촉매·용매 2

HCID 962Water용매HCID 6228Dimethylformamide용매2회

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온도
0 °C

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-651c13ffceca4145b177a0e947f08322
출처 데이터셋
uspto-grants-2013_07
특허 번호
US08481574B2

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