Trimethylsilylacetylene → HCID 21930937, 화합물

HRID 75244

반응식

HRID 75244 반응식
Br[C:2]1[CH:3]=[CH:4][C:5]2[N:11]3[CH:12]=[N:13][C:14]([C:15]([O:17][CH2:18][CH3:19])=[O:16])=[C:10]3[CH2:9][N:8]=[C:7]([C:20]3[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=3)[C:6]=2[CH:26]=1.[CH3:27][Si:28]([C:31]#[CH:32])([CH3:30])[CH3:29]>CC([O-])=O.CC([O-])=O.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Pd+2].C1(C)C=CC=CC=1>[CH3:27][Si:28]([C:31]#[C:32][C:2]1[CH:3]=[CH:4][C:5]2[N:11]3[CH:12]=[N:13][C:14]([C:15]([O:17][CH2:18][CH3:19])=[O:16])=[C:10]3[CH2:9][N:8]=[C:7]([C:20]3[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=3)[C:6]=2[CH:26]=1)([CH3:30])[CH3:29]

참가 물질

5

반응물 2

HCID 66111TrimethylsilylacetyleneHCID 21930956HCID 21930956, 화합물

생성물 1

HCID 21930937HCID 21930937, 화합물수율 93%

시약·촉매·용매 2

HCID 84538Palladium(2+) acetate--triphenylphosphane (1/2/2)촉매HCID 1140Toluene용매

실험 절차

A mixture of bromide 5 (0.3 g, 0.73 mmol), trimethylsilylacetylene (0.143 g, 1.46 mmol) and bis(triphenylphosphine)-palladium-(II) acetate (55 mg, 0.073 mmol) in a mixed solvent system of toluene (20 mL) and anhydrous TEA (50 mL) was heated to reflux under argon. After stirring for 12 hours at reflux, the mixture was cooled to room temperature and the precipitate which formed was removed by filtration. The filtrate was concentrated under reduced pressure and the residue was treated with a saturated aqueous solution of NaHCO3 (20 mL), and extracted with CHCl3 (3×25 mL). The combined extracts were washed with brine and dried (Na2SO4). After removal of solvent under reduced pressure, the residue was purified by flash chromatography (silica gel, EtOAc) to afford 6 (XLiXHeII-048) as a white solid (0.29 g, 93%). This benzodiazepine can also be obtained from 2 in 45% yield by following the same procedure 6 (XLiXHeII-048): mp: 170-172° C.; IR (KBr) 2958, 2152, 1718 cm−1; 1H NMR (CDCl3) δ 0.23 (s, 9H), 1.42 (t, 3H, J=7.2 Hz), 4.04 (d, 1H, J=12.6 Hz), 4.41 (m, 2H, J=7.2 Hz), 6.23 (d, 1H, J=12.6 Hz), 7.35-7.55 (m, 7H), 7.73 (dd, 1H, J=8.3 Hz, J=1.9 Hz), 7.93 (s, 1H); MS (EI) m/e (relative intensity) 427 (M+, 76), 412 (5), 381 (55), 353 (100) 303 (10), 287 (7). Anal. Calcd. for C25H25N3O2Si.1/3 EtOAc: C, 69.22; H, 6.01; N, 9.20. Found: C, 68.87; H, 5.81; N, 9.37.

후처리

  1. temperaturewas heated
  2. temperatureto reflux under argon
  3. temperatureat reflux
  4. customthe precipitate which formed
  5. customwas removed by filtration
  6. concentrationThe filtrate was concentrated under reduced pressure
  7. additionthe residue was treated with a saturated aqueous solution of NaHCO3 (20 mL)
  8. extractionextracted with CHCl3 (3×25 mL)
  9. washThe combined extracts were washed with brine
  10. dry with materialdried (Na2SO4)
  11. customAfter removal of solvent under reduced pressure
  12. customthe residue was purified by flash chromatography (silica gel, EtOAc)

출처 및 근거

ORD 기록
ord-1c80403410ea49b793bd2d64dc4ecc39
출처 데이터셋
uspto-grants-2014_09
특허 번호
US08835424B2

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