Trimethylsilylacetylene → HCID 21930937, Verbindung

HRID 75244

Reaktionsgleichung

Reaktionsgleichung von HRID 75244
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]

Komponenten

5

Edukt 2

HCID 66111TrimethylsilylacetyleneHCID 21930956HCID 21930956, Verbindung

Produkt 1

HCID 21930937HCID 21930937, VerbindungAusbeute 93 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 84538Palladium(2+) acetate--triphenylphosphane (1/2/2)KatalysatorHCID 1140TolueneLösungsmittel

Versuchsvorschrift

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.

Aufarbeitung

  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)

Quellen und Nachweise

ORD-Eintrag
ord-1c80403410ea49b793bd2d64dc4ecc39
Quelldatensatz
uspto-grants-2014_09
Patentnummer
US08835424B2

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