Allyltrimethylsilane → HCID 11360496, Verbindung

HRID 1838674

Reaktionsgleichung

Reaktionsgleichung von HRID 1838674
[CH3:1][O:2][C:3]1[C:4]2[C:20]3[C:11](=[C:12]4[C:17](=[CH:18][CH:19]=3)[NH:16][C:15]([CH3:22])([CH3:21])[CH:14]=[C:13]4[CH3:23])[CH:10]([OH:24])[O:9][C:5]=2[CH:6]=[CH:7][CH:8]=1.[CH2:25]([Si](C)(C)C)[CH:26]=[CH2:27]>C(Cl)Cl>[CH2:27]([O:24][CH:10]1[C:11]2=[C:12]3[C:17](=[CH:18][CH:19]=[C:20]2[C:4]2[C:3]([O:2][CH3:1])=[CH:8][CH:7]=[CH:6][C:5]=2[O:9]1)[NH:16][C:15]([CH3:21])([CH3:22])[CH:14]=[C:13]3[CH3:23])[CH:26]=[CH2:25]

Komponenten

4

Edukt 2

HCID 69808AllyltrimethylsilaneHCID 1108859510-methoxy-2,2,4-trimethyl-2,5-dihydro-1H-chromeno[3,4-f]quinolin-5-ol

Produkt 1

HCID 11360496HCID 11360496, VerbindungAusbeute 95,1 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

A three-necked round bottom flask was charged with the product from Example 6 (59.0 g, 0.182 mol) followed by CH2Cl2 (1.18 L). The resulting suspension was stirred briefly before adding allyltrimethylsilane (58 ml, 0.364 mol) all at once at room temperature. The suspension was cooled to 0° C. under nitrogen and was treated with BF3OEt2 (46.3 ml, 0.364 mol) dropwise keeping the reaction temperature below 2° C. After complete addition, the mixture was stirred at 0° C. for ˜1 hour. The completion of the reaction was monitored with HPLC until the starting material was consumed. The reaction mixture was poured into saturated NaHCO3 solution and stirred for 30 minutes. The organic layer was separated, washed with brine, dried over Na2SO4, treated with charcoal, filtered and concentrated to an oil. EtOH (200 ml) was added and the solution was concentrated to give a crystalline solid which was suspended with heptane at 0° C. for 2 hours before filtration to give a solid which was dried under reduced pressure at 45° C. to provide the title compound as a light yellow crystalline solid (60.1 g, 95.1%). Anal. Calcd for C23H25NO2: C, 79.51; H, 7.25; N, 4.03; Found: C, 79.26; H, 7.12; N, 3.80, 1H NMR [(CD3)2SO] δ1.16 (3H, s) 1.17 (3H, s), 2.18 (3H, s), 2.22 (1H, m), 2.46 (1H, m), 3.85 (3H, s), 5.01 (2H, m), 5.44 (1H, br s), 5.77 (1H, dd), 5.82 (1H, m), 6.10 (1H, br s), 6.52 (1H, d), 6.60 (1H, d), 6.70 (1H, d), 7.06 (1H, t,), 7.96 (1H, d); 13C NMR [(CD3)2SO] δ23.8, 28.8, 28.9, 36.5, 49.7, 55.6, 73.4, 105.6, 110.5, 113.4, 113.4, 116.1, 116.4, 127.3, 117.3, 127.3, 127.7, 132.2, 133.8, 134.5, 145.8, 151.1, 156.4. MS (APCI) m/z: 348 (M+H)+.

Aufarbeitung

  1. additionwas treated with BF3OEt2 (46.3 ml, 0.364 mol)
  2. customthe reaction temperature below 2° C
  3. additionAfter complete addition
  4. stirringthe mixture was stirred at 0° C. for ˜1 hour
  5. customwas consumed
  6. additionThe reaction mixture was poured into saturated NaHCO3 solution
  7. stirringstirred for 30 minutes
  8. customThe organic layer was separated
  9. washwashed with brine
  10. dry with materialdried over Na2SO4
  11. additiontreated with charcoal
  12. filtrationfiltered
  13. concentrationconcentrated to an oil
  14. additionEtOH (200 ml) was added
  15. concentrationthe solution was concentrated
  16. customto give a crystalline solid which
  17. filtrationwas suspended with heptane at 0° C. for 2 hours before filtration
  18. customto give a solid which
  19. customwas dried under reduced pressure at 45° C.

Quellen und Nachweise

ORD-Eintrag
ord-336fc357eb0d476cb04b5083027697e2
Quelldatensatz
uspto-grants-2004_01
Patentnummer
US06673930B2

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