Boron trifluoride etherate → HCID 13866540, Verbindung

HRID 1383048Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1383048
[CH3:1][C:2]1[NH:3][C:4]([CH3:22])=[C:5]([C:18]([O:20][CH3:21])=[O:19])[CH:6]([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[C:7]=1[C:8]([O:10][CH3:11])=[O:9].[CH2:23]([Si:26]([CH3:29])([CH3:28])[CH3:27])[CH:24]=[CH2:25].B(F)(F)F.CCOCC>C(Cl)(Cl)Cl>[CH3:22][C:4]12[CH2:25][CH:24]([CH2:23][Si:26]([CH3:29])([CH3:28])[CH3:27])[C:7]([C:8]([O:10][CH3:11])=[O:9])([CH:6]([C:12]3[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=3)[CH:5]1[C:18]([O:20][CH3:21])=[O:19])[C:2]([CH3:1])=[N:3]2

Komponenten

5

Edukt 3

HCID 8000Boron trifluoride etherateHCID 69808AllyltrimethylsilaneHCID 129839Dimethyl 2,6-dimethyl-4-phenyl-1,4-dihydropyridine-3,5-dicarboxylate

Produkt 1

HCID 13866540HCID 13866540, Verbindung

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6212ChloroformLösungsmittel

Versuchsvorschrift

To 1.0 g (3.3 mmol) dimethyl 2,6-dimethyl-4-phenyl-1,4-dihydropyridine-3,5-dicarboxylate (1) [B. Loev. et al., J. Med. Chem., 17, 956 (1974)] in 50 ml chloroform cooled in an ice-bath to 0°-5° there was added 7.5 g (66 mmol) commercially obtained allyltrimethylsilane (2) followed by 1.41 g (10 mmol) boron trifluoride etherate added dropwise via syringe. The reaction mixture was then stirred for 4 hours at 0°-10° and quenched by addition of saturated aqueous NaHCO3 solution. After the addition of 50 ml Et2O, the organic phase was separated, washed with brine and dried. Solvent removal left an oil that was purified by column chromatograhy on silica gel eluting with 7% isopropanol/hexane to give pure 3 as of oil, which crystallized after standing, mp. 152°-155°, formula: C23H33NO4Si; m.w., 415.606. mmr (CDCl3) δ 0.78(9H, s), 0.27(1H, dd), 0.47(1H, dd), 0.83(1H, dd), 1.57(3H, s), 2.46(1H, dd), 2.55(3H, s), 2.60(1H, dd), 2.76(1H, m), 3.58(3H, s), 3.74(1H, d), 3.79(3H, s), 7.16(2H, dd), 7.30(3H, m).

Aufarbeitung

  1. additionadded dropwise via syringe
  2. customquenched by addition of saturated aqueous NaHCO3 solution
  3. additionAfter the addition of 50 ml Et2O
  4. customthe organic phase was separated
  5. washwashed with brine
  6. customdried
  7. customSolvent removal
  8. waitleft an oil that
  9. customwas purified by column chromatograhy on silica gel eluting with 7% isopropanol/hexane
  10. customto give pure 3 as of oil, which
  11. customcrystallized

Quellen und Nachweise

ORD-Eintrag
ord-ee38f4c380bf4b1080d5e0d9b8e388df
Quelldatensatz
uspto-grants-1989_02
Patentnummer
US04808718

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