Boron trifluoride etherate → HCID 13866540, compound

HRID 1383048Notes

Reaction equation

HRID 1383048 reaction equation
[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

Participants

5

Reactant 3

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

Product 1

HCID 13866540HCID 13866540, compound

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

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).

Workup

  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

Sources & evidence

ORD record
ord-ee38f4c380bf4b1080d5e0d9b8e388df
Source dataset
uspto-grants-1989_02
Patent number
US04808718

Reaction notes

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