Boron trifluoride etherate → HCID 10907882, compound

HRID 1198798Notes

Reaction equation

HRID 1198798 reaction equation
[C:1]1([O:7][C:8]([N:10]2[CH:23]([C:24]#[C:25]/[CH:26]=[CH:27]\[C:28]#[C:29][Si:30]([CH3:33])([CH3:32])[CH3:31])[C:22]34O[C:17]3([CH:18]([O:35][Si](C(C)(C)C)(C)C)[CH2:19][CH2:20][CH2:21]4)[C:16]3[CH:15]=[CH:14][C:13]([O:43][C:44](=[O:49])[C:45]([CH3:48])([CH3:47])[CH3:46])=[CH:12][C:11]2=3)=[O:9])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.B(F)(F)F.CCOCC>C(Cl)(Cl)Cl.C(Cl)Cl>[C:1]1([O:7][C:8]([N:10]2[CH:23]([C:24]#[C:25]/[CH:26]=[CH:27]\[C:28]#[C:29][Si:30]([CH3:31])([CH3:33])[CH3:32])[C:22]3[CH2:21][CH2:20][CH2:19][C:18](=[O:35])[C:17]=3[C:16]3[CH:15]=[CH:14][C:13]([O:43][C:44](=[O:49])[C:45]([CH3:47])([CH3:46])[CH3:48])=[CH:12][C:11]2=3)=[O:9])[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1

Participants

5

Reactant 2

HCID 8000Boron trifluoride etherateHCID 86747540HCID 86747540, compound

Product 1

HCID 10907882HCID 10907882, compoundYield 36.4%

Reagents, catalysts & solvents 2

HCID 6212ChloroformSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
25 °C

Procedure

To a solution of Compound 210 (9.5 g, 13.6 mmol) in wet CHCl3 (150 mL) cooled at zero degrees C. was added BF3.OEt2 (8.4 mL, 68.0 mmol) followed by stirring at 25° C. for 10 minutes. The reaction mixture was diluted with CH2Cl2 (400 mL), washed with saturated aqueous NaHCO3, dried over anhydrous Na2SO4, and concentrated in vacuo. The residue was then dissolved in THF (50 mL) and treated with 48 percent aqueous HBr (5 mL) at 25° C. for 40 minutes with stirring. The reaction mixture was diluted with ethyl ether (400 mL), washed with saturated aqueous NaHCO3 and brine, dried over anhydrous Na2SO4, and concentrated in vacuo. Flash column chromatography of the residue (silica gel, 33 percent ethyl ether in petroleum ether) gave Compound 211 (2.80 g, 34 percent) and Compound 212 (1.30 g, 18 percent). Compound 211: Rf =0.52 (silica, 50 percent ethyl ether in petroleum ether); IR (CHCl3) νmax 2970, 1719, 1681, 1606, 1494, 1381, 1307, 1179, 1123, 846 cm-1 ; 1H NMR (300 MHz, CDCl3) δ 8.26 (d, J=8.7 Hz, 1 H, H1), 7.45-7.18 (m, 6 H, H4 and aromatic), 6.98 (dd, J=8.7, 2.4 Hz, 1 H, H2), 6.11 (d, J=0.9 Hz, 1 H, H6), 5.84 (d, J=11.1 Hz, 1 H, olefinic), 5.72 (dd, J=11.1, 1.7 Hz, 1 H, olefinic), 2.90 (dt, J=18.9, 4.5 Hz, 1 H, H9), 2.77-2.53 (m, 3 H, H7 and H9), 2.24-2.12 (m, 2 H, H8), 1.34 (s, 9 H, COC(CH3)3), 0.21 (s, 9 H, Si(CH3)3); MS (FAB+) m/e (rel intensity) 698 (M+Cs, 100), 565 (6); HRMS for C34H35NO5SiCs (M+Cs), calcd 698.1339, found 698.1339.

Workup

  1. washwashed with saturated aqueous NaHCO3
  2. dry with materialdried over anhydrous Na2SO4
  3. concentrationconcentrated in vacuo
  4. dissolutionThe residue was then dissolved in THF (50 mL)
  5. additiontreated with 48 percent aqueous HBr (5 mL) at 25° C. for 40 minutes
  6. stirringwith stirring
  7. additionThe reaction mixture was diluted with ethyl ether (400 mL)
  8. washwashed with saturated aqueous NaHCO3 and brine
  9. dry with materialdried over anhydrous Na2SO4
  10. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-5857b429a90d48aabeeb12c2fbcfc856
Source dataset
uspto-grants-1994_01
Patent number
US05281710

Reaction notes

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