Boron trifluoride etherate → HCID 22401272, compound

HRID 1198795Notes

Reaction equation

HRID 1198795 reaction equation
[C:1]1([O:7][C:8]([N:10]2[CH:23]([C:24]#[CH:25])[C:22]34O[C:17]3([CH:18]([O:27][Si](C(C)(C)C)(C)C)[CH2:19][CH2:20][CH2:21]4)[C:16]3[CH:15]=[CH:14][C:13]([O:35][C:36](=[O:41])[C:37]([CH3:40])([CH3:39])[CH3:38])=[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:1]1([O:7][C:8]([N:10]2[CH:23]([C:24]#[CH:25])[C:22]3[CH2:21][CH2:20][CH2:19][C:18](=[O:27])[C:17]=3[C:16]3[CH:15]=[CH:14][C:13]([O:35][C:36](=[O:41])[C:37]([CH3:39])([CH3:38])[CH3:40])=[CH:12][C:11]2=3)=[O:9])[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1

Participants

4

Reactant 2

HCID 8000Boron trifluoride etherateHCID 22401249HCID 22401249, compound2×

Product 1

HCID 22401272HCID 22401272, compoundYield 73%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Conditions

Temperature
25 °C

Procedure

To a solution of Compound 228 (7.0 g, 12.16 mmol) in wet CHCl3 (100 mL) was added BF3.OEt2 (7.48 mL, 60.82 mmol). The mixture was stirred at 25° C. (1. 5 hours) until TLC indicated complete conversion of Compound 228. Silica gel (10.0 g) was added to the reaction mixture followed by stirring at 25° C. for another 12 hours. Silica gel was filtered off through Celite and washed with ethyl ether (100 mL). The solvent was removed in vacuo, and the residue was purified by flash column chromatography (silica gel, 10 percent ethyl ether in benzene) to provide Compound 229 (3.91 g, 73 percent). A more polar component (about 1.0 g) was also isolated which could not be converted to Compound 229 in the presence of silica gel for prolonging reaction time. Compound 229: white solid; mp 140°-142° C.; Rf =0.44 (silica, 10 percent ethyl ether in benzene); IR (CHCl3) νmax 3305, 2977, 1737 (shoulder), 1720, 1705, 1684, 1607, 1577, 1495, 1382, 1306, 1201, 1178, 1122 cm-1 ; 1H NMR (300 MHz, CDCl3) δ 8.25 (d, J=8.7 Hz, 1 H, H1), 7.43-7.35 (m, 3 H, H4 and aromatic), 7.28-7.16 (m, 3 H, aromatic), 6.98 (dd, J=8.7, 2.4 Hz, 1 H, H2), 5.86 (d, J=2.4 Hz, 1 H, H6), 2.87-2.51 (m, 4 H, H7 and H9 ), 2.26 (d, J=2.4 Hz, 1 H, acetylenic), 2.24-2.08 (m, 2 H, H8), 1.33 (s, 9 H, COC(CH3)3); MS (FAB+) m/e (rel intensity) 444 (M+H, 82), 350 (15), 266 (20), 238 (15); HRMS for C27H26NO5 (M+H), calcd 444.1811, found 444.1842.

Workup

  1. additionSilica gel (10.0 g) was added to the reaction mixture
  2. stirringby stirring at 25° C. for another 12 hours
  3. filtrationSilica gel was filtered off through Celite
  4. washwashed with ethyl ether (100 mL)
  5. customThe solvent was removed in vacuo
  6. customthe residue was purified by flash column chromatography (silica gel, 10 percent ethyl ether in benzene)

Sources & evidence

ORD record
ord-c9bd54b474384608a09099c63e1f96e8
Source dataset
uspto-grants-1994_01
Patent number
US05281710

Reaction notes

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