Trifluoroacetic acid → HCID 66916166, compound

HRID 227174Notes

Reaction equation

HRID 227174 reaction equation
C(O)(C(F)(F)F)=O.[CH2:8]([O:50][CH:51]1[C@H:55]2[C@H:56](OC3CCCCO3)[N:57](C(OC(C)(C)C)=O)[C:58]3[CH:65]=[C:64]([O:66][CH3:67])[CH:63]=[CH:62][C:59]=3[C:60](=[O:61])[N:54]2[CH2:53][CH2:52]1)[CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][O:18][CH:19]1[C@H:23]2[C@H:24](OC3CCCCO3)[N:25](C(OC(C)(C)C)=O)[C:26]3[CH:33]=[C:32]([O:34][CH3:35])[CH:31]=[CH:30][C:27]=3[C:28](=[O:29])[N:22]2[CH2:21][CH2:20]1.C([O-])(O)=O.[Na+]>CO.C(Cl)(Cl)Cl>[CH2:17]([O:18][CH:19]1[C@@H:23]2[CH:24]=[N:25][C:26]3[CH:33]=[C:32]([O:34][CH3:35])[CH:31]=[CH:30][C:27]=3[C:28](=[O:29])[N:22]2[CH2:21][CH2:20]1)[CH2:16][CH2:15][CH2:14][CH2:13][CH2:12][CH2:11][CH2:10][CH2:9][CH2:8][O:50][CH:51]1[C@@H:55]2[CH:56]=[N:57][C:58]3[CH:65]=[C:64]([O:66][CH3:67])[CH:63]=[CH:62][C:59]=3[C:60](=[O:61])[N:54]2[CH2:53][CH2:52]1

Participants

5

Reactant 3

HCID 6422Trifluoroacetic acidHCID 516892Sodium BicarbonateHCID 86614407HCID 86614407, compound

Product 1

HCID 66916166HCID 66916166, compoundYield 90%

Reagents, catalysts & solvents 1

HCID 21584188Chloroform methanolSolvent

Procedure

95% TFA (3 mL) was added drop-wise to dimer compound 8h (191 mg, 0.18 mmol) at 0° C. This was then stirred for 1 hr and the mixture was poured into saturated NaHCO3 (30 mL) solution to naturalize the reaction mixture. The mixture was extracted with chloroform (3×20 mL). The organic layer was then washed water (20 mL), brine (20 mL) then dried (MgSO4) and filtrated. The excess solvent was removed under reduced pressure to give the crude product, which was subjected to flash column chromatography (SiO2, 2% methanol-chloroform). Removal of excess eluent under reduced pressure without heating afforded the final product 9h (103 mg, 0.16 mmol, 90%) as a solid: [α]20D=+387° (c=0.17, CHCl3); 1H NMR (CDCl3, 400 MHz): δ 1.25-1.50 (m, 12H, 14-H, 14′-H, 15-H, 15′-H, 16-H, 16′-H), 1.72-1.92 (m, 4H, 13-H, 13′-H), 1.98-2.09 (m, 4H, 2-H, 2′-H), 2.25-2.38 (m, 4H, 1-H, 1′-H), 3.52-3.62 (m, 2H, 3-H, 3′-H), 3.68-3.73 (m, 2H, 11a-H, 11a′-H), 3.76-3.85 (m, 2H, 3-H, 3′-H), 3.90 (s, 6H, 7-OMe, 7′-OMe), 3.95-4.19 (m, 4H, 12-H, 12′-H), 6.79 (s, 2H, 9-H; 9′-H), 7.50 (s, 2H, 6-H, 6′-H), 7.64 (d, 2H, J=4, 11-H, 11′-H); 13C NMR (CDCl3, 400 MHz): δ 24.1, 25.9, 29.0, 29.3, 29.4, 29.6, 46.6, 53.7, 56.0, 69.7, 109.6, 112.5, 120.2, 140.5, 147.1, 151.6, 162.2, 164.6; IR (neat): 3325, 2931, 1600, 1506, 1448, 1388, 1262, 1217, 1092, 1024 cm−1; MS (FAB) m/z (relative intensity) 695 ([M+2×MeOH]+., 14), 663 ([M+MeOH]+., 20), 631 (M+., 100).

Workup

  1. extractionThe mixture was extracted with chloroform (3×20 mL)
  2. dry with materialwashed water (20 mL), brine (20 mL) then dried (MgSO4)
  3. filtrationfiltrated
  4. customThe excess solvent was removed under reduced pressure
  5. customto give the crude product, which
  6. customRemoval of excess eluent under reduced pressure
  7. temperaturewithout heating

Sources & evidence

ORD record
ord-5c84e239e176480c997ed7d654d850d6
Source dataset
uspto-grants-2009_07
Patent number
US07557099B2

Reaction notes

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