Trifluoroacetic acid → HCID 86614432, compound

HRID 227193Notes

Reaction equation

HRID 227193 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]=[CH:64][C:63]([O:66][CH3:67])=[CH:62][C:59]=3[C:60](=[O:61])[N:54]2[CH2:53][C:52]1=[CH2:82])[CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][O:17][CH:18]1[C@H:22]2[C@H:23](OC3CCCCO3)[N:24](C(OC(C)(C)C)=O)[C:25]3[CH:32]=[CH:31][C:30]([O:33][CH3:34])=[CH:29][C:26]=3[C:27](=[O:28])[N:21]2[CH2:20][C:19]1=[CH2:49].C([O-])(O)=O.[Na+]>CO.C(Cl)(Cl)Cl>[CH2:16]([O:17][CH:18]1[C@@H:22]2[CH:23]=[N:24][C:25]3[CH:32]=[CH:31][C:30]([O:33][CH3:34])=[CH:29][C:26]=3[C:27](=[O:28])[N:21]2[CH2:20][C:19]1=[CH2:49])[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]=[CH:64][C:63]([O:66][CH3:67])=[CH:62][C:59]=3[C:60](=[O:61])[N:54]2[CH2:53][C:52]1=[CH2:82]

Participants

5

Reactant 3

HCID 6422Trifluoroacetic acidHCID 516892Sodium BicarbonateHCID 86614433HCID 86614433, compound

Product 1

HCID 86614432HCID 86614432, compoundYield 55%

Reagents, catalysts & solvents 1

HCID 21584188Chloroform methanolSolvent

Procedure

95% TFA (2 mL) was added dropwise to dimer compound 28b (89 mg, 0.085 mmol) at 0° C. which was stirred for 1 h and then poured into saturated aqueous NaHCO3 (30 mL). The mixture was extracted with chloroform (3×20 mL) and the organic layer washed with water (20 mL), brine (20 mL), dried (MgSO4) and filtered. 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 29b (30 mg, 0.046 mmol, 55%) as a solid: [α]27D=+308° (c=0.24, CHCl3); 1H NMR (CDCl3, 400 MHz): δ 1.30-1.39 (m, 6H, 15-H, 16-H), 1.40-1.50 (m, 4H, 14-H), 1.82-1.91 (m, 4H, 13-H), 2.89-2.97 (m, 2H, 1-H), 3.06-3.16 (m, 2H, 1-H), 3.81-3.90 (m, 2H, 11a-H), 3.93 (s, 6H, 7-OMe), 3.98-4.10 (m, 4H, 12-H), 4.28 (s, 4H, 3-H), 5.16-5.19 (m, 4H, 2a-H), 6.79 (s, 2H, 9-H), 7.48 (s, 2H, 6-H), 7.66 (d, 2H, J=4.44 Hz, 11-H); 13C NMR (CDCl3, 100 MHz): δ 25.8, 28.8, 29.2, 29.4, 35.2, 51.3, 53.8, 56.2, 69.0, 109.3, 110.3, 111.3, 119.5, 140.6, 141.7, 151.0, 162.4, 164.8; IR (neat): 2928, 2854, 1624, 1599, 1506, 1464, 1429, 1381, 1261, 1216, 1096, 729 cm−1; MS (ES+) m/z (relative intensity) 641 ([M+H]+., 100), 642 ([M+2H]+., 52), 339 (97).

Workup

  1. customat 0° C.
  2. extractionThe mixture was extracted with chloroform (3×20 mL)
  3. washthe organic layer washed with water (20 mL), brine (20 mL)
  4. dry with materialdried (MgSO4)
  5. filtrationfiltered
  6. customThe excess solvent was removed under reduced pressure
  7. customto give the crude product, which
  8. customRemoval of excess eluent under reduced pressure
  9. temperaturewithout heating

Sources & evidence

ORD record
ord-13fd8cedbaa54bd9ae885184803f91db
Source dataset
uspto-grants-2009_07
Patent number
US07557099B2

Reaction notes

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