Trifluoroacetic acid → HCID 86614415, compound

HRID 227180Notes

Reaction equation

HRID 227180 reaction equation
C(O)(C(F)(F)F)=O.[CH2:8]([O:45][CH:46]1[C@H:50]2[C@H:51](OC3CCCCO3)[N:52](C(OC(C)(C)C)=O)[C:53]3[CH:60]=[CH:59][C:58]([O:61][CH3:62])=[CH:57][C:54]=3[C:55](=[O:56])[N:49]2[CH2:48][CH2:47]1)[CH2:9][CH2:10][CH2:11][CH2:12][O:13][CH:14]1[C@H:18]2[C@H:19](OC3CCCCO3)[N:20](C(OC(C)(C)C)=O)[C:21]3[CH:28]=[CH:27][C:26]([O:29][CH3:30])=[CH:25][C:22]=3[C:23](=[O:24])[N:17]2[CH2:16][CH2:15]1.C([O-])(O)=O.[Na+]>CO.C(Cl)(Cl)Cl>[CH2:8]([O:45][CH:46]1[C@@H:50]2[CH:51]=[N:52][C:53]3[CH:60]=[CH:59][C:58]([O:61][CH3:62])=[CH:57][C:54]=3[C:55](=[O:56])[N:49]2[CH2:48][CH2:47]1)[CH2:9][CH2:10][CH2:11][CH2:12][O:13][CH:14]1[C@@H:18]2[CH:19]=[N:20][C:21]3[CH:28]=[CH:27][C:26]([O:29][CH3:30])=[CH:25][C:22]=3[C:23](=[O:24])[N:17]2[CH2:16][CH2:15]1

Participants

5

Reactant 3

HCID 6422Trifluoroacetic acidHCID 516892Sodium BicarbonateHCID 86614416HCID 86614416, compound

Product 1

HCID 86614415HCID 86614415, compoundYield 65%

Reagents, catalysts & solvents 1

HCID 21584188Chloroform methanolSolvent

Procedure

95% TFA (3 mL) was added drop-wise to dimer compound 15c (180 mg, 0.19 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 16c (70 mg, 0.12 mmol, 65%) as a solid: [α]20D=+626° (c=0.17, CHCl3); 1H NMR (CDCl3, 400 MHz): δ 1.62-1.71 (m, 2H, 14-H), 1.89-1.99 (m, 4H, 13-H, 13′-H), 2.0-2.11 (m, 4H, 2-H, 2′-H), 2.25-2.36 (m, 4H, 1-H, 1′-H), 3.53-3.62 (m, 2H, 3-H, 3′-H), 3.66-3.76 (m, 2H, 11a-H, 11a′-H), 3.77-3.85 (m, 2H, 3-H, 3′-H), 3.92 (s, 6H, 7-OMe, 7′-OMe), 4.01-4.16 (m, 4H, 12-H, 12′-H), 6.78 (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 22.5, 29.6, 46.6, 53.7, 56.1, 68.7, 110.5, 111.6, 120.1, 140.6, 147.8, 150.8, 162.3, 164.6; IR (neat): 3350, 2946, 1600, 1505, 1455, 1433, 1383, 1262, 1217, 1092, 1020 cm−1; MS (FAB) m/z (relative intensity) 625 ([M+2×MeOH]+., 4), 593 ([M+MeOH]+., 12), 547 (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-1ff3ae84aaf345289dede2673eb9584b
Source dataset
uspto-grants-2009_07
Patent number
US07557099B2

Reaction notes

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