Trifluoroacetic acid → HCID 86614412, compound

HRID 227178Notes

Reaction equation

HRID 227178 reaction equation
C(O)(C(F)(F)F)=O.[CH2:8]([O:43][CH:44]1[C@H:48]2[C@H:49](OC3CCCCO3)[N:50](C(OC(C)(C)C)=O)[C:51]3[CH:58]=[CH:57][C:56]([O:59][CH3:60])=[CH:55][C:52]=3[C:53](=[O:54])[N:47]2[CH2:46][CH2:45]1)[CH2:9][CH2:10][O:11][CH:12]1[C@H:16]2[C@H:17](OC3CCCCO3)[N:18](C(OC(C)(C)C)=O)[C:19]3[CH:26]=[CH:25][C:24]([O:27][CH3:28])=[CH:23][C:20]=3[C:21](=[O:22])[N:15]2[CH2:14][CH2:13]1.C([O-])(O)=O.[Na+]>CO.C(Cl)(Cl)Cl>[CH2:8]([O:43][CH:44]1[C@@H:48]2[CH:49]=[N:50][C:51]3[CH:58]=[CH:57][C:56]([O:59][CH3:60])=[CH:55][C:52]=3[C:53](=[O:54])[N:47]2[CH2:46][CH2:45]1)[CH2:9][CH2:10][O:11][CH:12]1[C@@H:16]2[CH:17]=[N:18][C:19]3[CH:26]=[CH:25][C:24]([O:27][CH3:28])=[CH:23][C:20]=3[C:21](=[O:22])[N:15]2[CH2:14][CH2:13]1

Participants

5

Reactant 3

HCID 6422Trifluoroacetic acidHCID 516892Sodium BicarbonateHCID 86614413HCID 86614413, compound

Product 1

HCID 86614412HCID 86614412, compoundYield 70%

Reagents, catalysts & solvents 1

HCID 21584188Chloroform methanolSolvent

Procedure

95% TFA (3 mL) was added drop-wise to dimer compound 15a (75 mg, 0.08 mmol) at 0° C. This was then stirred for 1 h 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 16a (30 mg, 0.05 mmol, 70%) as a solid: [α]20D=+477° (c=0.11, CHCl3); 1H NMR (CDCl3, 400 MHz): δ 2.01-2.06 (m, 4H, 2-H, 2′-H), 2.28-2.31 (m, 4H, 1-H, 1′-H), 2.39-2.42 (m, 2H, 13-H), 3.55-3.60 (m, 2H, 3-H, 3′-H), 3.67-3.73 (m, 2H, 11a-H, 11a′-H), 3.77-3.87 (m, 2H, 3-H, 3′-H), 3.91 (s, 6H, 7-OMe, 7′-OMe), 4.23-4.31 (m, 4H, 12-H, 12′-H), 6.84 (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, 28.4, 29.6, 46.6, 53.6, 56.1, 58.4, 65.4, 110.8, 111.6, 120.4, 140.6, 147.8, 150.6, 162.3, 164.6; IR (neat): 3350, 2951, 1600, 1505, 1434, 1262, 1217, 1021 cm−1; MS (FAB) m/z (relative intensity) 597 ([M+2×MeOH]+., 16), 565 ([M+MeOH]+., 5), 533 (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-bca2208486554311b2fab0f082c9fb64
Source dataset
uspto-grants-2009_07
Patent number
US07557099B2

Reaction notes

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