Trifluoroacetic acid → HCID 46917810, compound

HRID 425294Notes

Reaction equation

HRID 425294 reaction equation
B(Br)(Br)Br.FC(F)(F)C(O)=O.[CH2:12]([N:14]([CH2:41][CH3:42])[C:15]([C:17]1[CH:18]=[CH:19][C:20]2[C:21](=[C:33]3[CH2:39][CH:38]4[NH:40][CH:35]([CH2:36][CH2:37]4)[CH2:34]3)[C:22]3[C:27]([O:28][C:29]=2[CH:30]=1)=[CH:26][C:25]([O:31]C)=[CH:24][CH:23]=3)=[O:16])[CH3:13].[OH-].[NH4+]>ClCCl>[CH2:41]([N:14]([CH2:12][CH3:13])[C:15]([C:17]1[CH:18]=[CH:19][C:20]2[C:21](=[C:33]3[CH2:39][CH:38]4[NH:40][CH:35]([CH2:36][CH2:37]4)[CH2:34]3)[C:22]3[C:27]([O:28][C:29]=2[CH:30]=1)=[CH:26][C:25]([OH:31])=[CH:24][CH:23]=3)=[O:16])[CH3:42]

Participants

6

Reactant 4

HCID 6422Trifluoroacetic acidHCID 14923Ammonium HydroxideHCID 25134Boron tribromideHCID 11395993HCID 11395993, compound

Product 1

HCID 46917810HCID 46917810, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

A 1.0 M solution of boron tribromide in dichloromethane (2.14 mL, 2.14 mmol) was added to a solution of the trifluoroacetic acid salt of 9-(8-aza-bicyclo[3.2.1]oct-3-ylidene)-6-methoxy-9H-xanthene-3-carboxylic acid diethylamide (0.285 g, 0.535 mmol) in dichloromethane (10 mL) at 0° C. The resultant mixture was stirred at room temperature for 2 h. The mixture was cooled to 0° C., and treated with 10% aqueous ammonium hydroxide (˜20 mL). The organic layer was separated and the aqueous layer was extracted with dichloromethane. The combined organic layers were washed with brine and dried over sodium sulfate. The solvent was evaporated in vacuo, and the residues was dissolved in DMSO and applied to reverse phase C18 column for purification via HPLC, using a gradient of acetonitrile (10% to 90%) in water with trifluoroacetic acid (0.1%) as the eluant. Fractions containing the title compound were combined and further purified via reverse phase HPLC to give the purified title compound (0.035 g). MS: m/z 405.1 (MH+). 1H NMR (DMSO-d6): δ 1.0-1.2 (br m, 6H), 1.29 (d, 12H, J=8.1 Hz), 1.7-1.8 (br m, 2H), 2.8-3.0 (br m, 4H), 3.1-3.5 (br m, 4H), 3.99 (br s, 2H), 6.63-6.65 (m, 2H), 7.13 (d, 1H, J=7.9 Hz), 7.18-7.21 (m, 3H), 7.41 (d, 1H, J=7.9 Hz), 8.70 (br s, 1H), 9.01 br d, 1H) and 9.93 (br s 1H).

Workup

  1. customThe organic layer was separated
  2. extractionthe aqueous layer was extracted with dichloromethane
  3. washThe combined organic layers were washed with brine
  4. dry with materialdried over sodium sulfate
  5. customThe solvent was evaporated in vacuo
  6. dissolutionthe residues was dissolved in DMSO
  7. customfor purification via HPLC
  8. additionFractions containing the title compound
  9. customfurther purified via reverse phase HPLC
  10. customto give the
  11. custompurified title compound (0.035 g)

Sources & evidence

ORD record
ord-2ebf428d5d0e47ebb4aaa0c52c11c12b
Source dataset
uspto-grants-2012_01
Patent number
US08106207B2

Reaction notes

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