Trifluoroacetic acid → HCID 69075034, compound

HRID 1892624Notes

Reaction equation

HRID 1892624 reaction equation
C(OC([N:8]1[CH2:17][CH2:16][C:15]2[CH:14]=[C:13]3[O:18][CH2:19][O:20][C:12]3=[CH:11][C:10]=2[CH:9]1[CH2:21][C:22]1[CH:27]=[CH:26][C:25]([C:28]2[CH:29]=[N:30][CH:31]=[CH:32][C:33]=2[Cl:34])=[CH:24][CH:23]=1)=O)(C)(C)C.FC(F)(F)C(O)=O>ClCCl>[ClH:34].[ClH:34].[Cl:34][C:33]1[CH:32]=[CH:31][N:30]=[CH:29][C:28]=1[C:25]1[CH:26]=[CH:27][C:22]([CH2:21][CH:9]2[C:10]3[CH:11]=[C:12]4[O:20][CH2:19][O:18][C:13]4=[CH:14][C:15]=3[CH2:16][CH2:17][NH:8]2)=[CH:23][CH:24]=1

Participants

4

Reactant 2

HCID 6422Trifluoroacetic acidHCID 24986276HCID 24986276, compound

Product 1

HCID 69075034HCID 69075034, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of 5-[4-(4-chloropyridin-3-yl)benzyl]-7,8-dihydro-5H-[1,3]dioxolo[4,5-g]isoquinoline-6-carboxylic acid tert-butyl ester 40 (0.220 g, 0.459 mmol) in anhydrous dichloromethane (10 mL) was added trifluoroacetic acid (4.190 g, 36.744 mmol) at 0° C., the reaction mixture was warmed to room temperature and stirred at the same temperature for 2 h. The mixture was concentrated under reduced pressure, repeatedly evaporated using dichloromethane. The residue was treated with aqueous HCl and filtered. The filtrates were basified using 1N NaOH, extracted with CHCl3, washed with water, dried over Na2SO4 and evaporated under reduced pressure. The oily mass was dissolved in MeOH (15 mL) and then in diethyl ether (60 mL). 2 M HCl solution in diethylether (30 mL) was added to above solution at 0° C., the mixture was warmed to room temperature and stirred overnight. Filtered the reaction mixture, the residue was washed with ether, crystallized from methanol-ether to afford 42 as off white-solid (0.103 g, 50%). 1H NMR (300 MHz, DMSO-d6) δ 9.33 (bs, 2H, —NH2), 8.62 (s, 1H, ArH), 8.59 (d, J=5.4 Hz, 1H, ArH), 7.76 (d, J=5.4 Hz, 1H, ArH), 7.55 (s, 4H, ArH), 6.83 (s, 1H, ArH), 6.79 (s, 1H, ArH), 6.00 (s, 2H, —CH2), 4.72 (s, 1H, —CH—), 3.48-3.17 (m, 4H, 2*—CH2), 3.08-2.86 (m, 2H, —CH2). MS (ES+) m/z 379 [M-(2HCl)+H]+.

Workup

  1. concentrationThe mixture was concentrated under reduced pressure
  2. customrepeatedly evaporated
  3. additionThe residue was treated with aqueous HCl
  4. filtrationfiltered
  5. extractionextracted with CHCl3
  6. washwashed with water
  7. dry with materialdried over Na2SO4
  8. customevaporated under reduced pressure
  9. dissolutionThe oily mass was dissolved in MeOH (15 mL)
  10. addition2 M HCl solution in diethylether (30 mL) was added to above solution at 0° C.
  11. temperaturethe mixture was warmed to room temperature
  12. stirringstirred overnight
  13. filtrationFiltered the reaction mixture
  14. washthe residue was washed with ether
  15. customcrystallized from methanol-ether

Sources & evidence

ORD record
ord-93f2696372e44194aa29f287ffb3ca82
Source dataset
uspto-grants-2013_08
Patent number
US08507523B2

Reaction notes

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