Trifluoroacetic acid → p-Toluenesulfonic acid

HRID 340644Notes

Reaction equation

HRID 340644 reaction equation
[C:1]([C:5]1[S:9]/[C:8](=[N:10]\[C:11]([C:13]2[CH:31]=[C:30]([C:32]([F:35])([F:34])[F:33])[CH:29]=[CH:28][C:14]=2[O:15][CH2:16][C@@H:17]2[CH2:20][CH2:19][N:18]2C(OC(C)(C)C)=O)=[O:12])/[N:7]([CH2:36][CH:37]([CH3:39])[CH3:38])[CH:6]=1)([CH3:4])([CH3:3])[CH3:2].FC(F)(F)C(O)=O.O.[C:48]1([CH3:58])[CH:53]=[CH:52][C:51]([S:54]([OH:57])(=[O:56])=[O:55])=[CH:50][CH:49]=1>C(Cl)Cl.CCOC(C)=O>[C:48]1([CH3:58])[CH:49]=[CH:50][C:51]([S:54]([OH:57])(=[O:55])=[O:56])=[CH:52][CH:53]=1.[NH:18]1[CH2:19][CH2:20][C@H:17]1[CH2:16][O:15][C:14]1[CH:28]=[CH:29][C:30]([C:32]([F:33])([F:34])[F:35])=[CH:31][C:13]=1[C:11](/[N:10]=[C:8]1\[S:9][C:5]([C:1]([CH3:3])([CH3:4])[CH3:2])=[CH:6][N:7]\1[CH2:36][CH:37]([CH3:38])[CH3:39])=[O:12]

Participants

7

Reactant 3

HCID 6422Trifluoroacetic acidHCID 521998p-Toluenesulfonic acid monohydrateHCID 178448487HCID 178448487, compound

Product 2

HCID 6101p-Toluenesulfonic acidHCID 178448485HCID 178448485, compound

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of the product of Example 12B (0.33 g, 0.58 mmol) in CH2Cl2 (4 mL) was added trifluoroacetic acid (2 mL, 26 mmol). This mixture stirred at ambient temperature for 2 h then was concentrated under reduced pressure and purified via column chromatography (SiO2, 100% CH2Cl2 to 9:1:0.1 CH2Cl2:CH3OH:NH4OH). The material was dissolved in hexanes/EtOAc (1 mL/2 mL) and one equivalent of p-toluenesulfonic acid monohydrate in 1 mL EtOAc was added. Solids precipitated immediately and the p-toluenesulfonic acid salt of the title compound was isolated via filtration (0.13 g, 0.20 mmol, 35% yield). 1H NMR (300 MHz, CD3OD) δ ppm 0.99 (dd, J=6.8, 2.4 Hz, 6H), 1.39 (s, 9H), 2.24-2.34 (m, 1H), 2.36 (s, 3H), 2.58-2.80 (m, 2H), 4.04-4.20 (m, 4H), 4.35-4.42 (m, 1H), 4.49-4.56 (m, 1H), 4.86-4.95 (m, 1H), 7.18-7.25 (m, 3H), 7.34 (d, J=8.5 Hz, 1H), 7.68-7.71 (m, 2H), 7.79 (dd, J=8.6, 1.9 Hz, 1H), 8.38 (d, J=2.4 Hz, 1H); MS (DCI/NH3) m/z 470 (M+H)+. Anal. calculated for C23H30F3N3O2S.1.5 C7H8O3S.1.2H2O: Calc: C, 53.69; H, 5.97; N, 5.61. Found: 53.38; H, 6.13; N, 5.91.

Workup

  1. concentrationthen was concentrated under reduced pressure
  2. custompurified via column chromatography (SiO2, 100% CH2Cl2 to 9:1:0.1 CH2Cl2:CH3OH:NH4OH)
  3. dissolutionThe material was dissolved in hexanes/EtOAc (1 mL/2 mL)
  4. customSolids precipitated immediately

Sources & evidence

ORD record
ord-dd9fc06e427c489e91d78117f5be7b06
Source dataset
uspto-grants-2014_11
Patent number
US08895592B2

Reaction notes

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