Sodium Carbonate → HCID 86727133, compound

HRID 579312Notes

Reaction equation

HRID 579312 reaction equation
[CH3:1][N:2]1[CH:6]=[C:5](B2OC(C)(C)C(C)(C)O2)[CH:4]=[N:3]1.FC(F)(F)S(O[C:22]1[CH:27]=[CH:26][C:25]([C:28]2[S:29][C:30]([N:33]([CH3:44])[CH:34]3[CH2:39][C:38]([CH3:41])([CH3:40])[NH:37][C:36]([CH3:43])([CH3:42])[CH2:35]3)=[N:31][N:32]=2)=[C:24]([O:45][CH3:46])[CH:23]=1)(=O)=O.C([O-])([O-])=O.[Na+].[Na+]>O1CCOCC1.O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:46][O:45][C:24]1[CH:23]=[C:22]([C:5]2[CH:4]=[N:3][N:2]([CH3:1])[CH:6]=2)[CH:27]=[CH:26][C:25]=1[C:28]1[S:29][C:30]([N:33]([CH3:44])[CH:34]2[CH2:39][C:38]([CH3:40])([CH3:41])[NH:37][C:36]([CH3:43])([CH3:42])[CH2:35]2)=[N:31][N:32]=1

Participants

7

Reactant 3

HCID 10340Sodium CarbonateHCID 27739871-Methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazoleHCID 86727132HCID 86727132, compound

Product 1

HCID 86727133HCID 86727133, compoundYield 57.7%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
120 °C

Procedure

To a stirred solution of 1-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole (177 mg, 0.849 mmol) and 3-methoxy-4-(5-(methyl(2,2,6,6-tetramethylpiperidin-4-yl)amino)-1,3,4-thiadiazol-2-yl)phenyl trifluoromethanesulfonate (332 mg, 0.653 mmol) in dioxane (4 mL) was added Pd(PPh3)4 (38 mg, 0.033 mmol) followed by a solution of Na2CO3 (208 mg, 1.958 mmol) in water (1 mL). The resulting mixture was purged with nitrogen, sealed, and heated at 120° C. for 30 minutes under microwave irradiation. The reaction mixture was diluted with EtOAc (100 mL) and washed with water (50 mL). The organic phase was separated, dried over MgSO4, and filtered. To the filtrate was added SiliaMetS DMT (541 mg, 0.61 mmol/g, 0.33 mmols) and the resulting suspension stirred at room temperature for 18 hours. The SiliaMetS DMT was removed by vacuum filtration, rinsed with EtOAc, and the filtrate concentrated in vacuo to afford the crude product as a pale yellow solid. The crude material was recrystallized from MeOH (3 mL) to afford the title compound as a white solid (0.166 g, 57% yield). LC-MS: Rt 0.86 min; MS m/z 441.4 [M+H]+ [Method A]. 1H NMR (400 MHz, DMSO-d6) δ ppm 8.27 (s, 1H), 8.05 (d, J=8.08 Hz, 1H), 7.98 (s, 1H), 7.37 (d, J=1.52 Hz, 1H), 7.29 (dd, J=8.59, 1.52 Hz, 1H), 4.35 (tt, J=12.38, 3.28 Hz, 1H), 3.99 (s, 3H), 3.88 (s, 3H), 2.97 (s, 3H), 1.61 (dd, J=11.87, 3.28 Hz, 2H), 1.41 (t, J=12.13 Hz, 2H), 1.26 (s, 1H), 1.21 (s, 6H), 1.09 (s, 6H). LC-MS: Rt 1.60 min; MS m/z 440.4 [M+H]+ [Method B]. HR-MS: Rt 1.43 min; MS m/z 441.2419 [M+H]+ [Method C].

Workup

  1. customThe resulting mixture was purged with nitrogen
  2. customsealed
  3. additionThe reaction mixture was diluted with EtOAc (100 mL)
  4. washwashed with water (50 mL)
  5. customThe organic phase was separated
  6. dry with materialdried over MgSO4
  7. filtrationfiltered
  8. additionTo the filtrate was added SiliaMetS DMT (541 mg, 0.61 mmol/g, 0.33 mmols)
  9. customThe SiliaMetS DMT was removed by vacuum filtration
  10. washrinsed with EtOAc
  11. concentrationthe filtrate concentrated in vacuo
  12. customto afford the crude product as a pale yellow solid
  13. customThe crude material was recrystallized from MeOH (3 mL)

Sources & evidence

ORD record
ord-26f9c4f39c7647b8a46ca2a1f3b6b583
Source dataset
uspto-grants-2015_05
Patent number
US09040712B2

Reaction notes

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