Cesium carbonate → HCID 178434336, compound

HRID 2070902Notes

Reaction equation

HRID 2070902 reaction equation
[CH3:1][C:2]1[C:10]2[C:5](=[CH:6][C:7]([NH:11][C:12]3[N:28]=[C:15]4[CH:16]=[CH:17][CH:18]=[C:19]([NH:20][CH2:21][CH:22]5[CH2:27][CH2:26][O:25][CH2:24][CH2:23]5)[N:14]4[N:13]=3)=[CH:8][CH:9]=2)[N:4](S(C2C=CC(C)=CC=2)(=O)=O)[N:3]=1.C1(P(C2C=CC=CC=2)C2C3OC4C(=CC=CC=4P(C4C=CC=CC=4)C4C=CC=CC=4)C(C)(C)C=3C=CC=2)C=CC=CC=1.BrC1C=C2C(C(C)=NN2S(C2C=CC(C)=CC=2)(=O)=O)=CC=1.C(=O)([O-])[O-].[Cs+].[Cs+]>O1CCOCC1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].O>[CH3:1][C:2]1[C:10]2[C:5](=[CH:6][C:7]([NH:11][C:12]3[N:28]=[C:15]4[CH:16]=[CH:17][CH:18]=[C:19]([NH:20][CH2:21][CH:22]5[CH2:27][CH2:26][O:25][CH2:24][CH2:23]5)[N:14]4[N:13]=3)=[CH:8][CH:9]=2)[NH:4][N:3]=1

Participants

8

Reactant 4

HCID 10796Cesium carbonateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 59276162HCID 59276162, compoundHCID 90977722HCID 90977722, compound

Product 1

HCID 178434336HCID 178434336, compoundYield 80%

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

N2-(3-Methyl-1-tosyl-1H-indazol-6-yl)-N5-((tetrahydro-2H-pyran-4-yl)methyl)-[1,2,4]triazolo[1,5-a]pyridine-2,5-diamine. A mixture of tris(dibenzylideneacetone)dipalladium(0) (0.074 g, 0.081 mmol) and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (0.094 g, 0.162 mmol) in 1,4-dioxane (4 mL) was heated briefly with a heat gun until most of the solids had dissolved and then added to 6-bromo-3-methyl-1-tosyl-1H-indazole (0.295 g, 0.809 mmol), N5-((tetrahydro-2H-pyran-4-yl)methyl)-[1,2,4]triazolo[1,5-c]pyridine-2,5-diamine (0.200 g, 0.809 mmol), and finely ground cesium carbonate (1.080 g, 3.32 mmol) in a sealable vessel with a stirbar. Nitrogen was blown in to blow out air. The resulting mixture was sealed, stirred vigorously, and heated at 100° C. for 3.5 h. The resulting green mixture was cooled to room temperature. Water (10 mL) was added with vigorous stirring. Solids were collected by vacuum filtration and washed thoroughly with water. The solids were taken up in dimethyl sulfoxide and methanol. The resulting mixture was heated with a heat gun and then quickly filtered. The filtrate was capped and let stand at room temperature for 30 min. Solids were collected by vacuum filtration, washed with methanol and diethyl ether, and dried under high vacuum at 40° C. to give the desired product (0.345 g, 0.649 mmol, 80% yield) as an off-white solid. 1H NMR (400 MHz, DMSO-d6) δ (ppm) 10.12 (s, 1H), 8.95 (d, J=1.17 Hz, 1H), 7.78 (d, J=8.20 Hz, 2H), 7.60-7.67 (m, 1H), 7.53-7.60 (m, 1H), 7.49 (t, J=8.20 Hz, 1H), 7.38 (d, J=8.59 Hz, 2H), 6.82 (d, J=8.59 Hz, 1H), 6.20-6.31 (m, 2H), 3.76 (dd, J=3.32, 11.13 Hz, 2H), 3.29 (t, J=6.25 Hz, 2H), 3.18 (t, J=10.93 Hz, 2H), 2.41 (s, 3H), 2.31 (s, 3H), 1.87-2.03 (m, J=4.30, 7.36, 7.36, 7.36, 7.36, 11.16 Hz, 1H), 1.73 (d, J=12.49 Hz, 2H), 1.28 (qd, 2H); MS (ESI) m/z 532.2 [M+1]+.

Workup

  1. temperaturewas heated briefly with a heat gun until most of the solids
  2. dissolutionhad dissolved
  3. customThe resulting mixture was sealed
  4. temperatureThe resulting green mixture was cooled to room temperature
  5. filtrationSolids were collected by vacuum filtration
  6. washwashed thoroughly with water
  7. temperatureThe resulting mixture was heated with a heat gun
  8. filtrationquickly filtered
  9. customThe filtrate was capped
  10. filtrationSolids were collected by vacuum filtration
  11. washwashed with methanol and diethyl ether
  12. customdried under high vacuum at 40° C.

Sources & evidence

ORD record
ord-55adfafb88c2461bb1499d897f408d1e
Source dataset
uspto-grants-2012_10
Patent number
US08299056B2

Reaction notes

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