Sodium Carbonate → 5-(2-(4-Aminophenoxy)pyridin-3-yl)thiazol-2-amine

HRID 593950Notes

Reaction equation

HRID 593950 reaction equation
CC1(C)C(C)(C)OB([C:9]2[C:10]([O:15][C:16]3[CH:21]=[CH:20][C:19]([NH2:22])=[CH:18][CH:17]=3)=[N:11][CH:12]=[CH:13][CH:14]=2)O1.Br.Br[C:26]1[S:30][C:29]([NH2:31])=[N:28][CH:27]=1.C(=O)([O-])[O-].[Na+].[Na+].F[B-](F)(F)F.C([PH+](C(C)(C)C)C(C)(C)C)(C)(C)C>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].O1CCOCC1>[NH2:22][C:19]1[CH:18]=[CH:17][C:16]([O:15][C:10]2[C:9]([C:26]3[S:30][C:29]([NH2:31])=[N:28][CH:27]=3)=[CH:14][CH:13]=[CH:12][N:11]=2)=[CH:21][CH:20]=1

Participants

7

Reactant 4

HCID 10340Sodium CarbonateHCID 27238485-Bromothiazol-2-amine monohydrobromideHCID 2734635Tri-tert-butylphosphine tetrafluoroborateHCID 574164444-(3-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-2-yloxy)benzenamine

Product 1

HCID 577562445-(2-(4-Aminophenoxy)pyridin-3-yl)thiazol-2-amine

Reagents, catalysts & solvents 2

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

Conditions

Temperature
100 °C

Procedure

In a 20 mL sealed tube was added dioxane (1.0 mL), purged solvent with nitrogen for 5 minutes and the tube was sealed. 4-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-2-yloxy)benzenamine (0.144 g, 0.462 mmol), 5-bromothiazol-2-amine hydrobromide (0.100 g, 0.385 mmol), 2.0M aqueous sodium carbonate (0.385 mL) was added and the tube was purged flask with nitrogen, and again sealed. Tris(dibenzylideneacetone)dipalladium (0) (0.026 g, 0.029 mmol), tri-t-butylphosphonium tetrafluoroborate (0.025 g, 0.087 mmol) was added and the tube was purged with nitrogen, sealed and heated to 100° C. while stirring for 5 hours. The mixture was cooled to RT, passed through pad of silica, washing with 90:10:1 (CH2Cl2: MeOH: NH4OH). The eluent was concentrated and the product was purified by silica gel chromatography eluting with 0-100% CH2Cl2:MeOH(90:10)/CH2Cl2. The product fractions were concentrated to yield 5-(2-(4-aminophenoxy)pyridin-3-yl)thiazol-2-amine as tan solid. MS m/z=285 [M+1]+. Calc'd for C14H12N4OS: 284.34.

Workup

  1. customIn a 20 mL sealed tube
  2. custompurged solvent with nitrogen for 5 minutes
  3. customthe tube was sealed
  4. customthe tube was purged flask with nitrogen
  5. customagain sealed
  6. customthe tube was purged with nitrogen
  7. customsealed
  8. temperatureThe mixture was cooled to RT
  9. washwashing with 90:10:1 (CH2Cl2: MeOH: NH4OH)
  10. concentrationThe eluent was concentrated
  11. customthe product was purified by silica gel chromatography
  12. washeluting with 0-100% CH2Cl2:MeOH(90:10)/CH2Cl2
  13. concentrationThe product fractions were concentrated

Sources & evidence

ORD record
ord-f58ba438011d4c15b65771985290af52
Source dataset
uspto-grants-2016_01
Patent number
US09242961B2

Reaction notes

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