Cesium carbonate → HCID 86731659, compound

HRID 1504763Notes

Reaction equation

HRID 1504763 reaction equation
FC(F)(F)C(O)=O.Cl[C:9]1[CH:14]=[C:13]([C:15]([N:17]([CH3:19])[CH3:18])=[O:16])[CH:12]=[C:11]([CH3:20])[N:10]=1.C(=O)([O-])[O-].[Cs+].[Cs+].[C:27](=[NH:40])([C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1)[C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1.CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2>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>[C:28]1([C:27](=[N:40][C:9]2[CH:14]=[C:13]([C:15]([N:17]([CH3:19])[CH3:18])=[O:16])[CH:12]=[C:11]([CH3:20])[N:10]=2)[C:34]2[CH:35]=[CH:36][CH:37]=[CH:38][CH:39]=2)[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1

Participants

7

Reactant 4

HCID 10796Cesium carbonateHCID 136809Benzophenone imineHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 86731660HCID 86731660, compound

Product 1

HCID 86731659HCID 86731659, compound

Reagents, catalysts & solvents 2

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

Conditions

Temperature
80 °C

Procedure

Dioxane (2.7 mL), 2-chloro-N,N,6-trimethylpyridine-4-carboxamide trifluoroacetate (250 mg, 0.80 mmol), and cesium carbonate (782 mg, 2.40 mmol) were added to benzophenone imine (0.134 mL, 0.80 mmol) in a scintillation vial. The vial was purged and flushed with argon 3 times before adding Xantphos (69 mg, 0.12 mmol) and Pd2(dba)3 (73 mg, 0.080 mmol). The vial was purged and flushed with argon 3 times before sealing the system and heating to 80° C. for 10 hours. The reaction mixture was cooled to room temperature, and purified directly by silica gel chromatography (10-80% acetone/hexanes, linear gradient) to afford 2-[(diphenylmethylidene)amino]-N,N,6-trimethylpyridine-4-carboxamide. The isolated material was diluted with DCM (1 mL) and TFA (1 mL). The reaction mixture was stirred at room temperature for 2 hours, and then directly purified by reverse phase HPLC (5-30% acetonitrile/water with 0.1% TFA, linear gradient) to afford 2-amino-N,N,6-trimethylpyridine-4-carboxamide TFA salt. MS ESI calc'd. for C9H14N3O [M+H]+ 180. found 180. 1H NMR (500 MHz, CDCl3) δ 7.09 (s, 1H), 7.03 (s, 1H), 3.06 (s, 3H), 2.91 (s, 3H), 2.52 (s, 3H).

Workup

  1. customThe vial was purged
  2. customflushed with argon 3 times
  3. customThe vial was purged
  4. customflushed with argon 3 times
  5. temperatureThe reaction mixture was cooled to room temperature
  6. custompurified directly by silica gel chromatography (10-80% acetone/hexanes, linear gradient)

Sources & evidence

ORD record
ord-5d4d0b77b4c34a04b59b6838cdecf1ce
Source dataset
uspto-grants-2015_12
Patent number
US09216173B2

Reaction notes

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