2,6-Diaminopyridine → HCID 9926492, compound

HRID 2306024Notes

Reaction equation

HRID 2306024 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8](=O)[CH:9](O[Si](C(C)(C)C)(C)C)[C:10]2[CH:15]=[CH:14][N:13]=[CH:12][CH:11]=2)=[CH:4][CH:3]=1.[NH2:25][C:26]1[CH:31]=[CH:30][CH:29]=[C:28]([NH2:32])[N:27]=1.O.C1(C)C=CC(S(O)(=O)=O)=CC=1>C1(C)C(C)=CC=CC=1>[NH2:32][C:28]1[N:27]=[C:26]2[C:31]([C:9]([C:10]3[CH:11]=[CH:12][N:13]=[CH:14][CH:15]=3)=[C:8]([C:5]3[CH:4]=[CH:3][C:2]([F:1])=[CH:7][CH:6]=3)[NH:25]2)=[CH:30][CH:29]=1

Participants

5

Reactant 3

HCID 88612,6-DiaminopyridineHCID 521998p-Toluenesulfonic acid monohydrateHCID 10991586HCID 10991586, compound

Product 1

HCID 9926492HCID 9926492, compound

Reagents, catalysts & solvents 1

HCID 7237O-XyleneSolvent

Conditions

Temperature
135 °C

Procedure

1-(4-Fluorophenyl)-2-t-butyldimethylsiloxy-2-(4-pyridyl)ethanone (16) (3.45 g, 10.0 mmol), 2,6-diaminopyridine (1.09 g, 10.0 mmol), p-toluenesulfonic acid monohydrate (13.3 g, 70.0 mmol), and xylene (140 mL) were warmed to 60° C. under argon (note: all condensation reactions of this type were conducted behind an explosion shield). After 1 h at 60° C., the reaction was warmed to 135° C. for 3 h. After allowing the reaction to cool to 23° C., the top layer of xylene and p-toluenesulfonic acid was decanted from the bottom layer of gummy product residue. The lower product layer was partitioned between saturated bicarbonate (100 mL), and ethyl acetate (250 mL). The ethyl acetate layer was washed with brine (1×100 mL), and dried (Na2SO4). After concentration in vacuo, the residue was purified by applying flash chromatography (2 liters of ethyl acetate: hexane 7:3 followed by 100% ethyl acetate) to afford the cleanly separated regioisomer (17): Mass Spectrum (CI) 305 (MH+).

Workup

  1. customall condensation reactions of this type
  2. customthe reaction
  3. temperatureto cool to 23° C.
  4. customthe top layer of xylene and p-toluenesulfonic acid was decanted from the bottom layer of gummy product residue
  5. customThe lower product layer was partitioned between saturated bicarbonate (100 mL), and ethyl acetate (250 mL)
  6. washThe ethyl acetate layer was washed with brine (1×100 mL)
  7. dry with materialdried (Na2SO4)
  8. concentrationAfter concentration in vacuo
  9. customthe residue was purified

Sources & evidence

ORD record
ord-5fa7479a21d84fa8bf4aec04c66caf83
Source dataset
uspto-grants-2002_08
Patent number
US06440973B1

Reaction notes

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