Ethyl orthoformate → HCID 25115734, compound

HRID 450409Notes

Reaction equation

HRID 450409 reaction equation
[F:1][C:2]1[C:3]([NH:18][C@H:19]([C:21]2[N:26]=[CH:25][C:24]([F:27])=[CH:23][N:22]=2)[CH3:20])=[N:4][C:5]([NH:11][C:12]2[CH:16]=[C:15]([CH3:17])[NH:14][N:13]=2)=[C:6]([N+:8]([O-])=O)[CH:7]=1.O.O.Cl[Sn]Cl.[CH:33](OCC)(OCC)OCC>CCO>[F:1][C:2]1[CH:7]=[C:6]2[N:8]=[CH:33][N:11]([C:12]3[CH:16]=[C:15]([CH3:17])[NH:14][N:13]=3)[C:5]2=[N:4][C:3]=1[NH:18][C@H:19]([C:21]1[N:26]=[CH:25][C:24]([F:27])=[CH:23][N:22]=1)[CH3:20]

Participants

5

Reactant 3

HCID 31214Ethyl orthoformateHCID 61436Stannous chloride dihydrateHCID 68780045HCID 68780045, compound2×

Product 1

HCID 25115734HCID 25115734, compound

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
70 °C

Procedure

To a solution of 3-fluoro-N2-[(1S)-1-(5-fluoropyrimidin-2-yl)ethyl]-N6-(5-methyl-1H-pyrazol-3-yl)-5-nitropyridine-2,6-diamine (Intermediate 42, 3.05 mmol) in EtOH (5 ml) were added SnCl2.2H2O (1.74 g, 9.18 mmol) and triethyl orthoformate (0.652 ml). The resulting solution was heated to 70° C. overnight. The mixture was allowed to cool to room temperature and filtered through Celite® and washed with EtOAc. Evaporation of the volatiles under reduced pressure gave a colored residue that was purified by Gilson (5%→95% MeCN/H2O) to give the title compound. LC-MS: 357 [M+1]. 1H NMR δ 2.01 (d, 3H) 2.34 (s, 3H) 6.46-6.55 (m, 1H) 8.20 (s, 1H) 8.72 (s, 1H) 8.87 (s, 2H) 9.72 (s, 1H) 9.86 (s, 1H).

Workup

  1. temperatureto cool to room temperature
  2. filtrationfiltered through Celite®
  3. washwashed with EtOAc
  4. customEvaporation of the volatiles under reduced pressure
  5. customgave a colored residue that
  6. customwas purified by Gilson (5%→95% MeCN/H2O)

Sources & evidence

ORD record
ord-6b91d9ec0d994c2782a21acf0a95d7cb
Source dataset
uspto-grants-2013_07
Patent number
US08486966B2

Reaction notes

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