Stannous Chloride → 5-(4-{5-[(4-Fluorophenyl)methyl]-6-methylpyrimidin-4-yl}-2,3,4,5-tetrahydro-1,4-benzoxazepin-7-yl)pyridine-2,3-diamine

HRID 241193Notes

Reaction equation

HRID 241193 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][C:9]2[C:10]([N:16]3[CH2:22][C:21]4[CH:23]=[C:24]([C:27]5[CH:28]=[C:29]([N+:34]([O-])=O)[C:30]([NH2:33])=[N:31][CH:32]=5)[CH:25]=[CH:26][C:20]=4[O:19][CH2:18][CH2:17]3)=[N:11][CH:12]=[N:13][C:14]=2[CH3:15])=[CH:4][CH:3]=1.[Sn](Cl)Cl>C(O)(=O)C>[F:1][C:2]1[CH:3]=[CH:4][C:5]([CH2:8][C:9]2[C:10]([N:16]3[CH2:22][C:21]4[CH:23]=[C:24]([C:27]5[CH:28]=[C:29]([NH2:34])[C:30]([NH2:33])=[N:31][CH:32]=5)[CH:25]=[CH:26][C:20]=4[O:19][CH2:18][CH2:17]3)=[N:11][CH:12]=[N:13][C:14]=2[CH3:15])=[CH:6][CH:7]=1

Participants

4

Reactant 2

HCID 24479Stannous ChlorideHCID 668206145-(4-{5-[(4-Fluorophenyl)methyl]-6-methylpyrimidin-4-yl}-2,3,4,5-tetrahydro-1,4-benzoxazepin-7-yl)-3-nitropyridin-2-amine

Product 1

HCID 668206925-(4-{5-[(4-Fluorophenyl)methyl]-6-methylpyrimidin-4-yl}-2,3,4,5-tetrahydro-1,4-benzoxazepin-7-yl)pyridine-2,3-diamineYield 61.3%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Conditions

Temperature
50 °C

Procedure

To a solution of 5-(4-{5-[(4-fluorophenyl)methyl]-6-methylpyrimidin-4-yl}-2,3,4,5-tetrahydro-1,4-benzoxazepin-7-yl)-3-nitropyridin-2-amine (0.36 g, 0.75 mmol) in acetic acid (10 mL) was added tin (II) chloride (0.75 g, 3.8 mmol). The reaction mixture was heated (50° C.) for 2 h and then partitioned between ethyl acetate (10 mL) and 1 N aqueous sodium hydroxide (20 mL). The resulting mixture was filtered through Celite and the organic layer was washed with brine (10 mL), dried over anhydrous magnesium sulfate then filtered and concentrated. Column chromatography on silica (5% methanol/dichloromethane) provided 5-(4-{5-[(4-fluorophenyl)methyl]-6-methylpyrimidin-4-yl}-2,3,4,5-tetrahydro-1,4-benzoxazepin-7-yl)pyridine-2,3-diamine (0.21 g, 60% yield) as a pale yellow solid. MS (EI) for C26H25FN6O: 457 (MH+).

Workup

  1. custompartitioned between ethyl acetate (10 mL) and 1 N aqueous sodium hydroxide (20 mL)
  2. filtrationThe resulting mixture was filtered through Celite
  3. washthe organic layer was washed with brine (10 mL)
  4. dry with materialdried over anhydrous magnesium sulfate
  5. filtrationthen filtered
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-d002314192f14be6aedbbf917ed8c509
Source dataset
uspto-grants-2014_02
Patent number
US08648066B2

Reaction notes

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