Dichloromethane → HCID 13450735, compound

HRID 638187Notes

Reaction equation

HRID 638187 reaction equation
[CH3:1][N:2]1[CH2:7][CH2:6][CH:5]([N:8]2[C:14]3[CH:15]=[CH:16][CH:17]=[CH:18][C:13]=3[C:12]([C:19]3[CH:24]=[CH:23][CH:22]=[CH:21][C:20]=3[F:25])=[N:11][CH2:10][C:9]2=[O:26])[CH2:4][CH2:3]1.[N+:27]([O-])([O-:29])=[O:28].[K+].C(Cl)Cl>S(=O)(=O)(O)O>[N+:27]([C:17]1[CH:16]=[CH:15][C:14]2[N:8]([CH:5]3[CH2:4][CH2:3][N:2]([CH3:1])[CH2:7][CH2:6]3)[C:9](=[O:26])[CH2:10][N:11]=[C:12]([C:19]3[CH:24]=[CH:23][CH:22]=[CH:21][C:20]=3[F:25])[C:13]=2[CH:18]=1)([O-:29])=[O:28]

Participants

5

Reactant 3

HCID 6344DichloromethaneHCID 24434Potassium NitrateHCID 134506505-(2-Fluorophenyl)-1-(1-methylpiperidin-4-yl)-1,3-dihydro-2H-1,4-benzodiazepin-2-one

Product 1

HCID 13450735HCID 13450735, compoundYield 24.3%

Reagents, catalysts & solvents 1

HCID 1118Sulfuric AcidSolvent2×

Conditions

Temperature
-8 °C

Procedure

To conc. sulfuric acid (10 ml) is added 1-(1-methyl-4-piperidinyl)-1,3-dihydro-5-(2-fluorophenyl)-2H-1,4-benzdiazepin-2-one (2.09 g; 5.95 m mol) under cooling at temperature of -8° C. A solution of potassium nitrate (571 mg, 5.95×0.95 m mol) in conc. sulfuric acid (5 ml) is dropwise added to the mixture at the same temperature, which is allowed to stand at -5° C. over a period of 6 hours and then at room temperature over a period of 15 hours. The reaction mixture is poured onto ice (200 g), neutralized with conc. aqueous ammoniac solution, and shaken with methylene chloride. The organic layer is washed with water, dried over anhydrous magnesium sulfate and concentrated in vacuo. The residue is chromatographed on a column of alumina, which is eluted with ethyl acetate. The eluate is concentrated in vacuo and the residue is crystallized from methylene chloride-ether to give 7-nitro-1-(1-methyl-4-piperidinyl)-1,3-dihydro-5-(2 -fluorophenyl)-2H-1,4-benzdiazepin-2-one (544 mg) as crystals melting at 199° to 201° C. (dec.). The yield is 23%.

Workup

  1. waitat room temperature over a period of 15 hours
  2. additionThe reaction mixture is poured onto ice (200 g)
  3. washThe organic layer is washed with water
  4. dry with materialdried over anhydrous magnesium sulfate
  5. concentrationconcentrated in vacuo
  6. customThe residue is chromatographed on a column of alumina, which
  7. washis eluted with ethyl acetate
  8. concentrationThe eluate is concentrated in vacuo
  9. customthe residue is crystallized from methylene chloride-ether

Sources & evidence

ORD record
ord-5d83341b994f4589ac69f934312fbeb6
Source dataset
uspto-grants-1985_12
Patent number
US04560684

Reaction notes

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