HCID 87618346, compound → HCID 87619072, compound

HRID 2111418Notes

Reaction equation

HRID 2111418 reaction equation
C[O:2][C:3](=O)[CH:4]([CH3:20])[CH2:5][N:6]([CH2:17][CH:18]=[CH2:19])[C:7]1[C:12]([N+:13]([O-])=O)=[CH:11][N:10]=[C:9]([Cl:16])[N:8]=1>[Fe].C(O)(=O)C>[CH2:17]([N:6]1[CH2:5][CH:4]([CH3:20])[C:3](=[O:2])[NH:13][C:12]2[CH:11]=[N:10][C:9]([Cl:16])=[N:8][C:7]1=2)[CH:18]=[CH2:19]

Participants

4

Reactant 1

HCID 87618346HCID 87618346, compound

Product 1

HCID 87619072HCID 87619072, compoundYield 277%

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 176Acetic AcidSolvent

Procedure

To a solution of 2.55 g (0.002 mole) of (rac)-3-[allyl-(2-chloro-5-nitro-pyrimidin-4-yl)-amino]-2-methyl-propanoic acid methyl ester (IV-65) and 20 mL of acetic acid, was added 2.55 g (0.0457 g-atom) of iron powder. The mixture was heated at 80 degrees for 2 hours and then filtered through Celite while still hot. The filter cake was washed with 100 mL of ethyl acetate. The filtrate was washed successively with 100 mL of water, 100 mL of 7.4 M ammonium hydroxide, 100 mL of water and 100 mL of brine. The aqueous layers were back extracted with 100 mL of ethyl acetate. The ethyl acetate layers were combined, dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. The residue was recrystallized from dichloromethane—hexanes to give 1.40 g of (rac)-9-allyl-2-chloro-7-methyl-5,7,8,9-tetrahydro-pyrimido[4,5-b][1,4]diazepin-6-one (VI-65) as off-white crystalline solid.

Workup

  1. temperatureThe mixture was heated at 80 degrees for 2 hours
  2. filtrationfiltered through Celite while still hot
  3. washThe filter cake was washed with 100 mL of ethyl acetate
  4. washThe filtrate was washed successively with 100 mL of water, 100 mL of 7.4 M ammonium hydroxide, 100 mL of water and 100 mL of brine
  5. extractionThe aqueous layers were back extracted with 100 mL of ethyl acetate
  6. dry with materialdried over anhydrous magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. customThe residue was recrystallized from dichloromethane—hexanes

Sources & evidence

ORD record
ord-75bc96af5d8a4dde9630a4aa4db62ba9
Source dataset
uspto-grants-2009_04
Patent number
US07517873B2

Reaction notes

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