Acetylacetone → HCID 12296897, compound

HRID 1836721Notes

Reaction equation

HRID 1836721 reaction equation
O.O.[CH3:3][C:4]1[N:9]=[C:8]([CH3:10])[CH:7]=[C:6]([CH3:11])[N:5]=1.C(CC(=O)C)(=O)C.Cl.C(N)(=[NH:22])C.[C:24]1([CH3:37])[CH:29]=[C:28]([CH3:30])[CH:27]=[C:26]([CH3:31])[C:25]=1[S:32]([O:35]N)(=[O:34])=[O:33]>ClCCl>[C:24]1([CH3:37])[CH:29]=[C:28]([CH3:30])[CH:27]=[C:26]([CH3:31])[C:25]=1[S:32]([O-:35])(=[O:34])=[O:33].[NH2:22][N+:5]1[C:6]([CH3:11])=[CH:7][C:8]([CH3:10])=[N:9][C:4]=1[CH3:3]

Participants

6

Reactant 4

HCID 31261AcetylacetoneHCID 67170Acetamidine monohydrochlorideHCID 11830845O-(2,4,6-Trimethylbenzenesulfonyl)hydroxylamineHCID 222207642,4,6-Trimethylpyrimidine--water (1/2)

Product 1

HCID 12296897HCID 12296897, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

2,4,6-trimethylpyrimidine dihydrate (0.79 g, 5.0 mmole, prepared from acetylacetone and acetamidine hydrochloride according to A. Bowman, J. Chem. Soc. 1937;494-495) in dichloromethane (10 mL) was dried over Na2SO4 and filtered. Separately, O-(mesitylenesulfonyl)hydroxylamine containing ca. 25% water (1.57 g, ca. 5.4 mmole) was dissolved in dichloromethane (10 mL) and dried over Na2SO4 and filtered. The dry O-(mesitylenesulfonyl)hydroxylamine filtrate was added dropwise to the dry 2,4,6-trimethylpyrimidine filtrate at 0 C. Stirring was continued 5 hr at 0 C. and then 16 hr at 4 C. The reaction mixture was concentrated at reduced pressure to ca. 10 mL and treated with ca. 3 mL ether to cause separation of a white powder, which was filtered, washed with 10 mL 1:1 dichloromethane/ether, and dried to yield 1.27 of crude product in two crops. Recrystallization from methanol/dichloromethane/ether gave 1.18 g of the title compound, mp 183-185 C.

Workup

  1. dry with material1937;494-495) in dichloromethane (10 mL) was dried over Na2SO4
  2. filtrationfiltered
  3. dry with materialdried over Na2SO4
  4. filtrationfiltered
  5. additionThe dry O-(mesitylenesulfonyl)hydroxylamine filtrate was added dropwise to the dry 2,4,6-trimethylpyrimidine filtrate at 0 C
  6. custom16 hr
  7. concentrationThe reaction mixture was concentrated at reduced pressure to ca. 10 mL
  8. additiontreated with ca. 3 mL ether
  9. customseparation of a white powder, which
  10. filtrationwas filtered
  11. washwashed with 10 mL 1:1 dichloromethane/ether
  12. customdried
  13. customto yield 1.27 of crude product in two crops
  14. customRecrystallization from methanol/dichloromethane/ether

Sources & evidence

ORD record
ord-3105e4de783249528521bd55696a6d35
Source dataset
uspto-grants-2004_08
Patent number
US06777557B2

Reaction notes

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