Diethyl Ether → HCID 22220833, compound

HRID 1836723Notes

Reaction equation

HRID 1836723 reaction equation
[C:1]1([CH3:14])[CH:6]=[C:5]([CH3:7])[CH:4]=[C:3]([CH3:8])[C:2]=1[S:9]([O:12][NH2:13])(=[O:11])=[O:10].[NH2:15][C:16]1[N:21]=[C:20]([CH3:22])[CH:19]=[CH:18][N:17]=1.CO.ClCCl.CCOCC>ClCCl.CO>[C:1]1([CH3:14])[CH:6]=[C:5]([CH3:7])[CH:4]=[C:3]([CH3:8])[C:2]=1[S:9]([O-:12])(=[O:11])=[O:10].[NH2:13][N+:17]1[CH:18]=[CH:19][C:20]([CH3:22])=[N:21][C:16]=1[NH2:15]

Participants

7

Reactant 4

HCID 3283Diethyl EtherHCID 79392-Amino-4-methylpyrimidineHCID 11830845O-(2,4,6-Trimethylbenzenesulfonyl)hydroxylamineHCID 21226129Dichloromethane methanol

Product 1

HCID 22220833HCID 22220833, compound

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 6344DichloromethaneSolvent

Procedure

O-(Mesitylenesulfonyl)hydroxylamine containing ca. 18% water (3.5 g, 2.88 g dry wt., ca. 13.4 mmole) was dissolved in dichloromethane (18 mL) and dried over Na2SO4 and filtered. This was added dropwise to a solution of 2-amino-4-methylpyrimidine (1 g, 9.14 mmole) in 3:4 methanol-dichloromethane (14 mL) in an ice bath with stirring. Stirring was continued at 4 C. overnight. Ether (30 mL) was added and the mixture was stirred at 4 C. for 4 hr. Filtration and drying afforded a mixture of the crude aminated product. (2.4 g). This was dissolved in methanol and filtered, and concentrated under reduced pressure to 15-20 mL. Ether (20 mL) was added, and the mixture was stirred at room temp. for 2 hr. Filtration, washing with 1:1 dichloromethane-ether and drying gave 0.92 g of a fraction, mp 209-212 C., consisting mainly of 1,2-diamino-6(or 4)-methylpyrimidinium mesitylene-2-sulfonate. Storage of the filtrate overnight resulted in deposition of more crystals, which were filtered out and washed with 1:1 dichloromethane-ether to give 1.06 g of a fraction, mp 166-168 C, consisting mainly of 1,2-diamino-4(or 6)-methylpyrimidinium mesitylene-2-sulfonate. Isomer assignment is tentative.

Workup

  1. dry with materialdried over Na2SO4
  2. filtrationfiltered
  3. stirringStirring
  4. customovernight
  5. stirringthe mixture was stirred at 4 C
  6. filtrationFiltration
  7. customdrying
  8. customafforded
  9. additiona mixture of the crude aminated product
  10. filtrationfiltered
  11. concentrationconcentrated under reduced pressure to 15-20 mL
  12. additionEther (20 mL) was added
  13. stirringthe mixture was stirred at room temp. for 2 hr
  14. filtrationFiltration
  15. washwashing with 1:1 dichloromethane-ether
  16. customdrying
  17. customgave 0.92 g of a fraction, mp 209-212 C
  18. customStorage of the filtrate overnight resulted in deposition of more crystals, which
  19. filtrationwere filtered out
  20. washwashed with 1:1 dichloromethane-ether
  21. customto give 1.06 g of a fraction, mp 166-168 C

Sources & evidence

ORD record
ord-2ce28435f5c44515a180316e993c2e18
Source dataset
uspto-grants-2004_08
Patent number
US06777557B2

Reaction notes

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