Diethyl Ether → HCID 22220833, compound

HRID 1794032Notes

Reaction equation

HRID 1794032 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. customwas continued at 4 C overnight
  5. stirringthe mixture was stirred at 4 C for 4 hr
  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-4f4b297d5dcb452e83a3dee8b8aaac16
Source dataset
uspto-grants-2006_04
Patent number
US07022721B1

Reaction notes

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