Diethyl Ether → HCID 22220860, compound

HRID 1836724Notes

Reaction equation

HRID 1836724 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[CH:21]=[C:20]([CH3:22])[N:19]=[C:18]([CH3:23])[N:17]=1.CO.ClCCl.CCOCC>ClCCl>[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+:19]1[C:20]([CH3:22])=[CH:21][C:16]([NH2:15])=[N:17][C:18]=1[CH3:23]

Participants

6

Reactant 4

HCID 3283Diethyl EtherHCID 680392,6-Dimethyl-4-aminopyrimidineHCID 11830845O-(2,4,6-Trimethylbenzenesulfonyl)hydroxylamineHCID 21226129Dichloromethane methanol

Product 1

HCID 22220860HCID 22220860, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

O-(Mesitylenesulfonyl)hydroxylamine containing ca. 18% water (3.03 g, 2.56 g dry wt., ca. 11.9 mmole) was dissolved in dichloromethane (15 mL) and dried over Na2SO4 and filtered. This was added dropwise to a solution of 4-amino-2,6-dimethylpyrimidine (1 g, 8.12 mmole) in 1:6 methanol-dichloromethane (10.5 mL) in an ice bath with stirring for 2 hr. Ether (20 mL) was added and the mixture was stored at 4 C. for 18 hr. The crude aminated product was filtered out and dried (2.65 g). This was dissolved in a minimum amount of methanol, filtered and reduced in volume to ca. 20 mL under reduced pressure. This was diluted with dichloromethane (15 mL) and 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 0.73 g of a fraction, mp 262-264 C, consisting mainly of 1,6(or 4)-diamino-2,4(or 6)-dimethylpyrimidinium mesitylene-2-sulfonate. Storage of the filtrate resulted in deposition of more crystals, which were filtered out and washed with 1:1 dichloromethane-ether to give 1.39 g in two crops of a fraction, mp 194-196 C, consisting mainly of 1,4(or 6)-diamino-2,6(or 4)-dimethylpyrimidinium mesitylene-2-sulfonate. Isomer assignment is tentative.

Workup

  1. dry with materialdried over Na2SO4
  2. filtrationfiltered
  3. waitfor 18 hr
  4. filtrationThe crude aminated product was filtered out
  5. customdried (2.65 g)
  6. dissolutionThis was dissolved in a minimum amount of methanol
  7. filtrationfiltered
  8. additionThis was diluted with dichloromethane (15 mL) and ether (20 mL)
  9. additionwas added
  10. stirringthe mixture was stirred at room temp. for 2 hr
  11. filtrationFiltration
  12. washwashing with 1:1 dichloromethane-ether
  13. customdrying
  14. customgave 0.73 g of a fraction, mp 262-264 C
  15. customStorage of the filtrate resulted in deposition of more crystals, which
  16. filtrationwere filtered out
  17. washwashed with 1:1 dichloromethane-ether
  18. customto give 1.39 g in two crops of a fraction, mp 194-196 C

Sources & evidence

ORD record
ord-58fda1d844aa47d78c4a2af665bbfa66
Source dataset
uspto-grants-2004_08
Patent number
US06777557B2

Reaction notes

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