N,N-Diethylaniline → HCID 58071304, compound

HRID 1261974Notes

Reaction equation

HRID 1261974 reaction equation
[CH3:1][S:2][C:3]1[NH:15][C:14](=O)[C:6]2=[CH:7][C:8]3[C:13]([N:5]2[N:4]=1)=[CH:12][CH:11]=[CH:10][CH:9]=3.P(Cl)(Cl)([Cl:19])=O.C(N(CC)C1C=CC=CC=1)C>>[Cl:19][C:14]1[C:6]2=[CH:7][C:8]3[C:13]([N:5]2[N:4]=[C:3]([S:2][CH3:1])[N:15]=1)=[CH:12][CH:11]=[CH:10][CH:9]=3

Participants

4

Reactant 3

HCID 7061N,N-DiethylanilineHCID 24813Phosphorus oxychlorideHCID 1360651392-(Methylsulfanyl)[1,2,4]triazino[1,6-a]indol-4(1H)-one

Product 1

HCID 58071304HCID 58071304, compoundYield 71%

Procedure

A mixture of 2-methylsulfanyl-3H-[1,2,4]triazino[1,6-a]indol-4-one (3.00 g, 13.0 mmol), phosphoryl chloride (6.04 mL, 64.8 mmol), and N,N-diethylaniline (4.0 mL, 25.0 mmol) was allowed to sit for 30 min at room temperature and then refluxed for 1 hour. The mixture was then concentrated and the residue was azeotroped with toluene, cooled, and poured over ice. The resulting mixture was transferred to a separation funnel and the product was extracted in ether with 10-20% dichloromethane. The combined organic extracts were washed with dilute and cold aqueous HCl. then with dilute cold NaHCO3, and finally with cold water, dried over magnesium sulfate and concentrated. The product was purified by flash chromatography (ISCO, Silicagel, EtOAc/Hexanes 10-15%) to provide 4-chloro-2-methylsulfanyl-[1,2,4]triazino[1,6-a]indole (2.30 g, 71%). 1H-NMR (CDCl3) δ 8.11 (d, J=8.5 Hz, 1H), 7.86 (d, J=8.2 Hz, 1H), 7.49 (m, 1H), 7.41 (m, 1H), 7.14 (s, 1H), 2.68 (s, 3H); LC/MS (ESI+): 250.5 (M+H).

Workup

  1. temperaturerefluxed for 1 hour
  2. concentrationThe mixture was then concentrated
  3. customthe residue was azeotroped with toluene
  4. temperaturecooled
  5. additionpoured over ice
  6. customThe resulting mixture was transferred to a separation funnel
  7. extractionthe product was extracted in ether with 10-20% dichloromethane
  8. washThe combined organic extracts were washed
  9. additionwith dilute
  10. additionthen with dilute cold NaHCO3
  11. dry with materialfinally with cold water, dried over magnesium sulfate
  12. concentrationconcentrated
  13. customThe product was purified by flash chromatography (ISCO, Silicagel, EtOAc/Hexanes 10-15%)

Sources & evidence

ORD record
ord-0b5a9f32a6354e53aa5a7c46856bc6da
Source dataset
uspto-grants-2013_06
Patent number
US08471005B2

Reaction notes

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