Hydrogen Bromide → HCID 86667789, compound

HRID 509543Notes

Reaction equation

HRID 509543 reaction equation
[CH:1]([S:4]([C:7]1[N:8]=[CH:9][C:10](N)=[N:11][CH:12]=1)(=[O:6])=[O:5])([CH3:3])[CH3:2].[BrH:14].BrBr.N([O-])=O.[Na+].C([O-])(O)=O.[Na+]>C(O)(=O)C.O>[Br:14][C:10]1[CH:9]=[N:8][C:7]([S:4]([CH:1]([CH3:3])[CH3:2])(=[O:6])=[O:5])=[CH:12][N:11]=1

Participants

8

Reactant 5

HCID 260Hydrogen BromideHCID 24408BromineHCID 516892Sodium BicarbonateHCID 23668193Sodium NitriteHCID 67480039HCID 67480039, compound

Product 1

HCID 86667789HCID 86667789, compoundYield 44%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolvent2×HCID 962WaterSolvent

Procedure

5-Isopropylsulfonylpyrazin-2-amine was added to a rapidly stirring mixture of hydrobromic acid in acetic acid (2.150 mL of 45% w/v, 11.96 mmol) and acetic acid (649.6 μL) at 0° C. followed by the slow addition of bromine (1.433 g, 462.0 μL, 8.967 mmol) dropwise over a 10 minutes. A solution of sodium nitrite (515.5 mg, 237.8 μL, 7.472 mmol) in water (2.275 mL) was added dropwise over 10 minutes and the reaction mixture was stirred at 0° C. for a further 15 minutes. The reaction mixture was basified with 16 mL of saturated aqueous NaHCO3 at 0° C. and extracted with DCM (×3). The combined organic extracts were dried (MgSO4), filtered and concentrated in vacuo. The residue was purified by column chromatography (ISCO Companion™, 40 g column, eluting with 0 to 100% EtOAc/Petrol, loaded in DCM) to give the sub-title product as a cream solid (349 mg, 44% Yield). 1H NMR (400.0 MHz, DMSO) δ 1.24 (d, 6H), 3.69 (sept, 1H). 9.04 (s, 1H) and 9.17 (s, 1H); MS (ES+) 267.0.

Workup

  1. stirringthe reaction mixture was stirred at 0° C. for a further 15 minutes
  2. extractionextracted with DCM (×3)
  3. dry with materialThe combined organic extracts were dried (MgSO4)
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customThe residue was purified by column chromatography (ISCO Companion™, 40 g column, eluting with 0 to 100% EtOAc/Petrol, loaded in DCM)

Sources & evidence

ORD record
ord-ab0482f1365245ad9f3a6cb945ab9a6c
Source dataset
uspto-grants-2015_08
Patent number
US09096584B2

Reaction notes

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