2,4-Bis(4-phenoxyphenyl)-2,4-dithioxo-1,3,2,4-dithiadiphosphetane → 1-cyclohexyl-6-tosyl-6H-imidazo[1,5-a]pyrrolo[2,3-e]pyrazine

HRID 1628106Notes

Reaction equation

HRID 1628106 reaction equation
[S:1]([N:11]1[C:15]2=[N:16][CH:17]=[C:18]([CH2:20][NH:21][C:22]([CH:24]3[CH2:29][CH2:28][CH2:27][CH2:26][CH2:25]3)=O)[N:19]=[C:14]2[CH:13]=[CH:12]1)([C:4]1[CH:10]=[CH:9][C:7]([CH3:8])=[CH:6][CH:5]=1)(=[O:3])=[O:2].O(C1C=CC(P2(=S)SP(=S)(C3C=CC(OC4C=CC=CC=4)=CC=3)S2)=CC=1)C1C=CC=CC=1>C1COCC1.CCOC(C)=O.C([O-])(=O)C.[Hg+2].C([O-])(=O)C>[CH:24]1([C:22]2[N:19]3[C:14]4[CH:13]=[CH:12][N:11]([S:1]([C:4]5[CH:10]=[CH:9][C:7]([CH3:8])=[CH:6][CH:5]=5)(=[O:3])=[O:2])[C:15]=4[N:16]=[CH:17][C:18]3=[CH:20][N:21]=2)[CH2:29][CH2:28][CH2:27][CH2:26][CH2:25]1

Participants

6

Reactant 2

HCID 118134142,4-Bis(4-phenoxyphenyl)-2,4-dithioxo-1,3,2,4-dithiadiphosphetaneHCID 58009940HCID 58009940, compound

Product 1

HCID 580099171-cyclohexyl-6-tosyl-6H-imidazo[1,5-a]pyrrolo[2,3-e]pyrazineYield 25.9%

Reagents, catalysts & solvents 3

HCID 15337Mercuric acetateCatalyst2×HCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

To a solution of N-((5-tosyl-5H-pyrrolo[2,3-b]pyrazin-2-yl)methyl)cyclohexanecarboxamide (0.081 g, 0.196 mmol) in THF (1 mL) at rt was added 2,4-bis(4-phenoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide (0.104 g, 0.196 mmol, TCI). After about 15 h at rt, the mixture was concentrated under reduced pressure. The residue was suspended in EtOAc/DCM (1:1) and filtered through a plug of silica gel (5 g) eluting with EtOAc/DCM (1:1, approximately 100 mL). The filtrate was concentrated under reduced pressure to provide a residue. The residue was dissolved in THF (1 mL) and mercury(II) acetate (0.0626 g, 0.196 mmol) was added. After about 30 min at rt, additional mercury(II) acetate (0.0626 g, 0.196 mmol) was added. After about 4 h at rt, the mixture was diluted with EtOAc, filtered, concentrated under reduced pressure. The residue was purified by silica gel chromatography eluting with a gradient of 50 to 95% EtOAc in heptane to provide 1-cyclohexyl-6-tosyl-6H-imidazo[1,5-a]pyrrolo[2,3-e]pyrazine (0.020 g, 25%): LC/MS (Table 2, Method a) Rt=2.77 min; MS m/z: 395 (M+H)+.

Workup

  1. concentrationthe mixture was concentrated under reduced pressure
  2. filtrationfiltered through a plug of silica gel (5 g)
  3. washeluting with EtOAc/DCM (1:1, approximately 100 mL)
  4. concentrationThe filtrate was concentrated under reduced pressure
  5. customto provide a residue
  6. waitAfter about 30 min at rt
  7. waitAfter about 4 h at rt
  8. filtrationfiltered
  9. concentrationconcentrated under reduced pressure
  10. customThe residue was purified by silica gel chromatography
  11. washeluting with a gradient of 50 to 95% EtOAc in heptane

Sources & evidence

ORD record
ord-54ffc24c8a9f4534a38b550e7116c342
Source dataset
uspto-grants-2014_07
Patent number
US08785639B2

Reaction notes

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