Ethylenediamine → HCID 89955146, compound

HRID 705335Notes

Reaction equation

HRID 705335 reaction equation
[CH:1]1([C:4]2[C:5]([N:22]([CH2:27][C:28]3[CH:33]=[CH:32][C:31]([O:34][CH3:35])=[CH:30][CH:29]=3)[S:23]([CH3:26])(=[O:25])=[O:24])=[CH:6][C:7]3[O:11][C:10]([C:12]4[CH:17]=[CH:16][C:15]([F:18])=[CH:14][CH:13]=4)=[C:9]([CH:19]=O)[C:8]=3[CH:21]=2)[CH2:3][CH2:2]1.[CH2:36]([NH2:39])[CH2:37][NH2:38].BrN1C(=O)CCC1=O.CCCCCC.C(OCC)(=O)C>ClCCl>[CH:1]1([C:4]2[C:5]([N:22]([CH2:27][C:28]3[CH:33]=[CH:32][C:31]([O:34][CH3:35])=[CH:30][CH:29]=3)[S:23]([CH3:26])(=[O:24])=[O:25])=[CH:6][C:7]3[O:11][C:10]([C:12]4[CH:17]=[CH:16][C:15]([F:18])=[CH:14][CH:13]=4)=[C:9]([C:19]4[NH:38][CH2:37][CH2:36][N:39]=4)[C:8]=3[CH:21]=2)[CH2:2][CH2:3]1

Participants

6

Reactant 4

HCID 3301Ethylenediamine2×HCID 67184N-bromobutanimide2×HCID 21226206Ethyl acetate hexaneHCID 89955572HCID 89955572, compound

Product 1

HCID 89955146HCID 89955146, compoundYield 91%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

To a mixture of Example 1L (7.0 g, 14.18 mmol) in dichloromethane (117 mL) under nitrogen was added ethylenediamine (0.938 g/1.043 mL, 15.60 mmol) dissolved in 2 mL of dichloromethane (2 mL) in 200 μL portions over 7 minutes. The mixture was stirred at room temperature for 4.5 hours. The reaction mixture was immersed in an ice bath and N-bromosuccinimide (2.65 g, 14.89 mmol) and powdered 4 Å molecular sieves (3.63 g) were added over ˜1 minute. The reaction mixture was stirred in the ice bath for 10 minutes, then the ice bath was removed and the reaction mixture was stirred at room temperature for a total of 72 hours. Reaction progress was monitored by LCMS. After each 24 hour period, additional ethylenediamine and N-bromosuccinimide were added followed by continued stirring at room temperature for 64 hours. The resulting slurry was filtered through a pad of diatomaceous earth with dichloromethane (2×100 mL) washes. The combined dichloromethane layers were washed with 10% sodium bicarbonate and 10% sodium chloride and dried over anhydrous sodium sulfate. The drying agent was removed by filtration, and the organic layer was concentrated in vacuo to an oily residue. The residue is treated with dichloromethane/acetonitrile (4:1, 100 mL), and the solvent was removed in vacuo leaving a tan foamy solid. The foamy solid was stirred for 20 minutes with hexane/ethyl acetate (4:1, 35 mL), filtered and dried in vacuo giving the title compound as a tan solid (6.86 g, 91%).

Workup

  1. customThe reaction mixture was immersed in an ice bath
  2. additionwere added over ˜1 minute
  3. customthe ice bath was removed
  4. stirringthe reaction mixture was stirred at room temperature for a total of 72 hours
  5. customReaction progress
  6. stirringby continued stirring at room temperature for 64 hours
  7. filtrationThe resulting slurry was filtered through a pad of diatomaceous earth with dichloromethane (2×100 mL)
  8. washThe combined dichloromethane layers were washed with 10% sodium bicarbonate and 10% sodium chloride
  9. dry with materialdried over anhydrous sodium sulfate
  10. customThe drying agent was removed by filtration
  11. concentrationthe organic layer was concentrated in vacuo to an oily residue
  12. additionThe residue is treated with dichloromethane/acetonitrile (4:1, 100 mL)
  13. customthe solvent was removed in vacuo
  14. customleaving a tan foamy solid
  15. filtrationfiltered
  16. customdried in vacuo

Sources & evidence

ORD record
ord-1df2109fafa745c7822d43cf702e5796
Source dataset
uspto-grants-2015_11
Patent number
US09173887B2

Reaction notes

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