1,8-Diazabicyclo(5.4.0)undec-7-ene → HCID 53419445, compound

HRID 2194543Notes

Reaction equation

HRID 2194543 reaction equation
[NH2:1][C:2](=[NH:9])[CH2:3][C:4]([O:6][CH2:7][CH3:8])=[O:5].C1CCN2C(=NCCC2)CC1.C(O[CH:24]=[CH:25][C:26](=O)[C:27]([F:30])([F:29])[F:28])C>C(#N)C>[NH2:9][C:2]1[N:1]=[C:26]([C:27]([F:30])([F:29])[F:28])[CH:25]=[CH:24][C:3]=1[C:4]([O:6][CH2:7][CH3:8])=[O:5]

Participants

5

Reactant 3

HCID 811841,8-Diazabicyclo(5.4.0)undec-7-ene2×HCID 27803954-Ethoxy-1,1,1-trifluoro-3-buten-2-oneHCID 4599837Carbamimidoyl-acetic acid ethyl ester

Product 1

HCID 53419445HCID 53419445, compoundYield 63.3%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

19.5 g (0.12 mol) of ethyl 3-amino-3-iminopropanoate (described in Chemical and Pharmaceutical Bulletin, vol. 43, No. 5, p. 793 (1995)) was added to 100 mL of acetonitrile, and 18.6 g (0.12 mol) of 1,8-diazabicyclo[5.4.0]-7-undecene was added thereto at room temperature. The resulting mixture was stirred for 5 minutes. 20.6 g (0.12 mol) of 4-ethoxy-1,1,1-trifluoro-3-buten-2-one was added to the above mixture, and 18.6 g (0.12 mol) of 1,8-diazabicyclo[5.4.0]-7-undecene was added thereto. The resulting mixture was stirred for 3 hours at 80° C. The solvent was distilled off under reduced pressure from the reaction mixture, and the residue was concentrated to half the original volume. Ice water was added thereto. Crystals precipitated therefrom were separated by filtration, and were dissolved in ethyl acetate. The filtrate was extracted with ethyl acetate. The solution having the crystals dissolved therein and the organic phase extracted were combined, and the resultant was washed with brine, and then was dried and concentrated. The residue was purified by column chromatography (ethyl acetate:n-hexane=1:9 to 1:4), and thus 17.8 g of the title compound was obtained as colorless crystals (yield: 62%).

Workup

  1. additionwas added
  2. customat room temperature
  3. additionwas added
  4. stirringThe resulting mixture was stirred for 3 hours at 80° C
  5. distillationThe solvent was distilled off under reduced pressure from the reaction mixture
  6. concentrationthe residue was concentrated to half the original volume
  7. additionIce water was added
  8. customCrystals precipitated
  9. customtherefrom were separated by filtration
  10. dissolutionwere dissolved in ethyl acetate
  11. extractionThe filtrate was extracted with ethyl acetate
  12. dissolutiondissolved
  13. extractionthe organic phase extracted
  14. washthe resultant was washed with brine
  15. customwas dried
  16. concentrationconcentrated
  17. customThe residue was purified by column chromatography (ethyl acetate:n-hexane=1:9 to 1:4)

Sources & evidence

ORD record
ord-bdbcdb4edb35445e9851cdfadded63c5
Source dataset
uspto-grants-2012_12
Patent number
US08334236B2

Reaction notes

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