1,8-Diazabicyclo(5.4.0)undec-7-ene → HCID 66922157, compound

HRID 1434818Notes

Reaction equation

HRID 1434818 reaction equation
[N+](C(C)C(OC(=O)C)[CH2:6][CH2:7][C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)([O-])=O.[N+:19]([CH2:21][C:22]([O:24][CH2:25][CH3:26])=[O:23])#[C-:20].[CH2:27]1[CH2:37]CN2C(=NCCC2)C[CH2:28]1>O.C(OCC)C>[CH2:25]([O:24][C:22]([C:21]1([CH2:6][CH2:7][C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH2:28][C:27]([CH3:37])=[CH:20][NH:19]1)=[O:23])[CH3:26]

Participants

6

Reactant 3

HCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 533707Ethyl isocyanoacetateHCID 57435159HCID 57435159, compound

Product 1

HCID 66922157HCID 66922157, compoundYield 709.3%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 3283Diethyl EtherSolvent

Procedure

Acetic acid 2-nitro-1-phenethylpropyl ester (180) (10.4302 g, 44.2 mmol) and ethyl isocyanoacetate (4.957 g, 44.2 mmol) were weighed out into a 250 mL round bottom flask. The flask was sealed with a septum, purged with nitrogen, then dissolved in a solution of THF and iso-propyl alcohol (1.6:1, 44 mL, 1M). The reaction was cooled in an ice bath, then DBU (13.6 mL, 2.05 mmol) was added. The reaction was allowed to warm to room temperature, and was allowed to stir at room temperature until judged complete by HPLC (2 h, 25 min.). The reaction was diluted with H2O and diethyl ether, and the organic layer was removed, extracted with 2N HCl, H2O, and NaHCO3. The combined organics were dried with Na2SO4, filtered, and concentrated. The crude product was purified by purified by silica gel chromatography (Combiflash column, 95:5 Hexanes:EtOAc). The product crystallized from the combined Combiflash fractions to obtain a batch of 3.3224 g (29%) of pure 181 and 3.7709 g of 181 containing a small amount of impure material. HPLC: 11.27 min.

Workup

  1. customThe flask was sealed with a septum
  2. custompurged with nitrogen
  3. dissolutiondissolved in a solution of THF and iso-propyl alcohol (1.6:1, 44 mL, 1M)
  4. temperatureThe reaction was cooled in an ice bath
  5. customuntil judged complete by HPLC (2 h, 25 min.)
  6. customthe organic layer was removed
  7. extractionextracted with 2N HCl, H2O, and NaHCO3
  8. dry with materialThe combined organics were dried with Na2SO4
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customThe crude product was purified
  12. customby purified by silica gel chromatography (Combiflash column, 95:5 Hexanes:EtOAc)
  13. customThe product crystallized from the combined Combiflash fractions

Sources & evidence

ORD record
ord-cfcfb9dc6e8f4eeea58d45ff56f5a61c
Source dataset
uspto-grants-2009_11
Patent number
US07615572B2

Reaction notes

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