2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → HCID 67790572, compound

HRID 1650783Notes

Reaction equation

HRID 1650783 reaction equation
ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl.C([O:22][N:23]1[CH2:27][C@H:26]([CH2:28][CH3:29])[C@H:25]([NH:30]CC2C=CC(OC)=CC=2)[C:24]1=[O:40])C1C=CC=CC=1>ClCCl.O>[NH2:30][C@H:25]1[C@@H:26]([CH2:28][CH3:29])[CH2:27][N:23]([OH:22])[C:24]1=[O:40]

Participants

5

Reactant 2

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 67791159HCID 67791159, compound

Product 1

HCID 67790572HCID 67790572, compoundYield 45%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

Dichlorodicyanobenzoquinone (125 mg, 550 μmol) was added to a stirred solution of cis-1-benzyloxy-4-ethyl-3-(4-methoxybenzylamino) pyrrolidin-2-one (190 mg, 458 μmol) in dichloromethane (20 ml) and water (1 ml). After 90 min the mixture was evaporated, dissolved in dilute hydrochloric acid, and applied to a column containing DOWEX 50W-X8 (100-200 mesh, 2×2 cm, H+ form). After washing the column with water (100 ml), the product was eluted with dilute aqueous ammonia. Fractions containing the product were evaporated in vacuo, then purified by flash chromatography, eluting with dichloromethane: methanol (95:5 v/v). The resulting oil (62 mg) was hydrogenated on palladium black (30 mg) in ethanol (20 ml) and acetic acid (200 μl) at 50 p.s.i. for 2 h. After filtration and evaporation, the residue was dissolved in water and applied to a column containing DOWEX 50W-X8 (100-200 mesh, 2× 2 cm, H+ form) After washing the column with water (50 ml), the product was eluted with dilute aqueous ammonia. Fractions containing the desired product were freeze dried to give cis-3-amino-1-hydroxy-4-ethylpyrrolidin- 2-one (29.1 mg, 45%) as a white powder. 1H NMR (360 MHZ, D2O) δ3.82 (1 H, d, J=8.0 Hz, CHN), 3.69 (1 H, dd, J=7.3 and 10.0 Hz, NCHAHB), 3.38 (1 H , dd, J=4.8 and 10 0 Hz, NCHAHB), 2.45-2.55 (1 H, m, CHCH2), 1.5-1.6 and 1.3-1.4 (2 H, m, CH2CH3), 0.96 (3 H, t, J=7.3 Hz, CH3), m/z (CI, NH3) 145 (M+ +H).

Workup

  1. customAfter 90 min the mixture was evaporated
  2. dissolutiondissolved in dilute hydrochloric acid
  3. additioncontaining DOWEX 50W-X8 (100-200 mesh, 2×2 cm, H+ form)
  4. washAfter washing the column with water (100 ml)
  5. washthe product was eluted with dilute aqueous ammonia
  6. additionFractions containing the product
  7. customwere evaporated in vacuo
  8. custompurified by flash chromatography
  9. washeluting with dichloromethane: methanol (95:5 v/v)
  10. filtrationAfter filtration and evaporation
  11. dissolutionthe residue was dissolved in water
  12. additioncontaining DOWEX 50W-X8 (100-200 mesh, 2× 2 cm, H+ form)
  13. washAfter washing the column with water (50 ml)
  14. washthe product was eluted with dilute aqueous ammonia
  15. additionFractions containing the desired product
  16. customdried

Sources & evidence

ORD record
ord-f1bc2dc9ee2f4b0a90f8fbb38d99ae0b
Source dataset
uspto-grants-1990_05
Patent number
US04925867

Reaction notes

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