2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → HCID 178482133, compound

HRID 504159Notes

Reaction equation

HRID 504159 reaction equation
Cl[C:2]1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl.[CH2:15]([O:22][C:23](=[O:35])[NH:24][C@@H:25]([CH2:28][C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1)[CH:26]=O)[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1.[C:36]1([NH2:43])[CH:41]=[CH:40][CH:39]=[CH:38][C:37]=1[NH2:42]>CC#N>[CH2:15]([O:22][C:23](=[O:35])[NH:24][C@@H:25]([CH2:28][C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1)/[CH:26]=[N:42]/[C:37]1[CH:38]=[CH:39][CH:40]=[CH:41][C:36]=1[NH:43][CH3:2])[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1

Participants

5

Reactant 3

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 7243O-PhenylenediamineHCID 7021150Cbz-L-Phenylalaninal

Product 1

HCID 178482133HCID 178482133, compoundYield 28%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ, 0.20 g, 0.86 mmoles) was added to a room temperature solution of ((S)-1-Benzyl-2-oxo-ethyl)-carbamic acid benzyl ester (0.24 g, 0.86 mmoles) and 1,2-phenylenediamine (0.093 g, 0.86 mmoles) in CH3CN (10 mL). The reaction mixture was stirred at room temperature for 16 h, and then concentrated in vacuo. The residue was re-dissolved in EtOAc (150 mL), and washed with saturated aqueous NaHCO3 (3×125 mL). The organic layer was dried (MgSO4) and concentrated in vacuo to give a brown oily solid. Purification of the residue by flash chromatography on silica gel eluting with 10-40% EtOAc/heptane afforded 0.091 g (28% yield) of {(S)-1-Benzyl-2-[(E)-2-methylamino-phenylimino]-ethyl}-carbamic acid benzyl ester as a colorless oil: ES+ LC/MS m/e 372 (M+H), RT=3.03 min; 1H NMR (CDCl3) D9.90 (bd s, 1), 7.68 (bd s, 1), 7.21-7.33 (m, 11), 7.16 (d, 2, J=6.7 Hz), 5.64 (d, 1, J=7.2 Hz), 5.15 (dd, 1, J=15.2, 7.5 Hz), 5.07 (s, 2), 3.45 (d, 2, J=7.5 Hz).

Workup

  1. concentrationconcentrated in vacuo
  2. dissolutionThe residue was re-dissolved in EtOAc (150 mL)
  3. washwashed with saturated aqueous NaHCO3 (3×125 mL)
  4. dry with materialThe organic layer was dried (MgSO4)
  5. concentrationconcentrated in vacuo
  6. customto give a brown oily solid
  7. customPurification of the residue by flash chromatography on silica gel eluting with 10-40% EtOAc/heptane

Sources & evidence

ORD record
ord-4c5064587baf4d35a1efb860a621befd
Source dataset
uspto-grants-2010_08
Patent number
US07777042B2

Reaction notes

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