2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → HCID 126489439, compound

HRID 1770374Notes

Reaction equation

HRID 1770374 reaction equation
[C:1]([O:5][C:6]([NH:8][C@@H:9]([CH2:20][CH2:21][CH2:22][C@H:23]([O:42][CH2:43][CH2:44][CH3:45])[C@H:24]([C@@H:30]([O:32]CC1C=CC(OC)=CC=1)[CH3:31])[CH2:25][CH2:26][CH:27]([CH3:29])[CH3:28])[C:10]([O:12][CH2:13][C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)=[O:11])=[O:7])([CH3:4])([CH3:3])[CH3:2].C(C1C(=O)C(Cl)=C(Cl)C(=O)C=1C#N)#N.[OH-].[Na+]>O.C(Cl)Cl>[C:1]([O:5][C:6]([NH:8][C@@H:9]([CH2:20][CH2:21][CH2:22][C@H:23]([O:42][CH2:43][CH2:44][CH3:45])[C@H:24]([C@@H:30]([OH:32])[CH3:31])[CH2:25][CH2:26][CH:27]([CH3:29])[CH3:28])[C:10]([O:12][CH2:13][C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)=[O:11])=[O:7])([CH3:2])([CH3:3])[CH3:4]

Participants

6

Reactant 3

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 14798Sodium HydroxideHCID 131734629HCID 131734629, compound

Product 1

HCID 126489439HCID 126489439, compoundYield 92%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 6344DichloromethaneSolvent

Procedure

To a solution of (2S,6S,7S)-benzyl 2-((tert-butoxycarbonyl)amino)-7-((S)-1-((4-methoxybenzyl)oxy)-ethyl)-10-methyl-6-propoxyundecanoate (1.10 g, 1.75 mmol) in H2O (0.531 mL) and DCM (5.31 mL) was added DDQ (0.418 g, 1.84 mmol) at 0° C. The mixture was stirred vigorously at this temperature for 1 h and then 1N NaOH (1.84 mL, 1.84 mmol) and H2O (20 mL) were added. The phases were separated and the aqueous phase was extracted with DCM (3×15 mL). The combined organic extracts were washed with brine (8 mL), dried over Na2SO4, filtered, and the filtrate was treated with Celite® (2 scoopula tip-fulls). The solvent was removed under reduced pressure and the resulting adsorbed material was directly loaded onto a column and purified using flash column chromatography (40 g SiO2, 0→60% EtOAc/hexanes) to afford the title compound (815 mg, 1.61 mmol, 92%) as a colorless oil: 1H NMR (400 MHz, CDCl3) δ 7.41-7.30 (m, 5H), 5.17 (app q, J=12.4 Hz, 2H), 5.07 (d, J=8.5 Hz, 1H), 4.44-4.39 (m, 1H), 4.39-4.30 (m, 1H), 3.87-3.75 (m, 1H), 3.54 (app dt, J=9.0, 6.6 Hz, 1H), 3.42-3.33 (m, 1H), 3.26 (app dt, J=8.9, 6.6 Hz, 1H), 1.87-1.76 (m, 1H), 1.72-1.37 (m, 17H), 1.35-1.07 (m, 7H), 1.04-0.93 (m, 1H), 0.93-0.84 (m, 9H); 13C NMR (101 MHz, CDCl3) δ 172.66, 155.32, 135.39, 128.59, 128.42, 128.24, 82.50, 79.89, 71.42, 69.10, 66.99, 53.52, 45.46, 37.47, 32.82, 28.82, 28.31, 28.28, 25.27, 23.20, 22.68, 22.54, 22.44, 22.06, 10.66; ESIMS m/z 530 ([M+Na]+).

Workup

  1. customThe phases were separated
  2. extractionthe aqueous phase was extracted with DCM (3×15 mL)
  3. washThe combined organic extracts were washed with brine (8 mL)
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. additionthe filtrate was treated with Celite® (2 scoopula tip-fulls)
  7. customThe solvent was removed under reduced pressure
  8. custompurified

Sources & evidence

ORD record
ord-c0ab72dc3a574ae880a2099fd598a2ce
Source dataset
uspto-grants-2016_02
Patent number
US09247741B2

Reaction notes

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