2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → HCID 86628877, compound

HRID 1671419Notes

Reaction equation

HRID 1671419 reaction equation
[Cl:1][CH2:2][CH2:3][CH2:4][S:5]([O:8][CH2:9][C:10]([CH3:25])([CH3:24])[C@@H:11]([O:14]CC1C=CC(OC)=CC=1)[CH:12]=[CH2:13])(=[O:7])=[O:6].ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl>ClCCl.O>[Cl:1][CH2:2][CH2:3][CH2:4][S:5]([O:8][CH2:9][C:10]([CH3:25])([CH3:24])[C@@H:11]([OH:14])[CH:12]=[CH2:13])(=[O:7])=[O:6]

Participants

5

Reactant 2

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 86628872HCID 86628872, compound

Product 1

HCID 86628877HCID 86628877, compoundYield 91%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

Following the general procedure for the oxidative cleavage of (4-methoxy)benzyl ethers of Description 19, (3S)-3-[(4-methoxyphenyl)methoxy]-2,2-dimethylpent-4-enyl (3-chloropropyl)sulfonate (13a) (0.50 g, 1.3 mmol), dissolved in a mixture of dichloromethane (DCM) and water (10:1) (10 mL) was treated with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) (0.35 g, 1.5 mmol). After work-up, the crude material was purified by silica gel column chromatography using a mixture of ethyl acetate (EtOAc) and hexane (Hxn) to provide 0.32 g (91% yield) of the title compound (16a) as a colorless oil. Rf=0.48 (EtOAc/Hxn=1:2). 1H NMR (400 MHz, CDCl3): δ=0.95 (s, 3H), 1.00 (s, 3H), 1.75 (d, J=3.6 Hz, 1H), 2.32-2.39 (m, 2H), 3.31-3.35 (m, 2H), 3.70-3.73 (m, 2H), 3.97 (d, J=9.2 Hz, 1H), 4.02-4.04 (m, 1H), 4.26 (d, J=9.2 Hz, 1H), 5.25-5.33 (m, 2H), 5.87-5.96 (m, 1H) ppm. MS (ESI) m/z: 271.08 (M+H)+. The analytical data was consistent with the proposed structure.

Workup

  1. customAfter work-up, the crude material was purified by silica gel column chromatography
  2. additiona mixture of ethyl acetate (EtOAc) and hexane (Hxn)

Sources & evidence

ORD record
ord-23bba8be93bd42c89bbf822482fcf3b0
Source dataset
uspto-grants-2011_08
Patent number
US07994218B2

Reaction notes

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