2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → HCID 131729104, compound

HRID 1671447Notes

Reaction equation

HRID 1671447 reaction equation
[Cl:1][CH2:2][CH2:3][CH2:4][S:5]([O:8][CH2:9][C:10]([CH3:33])([CH3:32])[CH:11]([O:22]CC1C=CC(OC)=CC=1)[C:12]([O:14][CH2:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)=[O: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]([CH3:33])([CH3:32])[CH:11]([OH:22])[C:12]([O:14][CH2:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)=[O:13])(=[O:7])=[O:6]

Participants

5

Reactant 2

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 131729103HCID 131729103, compound

Product 1

HCID 131729104HCID 131729104, compoundYield 66%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

Following the general procedure for the oxidative cleavage of (4-methoxy)benzyl ethers of Description 19 phenylmethyl (2R/S)-4-[(3-chloropropyl)sulfonyloxy]-2-[(4-methoxyphenyl)methoxy]-3,3-dimethyl-butanoate (32a) (0.22 g, 0.4 mmol) dissolved in a mixture of dichloromethane (DCM) and water (10:1) (3 mL) was treated with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) (200 mg, 0.87 mmol). After work-up, the crude material was purified by silica gel column chromatography using a mixture of ethyl acetate (EtOAc) and hexane (Hxn) as eluent (EtOAc/Hxn=1:2) to provide 100 mg (60% yield) of the title compound (32b) as a colorless oil. 1H NMR (400 MHz, CDCl3): δ=0.95 (s, 3H), 1.08 (s, 3H), 2.27-2.34 (m, 2H), 3.04 (d, J=6.0 Hz, 1H), 3.26-3.29 (m, 2H), 3.65-3.69 (m, 2H), 3.97 (d, J=8.8 Hz, 1H), 4.08 (d, J=5.6 Hz, 1H), 4.16 (d, J=9.6 Hz, 1H), 5.24 (d, J=12.4 Hz, 1H), 5.28 (d, J=12.4 Hz, 1H), 7.36-7.38 (m, 5H) ppm. MS (ESI) m/z: 379.03 (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) as eluent (EtOAc/Hxn=1:2)

Sources & evidence

ORD record
ord-abd7d46f631c42869faf80512c54ac75
Source dataset
uspto-grants-2011_08
Patent number
US07994218B2

Reaction notes

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