2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → HCID 86629048, compound

HRID 1671453Notes

Reaction equation

HRID 1671453 reaction equation
[Cl:1][CH2:2][CH2:3][CH2:4][S:5]([O:8][CH2:9][C:10]([CH3:34])([CH3:33])[C@@H:11]([O:23]CC1C=CC(OC)=CC=1)[C:12]([O:14][C@H:15]([C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)[CH3:16])=[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])([CH3:34])[C@@H:11]([OH:23])[C:12]([O:14][C@H:15]([C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)[CH3:16])=[O:13])(=[O:7])=[O:6]

Participants

5

Reactant 2

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 86629046HCID 86629046, compound

Product 1

HCID 86629048HCID 86629048, compoundYield 93.1%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

Following the general procedure for the oxidative cleavage of (4-methoxy)benzyl ethers of Description 19, (1S)-1-phenylethyl (2R)-4-[(3-chloropropyl)sulfonyloxy]-2-[(4-methoxyphenyl)methoxy]-3,3-dimethylbutanoate (35a) (0.42 g, 0.82 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) (220 mg, 0.98 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=1:1) to provide 300 mg (93% yield) of the title compound (35b) as a colorless oil. Rf=0.39 (EtOAc/Hex=1:2). 1H NMR (400 MHz, CDCl3): δ=1.02 (s, 3H), 1.19 (s, 3H), 1.64 (d, J=6.4 Hz, 3H), 2.30-2.37 (m, 2H), 3.01 (d, J=5.6 Hz, 1H), 3.30-3.33 (m, 2H), 3.67-3.70 (m, 2H), 4.02-4.04 (m, 2H), 4.20 (d, J=9.2 Hz, 1H), 6.02 (q, J=6.8 Hz, 1H), 7.36-7.38 (m, 5H) ppm. MS (ESI) m/z: 414.09 (M+Na)+. The analytical data was consistant 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=1:1)

Sources & evidence

ORD record
ord-c1e7ea700b5f4f769c37c3483c2c5b5c
Source dataset
uspto-grants-2011_08
Patent number
US07994218B2

Reaction notes

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