Acetic Acid → 3-Nitro-6-[(1Z)-2-(3,4,5-trimethoxyphenyl)ethenyl]-1,2-benzenediol

HRID 218273Notes

Reaction equation

HRID 218273 reaction equation
[F-].C([N+](CCCC)(CCCC)CCCC)CCC.[N+:19]([C:22]1[C:23]([OH:50])=[C:24]([O:42][Si](C(C)(C)C)(C)C)[C:25](/[CH:28]=[CH:29]\[C:30]2[CH:35]=[C:34]([O:36][CH3:37])[C:33]([O:38][CH3:39])=[C:32]([O:40][CH3:41])[CH:31]=2)=[CH:26][CH:27]=1)([O-:21])=[O:20].C(O)(=O)C>C1COCC1.C(OC)(C)(C)C>[N+:19]([C:22]1[C:23]([OH:50])=[C:24]([OH:42])[C:25](/[CH:28]=[CH:29]\[C:30]2[CH:31]=[C:32]([O:40][CH3:41])[C:33]([O:38][CH3:39])=[C:34]([O:36][CH3:37])[CH:35]=2)=[CH:26][CH:27]=1)([O-:21])=[O:20]

Participants

6

Reactant 3

HCID 176Acetic AcidHCID 2724141Tetrabutylammonium FluorideHCID 601306873-Nitro-6-[(Z)-2-(3,4,5-trimethoxyphenyl)vinyl]-1-(t-butyldimethylsilyloxy)-2-hydroxybenzene

Product 1

HCID 601306793-Nitro-6-[(1Z)-2-(3,4,5-trimethoxyphenyl)ethenyl]-1,2-benzenediol

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 15413tert-Butyl methyl etherSolvent

Procedure

Tetrabutylammonium fluoride (0.77 mL, 0.769 mmol, 1M in THF) was added to a solution of 46 (0.355 g, 0.769 mmol) and glacial acetic acid (0.04 mL, 0.769 mmol) in THF (4 mL) at rt. The reaction mixture was stirred at rt for 3 h then diluted with t-BuOMe and washed successively with water and brine. The organic layer was dried (Na2SO4) and evaporated to dryness to give a crude product which was purified by column chromatography (three times—first with: EtOAc:cyclohexane 3:7+1% acetic acid, then with neat CH2Cl2 and finally with CH2Cl2:methanol 40:1) to yield ZSB-83 (65 mg, 25%):

Workup

  1. washwashed successively with water and brine
  2. dry with materialThe organic layer was dried (Na2SO4)
  3. customevaporated to dryness
  4. customto give a crude product which
  5. customwas purified by column chromatography (three times—first with: EtOAc:cyclohexane 3:7+1% acetic acid
  6. customwith neat CH2Cl2 and finally with CH2Cl2:methanol 40:1) to yield ZSB-83 (65 mg, 25%)

Sources & evidence

ORD record
ord-2a0ab7575abe4c2cb1d9fe41ebcba252
Source dataset
uspto-grants-2012_06
Patent number
US08198302B2

Reaction notes

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