5-Bromo-1,2,3-trimethoxybenzene → HCID 19754877, compound

HRID 1588909Notes

Reaction equation

HRID 1588909 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5](Br)[CH:6]=[C:7]([O:11][CH3:12])[C:8]=1[O:9][CH3:10].C([Li])CCC.[CH:19]([N:22]([CH:33]1[CH2:38][CH2:37][CH2:36][CH2:35][CH2:34]1)[C:23](=[O:32])[C:24]1[CH:31]=[CH:30][C:27]([CH:28]=[O:29])=[CH:26][CH:25]=1)([CH3:21])[CH3:20].OS([O-])(=O)=O.[K+]>C(OCC)C.C1COCC1>[CH:33]1([N:22]([CH:19]([CH3:21])[CH3:20])[C:23](=[O:32])[C:24]2[CH:25]=[CH:26][C:27]([CH:28]([OH:29])[C:5]3[CH:4]=[C:3]([O:2][CH3:1])[C:8]([O:9][CH3:10])=[C:7]([O:11][CH3:12])[CH:6]=3)=[CH:30][CH:31]=2)[CH2:34][CH2:35][CH2:36][CH2:37][CH2:38]1

Participants

7

Reactant 4

HCID 758855-Bromo-1,2,3-trimethoxybenzeneHCID 516920Potassium bisulfateHCID 54488742HCID 54488742, compoundHCID 178418339Butyllithium

Product 1

HCID 19754877HCID 19754877, compound

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-8 °C

Procedure

To a stirred, cold (-15° C.) solution of 3,4,5-trimethoxybromobenzene (965 mg, 3.9 mmol) in ethyl ether (15 ml) was added n-butyl lithium (3 ml of 1.6 M solution in hexane). The reaction mixture was stirred at -8° C. for 10 min., diluted with THF (5 ml) and warmed to 0° C. After stirring for 5 min., the reaction was cooled to -30° C. and a solution of terephthalaldehydic acid N-isopropyl-N-cyclohexyl amide (1.063 g, 3.9 mmol) in THF (5 ml) was added. After stirring at -30° C. for 10 min. and warming to room temperature, the reaction mixture was poured onto 0.5N KHSO4 and extracted with ethyl acetate. The organic layer was washed with saturated NaCl solution and dried (MgSO4). The drying agent was filtered and the filtrate concentrated in vacuo to give the crude product. This was chromatographed on silica gel using mixtures of ethyl acetate and hexane as eluents to give the title compound as a crystalline solid that could be recrystallized from cyclohexane containing a small amount of ethyl acetate, m. pt. 158-160° C.

Workup

  1. temperaturewarmed to 0° C
  2. stirringAfter stirring for 5 min.
  3. temperaturethe reaction was cooled to -30° C.
  4. stirringAfter stirring at -30° C. for 10 min.
  5. temperaturewarming to room temperature
  6. extractionextracted with ethyl acetate
  7. washThe organic layer was washed with saturated NaCl solution
  8. dry with materialdried (MgSO4)
  9. filtrationThe drying agent was filtered
  10. concentrationthe filtrate concentrated in vacuo
  11. customto give the crude product
  12. customThis was chromatographed on silica gel using mixtures of ethyl acetate and hexane as eluents

Sources & evidence

ORD record
ord-cf8820d2c573467784efa175c4fef380
Source dataset
uspto-grants-1993_06
Patent number
US05223539

Reaction notes

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