N,N,N',N'-Tetramethylethylenediamine → HCID 19757171, compound

HRID 1588161Notes

Reaction equation

HRID 1588161 reaction equation
[CH3:1][O:2][C:3]1[C:8]([CH2:9][CH2:10][CH2:11][CH3:12])=[C:7]([O:13][CH2:14][O:15][CH3:16])[C:6]([O:17][CH3:18])=[C:5]([CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][C:24]2[C:29]([O:30][CH2:31][O:32][CH3:33])=[C:28]([O:34][CH3:35])[CH:27]=[C:26]([O:36][CH2:37][O:38][CH3:39])[C:25]=2[O:40][CH3:41])[C:4]=1[O:42][CH2:43][O:44][CH3:45].CN(C)P(=[O:55])(N(C)C)N(C)C.CN(C)CCN(C)C.C([Li])CCC>C1(C)C=CC=CC=1.O1CCCC1.C(OCC)(=O)C>[CH3:1][O:2][C:3]1[C:8]([CH2:9][CH2:10][CH2:11][CH3:12])=[C:7]([O:13][CH2:14][O:15][CH3:16])[C:6]([O:17][CH3:18])=[C:5]([CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][C:24]2[C:29]([O:30][CH2:31][O:32][CH3:33])=[C:28]([O:34][CH3:35])[C:27]([OH:55])=[C:26]([O:36][CH2:37][O:38][CH3:39])[C:25]=2[O:40][CH3:41])[C:4]=1[O:42][CH2:43][O:44][CH3:45]

Participants

7

Reactant 4

HCID 8037N,N,N',N'-TetramethylethylenediamineHCID 12679HexamethylphosphoramideHCID 19757164HCID 19757164, compoundHCID 178418339Butyllithium

Product 1

HCID 19757171HCID 19757171, compound

Reagents, catalysts & solvents 2

HCID 8857Ethyl AcetateSolventHCID 22635083Tetrahydrofuran tolueneSolvent

Procedure

Under argon gas stream conditions 2 g of 1,4-dimethoxy-2,5-bis(methoxymethoxy)-6-butyl-3-{5-[2,5-dimethoxy-3,6-bis(methoxymethoxy)phenyl]pentyl}benzene was dissolved in 50 ml of a mixed solvent of anhydrous toluene-tetrahydrofuran (4:1), to this solution were added 10 ml of hexamethylphosphoric triamide and 0.94 ml of N,N,N',N'-tetramethylethylenediamine, then the whole mixture was cooled on a dry ice-acetone bath. 4 Milliliter of n-butyllithium (1.5 M, n-hexane solution) was added dropwise to the reaction mixture and stirred 30 minutes. Next, oxygen gas was bubbled into the reaction mixture for 30 minutes, then the temperature of the reaction mixture was returned back to room temperature by taking for 4 hours. The reaction mixture was concentrated, to the residue obtained was added 100 ml of ethyl acetate, then the ethyl acetate layer was washed twice with 30 ml of a saturated sodium bisulfite aqueous solution, once with 30 ml of water, further washed once with 30 ml of a saturated sodium chloride aqueous solution. The ethyl acetate layer was dried over anhydrous magnesium sulfate, and concentrated, then the residue obtained was purified by a silica gel column chromatography (eluent: ethyl acetate-n-hexane=1:9) to obtain 1.3 g of 1,4-dimethoxy-2,5-bis(methoxymethoxy)-6-butyl-3{5-[2,5-dimethoxy-3,6-bis(methoxymethoxy)-4-hydroxyphenyl]pentyl}benzene. Colorless oily substance.

Workup

  1. temperaturethe whole mixture was cooled on a dry ice-acetone bath
  2. customNext, oxygen gas was bubbled into the reaction mixture for 30 minutes
  3. customwas returned back to room temperature
  4. waitby taking for 4 hours
  5. concentrationThe reaction mixture was concentrated, to the residue
  6. customobtained
  7. washthe ethyl acetate layer was washed twice with 30 ml of a saturated sodium bisulfite aqueous solution, once with 30 ml of water
  8. washfurther washed once with 30 ml of a saturated sodium chloride aqueous solution
  9. dry with materialThe ethyl acetate layer was dried over anhydrous magnesium sulfate
  10. concentrationconcentrated
  11. customthe residue obtained
  12. customwas purified by a silica gel column chromatography (eluent: ethyl acetate-n-hexane=1:9)

Sources & evidence

ORD record
ord-9dd4d720d0fd4f568e65d33f50ba510a
Source dataset
uspto-grants-1993_06
Patent number
US05220042

Reaction notes

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