N,N,N',N'-Tetramethylethylenediamine → 1-[2,5-Dimethoxy-4-butyl-3,6-bis(methoxymethoxy)phenyl]-5-[2,5-dimethoxy-3,6-bis(methoxymethoxy)-4-(2-methoxymethyloxyethyl)phenyl]pentane

HRID 1588142Notes

Reaction equation

HRID 1588142 reaction equation
[CH3:1][O:2][C:3]1[C:8]([O:9][CH2:10][O:11][CH3:12])=[CH:7][C:6]([O:13][CH3:14])=[C:5]([O:15][CH2:16][O:17][CH3:18])[C:4]=1[CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][C:24]1[C:29]([O:30][CH2:31][O:32][CH3:33])=[C:28]([O:34][CH3:35])[C:27]([CH2:36][CH2:37][O:38][CH2:39][O:40][CH3:41])=[C:26]([O:42][CH2:43][O:44][CH3:45])[C:25]=1[O:46][CH3:47].CN(C)CCN(C)C.[CH2:56]([Li])[CH2:57][CH2:58][CH3:59].C(I)CCC>C1(C)C=CC=CC=1.CN(C)P(=O)(N(C)C)N(C)C.C(OCC)C>[CH3:1][O:2][C:3]1[C:8]([O:9][CH2:10][O:11][CH3:12])=[C:7]([CH2:56][CH2:57][CH2:58][CH3:59])[C:6]([O:13][CH3:14])=[C:5]([O:15][CH2:16][O:17][CH3:18])[C:4]=1[CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][C:24]1[C:29]([O:30][CH2:31][O:32][CH3:33])=[C:28]([O:34][CH3:35])[C:27]([CH2:36][CH2:37][O:38][CH2:39][O:40][CH3:41])=[C:26]([O:42][CH2:43][O:44][CH3:45])[C:25]=1[O:46][CH3:47]

Participants

8

Reactant 4

HCID 8037N,N,N',N'-TetramethylethylenediamineHCID 10962Butyl iodideHCID 197572501-[2,5-Dimethoxy-3,6-bis(methoxymethoxy)phenyl]-5-[2,5-dimethoxy-3,6-bis(methoxymethoxy)-4-(2-methoxymethyloxyethyl)phenyl]pentaneHCID 178418339Butyllithium

Product 1

HCID 197572401-[2,5-Dimethoxy-4-butyl-3,6-bis(methoxymethoxy)phenyl]-5-[2,5-dimethoxy-3,6-bis(methoxymethoxy)-4-(2-methoxymethyloxyethyl)phenyl]pentane

Reagents, catalysts & solvents 3

HCID 1140TolueneSolventHCID 3283Diethyl EtherSolventHCID 12679HexamethylphosphoramideSolvent

Conditions

Temperature
-78 °C

Procedure

550 Milligrams of 1-[2,5-dimethoxy-3,6-bis(methoxymethoxy)phenyl]-5-[2,5-dimethoxy-3,6-bis(methoxymethoxy)-4-(2-methoxymethyloxyethyl)phenyl]pentane was dissolved in a mixed solvent of 8 ml of toluene with 2 ml of hexamethylphosphoric triamide, to this solution was added 0.12 ml of N,N,N',N'-tetramethylethylenediamine and the whole mixture was cooled to -78° C. in a dry ice-acetone bath, then 0.64 ml of n-butyllithium was added to the reaction mixture. 15 Minutes later, 0.16 ml of n-butyl iodide was added to the reaction mixture, and temperature of the reaction mixture was gradually elevated to room temperature, and further stirred for 4 hours. 50 Milliliters of diethyl ether was added to the reaction mixture, and the organic layer was washed with water, a saturated sodium chloride aqueous solution, dried over anhydrous magnesium sulfate, and then concentrated. The residue obtained was purified by means of a silica gel column chromatography (diameter 2 cm×length 10 cm, adsorbent: "Silica gel 60" manufactured by E. Merck A. G., developing solvent: 30% ethyl acetate-hexane) to obtain 520 mg of 1-[2,5-dimethoxy-4-butyl-3,6-bis(methoxymethoxy)phenyl]-5-[2,5-dimethoxy-3,6-bis(methoxymethoxy)4-(2-methoxymethyloxyethyl)phenyl]pentane. Amorphous powdery substance.

Workup

  1. customwas gradually elevated to room temperature
  2. washthe organic layer was washed with water
  3. dry with materiala saturated sodium chloride aqueous solution, dried over anhydrous magnesium sulfate
  4. concentrationconcentrated
  5. customThe residue obtained
  6. customwas purified by means of a silica gel column chromatography (diameter 2 cm×length 10 cm, adsorbent

Sources & evidence

ORD record
ord-d96c51272d134112b077c625f0104480
Source dataset
uspto-grants-1993_06
Patent number
US05220042

Reaction notes

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