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

HRID 1588140Notes

Reaction equation

HRID 1588140 reaction equation
[CH3:1][O:2][CH2:3][O:4][CH2:5][CH2:6][C:7]1[C:12]([O:13][CH2:14][O:15][CH3:16])=[C:11]([O:17][CH3:18])[CH:10]=[C:9]([O:19][CH2:20][O:21][CH3:22])[C:8]=1[O:23][CH3:24].CN(C)CCN(C)C.C([Li])CCC.I[CH2:39][CH2:40][CH2:41][CH2:42][CH2:43][C:44]1[C:49]([O:50][CH2:51][O:52][CH3:53])=[C:48]([O:54][CH3:55])[CH:47]=[C:46]([O:56][CH2:57][O:58][CH3:59])[C:45]=1[O:60][CH3:61]>C1(C)C=CC=CC=1.CN(C)P(=O)(N(C)C)N(C)C.C(OCC)C>[CH3:61][O:60][C:45]1[C:46]([O:56][CH2:57][O:58][CH3:59])=[CH:47][C:48]([O:54][CH3:55])=[C:49]([O:50][CH2:51][O:52][CH3:53])[C:44]=1[CH2:43][CH2:42][CH2:41][CH2:40][CH2:39][C:10]1[C:9]([O:19][CH2:20][O:21][CH3:22])=[C:8]([O:23][CH3:24])[C:7]([CH2:6][CH2:5][O:4][CH2:3][O:2][CH3:1])=[C:12]([O:13][CH2:14][O:15][CH3:16])[C:11]=1[O:17][CH3:18]

Participants

8

Reactant 4

HCID 8037N,N,N',N'-TetramethylethylenediamineHCID 197571521-Methoxymethoxy-2-[2,5-dimethoxy-3,6-bis(methoxymethoxy)phenyl]ethaneHCID 197572171-(5-Iodopent-1-yl)-2,5-dimethoxy-3,6-bis(methoxymethoxy)benzeneHCID 178418339Butyllithium

Product 1

HCID 197572501-[2,5-Dimethoxy-3,6-bis(methoxymethoxy)phenyl]-5-[2,5-dimethoxy-3,6-bis(methoxymethoxy)-4-(2-methoxymethyloxyethyl)phenyl]pentane

Reagents, catalysts & solvents 3

HCID 1140TolueneSolvent2×HCID 3283Diethyl EtherSolventHCID 12679HexamethylphosphoramideSolvent

Conditions

Temperature
-78 °C

Procedure

1.0 Gram of 1-methoxymethoxy-2-[2,5-dimethoxy-3,6-bis(methoxymethoxy)phenyl]ethane was dissolved in a mixed solvent of 20 ml of toluene with 5 ml of hexamethylphosphoric triamide, to this solution was added 0.52 ml of N,N,N',N'-tetramethylethylenediamine and the whole mixture was cooled to -78° C. in a dry ice-acetone bath, then 2.7 ml of n-butyllithium (1.6 mole solution) was added dropwise to the reaction mixture. 15 Minutes later, a solution prepared by dissolving 1.56 g of 1-(5-iodopent-1-yl)-2,5-dimethoxy-3,6-bis(methoxymethoxy)benzene in 12 ml of toluene was added to the reaction mixture, and the temperature of the reaction mixture was gradually elevated to room temperature and the reaction mixture was stirred further for 4 hours. 50 Milliliters of diethyl ether was added to the reaction mixture, and the organic layer was washed with water, and with a saturated sodium chloride aqueous solution, then dried over anhydrous sodium sulfate. After concentration, the residue thus obtained was purified by means of a silica gel column chromatography (diameter 3 cm×length 10 cm, Merck, eluent: 30% ethyl acetate-n-hexane) to obtain 2.1 g of 1-[2,5-dimethoxy-3,6-bis(methoxymethoxy)phenyl]-5-[2,5-dimethoxy-3,6-bis(methoxymethoxy)-4-(2-methoxymethyloxyethyl)phenyl]pentane. Amorphous powdery substance.

Workup

  1. custom15 Minutes later, a solution prepared
  2. additionwas added to the reaction mixture
  3. customwas gradually elevated to room temperature
  4. washthe organic layer was washed with water
  5. dry with materialwith a saturated sodium chloride aqueous solution, then dried over anhydrous sodium sulfate
  6. concentrationAfter concentration
  7. customthe residue thus obtained
  8. customwas purified by means of a silica gel column chromatography (diameter 3 cm×length 10 cm, Merck, eluent: 30% ethyl acetate-n-hexane)

Sources & evidence

ORD record
ord-c4cd6510fa1e4078a81c7c4b8996c2ac
Source dataset
uspto-grants-1993_06
Patent number
US05220042

Reaction notes

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