N,N,N',N'-Tetramethylethylenediamine → 2,6,10,15,19,23-Hexamethyltetracosa-11,13-diyne-10,15-diol

HRID 596562Notes

Reaction equation

HRID 596562 reaction equation
[CH3:1][C:2]([OH:16])([CH2:5][CH2:6][CH2:7][CH:8]([CH3:15])[CH2:9][CH2:10][CH2:11][CH:12]([CH3:14])[CH3:13])[C:3]#[CH:4].CN(C)[CH2:19][CH2:20]N(C)C>N1C=CC=CC=1>[CH3:13][CH:12]([CH2:11][CH2:10][CH2:9][CH:19]([CH3:20])[CH2:7][CH2:6][CH2:5][C:2]([CH3:1])([OH:16])[C:3]#[C:4][C:4]#[C:3][C:2]([CH3:1])([OH:16])[CH2:5][CH2:6][CH2:7][CH:8]([CH3:15])[CH2:9][CH2:10][CH2:11][CH:12]([CH3:13])[CH3:14])[CH3:14]

Participants

4

Reactant 2

HCID 8037N,N,N',N'-TetramethylethylenediamineHCID 1026523,7,11-Trimethyldodecyn-3-ol

Product 1

HCID 214273422,6,10,15,19,23-Hexamethyltetracosa-11,13-diyne-10,15-diolYield 81.8%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Procedure

In a 1-l three-necked and round-bottomed flask 10.5 g of 3,7,11-trimethyldodeca-1-yne-3-ol, 5.0 g of cuprous chloride, 12.0 g of tetramethylethylenediamine and 675 ml of pyridine were placed and the mixture was subjected to oxydative coupling reaction at 50° ~ 55° C for 6 hours under an oxygen atmosphere. After completion of the reaction, there remained no unreacted starting alcohol. The pyridine was distilled off the reaction system and 300 ml of benzene and 200 ml of water were added to the residue and decanted. The organic layer was washed with 3N--H2SO4 and water, and dried. The benzene was distilled off to afford 8.55 g of 2,6,10,15,19,23-hexamethyltetracosa-11,13-diyne-10,15-diol. A 5.0 g portion of this product was dissolved in 10 ml of n-hexane and 0.25 g of 3 % palladium on active carbon was added thereto. The mixture was subjected to hydrogenation at a temperature of 60° C of under a hydrogen pressure of 3 ~ 5 kg/cm2 to give 4.6 g of the product consisting of the compounds (V) and (VI) in the ratio of 95.0 : 5.0 % respectively.

Workup

  1. customthe mixture was subjected to oxydative coupling reaction at 50° ~ 55° C for 6 hours under an oxygen atmosphere
  2. customAfter completion of the reaction, there
  3. distillationThe pyridine was distilled off the reaction system and 300 ml of benzene and 200 ml of water
  4. additionwere added to the residue
  5. customdecanted
  6. washThe organic layer was washed with 3N
  7. dry with materialH2SO4 and water, and dried
  8. distillationThe benzene was distilled off

Sources & evidence

ORD record
ord-35f25b637cbd4a0fb6c84688f60f58a6
Source dataset
uspto-grants-1977_03
Patent number
US04011277

Reaction notes

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