3,7,11-Trimethyldodeca-7,10-dien-1-yn-3-ol → HCID 54008155, compound

HRID 27674Notes

Reaction equation

HRID 27674 reaction equation
[CH3:1][C:2]([OH:16])([CH2:5][CH2:6][CH2:7][C:8]([CH3:15])=[CH:9][CH2:10][CH:11]=[C:12]([CH3:14])[CH3:13])[C:3]#[CH:4]>C1C=CC=CC=1.[Rh](Cl)(Cl)Cl.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH3:14][C:12](=[CH:11][CH2:10][CH2:9][C:8]([CH3:15])=[CH:7][CH2:6][CH2:5][C:2]([CH3:1])([OH:16])[CH:3]=[CH:4][C:4]#[C:3][C:2]([CH3:1])([OH:16])[CH2:5][CH2:6][CH:7]=[C:8]([CH3:15])[CH2:9][CH2:10][CH:11]=[C:12]([CH3:14])[CH3:13])[CH3:13]

Participants

4

Reactant 1

HCID 538924903,7,11-Trimethyldodeca-7,10-dien-1-yn-3-ol

Product 1

HCID 54008155HCID 54008155, compoundYield 94%

Reagents, catalysts & solvents 2

HCID 86736741HCID 86736741, compoundCatalystHCID 241BenzeneSolvent

Procedure

In contact with triphenylphosphine rhodium chloride [RhCl (PPh3)3 ] catalyst, 3,7,11-trimethyl-7,10-dodecadien-1-yn-3-ol was refluxed in benzene for 3 hours. The reaction mixture was concentrated and purified by column chromatography (developer system: benzene-chloroform =1:1). Analysis of the product by gel permeation chromatography showed that the starting material had substantially reacted to yield 2,6,10,15,19,23-hexamethyl-2,6,11,18,22-tetracosapentaen-13-yn-10,15-diol (94% selectivity). The resulting acetylenic diol was hydrogenated in n-hexane and in contact with 5% palladium-on-carbon at room temperature and elevated pressure of 80-100 kg/cm2 to yield 2,6,10,15,19,23-hexamethyltetracosa-10,15-diol (bp. 218-220° C. / 0.2 mm Hg). This product was subjected to hydrogenolysis in acetic acid in contact with palladium-on-carbon at a hydrogen pressure of 100 kg/cm2 and at a reaction temperature of 170-190° C. The resultant compound was analyzed by gas chromatography and nuclear magnetic resonance spectroscopy and the data comformed with a standard sample of squalane.

Workup

  1. concentrationThe reaction mixture was concentrated
  2. custompurified by column chromatography (developer system: benzene-chloroform =1:1)
  3. customhad substantially reacted

Sources & evidence

ORD record
ord-b8fdb427583d4de68a64add95f5d8384
Source dataset
uspto-grants-1980_09
Patent number
US04222963

Reaction notes

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