Triphenylphosphine → (+)-6-Decyloxy-2-(3-pentynyloxy-1-butynyl)naphthalene

HRID 1734396Notes

Reaction equation

HRID 1734396 reaction equation
[CH2:1]([O:11][C:12]1[CH:13]=[C:14]2[C:19](=[CH:20][CH:21]=1)[CH:18]=[C:17](Br)[CH:16]=[CH:15]2)[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH3:10].[C:23]([O:28][CH:29]([C:31]#[CH:32])[CH3:30])#[C:24][CH2:25][CH2:26][CH3:27].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[Cu](I)I.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C(N(CC)CC)C>[CH2:1]([O:11][C:12]1[CH:13]=[C:14]2[C:19](=[CH:20][CH:21]=1)[CH:18]=[C:17]([C:32]#[C:31][CH:29]([O:28][C:23]#[C:24][CH2:25][CH2:26][CH3:27])[CH3:30])[CH:16]=[CH:15]2)[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH3:10]

Participants

7

Reactant 3

HCID 11776TriphenylphosphineHCID 6138212-Bromo-6-decyloxynaphthaleneHCID 57202524(+)-2-Pentynyloxy-3-butyne

Product 1

HCID 57108781(+)-6-Decyloxy-2-(3-pentynyloxy-1-butynyl)naphthaleneYield 82%

Reagents, catalysts & solvents 3

HCID 83717Copper iodideCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8471TriethylamineSolvent

Procedure

18.2 g (0.05 mol ) of 6-decyloxy-2-bromonaphthalene (VI-60), 15.4 g (0.1 mol ) of (+)-2-pentynyloxy-3-butyne (VII*-60), 0.5 g of copper iodide, 0.8 g of triphenylphosphine, 0.4 g of bis(triphenylphosphine)-palladium chloride and 100 ml of triethylamine were stirred under reflux for 7 hours in an atmosphere of nitrogen gas. After completion of the reaction, the reaction mixture was poured into ice-aqueous hydrochloric acid and extracted with 200 ml of ethyl acetate. The organic layer was further washed with water and concentrated under reduced pressure. The residue was purified by silica gel chromatography using toluene-ethyl acetate as eluent to obtain 17.9 g (yield 82%) of optically active (+)-6-decyloxy-2-(3-pentynyloxy-1-butynyl)naphthalene (I'-60), [α]D20 =+93 (c=1, chloroform).

Workup

  1. temperatureunder reflux for 7 hours in an atmosphere of nitrogen gas
  2. customAfter completion of the reaction
  3. additionthe reaction mixture was poured into ice-aqueous hydrochloric acid
  4. extractionextracted with 200 ml of ethyl acetate
  5. washThe organic layer was further washed with water
  6. concentrationconcentrated under reduced pressure
  7. customThe residue was purified by silica gel chromatography

Sources & evidence

ORD record
ord-17fea2082a8347ee990c2a3f05f21026
Source dataset
uspto-grants-1996_07
Patent number
US05534188

Reaction notes

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