Triphenylphosphine → HCID 18980630, compound

HRID 2392943Notes

Reaction equation

HRID 2392943 reaction equation
[CH3:1][C:2]1([CH3:14])[CH2:11][CH2:10][C:9]([CH3:13])([CH3:12])[C:8]2[CH:7]=[CH:6][CH:5]=[CH:4][C:3]1=2.P(C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[CH2:34]([O:37][Si](C)(C)C)[C:35]#[CH:36].[SiH3]O[SiH3]>N1CCCCC1.[Cu]I.CCOCC>[CH3:12][C:9]1([CH3:13])[CH2:10][CH2:11][C:2]([CH3:14])([CH3:1])[C:3]2[CH:4]=[C:5]([C:36]#[C:35][CH2:34][OH:37])[CH:6]=[CH:7][C:8]1=2

Participants

8

Reactant 4

HCID 11776TriphenylphosphineHCID 79696Silane, trimethyl(2-propyn-1-yloxy)-HCID 811861,1,4,4-TetramethyltetralinHCID 123318Disiloxane

Product 1

HCID 18980630HCID 18980630, compound

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 3283Diethyl EtherSolventHCID 8082PiperidineSolvent

Procedure

114 g of crude 2-bromo-(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-naphthalene (GC-purity: 76.5%) was dissolved in 250 ml of piperidine and successively treated with 4.80 g of ((Ph)3P)4Pd, 0.95 g of CuI, and 1.35 g of (Ph)3P. The internal temperature was then raised to 90°-95° C. and 150 ml of propargyloxy-trimethylsilane were added via dropping funnel within 4 hours. After 1 additional hour the reaction mixture was poured onto crashed ice/HCl conc. and vigorously stirred until TLC indicated that all silylether had been cleaved. EtOEt was added, the layers were separated and the organic phase washed with H2O and brine. Drying over Na2SO4, evaporation of the solvent and purification by flash chromatography (silica gel, hexane/AcOEt=85:15) afforded 60.6 g of 3-(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-naphthalen-2-yl)-prop-2-yn-1-ol as ochre yellow crystals of m.p. 84°-85° C. (GC-purity >96%).

Workup

  1. temperatureThe internal temperature was then raised to 90°-95° C.
  2. customwithin 4 hours
  3. additionAfter 1 additional hour the reaction mixture was poured
  4. customthe layers were separated
  5. washthe organic phase washed with H2O and brine
  6. dry with materialDrying over Na2SO4, evaporation of the solvent and purification by flash chromatography (silica gel, hexane/AcOEt=85:15)

Sources & evidence

ORD record
ord-cec20c3bdba440b684b537b194224778
Source dataset
uspto-grants-1998_09
Patent number
US05801253

Reaction notes

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