Triphenylphosphine → 2,7-Bis(trimethylsilylethynyl)naphthalene

HRID 2283206Notes

Reaction equation

HRID 2283206 reaction equation
FC(F)(F)S(O[C:7]1[CH:16]=[CH:15][C:14]2[C:9](=[CH:10][C:11](OS(C(F)(F)F)(=O)=O)=[CH:12][CH:13]=2)[CH:8]=1)(=O)=O.C1C=CC(P([C:40]2[CH:45]=CC=CC=2)C2C=CC=CC=2)=CC=1.[C:46]([Si:48]([CH3:51])([CH3:50])[CH3:49])#[CH:47]>N1CCCCC1.[Cu]I.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:49][Si:48]([C:46]#[C:47][C:7]1[CH:16]=[CH:15][C:14]2[C:9](=[CH:10][C:11]([C:40]#[C:45][Si:48]([CH3:50])([CH3:49])[CH3:46])=[CH:12][CH:13]=2)[CH:8]=1)([CH3:51])[CH3:50]

Participants

7

Reactant 3

HCID 11776TriphenylphosphineHCID 66111TrimethylsilylacetyleneHCID 109387851,1'-(2,7-Naphthalenediyl) bis(1,1,1-trifluoromethanesulfonate)

Product 1

HCID 708180512,7-Bis(trimethylsilylethynyl)naphthalene

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 8082PiperidineSolvent

Procedure

A mixture of naphthalene-2,7-diyl bis(trifluoromethanesulfonate) 1 (1.00 g, 1.19 mmol), CuI (0.023 g, 0.12 mmol), Pd(PPh3)4 (0.14 g, 0.12 mmol) and PPh3 (0.062 g, 0.24 mmol) was dissolved in piperidine (30 ml) in the presence of molecular sieves and under an Ar2 atmosphere. Ethynyltrimethylsilane (0.69 g, 7.06 mmol) was added and the stirred mixture heated at reflux overnight. The solvent was evaporated in vacuo and the resulting brown oil purified by flash column chromatography (5% EtOAc in hexane). 2,7-bis((trimethylsilyl)ethynyl)naphthalene 2 was obtained as a colourless solid (0.69 g, 90%); Rf 0.37 [3% EtOAc in hexane]; mp: 127-129° C. (Lit. 62.5° C., Crisp et al., 1997); δH (CDCl3, 400 MHz) 7.91 (2H, s, 2×ArH), 7.71 (2H, d, J=8.4 Hz, 2×ArH), 7.50 (2H, m, 2×ArH), 0.28 (18H, m, 6×CH3Si); δC (CDCl3, 100 MHz) 132.34 (Ar—C), 132.26 (Ar—C), 131.64 (2×Ar—CH), 129.48 (2×Ar—CH), 127.70 (2×Ar—CH), 121.17 (2×Ar—C), 105.01 (2×C≡C), 95.17 (2×C≡C), −0.03 (6×CH3Si); HRMS m/z calc. C20H25Si2 [M+H]+321.1495. found [M+H]+321.1499; anal.CHN calcd. C20H25Si2 C, 74.9%; H, 7.5%. found C, 74.6%; H, 7.5%.

Workup

  1. temperaturethe stirred mixture heated
  2. temperatureat reflux overnight
  3. customThe solvent was evaporated in vacuo
  4. customthe resulting brown oil purified by flash column chromatography (5% EtOAc in hexane)

Sources & evidence

ORD record
ord-77080974e28b4425bbc4cc5a8b42303e
Source dataset
uspto-grants-2015_09
Patent number
US09145377B2

Reaction notes

Loading…