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Trimethylsilylacetylene → [3-(2-Methoxy-1,1-dimethyl-ethyl)-phenylethynyl]-trimethyl-silane

HRID 451610
Notes
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Reaction equation

HRID 451610 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([C:8]([CH3:13])([CH3:12])[CH2:9][O:10][CH3:11])[CH:3]=1.[CH3:14][Si:15]([C:18]#[CH:19])([CH3:17])[CH3:16]>CC#N.CCN(CC)CC.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.[Cu]I>[CH3:11][O:10][CH2:9][C:8]([C:4]1[CH:3]=[C:2]([C:19]#[C:18][Si:15]([CH3:17])([CH3:16])[CH3:14])[CH:7]=[CH:6][CH:5]=1)([CH3:13])[CH3:12]
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

6

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 671914112-(3-Bromophenyl)-2-methylpropyl methyl ether

Product 1

HCID 67187907[3-(2-Methoxy-1,1-dimethyl-ethyl)-phenylethynyl]-trimethyl-silaneYield 89%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)Catalyst
HCID 178418476
HCID 178418476, compound
Catalyst
HCID 21895542Acetonitrile triethylamineSolvent

Procedure

To a solution of 1-bromo-3-(2-methoxy-1,1-dimethyl-ethyl)-benzene (1.62 g, 6.69 mmol) and trimethylsilylacetylene (1.2 mL, 8.7 mmol, 1.3 eq.) in MeCN-Et3N (50 mL, 7:3) was added Pd(PPh3)2Cl2 (0.23 g, 0.33 mmol. 0.05 eq.), CuI (0.038 g, 0.2 mmol, 0.03 eq.) and the mixture refluxed for 16 h. After cooling to ambient temperature and concentration under reduced pressure the residue was chromatographed (EtOAc-hexane, 2:98) to obtain 1.54 g (89%) of the desired product. NMR (DMSO-d6): 7.28-7.00 (m, 4H), 3.16 (s, 2H), 2.98 (s, 3H), 1.00 (s, 6H), 0.1 (s, 9H). MS (DCI): 261 (M+1).

Workup

  1. temperaturethe mixture refluxed for 16 h
  2. concentrationconcentration under reduced pressure the residue
  3. customwas chromatographed (EtOAc-hexane, 2:98)

Sources & evidence

ORD record
ord-f839eab642924d65bb327e751c2414f3
Source dataset
uspto-grants-2013_07
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US08487116B2

Reaction notes

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On this pageParticipantsProcedureWorkupSources & evidenceReaction notes