Water → [2-(5-Chloro-2-methoxyphenyl)ethynyl]trimethylsilane

HRID 1776803Notes

Reaction equation

HRID 1776803 reaction equation
Br[C:2]1[CH:7]=[C:6]([Cl:8])[CH:5]=[CH:4][C:3]=1[O:9][CH3:10].[C:11]([Si:13]([CH3:16])([CH3:15])[CH3:14])#[CH:12].O>CCN(CC)CC.[Cu]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>[Cl:8][C:6]1[CH:5]=[CH:4][C:3]([O:9][CH3:10])=[C:2]([C:12]#[C:11][Si:13]([CH3:16])([CH3:15])[CH3:14])[CH:7]=1

Participants

7

Reactant 3

HCID 962WaterHCID 66111TrimethylsilylacetyleneHCID 5219352-Bromo-4-chloroanisole

Product 1

HCID 68489883[2-(5-Chloro-2-methoxyphenyl)ethynyl]trimethylsilaneYield 93.1%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8471TriethylamineSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of 2-bromo-4-chloro-1-methoxybenzene (1 g, 4.5 mmol), CuI (43 mg, 0.23 mmol), Pd(PPh3)2Cl2 (0.16 g, 0.23 mmol) in NEt3 (10 mL) was degassed, Then ethynyltrimethylsilane (0.5 g, 5 mmol) was added to the solution, the mixture was stirred at 80° C. for 6 hours. Then the mixture was cooled to 25° C., and added to H2O (50 mL). The mixture was extracted with ethyl acetate and washed with brine, dried over Na2SO4. After the combined organic layers were concentrated, the resulting residue was purified using prep-TLC (petroleum ether:EtOAc=10:1) to provide the product of ((5-chloro-2-methoxyphenyl)ethynyl)trimethylsilane (1 g, yield: 90%). 1H-NMR (CDCl3, 400 MHz) δ 7.40 (s, 1H), 7.21˜7.23 (m, 1H), 6.76˜6.78 (d, J=9.2 Hz, 1H), 3.86 (s, 3H), 0.26 (s, 9H). MS (M+H)+: 239/241

Workup

  1. customwas degassed
  2. temperatureThen the mixture was cooled to 25° C.
  3. extractionThe mixture was extracted with ethyl acetate
  4. washwashed with brine
  5. dry with materialdried over Na2SO4
  6. concentrationAfter the combined organic layers were concentrated
  7. customthe resulting residue was purified

Sources & evidence

ORD record
ord-bd6d26af1cbb469bbb279876016dfbe9
Source dataset
uspto-grants-2016_02
Patent number
US09265773B2

Reaction notes

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