Water → Trimethyl((2-nitrophenyl)ethynyl)silane

HRID 1817920Notes

Reaction equation

HRID 1817920 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[N+:8]([O-:10])=[O:9].[CH3:11][Si:12]([C:15]#[CH:16])([CH3:14])[CH3:13].O>C(N(CC)CC)C.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][Si:12]([CH3:14])([CH3:13])[C:15]#[C:16][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[N+:8]([O-:10])=[O:9]

Participants

7

Reactant 3

HCID 962WaterHCID 113411-Bromo-2-nitrobenzeneHCID 66111Trimethylsilylacetylene

Product 1

HCID 11333470Trimethyl((2-nitrophenyl)ethynyl)silaneYield 96%

Reagents, catalysts & solvents 3

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

Procedure

4 g (20 mmol) of ortho-bromonitrobenzene, 842 mg (1.2 mmol) of bis(triphenyl-phosphine)palladium(II) chloride and 230 mg (1.2 mmol) of copper(I) iodide were, under argon, initially charged in 40 ml of triethylamine. At room temperature, 2.95 g (30 mmol) of trimethylsilylacetylene were then added dropwise over a period of 10 min, and the mixture was stirred at room temperature for 2 days. The reaction mixture was poured into 50 ml of water and extracted three times with in each case 50 ml of diethyl ether, and the extracts were dried over sodium sulphate and concentrated. Column-chromatographic purification on silica gel 60 (mobile phase: cyclohexane/ethyl acetate 3:1) gave 4.2 g (96% of theory) of trimethyl-(2-nitrophenyl-ethynyl)silane [log P (pH 2.3)=4.12].

Workup

  1. extractionextracted three times with in each case 50 ml of diethyl ether
  2. dry with materialthe extracts were dried over sodium sulphate
  3. concentrationconcentrated
  4. customColumn-chromatographic purification on silica gel 60 (mobile phase: cyclohexane/ethyl acetate 3:1)

Sources & evidence

ORD record
ord-7ff16f9ba0e44e368e21d53d40c9fc6c
Source dataset
uspto-grants-2009_10
Patent number
US07598389B2

Reaction notes

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