Water → 3-(Trimethylsilylethynyl)pyridine

HRID 2362350

Reaction equation

HRID 2362350 reaction equation
Br[C:2]1[CH:3]=[N:4][CH:5]=[CH:6][CH:7]=1.C(N(CC)CC)C.[C:15]([Si:17]([CH3:20])([CH3:19])[CH3:18])#[CH:16].O>C(OCC)(=O)C.[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>[CH3:18][Si:17]([C:15]#[C:16][C:2]1[CH:3]=[N:4][CH:5]=[CH:6][CH:7]=1)([CH3:20])[CH3:19]

Participants

8

Reactant 4

HCID 962WaterHCID 8471TriethylamineHCID 122863-BromopyridineHCID 66111Trimethylsilylacetylene

Product 1

HCID 41008573-(Trimethylsilylethynyl)pyridine

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8857Ethyl AcetateSolvent

Procedure

A flask was charged with 3-bromopyridine (1.22 mL, 12.66 mmol) and triethylamine (40 mL) and sparged with nitrogen for 15 min. To this was added ethynyltrimethylsilane (1.97 mL, 13.92 mmol) and the reaction purged 15 min longer. To this was added copper(I) iodide (0.121 g, 0.633 mmol), and Pd(PPh3)2Cl2 (0.444 g, 0.633 mmol). The reaction was stirred at room temperature for 72 h. The reaction was diluted with ethyl acetate (60 mL) and poured into water. The black heterogeneous emulsion was filtered through a plug of celite and the layers separated. The organics were washed with brine, dried over magnesium sulfate, and concentrated. Column chromatography (5%-->15% EtOAc/Hex) gave 1.70 g (77%) as a dark oil. 1H-NMR (CDCl3, 500 MHz) δ 8.71 (m, 1H), 8.55 (dd, J=4.9, 1.5, 1H), 7.76 (ddd, J=7.9, 1.8, 1.8, 1H), 7.26 (ddd, J=7.9, 4.9, 0.6, 1H), 0.29 (s, 9H). 13C-NMR (CDCl3, 126 MHz) δ 152.8, 148.8, 138.9, 123.0, 120.4, 101.6, 98.3, −0.1. Mass spec.: 176.14 (MH)+.

Workup

  1. customsparged with nitrogen for 15 min
  2. customthe reaction purged 15 min longer
  3. filtrationThe black heterogeneous emulsion was filtered through a plug of celite
  4. customthe layers separated
  5. washThe organics were washed with brine
  6. dry with materialdried over magnesium sulfate
  7. concentrationconcentrated
  8. customColumn chromatography (5%-->15% EtOAc/Hex) gave 1.70 g (77%) as a dark oil

Sources & evidence

ORD record
ord-c3bbe896a5504bda80c5ea93decad170
Source dataset
uspto-grants-2014_04
Patent number
US08691821B2

Linked notes

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