Water → 2-Methyl-4-(2-(trimethylsilyl)ethynyl)-1,3-thiazole

HRID 2362352Notes

Reaction equation

HRID 2362352 reaction equation
Br[C:2]1[N:3]=[C:4]([CH3:7])[S:5][CH:6]=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>[CH3:7][C:4]1[S:5][CH:6]=[C:2]([C:16]#[C:15][Si:17]([CH3:20])([CH3:19])[CH3:18])[N:3]=1

Participants

8

Reactant 4

HCID 962WaterHCID 8471TriethylamineHCID 66111TrimethylsilylacetyleneHCID 27631864-Bromo-2-methyl-1,3-thiazole

Product 1

HCID 109214422-Methyl-4-(2-(trimethylsilyl)ethynyl)-1,3-thiazole

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 4-bromo-2-methylthiazole (400 mg, 2.247 mmol) and triethylamine (8 mL) and sparged with nitrogen for 15 min. To this was added ethynyltrimethylsilane (0.381 mL, 2.70 mmol) and purged 15 min longer. To this was added copper(I) iodide (21.39 mg, 0.112 mmol), and Pd(PPh3)2Cl2 (79 mg, 0.112 mmol). The reaction stirred at room temperature for 72 h. The reaction was diluted with ethyl acetate (16 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%-->6% EtOAc/Hex) gave 307 mg (70%) as a light amber oil. 1H-NMR (CDCl3, 500 MHz) δ 7.34 (s, 1H), 2.72 (s, 3H), 0.27 (s, 9H). 13C-NMR (CDCl3, 126 MHz) δ 165.6, 137.0, 123.0, 98.4, 94.6, 19.3, −0.1.

Workup

  1. customsparged with nitrogen for 15 min
  2. custompurged 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%-->6% EtOAc/Hex) gave 307 mg (70%) as a light amber oil

Sources & evidence

ORD record
ord-d16afa3cde9f41afa3155c1e69a656a3
Source dataset
uspto-grants-2014_04
Patent number
US08691821B2

Reaction notes

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