Trimethylsilylacetylene → Methyl 3-[(dipropylamino)carbonyl]-5-ethynylbenzoate

HRID 1350979Notes

Reaction equation

HRID 1350979 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH:9]=[C:10]([C:12]([N:14]([CH2:18][CH2:19][CH3:20])[CH2:15][CH2:16][CH3:17])=[O:13])[CH:11]=1)[C:5]([O:7][CH3:8])=[O:6].C[Si]([C:25]#[CH:26])(C)C>C(N(CC)CC)C.O.[Cu]I>[CH2:15]([N:14]([CH2:18][CH2:19][CH3:20])[C:12]([C:10]1[CH:9]=[C:4]([CH:3]=[C:2]([C:25]#[CH:26])[CH:11]=1)[C:5]([O:7][CH3:8])=[O:6])=[O:13])[CH2:16][CH3:17]

Participants

6

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 21939662Methyl 3-bromo-5-(dipropylcarbamoyl)benzoate

Product 1

HCID 21086178Methyl 3-[(dipropylamino)carbonyl]-5-ethynylbenzoateYield 111.3%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 962WaterSolventHCID 8471TriethylamineSolvent

Procedure

A mixture of methyl 3-bromo-5-[(dipropylamino)carbonyl]benzoate (XXI, 200 mg, 0.58 mmol), PdCl2(Ph3P)2 (16 mg, 0.03 mol %) and copper (I) iodide (6 mg, 0.05 mol %/o) in triethylamine (1.2 mL) is heated to reflux. (Trimethylsilyl) acetylene (100 microliter, 0.7 mmol) is added, and the mixture stirred for 3 hours, cooled to 20–25 degrees, diluted with water (20 mL), and extracted with chloroform (3×15 mL). The combined organic extracts are washed with saline (20 mL), dried over sodium sulfate and concentrated under reduced pressure to give methyl 3-[(dipropylamino)carbonyl]-5-ethynylbenzoate (XXXII, 185.5 mg), NMR (300 MHz, CDCl3): δ 7.95, 7.75, 7.43, 3.74, 3.25, 2.95, 1.49, 1.34, 0.79, 0.56 and 0.06.

Workup

  1. temperatureis heated to reflux
  2. temperaturecooled to 20–25 degrees
  3. extractionextracted with chloroform (3×15 mL)
  4. washThe combined organic extracts are washed with saline (20 mL)
  5. dry with materialdried over sodium sulfate
  6. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-ec402dbea02746099bc3fcbab6f76891
Source dataset
uspto-grants-2007_05
Patent number
US07214715B2

Reaction notes

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