N,N'-Dimethylethylenediamine → (5-Phenylethynyl-pyridin-3-yl)-carbamic acid tert-butyl ester

HRID 606918Notes

Reaction equation

HRID 606918 reaction equation
Br[C:2]1[CH:3]=[N:4][CH:5]=[C:6]([C:8]#[C:9][C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)[CH:7]=1.C(=O)([O-])[O-].[K+].[K+].[C:22]([O:26][C:27](=[O:29])[NH2:28])([CH3:25])([CH3:24])[CH3:23].CNCCNC>O1CCOCC1.[Cu]I>[C:22]([O:26][C:27](=[O:29])[NH:28][C:2]1[CH:3]=[N:4][CH:5]=[C:6]([C:8]#[C:9][C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)[CH:7]=1)([CH3:25])([CH3:24])[CH3:23]

Participants

7

Reactant 4

HCID 8070N,N'-DimethylethylenediamineHCID 11430Potassium CarbonateHCID 77922tert-Butyl carbamateHCID 670476693-Bromo-5-phenylethynylpyridine

Product 1

HCID 49855802(5-Phenylethynyl-pyridin-3-yl)-carbamic acid tert-butyl esterYield 15%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 312751,4-DioxaneSolvent

Procedure

Stir a mixture of 3-bromo-5-phenylethynyl-pyridine, (prepared as described in EXAMPLE 9), (2.5 g, 10 mmol), copper (I) iodide (0.190 g, 1 mmol), potassium carbonate (2.76 g, 20 mmol), carbamic acid tert-butyl ester (1.17 g, 10 mmol), N,N′-dimethylethylenediamine (0.220 mL, 2 mmol) in 1,4-dioxane (10 mL) at 110° C. in a sealed tube for 36 h. Cool to room temperature and concentrate. Purify by silica gel chromatography, eluting with 100:0 dichloromethane:methanol to 90:10 dichloromethane:methanol, and then crystallizing from ethyl acetate to give the title compound (430 mg, 15%).

Workup

  1. concentrationconcentrate
  2. customPurify by silica gel chromatography
  3. washeluting with 100:0 dichloromethane
  4. custommethanol to 90:10 dichloromethane:methanol, and then crystallizing from ethyl acetate

Sources & evidence

ORD record
ord-c949d68c555b4891a2a383ab2a0f2a1a
Source dataset
uspto-grants-2011_03
Patent number
US07915424B2

Reaction notes

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