Trimethylsilylacetylene → 2,6-Pyridinediamine, 3-[2-(trimethylsilyl)ethynyl]-

HRID 1891554Notes

Reaction equation

HRID 1891554 reaction equation
I[C:2]1[C:3]([NH2:9])=[N:4][C:5]([NH2:8])=[CH:6][CH:7]=1.[CH3:10][Si:11]([C:14]#[CH:15])([CH3:13])[CH3:12]>[Cu]I.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CN1CCCC1=O>[CH3:10][Si:11]([C:14]#[C:15][C:2]1[C:3]([NH2:9])=[N:4][C:5]([NH2:8])=[CH:6][CH:7]=1)([CH3:13])[CH3:12]

Participants

6

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 4762183-Iodopyridine-2,6-diamine

Product 1

HCID 592554712,6-Pyridinediamine, 3-[2-(trimethylsilyl)ethynyl]-Yield 60%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 13387N-methyl-2-pyrrolidoneSolvent

Procedure

To a mixture of 3-iodo-pyridin-2,6-diamine (20.0 g, 85.2 mmol) described in Manufacturing Example 13-1-1, trimethylsilyl acetylene (24.2 mL, 170 mmol), copper (I) iodide (3.25 g, 17.0 mmol) N,N-diisopropylethylamine (19.1 g, 148 mmol) and N-methylpyrrolidinone (286 mL) was added tetrakis(triphenylphosphine)palladium (0) (9.81 g, 8.52 mmol) under argon atmosphere, which was stirred for 30 minutes at room temperature. The reaction solution was partitioned into water and ethyl acetate. The ethyl acetate layer was washed with water 4 times and dried over sodium sulfate, and the solvent was evaporated under a reduced pressure. The residue was purified by NH silica gel chromatography (heptane:ethyl acetate=4:1 then 1:1). The solids obtained by concentrating the eluate under a reduced pressure were washed with heptane containing a small amount of ethyl acetate to obtain the title compound (10.5 g, 60.0%).

Workup

  1. customThe reaction solution was partitioned into water and ethyl acetate
  2. washThe ethyl acetate layer was washed with water 4 times
  3. dry with materialdried over sodium sulfate
  4. customthe solvent was evaporated under a reduced pressure
  5. customThe residue was purified by NH silica gel chromatography (heptane
  6. customThe solids obtained
  7. concentrationby concentrating the eluate under a reduced pressure
  8. washwere washed with heptane containing a small amount of ethyl acetate

Sources & evidence

ORD record
ord-657253b90dfc4240bf7087bfe2ec7f72
Source dataset
uspto-grants-2013_08
Patent number
US08507530B2

Reaction notes

Loading…