N-methyl-2-pyrrolidone → 2,6-Pyridinediamine, 3-[2-(trimethylsilyl)ethynyl]-

HRID 1927218Notes

Reaction equation

HRID 1927218 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].C(N(CC)C(C)C)(C)C.CN1C(=O)CCC1>[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.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

8

Reactant 4

HCID 13387N-methyl-2-pyrrolidoneHCID 66111TrimethylsilylacetyleneHCID 81531DiisopropylethylamineHCID 4762183-Iodopyridine-2,6-diamine

Product 1

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

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolvent

Procedure

To a mixture of 3-iodo-pyridin-2,6-diamine (20 g) described in Manufacturing Example 4-1, trimethylsilyl acetylene (24 mL), copper(I) iodide (3.3 g), N,N-diisopropylethylamine (19 g), and NMP (290 mL) was added tetrakis(triphenylphosphine)palladium(0) (9.8 g), which was stirred for 30 minutes at room temperature under an argon atmosphere. Water was added to the reaction solution, which was then extracted with ethyl acetate. The ethyl acetate layer thus obtained was washed with water 4 times and dried over sodium sulfate. The sodium sulfate was filtered off, the solvent was evaporated under a reduced pressure, and the residue was purified by NH silica gel chromatography (heptane:ethyl acetate=4:1, then 1:1). The eluate was concentrated under a reduced pressure, and the resulting solids were washed with heptane containing a small amount of ethyl acetate to obtain the titled compound (11 g).

Workup

  1. extractionwas then extracted with ethyl acetate
  2. customThe ethyl acetate layer thus obtained
  3. washwas washed with water 4 times
  4. dry with materialdried over sodium sulfate
  5. filtrationThe sodium sulfate was filtered off
  6. customthe solvent was evaporated under a reduced pressure
  7. customthe residue was purified by NH silica gel chromatography (heptane
  8. concentrationThe eluate was concentrated under a reduced pressure
  9. washthe resulting solids were washed with heptane containing a small amount of ethyl acetate

Sources & evidence

ORD record
ord-24b1304f66654284a21d37cb06dbd23e
Source dataset
uspto-grants-2012_05
Patent number
US08183264B2

Reaction notes

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