Trimethylsilylacetylene → 3-Nitro-5-((trimethylsilyl)ethynyl)pyridine

HRID 2271653

Reaction equation

HRID 2271653 reaction equation
Br[C:2]1[CH:3]=[N:4][CH:5]=[C:6]([N+:8]([O-:10])=[O:9])[CH:7]=1.[C:11]([Si:13]([CH3:16])([CH3:15])[CH3:14])#[CH:12]>C(N(CC)CC)C.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.[Cu](I)I>[N+:8]([C:6]1[CH:5]=[N:4][CH:3]=[C:2]([C:12]#[C:11][Si:13]([CH3:16])([CH3:15])[CH3:14])[CH:7]=1)([O-:10])=[O:9]

Participants

6

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 27628983-Bromo-5-nitropyridine

Product 1

HCID 667157023-Nitro-5-((trimethylsilyl)ethynyl)pyridineYield 159.3%

Reagents, catalysts & solvents 3

HCID 83717Copper iodideCatalystHCID 178418397HCID 178418397, compoundCatalystHCID 8471TriethylamineSolvent

Conditions

Temperature
80 °C

Procedure

To a suspension of 3-bromo-5-nitropyridine (1.0 g, 4.90 mmol), Pd(Ph3P)4 (0.57 g, 0.49 mmol), and copper iodide (0.19 g, 0.98 mmol) in triethylamine (30 mL) was added ethynyltrimethylsilane (1.0 mL, 7.35 mmol) and the reaction was purged with N2. The mixture was stirred at 80° C. for 2 h. The reaction mixture was filtered through celite and washed with ethyl acetate. The filtrate was washed with saturated solutions of NaHCO3 and NaCl. The organic layer was concentrated to afford the crude product (1.72 g) as a light brown solid: ESI MS m/z 221 [C10H12N2O2Si+H]+.

Workup

  1. customthe reaction was purged with N2
  2. filtrationThe reaction mixture was filtered through celite
  3. washwashed with ethyl acetate
  4. washThe filtrate was washed with saturated solutions of NaHCO3 and NaCl
  5. concentrationThe organic layer was concentrated

Sources & evidence

ORD record
ord-ca7f18693e3641b992c4d5a3cef535c2
Source dataset
uspto-grants-2015_09
Patent number
US09120749B2

Linked notes

Loading…