Trimethylsilylacetylene → HCID 86222791, compound

HRID 475271Notes

Reaction equation

HRID 475271 reaction equation
[NH2:1][C:2]1[C:9](I)=[CH:8][C:5]([C:6]#[N:7])=[C:4]([Cl:11])[CH:3]=1.CCN(C(C)C)C(C)C.[C:21]([Si:23]([CH3:26])([CH3:25])[CH3:24])#[CH:22]>[Cu]I>[NH2:1][C:2]1[C:9]([C:22]#[C:21][Si:23]([CH3:26])([CH3:25])[CH3:24])=[CH:8][C:5]([C:6]#[N:7])=[C:4]([Cl:11])[CH:3]=1

Participants

5

Reactant 3

HCID 66111TrimethylsilylacetyleneHCID 81531DiisopropylethylamineHCID 109128704-amino-2-chloro-5-iodobenzonitrile

Product 1

HCID 86222791HCID 86222791, compoundYield 48.2%

Reagents, catalysts & solvents 1

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)Catalyst

Conditions

Temperature
70 °C

Procedure

A round bottom bottle was charged with 236 (2.78 g, 0.01 mol), CuI (95 mg, 0.5 mmol), Pd(PPh3)Cl2 (200 mg, 0.5 mmol), DIPEA (3.87 g, 0.03 mol) and ethynyltrimethylsilane (2.94 g, 0.03 mol). The mixture was heated under nitrogen atmosphere at 70° C. overnight then cooled and partitioned between EtOAc (500 mL) and H2O (100 mL). The organic layer was concentrated to dryness in vacuo. The crude was purified by SiO2 chromatography eluting with 10% EtOAc/petroleum ether to afford 1.2 g (48%) of 4-amino-2-chloro-5-((trimethylsilyl)ethynyl)benzonitrile (238) as brown solid: MS (ESI) m/z=249.1 [M+1]+

Workup

  1. temperaturethen cooled
  2. custompartitioned between EtOAc (500 mL) and H2O (100 mL)
  3. concentrationThe organic layer was concentrated to dryness in vacuo
  4. customThe crude was purified by SiO2 chromatography
  5. washeluting with 10% EtOAc/petroleum ether

Sources & evidence

ORD record
ord-2f72a036910d4624a235a422db855eee
Source dataset
uspto-grants-2014_01
Patent number
US08637537B2

Reaction notes

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