Trimethylsilylacetylene → HCID 178463856, compound

HRID 1011922Notes

Reaction equation

HRID 1011922 reaction equation
Br[C:2]1[CH:3]=[C:4]([C:8]2[NH:12][N:11]=[C:10]([C:13]([N:15]3[CH2:19][CH2:18][CH:17]([N:20]([CH2:23][CH3:24])[CH2:21][CH3:22])[CH2:16]3)=[O:14])[C:9]=2[CH3:25])[CH:5]=[CH:6][CH:7]=1.[C:26]([Si:28]([CH3:31])([CH3:30])[CH3:29])#[CH:27]>N1CCCCC1.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>[CH2:21]([N:20]([CH2:23][CH3:24])[CH:17]1[CH2:18][CH2:19][N:15]([C:13]([C:10]2[C:9]([CH3:25])=[C:8]([C:4]3[CH:5]=[CH:6][CH:7]=[C:2]([C:27]#[C:26][Si:28]([CH3:31])([CH3:30])[CH3:29])[CH:3]=3)[NH:12][N:11]=2)=[O:14])[CH2:16]1)[CH3:22]

Participants

6

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 178463850HCID 178463850, compound

Product 1

HCID 178463856HCID 178463856, compoundYield 64%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 8082PiperidineSolvent2×

Conditions

Temperature
50 °C

Procedure

The synthesis was performed following a procedure of Stara, Irena G.; Stary, Ivo; Kollarovic, Adrian; Teply, Filip; Saman, David; Fiedler, Pavel. Coupling reactions of halobenzenes with alkynes. The synthesis of phenylacetylenes and symmetrical or unsymmetrical 1,2-diphenylacetylenes. Collect. Czech. Chem. Commun. (1999), 64(4), 649-672. A solution of 0.405 g (1.00 mmol) of [5-(3-bromo-phenyl)-4-methyl-1H-pyrazol-3-yl]-(3-diethylamino-pyrrolidin-1-yl)-methanone in 5 ml piperidine was degassed (argon) and treated with 58 mg (0.05 mmol) Pd(PPh3)4 and 10 mg (0.05 mmol) CuI. The reaction mixture was stirred at 50° C. for 10 min and then slowly (60 min) treated with 0.17 ml (1.20 mmol) of ethynyltrimethylsilane in 5 ml piperidine. After 30 min the bath was slowly (30 min) heated to 80° C. The reaction mixture was stirred at this temperature for 2.5 h and then partitioned between chilled water sat. KHCO3/EtOAc (3×). The organic phases were washed with aqueous 10% NaCl, dried (Na2SO4) and evaporated. Purification by flash-chromatography on silica gel (CH2Cl2/MeOH 98:2 to 92:8) yielded 0.27 g (64%) of the title compound as yellow viscous oil. MS: 423.3 (MH+).

Workup

  1. customCollect
  2. waitAfter 30 min the bath was slowly
  3. temperature(30 min) heated to 80° C
  4. stirringThe reaction mixture was stirred at this temperature for 2.5 h
  5. custompartitioned
  6. temperaturebetween chilled water sat. KHCO3/EtOAc (3×)
  7. washThe organic phases were washed with aqueous 10% NaCl
  8. dry with materialdried (Na2SO4)
  9. customevaporated
  10. customPurification by flash-chromatography on silica gel (CH2Cl2/MeOH 98:2 to 92:8)

Sources & evidence

ORD record
ord-5af757eecc3844ea9578dd78e156a590
Source dataset
uspto-grants-2011_07
Patent number
US07977358B2

Reaction notes

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