Trimethylsilylacetylene → 8-fluoro-4,5-dihydro-5-methyl-3-[(trimethylsilyl)ethynyl]-6H-imidazo-[1,5-a][1,4]benzodiazepin-6-one

HRID 1607010Notes

Reaction equation

HRID 1607010 reaction equation
[F:1][C:2]1[CH:3]=[CH:4][C:5]2[N:11]3[CH:12]=[N:13][C:14](I)=[C:10]3[CH2:9][N:8]([CH3:16])[C:7](=[O:17])[C:6]=2[CH:18]=1.[C:19]([Si:21]([CH3:24])([CH3:23])[CH3:22])#[CH:20]>C(NCC)C.C(Cl)CCl.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I>[F:1][C:2]1[CH:3]=[CH:4][C:5]2[N:11]3[CH:12]=[N:13][C:14]([C:20]#[C:19][Si:21]([CH3:24])([CH3:23])[CH3:22])=[C:10]3[CH2:9][N:8]([CH3:16])[C:7](=[O:17])[C:6]=2[CH:18]=1

Participants

7

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 198306858-fluoro-4,5-dihydro-3-iodo-5-methyl-6H-imidazo[1,5-a][1,4]benzodiazepin-6-one

Product 1

HCID 198515228-fluoro-4,5-dihydro-5-methyl-3-[(trimethylsilyl)ethynyl]-6H-imidazo-[1,5-a][1,4]benzodiazepin-6-one

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 111,2-DichloroethaneSolventHCID 8021DiethylamineSolvent

Procedure

67.8 g (190 mmol) of 8-fluoro-4,5-dihydro-3-iodo-5-methyl-6H-imidazo[1,5-a][1,4]benzodiazepin-6-one was heated to boiling under reflux for 8 hours with 23.4 g (238 mmol) of ethynyltrimethylsilane, 300 mg of bis-(triphenylphosphine)-palladium(II) dichloride and 70 mg of copper(I) iodide in 280 ml of diethylamine and 25 ml of ethylene chloride. The reaction mixture was evaporated and the residue was chromatographed on silica gel while eluting with chloroform/ethyl acetate (3:1). By recrystallization from ethyl acetate there was obtained 8-fluoro-4,5-dihydro-5-methyl-3-[(trimethylsilyl)ethynyl]-6H-imidazo-[1,5-a][1,4]benzodiazepin-6-one of melting point 184°-185°.

Workup

  1. customThe reaction mixture was evaporated
  2. customthe residue was chromatographed on silica gel
  3. washwhile eluting with chloroform/ethyl acetate (3:1)
  4. customBy recrystallization from ethyl acetate

Sources & evidence

ORD record
ord-5e0a726eae744e7d984a76fc22f55f1c
Source dataset
uspto-grants-1989_09
Patent number
US04863920

Reaction notes

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