Benzene, 1-chloro-4-ethynyl- → 3-[(p-chlorophenyl)ethynyl]-8-fluoro-4,5-dihydro-5-methyl-6H-imidazo[1,5-a][1,4]benzodiazepin-6-one

HRID 1607004Notes

Reaction equation

HRID 1607004 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.[Cl:19][C:20]1[CH:25]=[CH:24][C:23]([C:26]#[CH:27])=[CH:22][CH:21]=1>C(NCC)C.C(Cl)Cl.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>[Cl:19][C:20]1[CH:25]=[CH:24][C:23]([C:26]#[C:27][C:14]2[N:13]=[CH:12][N:11]3[C:5]4[CH:4]=[CH:3][C:2]([F:1])=[CH:18][C:6]=4[C:7](=[O:17])[N:8]([CH3:16])[CH2:9][C:10]=23)=[CH:22][CH:21]=1

Participants

7

Reactant 2

HCID 70118Benzene, 1-chloro-4-ethynyl-HCID 198306858-fluoro-4,5-dihydro-3-iodo-5-methyl-6H-imidazo[1,5-a][1,4]benzodiazepin-6-one

Product 1

HCID 198515413-[(p-chlorophenyl)ethynyl]-8-fluoro-4,5-dihydro-5-methyl-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 6344DichloromethaneSolventHCID 8021DiethylamineSolvent

Procedure

3.6 g (10 mmol) of 8-fluoro-4,5-dihydro-3-iodo-5-methyl-6H-imidazo[1,5-a][1,4]benzodiazepin-6-one was stirred at room temperature for 16 hours with 1.5 g (11 mmol) of p-chlorophenylacetylene, 70 mg of bis-(triphenylphosphine)-palladium(II) dichloride and 15 mg of copper(I) iodide in 35 ml of diethylamine. The reaction mixture was diluted with 175 ml of methylene chloride and washed three times with water. The organic phase was dried over magnesium sulphate and evaporated. By chromatography of the residue on silica gel and subsequent recrystallization from methylene chloride and ethyl acetate there was obtained 3-[(p-chlorophenyl)ethynyl]-8-fluoro-4,5-dihydro-5-methyl-6H-imidazo[1,5-a][1,4]benzodiazepin-6-one of melting point 221°-222°.

Workup

  1. washwashed three times with water
  2. dry with materialThe organic phase was dried over magnesium sulphate
  3. customevaporated
  4. customBy chromatography of the residue on silica gel and subsequent recrystallization from methylene chloride

Sources & evidence

ORD record
ord-1774a280085544d59b064a2ec39faafd
Source dataset
uspto-grants-1989_09
Patent number
US04863920

Reaction notes

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