Phenylacetylene → HCID 19851598, compound

HRID 1607027Notes

Reaction equation

HRID 1607027 reaction equation
I[C:2]1[N:3]=[CH:4][N:5]2[C:11]3[S:12](=O)[CH:13]=[CH:14][C:10]=3[CH2:9][N:8]([CH3:16])[CH2:7][C:6]=12.[C:17]1([C:23]#[CH:24])[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1>C(NCC)C.CN(C)C=O.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>[CH3:16][N:8]1[CH2:9][C:10]2[CH:14]=[CH:13][S:12][C:11]=2[N:5]2[CH:4]=[N:3][C:2]([C:24]#[C:23][C:17]3[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=3)=[C:6]2[CH2:7]1

Participants

7

Reactant 2

HCID 10821PhenylacetyleneHCID 70394533HCID 70394533, compound

Product 1

HCID 19851598HCID 19851598, compound

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 6228DimethylformamideSolventHCID 8021DiethylamineSolvent

Procedure

5.1 g of 5,6-dihydro-7-iodo-5-methyl-4H-imidazo[1,5-a]thieno[3,2-f][1,4]diazepine-one (prepared in accordance with Example 73) was dissolved in 47 ml of diethylamine and 20 ml of dimethylformamide. 1.75 ml of phenylacetylene, 105 mg of bis-(triphenylphosphine)-palladium(II) chloride and 17 mg of copper(I) iodide were then added. The mixture was stirred at room temperature for 2 hours and then concentrated in a vacuum. The residue was diluted with 200 ml of dichloromethane and washed twice with water. The aqueous washings were extracted twice with dichloromethane. The combined dichloromethane solutions were dried over sodium sulphate and chromatographed through 300 g of silica gel. Elution was carried out first with trichloromethane and trichloromethane/ethanol mixtures 199:1 and 99:1. There was then eluted with a trichloromethane/ethanol mixture 97:3 an oily substance which can be crystallized from isopropanol/water. After repeated recrystallizations from isopropanol/water there was obtained 5,6-dihydro-5-methyl-7-(phenylethynyl)-4H-imidazo[1,5-a]thieno[3,2-f][1,4]diazepine one of melting point 143°-144°.

Workup

  1. concentrationconcentrated in a vacuum
  2. additionThe residue was diluted with 200 ml of dichloromethane
  3. washwashed twice with water
  4. extractionThe aqueous washings were extracted twice with dichloromethane
  5. dry with materialThe combined dichloromethane solutions were dried over sodium sulphate
  6. customchromatographed through 300 g of silica gel
  7. washElution
  8. washThere was then eluted with a trichloromethane/ethanol mixture 97:3 an oily substance which
  9. customcan be crystallized from isopropanol/water
  10. customrecrystallizations from isopropanol/water there

Sources & evidence

ORD record
ord-8a62aaf8f08e4273b7f0fc33d7ebf1c2
Source dataset
uspto-grants-1989_09
Patent number
US04863920

Reaction notes

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