2-Methyl-3-butyn-2-ol → HCID 70394546, compound

HRID 1607026Notes

Reaction equation

HRID 1607026 reaction equation
I[C:2]1[N:3]=[CH:4][N:5]2[C:11]3[S:12](=[O:15])[CH:13]=[CH:14][C:10]=3[CH2:9][N:8]([CH3:16])[CH2:7][C:6]=12.[CH3:17][C:18]([OH:22])([C:20]#[CH:21])[CH3:19]>C(NCC)C.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>[OH:22][C:18]([CH3:19])([CH3:17])[C:20]#[C:21][C:2]1[N:3]=[CH:4][N:5]2[C:11]3[S:12](=[O:15])[CH:13]=[CH:14][C:10]=3[CH2:9][N:8]([CH3:16])[CH2:7][C:6]=12

Participants

6

Reactant 2

HCID 82582-Methyl-3-butyn-2-olHCID 70394533HCID 70394533, compound

Product 1

HCID 70394546HCID 70394546, compound

Reagents, catalysts & solvents 3

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

Procedure

5.52 g of 5,6-dihydro-7-iodo-5-methyl-4H-imidazo[1,5-a]thieno[3,2-f][1,4]diazepine-one in 30 ml of diethylamine was treated with 1.92 ml of 2-methyl-3-butyn-2-ol, 75 mg of bis-(triphenylphosphine)-palladium(II) chloride and 13 mg of copper(I) iodide. The mixture was stirred at reflux temperature for 2 hours. The reaction mixture was then evaporated in a vacuum. The residue was dissolved in dichloromethane and this solution was washed twice with water. After drying over sodium sulphate this solution was chromatographed through 300 g of silica gel. Unreacted starting material was first recovered with dichloromethane/ethanol mixtures 99:1, 98:2 and 97:3. There was then eluted with dichloromethane/ethanol mixtures 96:4 and 95:5 an oily substance which crystallized from ethyl acelate/diethyl ether. There was obtained 5,6-dihydro-7-(3-hydroxy-3-methyl-1-butynyl)-5-methyl-4H-imidazo[1,5-a]-thieno[3,2-f][1,4]diazepine-one of melting point 180°-181°.

Workup

  1. temperatureat reflux temperature for 2 hours
  2. customThe reaction mixture was then evaporated in a vacuum
  3. dissolutionThe residue was dissolved in dichloromethane
  4. washthis solution was washed twice with water
  5. dry with materialAfter drying over sodium sulphate this solution
  6. customwas chromatographed through 300 g of silica gel
  7. customwas first recovered with dichloromethane/ethanol
  8. washThere was then eluted with dichloromethane/ethanol
  9. customcrystallized from ethyl acelate/diethyl ether

Sources & evidence

ORD record
ord-d120f6813d3e4908b1503625f82020a6
Source dataset
uspto-grants-1989_09
Patent number
US04863920

Reaction notes

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