HCID 53705407, compound → HCID 54006089, compound

HRID 1154478Notes

Reaction equation

HRID 1154478 reaction equation
[Cl:1][C:2]1[C:7]2[C:8](=[O:25])[N:9]3[CH2:24][CH2:23][C@H:10]3[C:11]3[N:12]([CH:13]=[N:14][C:15]=3[C:16]([O:18]C(C)(C)C)=[O:17])[C:6]=2[CH:5]=[CH:4][CH:3]=1>CCO.CCO.CCO.CCO.[Ti].C(O)C1C=CC=CC=1>[Cl:1][C:2]1[C:7]2[C:8](=[O:25])[N:9]3[CH2:24][CH2:23][C@H:10]3[C:11]3[N:12]([CH:13]=[N:14][C:15]=3[C:16]([O:18][CH2:8][C:7]3[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=3)=[O:17])[C:6]=2[CH:5]=[CH:4][CH:3]=1

Participants

4

Reactant 1

HCID 53705407HCID 53705407, compound

Product 1

HCID 54006089HCID 54006089, compound

Reagents, catalysts & solvents 2

HCID 2724286Titanium(IV)ethoxideCatalystHCID 244Benzyl AlcoholSolvent

Procedure

A mixture of 3.59 g (10 mmol) of tert.butyl (S)-8-chloro-12,12a-dihydro-9-oxo-9H,11H-azeto[2,1-c]imidazo[1,5-a][1,4]benzodiazepine-1-carboxylate, 1.5 g (6 mmol) of tetraethyl orthotitanate and 30 ml of benzyl alcohol is stirred at 130° for 6 hours, a small amount of solvent being distilled off in vacuo twice. The mixture is subsequently evaporated in a high vacuum, the residue is taken up in 40 ml of chloroform, the solution is treated with 40 ml of concentrated hydrochloric acid/water (1:1) and the mixture is stirred until both phases are clear. The chloroform solution is washed successively with 20 ml of 1N hydrochloric acid and saturated sodium bicarbonate solution, dried over magnesium sulphate and evaporated to dryness. The residue is crystallized from ethyl acetate and there is obtained benzyl (S)-8-chloro-12,12a-dihydro-9-oxo-9H,11H-azeto[2,1-c]imidazo[1,5-a][1,4]benzodiazepine-1-carboxylate of melting point 180°-182°.

Workup

  1. distillationa small amount of solvent being distilled off in vacuo twice
  2. customThe mixture is subsequently evaporated in a high vacuum
  3. additionthe solution is treated with 40 ml of concentrated hydrochloric acid/water (1:1)
  4. stirringthe mixture is stirred until both phases
  5. washThe chloroform solution is washed successively with 20 ml of 1N hydrochloric acid and saturated sodium bicarbonate solution
  6. dry with materialdried over magnesium sulphate
  7. customevaporated to dryness
  8. customThe residue is crystallized from ethyl acetate

Sources & evidence

ORD record
ord-3a3c9287f5a14431bbd9d6ad12fc9578
Source dataset
uspto-grants-1984_12
Patent number
US04489003

Reaction notes

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