3-Methoxybenzyl alcohol → HCID 54543191, compound

HRID 1154495Notes

Reaction equation

HRID 1154495 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.[CH3:26][O:27][C:28]1[CH:29]=[C:30]([CH:33]=[CH:34][CH:35]=1)[CH2:31]O>CCO.CCO.CCO.CCO.[Ti]>[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][CH2:31][C:30]3[CH:33]=[CH:34][CH:35]=[C:28]([O:27][CH3:26])[CH:29]=3)=[O:17])[C:6]=2[CH:5]=[CH:4][CH:3]=1

Participants

4

Reactant 2

HCID 814373-Methoxybenzyl alcoholHCID 53705407HCID 53705407, compound

Product 1

HCID 54543191HCID 54543191, compound

Reagents, catalysts & solvents 1

HCID 2724286Titanium(IV)ethoxideCatalyst

Procedure

A mixture of 3.6 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, 1.7 g (7.2 mmol) of tetraethyl orthotitanate and 20 ml of 3-methoxybenzyl alcohol is stirred at 120° for 5 hours, a small amount of solvent being removed in vacuo three times during this time. The excess 3-methoxybenzyl alcohol is subsequently distilled off in a high vacuum, the residue is taken up in 30 ml of chloroform, the chloroform solution is treated with 25 ml of water, stirred for 1.25 hours and filtered through siliceous earth. The organic phase is separated, the aqueous phase is extracted once with chloroform, the combined chloroform extracts are dried over magnesium sulphate and evaporated. The crude product is chromatographed on silica gel while eluting with ethyl acetate. By recrystallization from ethyl acetate/n-hexane there is obtained m-methoxybenzyl (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 126°-127°.

Workup

  1. customa small amount of solvent being removed in vacuo three times during this time
  2. distillationThe excess 3-methoxybenzyl alcohol is subsequently distilled off in a high vacuum
  3. additionthe chloroform solution is treated with 25 ml of water
  4. stirringstirred for 1.25 hours
  5. filtrationfiltered through siliceous earth
  6. customThe organic phase is separated
  7. extractionthe aqueous phase is extracted once with chloroform
  8. dry with materialthe combined chloroform extracts are dried over magnesium sulphate
  9. customevaporated
  10. customThe crude product is chromatographed on silica gel
  11. washwhile eluting with ethyl acetate
  12. customBy recrystallization from ethyl acetate/n-hexane there

Sources & evidence

ORD record
ord-b6390e880c12413eb8f49d9060ef09a8
Source dataset
uspto-grants-1984_12
Patent number
US04489003

Reaction notes

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