4-Nitrobenzyl chloroformate → HCID 22881641, compound

HRID 362023Notes

Reaction equation

HRID 362023 reaction equation
[CH3:1][O:2][C:3]1[CH:37]=[CH:36][C:6]([CH2:7][S:8][C@@H:9]2[CH2:13][NH:12][C@@:11]([C:27]([N:29]3[CH2:34][CH2:33][NH:32][CH2:31][CH:30]3[CH3:35])=[O:28])(C(OCC3C=CC([N+]([O-])=O)=CC=3)=O)[CH2:10]2)=[CH:5][CH:4]=1.Cl[C:39]([O:41][CH2:42][C:43]1[CH:48]=[CH:47][C:46]([N+:49]([O-:51])=[O:50])=[CH:45][CH:44]=1)=[O:40]>CN(C)C1C=CN=CC=1.C(#N)C>[CH3:1][O:2][C:3]1[CH:4]=[CH:5][C:6]([CH2:7][S:8][C@@H:9]2[CH2:13][N:12]([C:39]([O:41][CH2:42][C:43]3[CH:48]=[CH:47][C:46]([N+:49]([O-:51])=[O:50])=[CH:45][CH:44]=3)=[O:40])[C@H:11]([C:27]([N:29]3[CH2:34][CH2:33][N:32]([C:39]([O:41][CH2:42][C:43]4[CH:44]=[CH:45][C:46]([N+:49]([O-:51])=[O:50])=[CH:47][CH:48]=4)=[O:40])[CH2:31][CH:30]3[CH3:35])=[O:28])[CH2:10]2)=[CH:36][CH:37]=1

Participants

5

Reactant 2

HCID 782054-Nitrobenzyl chloroformateHCID 54382369HCID 54382369, compound

Product 1

HCID 22881641HCID 22881641, compoundYield 154.3%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6342AcetonitrileSolvent2×

Procedure

0.51 g of 4-dimethylaminopyridine was added dropwise at room temperature to a solution of 1.83 g of (2S,4S)-4-(4-methoxybenzylthio)-2-(2-methylpiperazin-1-yl-carbonyl)-2-(4-nitrobenzyloxycarbonyl)pyrrolidine [prepared as described in step (ii) above] in 25 ml of dry acetonitrile, and then a solution of 0.90 g of 4-nitrobenzyl chloroformate in 15 ml of dry acetonitrile was added dropwise to the resulting mixture, whilst ice-cooling. The reaction mixture was stirred at room temperature for 30 minutes, after which it was concentrated by evaporation under reduced pressure, and the residue was diluted with ethyl acetate. The diluted solution was washed with water and with an aqueous solution of sodium chloride, in that order, after which it was dried over anhydrous magnesium sulfate. The solvent was removed by distillation under reduced pressure, and the resulting residue was purified by column chromatography through silica gel, using a 7:3 by volume mixture of ethyl acetate and cyclohexane as the eluent, to give 2.28 g of the title compound, as an amorphous solid.

Workup

  1. temperaturecooling
  2. concentrationafter which it was concentrated by evaporation under reduced pressure
  3. additionthe residue was diluted with ethyl acetate
  4. washThe diluted solution was washed with water and with an aqueous solution of sodium chloride, in that order
  5. dry with materialafter which it was dried over anhydrous magnesium sulfate
  6. customThe solvent was removed by distillation under reduced pressure
  7. customthe resulting residue was purified by column chromatography through silica gel
  8. additionby volume mixture of ethyl acetate and cyclohexane as the eluent

Sources & evidence

ORD record
ord-7273118bf4fc43feafba655a1866d75f
Source dataset
uspto-grants-1999_02
Patent number
US05866564

Reaction notes

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