4-Nitrobenzyl chloroformate → HCID 13219817, compound

HRID 1460442Notes

Reaction equation

HRID 1460442 reaction equation
C([N:4]([CH2:8][CH3:9])[CH:5]([CH3:7])C)(C)C.Cl.[SH:11]N.ClC[SiH3].Cl[C:17]([O:19][CH2:20][C:21]1[CH:26]=[CH:25][C:24]([N+:27]([O-:29])=[O:28])=[CH:23][CH:22]=1)=[O:18]>CC#N.CCOC(C)=O>[N+:27]([C:24]1[CH:25]=[CH:26][C:21]([CH2:20][O:19][C:17]([N:4]2[CH2:5][CH2:7][C@@H:9]([SH:11])[CH2:8]2)=[O:18])=[CH:22][CH:23]=1)([O-:29])=[O:28]

Participants

7

Reactant 4

HCID 782054-Nitrobenzyl chloroformateHCID 81531Diisopropylethylamine2×HCID 19981901HCID 19981901, compoundHCID 71355825HCID 71355825, compound

Product 1

HCID 13219817HCID 13219817, compound

Reagents, catalysts & solvents 2

HCID 6342AcetonitrileSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

N,N-Diisopropylethylamine 496 l, 2.85 mmol) was added to a suspension of mercaptoamine hydrochloride 7* (173 mg, 1.24 mmol) in anhydrous MeCN (0.93 ml) and the resulting mixture was stirred under a N2 atmosphere with ice bath cooling for 5 minutes. Chloromethyl silane (204 l, 1.61 mmol) was added and the mixture was stirred at 0° for 10 minutes. A solution of p-nitrobenzyl chloroformate (267 mg, 1.24 mmol) in MeCN (0.31 ml) and more N,N-diisopropylethylamine (216 l, 1.24 mmol) were added and the resulting mixture was stirred at 0° for 30 minutes and at room temperature for 60 minutes. The mixture was diluted with EtOAc, washed with H2O, 1N HCl, 5% aq. NaHCO3, and brine, dried with MgSO4, filtered and evaporated i.v., to a pale yellow oil. The crude product was chromatographed on a EM silica gel 60 column (20 g) that was eluted with 2:1 hexane-ethyl acetate at a rate of 8 ml fractions/3.5 minutes. Fractions 16-22 gave the product 25* (198 mg) as a pale yellow oil which crystallized to an off-white solid on storage in a refrigeration.

Workup

  1. temperaturecooling for 5 minutes
  2. stirringthe mixture was stirred at 0° for 10 minutes
  3. stirringthe resulting mixture was stirred at 0° for 30 minutes and at room temperature for 60 minutes
  4. washwashed with H2O, 1N HCl, 5% aq. NaHCO3, and brine
  5. dry with materialdried with MgSO4
  6. filtrationfiltered
  7. customevaporated i.v
  8. customThe crude product was chromatographed on a EM silica gel 60 column (20 g) that
  9. washwas eluted with 2:1 hexane-ethyl acetate at a rate of 8 ml fractions/3.5 minutes
  10. customFractions 16-22 gave the product 25* (198 mg) as a pale yellow oil which
  11. customcrystallized to an off-white solid on storage in a refrigeration

Sources & evidence

ORD record
ord-9a8f8468bc33426585564fe407ccb9a2
Source dataset
uspto-grants-1991_12
Patent number
US05071843

Reaction notes

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