4-Nitrobenzyl chloroformate → HCID 13175759, compound

HRID 981855Notes

Reaction equation

HRID 981855 reaction equation
C([O-])(O)=O.[Na+].Cl.[NH2:7][CH2:8][C@@H:9]([SH:11])[CH3:10].Cl[C:13]([O:15][CH2:16][C:17]1[CH:22]=[CH:21][C:20]([N+:23]([O-:25])=[O:24])=[CH:19][CH:18]=1)=[O:14]>CCOCC.O>[N+:23]([C:20]1[CH:19]=[CH:18][C:17]([CH2:16][O:15][C:13]([NH:7][CH2:8][C@@H:9]([SH:11])[CH3:10])=[O:14])=[CH:22][CH:21]=1)([O-:25])=[O:24]

Participants

6

Reactant 3

HCID 782054-Nitrobenzyl chloroformateHCID 516892Sodium BicarbonateHCID 12469167HCID 12469167, compound

Product 1

HCID 13175759HCID 13175759, compoundYield 86.6%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 3283Diethyl EtherSolvent2×

Procedure

Saturated aqueous NaHCO3 (8 ml) was added dropwise to an ice-cold, stirring mixture of (S)-(+)-1-amino-2-propanethiol hydrochloride (363 mg, 2.85 mmol) in Et2O (75 ml) and H2O (8 ml) and the resulting slurry was stirred in the cold for 30 min. A solution of p-nitrobenzyl chloroformate (693 mg, 3.21 mmol) in Et2O (25 ml) was then added dropwise over 35 min. After having been stirred in the cold an additional 50 min., the reaction mixture was transferred to a separately funnel and the layers were separated. The organic portion was washed with ice-cold 0.025N HCl and brine, dried with MgSO4, filtered, and evaporated under a vacuum to a yellow oil (886 mg) which solidified on standing. The crude product was purified by preparative TLC on four 0.1×20×40 cm silica gel GF plates using 30:1 CH2Cl2 -EtOAc as developing solvent. The product band provided a yellow oil (667 mg) which crystallized on scratching. Recrystallization from Et2O-petroleum ether offorded the title compound B3) in two crops; crop 1 consisted of tiny, white crystals (216 mg) having mp 55.5°-60.5° and crop 2 afforded larger, off-white crystals (284 mg) having mp 55.5°-62°, [α]D +21.5° (Cl.32 in CHCl3).

Workup

  1. stirringthe resulting slurry was stirred in the cold for 30 min
  2. stirringAfter having been stirred in the cold an additional 50 min.
  3. customthe layers were separated
  4. washThe organic portion was washed with ice-cold 0.025N HCl and brine
  5. dry with materialdried with MgSO4
  6. filtrationfiltered
  7. customevaporated under a vacuum to a yellow oil (886 mg) which
  8. customThe crude product was purified by preparative TLC on four 0.1×20×40 cm silica gel GF plates

Sources & evidence

ORD record
ord-58728f714a4e4c8ba4f97cb3430b060f
Source dataset
uspto-grants-1991_02
Patent number
US04992542

Reaction notes

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