Benzyl chloroformate → HCID 140536904, compound

HRID 1667606Notes

Reaction equation

HRID 1667606 reaction equation
C(O)(=O)C.[C:5]([C:8]1[CH:32]=[CH:31][C:11]([O:12][CH:13]([C:18]2[CH:23]=[CH:22][C:21]([O:24][CH:25]([CH3:27])[CH3:26])=[C:20]([O:28][CH2:29][CH3:30])[CH:19]=2)[C:14]([O:16][CH3:17])=[O:15])=[CH:10][CH:9]=1)(=[NH:7])[NH2:6].C([O-])(O)=O.[Na+].Cl[C:39]([O:41][CH2:42][C:43]1[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=1)=[O:40]>C(Cl)Cl>[CH2:42]([O:41][C:39]([NH:7][C:5]([C:8]1[CH:9]=[CH:10][C:11]([O:12][CH:13]([C:18]2[CH:23]=[CH:22][C:21]([O:24][CH:25]([CH3:26])[CH3:27])=[C:20]([O:28][CH2:29][CH3:30])[CH:19]=2)[C:14]([O:16][CH3:17])=[O:15])=[CH:31][CH:32]=1)=[NH:6])=[O:40])[C:43]1[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=1

Participants

5

Reactant 3

HCID 10387Benzyl chloroformate2×HCID 516892Sodium BicarbonateHCID 67445382HCID 67445382, compound2×

Product 1

HCID 140536904HCID 140536904, compoundYield 97.8%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Procedure

To a suspension of 9C (570 mg, 1.12 mmol) in CH2Cl2 (12 mL) was added 1.0 M NaHCO3 (11.2 mL, 11.2 mmol), followed by benzyl chloroformate (0.22 mL, 1.5 mmol) in CH2Cl2 (3.0 mL). The mixture was stirred at rt for 30 min. TLC indicated some 9C still present. Another portion of benzyl chloroformate (0.1 mL, 0.84 mmol) in CH2Cl2 (3.0 mL) was added. After stirring at rt for 1.0 h, the reaction was quenched with ammonium hydroxide (0.65 mL), and extracted with CH2Cl2. The organic extract was washed with brine and dried over Na2SO4. After removal of the solvent, the crude product was purified by flash column chromatography eluting with ethyl acetate/hexanes (1:1) to give 9D (570 mg, 73% yield) as a white solid. 1H NMR (400 MHz, CDCl3) δ ppm 1.32 (d, J=6.16 Hz, 6H) 1.38 (t, J=7.03 Hz, 3H) 3.71 (s, 3H) 4.04 (q, J=7.03 Hz, 2H) 4.46 (m, 1H) 5.18 (s, 2H) 5.58 (s, 1H) 6.85 (d, J=8.8 Hz, 1H) 6.90 (d, J=8.35 Hz, 2H) 7.09 (m, 2H) 7.20-7.40 (m, 6H), 7.82 (d, J=9.20 Hz, 2H).

Workup

  1. stirringAfter stirring at rt for 1.0 h
  2. customthe reaction was quenched with ammonium hydroxide (0.65 mL)
  3. extractionextracted with CH2Cl2
  4. extractionThe organic extract
  5. washwas washed with brine
  6. dry with materialdried over Na2SO4
  7. customAfter removal of the solvent
  8. customthe crude product was purified by flash column chromatography
  9. washeluting with ethyl acetate/hexanes (1:1)

Sources & evidence

ORD record
ord-06b5b527aac046b796e24ace133af1a4
Source dataset
uspto-grants-2011_10
Patent number
US08044242B2

Reaction notes

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