Ethyl Acetate → HCID 90971125, compound

HRID 2040498Notes

Reaction equation

HRID 2040498 reaction equation
[NH:1]([C:10]([O:12][CH2:13][C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)=[O:11])[C@H:2]([C:7]([OH:9])=O)[CH2:3][CH2:4][CH2:5][CH3:6].Br[CH2:21][C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23].[OH-].[Na+].C(OCC)(=O)C>C1C=CC=CC=1.[N+](CCCC)(CCCC)(CCCC)CCCC.[O-]S(O)(=O)=O.O>[CH2:13]([O:12][C:10]([NH:1][C@@H:2]([CH2:3][CH2:4][CH2:5][CH3:6])[CH2:7][O:9][CH2:21][C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])=[O:11])[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1

Participants

8

Reactant 4

HCID 8857Ethyl AcetateHCID 14798Sodium HydroxideHCID 79177tert-Butyl bromoacetateHCID 6993403Z-Nle-OH

Product 1

HCID 90971125HCID 90971125, compoundYield 74%

Reagents, catalysts & solvents 3

HCID 94433Tetrabutylammonium hydrogen sulfateCatalystHCID 241BenzeneSolventHCID 962WaterSolvent

Procedure

To a stirred solution of Z-L-Nle-ol (0.20 g, 0.8 mmol) in benzene (0.8 mL), tert-butyl bromoacetate (0.47 g, 2.4 mmol) and subsequently aqueous NaOH 50% (0.8 mL) and the phase transfer catalyst Bu4NHSO4 (0.07 g, 0.2 mmol) were added. The reaction mixture was vigorously stirred for 2 h. Ethyl acetate (10 mL) and H2O (10 mL) were added and the aqueous layer was separated and extracted with ethyl acetate (2×10 mL). The combined organic layers were washed with brine and dried over Na2SO4. The organic solvent was evaporated under reduced pressure and the residue was purified by column-chromatography using petroleum ether (bp 40-60° C.)/ethyl acetate 8:2 as eluent. Yield 74%; Oil; [a]D=−12.2 (c 1CHCl3); 1H NMR (200 MHz, CDCl3) δ 7.34-7.22 (m, 5H), 5.30 (d, J=8 Hz, 1H), 5.06 (s, 2H), 3.91 (s, 2H), 3.80-3.62 (m, 1H), 3.55 (dd, Ji=9.0 Hz, J2=4.0 Hz, 1H), 3.46 (dd, Ji=9.2 Hz, J2=4.2 Hz, 1H), 1.62-1.45 (m, 2H), 1.43 (s, 9H), 1.37-1.21 (m, 4H), 0.85 (t, J=6.8 Hz, 3H); 13C NMR (50 MHz, CDCl3) δ 169.5, 156.0, 136.6, 128.3, 128.0, 127.8, 81.5, 73.0, 68.7, 66.3, 50.9, 31.4, 28.0, 27.9, 22.4, 13.8. Anal. Calcd for C20H31NO5: C, 65.73; H, 8.55; N, 3.83. Found: C, 65.52; H, 8.71; H, 3.70.

Workup

  1. customthe aqueous layer was separated
  2. extractionextracted with ethyl acetate (2×10 mL)
  3. washThe combined organic layers were washed with brine
  4. dry with materialdried over Na2SO4
  5. customThe organic solvent was evaporated under reduced pressure
  6. customthe residue was purified by column-chromatography

Sources & evidence

ORD record
ord-b05f0249f16b470c99d5c77c77b4d4d9
Source dataset
uspto-grants-2013_11
Patent number
US08580852B2

Reaction notes

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