(Z)-Benzaldehyde oxime → tert-Butyl 3-phenyl-1-oxa-2,7-diazaspiro[4.5]dec-2-ene-7-carboxylate

HRID 2044087Notes

Reaction equation

HRID 2044087 reaction equation
Cl[O-].[Na+].[CH2:4]=[C:5]1[CH2:10][CH2:9][CH2:8][N:7]([C:11]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:12])[CH2:6]1.[CH:18](=[N:25][OH:26])[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1>C(Cl)Cl>[C:19]1([C:18]2[CH2:4][C:5]3([CH2:10][CH2:9][CH2:8][N:7]([C:11]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:12])[CH2:6]3)[O:26][N:25]=2)[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1

Participants

5

Reactant 3

HCID 12143(Z)-Benzaldehyde oximeHCID 112525943-Methylene-piperidine-1-carboxylic acid tert-butyl esterHCID 23665760Sodium Hypochlorite

Product 1

HCID 57489637tert-Butyl 3-phenyl-1-oxa-2,7-diazaspiro[4.5]dec-2-ene-7-carboxylateYield 73.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

A 10% aqueous sodium hypochlorite solution (2.88 mL, 4.66 mmol) was added dropwise to a solution of tert-butyl 3-methylenepiperidine-1-carboxylate (230 mg, 1.166 mmol) and benzaldehyde oxime (282 mg, 2.332 mmol) in CH2Cl2 (5 mL) at 0° C. After 2 h at 0° C., the mixture was diluted CH2Cl2 (50 mL) and washed with water (10 mL). The aqueous phase was extracted with CH2Cl2 (3×20 mL). The combined organic extracts were washed with brine (10 mL), dried (MgSO4) and concentrated. Silica gel chromatography, eluting with 0 to 15% ethyl acetate in hexanes, gave the expected product as a colorless oil (270 mg, 73% yield). LCMS: (M+Na)+=339.12. 1H NMR (400 MHz, chloroform-d) δ ppm 7.55-7.79 (2H, m), 7.31-7.47 (3H, m), 3.57-3.93 (2H, m), 2.90-3.29 (4H, m), 1.78-2.04 (2H, m), 1.51-1.65 (2H, m), 1.46 (9H, s).

Workup

  1. washwashed with water (10 mL)
  2. extractionThe aqueous phase was extracted with CH2Cl2 (3×20 mL)
  3. washThe combined organic extracts were washed with brine (10 mL)
  4. dry with materialdried (MgSO4)
  5. concentrationconcentrated
  6. washSilica gel chromatography, eluting with 0 to 15% ethyl acetate in hexanes

Sources & evidence

ORD record
ord-bb482630ef144a578691c39bcb5751f6
Source dataset
uspto-grants-2013_11
Patent number
US08586751B2

Reaction notes

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