Acetate → 2-[4-(1,4-Dioxa-8-aza-spiro[4.5]dec-8-yl)-benzylidene]-malonic acid diethyl ester

HRID 1061295Notes

Reaction equation

HRID 1061295 reaction equation
[O:1]1[C:5]2([CH2:10][CH2:9][N:8]([C:11]3[CH:18]=[CH:17][C:14]([CH:15]=O)=[CH:13][CH:12]=3)[CH2:7][CH2:6]2)[O:4][CH2:3][CH2:2]1.[C:19]([O:27][CH2:28][CH3:29])(=[O:26])[CH2:20][C:21]([O:23][CH2:24][CH3:25])=[O:22].C([O-])(=O)C>C1(C)C=CC=CC=1>[CH2:24]([O:23][C:21](=[O:22])[C:20](=[CH:15][C:14]1[CH:17]=[CH:18][C:11]([N:8]2[CH2:9][CH2:10][C:5]3([O:4][CH2:3][CH2:2][O:1]3)[CH2:6][CH2:7]2)=[CH:12][CH:13]=1)[C:19]([O:27][CH2:28][CH3:29])=[O:26])[CH3:25]

Participants

5

Reactant 3

HCID 175AcetateHCID 7761Diethyl MalonateHCID 27643354-(1,4-Dioxa-8-azaspiro[4.5]decan-8-yl)benzaldehyde

Product 1

HCID 696550422-[4-(1,4-Dioxa-8-aza-spiro[4.5]dec-8-yl)-benzylidene]-malonic acid diethyl ester

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

A solution of 4-(1,4-dioxa-8-aza-spiro[4.5]dec-8-yl)-benzaldehyde (2.47, 10 mmol) (Taylor, E. C., Skotnicki, J. S. Synthesis, 1981, 606) and diethyl malonate (2.0 g, 12.5 mmol) in toluene (100 mL) containing a catalytic quantity of piperidineum acetate was refluxed for 18 hours. After cooling to room temperature the solution was washed with water, dried over sodium sulfate and concentrated. Purification by column chromatography on silica gel using ethyl acetate/hexanes as the eluent gave the title compound as a yellowish gum; 1H NMR (300 MHz, CDCl3) δ 1.28 (t, J=7.1 Hz, 3H), 1.29 (t, J=7.1 Hz, 3H), 1.79 (t, J=5.8 Hz, 4H), 3.46 (t, J=5.8 Hz, 4H), 4.27 (q, J=7.1 Hz, 2H), 4.31 (q, J=7.1 Hz, 2H), 6.85 (d, J=8.9 Hz, 2H), 7.33 (d, J=8.9 Hz, 2H), 7.61 (s, 1H); MS (ES) m/z: 390.0 (MH+); HRMS Calcd. for C21H27NO6 (MH+): 390.1911. Found: 390.1910.

Workup

  1. temperaturewas refluxed for 18 hours
  2. washwas washed with water
  3. dry with materialdried over sodium sulfate
  4. concentrationconcentrated
  5. customPurification by column chromatography on silica gel

Sources & evidence

ORD record
ord-5a036fd8f0784da29a66f7869b0cd406
Source dataset
uspto-grants-2003_02
Patent number
US06525202B2

Reaction notes

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