Benzylamine → HCID 59679476, compound

HRID 2354877Notes

Reaction equation

HRID 2354877 reaction equation
[CH2:1](C(O)=O)[C:2]([CH2:4]C(O)=O)=[O:3].C([O-])(=O)C.[Na+].[CH2:16]([O:18][C:19](=[O:27])[CH:20]([CH2:24][CH:25]=O)[CH2:21][CH:22]=O)[CH3:17].[CH2:28]([NH2:35])[C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1.C(=O)([O-])[O-].[K+].[K+]>O.Cl>[CH2:16]([O:18][C:19]([CH:20]1[CH2:24][CH:25]2[N:35]([CH2:28][C:29]3[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=3)[CH:22]([CH2:1][C:2](=[O:3])[CH2:4]2)[CH2:21]1)=[O:27])[CH3:17]

Participants

8

Reactant 5

HCID 7504BenzylamineHCID 11430Potassium CarbonateHCID 68328Acetonedicarboxylic acidHCID 517045Sodium AcetateHCID 3252325HCID 3252325, compound

Product 1

HCID 59679476HCID 59679476, compoundYield 40.8%

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolventHCID 962WaterSolvent

Procedure

Acetone-1,3-dicarboxylic acid (8.81 g, 60.36 mmol) and sodium acetate (5.04 g, 61.5 mmol) were added to a solution of 4-oxo-2-(2-oxo-ethyl)-butyric acid ethyl ester (European Patent EP 0330788A1) (10.3 g, 60.36 mmol) in H2O (75 mL). Benzylamine (6.59 mL, 60.36 mmol) was dissolved in aqueous HCl (3 N, 41 mL) and was subsequently added to the stirring solution of the dialdehyde and the dicarboxylic acid over a 15 minute period. The reaction mixture was stirred for 3 days at room temperature after which the pH was adjusted to 8 by the addition of potassium carbonate. The resulting solution was extracted with methylene chloride (4×50 mL), the organic extracts dried (Na2SO4), filtered and concentrated under vacuum. The resulting residue was purified by silica gel chromatography, (eluant hexane/EtOAc 9/1 to 1/1, v/v) to give 7.43 g (40%) of 9-benzyl-7-oxo-9-aza-bicyclo[3.3.1]nonane-3-carboxylic acid ethyl ester as a brown oil. Retention time (min)=0.963, method [1], MS (ESI) 302.2 (M+H); 1H NMR (300 MHz, CDCl3) δ 7.43-7.10 (m, 5H), 4.10 (q, J=7.1 Hz, 2H), 3.91 (s, 2H), 3.41-3.38 (m, 2H), 2.74 (dd, J=16.5, 6.6 Hz, 2H), 2.61-2.48 (m, 1H), 2.30 (d, J=16.5 Hz, 2H), 2.08 (dt, J=3.8 Hz, J=13.2 Hz, 2H), 1.81-1.72 (m, 2H), 1.22 (t, J=7.1 Hz, 3H).

Workup

  1. extractionThe resulting solution was extracted with methylene chloride (4×50 mL)
  2. dry with materialthe organic extracts dried (Na2SO4)
  3. filtrationfiltered
  4. concentrationconcentrated under vacuum
  5. customThe resulting residue was purified by silica gel chromatography

Sources & evidence

ORD record
ord-3ed4d80946f24a8182276534c8369edc
Source dataset
uspto-grants-2010_07
Patent number
US07754712B2

Reaction notes

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