2-Nitrobenzaldehyde → 1-(Diphenylmethyl)-3-[(2-nitrophenylmethyl)amino]-azetidine

HRID 1766181Notes

Reaction equation

HRID 1766181 reaction equation
[NH2:1][CH:2]1[CH2:5][N:4]([CH:6]([C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[C:7]2[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=2)[CH2:3]1.[N+:19]([C:22]1[CH:29]=[CH:28][CH:27]=[CH:26][C:23]=1[CH:24]=O)([O-:21])=[O:20].[BH4-].[Na+]>CO>[C:13]1([CH:6]([C:7]2[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=2)[N:4]2[CH2:5][CH:2]([NH:1][CH2:24][C:23]3[CH:26]=[CH:27][CH:28]=[CH:29][C:22]=3[N+:19]([O-:21])=[O:20])[CH2:3]2)[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1

Participants

5

Reactant 3

HCID 111012-NitrobenzaldehydeHCID 4311764Sodium borohydride3×HCID 57445463-Amino-1-(diphenylmethyl)azetidine

Product 1

HCID 211099031-(Diphenylmethyl)-3-[(2-nitrophenylmethyl)amino]-azetidine

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent2×

Procedure

A mixture of 45.0 g (0.189 mol) of 3-amino-1-(diphenylmethyl)-azetidine, 28.7 g (0.190 mol) of 2-nitrobenzaldehyde and 280 ml of methanol was stirred for 3 hours at ambient temperature. Then 7.4 g (0.196 mol) of sodium borohydride were added followed, after a further 2 hours, by another 6.0 g of sodium borohydride and 300 ml of methanol and after a further 16 hours by 4.0 g of sodium borohydride, and the mixture was stirred for a further 4 hours at ambient temperature. The mixture was concentrated by evaporation in vacuo and the residue was treated with 200 ml dichloromethane and 200 ml of water. It was filtered, the methylene chloride phase was dried over sodium sulphate and freed from solvent. The residue was purified by chromatography on silica gel (30–60 μm) using dichloromethane/EE/MeOH/cyclohexane/conc. ammonia (59/25/7.5/7.5/1 v/v/v/v/v) as eluant, then on silica gel using dichloromethane/EE (1/1 v/v) as eluant. After the appropriate fractions had been worked up, 20.0 g (28% of theoretical) of the desired compound were obtained in the form of a pale yellow oil.

Workup

  1. stirringthe mixture was stirred for a further 4 hours at ambient temperature
  2. concentrationThe mixture was concentrated by evaporation in vacuo
  3. additionthe residue was treated with 200 ml dichloromethane and 200 ml of water
  4. filtrationIt was filtered
  5. dry with materialthe methylene chloride phase was dried over sodium sulphate
  6. customThe residue was purified by chromatography on silica gel (30–60 μm)

Sources & evidence

ORD record
ord-557233c6977f457c8428c8c65e67106b
Source dataset
uspto-grants-2007_06
Patent number
US07230001B1

Reaction notes

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