Chloroform → N-(4-tertiary-butylbenzyl)-N-methyl-3-phenoxybenzylamine

HRID 369375

Reaction equation

HRID 369375 reaction equation
[C:1]([C:5]1[CH:13]=[CH:12][C:8]([CH2:9]CN)=[CH:7][CH:6]=1)([CH3:4])([CH3:3])[CH3:2].C(=O)([O-])[O-].[Na+].[Na+].[O:20]([C:27]1[CH:28]=[C:29]([CH:32]=[CH:33][CH:34]=1)[CH2:30]Br)[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1.C(Cl)(Cl)Cl.[CH3:39][N:40](C)C=O>O>[C:1]([C:5]1[CH:6]=[CH:7][C:8]([CH2:9][N:40]([CH2:30][C:29]2[CH:32]=[CH:33][CH:34]=[C:27]([O:20][C:21]3[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=3)[CH:28]=2)[CH3:39])=[CH:12][CH:13]=1)([CH3:2])([CH3:3])[CH3:4]

Participants

7

Reactant 5

HCID 6212ChloroformHCID 6228Dimethylformamide2×HCID 10340Sodium CarbonateHCID 945441-(Bromomethyl)-3-phenoxybenzeneHCID 27356892-(4-Tert-butylphenyl)ethan-1-amine

Product 1

HCID 23286207N-(4-tertiary-butylbenzyl)-N-methyl-3-phenoxybenzylamineYield 87.8%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

Following the process to be described below, Compound 1 was prepared. Namely, 10.16 g of m-phenoxytoluene, 9.82 g of N-bromosuccinimide and 0.15 g of benzoyl peroxide were weighed and added to 90 ml of carbon tetrachloride as a solvent. The resulting mixture was heated under reflux for 3 hours to conduct a reaction. The reaction mixture was allowed to cool down, the insoluble matter was filtered off, and the filtrate was then concentrated. The concentrate was purified by chromatography on a silica gel column (eluent: chloroform), whereby 10.9 g of 3-phenoxybenzyl bromide were obtained. In 20 ml of N,N-dimethylformamide, 2.79 g of N-(4-tert-butylbenzyl)methylamine and 1.67 g of sodium carbonate were mixed, to which a solution of 3.77 g of 3-phenoxybenzyl bromide in 25 ml of N,N-dimethylformamide was added dropwise under ice cooling. The temperature of the reaction mixture was allowed to rise to room temperature, at which a reaction was allowed to proceed for 12 hours. Chloroform and water were added to the reaction mixture to conduct liquid-liquid extraction. An organic layer was collected and then washed with water and a saturated aqueous solution of sodium chloride. The resulting solution was dried over anhydrous sodium sulfate and was then concentrated. The concentrate was purified by chromatography on a silica gel column (eluent:hexane:chloroform:ethyl acetate=9:1:0→0:10:0→0:0:100). Relevant fractions were concentrated, whereby 4.49 g of N-(4-tertiary-butylbenzyl)-N-methyl-3-phenoxybenzylamine (Compound 1) were obtained (yield: 87.8%). The following is its NMR data (CDCl3 δ ppm): 1.28(9H,s), 2.18(3H,s), 3.476(2H,s), 3.483(2H,s), 6.86-7.35(13H,m).

Workup

  1. additionwas added dropwise under ice cooling
  2. customto rise to room temperature, at which
  3. extractionliquid-liquid extraction
  4. customAn organic layer was collected
  5. washwashed with water
  6. dry with materialThe resulting solution was dried over anhydrous sodium sulfate
  7. concentrationwas then concentrated
  8. customThe concentrate was purified by chromatography on a silica gel column (eluent:hexane:chloroform:ethyl acetate=9:1:0→0:10:0→0:0:100)
  9. concentrationRelevant fractions were concentrated

Sources & evidence

ORD record
ord-c98210b707314d7a8dded572e9cca4cc
Source dataset
uspto-grants-2000_10
Patent number
US06136863

Linked notes

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