Toluene → 1-[2-(2-Amino-4,5-dichlorophenyl)-ethylamino]-3-[N-methyl-N-(6,7-dimethoxy-1,2,3,4-tetrahydronaphth-2-yl)-amino]-propane

HRID 1380872Notes

Reaction equation

HRID 1380872 reaction equation
[NH2:1][C:2]1[CH:7]=[C:6]([Cl:8])[C:5]([Cl:9])=[CH:4][C:3]=1[CH2:10][C:11]([NH:13][CH2:14][CH2:15][CH2:16][N:17]([CH3:32])[CH:18]1[CH2:27][CH2:26][C:25]2[C:20](=[CH:21][C:22]([O:30][CH3:31])=[C:23]([O:28][CH3:29])[CH:24]=2)[CH2:19]1)=O.C1(C)C=CC=CC=1>O1CCCC1>[NH2:1][C:2]1[CH:7]=[C:6]([Cl:8])[C:5]([Cl:9])=[CH:4][C:3]=1[CH2:10][CH2:11][NH:13][CH2:14][CH2:15][CH2:16][N:17]([CH3:32])[CH:18]1[CH2:27][CH2:26][C:25]2[C:20](=[CH:21][C:22]([O:30][CH3:31])=[C:23]([O:28][CH3:29])[CH:24]=2)[CH2:19]1

Participants

4

Reactant 2

HCID 1140TolueneHCID 53641682HCID 53641682, compound

Product 1

HCID 233245711-[2-(2-Amino-4,5-dichlorophenyl)-ethylamino]-3-[N-methyl-N-(6,7-dimethoxy-1,2,3,4-tetrahydronaphth-2-yl)-amino]-propane

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
80 °C

Procedure

Next, 1-[2-(2-amino-4,5-dichlorophenyl)-1-oxo-ethylamino]-3-[N-methyl-N-(6,7-dimethoxy-1,2,3,4-tetrahydronaphth-2-yl)-amino]-propane (4.8 g, 0.01 mol) is dissolved in absolute tetrahydrofuran (100 ml) and mixed with boron trifluoride-diethyl ether complex (1.25 g, 1.1 ml). Then, a 10M toluene solution of borane-dimethylsulphide complex (1.6 ml) diluted with absolute tetrahydrofuran (20 ml) is added to the reaction mixture with stirring, under a nitrogen atmosphere and with heating to reflux temperature, and the resulting mixture is refluxed for a further 8 hours. The solvent is distilled off in vacuo, the residue is heated in 6M hydrochloric acid (100 ml) to 80° C. for one hour, cooled and extracted twice with ethyl acetate. The hydrochloric acid solution is then made alkaline with 50% sodium hydroxide solution while cooling with ice water and extracted several times with methylene chloride. The extract is dried over magnesium sulphate, concentrated by evaporation in vacuo and the residue is purified by column chromatography over alumina N (170 g) [activity II, eluant: methylene chloride and increasing amounts of ethanol (up to 5%). Yield: 1 g.

Workup

  1. additionmixed with boron trifluoride-diethyl ether complex (1.25 g, 1.1 ml)
  2. additionis added to the reaction mixture
  3. temperaturewith heating
  4. temperatureto reflux temperature
  5. temperaturethe resulting mixture is refluxed for a further 8 hours
  6. distillationThe solvent is distilled off in vacuo
  7. temperaturecooled
  8. extractionextracted twice with ethyl acetate
  9. temperaturewhile cooling with ice water
  10. extractionextracted several times with methylene chloride
  11. dry with materialThe extract is dried over magnesium sulphate
  12. concentrationconcentrated by evaporation in vacuo
  13. customthe residue is purified by column chromatography over alumina N (170 g) [activity II, eluant
  14. temperaturemethylene chloride and increasing amounts of ethanol (up to 5%)

Sources & evidence

ORD record
ord-8411fb30f2e14f35af0fee7c4e013081
Source dataset
uspto-grants-1986_04
Patent number
US04584293

Reaction notes

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