Dichloromethane → HCID 68554659, compound

HRID 2359896Notes

Reaction equation

HRID 2359896 reaction equation
[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([N+:21]([O-])=O)=[C:6]([CH2:8][NH:9][CH2:10][C:11]2[C:16]([O:17][CH3:18])=[CH:15][CH:14]=[CH:13][C:12]=2[O:19][CH3:20])[CH:7]=1.O.NN.ClCCl>CO.[Fe](Cl)(Cl)Cl>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([NH2:21])=[C:6]([CH2:8][NH:9][CH2:10][C:11]2[C:12]([O:19][CH3:20])=[CH:13][CH:14]=[CH:15][C:16]=2[O:17][CH3:18])[CH:7]=1

Participants

6

Reactant 3

HCID 6344DichloromethaneHCID 24654Hydrazine hydrate (1:1)HCID 68551576HCID 68551576, compound

Product 1

HCID 68554659HCID 68554659, compound

Reagents, catalysts & solvents 2

HCID 24380Iron chloride (FeCl3)CatalystHCID 887MethanolSolvent

Conditions

Temperature
64 °C

Procedure

1-(5-Chloro-2-nitrophenyl)-N-(2,6-dimethoxybenzyl)methanamine (19.2 g, 57.0 mmol) was dissolved in 400 mL methanol in the heat. Activated carbon (20.0 g) and catalytic amounts of sublimed iron trichloride (0.24 g, 1.48 mmol) were added at room temperature. Finally, hydrazine hydrate (11.10 mL, 228.0 mmol) was added slowly by drops at 64° C. In doing so, it foamed up somewhat. After heating for 2 hours at 64° C., the reaction was concluded. After cooling the reaction mixture to room temperature, the batch was filtered through Hyflo Super Cel and the solid constituents were separated out. The solvent was removed in vacuo. The colorless oil was again dissolved in dichloromethane and extracted with water (3×) and with 2N hydrochloric acid (3×). The hydrochloric two-phase mixture was adjusted to a pH of 11 with 2N sodium hydroxide solution, at which point a bulky colorless precipitate was formed. When dichloromethane was added, the solids dissolved again in the organic phase which was dried over sodium sulfate after separating the aqueous phase, then filtered and freed of the solvent in vacuo. By storing into petroleum ether, a colorless precipitate was obtained from the oily yellow crude product, then filtered with suction and dried. By fractional crystallization of the mother liquor, the yield was further increased. Yield: 11.5 g (37.5 mmol, 66%).

Workup

  1. temperatureAfter cooling the reaction mixture to room temperature
  2. filtrationthe batch was filtered through Hyflo Super Cel
  3. customthe solid constituents were separated out
  4. customThe solvent was removed in vacuo
  5. dissolutionThe colorless oil was again dissolved in dichloromethane
  6. extractionextracted with water (3×) and with 2N hydrochloric acid (3×)
  7. customwas formed
  8. dissolutionthe solids dissolved again in the organic phase which
  9. dry with materialwas dried over sodium sulfate
  10. customafter separating the aqueous phase
  11. filtrationfiltered

Sources & evidence

ORD record
ord-cebd741e46f64ffaaf9e84f1b383657c
Source dataset
uspto-grants-2014_04
Patent number
US08686002B2

Reaction notes

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