4-Chlorobenzylamine → HCID 178522918, compound

HRID 2289893Notes

Reaction equation

HRID 2289893 reaction equation
[F:1][C:2]1[CH:3]=[C:4]([OH:11])[CH:5]=[CH:6][C:7]=1[N+:8]([O-])=O.[CH:12]([O-:14])=O.[NH4+].[Cl:16][C:17]1[CH:24]=[CH:23][C:20]([CH2:21][NH2:22])=[CH:19][CH:18]=1>O1CCCC1.CO.C(OCC)C.[Pd]>[Cl:16][C:17]1[CH:24]=[CH:23][C:20]([CH2:21][NH:22][C:4]([C:3]2[CH:2]=[N:8][C:7]3[C:6]([C:12]=2[OH:14])=[CH:5][C:4]([OH:11])=[CH:3][C:2]=3[F:1])=[O:11])=[CH:19][CH:18]=1

Participants

8

Reactant 3

HCID 660364-ChlorobenzylamineHCID 5209483-Fluoro-4-nitrophenolHCID 2723923Ammonium formate

Product 1

HCID 178522918HCID 178522918, compound

Reagents, catalysts & solvents 4

HCID 23938PalladiumCatalystHCID 887MethanolSolventHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a mixture of 10% Pd/C and 2.0 g of 3-fluoro-4-nitrophenol in 10 mL of tetrahydrofuran and 10 mL of methanol is added 4.817 g of ammonium formate. After the reaction stirred at room temperature for 1 h, it is filtered through celite and condensed. To the residue is then added 2.57 mL of diethylethoxymethylenemalonate and 10 mL xylene. The mixture is heated to 135 ° C. for 1 h with a Dean-Stark trap to remove formed ethanol. The reaction is cooled. The resulting solid is collected, washed with hexanes, and dried. The solid is then dissolved in 50 mL of diphenyl ether and heated to 250° C. for 3 h with a Dean-Stark trap to collect ethanol. The solution is cooled and diluted with hexanes. The resulting solid is collected and dried to yield 0.527 g. A solution of 0.415 g of that solid in 4 mL of 4-chlorobenzylamine is heated to 180° C. for 1 h. The solution is cooled and diluted with diethyl ether. The resulting solid is collected and recrystallized from acetone/hexanes to yield 0.226 g of the title compound as a tan solid.

Workup

  1. filtrationit is filtered through celite and condensed
  2. additionTo the residue is then added 2.57 mL of diethylethoxymethylenemalonate and 10 mL xylene
  3. temperatureThe mixture is heated to 135 ° C. for 1 h with a Dean-Stark trap
  4. customto remove
  5. customformed ethanol
  6. temperatureThe reaction is cooled
  7. customThe resulting solid is collected
  8. washwashed with hexanes
  9. customdried
  10. dissolutionThe solid is then dissolved in 50 mL of diphenyl ether
  11. temperatureheated to 250° C. for 3 h with a Dean-Stark trap
  12. customto collect ethanol
  13. temperatureThe solution is cooled
  14. additiondiluted with hexanes
  15. customThe resulting solid is collected
  16. customdried
  17. customto yield 0.527 g
  18. temperatureThe solution is cooled
  19. customThe resulting solid is collected
  20. customrecrystallized from acetone/hexanes

Sources & evidence

ORD record
ord-07f2d9a6840a49a6b445d1119f23ce5c
Source dataset
uspto-grants-2000_07
Patent number
US06093732

Reaction notes

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