Tetrahydrofuran → 1,2-Bis(phenylmethyl) 1,2-hydrazinedicarboxylate

HRID 1396839Notes

Reaction equation

HRID 1396839 reaction equation
[OH-:1].[Na+].O.[NH2:4][NH2:5].[CH:6]1[CH:11]=[CH:10][C:9]([CH2:12][O:13][C:14](Cl)=[O:15])=[CH:8][CH:7]=1.[CH2:17]1[CH2:21][O:20][CH2:19][CH2:18]1>O>[NH:4]([C:19]([O:20][CH2:21][C:17]1[CH:18]=[CH:8][CH:7]=[CH:6][CH:11]=1)=[O:1])[NH:5][C:14]([O:13][CH2:12][C:9]1[CH:10]=[CH:11][CH:6]=[CH:7][CH:8]=1)=[O:15]

Participants

6

Reactant 4

HCID 8028Tetrahydrofuran2×HCID 10387Benzyl chloroformateHCID 14798Sodium HydroxideHCID 24654Hydrazine hydrate (1:1)

Product 1

HCID 2205541,2-Bis(phenylmethyl) 1,2-hydrazinedicarboxylateYield 65%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
0 °C

Procedure

A solution of sodium hydroxide (2.50 kg, 62.5 mol) in water (40 L) was charged into an 100 L reactor. Hydrazine hydrate (2.00 kg, 40 mol) and THF (8 L) were added into the above solution. The mixture solution was cooled at 0° C. A pre-prepared solution of Cbz-Cl (13.60 kg CbzCl, 61.99 mol) in 2 L THF was added dropwise to the solution while maintaining the temperature at 0° C. The reaction was allowed to stir for an additional 4 h and a solid precipitated from the solution. The solid was collected by filtration, which was suspended in toluene (5 L). The suspended solution was heated at 80° C., which became clear. The water in the crude product was removed completely under reflux using a Dean-Stark apparatus. The resulting solution was cooled to room temperature and the product precipitated. The product was obtained after filtration to afford bis(phenylmethyl) 1,2-hydrazinedicarboxylate (7.8 Kg, 26 mol, 65%) as a white solid.

Workup

  1. temperaturewhile maintaining the temperature at 0° C
  2. customa solid precipitated from the solution
  3. filtrationThe solid was collected by filtration, which
  4. temperatureThe suspended solution was heated at 80° C.
  5. customThe water in the crude product was removed completely
  6. temperatureunder reflux
  7. temperatureThe resulting solution was cooled to room temperature
  8. customthe product precipitated
  9. customThe product was obtained
  10. filtrationafter filtration

Sources & evidence

ORD record
ord-3dbcb5c3bc65497eb26c25b108d0bb64
Source dataset
uspto-grants-2014_12
Patent number
US08901119B2

Reaction notes

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