Tert-butyl 3-(4-methoxybenzylidene)carbazate → 1,1-Dimethylethyl 2-[(4-methoxyphenyl)methyl]hydrazinecarboxylate

HRID 597852Notes

Reaction equation

HRID 597852 reaction equation
[CH3:1][O:2][C:3]1[CH:18]=[CH:17][C:6](/[CH:7]=[N:8]/[NH:9][C:10]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11])=[CH:5][CH:4]=1.[H][H]>[Pd].CC(=O)OCC.O1CCCC1>[CH3:1][O:2][C:3]1[CH:4]=[CH:5][C:6]([CH2:7][NH:8][NH:9][C:10]([O:12][C:13]([CH3:14])([CH3:16])[CH3:15])=[O:11])=[CH:17][CH:18]=1

Participants

6

Reactant 2

HCID 6876678Tert-butyl 3-(4-methoxybenzylidene)carbazateHCID 178418361HCID 178418361, compound2×

Product 1

HCID 107533141,1-Dimethylethyl 2-[(4-methoxyphenyl)methyl]hydrazinecarboxylateYield 104.3%

Reagents, catalysts & solvents 3

HCID 23938PalladiumCatalystHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

Add 10% palladium on carbon (water wet, 20 g) slurried in EA (100 mL) to a sealed pressure reactor via vacuum transfer. Rinse transfer line with a minimal amount of EA. Charge (E)-tert-butyl 2-(4-methoxybenzylidene)hydrazinecarboxylate (320 g, 1.28 mol) dissolved in tetrahydrofuran (THF, 1000 mL) via vacuum transfer and rinse line with a minimal amount of THF. Pressurize the reactor to 50 PSI with H2 and mix the contents of the reactor at 20±10° C. Continue the reaction, maintaining the hydrogen pressure at 50 PSI, until no further hydrogen uptake is observed. Filter the reaction solution to remove the catalyst and wash the catalyst filter-cake with THF (500 mL). Add the wash to the reaction filtrate. Concentrate the solution in vacuo to obtain the title compound (337 g, 86%) as an oil. 1H NMR (400 MHz, DMSO-d6) δ 8.1-8.3 (s, 1H), 7.1-7.3 (d, 2H), 6.8-6.9 (d, 2H), 4.4-4.6 (bs, 1H), 3.7-3.8 (s, 2H), 3.6-3.7 (s, 3H), 1.3-1.5 (s, 9H).

Workup

  1. washRinse transfer line with a minimal amount of EA
  2. washrinse line with a minimal amount of THF
  3. additionmix the contents of the reactor at 20±10° C
  4. customthe reaction
  5. filtrationFilter the reaction solution
  6. customto remove the catalyst
  7. washwash the catalyst
  8. filtrationfilter-cake with THF (500 mL)
  9. additionAdd the
  10. washwash to the reaction filtrate
  11. concentrationConcentrate the solution in vacuo

Sources & evidence

ORD record
ord-7ce3007b59c24c1b9b62499d35c6c4d8
Source dataset
uspto-grants-2011_03
Patent number
US07897600B2

Reaction notes

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