Sodium Hydroxide → tert-Butyl 2-{1-[4-(ethoxycarbonyl)phenyl]ethyl}hydrazine-1-carboxylate

HRID 1817756Notes

Reaction equation

HRID 1817756 reaction equation
[BH3-]C#N.[Na+].[C:5]([O:9][C:10]([NH:12][N:13]=[C:14]([C:16]1[CH:21]=[CH:20][C:19]([C:22]([O:24][CH2:25][CH3:26])=[O:23])=[CH:18][CH:17]=1)[CH3:15])=[O:11])([CH3:8])([CH3:7])[CH3:6].O.C1(C)C=CC(S(O)(=O)=O)=CC=1.[OH-].[Na+]>C1COCC1.CCOC(C)=O.C(Cl)Cl>[CH2:25]([O:24][C:22]([C:19]1[CH:20]=[CH:21][C:16]([CH:14]([NH:13][NH:12][C:10]([O:9][C:5]([CH3:7])([CH3:6])[CH3:8])=[O:11])[CH3:15])=[CH:17][CH:18]=1)=[O:23])[CH3:26]

Participants

8

Reactant 4

HCID 14798Sodium HydroxideHCID 521998p-Toluenesulfonic acid monohydrateHCID 5003444Sodium cyanoborohydrideHCID 578827471,1-Dimethylethyl 2-[1-[4-(ethoxycarbonyl)phenyl]ethylidene]hydrazinecarboxylate

Product 1

HCID 67482189tert-Butyl 2-{1-[4-(ethoxycarbonyl)phenyl]ethyl}hydrazine-1-carboxylate

Reagents, catalysts & solvents 3

HCID 6344DichloromethaneSolvent2×HCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

In a N2 filled round-bottomed flask equipped with serum caps and magnetic stirrer, NaBH3CN (6.0 g, 0.095 mol) and tert-butyl-2-{1-[4-(ethoxycarbonyl)phenyl]ethylidene}hydrazinecarboxylate (25.6 g, 0.084 mol) were dissolved in THF (200 mL). A solution of p-toluenesulfonic acid monohydrate (17.3 g, 0.091 mol) in THF (50 mL) was slowly added via syringe pump. Completion of addition required about 10 h. The mixture was diluted with EtOAc (200 mL) and the suspension extracted with brine (150 mL). The organic phase was separated, dried (Na2SO4) and concentrated on a rotovap to give white solid. The white solid was taken in CH2Cl2 (100 mL) and 1 N NaOH (100 mL) was added. The suspension was stirred vigorously at r.t. for 1 h and then diluted with CH2Cl2 (100 mL). The organic phase was separated and extracted with 1N HCl (2×150 mL), brine (2×150 mL), dried (Na2SO4) and concentrated to approximately 50 mL. Product precipitated as white solid and was collected by filtration and washed with hexane to yield tert-butyl 2-{1-[4-(ethoxycarbonyl)phenyl]ethyl}hydrazinecarboxylate. HPLC/MS: m/z=331.3 (M+Na)+, Rt=3.24 min. 1H NMR (500 MHz, CDCl3): δ 8.03 (2H, d, J=8.0 Hz), 7.44 (2H, d, J=8.0 Hz), 5.99 (1H, br s), 4.40 (2H, q, J=7.0 Hz), 4.29 (1H, m), 1.45 (9H, s), 1.41 (3H, t, J=7.0 Hz), 1.35 (3H, d, J=6.5 Hz).

Workup

  1. additionCompletion of addition required about 10 h
  2. extractionthe suspension extracted with brine (150 mL)
  3. customThe organic phase was separated
  4. dry with materialdried (Na2SO4)
  5. concentrationconcentrated on a rotovap
  6. customto give white solid
  7. customThe organic phase was separated
  8. extractionextracted with 1N HCl (2×150 mL), brine (2×150 mL)
  9. dry with materialdried (Na2SO4)
  10. concentrationconcentrated to approximately 50 mL
  11. customProduct precipitated as white solid
  12. filtrationwas collected by filtration
  13. washwashed with hexane

Sources & evidence

ORD record
ord-a80932ef93604ac78e89fdc7d8ac8898
Source dataset
uspto-grants-2009_10
Patent number
US07598285B2

Reaction notes

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