Sodium cyanoborohydride → Tert-butyl 2-(1-benzhydrylazetidin-3-yl)hydrazinecarboxylate

HRID 1473339Notes

Reaction equation

HRID 1473339 reaction equation
[CH:1]([N:14]1[CH2:17][C:16](=[N:18][NH:19][C:20]([O:22][C:23]([CH3:26])([CH3:25])[CH3:24])=[O:21])[CH2:15]1)([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C([BH3-])#N.[Na+]>C(O)(=O)C>[CH:1]([N:14]1[CH2:17][CH:16]([NH:18][NH:19][C:20]([O:22][C:23]([CH3:26])([CH3:25])[CH3:24])=[O:21])[CH2:15]1)([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

4

Reactant 2

HCID 5003444Sodium cyanoborohydrideHCID 59436533Tert-butyl 2-(1-benzhydrylazetidin-3-ylidene)hydrazinecarboxylate

Product 1

HCID 59436626Tert-butyl 2-(1-benzhydrylazetidin-3-yl)hydrazinecarboxylateYield 94.1%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

The title compound was prepared as described in WO2010079443A1. To a solution of tert-butyl 2-(1-benzhydrylazetidin-3-ylidene)hydrazinecarboxylate (16.9 g, 48.1 mmol) in acetic acid (150 mL), sodium cyanoborohydride (3 g, 48.1 mmol) was added portionwise at 25° C. and stirred at the same temperature for 4 h under a nitrogen atmosphere. The solvent was completely evaporated off. The pH was adjusted to 8 to 10 with 1 M aqueous sodium hydroxide solution. The whole was extracted with dichloromethane (2×500 mL). Organic part was dried over sodium sulfate, filtered and concentrated in vacuum to give the crude tert-butyl 2-(1-benzhydrylazetidin-3-yl)hydrazinecarboxylate (16 g, 94%) as a white solid. This material was used as is for the next reaction. MS (ESI, positive ion) m/z (M+1): 354.4. 1H NMR (400 MHz, DMSO) δ 8.26 (s, 1H), 7.40 (d, J=7.5 Hz, 4H), 7.26 (t, J=7.5 Hz, 4H), 7.16 (t, J=7.2 Hz, 2H), 4.68 (t, J=4.6 Hz, 1H), 4.33 (s, 1H), 3.50 (dd, J=12.5, 6.2 Hz, 1H), 3.16 (t, J=7.0 Hz, 2H), 2.78 (t, J=6.9 Hz, 2H), 1.36 (s, 9H).

Workup

  1. customThe solvent was completely evaporated off
  2. extractionThe whole was extracted with dichloromethane (2×500 mL)
  3. dry with materialOrganic part was dried over sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated in vacuum

Sources & evidence

ORD record
ord-f2c9f1c6af0a428a80d406ab887b6b6b
Source dataset
uspto-grants-2015_04
Patent number
US09012443B2

Reaction notes

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