Sodium Hydroxide → N-(4-chloro-3-hydrazinylbenzyl)cyclopropanecarboxamide

HRID 59329Notes

Reaction equation

HRID 59329 reaction equation
[NH2:1][C:2]1[CH:3]=[C:4]([CH:12]=[CH:13][C:14]=1[Cl:15])[CH2:5][NH:6][C:7]([CH:9]1[CH2:11][CH2:10]1)=[O:8].[N:16]([O-])=O.[Na+].[OH-].[Na+]>Cl.O>[Cl:15][C:14]1[CH:13]=[CH:12][C:4]([CH2:5][NH:6][C:7]([CH:9]2[CH2:11][CH2:10]2)=[O:8])=[CH:3][C:2]=1[NH:1][NH2:16]

Participants

6

Reactant 3

HCID 14798Sodium HydroxideHCID 23668193Sodium NitriteHCID 89035202N-(3-amino-4-chlorobenzyl)cyclopropanecarboxamide

Product 1

HCID 90019904N-(4-chloro-3-hydrazinylbenzyl)cyclopropanecarboxamideYield 75%

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolvent2×HCID 962WaterSolvent

Procedure

To a cold solution of N-(3-amino-4-chlorobenzyl)cyclopropanecarboxamide (2.00 g, 8.90 mmol) in conc. HCl (25 mL) was added aqueous solution of sodium nitrite (0.676 g, 9.7 mmol) at −20° C. to −25° C. The reaction mass was stirred at −20° C. to −25° C. for 30 min, followed by addition of stannous chloride solution (5.0 g, 22.2 mmol) in conc. HCl slowly. The reaction mass was stirred at −20° C. to −25° C. for 1 h. The reaction mass was basified with aqueous NaOH at below 0° C. The reaction mass was diluted with water, extracted with 10% MeOH:DCM and concentrated to afford 1.6 g of desired product. 1H NMR (300 MHz, DMSO d6): δ 0.66 (m, 4H), 1.58 (m, 1H), 4.10 (s, 2H), 4.18 (d, J=5.4 Hz, 2H), 6.47 (m, 2H), 7.11 (m, 2H), 8.51 (br s, 1H); MS (m/z): 240.05 (M+FI)+.

Workup

  1. stirringThe reaction mass was stirred at −20° C. to −25° C. for 1 h
  2. extractionextracted with 10% MeOH
  3. concentrationDCM and concentrated

Sources & evidence

ORD record
ord-f8c44053173c4b85b3602ec263930f6b
Source dataset
uspto-grants-2016_09
Patent number
US09439890B2

Reaction notes

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