Triethylamine → N'-(3-chloro-2-fluoro-phenyl)-N-methyl-hydrazinecarboxylic acid tert-butyl ester

HRID 1438043Notes

Reaction equation

HRID 1438043 reaction equation
[C:1]([O:5][C:6]([N:8]([CH3:10])[NH2:9])=[O:7])([CH3:4])([CH3:3])[CH3:2].[Cl:11][C:12]1[C:13]([F:21])=[C:14](B(O)O)[CH:15]=[CH:16][CH:17]=1.C(N(CC)CC)C>ClCCCl.C([O-])(=O)C.[Cu+2].C([O-])(=O)C>[C:1]([O:5][C:6]([N:8]([CH3:10])[NH:9][C:14]1[CH:15]=[CH:16][CH:17]=[C:12]([Cl:11])[C:13]=1[F:21])=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 37482801-Boc-1-methylhydrazine2×HCID 162171583-Chloro-2-fluorophenylboronic Acid

Product 1

HCID 57941360N'-(3-chloro-2-fluoro-phenyl)-N-methyl-hydrazinecarboxylic acid tert-butyl esterYield 47.2%

Reagents, catalysts & solvents 2

HCID 8895Cupric acetateCatalystHCID 111,2-DichloroethaneSolvent

Conditions

Temperature
50 °C

Procedure

A mixture of N-methyl-hydrazinecarboxylic acid tert-butyl ester (Intermediate 1; 500 mg, 3.4 mmol), 3-chloro-2-fluorophenylboronic acid (Aldrich; 584 mg, 3.35 mmol), copper(II) acetate (621 mg, 3.4 mmol) and triethylamine (480 μL, 3.4 mmol) in 1,2-dichloroethane (4 mL) was heated in an oil bath at 50° C. for 3 h. The mixture was allowed to cool, and it was then adsorbed onto silica gel and purified by chromatography using an ISCO 40 g column, eluting with 20-40% ethyl acetate/hexanes, to give N′-(3-chloro-2-fluoro-phenyl)-N-methyl-hydrazinecarboxylic acid tert-butyl ester (434 mg, 46%) as a colorless oil which solidified on standing.

Workup

  1. temperatureto cool
  2. custompurified by chromatography
  3. washeluting with 20-40% ethyl acetate/hexanes

Sources & evidence

ORD record
ord-6e795915622f4757beeb6008b714e0e4
Source dataset
uspto-grants-2009_11
Patent number
US07622492B2

Reaction notes

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