Potassium Carbonate → Tert-butyl 2-({1-[4-(5-cyanopyridin-2-yl)phenyl]cyclopropyl}carbonyl)hydrazinecarboxylate

HRID 1424090Notes

Reaction equation

HRID 1424090 reaction equation
[C:1]([O:5][C:6]([NH:8][NH:9][C:10]([C:12]1([C:15]2[CH:20]=[CH:19][C:18](B3OC(C)(C)C(C)(C)O3)=[CH:17][CH:16]=2)[CH2:14][CH2:13]1)=[O:11])=[O:7])([CH3:4])([CH3:3])[CH3:2].Cl[C:31]1[CH:36]=[CH:35][C:34]([C:37]#[N:38])=[CH:33][N:32]=1.C(=O)([O-])[O-].[K+].[K+]>COCCOC.O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[C:37]([C:34]1[CH:35]=[CH:36][C:31]([C:18]2[CH:19]=[CH:20][C:15]([C:12]3([C:10]([NH:9][NH:8][C:6]([O:5][C:1]([CH3:4])([CH3:2])[CH3:3])=[O:7])=[O:11])[CH2:14][CH2:13]3)=[CH:16][CH:17]=2)=[N:32][CH:33]=1)#[N:38]

Participants

7

Reactant 3

HCID 11430Potassium CarbonateHCID 51520946-Chloro-3-pyridinecarbonitrileHCID 86712939Tert-butyl2-({1-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]cyclopropyl}carbonyl)hydrazinecarboxylate

Product 1

HCID 86712938Tert-butyl 2-({1-[4-(5-cyanopyridin-2-yl)phenyl]cyclopropyl}carbonyl)hydrazinecarboxylateYield 26%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 80711,2-DimethoxyethaneSolvent

Procedure

A mixed solution of the compound (100 g, 249 mmol) obtained in Example 60-1), 2-chloro-5-cyanopyridine (44.8 g, 323 mmol), potassium carbonate (68.7 g, 497 mmol), and tetrakis(triphenylphosphine)palladium (14.4 g, 12.4 mmol) in 1,2-dimethoxyethane (800 mL) and water (200 mL) was stirred at 100° C. for 8 h, then at 80° C. for 14 h, and further at 100° C. for 5 h. The reaction mixture was cooled to room temperature, insoluble substances were filtered off, dichloromethane was added to the filtrate, and the organic layer was washed with saturated aqueous sodium hydrogencarbonate and saturated sodium chloride solution in this order. The solvent was distilled off under reduced pressure, and the residue was washed with dichloromethane and hexane and then purified by silica gel column chromatography (ethyl acetate:methanol=1:1) to obtain the title compound (24.1 g, 26%) as a white solid.

Workup

  1. waitfurther at 100° C. for 5 h
  2. filtrationinsoluble substances were filtered off
  3. additiondichloromethane was added to the filtrate
  4. washthe organic layer was washed with saturated aqueous sodium hydrogencarbonate and saturated sodium chloride solution in this order
  5. distillationThe solvent was distilled off under reduced pressure
  6. washthe residue was washed with dichloromethane and hexane
  7. custompurified by silica gel column chromatography (ethyl acetate:methanol=1:1)

Sources & evidence

ORD record
ord-56cae7efc759474caca997ff0a03651f
Source dataset
uspto-grants-2015_01
Patent number
US08927536B2

Reaction notes

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