Nitrogen → HCID 71255741, compound

HRID 1508336Notes

Reaction equation

HRID 1508336 reaction equation
N#N.[C:3]([O:7][C:8]([CH3:11])([CH3:10])[CH3:9])(=[O:6])[NH:4][NH2:5].Br[C:13]1[CH:18]=[C:17]([Cl:19])[CH:16]=[CH:15][N:14]=1.C([O-])([O-])=O.[Cs+].[Cs+]>[Cl-].[Na+].O.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].C(Cl)Cl.O.C1(C)C=CC=CC=1>[Cl:19][C:17]1[CH:16]=[CH:15][N:14]=[C:13]([NH:5][NH:4][C:3]([O:7][C:8]([CH3:11])([CH3:10])[CH3:9])=[O:6])[CH:18]=1

Participants

9

Reactant 4

HCID 947NitrogenHCID 10796Cesium carbonateHCID 70091tert-Butyl carbazateHCID 27628362-Bromo-4-chloropyridine

Product 1

HCID 71255741HCID 71255741, compoundYield 35%

Reagents, catalysts & solvents 4

HCID 178418807HCID 178418807, compoundCatalystHCID 962WaterSolventHCID 1140TolueneSolventHCID 57417360Sodium chloride; waterSolvent

Conditions

Temperature
100 °C

Procedure

4-Chloro-2-hydrazinylpyridine, 2HCl: In microwave vial was added toluene (4 mL) and purged with N2 for 5 min. tert-Butyl carbazate (66.6 mg, 0.494 mmol), 2-bromo-4-chloropyridine (95 mg, 0.494 mmol), Cs2CO3 (161 mg, 0.494 mmol), and PdCl2(dppf)-CH2Cl2 adduct (4.03 mg, 4.94 μmol) were added. The sealed tube was heated at 100° C. for 5 h. To the reaction mixture was added water, brine and the mixture was extracted with EtOAc (2×). The combined organic layer was concentrated and purified by silica gel chromatography to provide tert-butyl 2-(4-chloropyridin-2-yl)hydrazinecarboxylate (42 mg, 35%) as red oil. MS(ESI) m/z: 244.2 (M+H)+. To the above oil was added 4 N HCl in dioxane (2 mL) and the reaction was stirred at rt for 2 h. The mixture was concentrated to dryness to give the desired (36 mg, 34%) as a white solid. MS(ESI) m/z: 144.0 (M+H)+.

Workup

  1. additionwere added
  2. extractionthe mixture was extracted with EtOAc (2×)
  3. concentrationThe combined organic layer was concentrated
  4. custompurified by silica gel chromatography

Sources & evidence

ORD record
ord-f344138185a94242bb08fa070c5e1621
Source dataset
uspto-grants-2015_12
Patent number
US09221818B2

Reaction notes

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