2-Chloro-3-nitropyridine → HCID 89760889, compound

HRID 523117Notes

Reaction equation

HRID 523117 reaction equation
[Mg+2].[Cl-].[Cl-].[Cl:4][C:5]1[C:10]([N+:11]([O-:13])=[O:12])=[CH:9][CH:8]=[CH:7][N:6]=1.I[C:15]1[CH:25]=[CH:24][C:18]([C:19]([O:21][CH2:22][CH3:23])=[O:20])=[CH:17][CH:16]=1.O1C=CC=C1P(C1OC=CC=1)C1OC=CC=1>C1COCC1.[NH4+].[Cl-].C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd]>[Cl:4][C:5]1[C:10]([N+:11]([O-:13])=[O:12])=[C:9]([C:15]2[CH:25]=[CH:24][C:18]([C:19]([O:21][CH2:22][CH3:23])=[O:20])=[CH:17][CH:16]=2)[CH:8]=[CH:7][N:6]=1

Participants

8

Reactant 4

HCID 796132-Chloro-3-nitropyridineHCID 142891Ethyl 4-iodobenzoateHCID 521585Tris(furan-2-yl)phosphaneHCID 5360315Magnesium Chloride

Product 1

HCID 89760889HCID 89760889, compoundYield 58%

Reagents, catalysts & solvents 3

HCID 6505921(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; palladiumCatalystHCID 8028TetrahydrofuranSolvent2×HCID 25517Ammonium ChlorideSolvent

Procedure

A dry, argon-filled Schlenk tube with a magnetic stirrer bar and septum is initially charged with (TMP)2Zn.MgCl2 (3.16 ml, 1.2 mmol). After adding 2-chloro-3-nitropyridine (159 mg, 1 mmol) in anhydrous THF (2 ml) at 25° C., the mixture is stirred for 1 min, then a solution of ethyl 4-iodobenzoate (387 mg, 1.4 mmol), bis(dibenzylideneacetone)palladium(0) (17 mg, 3 mol %) and tri-2-furylphosphine (14 mg, 6 mol %) in anhydrous THF (2 ml) is added dropwise and the mixture is stirred at 25° C. for 1 h. For workup, the mixture is diluted with aqueous sat. NH4Cl solution (30 ml) and extracted with ethyl acetate (3×30 ml). After the combined organic phases have been dried over Na2SO4, the solvent has been distilled off and purification has been effected by column chromatography on silica gel (heptane:ethyl acetate), the desired compound (177 mg, 58% of theory) was obtained as a yellowish oil.

Workup

  1. additionA dry, argon-filled Schlenk tube with a magnetic stirrer bar
  2. additionseptum is initially charged with (TMP)2Zn
  3. stirringthe mixture is stirred at 25° C. for 1 h
  4. extractionextracted with ethyl acetate (3×30 ml)
  5. dry with materialAfter the combined organic phases have been dried over Na2SO4
  6. distillationthe solvent has been distilled off
  7. custompurification

Sources & evidence

ORD record
ord-6d0b93a4913743268c4842b9ee2cf615
Source dataset
uspto-grants-2016_05
Patent number
US09334292B2

Reaction notes

Loading…