Potassium Phosphate, Tribasic → 3-Benzyl-5-nitropyridine

HRID 2367682

Reaction equation

HRID 2367682 reaction equation
Br[C:2]1[CH:3]=[N:4][CH:5]=[C:6]([N+:8]([O-:10])=[O:9])[CH:7]=1.[CH2:11](B1OC(C)(C)C(C)(C)O1)[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.[O-]P([O-])([O-])=O.[K+].[K+].[K+]>O1CCOCC1.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]>[CH2:11]([C:2]1[CH:3]=[N:4][CH:5]=[C:6]([N+:8]([O-:10])=[O:9])[CH:7]=1)[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1

Participants

6

Reactant 3

HCID 62657Potassium Phosphate, TribasicHCID 27628983-Bromo-5-nitropyridineHCID 38649642-Benzyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

Product 1

HCID 735549143-Benzyl-5-nitropyridineYield 37.2%

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 312751,4-DioxaneSolvent

Procedure

To a solution of 3-bromo-5-nitropyridine (LXXVII) (295 mg, 1.45 mmol) in dioxane (14 mL) was added 2-benzyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (LXXVIII) (420 μL, 1.89 mmol), PdCl2(dppf)2, (120 mg, 0.15 mmol) and 2M aqueous K3PO4 (2.2 mL, 4.36 mmol). The reaction was microwaved at 90° C. for 2 h. The reaction was cooled and the organic phase was separated, dried over MgSO4 and evaporated under vacuum. The residue was purified by silica gel column chromatography (100% hexane 6:94 EtOAc:hexane) to give 3-benzyl-5-nitropyridine (LXXIX) as brown oil (117 mg, 0.54 mmol, 37% yield). 1H NMR (DMSO-d6) δ ppm 4.16 (s, 2H), 7.21-7.25 (m, 1H), 7.31-7.33 (m, 4H), 8.45-8.46 (m, 1H), 8.93 (d, J=2 Hz, 1H), 9.21 (d, J=3 Hz, 1H); ESIMS found for C12H10N2O2 m/z 215 (M+H).

Workup

  1. customThe reaction was microwaved at 90° C. for 2 h
  2. temperatureThe reaction was cooled
  3. customthe organic phase was separated
  4. dry with materialdried over MgSO4
  5. customevaporated under vacuum
  6. customThe residue was purified by silica gel column chromatography (100% hexane 6:94 EtOAc:hexane)

Sources & evidence

ORD record
ord-3f2a847532cb4b7ca30ab5f32ea63aba
Source dataset
uspto-grants-2014_04
Patent number
US08697887B2

Linked notes

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