Triphenylphosphine → 2-(3,6-dihydro-2H-pyran-4-yl)-4-nitro-pyridine

HRID 917469Notes

Reaction equation

HRID 917469 reaction equation
Cl[C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[CH:4][N:3]=1.C([Sn](CCCC)(CCCC)[C:16]1[CH2:17][CH2:18][O:19][CH2:20][CH:21]=1)CCC.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Cl-].[Li+].C(C1C(O)=C(C(C)(C)C)C=C(C)C=1)(C)(C)C>CN(C)C=O.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[O:19]1[CH2:18][CH:17]=[C:16]([C:2]2[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[CH:4][N:3]=2)[CH2:21][CH2:20]1

Participants

8

Reactant 5

HCID 11776TriphenylphosphineHCID 314042,6-Di-tert-butyl-4-methylphenolHCID 433294Lithium ChlorideHCID 7351522-Chloro-4-nitropyridineHCID 222522584-Tributylstannyl-3,6-dihydro-2H-pyran

Product 1

HCID 589627032-(3,6-dihydro-2H-pyran-4-yl)-4-nitro-pyridineYield 23%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
100 °C

Procedure

To a stirred solution of 7.00 g (44.2 mmol) 2-chloro-4-nitropyridine in 150 ml N,N-dimethylformamide were added 16.8 g (45.0 mmol) tributyl-(3,6-dihydro-2H-pyran-4-yl)stannane, 3.72 g (5.30 mmol) bis(triphenylphosphine)palladium(II) chloride, 6.95 g (26.5 mmol) triphenylphosphine, 15.0 g (353 mmol) lithium chloride and 0.97 g (4.42 mmol) 2,6-di-tert-butyl-p-cresol. The mixture was heated at 100° C. for 4 h and then cooled to room temperature and concentrated in vacuo. Flash chromatography (heptane/ethyl acetate 9/1 then ethyl acetate) afforded 2.10 g (23%) 2-(3,6-dihydro-2H-pyran-4-yl)-4-nitro-pyridine as an orange solid. ES-MS m/e (%): 207 (M+H+, 100).

Workup

  1. temperaturecooled to room temperature
  2. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-c43bf915c4d7416cbe305d1c99198453
Source dataset
uspto-grants-2007_09
Patent number
US07273865B2

Reaction notes

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