1,4-Bis(diphenylphosphino)butane → Methyl 3-Chloro-5-(methoxymethyl)-2-pyridinecarboxylate

HRID 377015Notes

Reaction equation

Cl[C:2]1[C:7]([Cl:8])=[CH:6][C:5]([CH2:9][O:10][CH3:11])=[CH:4][N:3]=1.[C:12]1(P(C2C=CC=CC=2)CCCCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[C:42]([O-:45])(=[O:44])C.[Na+]>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.CO>[Cl:8][C:7]1[C:2]([C:42]([O:45][CH3:12])=[O:44])=[N:3][CH:4]=[C:5]([CH2:9][O:10][CH3:11])[CH:6]=1

Participants

Conditions

Temperature: 165 °C

Procedure

An autoclave was charged with 1.16 g (5.6 mmol) of 2,3-dichloro-5-(methoxymethyl)pyridine, 72 mg of 1,4-bis(diphenylphosphino)butane [3 mol percent based on the 2,3-dichloro-5-(methoxymethyl)pyridine], 8 mg of bis(triphenylphosphine)palladium(II) chloride [0.2 mol percent based on the 2,3-dichloro-5-(methoxymethyl)pyridine], 1.39 g (17 mmol) of sodium acetate and 16 ml of methanol. The autoclave is repeatedly flushed with carbon monoxide to replace the air by carbon monoxide. A carbon monoxide pressure of 15 bar was then applied to the autoclave. The reaction mixture was heated to 165° C. (bath temperature) and stirred for 6 hours. After cooling to room temperature, the crude product was concentrated under reduced pressure (30 mbar), chromotographed over silica gel 60 (eluent:hexane/ethyl acetate 3:1), analyzed by gas chromatography and characterized by 1H NMR and MS/GC-MS. The yield of the product was 1.05 g (87 percent) of a colorless oil. Other data concerning the product was:

Workup

customThe autoclave is repeatedly flushed with carbon monoxide
temperatureAfter cooling to room temperature
concentrationthe crude product was concentrated under reduced pressure (30 mbar)

Sources & evidence

ORD record: ord-0eda85f6af0a44339acac271c5fbe2de
Source dataset: uspto-grants-2000_02
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06022973

Reaction notes

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