Triethyl phosphite → Diethyl 3-bromo-5-(5-(trifluoromethyl)pyridin-2-yloxy)benzylphosphonate

HRID 1666459Notes

Reaction equation

[Br:1][C:2]1[CH:3]=[C:4]([CH:16]=[C:17]([CH2:19]Cl)[CH:18]=1)[O:5][C:6]1[CH:11]=[CH:10][C:9]([C:12]([F:15])([F:14])[F:13])=[CH:8][N:7]=1.[CH2:21]([O:23][P:24]([O:28]CC)[O:25][CH2:26][CH3:27])[CH3:22]>>[Br:1][C:2]1[CH:18]=[C:17]([CH:16]=[C:4]([O:5][C:6]2[CH:11]=[CH:10][C:9]([C:12]([F:15])([F:14])[F:13])=[CH:8][N:7]=2)[CH:3]=1)[CH2:19][P:24](=[O:28])([O:25][CH2:26][CH3:27])[O:23][CH2:21][CH3:22]

Participants

Reactant 2

HCID 31215Triethyl phosphite

HCID 66875930HCID 66875930, compound

Product 1

HCID 86623908Diethyl 3-bromo-5-(5-(trifluoromethyl)pyridin-2-yloxy)benzylphosphonateYield 63.3%

Conditions

Temperature: 160 °C

Procedure

2-(3-Bromo-5-(chloromethyl)phenoxy)-5-(trifluoromethyl)pyridine (4.7 g, 12.82 mmol) was dissolved in triethylphosphite (18.7 mL, 107.7 mmol) and refluxed at 160° C. for 4 h. It was then purified by silica gel column chromatography (30-40% ethyl acetate/hexane) to give the title compound (3.8 g, 63%). 1H NMR (500 MHz, CDCl3): δ 8.42 (s, 1H), 7.91 (d, J=10.75 Hz, 1H), 7.33 (s, 1H), 7.24 (s, 1H), 7.07 (s, 1H), 7.02 (d, J=8.6 Hz, 1H), 4.04 (q, J=7.5 Hz, 4H), 3.14 (s, 1H), 3.10 (s, 1H), 1.25 (t, J=7 Hz, 6H); m/z (468.1, 470.1, M+ H+).

Workup

customIt was then purified by silica gel column chromatography (30-40% ethyl acetate/hexane)

Sources & evidence

ORD record: ord-58dab16164f94cbea1a1c2eee6abe3c4
Source dataset: uspto-grants-2011_10
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08044052B2

Reaction notes

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