Carbon Dioxide → HCID 66890939, compound

HRID 253312Notes

Reaction equation

N[C:2]1[CH:3]=[C:4]([O:17][CH2:18][CH2:19][O:20][CH3:21])[C:5]([O:12][CH2:13][CH2:14][O:15][CH3:16])=[C:6]([CH:11]=1)[C:7]([O:9][CH3:10])=[O:8].C(=O)=O.B(F)(F)[F:26].CCOCC.C(ON=O)(C)(C)C>COCCOC.CCOCC>[F:26][C:2]1[CH:3]=[C:4]([O:17][CH2:18][CH2:19][O:20][CH3:21])[C:5]([O:12][CH2:13][CH2:14][O:15][CH3:16])=[C:6]([CH:11]=1)[C:7]([O:9][CH3:10])=[O:8]

Participants

Conditions

Temperature: 110 °C

Procedure

A solution of methyl 5-amino-2,3-bis{[2-(methyloxy)ethyl]oxy}benzoate (2.2 g, 7.4 mmol) in 1,2-dimethoxyethane (5 mL) was cooled at −4° C. and then cooled in solid dry-ice. To this mixture was added first boron trifluoride diethyl etherate (1.3 mL, 10 mmol), and then tert-butylnitrite (1.4 mL, 12 mmol), and the resulting mixture was stirred at −4° C. for 2 hours. It was then diluted with ether (100 mL) and a solid precipitated and was collected and washed with ether. The solid was suspended in 1,2,4-trichlorobenzene (20 mL) and heated at 110° C. for 18 hours. After cooling to room temperature, it was applied directly onto a silica gel column with hexane, and then chromatographed (30% ethyl acetate-hexane) to give methyl 5-fluoro-2,3-bis{[2-(methyloxy)ethyl]oxy}benzoate (0.35 g, 1.2 mmol, 16% yield). 1H NMR (400 MHz, CDCl3): 7.05-7.02 (d, d, 1H), 6.83-6.80 (d, d, 1H), 4.20-4.13 (m, 4H), 3.90 (s, 3H), 3.79-3.72 (m, 4H), 3.44 (s, 6H).

Workup

customa solid precipitated
customwas collected
washwashed with ether
temperatureAfter cooling to room temperature
customchromatographed (30% ethyl acetate-hexane)

Sources & evidence

ORD record: ord-e3da94f08fb54c2781c3c88d00872227
Source dataset: uspto-grants-2011_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07872014B2

Reaction notes

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