3-Chloro-2-methyl-1-propene → 2-Methylallyl 2,3-difluoro-6-(2-methylallyloxy)benzoate

HRID 445869Notes

Reaction equation

[F:1][C:2]1[C:10]([F:11])=[CH:9][CH:8]=[C:7]([O:12][CH2:13][C:14]([CH3:16])=[CH2:15])[C:3]=1[C:4]([OH:6])=[O:5].Cl[CH2:18][C:19]([CH3:21])=[CH2:20].C(=O)([O-])[O-].[K+].[K+]>CN(C=O)C>[F:1][C:2]1[C:10]([F:11])=[CH:9][CH:8]=[C:7]([O:12][CH2:13][C:14]([CH3:16])=[CH2:15])[C:3]=1[C:4]([O:6][CH2:20][C:19]([CH3:21])=[CH2:18])=[O:5]

Participants

Conditions

Temperature: 65 °C

Procedure

A mixture of 2,3-difluoro-6-(2-methylallyloxy)benzoic acid (732) (1.45 g, 6.35 mmol), 3-chloro-2-methylpropene (0.77 mL, 7.62 mmol), and potassium carbonate (1.76 g, 12.7 mmol) in anhydrous DMF was stirred at 65° C. under N2 overnight. The mixture was filtered and the filtrate was evaporated to dryness. The residue was purified by flash column chromatography eluting with hexanes-EtOAc (4:1) to provide 2-methylallyl 2,3-difluoro-6-(2-methylallyloxy)benzoate (733) (1.55 g, 87%). 1H NMR (400 MHz, CDCl3) δ 7.14 (q, J=9.5 Hz, 1H), 6.63-6.60 (m, 1H), 5.09 (s, 1H), 5.06 (s, 1H), 4.98 (s, 2H), 4.78 (s, 2H), 4.45 (s, 2H), 1.81 (s, 3H), 1.79 (s, 3H).

Workup

filtrationThe mixture was filtered
customthe filtrate was evaporated to dryness
customThe residue was purified by flash column chromatography
washeluting with hexanes-EtOAc (4:1)

Sources & evidence

ORD record: ord-52942a469d344d1887e3060284a83d88
Source dataset: uspto-grants-2013_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08476308B2

Reaction notes

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