2,2,3,3,4,4,4-heptafluoro-1-phenylbutan-1-one → HCID 21740024, compound

Participants

Reaction Conditions

Reaction Steps

A mixture of 159 g (0.5 mole) 1,3-bis(3,4-dimethylphenoxy)benzene, 274 g (1.0 mole) phenyl heptafluoropropyl ketone, and 280 g (14 moles) HF was heated in an autoclave for 8 hours at 140° C. After cooling, and venting off excess HF, the autoclave contents were transferred to a 1-gallon polyethylene jar, half filled with ice water, and containing 500 ml of 50% sodium hydroxide. The autoclave was rinsed out with methylene chloride, and the washings were added to the jar. The product was extracted with methylene chloride, the extracts were filtered through a layer of alumina, and the solvent was stripped off at atmospheric pressure yielding 312 g of a taffy-like residue, which was very soluble in acetone. The residue was extracted with several 500 ml portions of boiling methanol, and then was stirred with isopropyl alcohol, producing a solid in 21.3 g (5.1 % yield) with a sharp IR spectrum, devoid of OH bands, and melting in the 198-220° C. range, and after recrystallization from heptane at 237-238° C. NMR of the product melting over the wide range showed presence of cis- and trans- isomers: aromatic protons as multiplets 7.05-7.25, 6.85-7.0, broad s 6.66, two broad singlets at 6.58 and 6.50, and methyl singlets at 2.20 and 2.02 ppm in 6:7:2:1(total of the 6.58 and 6.50 peaks): 6:6 ratio. The recrystallized material was a single isomer, by NMR m 7.1, m 7.0, s 6.94, s 6.86, broad s 6.65, broad s 6.47, s 2.23 and s 2.04 ppm in 4:6:2:1:2:1:6:6 ratio. Analysis: calc. for C42H28F14O2 : C 60.7; H 3.37, F 32.0; F 32.0; found C 70.0; H 3.61, F 30.1%.

Provenance & Evidence