Non-fluorinated Parent Research Articles

Photochemistry of 2-(Perfluoroalkyl)cycloalkanones

Abstract In an earlier study [1] we had compared the photochemical behaviour of 2-trifluoromethylcyclohexanone ( 1a ) to that of the non-fluorinated parent ketone 2-methylcyclohexanone. Substitution of the methyl group on C(2) by a CF3-group strongly enhances bimolecular reactions such as reduction product formation in 2-propanol or oxetane formation in the presence of alkenes. We now report preliminary results on monomolecular photochemical reactions of several 2-(perfluoroalkyl)cycloalkanones.

ChemInform Abstract: PHOTOCHEMISTRY OF 2‐(TRIFLUOROMETHYL)CYCLOHEXANONE

AbstractDas photochemische Verhalten der Titelverbindung (I) wird mit dem bereits bekannten Verhalten von 2‐Methylcyclohexanon verglichen.

The structure of 4′,4″-diethylstilbestrol (DES) quinone

The structure of 4′,4″-diethylstilbestrol quinone (DES quinone), a short-lived metabolic intermediate of the synthetic estrogen E-diethylstilbestrol (DES), was investigated by 13C- and 1H-nmr. Selected homonuclear decoupling experiments were carried out to identify the carbons and protons with which resonances were associated. The 1H-nmr spectrum of DES quinone remained unchanged in the temperature range from 25°C to 65°C. The spectral results suggested the structure of DES quinone to be planar or time-averaged planar with the exception of the freely rotating ethyl groups. The conformation of this intermediate was found to be transoid without any indication of conversion through a cisoid conformation. The similarity of the 1H-nmr spectrum of 3′,3″,-5′,5″-tetrafluoro-4′,4″-diethylstilbestrol quinone (TF-DES quinone) and that of the non-fluorinated parent suggested a high degree of structural similarity. The planar structures of the quinone intermediates differed from those of DES or Z,Z-dienestrol which were not coplanar with respect to the aromatic ring systems.

The biological activity of a series of 6,6-difluoro norethindrone derivatives

When administered orally in the McPhail assay, 17α-ethynl-6,6-difluoro-17 β -hydroxyestr-4-en-3-one (I) elicited twice the progestational activity of the nonfluorinated parent. The 17 β -acetoxy (II), 3 β, 17 β -diacetoxy (III), and 3-ethylene ketal (IV) derivatives demonstrated 2, 2–3, and approximately 1 times the activity of norethindrone respectively. When tested for oral anti-uterotrophic activity in mice, I, II, III, and IV elicited 3.9, 1.4, 3.2 and ≥1 times the activity of norethindrone respectively.

Cytotoxicity of steroids to mammalian cells in tissue culture.

SummaryThe cytotoxicity of a number of steroids to Earle's L cells (NCTC 929), Gey's adrenal cells (3G29), and Ehrlich ascites cells (Squibb #2) was determined using cells grown in suspension culture in serum-containing media. The L cells were much more sensitive to fluorinated steroids than they were to the non-fluorinated parent compounds; progesterone derivatives were more toxic than corticosteroids. The adrenal cells were quite insensitive to the fluorinated steroids, while the Ehrlich ascites cells were less sensitive than the L cells but more sensitive than the adrenal cells. The adrenal cells were found to convert progesterone to: Δ4-pregnene-20α-ol-3-one; Δ4-pregnene-20β/-ol-3-one; Δ4-pregnene-6α-ol-3,20-dione; and Δ4-pregnene-6β-ol-3,20-dione, as determined by filter paper chromatographic methods and spot tests. A similar series of compounds was formed from 11α-hydroxyprogesterone by this cell line.