Synthesis of tertiary ¹⁴C‐labelled nonylphenol isomers

Abstract

SummaryThe ring-14 C-labelled p-nonylphenol (NP) isomers 4(3 0 ,50 -heptyl)-phenol (p262NP) were synthesized for application in metabolism and sorption studies. Friedel-Crafts alkylation of 14 C-labelled phenol and the corresponding tertiary nonylalcohol with BF 3 as catalyst was used. After clean-up of p262NP and p363NP by preparative thin-layer chromatography radiochemical yields amounted to 62.8 and 64.6%, specific radioactivities were 332 and 88.2 MBq/mmol, and radiochemical purities 97.6 and 99.0%. For both isomers, a large-scale synthesis with non-labelled phenol was additionally developed, which led to pure products (96 and 99%, respectively) without further purification steps. In the case of p353NP, which was formed as a diastereomeric mixture, the crude synthetic product had a radiochemical purity of 96.9% (radiochemical yield: 76.0%; specific activity: 298 MBq/mmol); thus, purification was not necessary. All products were characterized by means of gas chromatography-mass spectroscopy, 1 H-and 13 C-NMR, as well as IR.

Degradation of a Nonylphenol Single Isomer by Sphingomonas sp. Strain TTNP3 Leads to a Hydroxylation-Induced Migration Product

“…For 60 min, 880 mg of hydroquinone (99%; Fluka), 1.4 ml of 3,5-dimethyl-3-heptanol (nonanol, 99%; Avocado), 5.0 ml of diethyl ether (Acros), and 10 ml of BF 3 -ether complex (for synthesis; Merck) were incubated together at 60°C, as described previously (27). The product yield was 134.5 mg of o353NHQ with a purity of 49% (gas chromatography [GC]-MS analyses).…”

“…The product yield was 134.5 mg of o353NHQ with a purity of 49% (gas chromatography [GC]-MS analyses). GC-MS was used for identification and characterization of the reaction product (27). In addition, 3 mg of o353NHQ was purified by semipreparative HPLC (see above), and a 1 H solution-state nuclear magnetic resonance ( 1 H-NMR) with CDCl 3 was recorded as reported previously (27).…”

“…GC-MS was used for identification and characterization of the reaction product (27). In addition, 3 mg of o353NHQ was purified by semipreparative HPLC (see above), and a 1 H solution-state nuclear magnetic resonance ( 1 H-NMR) with CDCl 3 was recorded as reported previously (27). The following 1 H-NMR chemical shifts are given in parts per million relative to the internal standard tetramethylsilane at 400 MHz, and the coupling constants of J are given in hertz (for position of atoms, see Fig.…”

Optical Resolution and Absolute Configuration of Branched 4-Nonylphenol Isomers and Their Estrogenic Activities

“…4-(3-Ethyl-2-Methylhexan-2-yl)Phenol (NP-I) --The title compound was synthesized by Vinken's procedure. 14) To a stirred solution of 3-ethyl-2-methyl-2-hexanol (203 mg, 1.41 mmol) and phenol (550 mg, 5.80 mmol) in petroleum ether (100 ml), BF 3 ·Et 2 O (250 ml, 1.45 mmol) was added at room temperature under argon atmosphere. The reaction mixture was stirred at room temperature for 12 hr, and then crushed ice and water (100 ml) were added.…”

“…10,11) Consequently, in the field of NP research, it is absolutely necessary to consider NPs from an isomer-specific viewpoint. 12) Although a few groups have reported the synthesis of NP isomers, [13][14][15][16][17] all of these NP isomers were optically inactive (racemic) compounds. In our previous studies, we described preparative fractionation of a commercial NP mixture using HPLC to afford fourteen NP isomers (Fig.…”