The synthesis of the epoxide and some other possible metabolites of precocene I

Chemistry of Acronycine; Part 1. Synthesis of 1-Hydroxy-1,2-dihydroacronycine and 2-Hydroxy-1,2-dihydroacronycine

“…A potential precursor of the benzylic alcohol 2 is the bromohydrin 4. The reactivity of 1 towards N-bromosuccinimide (NBS) has been studied in a first attempt to verify the feasibility of the above approach (18). When treated with NBS in anhydrous medium, 1 gives rise to the adduct Sin 54% yield accompanied by small amounts of 2-bromoacronycine (6) and 2,5-dibromoacronycine (7).…”

“…419 (M, 21), 417 (M4-, 21), 401(12), 399(12), 390(18), 388(18), 372 (5), 370(5), 337 (37), 320(20), 308 (40), 44 (100) UV: 213 (sh), 230, 265 (sh), 276, 300, 320 (sh), 384; IR: 3420,2968, 2920, 1620, 1594, 1583, 1118, 752, 642; 1H-NMR (CDCI3, TMS) 8.18 (1H, dd, J 8 and 1.5, H-8), 7.65 (1H, td, J = 8 and 1.5, H-b), 7.35 (1H, dd, J = 8 and 1.5, H-li), 7.23 (1H, td, J = 8 and 1.5, H-9), 5.13 (1H, br.s, D20 exch., OH-i), 5.11 (1FI, d, J = 9, H-i), 5.04 (1H, s, H-5), 4.93 (1H, d,…”

Synthesis of Models of Metabolites: Oxidation of Variously Substituted Chromenes Including Acronycine, by a Porphyrin Catalytic System.

“…The solvent for the second chromatography was cyclohexane/ ethyl acetate (1/1, v/v). 3,4-Dihydroxy-7-methoxy-2,2-dimethylchromane 12 (yield: 13%) was a known compound [30][31][32].…”

Physiological Activities of Anti-Juvenile Hormone Agents Against Insects and Their Role For Devising Fourth Generation Insecticides: A Comprehensive Review

“…As previously discussed (see the section of 'Action mechanisms of anti-JH agents'), precocenes are probably biotransformed into a highly reactive 3,4-epoxide intermediate through the action of monooxygenases in the CA of insects. The eucaryotic metabolism of PI, by the insect and animal enzyme systems, involves oxidation to an unstable compound 3,4-epoxy-7-methoxy-2,2-dimethyl-chromene which produces the corresponding trans-5 and cis-6-diols (Halpin et al, 1982(Halpin et al, , 1984Jennings and Ottridge, 1984). Considering the metabolism of PII in several insect species, Ohta et al (1977) reported that its metabolism showed that the 6,7dimethoxy-2,2-dimethylchromene-3,4-diol (PII diol) was the major organosoluble metabolite while the 6,7-dimethoxy-2,2-dimethylchroman-3-ol (PII 3-oi) was a minor metabolite.…”