Novel analgetics and molecular rearrangements in the morphine-thebaine group. XVIII. 3-Deoxy-6,14-endo-etheno-6,7,8,14-tetrahydrooripavines

Deoxymorphines: role of the phenolic hydroxyl in antinociception and opiate receptor interactions

“…N-Allyl-3-deoxydihydronormorphine (8). A mixture of 2.32 g (9 mmol) of 3-deoxydihydronormorphine (7), 1.13 g (9.3 mmol) of allyl bromide, and 3.0 g (21.7 mmol) of K2C03 in 30 mL of DMF was heated and stirred at 100 °C for 2 h. After cooling the mixture, the inorganic material was filtered and washed with CHC13, and the combined filtrate and washings were evaporated.…”

“…An analytical sample was obtained by filtration of this material through silica gel (60% Et20/petroleum ether) and recrystallization (EtOH/octane): mp 151.5-154.5 °C; MS M+ 483; NMR (CDC13) 1.27 (t, 3 H. J = 8 Hz, CH3), 3.77 (dd, 1 H, J = 2.8 and 2. 8 Hz, H-7), 4.15 (q, 2 H, J = 8 Hz, C02CH2-), 5.34 (s, 1 H, C-5 ), 6.70 (m, 2 H. C-l and C-2 ), 7.07 (m, 1 H, C-3 ), 7.30 and 7.44 (2 m, 5 H, SeC6H6); IR (Nujol) 1704 (>C=0) and 1682 (>NHCO) cm h Anal. (C25H25N04Se) C, , N.…”

“…The analytical sample was prepared by preparative TLC (silica gel, 40% EtOAc/hexane, three developments), followed by Darco treatment, filtration through a short silica column (50% EtOAc/hexane), and recrystallization from 50% EtOAc/hexane. The desired ,/3-unsaturated ketone was obtained as white crystals: mp 164-167 °C; MS M+ 325; NMR (CDC13) 1.28 (t, 3 H, J = 8 Hz, CH3), 4.16 (q, 2 H, J = 8 Many of the biotransformation processes observed in the metabolism of xenobiotics are mediated by hepatic mixed-function oxidases with cytochrome P-450 as the terminal oxidase. Metabolic oxidations of aliphatic amines often occur at carbon atoms bonded to nitrogen, presumably with the initial formation of chemically unstable carbinolamines which may undergo spontaneous carbon-nitrogen bond cleavage to the corresponding dealkylated amines and aldehydes or ketones.…”

Total synthesis of (.+-.)-3-deoxy-7,8-dihydromorphinone

“…Confirmation of the ester formation was indicated by the downfield shift of the aromatic signal in NMR from 6.2 to 6.57. The phosphate ester 18 was reduced to 19 with Li/NH3/THF without purification.…”

Metabolic oxidation of nicotine to chemically reactive intermediates

“…In 1973, Murphy68 repeated Rucker's work and reported evidence for the presence of a cyanonicotine derivative in the incubation mixture. He postulated that the initial metabolic hydroxylation product 2 ionizes to the electron-deficient nicotin-Ar(5)-iminium ion (8), which is trapped by cyanide ion to form the stable adduct 5'cyanonicotine (9). The partial structure of 96b was established by spectral evidence and by synthesis via mercuric acetate oxidation of nicotine in the presence of cyanide ion.…”