7,8-Dioxochlorpromazine,synthesis and properties

7,8-Dihydroxychlorpromazine and 2-chloro-7,8-dihydroxyphenothiazine were converted to the corresponding 7,8-dioxo compounds by oxidation with tetrachloro-o-quinone. Spectral properties indicate that the 7,8-dioxo compounds exist in zwitterionic forms reminiscent of aminochromes. The 7,8-dioxochlorpromazine is proposed as a possible metabolite of chlorpromazine.     

The synthesis of possible hydroxylated metabolites of 2-chlorophenothiazine derivatives

The synthesis of 7-hydroxy, 8-hydroxy and 7,8-dihydroxy prochlorperazines (3a) and per-phenazines (3b) is reported. The parent ehlorophenothiazines were prepared analogously to previously reported chlorpromazine (3e) metabolite syntheses. The prochlorperazine side chain was introduced in one step using 1-(3-chloropropyl)-4-methylpiperazine and the perphenazine side chain in two steps, first reaction with 1-bromo-3-chloropropane followed by reaction with 1-piperazineethanol. The methoxymethyleneoxy O-proteetive groups were removed under mild conditions using methanolic hydrogen chloride. The preparations of 7-hydroxydesmethylprochlorperazine and 7-hydroxychlorpromazine quaternary methyl iodide are also reported.     

Intrinsic and 1-aminonaphthalene-4-sulfonate-specific extrinsic lyoluminescences of X-ray irradiated sodium chloride

1-Aminonaphthalene-4-sulfonate (ANS)-specific extrinsic lyoluminescence (LL) of X-ray irradiated sodium chloride is observed at 425 nm when the irradiated salt is dissolved in an aqueous solution of ANS. The paper discusses, in detail, the mechanism of the ANS-specific LL and its analytical applicability. Also, the intrinsic LL of X-ray irradiated sodium chloride is studied. Hydrated electron as well as hole scavenger experiments support the proposal that in the case of the intrinsic LL of X-ray irradiated sodium chloride, trapped electrons (mainly F-center electrons) are released and hydrated whereas trapped holes (V-centers) remain surface-bound and are only partially hydrated before recombination occurs. These hydrated electrons and dissolving solid surface-bound hole centers, which are probably only partially hydrated, are able to act as reducing and oxidizing agents, respectively, in the luminophore oxidation-initiated reductive excitation pathway of ANS. Solution additives (halides and pseudohalides) show that in the chemiluminescence processes in question, oxidizing agents will follow the Marcus theory of electron transfer reactions. The LL method described allows the determination of ANS in the concentration range ≈10⁻¹¹ − 10⁻⁷ M. This suggests that aminonaphthalene derivatives can be used as label molecules in high sensitivity lyoluminobioaffinity assays.     

Conformational study of 1,4-thiazinan-3-one

The proton NMR spectra of several 1,4-thiazinan-3-ones were analyzed using LAOCOON. The geminal and vicinal coupling constants indicate that the ring conformation of this heterocycle is a half-chair similar to δ-valerolactam. Molecular mechanics calculations show that the energy of the boat is only slightly higher than that of the half-chair. The conformational equilibria of methyl-substituted compounds were calculated by the coupling constant method. These energies are compared to those obtained by molecular mechanics.     

Synthesis of 3-Chloro-2-hydroxyimipramine and 3-chloro-8-hydroxyimipramine,Hypothetical metabolites of clomipramin

Fremy salt oxidation of 3-chloroiminodibenzyl yields a mixture of two isomeric iminequinones, which can be separated and reduced to aminophenols and the phenolic group protected with addition of dihydropyran. Introduction of the N,N-dimethylaminopropyl side chain and removal of the protective group provided the two chlorohydroxyimipramines, which can serve as standards for the identification of possible biotransformation products of the parent drug, clomipramine.     

Pleistocene age paleo-groundwater inferred from water-stable isotope values in the central part of the Baltic Artesian Basin

A new data set of δ²H and δ¹⁸O in the groundwater from the central part of the Baltic Artesian Basin is presented. The hydrogeological section is subdivided into stagnation, slow exchange and active exchange zones. Na–Ca–Cl brine found at the deepest part – the stagnation zone – is characterized by δ¹⁸O values above ?5?‰ and δ²H values approaching ?40?‰ with respect to Vienna Standard Mean Ocean Water. The slow exchange zone where waters of mostly intermediate salinity reside is characterized by δ¹⁸O values around ?11.7?‰ and δ²H values around ?85.3?‰. Mean δ¹⁸O and δ²H values of the fresh groundwater in the active water exchange zone are ?11.1 and ?79.9?‰, respectively. Characteristically, the groundwater in the active and slow exchange zone is isotopically more depleted compared with the precipitation values observed, and the depletion increases with depth down to the level where strongly enriched brines are encountered.     

The Synthesis of possible di- and trihydroxylated chlorpromazine metabolites

The syntheses of di- and trihydroxychlorpromazines, I, II, III, and V, and of dioxo derivatives, IV and VI, are described.     

The synthesis of 6,9-dioxo-, 6,9- and 7,9-dihydroxyehlorpromazines,possible metabolites of chlorpromazinem

The syntheses of dioxogenated chlorpromazines 1, 2 , and 3 via the reductive ring closure of substituted nitrodiphenyl sulfides are described.