17544-07-9

A green, efficient N-alkylation of amines with simple alcohols has been achieved in aqueous solution via an electrochemical version of the so-called "borrowing hydrogen methodology". Catalyzed by Ru on activated carbon cloth (Ru/ACC), the reaction works well with methanol, and with primary and secondary alcohols. Alkylation can be accomplished by either of two different electrocatalytic processes: (1) in an undivided cell, alcohol (present in excess) is oxidized at the Ru/ACC anode; the aldehyde or ketone product condenses with the amine; and the resulting imine is reduced at an ACC cathode, combining with protons released by the oxidation. This process consumes stoichiometric quantities of current. (2) In a membrane-divided cell, the current-activated Ru/ACC cathode effects direct C-H activation of the alcohol; the resulting carbonyl species, either free or still surface-adsorbed, condenses with amine to form imine and is reduced as in (1). These alcohol activation processes can alkylate primary and secondary aliphatic amines, as well as ammonia itself at 25-70 °C and ambient pressure.

Studies of acid-base catalysis, H/D exchange, and solvent isotope effect on the β-elimination reactions with formation of p-nitrostyrene in acetohydroxamate/acetohydroxamic acid buffers at pH 9.05, H2O, μ = 1 M KCl, from N-alkylammonium ions with different leaving groups, such as N-methylpyrrolidine 1, N-ethylpyrrolidine 2, N-isopropylpyrrolidine 3, N-methylpiperidine 5, and N-methylazepane 6, show a change a partially reversible E1cb mechanism with 1, 2, and 4 to an irreversible E1cb mechanism with 3, 5, and 6.The change in the rate-determining step is related to the increased steric requirement of the leaving group.A steric acceleration from the carbanion intermediate to product step is proposed.

The present invention provides novel derivatives of leukotrienes A and C which are useful in inhibiting the smooth muscle contracting effects of SRS-A; inhibiting platelet aggregation; and inhibiting the biosynthesis of thromboxane A2.

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Primary and secondary alcohols effect alkylation of primary and secondary amines in the presence of rhodium, iridium, and ruthenium compounds at = 100 deg C, whereby selective monoalkylation of primary amines can be achieved, and heterocyclic rings can be constructed by both inter- and intra-molecular processes.

Prostacyclin and prostacyclin-type derivatives having a 19-hydroxy feature are disclosed, including processes for preparing them and the appropriate intermediates. The compounds are useful for pharmacological purposes such as inhibition of blood platelate aggregation.

Prostaglandin derivatives having a 19,20-didehydro, a 19-hydroxy, or a 19-keto feature are disclosed, including processes for preparing them and the appropriate intermediates. A typical 19-hydroxy compound of this invention is 19-hydroxy-19-methyl-PGF2α, methyl ester, represented by the formula STR1