The preparation of 2,6-diaminopyrazine, 2,6-diazidopyrazine and some of their derivatives

A much improved synthesis of the heretofore difficultly obtainable 2,6-diaminopyrazine (4) was afforded by the low-pressure catalytic hydrogenation (palladium on carbon) of 2,6-diazido-pyrazine (2) ; reaction of 2,6-dichloropyrazine (1) and sodium azide gave 2 in 84% yield. The outcome of the reduction was found to be solvent dependent: 1,2-dimethoxyethane containing aqueous ammonia gave 4 in 83% yield; 1,2-dimethoxyethane alone gave 5-aminotetrazolo[1,5-a]-pyrazine (3) in 26% yield. Additional alternative syntheses of 3 and 4 are described. A number of acyl and azo derivatives of 4 were prepared. Reactions of 2 with dimethyl acetylenedicarboxylate and ethyl acetate (base catalyzed) leading to vic-triazole derivatives are also described.     

Differential thermal analysis of fluxed melts and its application to the system NiFe2O4-BaO-B2O3

The application of DTA to fluxed melts is discussed, and an apparatus for the determination of the solubility of crystalline materials in molten solutions is described. An exploratory study of the crystallization of nickel ferrite from barium borate fluxes is also described, and solubility curves are presented for fluxes which favour crystal growth. The heat of solution of nickel ferrite was found to be 73 ± 2 Kjoule mole^–1.

---

Zusammenfassung Es wurde über die Anwendung der DTA Methode bei der Untersuchung von Flußmittel enthaltenden Schmelzen berichtet und ein Apparat zur Bestimmung der Löslichkeit von kristallinischen Substanzen in Flüssen beschrieben. Eingehend wurden die Kristallisation von Nickelferrit aus Bariumborat-Flüssen untersucht und Löslichkeitskurven für den Kristallwachstum begünstigende Flüssen gegeben. Die Lösungswärme von Nickelferrit betrug 73 ± 2 Kjoule Mol^–1.

---

Résumé On a décrit l'application de la méthode ATD à l'étude des fusions avec fondant et un appareil adapté à la détermination de la solubilité des substances crystallines dans les fondants. On a étudié la cristallisation de ferrite de nickel des flux de borate de baryum. Des courbes de solubilité pour des flux favorisant les grossissement des cristaux sont présentées. La chaleur de solution du ferrite de nickel a été trouvée 73 ± 2 kjoule mole^–1.

---

A ( ). , . 73±2 ^–1.

     

A short,three-component total synthesis of 12-hydroxyeicosa-5,8,14(Z), 10(E)-tetraenoic acid (12-HETE) via the corresponding ketone

A highly effective synthesis of (±)-12-HETE (1) from the components 2, 3 and 6 is described which employs a new class of cuprate reagents.     

Dithioannulation of Alkynes

A direct method for the preparation of 2,3-diphenyl-1,4-dithiins has been developed. The process involves treating alkynes with nickel bisdiphenyl-dithiolene in refluxing chlorobenzene in the presence of pyridine. Pyridine appears to be essential in order to avoid further transformation of 1,4-dithiins to thiophenes.     

Activation of methylenetriphenylphosphorane by reaction with t-butyl- or sec-butyllithium

Experimental details are provided to support a previous report that α-methylenetriphenylphosphorane ($\text{1}$) may be activated for reaction with unreactive substrates such as epoxides and hindered ketones by α-metallation to $\text{2}$.