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.     

Analytische Trennung und photometrische Bestimmung von Palladium und Platin

Zusammenfassung Zur colorimetrischen Bestimmung von Palladium und Platin werden die beiden Metalle zunächst durch Extraktion mit 2-Chlorpyridin von Verunreinigungen abgetrennt. Sodann wird Pt mit einer schwach sauren Pufferlösung extrahiert und als SnCl₂-PtCl₄-Komplex bei 401 nm photometriert. Pd wird als Jodo-Chlorpyridin-Komplex bei 525 nm photometrisch bestimmt. Von den geprüften Fremdionen stört nur Ir^IV die Pt- und Au^III die Pd-Bestünmung.Der Autor möchte auch an dieser Stelle der großzügigen Hustinx Research Laboratoria, Maastricht für die Zuerkennung des Hustinx-Preises für die vorliegende Arbeit danken.Herzlichen Dank gebührt ebenfalls der Geschäftsleitung der Cilag-Chemie A.G., Schaffhausen, für die Erlaubnis zur Teilnahme an der Hustinx-Research-Laboratoria-Preisfrage.     

Pyrolysis-mass spectrometry correlations of crosslink density in natural rubber vulcanizates

A set of twelve natural rubber vulcanizates was analyzed by Curie-point pyrolysis-mass spectrometry (Py-MS). Multivariate analysis successfully correlated the Py-MS data with either total or polysulfidic crosslink density measurements. (Polysulfidic means two or more sulfurs.) The principal correlation observed was an increase in the ratio of monomer to dimer pyrolyzate yield with an increase in crosslink density. The feasibility of using Py-MS for total crosslink density determination has thus been demonstrated. The Py-MS data, however, did not allow us to distinguish different types of crosslinks.     

The utilization of chemical shift and spin-lattice (T1) relaxation time data for the discrimination of isomeric indenoisoxazoles

Treatment of 2-pivaloyl-1,3-indandione with hydroxylamine leads to the formation of a pair of isomeric indenoisoxazoles, the product formed dependent upon the cyclization conditions. Under acidic conditions, 8-t-butylindeno[1,2-c]isoxazol-7-one ( 5 ) is formed while under neutral or basic conditions, an oxime, 2 , is generated which may then be cyclized under acidic conditions to give 3-t-butylindeno[1,2-c]isoxazol-4-one ( 4 ). Although these isomeric indenoisoxazoles may be discriminated by chemical means, we were interested in developing an unequivocal method for distinguishing these and potentially other isomeric pairs by spectroscopic means. A ¹³C-nmr based method for the discrimination of these isomers which is based on the utilization of chemical shift arguments and spin-lattice relaxation data is thus presented.     

Collision induced dissociations of ions produced in the field free regions of a triple sector mass spectrometer

Molecular or fragment ions can be prepared by a large variety of reactions in the field free regions of a mass spectrometer; these reactions involve spontaneous dissociation as well as collision induced excitation of singly or doubly charged precursors. Some typical examples show the different means which can lead to a given ion and how they can be studied by collisional activation. It also appears that in most cases the use of a triple sector (E/B/E) mass spectrometer facilitates these experiments as interfering artefacts are suppressed.     

Amidinoethylation—a new reaction—IV : The amidinoethylation of alcohols: a facile synthesis of 3-alkoxy-N,N'-substituted-propanamidines

The amidinoethylation of alcohols takes place by the addition of sodium alkoxides 2 (R¹ = Me, Et) to the CC double bond of a variety of N,N'-substituted-propenamidines 1 (Method A). This illustrates the activation of the CC double bond by the conjugated amidine function and provides a new class of Michael acceptors for alcohols. However, this activation is poorer than with other nucleophiles or Michael acceptors. The amidinoethylation makes available 3-alkoxy-N,N'-substituted-amidines not easily accessible by other classical methods. However, it is demonstrated that the general N,N'-substituted-amidine synthesis via the nitrilium salts can also apply to nitrile compounds having an alkoxygroup present on the molecule (method B). Since the cyanoethylation of alcohols (4) is a very fast and facile reaction the method B is the preferred strategy for the synthesis of 3-alkoxy-N,N'-substituted-propanamidines 3.     

Observations on clear solution silicalite-1 growth by nanoslabs

Several research groups have reported the presence of nanometer-sized particles (nanoslabs) in clear solutions, which precipitate the crystalline MFI (ZSM-5) structure. Debate about the growth mechanism for Al-free ZSM-5 (silicalite-1) has revolved around growth by small silicate units (monomers, dimers, etc.) from solution vs growth by nanoslab addition. A model developed for precipitation of uniform sized colloids by addition of sub-colloidal precursor units has been adapted for this zeolite synthesis system. Parameter values were adjusted for the simulation results to match experimental observations from work reported previously, at least to the extent possible. The model involved the simultaneous solution of up to 6000 ordinary differential equations, and required computation times of up to 24 h. The results shed light on the crystal growth mechanism, but pose questions for further investigations of the nucleation mechanism.     

The mixed-aldehyde synthesis of difunctional tetraarylporphyrins

The synthesis is reported of nine unsymmetrical, meso-substituted porphyrins. Among the compounds prepared are the following 5-(R)-10,15,20-tri-p-tolylporphyrins; R = 2,6-dinitrophenyl, 4-hydroxy-3-ethoxy-phenyl, 4-hydroxy-3-methoxy-5-nitrophenyl, 5-hydroxy-2-nitrophenyl and 4-hydroxy-3-nitrophenyl. Other porphyrins reported include 5-(2-(1-butoxy)phenyl)-15-(2-nitrophenyl)-10-15-di-p-tolylporphyrin and the two 5-(R)-10-15,20-tripropylporphyrins in which R = 2-nitrophenyl and 2-hydroxyphenyl. The disubstituted porphyrins offer a rational route to the synthesis of difunctional “tailed-porphyrins”.     

Optically detected zero-field triplet state magnetic resonance in photosynthetic bacteria

Triplet state transitions of the photosynthetic bacteria Rhodospirillum Rubrum, Rhodopseudomonas Spheroides and Chromatium Vinosum in chemically reduced preparations have been observed by zero-field optical detection of magnetic resonance at 2 K. For each bacterial preparation two sharp, structureless, zero-field EPR transitions were observed as microwave-induced decreases in the fluorescence intensity of the frozen cellular preparations. The depopulating rate constants for the spin sublevels of the triplet states observed in R Rubrum and R Spheroides were also measured. The similarities of the triplet state frequencies, spectral features and intersystem crossing rates suggest a common structure for the reaction centers in the photosynthetic bacteria.