Formation Of Azine Research Articles

On the mechanism of formation of azines from hydrazones

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTOn the mechanism of formation of azines from hydrazonesVera M. Kolb, Andrew C. Kuffel, Harry O. Spiwek, and Timothy E. JanotaCite this: J. Org. Chem. 1989, 54, 11, 2771–2775Publication Date (Print):May 1, 1989Publication History Published online1 May 2002Published inissue 1 May 1989https://doi.org/10.1021/jo00272a064RIGHTS & PERMISSIONSArticle Views799Altmetric-Citations33LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (686 KB) Get e-Alerts Get e-Alerts

Stereoselective azine formation in the decomposition of phenyldiazomethanes

Stereoselective azine formation in the decomposition of phenyldiazomethanes

Synthesis and binding of 3H-oxymorphazone to rat brain membranes

Oxymorphazone is a 14-hydroxydihydromorphinone derivative which contains a C-6 hydrazone group and hence could serve as an irreversible label for opioid receptors. 3H-oxymorphazone was synthesized by the reaction of 3H-oxymorphone with excess hydrazine. A specific radioactivity of 640 GBq/mmol (17, 3 Ci/mmol) was achieved. Both the unlabelled compound and the tritiated ligand show high affinity to mu and kappa opiate receptor subtypes in rat brain membranes. Two binding sites were detected by equilibrium binding studies, with apparent K d values of 0.62 nM and 28 nM. About 20% of the 3H-oxymorphazone specific binding is irreversible after reaction at 1 nM ligand concentration, and this can be enhanced by a higher concentration of tritiated ligand. No azine formation was detected. Preincubation of the membranes with unlabelled oxymorphazone resulted in an irreversible blockade of the high affinity 3H-naloxone binding sites.

A facile synthesis of unsymmetrical heterocyclic azines by cyclodesulfurization: Reaction of methyl arylalkylidenehydrazinecarbodithioates with diamines

AbstractA new and facile synthesis of unsymmetrical heterocyclic azines is described. Methyl arylalkylidenehydraz‐inecarbodithioates, prepared by the condensation of ketones or aldehydes with methyl hydrazinecarbodithioate, were heated under reflux with various diamines in ethanol. Secondary diamines, such as N,N′‐dimethyl‐ethylenediamine, N,N′‐dimethyl‐1,3‐diaminopropane or N,N′‐dimethyl‐o‐phenylenediamine, reacted smoothly with loss of hydrogen sulfide to give good yields of unsymmetrical azines. However, primary diamines, such as ethylenediamine or o‐phenylenediamine, and primary/secondary diamines, such as N‐methylethyl‐enediamine and N‐methyl‐1,3‐diaminopropane gave, instead, only the corresponding uncyclized thiosemi‐carbazones. A cyclodesulfurization mechanism for azine formation is discussed.

Naloxonazine, a potent, long-lasting inhibitor of opiate binding sites

Naloxazone, the hydrazone derivative of naloxone, has proven useful in studies of opiate binding site heterogeneity both in vivo and in vitro based on its long-acting inhibition of high affinity, or mu 1, binding sites. However, the need for high doses of naloxazone to inactivated the mu 1 sites raised the possibility that its actions might result from lower concentrations of a more active compound. We now present evidence suggesting that this more active compound is the azine derivative of naloxone. In acidic solutions, approximately 35% of naloxazone, spontaneously rearranges to the azine, naloxonazine. Unlike naloxazone, naloxanazine is relatively stable in solution. It does not appreciably dissociate into naloxone and naloxazone and no additional compounds can be detected. Under assay conditions under which no azine formation can be detected, no inhibition of binding of either 3H-dihydromorphine or 3H-DADL is found after incubating tissue with naloxazone at concentrations up to 2000 nM followed by extensive washing. Naloxonazine, on the other hand, produces a potent, dose-dependent inhibition of binding which is resistant to washing. Despite the washes, naloxonazine at 50 nM abolishes high affinity binding with some inhibition seen at concentrations down to 10 nM.

Mechanism for the formation of azine in the decomposition of diazo-alkanes and diazarines

Mechanism for the formation of azine in the decomposition of diazo-alkanes and diazarines

A synthetic approach to 1,3,4-thiadiazolidine-2-thiones

The course of the reaction between dithiocarbazic acid and aldehydes and ketones has been examined. Aliphatic and π-deficient heterocyclic aldehydes and ketones form 1,3,4-thiadiazolidine-2-thiones. Aromatic and π-excessive heterocyclic aldehydes and ketones, however, form azines. A similar course occurs in the reaction between the hydrazones and carbon disulphide. Alkyl dithiocarbazic acids (azine formation being excluded) form 3-alkyl-1,3,4-thiadiazolidine-2-thiones with aliphatic, aromatic as well as with heterocyclic aldehydes and ketones. These thiones can also be prepared from alkyl hydroazones and carbon disulphide. Aryl hydrazones, however, do not react with carbon disulphide.

Aliphatic diazo compounds—VII

Abstract The formation of azines in the reaction of diazoethane with α-diazo- p -nitroacetophenone and α-diazo- p -nitropropiophenone has been confirmed by the elucidation of the nature of certain of their further reaction products.

Azine化合物に関する研究 (第6報)

Reactivity of carbonyl group was observed by the formation of azines. The activity of the ketone group is weaker than that of aldehyde group due to the +I effect of the alkyl radical. Although negative substituents increase the activity of the carbonyl, the effect of nuclear substituent is generally smaller than the activity increase by the catalytic action of proton, or the activity decrease due to +I effect of the alkyls and the +T effect of the phenyl group. The formation of thiosemicarbazones by the reaction of thiosemicarbazide on the azines is assumed to be anionic addition to the carbon atom of the azimethylene group but when there are strong negative substituents such as the nitro group in the azine, the nucleophilic acitivity of the carbon in azimethylene is decreased by the contribution of reversed polarity due to electron attraction of the nitro group.