The Reactions of Cyanogen Chloride. I. Addition to Olefins

SummaryIn the presence of ultrasound various mono-, di-, and a$-unsaturated cyanides were reduced with Cu-A1 alloy in NaOD-DzO and THF to the corresponding deuteriated aliphatic amines, such as nonylamines, Putrescine, and 1,6-hexanediamine, in high deuterium content.Key words: Deuteriation, Reduction, a$-Unsaturated cyanides, Deuteriated amine Raney copper-aluminium alloy, UltrasoundCustomarily, most amines have been prepared directly from nitrile compounds by converting the nimle group into an aminomethyl group under either heterogeneous or homogeneous reaction conditions [ I]. Deuterium labelled amines have played a significant role as tracers or internal references in the elucidation of biosynthetic pathways, e.g. amino acids, choline, and alkaloids have been used for investigating metabolic processes. It is also known that the activity of Na+-K+ATPase in a dog cerebrum is inhibited by long-chained alkyl amines [2]. It has been previously reported that deuteriated aliphatic carboxylic acids can be prepared utilizing the reducing system, Raney alloy and alkaline deuterium oxide [3]. We were therefore interested in the synthesis of deuteriated amines by the reduction of a$-unsaturated nitriles. In the present study, we have deployed the above methodology towards the synthesis of the title compounds.The effects of sonication on chemical reactions have been attracting great interest in organic synthesis. There are, however, relatively few examples concerning the benefit of sonication on the heterogeneous catalytic reduction, although a number of synthetically useful applications have been devised [4]. In the course of preliminary study using aqueous NaOH as base. we have found that the use of ultrasound provided a significant improvement; when the reduction of octyl cyanide (1) with copper-aluminium (Cu-A1) alloy in a mixture of an aqueous NaOH and tetrahydrofuran (THF) was

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“…81%; b.p. 60 O C / 1.8 Torr (lit., [9] 68-70 OC / 2 Torr as for 2Ho form); v (NaCI) 2956. 2930, 2856, 2260, 2220, 1602, 1466, 1379, 723.…”

Section: Methodsmentioning

confidence: 99%

Ultrasound-assisted reduction of cyanides to deuteriated aliphatic amines

Tsuzuki

Harada

Mukumoto

et al. 1996

J Label Compd Radiopharm

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TheRitter Reaction

Krimen

Cota

2011

Organic Reactions

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The formation of N‐substituted amides by the addition of nitriles to alkenes in the presence of concentrated sulfuric acid was first described by Ritter in 1948. The reaction has been extended to the addition of nitriles to a wide variety of compounds capable of forming a carbonium ion, and it constitutes the only really useful procedure for the preparation of amides of tertiary carbinamines. In its most general form, the Ritter reaction involves the nucleophilic addition of a nitrile to a carbonium ion in the presence of sulfuric acid. Attention has been given to reactions in which the carbonium ion is generated in sulfuric acid, or less commonly in sulfonic acids, phosphoric acids, or boron trifluoride. For comparison, analogous reactions, which are initiated by a nitrilium ion, formed from a nitrile and a Friedel‐Crafts catalyst, have been included in this chapter.

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Ritter Reaction

2010

Comprehensive Organic Name Reactions and Reagents

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The strong acid‐promoted amidation of alcohol or olefin with nitrile is generally known as the Ritter reaction. It has been reported that some other types of molecules can also undergo this reaction under similar conditions by the formation of carbocations, such as trioxane, N ‐tosylazetidine, aziridine, oxirane, and epoxide. The outcome of this reaction depends on the reactivity of nitriles and the stability of carbocations. The study finds that the temperature may affect the reaction. Furthermore, it has been found that stereochemistry is completely retained in this reaction when a bromo group is present at the neighboring position. Various modifications of the original protocol of this reaction have been discussed. This reaction has very wide applications in organic synthesis.

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The Reactions of Cyanogen Chloride. I. Addition to Olefins

Cited by 7 publications

References 4 publications

Ultrasound-assisted reduction of cyanides to deuteriated aliphatic amines

Ultrasound-assisted reduction of cyanides to deuteriated aliphatic amines

TheRitter Reaction

Ritter Reaction

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