Reactions of 2-Acyl-1,3-indandiones with Nitrogen Nucleophiles

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Title:Reactions of 2-Acyl-1,3-indandiones with Nitrogen Nucleophiles
Creators:
Hrnčiar, Pavel
Švanygová, Eva
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 59, 12, pp. 2734-2740

Abstract

<p>Reactions of 2-acyl-1,3-indandiones with nitrogen nucleophiles were studied rarely. The question, if they react with carbonyl carbon of acyl group or indandione skeleton, has not been answered unambiguously. To make clear the question which carbonyl carbon of 2-acyl-1,3-indandiones enters the reaction with nitrogen nucleophiles we carried out the reactions with 2-acetyl- (<i>Ia</i>), 2-propionyl- (<i>Ib</i>), 2-pivaloyl- (<i>Ic</i>), and 2-benzoyl-1,3-indandione (<i>Id</i>). We used different 2-acyl-1,3-indandiones with the aim to find out if the character of acyl group affects the course of reaction. We used ethoxyamine, primary amines, phenylhydrazine, hydrazine and methylhydrazine as nucleophile reactants. The reactions were carried out in methanol at reflux at 10% excess of nitrogen base. The reactions with phenylhydrazine, hydrazine and methylhydrazine were performed with twofold excess of nitrogen base. The separation of reaction products was carried out by chromatography on silica gel. We found that 2-acyl-1,3-indandiones <i>I</i> react with ethoxyamine both at the acylcarbonyl carbon to produce 2-(1-ethoxyiminoalkyl)-1,3-indandiones <i>II</i> and the carbonyl carbon of indandione skeleton to give rise 3-(ethoxyimino)-2-acyl-1-indanones <i>III</i>. In all cases, the carbonyl carbon of acyl group was preferred (the observed ratio of products <i>II</i> to <i>III</i> was 6 - 8 : 1). From the reaction of 2-acyl-1,3-indandiones with primary amines only the products <i>IV</i> of reaction with the acylcarbonyl carbon were isolated. The hydrazines used reacted with 2-acyl-1,3-indandiones also at carbonyl carbon of acyl group in the first step to produce hydrazones. However, the products isolated in most cases were formed by the attack of hydrazone nitrogen at carbonyl carbon of indandione skeleton giving rise to derivatives of indeno[2,3-<i>d</i>]pyrazole-4-one <i>V</i>. It is interesting that 2-acetyl-1,3-indandione and 2-propionyl-1,3-indandione, reacting with phenylhydrazine and hydrazine, yielded only corresponding hydrazones <i>VI</i>.

Title:Reactions of 2-Acyl-1,3-indandiones with Nitrogen Nucleophiles
Creators:
Hrnčiar, Pavel
Švanygová, Eva
Divisions:Life and Chemical Sciences > Institute of Organic Chemistry and Biochemistry > Collection of Czechoslovak Chemical Communications
Journal or Publication Title:Collection of Czechoslovak Chemical Communications
Volume:59
Number:12
Page Range:pp. 2734-2740
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc19942734UNSPECIFIED
ID Code:692
Item Type:Article
Deposited On:06 Feb 2009 17:03
Last Modified:06 Feb 2009 16:03

Citation

Hrnčiar, Pavel; Švanygová, Eva (1994) Reactions of 2-Acyl-1,3-indandiones with Nitrogen Nucleophiles. Collection of Czechoslovak Chemical Communications, 59 (12). pp. 2734-2740. ISSN 0010-0765

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