Eine allgemeine Methode zur Herstellung von Carbonsäureamiden aus den entsprechenden Nitrilen, II

Becke, Friedrich; Fleig, Helmut; Pässler, P.

doi:10.1002/jlac.19717490123

Cited by 35 publications

(9 citation statements)

References 2 publications

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“…In contrast to reported conversions of nitriles into carboxamides by formic acid which require either heating at 180 -200 °C [2], or the presence hydrogen halides [3], our reaction occurs under rather mild conditions. In order to determine the structural features essential for this conversion and to study its scope, several other α-aminonitriles were treated with formic acid at room temperature.…”

mentioning

confidence: 55%

A Selective Conversion of Nitriles into Carboxamides by Formic Acid

Friedrich¹,

Zamkanei

Zimmer

2000

J. prakt. Chem.

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The thiocarbonyl group of N-acylated cyanothioformamides exhibits pronounced dienophilic reactivity. Thus, with a variety of 1,3-dienes, we obtained the corresponding Diels-Alder adducts 1 [1].Investigating possible transformations of adducts 1, we observed that dissolving them in concentrated formic acid at room temperature resulted in a specific conversion of the nitrile moiety into the corresponding carboxamides 2a -e,g,h with concomitant formation of one mole of carbon monoxide. In most cases, the reaction was complete within 15 -20 minutes and the amides could be isolated in 22 -94% yield (Scheme1). Abstract. Aliphatic α-(acylamino)nitriles react with formic acid at room temperature to give the corresponding α-(acylamino)carboxamides with concomitant formation of one mole of carbon monoxide. This new reaction, which was first observed with 2-acylamino-2-cyano-3,6-dihydro-2H-thiapyIn contrast to reported conversions of nitriles into carboxamides by formic acid which require either heating at 180 -200 °C [2], or the presence hydrogen halides [3], our reaction occurs under rather mild conditions. In order to determine the structural features essential for this conversion and to study its scope, several other α-aminonitriles were treated with formic acid at room temperature. Neighbouring GroupBecause the two α-aminonitriles 1f and 1i [1], both lacking the N-acyl functionality present in the other members of the group, were not altered by formic acid at room temperature, we came to the conclusion that the N-acyl group is essential for the reaction and that other special features such as the thioether moiety present in the Diels-Alder adducts 1 are no prerequisites for the reaction. Accordingly, N-(cyanomethyl)benzanilide (3) [4] after 3 h gave the corresponding acetamide 4 in 93% yield together with 0.9 equivalents of carbon monoxide. The two cyano groups in N,N-bis(cyanomethyl)benzamide (5) [5] could also be converted into carboxamido groups, affording the triamide 6 in 74% yield. In this case, measured by the rate of carbon monoxide evolution, the conversion of the first nitrile needed about 16 h, whereas the whole reaction was complete after about 64 h (Scheme 2).Whereas compounds 1, 3 and 5 on treatment with formic acid yielded the corresponding amides, 2-(Nphenylbenzamido)isobutyronitrile (7) [6], the only other nitrile without α-hydrogen atoms studied, afforded 83% of acid 8 together with only 5% of amide 9.In a one-pot reaction α-(N-formyl)carboxamides 11a -c could be synthesized from α-aminonitriles 10a -c usranes 1, can also be used to convert other N-(α-cyanoalkyl) amides such as N-cyanomethylbenzamides 3, 5 and the 3,4-dihydro Reissert compound 16 into the corresponding carboxamides. Another application is a synthesis of 2-formylaminoacetamides 11. A mechanism for the reaction is proposed.

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confidence: 55%

A Selective Conversion of Nitriles into Carboxamides by Formic Acid

Friedrich¹,

Zamkanei

Zimmer

2000

J. prakt. Chem.

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“…N -Benzhydrylacetamide (18), obtained in the reaction between ethyl cyanoacetate and benzhydrol, is most likely formed from the initial Ritter reaction product by subsequent acidolysis [15] of the ester group and decarboxylation. Interestingly, despite the fact that formic acid is known to hydrolyze nitriles to amides [16,17] and to carboxylate carbocations, [18,19] neither nitrile hydrolysis products nor products of Koch-Haaf carboxylation of the benzhydryl cation were isolated. These results indicate that there is an apparent threshold enol content for the C-alkylation reaction to occur, but the nature of the correlation between isolated yield and reaction time is not straightforward.…”

Section: Oh Phmentioning

confidence: 91%

“…The reactions of benzhydrol with ethyl acetoacetate (12) and acetylacetone (14) gave the expected β-dicarbonyl compounds (17) and (19) as the final products, [11] and Meldrum's acid (11) gave 3,3-diphenylpropanoic acid (16), almost certainly formed by hydrolysis and decarboxylation of the dioxanedione initially formed by C-alkylation of the enol (this type of formolysis and decarboxylation has been reported for other β-diesters [12] ). Surprisingly, however, neither diethyl malonate, nor ethyl cyanoacetate, nor malononitrile gave any C-alkylation products (which we had expected by analogy with, for example, the reactions of these active methylene compounds in the Knoevenagel and Claisen-Schmidt condensations.…”

Section: Oh Phmentioning

confidence: 91%

Reactions of Active Methylene Compounds with Benzhydrol During Solvolysis in Formic Acid

Gullickson¹,

Lewis²

2003

Aust. J. Chem.

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Formic acid reacts with benzhydrol to give benzhydryl formate, which reacts with active methylene compounds in refluxing formic acid to give either C-alkylation or Ritter reaction products. The product formed is determined by the equilibrium enol content of the active methylene compound. These reaction conditions avoid the use of halogenated reaction solvents, and the pure products are isolated without recourse to chromatography.

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“…They have been used as the precursors of oxindoles, bioactive heterocycles, amino acids, bioactive malonamides, and starting materials for asymmetric reactions . However, the preparation methods for monoamides such as the aminolysis of the corresponding diester, enzymatic methods, hydrolysis of α‐cyanoacetate, or amination of ethyl malonyl chloride are not efficient because of moderate yields or multistep reactions. Better preparation methods should be developed for their practical synthesis.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Dissymmetric Malonic Acid Monoamides from Symmetric Dithiomalonates

et al. 2016

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We report a highly selective synthesis of dissymmetric S,N‐malonates from symmetric dithiomalonates under mild conditions. This reaction was accelerated using a Cu(II) catalyst developed by us. When an aliphatic amine was used as the nucleophile, the amine also worked as a base and accelerated the amination reaction. Kinetic studies indicated that the key step of this reaction is the thermal formation of an acylketene; its stability mainly contributes to the selectivity of the reaction. The synthetic utility of dissymmetric S,N‐malonates is also shown by the synthesis of linomide.

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Eine allgemeine Methode zur Herstellung von Carbonsäureamiden aus den entsprechenden Nitrilen, II

Cited by 35 publications

References 2 publications

A Selective Conversion of Nitriles into Carboxamides by Formic Acid

A Selective Conversion of Nitriles into Carboxamides by Formic Acid

Reactions of Active Methylene Compounds with Benzhydrol During Solvolysis in Formic Acid

Synthesis of Dissymmetric Malonic Acid Monoamides from Symmetric Dithiomalonates

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