42. Reactions of aliphatic diazo-compounds with carbonyl derivatives

Adamson, D. W.; Kenner, J.

doi:10.1039/jr9390000181

Cited by 17 publications

(9 citation statements)

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“…The reactivity of cyclic ketones in such processes follows the general order of 3 > 4 > 6 > 7 ≥ 5 membered rings . While the homologation of cyclopropanones and cyclobutanones can be achieved with diazomethane in reasonable reaction times (Scheme ), , larger rings need slightly harsher conditions and the desired product is usually accompanied by considerable amounts of the epoxide. , Furthermore, due to the somewhat slow process, the newly formed cyclic ketones can undergo an additional ring expansion reaction affording mixtures of homologated products.…”

Section: Reaction Of Ketones With Diazoalkanesmentioning

confidence: 99%

“…More electrophilic ketones react faster than less electrophilic ones (mostly toward formation of epoxides), and more electron-rich substituents are typically the ones to undergo migration. Although carbon-chain extension of acyclic ketones with diazo compounds is very sensitive to the chain length, where only simplest ketones can be homologated with diazoalkanes, the ring expansion of cyclic ketones is a more general, controllable, and studied process. − …”

Section: Introductionmentioning

confidence: 99%

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Homologation Reaction of Ketones with Diazo Compounds

2016

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This review covers the addition of diazo compounds to ketones to afford homologated ketones, either in the presence or in the absence of promoters or catalysts. Reactions with diazoalkanes, aryldiazomethanes, trimethylsilyldiazomethane, α-diazo esters, and disubstituted diazo compounds are covered, commenting on the complex regiochemistry of the reaction and the nature of the catalysts and promoters. The recent reports on the enantioselective version of ketone homologation reactions are gathered in one section, followed by reports on the use of cyclic ketones ring expansion in total synthesis. Although the first reports of this reaction appeared in the literature almost one century ago, the recent achievements, in particular, for the asymmetric version, forecast the development of new breakthroughs in the synthetically valuable field of diazo chemistry.

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Section: Reaction Of Ketones With Diazoalkanesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Homologation Reaction of Ketones with Diazo Compounds

2016

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“…The lactam was hydrolyzed and esterified; the ethyl e-aminocaproate was converted successively into ethyl e-carbethoxyamino- VOL. 20 caproate (VIII), and the N-nitroso derivative (IX) (10). Using conditions similar to those employed by Bollinger,et al (11) for the decomposition of N-nitroso-Ncyclohexylurethan, the base-catalyzed decomposition of ethyl N-nitroso-ecarbethoxyaminocaproate (IX) was studied.…”

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confidence: 99%

“…Decomposition of ethyl N-nitroso-e-carbethoxyaminocaproate. Ethyl N-nitroso-e-carbethoxyaminocaproate (21 g., crude), prepared according to Adamson and Kenner (10), was added slowly to a suspension of 0.05 g. of finely powdered anhydrous potassium carbonate in 12 ml. of methanol (previously dried over potassium carbonate).…”

mentioning

confidence: 99%

“…The isomeric lactams were also converted into 7-methyl-9-ethyl-and 7-ethyl-9-methyl-pentamethylenetetrazole. The latter has been shown to be identical with the methylethylpentamethylene- 10 All operations involving hydrazoic acid should be conducted in a hood with good ventilation. tetrazole obtained by interaction of 3-methyl-5-ethylcyclohexanone oxime with sodium azide and chlorosulfonic acid.…”

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A STUDY OF THE STRUCTURE OF SOME CYCLIC AMIDES AND RELATED TETRAZOLES¹

Burke¹,

Herbst²

1955

J. Org. Chem.

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The treatment of alkylcyclohexanone oximes with sodium azide and chlorosulfonic acid has been shown to lead through ring expansion and a second cyclization to alkylpentamethylenetetrazoles (1). When this reaction was applied to unsymmetrically substituted cyclohexanone oximes (I), structurally isomeric pentamethylenetetrazoles (II and III) could result depending upon the extent of 1-2 or 1-6 bond rupture occurring in the cyclohexanone oxime ring. When the reaction was applied to 3,5-dialkylcyclohexanone oximes, pure dialkylpentamethylenetetrazoles were isolated, but no attempt was made to determine the position of the substituents in the products (1). It has been the purpose of this investigation to determine the position of the substituents in such dialkylpentamethylenetetrazoles.The initial stage of tetrazole formation from the cyclohexanone oximes was assumed to be similar to the Beckmann rearrangement; at some point after ring expansion but before completion of the rearrangement by amide formation, the addition of the azide group caused tetrazole formation (1). Although amides do not react directly with hydrazoic acid or sodium azide to form tetrazoles, this conversion may be accomplished indirectly if the amide is first allowed to react with phosphorus pentachloride. The imide chloride so formed reacts readily with hydrazoic acid to form a tetrazole (2-4). It appeared feasible to accomplish stepwise conversion of cyclohexanone oximes to pentamethylenetetrazoles by first rearranging the oxime and determining the structure of the cyclic amides (IV and V) formed, and second, converting the cyclic amides into pentamethylenetetrazoles by way of their imide chlorides. This procedure has now been employed to establish the position of the substituents in 7-methyl-9-ethylpentamethylenetetrazole (II)3 and its isomer, 7-ethyl-9-methylpentamethylenetetrazole (III) and to establish the identity of the methylethylpentamethylenetetrazole described by Harvill, et al. (1).Since the structures of the pentamethylenetetrazoles would depend on knowledge of the structures of the lactams, a satisfactory method of converting the lactams into saturated aliphatic acids or other easily identifiable compounds was essential. The conversion of the parent e-caprolactam into n-caproic acid was reinvestigated for this purpose. Attempts to reduce e-caprolactam or e-amino-1 Based on a thesis submitted to the School of Graduate Studies at Michigan State College in 1952 by Richard L. Burke in partial fulfillment of the requirements for the degree of Doctor of Philosophy.

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The Reaction of Diazomethane and its Derivatives with Aldehydes and Ketones

Gutsche¹

2011

Organic Reactions

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Diazomethane and its derivatives react with aldehdyes and ketones usually under very mild conditions to yield a variety of interesting and often useful products. The reaction is most often carried out by either allowing the carbonyl compound to react with an ethereal solution of the diazomethane derivative with or without the addition of a catalyst, or by treating a methanol solution of the carbonyl compound with a nitrosoalkylurethane in the presence of a base, Only the reactions of diazomethane and its alkyl and aryl derivatives are discussed in detail.

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42. Reactions of aliphatic diazo-compounds with carbonyl derivatives

Cited by 17 publications

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Homologation Reaction of Ketones with Diazo Compounds

Homologation Reaction of Ketones with Diazo Compounds

A STUDY OF THE STRUCTURE OF SOME CYCLIC AMIDES AND RELATED TETRAZOLES¹

The Reaction of Diazomethane and its Derivatives with Aldehydes and Ketones

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42. Reactions of aliphatic diazo-compounds with carbonyl derivatives

Cited by 17 publications

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Homologation Reaction of Ketones with Diazo Compounds

Homologation Reaction of Ketones with Diazo Compounds

A STUDY OF THE STRUCTURE OF SOME CYCLIC AMIDES AND RELATED TETRAZOLES1

The Reaction of Diazomethane and its Derivatives with Aldehydes and Ketones

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A STUDY OF THE STRUCTURE OF SOME CYCLIC AMIDES AND RELATED TETRAZOLES¹