THE MICHAEL CONDENSATION.<sup>1</sup> VI. THE INSTABILITY OF SOME ADDITION PRODUCTS<sup>2</sup>

deBenneville, Peter L.; Clagett, Dorothy Dyott; Connor, Ralph

doi:10.1021/jo01205a004

Cited by 6 publications

References 4 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

The Alkylation of Esters and Nitriles

2011

View full text Add to dashboard Cite

This chapter is concerned with the reactions of metal salts (enolates) of active methylene compounds with alkylating agents such as alkyl halides to produce allyl derivatives. The first example of this reaction is found in the literature when Geuther prepared ethyl alpha‐ethyl acetoacetate by the reaction of the sodium enolate of ethyl acetoacetate with ethyl iodide. The active methylene compounds considered in the chapter include malonic esters, cyanoacetic esters, malonitriles, monocarboxylic esters and mononitriles. These classes of compounds are characterized by the presence of one or more acidic hydrogen atoms attached to carbon. Only C‐alkylation has been observed with active methylene compounds and are discussed here. Several alternative methods for the preparation of alkyl and aryl derivatives of carboxylic esters and nitriles have been included.

show abstract

The Alkylation of Esters and Nitriles

2011

View full text Add to dashboard Cite

show abstract

TheMichael Reaction*This cooperative study was begun when the three authors were working at the Weizmann Institute of Science, Rehovoth.

Bergmann¹,

Ginsburg

Pappo

2011

Organic Reactions

View full text Add to dashboard Cite

The Michael condensation in its original scope is the addition of an addend or donor containing an alpha‐hydrogen atom in the system OCCH to a carbon‐carbon double bond that forms part of a conjugated system of the general formula CCCO in an acceptor. The condensation takes place under the influence of alkaline reagents, typically alkali metal alkoxides. The range of addends is very broad. Typical acceptors are alpha, beta‐unsaturated aldehydes, keotnes, and acid derivatives. As an extension of the original scope, the Michael condensation has come to be understood to include addends and acceptors activated by groups other than carbonyl and carboxalkoxy. The wider scope is encompassed in this survey.

show abstract

Zur Kenntnis der β‐Dicarbonyl‐Verbindungen, III. Mitteil.:CH‐Acidität elektromerer Effekt und Reaktionsfähigkeit

Henecka

1948

Chem. Ber.

View full text Add to dashboard Cite

Nr. 31 19481 H e n e c k a : 8-Dicarbonyl-Verbindungen (111.).197 an -B u t yllert ,v a l e r y 1e a sign ii ureiit h y le s t e r (XVI) wurdc analog durclidlky--liemn des tefi.-Valeryl-esaigha als wasserhello Fliissigkeit erhalten ; Sdp. ,I 130-132O. C13H,,0, (B8.2) Bor. C 65.42 H 10.52 Gef. C 68.35 H 10.55. an -B u t y l -benzoyleeaigsiiure -8 t h y les t e r wurde a m Benzoylessigester und n-Butyl-bromid wie iiblich erhalten. Wiiaserhelle Eliissiykcit; Sdp.,., 181O. CI,H,oO, (248.2) Ber. C 72.58 H 8.07 Gef. C 72.81 H 8.18. 31. Hans Hen eeka : Zur Kenntnis der 9 -Diearbonyl -Yerbindungen, 1 . 111. Mittail.*) : CH-Aeiditiit, elekhmerer Efiekt nnd Reaktionsiiihigkeit. [Aue dem wissenschaftlichen Forschungalrrboratrium der Farhnfabriken Bayer, Wupprtd-Elkrfeld.]Es wird gezcigt, daU aowohl Reaktionaeintritt untl Gleicbgewichtahgo der Micheelschonriddition, ah ouch die Moglichkeit des Kintritta von Polgereaktionen weitgehend behorrscht werden durch htononbeweglichkeit und elektromerc Effekte bei den Heaktionepertnern; gleichzeitig wird gezoigt, drU der Eintritt dcr Claisen-Kondensation alicyclischer Rotone mit Oxidester lrei Gegenwart von Natriumiithylat abhlngt von der CH-Aciditiit der kondeneationsfiihigen CH,-Gruppe dee alicycliachon Ketons.Eine Rea.ktion, die vornehmlich geeignet ist, die Zusarnmdnhiinge zwischen CH-Aciditiit, elektromerem Effekt und Hellktionsfiihigkeit zu untersuchen, iat die von Claia'ed) entdeckte und von Michae12) eingehend studierte Addition von Verbindungen mit reeJctionsfiihigm aciden Methylengruppen vom T-vp der P-Dicarbonyl-Verbindungen an a,$-ungesiittigte Carbonxl-Verbindungen. Der Mechanismus dieser wicht,igen Synt h e x sri zuiiachst an einern einfachen Beispiel, der Addition ron -4cetcssigester an Methyl-vinyl-keton, niiher zergliedert. Die Reaktion wird katdysiert durch die Gegenwert einer geringen AXenge Alkali oder baaischer Stoffe, die xunachst ein Proton der P-Dicarbonyl-Verbindung, hier des Acetessigesters, anfnehmen unter Bildung des. Anions, das in der Ca.rbenint-Clrenzforni reagicrt :

show abstract

THE MICHAEL CONDENSATION.¹ VI. THE INSTABILITY OF SOME ADDITION PRODUCTS²

Cited by 6 publications

References 4 publications

The Alkylation of Esters and Nitriles

The Alkylation of Esters and Nitriles

TheMichael Reaction*This cooperative study was begun when the three authors were working at the Weizmann Institute of Science, Rehovoth.

Zur Kenntnis der β‐Dicarbonyl‐Verbindungen, III. Mitteil.:CH‐Acidität elektromerer Effekt und Reaktionsfähigkeit

Contact Info

Product

Resources

About

THE MICHAEL CONDENSATION.1 VI. THE INSTABILITY OF SOME ADDITION PRODUCTS2

Cited by 6 publications

References 4 publications

The Alkylation of Esters and Nitriles

The Alkylation of Esters and Nitriles

TheMichael Reaction*This cooperative study was begun when the three authors were working at the Weizmann Institute of Science, Rehovoth.

Zur Kenntnis der β‐Dicarbonyl‐Verbindungen, III. Mitteil.:CH‐Acidität elektromerer Effekt und Reaktionsfähigkeit

Contact Info

Product

Resources

About

THE MICHAEL CONDENSATION.¹ VI. THE INSTABILITY OF SOME ADDITION PRODUCTS²