The Beckmann Rearrangement. Iv. Study of the Rates of Some Aliphatic and Alicyclic Oximes

Scott, Paul T.; Pearson, D. E.; Bircher, Louis J.

doi:10.1021/jo01376a016

Cited by 9 publications

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Introduction to Pyrrolidone and Caprolactam Chemistry

Chenault

2021

Handbook of Pyrrolidone and Caprolactam Based Materials

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Pyrrolidones and caprolactams are important structural components of solvents, surfactants, polymers, natural products, and pharmaceuticals. This chapter provides an introduction to the structure, conformation, physical properties and reactivity of pyrrolidones and caprolactams. It begins with an overview of the nomenclature of lactams since there are several systems of nomenclature in practice, plus common names and various syncretisms. Next, the structures of pyrrolidone and caprolactam are discussed, starting with the X-ray crystal structures of pyrrolidone, N-methylpyrrolidone (NMP) and caprolactam. The conformational flexibility and ring strain of the two ring systems are also covered.Physical properties, such as dipole moments, the enthalpies of formation, vaporization and fusion, boiling points and melting points, are described. An attempt is made to put the properties of pyrrolidones and caprolactams into context with those of other lactams, amides and even lactones and cyclic ketones. Brønsted and Lewis basicity, acidity, hydrogen bonding and solubility are covered.Finally, a brief description of the basic reactivity of pyrrolidones and caprolactams is given. Topics covered are N-, O-, and α-C-alkylation, hydrolysis, reactions with organometallics, reduction, oxidation, and ring-opening polymerization. The intent is to give a concise physical organic perspective on reactivity (and stability) more than an extended treatise on synthetic elaborations. Definition and Nomenclature of LactamsLactams are cyclic amides in which both the carbonyl carbon and nitrogen atom of the amide group are part of a ring. The name, lactam, is a portmanteau of lactone (cyclic ester) and amide.Nomenclature of lactams follows a variety of conventions (Figure 1 and Table 1). The International Union of Pure and Applied Chemistry (IUPAC) recommends naming lactams as heterocyclic pseudoketones (IUPAC method 1) or by substituting lactam for the

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Introduction to Pyrrolidone and Caprolactam Chemistry

Chenault

2021

Handbook of Pyrrolidone and Caprolactam Based Materials

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Introduction to Pyrrolidone and Caprolactam Chemistry

Chenault¹

2022

Handbook of Pyrrolidone and Caprolactam Based Materials

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Weitere Kinetische Untersuchungen zur Beckmann‐Umlagerung der Aryl‐Alkyl‐Ketone

1957

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In den unti-AlkyI-phenyl-ketoxim-2.4.6-trinitrophenyl-athern beeinfluDt der Alkylrest die Wanderungsneigung des Phenyls charakteristisch, wie die Kinetik der CHAPMAN-UmkigerUng lehrt. Bei den syn-Oxim-athern scheint allgemein die Umlagerungsgeschwindigkeit in der Folge prim., sek., tert. Alkyl zu steigen. An den isomeren I-und 3-Methoxy-2-acetonaphthon-oxim-athern wird das Zusammenspiel des sterischen und elektronischen Substituenteneffekts studiert.Die Arylwanderung bei der BECKMANN-Umhgerung passiert die Zwischenstufe eines verbruckten Kations I1 rnit Azirin-Ring ; sie schlieBt damit eine elektrophile Substitution des wandernden Awls ein1.2). Bei der kinetischen Untersuchung der Chapman-Isomerisierung der Oxirn-2.4.6-trinitrophenyl-ather miDt man die Neigung zur Beckrnann-Urnlagerung, die den geschwindigkeitsbestimmenden Teilschritt bei der Bildung des N-Trinitrophenyl-isoxims ausmacht 3.4). Die Chapman-Umlagerung kernsubstituierter Acetophenon-anti-oxim-trinitrophenyl-ather (1, R =CH3) zeigte in ihrer Geschwindigkeit den erwarteten EinfluD des induktiven und rnaomeren Substituenteneffekts: Elektronen-liefernde Substituenten im Kern beschleunigen, Elektronen-anziehende wirken ihr entgegen 1). 1 r n k Den EinfluB der Seitenkette R in I auf die Geschwindigkeit der Arylwanderung kann man diskutieren, wenn man sich wie in den vorausgehenden Arbeiten auf die Verrnutung stutzt, da8 der RG-bestimmende Ubergangszusfand der Zwischenstufe I1 strukturell ahnlich ist. Urn den Hybridisierungszustand des dreigliedrigen Ringes in 11 a in der Valenzschreibweise zu syrnbolisieren, darf man mit einer beachtlichen Be-1 ) R. HUISGEN, J. WITTE, H.

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The Beckmann Rearrangement. Iv. Study of the Rates of Some Aliphatic and Alicyclic Oximes

Abstract: Considerable data have been accumulated concerning the rates of rearrangement of aromatic oximes, particularly of substituted acetophenone oximes (1-3). The purpose of the present work was to extend the study to aliphatic types.

Cited by 9 publications

References 8 publications

Introduction to Pyrrolidone and Caprolactam Chemistry

Introduction to Pyrrolidone and Caprolactam Chemistry

Introduction to Pyrrolidone and Caprolactam Chemistry

Weitere Kinetische Untersuchungen zur Beckmann‐Umlagerung der Aryl‐Alkyl‐Ketone

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