The action of Grignard reagent on the amide group. XXXV. Reaction of 1-methyl-1-azacycloundecanone-(2) and 1-methyl-1-azacyclotridecanone-(2)

Lukes, Robert M.; Havlíčková, L.

doi:10.1135/cccc19612245

Cited by 7 publications

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“…Caprolactam hydrolyzes when heated in concentrated (37%) hydrochloric acid at 90 °C for 15 hours (368). N-Methylcaprolactam heated at reflux for 10 hours in 10% sulfuric acid gave 6-(methylamino)caproic acid (originally identified incorrectly as 2-(methylamino)caproic acid) (369). Pyrrolidone, when heated in 85% aqueous methanesulfonic acid at 100-105 °C for six hours, gave 4-aminobutyric acid (370).…”

Section: Acid-catalyzed Hydrolysis Of Pyrrolidones and Caprolactamsmentioning

confidence: 99%

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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Section: Acid-catalyzed Hydrolysis Of Pyrrolidones and Caprolactamsmentioning

confidence: 99%

Introduction to Pyrrolidone and Caprolactam Chemistry

Chenault

2021

Handbook of Pyrrolidone and Caprolactam Based Materials

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“…The larger-ring lactams yield mainly acyclic amino ketones as the sole pro duct [69][70][71][72][73][74]. [75] …”

Section: + C 6 H 5 Mgbrmentioning

confidence: 99%

Enamines

1971

Organic Chemistry: A Series of Monographs

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The chemistry of enamines has been described in several reviews [25][26][27][28][29] and in a recent monograph [30]. CONDENSATION REACTIONS A. Condensation of Secondary Amines with Aldehydes and KetonesThe most widely used method for preparing enamines involves the conden sation of aldehydes and ketones with secondary amines (Eq. 6). In 1936, Mannich and Davidsen [31] were the first to describe the reaction of secondary amines with aldehydes in the presence of anhydrous potassium carbonate at approximately 0°C to give enamines (Eqs. 6, 7). R-CH 2 CH=0 + 2HNR , R-C-CH R' + HNRJ II oMannich and Davidsen [31] also reported that most of the aldehydes were first converted to a diamino intermediate which on distillation afforded the enamine. Less successful was the attempt to extend the reaction to ketones. Only with the use of calcium oxide at elevated temperatures were the enamines directly obtained, but in poor yields. Herr and Heyl [32,33] found that better yields of enamines from ketones can be obtained by the azeotropic removal of water in the presence or absence [32,33] of acid catalysts [12a, b, 34, 35]

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Polymerisation höhergliedriger cyclischer imine

Rentsch

Lüssi

1972

Makromol. Chem.

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ZUSAMMENFASSUNG:Dodecamethylenimin und N-Methyldodecamethylenimin lassen sich bei Temperaturen oberhalb 200 O C polymerisieren. Als Katalysatoren dienen die Salze der Monomeren, LEWIS-Sauren und Alkytierungsmittel. Zuerst bilden sich Oligomere, welche erst spater in hohere Polymere und schliefllich in vernetzte Produkte ,iibergehen. Gleichzeitig werden kleine Mengeu Aminoniak bzw. Trimethylamin gebildet. Der Vorgang beruht im wesentlichen auf einer Umalkylierung, an der samtliche Aminogruppen teilnehmen. Demzufolge lassen sich die gleicben Polymeren unter ahnlichen Bedingungen auch durch Polykondensation aus Diaminen unter Ammoniakabspaltung herstellen. Andere cyclische Imine mit mehr als 7 Ringgliedern verhalten sich ahnlich. Hexamethylenimin fuhrt infolge der thermodynamischen Stabilitat der sich bildenden N-substituierten 7-gliedrigen Iminringe nur aur Bildung niedermolekularer Produkte. Das gleiche gilt auch fur das N-Methylhexamethylenimin. SUMMARY:Dodecamethylene imine and N-methyldodecamethylene imine can be polymerized a t temperatures above 200 ' C. Monomer salts, LEWIS acids and alkylating agents are catalysts.At first only oligomers are formed, which are converted to higher polymers as the reaction proceeds yielding finally crosslinked products. At the same time some ammonia or trimethylamine respectively are formed. The process consists essentially in a transalkylation a t which all amino groups participate. Consequently the same polymers can be prepared under similar conditions by polycondensation of diamines with elimination of ammonia. Other cyclic imines with more than 7 atoms in the ring behave similarly. Hexamethylene imine yields only oligomers due to the thermodynamic stability of the formed N-substituted 7-membered imine rings. The same holds for N-methylhexamethylene imine.

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The action of Grignard reagent on the amide group. XXXV. Reaction of 1-methyl-1-azacycloundecanone-(2) and 1-methyl-1-azacyclotridecanone-(2)

Cited by 7 publications

References 0 publications

Introduction to Pyrrolidone and Caprolactam Chemistry

Introduction to Pyrrolidone and Caprolactam Chemistry

Enamines

Polymerisation höhergliedriger cyclischer imine

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