Struktur und Reaktivität heterosubstituierter Nitrile. 24 Kinetik und Mechanismus der Reaktion von o-Phenylendiamin mit Arylcyanaten

Structure and Reactivity of Heterosubstituted Nitriles. 24. Kinetics and Mechanism of the Reaction of o-Phenylen diamine with Aryl Cyanates The second and third order rate constants for the reaction of o-phenylene diamine with aryl cyanates to 2-amino benzimidazole phenylester imide in water/dioxane have been determined by i.r. measurements. The reaction proceeds through a bimolecular and a trimolecular mechanism simultaneously. In the slow step of the bimolecular process an electrophilic attack of the aryl cyanate on o-phenylene diamine takes place in a seven membered cyclic transition state. The slow step of the trimolecular mechanism consists of a nucleophilic attack of the diamine on a phenole aryl cyanate associate by a six membered cyclic transition state. The final products of both reactions are formed by successive fast reactions.     

Struktur und Reaktivität heterosubstituierter Nitrile. XVI[1]. Kinetik und Mechanismus der Arylcyanatbildung aus Bromcyan und Phenolen

Structure and Reactivity of Heterosubstituted Nitriles. XVI. Kinetics and Mechanism of the Formation of Arylcyanates from Cyanogen Bromide and Phenoles The first-order and second-order rate constants of the reaction of cyanogen bromide with phenoles in the presence of tertiary aliphatic amines were determined in absolute acetone. The first step of the reaction is the nucleophilic attack of the tertiary amine at the cyanogen bromide. By a fast equilibrium reaction an N-cyano-N,N,N-trialkylammonium bromide is formed, which is attacked by the phenol as a nucleophile or dissociates in the slowest steps of the reaction. The nucleophilicity and the steric hinderance of the tertiary amine, and the nucleophilicity of the phenole as well determine, which of these reactions is favoured.     

Struktur und Reaktivität heterosubstituierter Nitrile. XIX [1]. Kinetik und Mechanismus der Addition sekundärer aliphatischer Amine an Arylcyanate

Structure and Reactivity of Heterosubstituted Nitriles. XIX. Kinetics and Mechanism of the Addition of Secondary Aliphatic Amines to Aryl Cyanates The N,N-dialkyl-O-aryl isourea formation by the addition of secondary aliphatic amines to aryl cyanates was studied by kinetic methods in dioxane and dioxane water mixtures. Linear relationships between the rate constants and the water concentrations, the basicity of the amines and the electrophilicity of the aryl cyanates have been found. These data and the activation parameters support two concurrent reactions, a direct nucleophilic attack of the amine to aryl cyanate and one involving a six membered transition state between a molecule of cyanate, amine and water.     

Struktur und Reaktivität heterosubstituierter Nitrile. XX [1]. Kinetik und Mechanismus der Addition primärer aliphatischer Amine an Arylcyanate

Structure and Reactivity of Heterosubstituted Nitriles. XX. Kinetics and Mechanism of the Addition of Primary Aliphatic Amines to Aryl Cyanates The addition rate of primary aliphatic amines to aryl cyanates in water/dioxane mixtures was measured by u.v.-spectroscopy. The second order rate constants give a linear correlation with the concentration of water. The rate of the addition is increased by growing electrophilicity of the aryl cyanates and decreased by steric hindrance of the amine substituents. The nucleophilicity of the amine has no influence on the reaction rate. The results are explained by a six-membered cyclic transition state, in which the nucleophilic attack and the proton transfer proceed with equal rate.     

Struktur und Reaktivität heterosubstituierter Nitrile. XVII [1]. Kinetik und Mechanismus der Phenol-Addition an Arylcyanate in Gegenwart tertiärer Amine

Structure and Reactivity of Heterosubstituted Nitriles. XVII. Kinetics and Mechanism of the Addition of Phenols to Aryl Cyanates in Presence of Tertiary Amines The rate of carbonic acid diaryl ester imides formation by the addition of phenols to aryl cyanates in the presence of tertiary amines was determined by IR-spektroscopy. The rate constants are first order in aryl cyanates and correlate linear with [ArOH] [ArO⁻ ∥ R₃NH⁺]. The third order rate constants depend linear on the (σ + σ⁻)-values of the phenol substituents, the σ⁰-values of the aryl cyanate substituents, and the pK_a of the tertiary ammonium salts. These results support a transition state formed by the nucleophilic attack of a phenoxide trialkyl ammonium ion pair to an aryl cyanate phenol associate.     

Struktur und Reaktivität heterosubstituierter Nitrile. XVIII [1]. Kinetik und Mechanismus der Alkohol-Addition an Arylcyanate in Gegenwart tertiärer Amine

Structure and Reactivity of Heterosubstituted Nitriles. XVIII. Kinetics and Mechanism of the Addition of Alcohols to Aryl Cyanates in Presence of Tertiary Amines The mechanism of the carbonic acid arylester imide or carbamic acid arylester formation by the addition of alcohols or water to aryl cyanates in the presence of tertiary amines has been studied. After a slow formation of an autocatalyst, an intermediate is formed in a fast equilibrium between this one and a molecule of aryl cyanate and tertiary amine. This intermediate is slowly alcoholyzed to carbonimidic acid diester which in part is fragmented by the base to phenole and alkyl cyanate. The alkyl cyanate undergoes further reaction with the alcohol and the amine to dialkyl ether and trialkyl ammonium cyanate in the reaction mixture.     

Kinetik und Mechanismus der Reaktion von Arylisocyanaten mit Alkylhydroperoxiden

Kinetics and Mechanism of the Reaction of Aryl Isocyanates with Alkyl Hydroperoxides Sec-alkyl peroxycarbamates, prepared from phenyl isocyanate and sec-alkyl hydroperoxides, are instable at normal temperatures and decompose to yield ketones, carbon dioxide and aniline which reacts further to diphenylurea. The reactions of phenyl isocyanate with tetraline hydroperoxide, t-butyl hydroperoxide, aniline, and tert.-butanol in dioxane have been studied kinetically and the catalytic constants of diazabicyclooctane, triethylamine, and stannous octoate as catalysts have been determined. Rate constants of the reactions with hydroperoxides decrease with increasing hydroperoxide concentration caused by association of the catalyst with the hydroperoxide. Compared to their basicities, alkyl hydroperoxides are very reactive towards isocyanates.     

Acylierung von Heterocyclen mit Kohlensäurederivaten. I. Kinetik und Mechanismus der Reaktion von 2-Aminobenzimidazolen mit Arylcyanaten

Acylation of Heterocycles with Carbonic Acid Derivatives. I. Kinetics and Mechanism of the Reaction of 2-Aminobenzimidazoles with Aryl Cyanates The second order rate constants for the reaction of 2-amino-benzimidazoles (2-ABI) with aryl cyanates forming 2-amino-benzimidazole aryl ester imide 3 have been determined in dependence on substituent effects by u. v. measurements. The results are interpreted by a six-membered cyclic transition state in which the electrophilic attack of the cyanate on the endocyclic N atom is catalyzed by an H bridge interaction of the exocyclic amino group of 2-ABI with the OCN group.     

Nucleophile Substitution in der 1,3,5-Triazinreihe. IX. Kinetik und Mechanismus der Reaktion von Cyanurchlorid mit 4′-substituierten 4-Aminoazobenzenen

Nucleophilic Substitutions in 1,3,5-Triazines. VII. The Kinetic and ¦ Mechanism of Cyanuric Chloride with 4′-Substituted 4-Aminoazobenzens The kinetic and mechanism of cyanuric chloride reaction with 4′-substituted 4-aminoazobenzens in dioxan-water was studied by conductometry. An addition-elimination mechanism with a monomolecular elimination of chlorine ion at low water concentrations or a nucleophilic attack of 4-aminoazobenzens at high water concentration as low step has been supported by experimental data.     

Nucleophile Substitutionen an Kohlensäurederivaten. XII. Kinetik und Mechanismus der Reaktion von N-Nitro-N-alkylurethanen mit primären aliphatischen Aminen

Nucleophilic Substitutions to Carbonic Acid Derivates. XII. Kinetics and Mechanism of the Reaction of N-Nitro-N-alkyl-urethanes with Primary Aliphatic Amines The aminolysis of N-alkyl-N-nitrourethanes takes place, as the kinetical studies demonstrate, by means of several consecutive steps. The nucleophilic attack of the amine (first step; reaction B), as well as the proton-transfere (second step; reaction C), are quick pre-equilibres, followed by the slow, rate-determining elimination of the nitramino-group (reaction D). During the deprotonation, an intermediate with two to the nitramino-group antiperiplanar orbitals is formed, providing the necessary mesomeric assistance of the elimination.     

Studium der Reaktivität von aromatischen Diaminen mit Epoxidharzen

It was found that the deciding factor for the reactivity of aromatic diamines with epoxide resins are basic values of electron structure and chemical reactivity on the end amino-groups. A linear dependence was determined between logarithm of gelatinization time and electron density of the amino-group which was calculated using principles of quantum chemistry. Changes in the structure of aromatic diamines leading to changes of the electron density of amino-group cause a reactivity change of these compounds during polyaddition. This method shows possibilities offered by quantum chemistry in the field of plastics.     

Acylierung von Heterocyclen mit Kohlensäurederivaten. IV. Umsetzung von Benzoxazolin 2-thion mit Arylcyanaten. Kinetik und Mechanismus

Acylation of Heterocycles with Carbonic Acid Derivatives. IV. Reaction of Benzoxazolin-2-thione with Aryl Cyanates. Kinetics and Mechanism The arylcyanate benzoxazoline-2-thione ( 1 ) reaction in the presence and absence of the tertiary amines yields 1-aryloxyiminocarbonylbenzoxazoline-2-thione ( 2 ) and 2-thiocyanatobenzoxazole (4). A mechanism is proposed based on the influences of the reactants concentration, the concentration and basicity of tertiary amines, the solvent-water concentration, the arylcyanate substituents electronic effects on the reaction rate and the apparent activation parameters. This mechanism consists in the nucleophilic attack of the benzoxazoline-2-thione S-atom on the cyanate, followed by rearrangement through a four-center transition state.     

Darstellung,Struktur und Reaktivität quartärer Ammoniumcellulosate

Tetraalkylammonium cellulosates were prepared by means of an exchange reaction between cellulose and tetraalkylammonium methoxides in anhydrous methanol and dimethylsulfoxide up to a degree of substitution of about 0,7 without chain degradation. The course of this reaction and the structure of the cellulosates in comparison to lithium and sodium cellulosate has been studied. The reaction rate and the equilibrium substitution decreased with increasing size of the cation in the methoxide. The distribution of the alcoholate groups in equilibrium at C-2, C-3 and C-6 of the glucopyranosyl unit in the cellulosates, which was investigated by methylation, hydrolysis of the methylcelluloses, and analysis of the methylglucoses by gas chromatography, was independent of the nature of the cation. Under the given reaction conditions the hydroxyl group at C-2 was more acidic than those at C-3 and C-6, while for the latter practically no difference was found. The tetraalkylammonium cellulosates are highly reactive intermediates for the preparation of cellulose derivatives. The reactivity of the cellulosates increased with increasing size of the cation, Li^⊕ < Na^⊕ < N(CH₃)₄^⊕ <[(CH₃)₃N? CH₂? C₆H₅]^⊕.