Quantum-chemical study on the reaction of phenyl isocyanate with linear methanol associates: II. Addition at the C=O bond

Addition of linear methanol associates at the C=O group of phenyl isocyanate involves a concerted cyclic asymmetric late transition state. The reaction is accompanied by formation of pre- and post-reaction complexes. Isomerization of intermediate methyl hydrogen phenylimidocarbonate into methyl phenylcarbamate is characterized by a considerable energy barrier. The reactivity of methanol molecules increases in parallel with the degree of their association, which is related to increase in their electron-donor power. Comparison of the calculated parameters for the addition of methanol associates at the C=N and C=O bonds of phenyl isocyanate clearly indicates that the first path is preferred.     

The thermodynamic parameters of reactions of phenyl isocyanate with methanol associates

The thermodynamic parameters of reactions of phenyl isocyanate with methanol monomer, dimer, and trimer were calculated by the B3LYP and MP2 quantum-chemical methods. The enthalpies and entropies of transformations were found to increase as the degree of methanol association grew. An isokinetic dependence was observed for the transformations under consideration. The influence of the polarity of solvents on the Gibbs energies of these reactions was estimated.     

Quantum-Chemical Study on Reactions of Isocyanates with Linear Methanol Associates: III.* Reaction of Methyl Isocyanate with Linear Methanol Associates

Addition of linear methanol associates at the C=N and C=O bonds of methyl isocyanate was studied in terms of the B3LYP/6-311++G(df,p) hybrid quantum-chemical method. The addition at the C=N bond is more favorable than the reaction at the carbonyl group. All reactions involve late asymmetric cyclic transition states. The activity of the reacting system increases in parallel with the degree of methanol association. Isomerization of methyl hydrogen methylcarbonimidate into carbamate is catalyzed by methanol associates. Thermal decomposition of carbamates with formation of isocyanates can occur in autocatalytic mode.     

Kinetics and mechanism of urethane reactions: Phenyl isocyanate–alcohol systems

Urethane reactions of phenyl isocyanate alcohol systems with toluene as solvent and various aprotic polar solvents (including tertiary amines) as additives were carried out at constant temperature of 10–40°C. Analysis of the variation of the second order rate constants of these systems and those available in the literature indicates that formation of the hydrogen bonding complexes (alcohol with phenyl isocyanate and with aprotic solvent) and electron donor number (DN) of the aprotic solvent are the two factors allowing satisfactory explanation of the catalysis and inhibition effects of the wide range of aprotic solvents (including amines, amides, etc.). Based on these considerations, an ion-pair mechanism and the resulting kinetic equation for the urethane reaction are proposed. Verification on the kinetic equation with experimental results for the systems of phenyl isocyanate with alcohol in toluene (for the self catalysis of the alcohol), with dimethyl formamide and dimethyl sulfoxide in toluene (for the catalysis of the aprotic solvents), and with triethylamine in toluene (for the catalysis of the tertiary amines) shows satisfactory. In the mechanism, the aprotic solvent is considered to solvate the complex of phenyl isocyanate/alcohol at the active hydrogen to form an ion-pair which can undergo the urethane reaction more easily.     

Theoretical study on the reaction mechanism of the alcoholysis of isocyanates

In this paper, the reactions of HNCO or CH₃NCO with methanol have been studied using the ab initio MO method. The geometries of the reactants and products have been optimized by the energy gradient method. The calculated results are in accordance with experiment. Using Powell's method, by the minimization of the Euclidean norm σ of the gradient, the structures of the transition state (TS ) for the two reactions were obtained. The structures have been further confirmed as TS by finding that there is one and only one negative eigenvalue for their force constant matrix. The imaginary vibration mode corresponding to the TS was also discussed. The calculated activation barriers of these two reactions are 96.02 and 95.13 kJ/mol, respectively. It can be concluded that the alcoholysis reaction of isocyanate is a nucleophilic addition reaction with methanol as an electronic donor and isocyanate as an acceptor and that the hydroxyl hydrogen of CH₃OH plays an important role in the reaction.     

Spectroscopic study of complex formation by methanol and phenyl isocyanate with bis(acetylacetonato) copper

It has been shown that the reaction of phenyl isocyanate with methanol in dioxane in the presence of bis(acetylacetonato) copper involves the formation of intermediate complexes. The isocyanate is coordinated to the copper ion of the catalyst, and the alcohol is joined to the oxygen of the chelate rings of bis(acetylacetonato) copper together and hydrogen bond. This brings the reacting molecules closer together and orients them relative to one another, thus facilitating their interaction. The phenylmethylurethan formed is also coordinated to the catalyst, and when it appears in the system, equilibrium is established between the complexes formed by the catalyst with the solvent, the isocyanate, and the urethan.     

Quantum-chemical study on reactions of isocyanates with linear methanol associates: VIII. Relative reactivity of linear phenol and methanol associates toward methyl isocyanate

The mechanisms of the reactions of methyl isocyanate with phenol monomer and linear dimer were studied at the B3LYP/6-311++G(df,p) level of theory, and the results were compared with those obtained for the reactions with methanol associates. All the examined reactions involve asymmetric concerted transition states. The addition of phenol is electrophilic, whereas the addition of methanol is nucleophilic. The formation of H-complexes with phenol and methanol molecules increases not only electron-donating power but also gasphase acidity and basicity.     

Quantum-chemical study of thermodynamics of hydrogen-bonded methylamine-methanol complexes reaction with dimethyl carbonate

Thermodynamic parameters of the reactions of dimethyl carbonate cis-cis and cis-trans conformers with methylamine, methylamine dimer, and methylamine complexes involving linear methanol associates have been computed with the B3LYP and WB97XD quantum-chemical methods. The both methods have given similar results. Thermodynamically, reactions of the cis-trans conformer are preferred over the analogous reactions of the cis-cis conformer, and the reactions with methylamine dimer and methylamine-methanol trimer complex are preferred over the reactions with methylamine monomer. The acid-base properties of the hydrogen-bonded methanol complexes are significantly enhanced with increasing degree of association. Stability of the methylamine complexes with methanol clusters is increased with more of the alcohol molecules involved.     

Kinetic studies on light-induced cationic ring-opening reactions on 2,3-epoxypropyl phenyl ether

Light-induced cationic ring-opening reactions of 2,3-epoxypropyl phenyl ether (phenyl glycidyl ether, PGE) in acetone, methanol and bulk were studied. Cations are produced by electron transfer from excited sensitizers (anthracene, An; 9,10-phenanthrenequinone, PQ; benzophenone, BP) or from photolytically cleaved sensitizer (benzoin isoproyl ether, BIPE) to diphenyliodonium hexafluorophosphate. With excess of acetone and methanol, addition reactions take place resulting in 2,2-dimethyl-4-phenoxymethyl-1,3-dioxolane and 1-methoxy-3-phenoxy propan-2-ol as main products. The efficiency of the sensitizers taken from the quantum yields of PGE conversion, follows the order An ? BIPE > PQ > BP in acetone and An ～ BP > BIPE ? PQ in methanol. Unlike bulk polymerization, in these addition reactions no steady-state concentration of cations exists and the reaction accelerates with time. When alcohol is added in only small proportions, the initial addition reactions goes over into a linear oligomerization. The relatively higher basicity of methanol over PGE influences the nature of the active center, and the course of reaction depends on methanol concentration. Kinetic expressions, which account for all possible types of active centers, have been derived to express the rate of PGE reactions in methanol.     

Substituent effect of N‐aryl‐N′‐pyridyl ureas as thermal latent initiators on ring‐opening polymerization of epoxide

A series of N‐aryl‐N′‐pyridyl ureas were synthesized by the reactions of 4‐aminopyridine (4AP) with the corresponding isocyanates such as phenyl isocyanate, 4‐methylphenyl isocyanate, 4‐methoxyphenyl isocyanate, 4‐chlorophenyl isocyanate, 4‐(trifluoromethyl)phenyl isocyanate, and 4‐nitrophenyl isocyanate. Bulk polymerization of diglycidyl ether of bisphenol A (DGEBA) in the presence of the ureas as initiators was evaluated by differential scanning calorimetry (DSC) at a heating rate of 10 °C/min. The resulting DSC profiles indicated exothermic peaks above 140 °C, while the DSC profile measured for a formulation composed of DGEBA and pristine 4AP indicated an exothermic peak at around 120 °C, implying that the derivation of 4AP into the corresponding ureas is a useful strategy to achieve thermal latency. The peak top temperatures were correlated with the electron density of the aromatic ring of the ureas, that is, as the electron‐withdrawing nature of the substituent on the aromatic ring became larger, the peak increases. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2569–2574     

Model reactions for crosslinking polydiacetylene materials

A series of reactions are presented which allowed us to crosslink polydiacetylenes containing carbamate groups in the side chain without attacking the triple bond. These reactions involved syntheses of carbamates and allophanates from butyl alcohol and phenyl isocyanate with metal and tertiary amine catalysts using a model compound, 2,4,7,9-tetramethyl-5-decyn-4,7-diol. Elemental analysis, IR and UV spectroscopy, and high performance liquid chromatography (HPLC) were used as analytical tools. Metal catalysts were found to favor the formation of allophanates in higher yields and purity as compared to tertiary amine catalysts.     

Novel glutathione conjugates of phenyl isocyanate identified by ultra‐performance liquid chromatography/electrospray ionization mass spectrometry and nuclear magnetic resonance

Phenyl isocyanate is a highly reactive compound that is used as a reagent in organic synthesis and in the production of polyurethanes. The potential for extensive occupational exposure to this compound makes it important to elucidate its reactivity towards different nucleophiles and potential targets in the body. In vitro reactions between glutathione and phenyl isocyanate were studied. Three adducts of glutathione with phenyl isocyanate were identified using ultra‐performance liquid chromatography/electrospray ionization mass spectrometry and nuclear magnetic resonance (NMR). Mass spectrometric data for these adducts have not previously been reported. Nucleophilic attack on phenyl isocyanate occurred via either the cysteinyl thiol group or the glutamic acid α‐amino group of glutathione. In addition, a double adduct was formed by the reaction of both these moieties. NMR analysis confirmed the proposed structure of the double adduct, which has not previously been described. These results suggest that phenyl isocyanate may react with free cysteines, the α‐amino group and also with lysine residues whose side chain contains a primary amine. Copyright © 2014 John Wiley & Sons, Ltd.     

Quantum-chemical analysis of the reactivity of methanol dimers in their reaction with isocyanates

The CNDO/2 method has been used to investigate the reactivity of methanol dimers of various structures in nucleophilic addition reactions at the N=C bond of isocyanates. It is shown that effect of dimerization on the reactivity of the alcohol is in the same direction as the effect of an electron donating catalyst on the monomer, depending on the structure of the dimer and, in some instances, also on the conformation of the isocyanate.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 26, No. 3, pp. 345–348, May–June, 1990.     

Isocyanate–catalyst and hydroxyl–catalyst complex formation

As part of an investigation for evidence of isocyanate–catalyst and alcohol–catalyst complex formations, determinations of molecular weights were made by means of the freezing point depression of benzene solutions. Mixtures of 1-methoxy-2-propanol and dibutyltin dilaurate and mixtures of 1-methoxy-2-propanol and triethylamine both gave strong evidence of the formation of complexes. Complex formations were also detected when the alcohol was replaced by phenyl isocyanate. Significantly larger concentrations of the catalyst were involved in isocyanate complexes than were shown to be the case with the alcohol complexes. These results appear to be experimental evidence for the previously proposed ternary complex as an intermediate in the metal-catalyzed formation of urethanes.     

Solvent-assisted alcohol-isocyanate kinetics

The dependence of the reaction rate of cyclopentanol with phenyl isocyanate on the concentration of monomeric alcohol [1] in toluene, di-n-butyl ether and acetonitrile suggests a reaction scheme involving various complexes.     

Cycloaddition-elimination reactions of 5-imino-1,2,4-dithiazolidin-3-ones with heterocumulenes

5-Benzylimino-1,2,4-dithiazolidin-3-one ( 2a ) reacts with heterocumulenes (isocyanates, isothiocyanates, ketenes) with elimination of carbonyl sulfide, yielding the heterocycles 6–8 . The thiadiazolidine 6a , obtained from 2a and phenyl isocyanate, underwent similar reactions but under milder conditions, indicating that phenyl isocyanate is a better leaving group than carbonyl sulfide.     

Kinetics and mechanism of urethane formation catalyzed by organotin compounds. II. The reaction of phenyl isocyanate with methanol in DMF and cyclohexane under the action of dibutyltin diacetate

The kinetics of the dibutyltin diacetate (DBTDA)-catalyzed reaction of phenyl isocyanate with methanol in DMF and cyclohexane have been studied by monitoring the rate of change of the absorbance of the reaction mixture at 281.6 and 280.9 nm, respectively. Our results indicate that the mechanism of the reaction is independent of the nature of the (inert) solvent. The subsequent reaction steps are (i) complexation of methanol to DBTDA, (ii) dissociation of the complex into a proton and an anion of composition [(n-C₄H₉)₂Sn(OCOCH₃)₂(OCH₃)]^?, (iii) insertion of the isocyanate into the tin—alkoxy bond (the rate-determining step), and (iv) methanolysis of the thus-formed urethane precursor with simultaneous regeneration of the anion. The rate of the catalyzed reaction increases on goin from coordinating to noncoordinating solvents. The following sequence in order of increasing rate constant was observed: DMF < dibutyl ether < cyclohexane. This is because in coordinating solvents, DBTDA and methanol, apart from forming a complex with each other, also form complexes with the solvent.     

Promoting effects of urethane derivatives of phenols on the ring‐opening polymerization of 1,3‐benzoxazines

For the purpose of reducing the induction period of the ring‐opening polymerization of N‐methyl‐1,3‐benzoxazines, several urethanes were examined as promoters. The examined promoters 3a – d were the adducts of resorcinol and phenyl isocyanate, that of bisphenol A and phenyl isocyanate, that of resorcinol and butyl isocyanate, and that of 1,3‐propanediol and phenyl isocyanate, respectively. The aromatic urethanes 3a and 3b , which were adducts of the phenolic compounds and phenyl isocyanate, exhibited significant promoting effects. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Reactions of group IV organometallic compounds : XXVII. Some reactions of [(trimethylsilyl)imino]phosphorane

The reaction of [(trimethylsilyl)imino]methyldiphenylphosphorane: Ph₂MePNSiMe₃ (I) with several acid anhydrides or alkyl isocyanates took place by the simple cleavage of silicon-nitrogen bond. In contrast the interaction of (I) with phenyl isocyanate, isothiocyanate or carbon disulphide led to addition-elimination reactions of the Wittig type. Detailed investigation in the case of phenyl isocyanate indicated the usual elimination of Ph₂MePO is suppressed by the strong affinity of the trimethylsilyl group for anionic oxygen atom.     

Umsetzungen einiger Malonester-enolbetaine mit Phenylisocyanat Über Reaktionen mit Betain, 7. Mitt.

Zusammenfassung Bis-alkoxycarbonylmethyl-pyridiniumenolbetaine, die als mesomere Enolbetaine vorliegen, reagieren mit Phenylisocyanat unter Abspaltung von Alkohol zu Pyrido-pyraziniumbetainen. Bis-phenoxymalonesterbetaine setzen sich dagegen, entsprechend ihrem Ylidcharakter, mit dem genannten Reagens unter Eliminierung von Diphenylcarbonat zu Derivaten des Pyridino-1.2.3.4-tetrahydro-pyrimidin-6-olates um.

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Reactions with betaine, VII: reactions of ethyl malonate-enolbetaines with phenyl isocyanate

Bis-alkoxycarbonylmethyl-pyridinium enolbetaines, which exist as mesomeric enolbetaines, react with phenyl isocyanate under the loss of ethanol to give pyrido-pyraziniumbetaines. However, phenyl malonate betaines react with phenyl isocyanate, according to their ylid character, to yield derivatives of 1.2.3.4-tetrahydro-pyrimidin-6-olates.

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Herrn Prof. Dr.M. Pailer, Wien, mit besten Wünschen zum 60. Geburtstag gewidmet.