Reaction Of Phenyl Isocyanate Research Articles

Kinetic investigation of the synthesis of polycyanoureas and of the model N-phenyl-N′-( o-cyanhenyl)Urea

A kinetic study has been made of the model reaction of phenyl isocyanate with anthranylonitrile and the polycondensation reaction of 4,4′-diamino-3,3′-dicyanodiphenyl oxide with 4,4′-diphenylmethanediisocyanate has been investigated. It is shown that the low molecular weight of the resulting polycyanoureas is related to the low reactivity of bis-( o-aminonitriles). Kinetic studies have been made in regard to the reaction of o-cyanophenylisocyanate with aniline, and the reaction of polycondensation of the corresponding bifunctional compounds. It was found that polycyanoureas of rather high molecular weight are obtainable by polycondensation of bis-(o-cyanoisocyanates) with diamines.

Quinolines and uracils from reactions of isocyanates with aliphatic aldehydes

Reactions of phenyl isocyanate (1a) with n-alkanaldehydes (2a—c) afforded 3-alkyl-4-anilinoquinolines (3a—c), 5-alkyl-1,3-diphenyluracils (4a—c), and diphenylurea (5a). Upon treatment of (1a) with isobutyraldehyde (2d), the dihydrouracil derivative (13) was obtained. From the reactions of α-naphtyl isocyanate (1d) with n-alkanaldehydes (2a and b), 3-alkyl-4-α-naphthylaminobenzo[h]quinolines (21a and b) and 2,3-dialkylbenzo[h]quinolines (22a and b) were isolated. On the other hand, 2,3-dialkylbenzo[f]quinolines (28a and b), β-naphthylamine, and urea (5e) were isolated from the corresponding reactions of β-naphthyl isocyanate (1e). The routes to these products are discussed.

Studies on ketene and its derivatives. LXXIII. Synthesis of pyrido(1,2-a)pyrimidin-4-one and pyrido(1,2-a)sym-triazin-4-one derivatives.

Ethyl N-(2-pyridyl) formimidate (Va) reacted with diketene to give 3-acetyl-4H-pyrido [1, 2-a] pyrimidin-4-one (VIIa) and ethyl 2-(2-pyridylaminomethylene) acetoacetate (VIIIa). Reaction of diketene with ethyl N-(2-pyridyl) acetimidate (Vb) and ethyl N-(2-pyridyl) propionimidate (Vc) afforded 4H-pyrido [1, 2-a] pyrimidine derivatives (VIIb and VIIc), respectively. Similarly 2-benzylideneaminopyridine (VIa) reacted with diketene to give 3-acetyl-4-hydroxy-2-phenyl-4H-pyrido-[1, 2-a] pyrimidine (XI). On the other hand, reaction of trimethylsilyl isocyanate with Va, Vb, and Vc gave rise to 4H-pyrido [1, 2-a]-sym-triazin-4-one derivatives (XIXa, XIXb, and XIXc), respectively. Reaction of phenyl isocyanate with VIa afforded 2, 3-diphenyl-4H-pyrido [1, 2-a]-sym-2, 3-dihydrotrazin-4-one (XX).

�ber die Einschiebung von Phenylisocyanat in eine Silicium-Schwefelbindung

S-Methyl-N-phenyl-iminothiocarbonic acid-tri-O.O′.O″-isopropylsilicic acid anhydride,1 is obtained from the reaction of phenyl isocyanate and methylthiotriiso-propoxysilan.1 readily hydrolyses forming S-methylthiocarbanilide. Substances are characterized by their mass and1H-NMR spectra.

37—THE SITES OF REACTION OF PHENYL ISOCYANATE WITH WOOL

An investigation is described in which some of the sites of reaction of phenyl isocyanate with wool in dimethylformamide solution were identified by analysis of enzyme hydrolysates of the treated wool. These hydrolysates were prepared by oxidation of the wool with performic acid, followed by digestion with three proteolytic enzymes. This procedure releases amino-acid derivatives, which would be converted to the parent amino acids by conventional acid hydrolysis. In one case, the analysis was facilitated by the use of radioactively labelled phenyl isocyanate. Four amino-acid derivatives, arising from the reaction of phenyl isocyanate with the side chains of lysine, serine, threonine, and glutamic acid, were found in the hydrolysates. Their identities were confirmed by comparison with authentic samples, whose synthesis is described.

Reaction of phenyl isocyanate with N-methyl-2-pyrrolidinone

Reaction of phenyl isocyanate with N-methyl-2-pyrrolidinone

The reaction kinetics of urethane formation in the presence of metal compounds and tertiary amines

The preparation of polyurethane foams or film and varnish coatings from multi-component reaction systems sometimes necessitates selective monitoring of the individual stages in the reaction depending on the technological nature of the process. Accordingly various additives are introduced into the reaction mixtures to accelerate or inhibit the interaction of aocyanates with certain compounds having a labile hydrogen atom. Information has been published regarding the way in which a mixture of amine and organotin catalysts led to the discovery of the synergetic effect during the interaction of isocyanates with alcohols and water [1,2]. The reaction of phenylisocyanate with n-butyl alcohol in the presence of a mixed catalyst took place at a much higher rate than would have been expected in view of the rates of these reactions in the presence of each of the catalysts used by itself.

The reaction kinetics of polydiethylene glycol adipate and mono- or diisocyanates

The kinetics of the reaction of phenyl isocyanate and 4,4′-diphenylmethane isocyanate with polydiethylene glycol adipate (PDEGA) were studied at 50–70°C in a bulk process, and also in a model solvent as a function of the molecular weight of the polymer and the initial ratio of the reagents. The heats of reactions of the systems were determined and also the shrinkage limits of urethane formation.

The reaction of phenyl isocyanate with dimethylacetamide

The reaction of phenyl isocyanate with dimethylacetamide

Insertion reactions of diethylaluminium derivatives : V. reactions of diethylaluminium alkoxides with phenyl isocyanate

Reaction of phenyl isocyanate and diethylaluminium alkoxide, Et 2AlOR (R = Me, Et, i-Pr, t-Bu and benzyl) in equimolar or 3/1 molar ratios gave mainly diethylaluminium derivatives of N-phenyl carbamate esters, in contrast to the corresponding reactions with Et 2AlNMe 2 or Et 2AlSEt. The diethylaluminium allophanate, [PhN(AlEt 2)CON PhCO 2R], was found to be unstable, readily decomposing to the carbamate and isocyanate.

Catalyzed Urethane Formation

The reaction of phenylisocyanate with various substituted alcohols using 1, 4-diazabicyclo[2.2.2]octane(DABCO)as a tertiary amine catalyst or di-n-butyltindilaurate(DBTDL)as a metal catalyst, has been carried out in toluene. By comparing IR spectra of alcohols alone with those of alcohol-catalyst mixtures in toluene, an evidence was obtained which shows the complex formation between the alcohols and catalyst. It has been found that the urethane formation follows the second order kinetics in each catalyzed system and that[Cat]is proportional to the alcoholconcentration in the presence of DABCO and to the isocyanate concentration in the presence of DBTDL. On the basis of the complex formation between the alcohols and catalysts, it is apparent that the complex forming step is in equilibrium in the former case, and that the complex concentration is extremely low and the stationary state is applicable in the latter. The rate constants for the rate determining step in both cases were calculated. In regard to the substituent effect of the alcohols for the urethane formation, it has been found that Taft prime; s plot of against shows a linear relationship, and that the reaction is dominated by the polar and steric effects.

Preparation of a polyimide foam

AbstractThe reaction of phenyl isocyanate with phthalic anhydride to form N‐phenylphthalimide is strongly solvent dependent and catalyzed by tertiary amines. Water and alcohol promote imide formation, but Lewis acids and organometallic compounds are ineffective. In DMSO solvent, benzophenone tetracarboxylic dianhydride (BTDA) and polymethylene polyphenol isocyanate (PAPI) polymerize with the evolution of carbon dioxide to yield a foamed polyimide. The solvent‐freed open‐celled foams exhibit exceptional fire resistance and thermal stability.

The reaction of phenyl isocyanate with purines, pyrimidines and deoxyribonucleic acid

Reaction of phenyl isocyanate with cytosine, adenine and guanine gave 4-N-phenylcarbamylcytosine, 6-N-phenylcarbamyladenine and 2-N-phenylcarbamylguanine respectively. Uracil did not react. Reaction of DNA (as the Cetavlon salt) with phenyl isocyanate at 0–4° for 10 days resulted in the almost complete substitution of the cytosine, adenine and guanine residues. From the analytical results and the fact that 3′,5′-O-diacetylthymidine did not react it was concluded that the thymine residues were unaffected.

The esterificaiton of tin(II) oxide

Aromatic o-hydroxy-ethers react with blue-black stannous oxide (1) to give o-phenylenedioxytin(II), water and the corresponding o-dialkoxy-benezene. Salicylic acid also reacts to produce a novel, six membered, tin(II)-containing ring system (3) for which infrared evidence shows intermolecular bonding through the carbonyl oxygen in the solid. (3) dissolves in and forms a 1:1 complex with triethylamine where the tin (II) atom is three-coordinate. Catechol produces (2) and hydrogen sulfide from stannous sulfide, suggesting (1) as the original of the water oxygen in these reactions. The esterification of hydrous tin(II) oxide 4 by catechol and o-methoxyphenol procees uncatalyzed to produce (2) Monofunctional alcohols (which require a catalyst) and phenols also reac with (4) to produce products of the composition RO(SnO)2R whre n = 1, 2 or 3 as shown by microanalytical and molecular weight data. These compounds hydrolyze to regenerate the starting alcohol or phenol. Ethylene glycol gives a polymer of the back-bone structure [OCH2CH2OSn]. The presence of tin(II) is established by treatment with mercuric chloride and by Sn119m Mössbauer spectroscopy. Mössbauer data indicate that slow hydrolysis in air is accompanied by oxidation to tin(IV) oxide. Catalysis in the alcohol in the alcohol reactions increases in effectiveness Cu>CuO>1:1Cu+Cu2O>Cu2O in competition with the dehydration of (4). Alkyl and arylthiols give tetrathiotin(IV) derivatives with (4) but with (1) thiophenol produces the simple tin(II) mercaptide. The insertion reactions of phenyl isocyanate with tin(II) dimethoxide and phenoxide yield tin(II) carbamate compounds with a tin(II)-nitrogen bond. The insertion of phenyl isocyante into the tin(II)-oxygen bonds of 2,2′ biphenylenedioxytin(II) results in ring expansion to a novel element-membered heterocycle. The reactions of tin(II) acetate with alcohols and phenols are also described.

Solvent-derived products from reactions of phenyl isocyanate in dimethyl sulfoxide

Solvent-derived products from reactions of phenyl isocyanate in dimethyl sulfoxide

Reactions of phenyl isocyanate and phenyl isothiocyanate with indole and metal derivatives of indole

Reactions of phenyl isocyanate and phenyl isothiocyanate with indole and metal derivatives of indole

2-amino-1,3,2-dioxaborolanes and their properties

The preparation and properties of some 2-amino-1,3,2-dioxaborolanes, ▪ (R = R′ = Me; R = H and R′ = Me, Et, Pr′, Bu n, Bu i, Bu t and Ph) are described and their association is discussed. Reaction of phenyl isocyanate with 2-dimethylamino-1,3,2-dioxaborolane is exocyclic showing that the relative migratory aptitude is R 2N > OR.

Nucleophilic Activity of the Phosphoryl Group. Oxygen-18 Transfer in Reactions of Phenyl Isocyanate with Labeled Phosphine Oxides1a

Nucleophilic Activity of the Phosphoryl Group. Oxygen-18 Transfer in Reactions of Phenyl Isocyanate with Labeled Phosphine Oxides^1a

Reactions of Phenyl Isocyanate with Some Metal Derivatives of Pyrrole

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTReactions of Phenyl Isocyanate with Some Metal Derivatives of PyrroleE. P. Papadopoulos and H. S. HabibyCite this: J. Org. Chem. 1966, 31, 1, 327–329Publication Date (Print):January 1, 1966Publication History Published online1 May 2002Published inissue 1 January 1966https://doi.org/10.1021/jo01339a507RIGHTS & PERMISSIONSArticle Views205Altmetric-Citations13LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (486 KB) Get e-Alerts Get e-Alerts

Reactions of phenyl isocyanate with vinyl ethers

Reactions of phenyl isocyanate with vinyl ethers