Reaction Of Triethyl Phosphite Research Articles

Interaction of Mannich bases with triethyl phosphite

In a namber of studies it has been postulated that the reaction of triethyl phosphite with the salt form of a Mamfich base can proceed in several steps [I, 2]. In this case the question of the nature and mechanism of the first step of the reaction is most disputed. The most information on the mechanism of this step can be obtained in a study of the kinetics of the reaction according to the rate of liberation of free amine. However, ir the following stages of the reaction the free amine is converted to an ammonium salt. Thus, in order for a kinetic study of the reaction according to the rate of liberation of amine to become possible, it is necessEtry to find a modification of the reaction procedure in which chemical bonding of the amine in the subsequent steps is excluded. We have found such a method of conducting the reaction [3]. As a result, it has proved possible to study the kinetics of ~he reaction triethy[ phosphite with ketone Mannieh bases (KMB) in the presence of acetic acid according to the rate of evolution of the amine (diethylamine). This communical;ion presents the results of this study.

The reactivity of organophosphorus compounds. Part XXIII. Reactions of triethyl phosphite with carbon tetrachloride and bromotrichloromethane in the presence and absence of butane-1-thiol

The thermal reaction of triethyl phosphite with carbon tetrachloride in the dark, in vacuo, has been shown to be heterolytic. In the presence of added azobisisobutyronitrile (AIBN) at least part of the product [(EtO)2P(O)CCl3] is formed homolytically. The reaction of the phosphite, carbon tetrachloride, and butane-1-thiol is (a) ionic in the presence of t-butylcatechol, (b) homolytic in the presence of AlBN, and (c) has both ionic and homolytic components in the absence of additives. The corresponding reactions of bromotrichloromethane are less clearly defined and both radical and ionic pathways may be followed. In hexane, the thermal reaction of bromotrichloromethane with the phosphite is ionic, whereas in the presence of AlBN it is radical, at least in part.

Reduction of nitro- and nitroso-compounds by tervalent phosphorus reagents. Part V. Reduction of alkyl- and methoxy-nitrobenzenes, and nitrobenzene by trialkyl phosphites

Reactions of triethyl- and trimethyl-phosphites with o-, m-, and p-nitrotoluene, o- and p-ethylnitrobenzene, o- and p-nitroanisole, and nitrobenzene give the corresponding dialkyl N-arylphosphoramidates, and dialkyl N-alkyl-N-arylphosphoramidates, and, in some cases, trialkyl N-arylphosphorimidates, the probable precursors of the above amidates. In some cases low (⩽18%) yields of dialkyl alkyl-3H-azepin-7-ylphosphonates are formed, indicating the intermediacy of nitrenoid species. Reaction of triethyl phosphite with p-ethyl-, p-methyl-, and p-methoxynitrobenzenes, and of trimethyl phosphite with o-nitroanisole and p-nitrotoluene give low yields of the corresponding dialkyl arylphosphonates, representing the first recorded instances of displacement of a simple aromatic nitrogroup unactivated by either electronic influences or special steric factors.

Kinetics of the reaction of triethylphosphite with ?-acetoxyethylmethyl ketone

The kinetics of the reaction of triethylphosphite withβ-acetoxyethylmethyl ketone was studied by infrared spectroscopy, and was found to be of the second order.

Reaction of triethyl phosphite with?-substituted nitriles

Reaction of triethyl phosphite with?-substituted nitriles

Reaction of triethyl phosphite with vinyl esters

Reaction of triethyl phosphite with vinyl esters

Reaction of triethyl phosphite with?-acetoxyethyl methyl ketone

Reaction of triethyl phosphite with?-acetoxyethyl methyl ketone

On the reaction of triethyl phosphite with diethylaminoacetonitrile

On the reaction of triethyl phosphite with diethylaminoacetonitrile

Reaction of triethyl phosphite with hydrochlorides of ketonic mannich bases

The reaction of triethyl phosphite with a number of hydrochlorides of substitutedβ-diethylaminopro-piophenones has been studied. The evolution of the diethylamine and ethyl chloride formed enables the course of the reaction to be followed easily.

Reaction of? aminoethers with triethyl phosphite

1. The reactions of triethyl phosphite with diethylaminomethyl methyl, diethylaminomethyl ethyl, diethylaminomethyl propyl, diethylaminoethyl butyl, and methylphenylaminomethyl ethyl ethers in the presence of acetic acid and with diethylaminomethyl ethyl ether hydrochloride and diethylaminomethyl ethyl ethiodide have been studied. 2. In the case of a salt-forming agent having a labile hydrogen atom, rupture of a C-O bond in the α-aminoether takes place with the formation of only diethyl diethylaminomethylphosphonate. Salt-forming agents of the type of alkyl halides lead to the formation of diethyl alkoxymethylphosphonates.

The reactivity of organophosphorus compounds. Part XXII. Preparation of diethyl trichloromethylphosphonite and diethyl dichloromethylphosphonate

Diethyl trichloromethylphosphonite has been prepared from trichloromethyldichlorophosphine and ethanol in the presence of base, and some of its reactions have been investigated. Diethyl dichloromethylphosphonate has been obtained by reaction of triethyl phosphite with diethyl trichloromethylphosphonate in hexanol.

Reactions of Triethyl Phosphite with 4-Trihalomethylcyclohexa-2,5-dienones. Evidence for Displacement of a Tribromomethyl Anion by SN2' Attack on Oxygen1

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTReactions of Triethyl Phosphite with 4-Trihalomethylcyclohexa-2,5-dienones. Evidence for Displacement of a Tribromomethyl Anion by SN2' Attack on Oxygen1Bernard MillerCite this: J. Am. Chem. Soc. 1966, 88, 8, 1841–1842Publication Date (Print):April 1, 1966Publication History Published online1 May 2002Published inissue 1 April 1966https://doi.org/10.1021/ja00960a064RIGHTS & PERMISSIONSArticle Views85Altmetric-Citations6LEARN 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 (245 KB) Get e-Alerts Get e-Alerts

Reactions of triethyl phosphite with activated olefins

Reaction of triethyl phosphite with a series of α,β-unsaturated esters, ketones, aldehydes, amides and nitriles in protonating solvents proceeds smoothly to furnish β-substituted phosphonate esters. This process, termed hydrophosphinylation, is quite general in contrast to reduction and reductive dimerization, the alternative reaction pathways previously observed for dibenzoylethylene. The most active olefins (methyl vinyl ketone, crotonaldehyde, cinnamaldehyde) are transformed even at 0° to furnish analogous products, predominantly in the form of their acetals or ketals. Evidence bearing on the mechanism of these transformations, particularly that concerning the site of initial attack, the origin of acetal and ketal, and the role of the solvent is discussed.

Radical ions in the reactions of p-chloranil with triphenylphosphine and with triethyl phosphite : Electron spin resonance and ultraviolet absorption spectra

The colour and the ESR spectrum which develop during the reaction of triphenylphosphine with p-chloranil are due to a phenoxy-O-phosphonium radical cation and to a semiquinone radical anion. These are formed by oxidation of the phosphine, or of a phosphine-quinone complex, by quinone. The radical ions are not formed by oxidation of the final product of the reaction (a phenoxide-O-phosphonium dipolar ion) by p-chloranil in solution. The reaction of triethyl phosphite with p-chloranil produces analogous coloured species with unpaired electrons. The g-factors and the hyperfine constants (ΔH) for the radical cations from triphenylphosphine and triethyl phosphite, are, respectively: 2·0050, 2·42 gauss and 2·0051, 1·83 gauss.

Duality of mechanism in the reaction of triethyl phosphite and carbon tetrachloride

Duality of mechanism in the reaction of triethyl phosphite and carbon tetrachloride

The reaction of triethyl phosphite with o-dinitrobenzene: evidence for aromatic substitution by tervalent phosphorus

The reaction of triethyl phosphite with o-dinitrobenzene: evidence for aromatic substitution by tervalent phosphorus

840. The reactivity of organophosphorus compunds. Part XVIII. The reaction of triethyl phosphite with chloroform

840. The reactivity of organophosphorus compunds. Part XVIII. The reaction of triethyl phosphite with chloroform

Reaction of triethyl phosphite with ?, ?-dichloro-?-iodoperfluoroalkanes

1. Perfluoroiodoalkanes do not undergo the Arbuzov reaction with triethyl phosphite. 2. A method is proposed for the preparation of ω-iodoperfluoro-1-alkenes. Previously unknown 6-iodoperfluoro-1-hexene and 8-iodoperfluoro-1-octene were prepared. 3. The following new esters were prepared: diethyl 4-iodoperfluoro-1-butenylphosphonate; diethyl 6-iodoperfluoro-1-hexenylphosphonate; diethyl 8-iodoperfluoro-1-octenylphosphonate; tetraethyl perfluoro-1,7-octadienylenediphosphonate.

573. The reactivity of organophosphorus compounds. Part XIII. Radical-chain transfer reactions of triethyl phosphite: a new phosphorothiolate synthesis

573. The reactivity of organophosphorus compounds. Part XIII. Radical-chain transfer reactions of triethyl phosphite: a new phosphorothiolate synthesis

?-Keto phosphonic esters Communication 3. Structures of the products of the reaction of some halo ketones with triethyl phosphite and with sodium diethyl phosphite

1. Reaction of triethyl phosphite with chloro- and bromo-acetones* and 1-bromo-2-butanone gives the corresponding β-keto phosphonic esters. 2. The products obtained by methylating the potassium derivatives of diethyl acetonylphosphonate and of diethyl 1-methylacetonylphosphonate with methyl iodide are sB-keto phosphonic esters. 3. Reaction of sodium diethyl phosphite with chloro- and bromo-acetones and 3~bromo-2-butanone gives epoxy phosphonic esters. The structures of these were proved by confirmatory synthesis and by analysis of their Raman spectra. 4. In spite of Kreutzkamp and Kayser's results, reaction of sodium diethyl phosphite with chloro- or bromoacetone does not give an unsaturated ester (diethyl isopropenyl phosphate); the products are diethyl epoxy-1-methylethylphosphonate and diethyl acetonylphosphonate. 5. The product of the reaction of 5-chloro-2-pentanone with sodium diethyl phosphite is diethyl tetrahydro2-methyl-2-furylphosphonate.