Diethyl Benzoylphosphonate Research Articles

Stereoselectivity in the Wittig‐Horner‐Emmons Synthesis of Vinylphosphonates by the Reaction of Acylphosphonates with Acyclic or Heterocyclic Phosphonoacetates

AbstractA new synthetic approach to vinylphosphonates is presented. The reaction of diethyl benzoylphosphonate (1) with diethyl methoxycarbonyl‐methyl‐phosphonate (2) gives diethyl 2‐methoxycarbonyl‐l‐styrylphosphonate (3) as a mixture of geometrical isomers (Z‐3) and (E‐3) in the ratio of 83:17. In contrast, reaction of 1 with the heterocyclic phosphonate reagent, 2‐methoxycarbonyl‐methyl‐2‐oxo‐4,5‐dimethyl [1,3,2] dioxaphospholane (4) leads to a mixture of the isomers (Z‐3) and (E‐3) in the ratio of 20:80.

Experimental tests of the stereoelectkoic effect at phosphoru: Michaelis-Arbusov reactivity of phosphite esters

Whereas triethyl phosphite readily reacts with benzoyl chloride to yield the Michaelis-Arbusov product, diethyl benzoyl phosphonate, 1-methyl-4-phospha-3,5,8-trioxabi)cyclo[2.2.2]octane, 1 , is essentially unreactive, even at a higher temperature. The bicyclic phosphite 1 also reacts slower than the triethyl phosphite 2 In an oxidation with t-butyl hydroperoxide. These results are interpreted in terms of the stereoelectronic effect.

Characterization of polymeric metal complexes formed by reaction of excess diethyl acetyl- or diethyl benzoyl-phosphonate with metal chlorides at elevated temperatures

Reactions of some metal chlorides with diethyl acetyl- or diethyl benzoyl-phosphonate at elevated temperatures lead to products of varying types, i.e. Al(eap) 3, M(ebp) 3(M = Al, Cr), V(ehp) 3, M(ehp) 4(M = Th, U) (eap: ethyl acetylphosphonate; ebp: ethyl benzoylphosphonate; ehp: ethyl hydrogenphosphonate), as well as several mixed ligand complexes of the Ti(eap) 2(ehp), M(eap)(ehp) 2(M = Dy, Cr, Fe), M(ebp) 2(ehp) (M = Dy, Ti, V, Fe) and U(ebp) 3(ehp). Characterization studies suggest that the new metal complexes are linear chainlike polymers, involving triple- or quadruple-bridges of the anionic phosphonate ligands between adjacent metal ions. Among the ligands under study, ehp acts as bidentate bridging, coordinating through its two POO oxygens. In the cases of eap and ebp complexes, two different fashions of bridging were established. In most occasions, these ligands act as bidentate bridging, coordinating through the CO and one of the POO oxygens, but in a few cases, bridging through the two POO oxygens occurs instead.

Dialkyl acylphosphonates: a new acylating agent of alcohols

Diethyl benzoylphosphonate ( 1 ) underwent facile benzoylation of alcohols in the presence of DBU. Reactions of diols containing primary and secondary hydroxyl groups with 1 gave predominantly monobenzoates in which primary hydroxyl groups were highly selectively benzoylated. Related acylations were also described.

On the reaction of dialkyl acylphosphonate with 2-methyl-1,3,4-thiadiazolium salts.

Dialkyl acylphosphonate acted as an acylating agent for the 2-methyl group in 1, 3, 4-thiadiazolium salts, as well as 2-methylthiazolium and thiazolinium salts, to give 2-acylidenethiadiazoline derivatives. The reaction of diethyl benzoylphosphonate (1) with 5-amino-2, 3-dimethyl-1, 3, 4-thiadiazolium iodide (2c) gave the N-monobenzoate inner salt (6), C-monobenzoate (7), C, N-dibenzoate (8) and 5-benzoylamido-2-styryl-thiadiazolium hydroxide inner salt (9) ; the extent of N-acylation was greater than that of C-acylation. The structures of the inner salt products (6 and 9) were confirmed by an alternative synthesis. A proposed mechanism for the acylphosphonate reaction with 2-methyl-1, 3, 4-thiadiazolium salts is presented, and is consistent with the 13C-nuclear magnetic resonance chemical shifts of the 2-methyl groups of the 1, 3-azolium salts.

ChemInform Abstract: HYDROLYSIS OF DIETHYL BENZOYLPHOSPHONATE IN AQUEOUS AND HYDROCHLORIC ACID SOLUTIONS. POSTULATION OF A STABLE PENTAVALENT PHOSPHORUS‐CONTAINING INTERMEDIATE

Chemischer InformationsdienstVolume 10, Issue 15 Organoelement Compounds ChemInform Abstract: HYDROLYSIS OF DIETHYL BENZOYLPHOSPHONATE IN AQUEOUS AND HYDROCHLORIC ACID SOLUTIONS. POSTULATION OF A STABLE PENTAVALENT PHOSPHORUS-CONTAINING INTERMEDIATE K. S. NARAYANAN, K. S. NARAYANANSearch for more papers by this authorK. D. BERLIN, K. D. BERLINSearch for more papers by this author K. S. NARAYANAN, K. S. NARAYANANSearch for more papers by this authorK. D. BERLIN, K. D. BERLINSearch for more papers by this author First published: April 10, 1979 https://doi.org/10.1002/chin.197915299AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume10, Issue15April 10, 1979 RelatedInformation

Hydrolysis of diethyl benzoylphosphonate in aqueous and hydrochloric acid solutions. Postulation of a stable pentavalent phosphorus-containing intermediate

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTHydrolysis of diethyl benzoylphosphonate in aqueous and hydrochloric acid solutions. Postulation of a stable pentavalent phosphorus-containing intermediateK. S. Narayanan and K. D. BerlinCite this: J. Am. Chem. Soc. 1979, 101, 1, 109–116Publication Date (Print):January 1, 1979Publication History Published online1 May 2002Published inissue 1 January 1979https://doi.org/10.1021/ja00495a018RIGHTS & PERMISSIONSArticle Views154Altmetric-Citations20LEARN 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 (847 KB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

Diethyl benzoylphosphonate as a ligand

Complexes (2 : 1) of diethyl benzoylphosphonate (debp) with 3d metal perchlorates were synthesized and characterized by means of i.r. and electronic spectral, magnetic susceptibility and conductance measurements. In new complexes of the types [M(debp)2(OClO3)(OH2)](ClO4) (M = Fe, Co, Zn) and [Fe(debp)2(OClO3)(OH2)](ClO4)2, both debp ligands function as bidentate chelating agents, coordinating through the P=O and C=O oxygens. In contrast, in the manganese(II) and nickel(II) complexes, which are of the [M(debp)2(OClO3)(OH2)2](ClO4) type, one debp acts as a bidentate chelating ligand, while the second debp is unidentate, coordinating only through the P=O oxygen. Hexacoordination in the new cationic complexes is completed by coordination of aqua and unidentate perchlorato ligands, which are in competition for sites in the inner coordination sphere of the central metal ion with the weak debp ligand. On the other hand, debp, owing to its bulkiness, and especially the presence of the benzoyl substituent, introduces sufficiently severe steric hindrance during coordination. As a result of this, the formation of [M(debp)3]n+ tris-chelate cationic complexes with the 3 d metal ions under study does not seem to be possible.

On the reaction of dialkyl acylphosphonate with 2-methylthiazolium salts.

Dialkyl acylphosphonate worked as an acylating agent on 2-methylthiazolium and thiazolinium salts in the presence of base, to give 2-acylidenethiazoline and thiazolidine derivatives, respectively. Dialkyl [1-aryl (alkyl)-1-dialkylphosphatomethyl] phosphonate was also isolated as a by-product in the same reaction. Dialkyl acylphosphonate afforded 2-acylidenethiazolines in better yield compared with acyl chlorides and showed on apparent affinity for carbanions. Application of diethyl benzoylphosphonate to 1, 2, 3-trimethylbenzimidazolium iodide, however, formed a dimeric salt, 1, 1', 3, 3'-tetramethyl-2, 2'-(2-phenyltrimethylene) di (benzimidazolium) diiodide in addition to 2-(1, 3-dimethylbenzimidazolin-2-ylidene) acetophenone. On the basis of the reactivity difference between the 2-methylthiazolium and 2-methylimidazolium salts and the kinetic experiments, the mechanism of the acylating reaction was proposed.

Photochemische Cycloadditionen von 3‐Phenyl‐2H‐azirinen mit Benzoyl‐, Äthoxycarbonyl‐ und Vinylphosphonaten 34. Mitteilung über Photoreaktionen

AbstractThe irradiation of the 3‐phenyl‐2H‐azirines 1a–c in the presence of diethyl benzoylphosphonate (8) in cyclonexane solution, using a mercury high pressure lamp (pyrex filter), yields the diethyl (4, 5‐diphenyl‐3‐oxazolin‐5‐yl)‐phosphonates 9a–c (Scheme 3). In the case of 1b a mixture of two diastereomeric 3‐oxazolines, resulting from a regiospecific but non‐stereospecific cycloaddition of the benzonitrile‐benzylide dipole 2b to the carbonyl group of the phosphonate 8, was isolated.Benzonitrile‐isopropylide (2a), generated from 2,2‐dimethyl‐3‐phenyl‐2H‐azirine (1a), undergoes a cycloaddition reaction to the ester‐carbonyl group of diethyl ethoxycarbonylphosphonate (15) with the same regiospecificity to give the 3‐oxazoline derivative 16 (Scheme 5).The azirines 1a–c, on irradiation in benzene in the presence of diethyl vinylphosphonate (17) give non‐regiospecifically the Δ1‐pyrrolines 13a–c and 14a–c (Scheme 6).

Studies on pyrimidine derivatives and related compounds. LXXXVII. Reaction of thiamine analogues with diethyl benzoylphosphonate.

Reaction of thiamine analogues lacking the 5-hydroxyethyl group (6a-e) with diethyl benzoylphosphonate (7) was carried out. Comparison of reactivity in 4'-substituted thiamine analogues and those lacking the hydroxyethyl group suggests the presence of an interaction in the thiamine molecule between the pyrimidine ring and the hydroxyethyl group in an aprotic solvent. Reactivity at the 2 position (the active center in enzymatic decarboxylation) in 4'-substituted thiamine analogues may be affected by this interaction.

Studies on Pyrimidine Derivatives and Related Compounds. LXXVII. Reaction of Thiamine Analogues with Diethyl Benzoylphosphonate

Reaction of thiamine analogues (8, 14, and 17) with diethyl benzoylphosphonate (20) was carried out and an interesting difference in reactivity in aprotic solvent according to substituents and nuclei was observed.

Photochemical Studies of the Esters of Aroylphosphonic Acids

Abstract The photochemical behavior of several dialkyl benzoylphosphonates and para-substituted benzoylphosphonates in various solvents has been studied using product isolation, ultravioletspectral change, the electron spin resonance (ESR) technique, and quantum yield measurements. Upon irradiation to a degassed solution of these benzoylphosphonates through a Pyrex filter, the photo-pinacolization reaction was observed, except in the case of diethyl benzoylphosphonate; it was effectively quenched by 1,3-pentadiene or oxygen. On the other hand, the ESR spectra of photo-irradiated aroylphosphonates at 77°K have a large anisotropic doublet of 53–128 gauss separation; this separation is thought to be due to the interaction between an unpaired electron and the phosphorus nucleus. The structure of these radicals is also discussed. From these observations, it can be considered that the photochemical reaction proceeds via the ketyl radical formed by the hydrogen abstraction of the lowest excited triplet state of these aroylphosphonates. Irradiation to the diethyl benzoylphosphonate solutions in various solvents gave, not the pinacolized product, but 2,4,6-triphenyl-2,4,6-tris[diethylphosphoryl]-1,3,5-trioxane almost quantitatively. The quantum yields (Φ) of the disappearance of several para-substituted derivatives are highly sensitive to the electron-inductive abilities of the substituents; that is, Φ drops from 2.10 in the p-methoxybenzoylphosphonate derivative to 1.79 in the p-chloro derivative at room temperature. Such a substituent effect can be considered to result in the difference in the conformation between the carbonyl and phosphoryl groups. On the basis of these studies, the mechanism of the photochemical reaction of aroylphosphonates is described and discussed.

Studies on Pyrimidine Derivatives and Related Compounds. LXIII. Reactions of Thiazolium Salts with Dialkyl Acylphosphonates : Takamizawa Reaction 8

The reactions of diethyl acetyl-and diethyl benzoylphosphonate (2, 3) with 3, 4-dimethylthiazolium bromide (8) afforded 2-(1-diethylphosphoroyl) ethyl-and 2-(1-diethyl-phosphoroyl) benzyl-3, 4-dimethylthiazolium bromides (9, 10), which were decomposed to give 2-methyl-and 2-phenyl-4, 5-dimethyl-2, 3-dihydro-4H-1, 4-thiazin-3-ones (11, 12) by alkaline treatment. The reactions of 8 with dimethyl acetyl-and dimethyl benzoyl-phosphonate (13, 14) gave the inner salts of O-methyl-O-1-(3, 4-dimethyl-2-thiazolium)-ethyl-and O-methyl-O-1-(3, 4-dimethyl-2-thiazolium) benzyl phosphoric acid (15, 16). Similar adducts (18, 24) were obtained from the reactions of 1b with 13 and 14. In a careful treatment, the inner salt (26) was found to be produced from 2-(1-diethylphos-phoroyl) ethyl-3-benzyl-4-methyl-5-(2-benzoyloxy) ethylthiazolium bromide (4).

Studies on pyrimidine derivatives and related compounds. XLI. Reaction of diethyl benzoylphosphonate with thiamine (Takamizawa reaction 3).

Studies on pyrimidine derivatives and related compounds. XLI. Reaction of diethyl benzoylphosphonate with thiamine (Takamizawa reaction 3).

Studies on the pyrimidine derivatives and related compounds. XL. Reaction of 3-benzyl-4-methyl-5-(2-hydroxyethyl)thiazolium salts with diethyl benzoylphosphonate.

Reaction of 3-benzyl-4-methyl-5-(2-hydroxyethyl)thiazolium chloride (V) with diethyl benzoylphosphonate (VII) was studied successively as an analogue of thiamine. It is also appeared in this case that a novel reaction took place accompanied by the ring expansion from thiazole to 1, 4-thizzine ring.

Studies on the pyrimidine derivatives and related compounds. XXXV. On the reaction product of thiamine with diethyl benzoylphosphonate.

Studies on the pyrimidine derivatives and related compounds. XXXV. On the reaction product of thiamine with diethyl benzoylphosphonate.