Reaction Of Triethyl Phosphite Research Articles

Microwave-promoted syntheses of fluoren-9-ones and benzisoxazoles

Synthesis of some new fluoren-9-ones and benzisoxazoles under both thermal and microwave conditions is reported. The prepared products under microwave conditions are obtained with high yields and within shorter reaction times. Reaction of lithiated bromobenzene with aromatic aldehydes 2a,b delivered diarylmethanols 3a,b that were oxidized to 4a,b. Compound 4a was cyclized to give methoxyfluoren-9-one 5, which was demethylated affording hydroxyfluoren-9-one 6. Compound 4b was reacted with triethyl phosphite to produce benzisoxazole 10. On the other hand, reaction of triethyl phosphite with 13a,b afforded a mixture of phosphoramidates 14a,b and benzisoxazoles 15a,b. The structures of the synthesized compounds have been elucidated unambiguously by NMR-spectroscopic methods including HH COSY, HSQC, and HMBC experiments.

Diastereoselective synthesis of α-aminoalkylphosphonic acid derivatives of Betti base

A reaction of triethyl phosphite with 3-alkyl-1-phenylnaphthoxazines in the presence of halotrimethylsilanes with subsequent removal of the trimethylsilyl group by hydrolysis furnished diastereomeric α-aminoalkylphosphonic derivatives of Betti base. The highest diastereomeric excess was observed in the reaction with bromotrimethylsilane at low temperature. In the case of 3-isobutyl-1-phenylnaphthoxazine, a major diastereomer was isolated from the reaction mixture by crystallization. X-ray diffraction analysis was used to establish relative configuration of its chiral centers. This method can be also used for the preparation of α-aminobenzylphosphonic derivatives, which was shown using 1,3-diphenylnaphthoxazine as an example. Major diastereomers of α-aminobenzyl- and α-aminoalkylphosphonic acid derivatives of Betti base obtained according to this procedure have different relative configurations of their chiral centers.

Synthesis and antiproliferative activity of aromatic and aliphatic bis[aminomethylidene(bisphosphonic)] acids

A series of aromatic and aliphatic bis[aminomethylidene(bisphosphonic)] acids was synthesized in the reaction of triethylphosphite with isonitriles followed by hydrolysis or dealkylation. The in vitro anti-proliferative effect of all synthesized tetraphosphonic acids against MCF-7 breast cancer cells, J774E macrophages and HL-60 promyelocytic leukemia cells was determined. Three aromatic derivatives (5a, 5f and 5j) showed a similar or higher anti-proliferative activity than zoledronic acid.

Studies on Organophosphorus Compounds XI:* The Reaction of Phosphorus Reagents With Hydrazonoyl Halides, Hydrazonoyl Azides, and Shiff's Bases

N-(chloro-furan-2-yl)methylene-N′-(4-nitrophenyl)hydrazone (I) reacted with triethylphosphite to produce the phosphonate derivative III. The tetrazine derivative VI was produced by the interaction of I with diethyl-phosphite. Hydrazonoyl azide derivatives VIIIa–c reacted with triphenyl phosphine to form the iminophosphorane derivatives Xa–c. On the other hand, the azide derivative VIIIc reacted with the phosphonium ylide XI to form the 1,2,3-triazole adduct XIII. The reaction of triethyl phosphite with Shiff's bases XIVa–c yielded the corresponding phosphonates XVa–c. The structures of the newly prepared compounds were confirmed with the analytical and spectroscopic evidences. *C.f. Reference 20.

First Synthesis of γ,γ′-Diphosphonylketones and Their Reactivity in the Fischer Reaction

Two synthetic methods leading to the new n , n '-diphosphonylketones 2 and 2 ' are reported. The first method involves the base-catalyzed addition of diethylphosphite to diarylideneketones. The second one utilizes the reaction of triethylphosphite and ethoxydiphenylphosphine with g , g '-bis(dimethylamino)ketone hydrochlorides. On reaction with phenylhydrazine hydrochloride, compounds 2 and 2 ' give the corresponding 2-(phosphonoethyl)3-(phosphonomethyl)indoles 3 . The structure of all obtained products is confirmed by NMR ( 1 H, 31 P, 13 C) and IR spectroscopy.

Reactions of phosphite esters and trisdialkylaminophosphines with 5‐substituted 1,3,4‐thiadiazol derivatives

Abstract5‐{[(1E)‐(4‐methoxyphenyl)methylene]amino}‐1,3,4‐thiadiazole‐2‐thiol (1a) reacts with trialkyl phosphites (2a–c) to give the respective dialkyl phosphonate adducts (4a–c). On the other hand, the reactions of trisdialkylaminophosphines (3a,b) with 1a, 5‐{[(1E)‐(4‐phenyl)methylene]amino}‐1,3,4‐thiadiazole‐2‐thiol (1b) yield the corresponding open dipolar structures 6a–c. In the case of the reaction of triethyl phosphite (2a) with 1b, both the dialkyl phosphonate adduct (7) and the dipolar product (8a) are obtained. Moreover, triisopropyl phosphite (2c) reacts with 1b to give both the S‐alkyl and the N‐alkyl phosphonate adducts (9a,b), respectively. Mechanisms are proposed to explain the formation of the new products, and their structures were confirmed on the basis of elemental analysis and spectral studies. © 2001 John Wiley & Sons, Inc. Heteroatom Chem 12:594–601, 2001

Reaction of Triethyl Phosphite with Boron Tribromide

Reaction of boron tribromide with triethyl phosphite led to the formation of triethyl tribromoborophosphate 1, a complex bearing a P→B bond.

DIFFÉRENCE DE COMPORTEMENT ENTRE LES RÉACTIFS ELECTROPHILES DIÉTHYLTRICHLOROMÉTHYLPHOS- PHONATE ET TÉTRACHLORURE DE CARBONE OPPOSÉS AU TRIÉTHYLPHOSPHITE

The reaction of triethylphosphite 1 with diethyltrichloromethylphosphonate 2b in the absence of solvents and catalysts yields mainly diethyl(1,1-dichloropropyl)phosphonate 4 and diethyldichloromethylphosphonate 7. These main products are accompanied by a variety of by-products which differ considerably from those obtained in the reaction between triethyl phosphite and CCl4. Both reactions would begin by a halophilic substitution of triethylphosphite on the positive halogen. For diethyltrichloromethylphosphonate 2b the formed carbanion would then attack preferentially the carbon β to P+ and the hydrogen γ to P+ on heterophosphonium cation. In contrast, the less sterically hindered trichloromethyl carbanion formed by the halophilic attack of triethylphosphite on carbon tetrachloride would rather attack mainly the positive P+ of this cation. The tetraethyl(dichloromethylene)bisphosphonate 8 previously reported by Kukhar and Sagina to be the main product formed in the thermal reaction between triethylphosphite and diethyltrichloromethylphosphonate was not found under our conditions. We observed its formation only under photochemical irradiation.

ChemInform Abstract: Reaction of Triethyl Phosphite (II) with 2,5‐Dibromo‐3‐methyl‐4‐ phenylthiophene (I).

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform Abstract: Reaction of Triethyl Phosphite with β‐Chlorolactic Acid Derivatives.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Reactions of Phosphites with 1,4‐Benzoquinone Monoimines

AbstractTrimethyl phosphite (2a) reacts with N‐(phenylsulfonyl)‐1,4‐benzoquinone monoimine (1a) to give the respective phosphonate 3c, phosphates 3d, 3e and the alkylated products 3a and 3b. The reaction of triethyl phosphite (2b) with the same quinone imine 1a yields only the phosphate adduct 3f and the amide 3g. Triisopropyl phosphite (2c) reacts with 1a to form the alkylated product 3h. Trimethyl phosphite (2a) gives the phosphate 4a on reaction with N‐(methylsulfonyl)‐ 1,4‐benzoquinone monoimine (1b). In case of the reaction of triethyl and triisopropyl phosphites (2b, c) with 1b only the respective alkylated products 4b–d are obtained. A mechanism is proposed to explain the formation of the new adducts.

The reactions of halogenated phenylnitromethanes with triethyl phosphite

Dibromo and dichloro phenylnitromethanes reacted with triethyl phosphite to yield mainly benzonitrile, ethyl halide, and triethyl phosphate. In addition, the products of molecular rearrangement, N,N-diphenylurea, N-phenylbenzamide, and aniline, were isolated. It is proposed that they arise from the rearrangement of an intermediate, benzonitrile oxide, to phenyl isocyanate. A seventh type of product, chlorobenzalimino diethyl phosphate (9), was obtained from dichlorophenylnitromethane. No rearranged product was isolated from the reaction of triethyl phosphite with the monohalogenated phenylnitromethanes which gave the same main products as their dihalogenated analogues.

Synthesis and Ldasic Properties of O,O,O-Triethyl-N-(2-Pyridyl) Imidophosphates

Abstract The phosphorus (111) compounds are known to react readily with arylazides resulting in the formation of imi-dophosphorus compounds (Staudinger reaction)1. We nave obtained O,O,O-triethyl-Ii-(2-pyridyl)imido-pnosphates by the reaction of triethylphosphites with 2-pyridylazides (existing as tetrazoles) with a good yield.

ChemInform Abstract: Reaction of Triethylphosphite with Oximes of α,β‐Unsaturated Aldehydes and α‐Di‐ carbonyl Compounds.

AbstractDas Oxim (I) wird durch Triethylphosphit (II) zum Nitril (III) dehydratisiert.

Reactions of triethyl phosphite with triethyl orthoformate in the presence of strong electrophilic reagents

Reactions of triethyl phosphite with triethyl orthoformate in the presence of strong electrophilic reagents

α-Cuprophosphonates. V. The Reaction of 3 and 4-Oxoalkane Phosphonates and Their Use in Aminoalkanephosphonic Acids Synthesis

Abstract In connection with our synthetic work on aminoalkanephosphonic acids we needed several 3 and 4-oxoalkanephosphonates. These compounds are generally prepared by addition of a dialkylphosphite to an α,β-unsaturated ketone1 or by condensation of the appropriate halo-ketone with a sodium dialkylphosphite2; an alternative synthesis is via the reaction of triethylphosphite with α,β-unsaturated ketones3 or with Mannich base methiodides and hydrochlorides4. We now wish to report another route to 3 and 4-oxoalkanephosphonates through 3 or 4-haloalk-3-ene phosphonates. When a dihaloalkene is added at low temperature to a solution of an equivalent of α-lithioalkanephosphonate in THF/hexane, the

Reaction of triethyl phosphite with polyfluoroaromatic compounds that contain activated fluorine atoms

Polyfluoroaromatic compounds that contain activated fluorine atoms enter into the Arbuzov reaction with triethyl phosphite to give the corresponding diethyl esters of arylphosphonic acids.

Syntheses of dialkyl trichloromethylphosphonates and their properties for additives

AbstractNine dialkyl trichloromethylphosphonates (TCMPs) were synthesized by the Arbusov reaction from the corresponding trialkyl phosphite and carbon tetrachloride. Some characteristics of these compounds were studied. The alkyl groups contained from 2 to 18 even carbon atoms. The reaction of triethyl phosphite and carbon tetrachloride was completed in about 4 hr under an indoor natural light. However, in the preparation of the lower dialkyl TCMPs the mixture of trialkyl phosphite and carbon tetrachloride was refluxed for 8 hr. With alkyl groups higher than decyl, a reaction time of 8 hr was insufficient. Utilization of these dialkyl TCMPs was discussed. These compounds were shown to be effective chelating, antistatic and flame resistant additives in a formulation of polyvinyl chloride. Moreover, they were found to be very excellent extreme pressure additives for lubricating oil; especially the dibutyl TCMP which was extremely effective at concentrations as low as 0.25%.

The Reaction between Triethyl Phosphite and N-bromoacetamide

An attempt to prepare N-acetylphosphoroamidate by the reaction of triethyl phosphite with N-bromoacetamide in ether was unsuccessful, and the reaction did not produce acetonitrile. In this reaction it was found that diacetamide hydrobromide and triethyl phosphate were formed neanly quantitatively. It seemed reasonable to assume that the phosphonium intermediate in this reaction is extremely unstable against moisture. The infrared and mass spectra of diacetamide hydrobromide were also determined.

Mechanism of the interaction of o-hydroxybenzyl alcohol with trialkyl phosphites

On the basis of a study of the reaction of triethyl phosphite with o-hydroxybenzyl alcohol by methods of IR and NMR spectroscopy and the kinetic data, it was established that the reaction is first order and proceeds according to the classical scheme of the Arbuzov rearrangement, with intermediate formation of a quasiphosphonium-type complex.