Interactions of carborane-containing electrophiles with triethyl phosphite. Synthesis of new carborane-containing phosphonates

The reactions ofo-carboran-l-ylethyl mesylates with triethyl phosphite and sodium diethyl phosphite were studied. Carborane-containing phosphonates were synthesized. The reaction ofo-carboranylacetyl chloride with triethyl phosphite affordedO,O-diethyl (E)-2-(o-carboran-l-yl)-1-(o-carboran-1-ylacetoxy) vinylphosphonate rather than oxo phosphonate. Dedicated to the memory of Academician M. I. Kabachnik on his 90th birthday. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2041–2044, October, 1998.     

Electrochemical Oxidation of Catechols in the Presence of Triethyl Phosphite

The mechanism of electrochemical oxidation of catechol and some of its derivatives have been studied in the presence of triethyl phosphite as a nucleophile in aqueous solution. Voltammetric studies indicate that the quinones derived from catechol, and its derivatives, participate in Michael addition reaction with triethyl phosphite. The reaction mechanism consists of electron transfer followed by a chemical reaction which is named as an EC mechanism. The homogeneous rate constants (k_obs) were estimated by comparing the experimental cyclic voltammograms with the digitally simulated voltammograms based on EC mechanism. Also the effects of nucleophile concentration and substituted group of catechols on voltammetric behavior and the rate constants of chemical reactions were examined.     

Convenient and Regioselective One‐Pot Solvent‐Free Synthesis of ß‐Hydroxyphosphonates

A simple, efficient, regioselective, and solvent‐free method has been developed for the synthesis of β‐hydroxyphosphonates from epoxides and triethyl phosphite using ZnCl₂ in high yields under mild conditions.     

Nickel-catalyzed Arbuzov reactions of aryl triflates with triethyl phosphite

An efficient method was developed for the nickel-catalyzed phosphonylation of aryl triflates with triethyl phosphite, in which KBr as an additive promoted the S_N2 catalytic step. To the best of our knowledge, this is the first example of nickel-catalyzed Arbuzov reactions of aryl triflates. Most of the substrates showed good reactivity under this catalytic system.     

Ionic liquids as novel and recyclable reaction media for N-alkylation of amino-9,10-anthraquinones by trialkyl phosphites

Ionic liquids such as 1,3-dialkylimidazolium bromides make excellent catalysts and solvents for N-alkylation of amino-9,10-anthraquinones in the presence of trialkyl phosphites. For triethyl phosphite, [bpim][Br] gave better results. The ionic liquids are successfully regenerated and reused.     

Reaction of Triethyl Phosphite with Boron Tribromide

Summary.  Reaction of boron tribromide with triethyl phosphite led to the formation of triethyl tribromoborophosphate 1, a complex bearing a P→B bond. Received November 19, 1999. Accepted (revised) January 21, 2000     

Development of the radical C–O coupling reaction of phenols toward the synthesis of natural products comprising a diaryl ether skeleton

Compounds comprising a diaryl ether skeleton exist among natural phenols. The diaryl ether skeleton is thought to be biosynthesized through the coupling of two or more phenols. It is an important structural feature in medicines and agrochemicals, and it is imperative to develop methods for constructing such skeletons in organic synthesis. However, by the synthesis method through the coupling of phenols, coupling occurs preferentially at the ortho-substituted carbon atom of phenols. In this study, various radical-generating reagents and conditions were investigated with the aim of developing a short-step construction method of the diaryl ether skeleton by the radical homo-coupling of two phenol molecules. In addition, cross-coupling reactions between radicals of 2,4,6-tri-tert-butylphenol and p-substituted phenol were conducted to synthesize eight C (ortho)–O coupling products. Based on the results, a computational chemical approach was employed to verify the cause of C (ortho)–O bond formation.     

Formal Aniline Synthesis from Phenols through Deoxygenative N-Centered Radical Substitution

Phenolic, lignin-derived substrates have emerged as desirable biorenewable chemical feedstocks for coupling reactions. A radical-mediated conversion of phenol derivatives to anilines is reported, using unfunctionalized hydroxamic acids as the N-centered radical source. The applicability of this triethyl phosphite mediated O-atom transfer approach, which tolerates a range of steric and electronic demands to naturally occurring phenols and lignin models, has been demonstrated in this work to access the corresponding aniline derivatives.     

An efficient multi-component synthesis of (2-amino-3-cyano-4H-chromen-4-yl) phosphonic acid diethyl ester

(2-Amino-3-cyano-4H-chromen-4-yl) phosphonic acid diethyl esters are prepared via a single-step multi-component reaction of structurally diverse salicylaldehydes with malononitrile and triethyl phosphite using a catalytic amount of potassium phosphate in ethanol at ambient temperature. Use of potassium phosphate as an inexpensive catalyst makes the protocol more economical. Mild reaction conditions, simple work-up procedure are the added advantages of the present method.     

碘催化合成三乙基膦酰乙酸酯

首次报道了碘对M ichaelArbuzov重排反应的催化作用.以亚磷酸三乙酯与2-卤代乙酸乙酯为原料,碘作催化剂,反应温度80℃,反应时间2 h,三乙基膦酰乙酸酯的产率达到90%-98%.     

Synthesis of 3-Fluoro-2-(Diethoxyphosphoryl) Imidazo[1,2-A]Pyrimidine

Abstract

The first representative of 3-fluoro-2-(dialkoxyphosphoryl)imidazo[1,2-a]pyrimidi nes has been synthesized by the reaction of N-(pyrimidin-2-yl)-2,2,2-trifluoroacetimidoyl chloride with triethyl phosphite.

[Supplemental materials are available for this article. Go to the publisher's online edition ofPhosphorus, Sulfur, and Silicon and the Related Elements to view the following free supplemental file: Figures]     

Visible-light-promoted synthesis of diaryl sulfides under air

A convergent, organocatalytic visible-light-mediated process for the synthesis of diaryl sulfides has been developed. A broad range of aryl thiols reacted with various aryl diazonium salts in the presence of eosin Y under air atmosphere to afford the desired diaryl sulfides in high yields. This novel and environmentally friendly method provides an alternative route to established synthetic approaches.     

N-Acylsuccinimides: Efficient acylative coupling reagents in palladium-catalyzed Suzuki coupling via CN cleavage

An acylative Suzuki coupling of activated amides with aryl boronic acids has been reported via palladium-catalyzed CN bond cleavage. This protocol demonstrate amides can be activated by an atom-economic and cheap succinimide, which can be efficiently utilized to synthesize broad array of diaryl ketones in moderate to good yields.     

Alum： An efficient catalyst for one-pot synthesis of α-aminophosphonates

Alum (KAl(SO ₄) ₂·12H ₂O) is an inexpensive, efficient, non-toxic and mild catalyst for the one-pot synthesis of α-aminophosphonates.A three component reaction of an aldehyde/ketone, an amine and triethyl phosphite was carried out under solvent-free conditions to afford the corresponding a-aminophosphonates in short reaction times and high yields with the green aspects by avoiding toxic catalysts and solvents.     

Copper mediated coupling of 2-(piperazine)-pyrimidine iodides with aryl thiols using Cu(I)thiophene-2-carboxylate

A copper-mediated synthesis of diaryl sulfides utilizing Cu(I)-thiophene-2-carboxylate (CuTC) is described. We demonstrate the use of CuTC as a soluble, non-basic catalyst in the coupling of aryl iodides and aryl thiols in the synthesis of synthetically advanced diaryl sulfides. This method allows for the successful coupling of challenging substrates including ortho-substituted and heteroaryl iodides and thiols. Additionally, most of the aryl iodide substrates used here contain the privileged piperazine scaffold bound to a pyrimidine, pyridine, or phenyl ring and thus this method allows for the elaboration of complex piperazine scaffolds into molecules of biological interest. The method described here enables the incorporation of late-stage structural diversity into diaryl sulfides containing the piperazine ring, thus enhancing the number and nature of derivatives available for SAR investigation.     

A Rapid and Efficient Synthesis of Diaryl Thioureas via Solvent-Free Reaction Using Microwave

The application of microwave techniques for chemical synthesis has attracted considerable interest in recent years1-5. The reason is that technology can enhance the selectivity and reactivity6,7, increase the chemical yields and shorten the reaction time8,9. In order to provide a method that is economic, without pollution, easy to carry out, we coupled the solvent-free reaction with microwave.As we know, thiourea compounds are associated with a serious biological activities such as antiviral10…     

Cu-nanoparticle catalyzed O-arylation of phenols with aryl halides via Ullmann coupling

Recyclable Cu-nanoparticles provide an efficient, economic, and novel method for the synthesis of diaryl ethers via Ullmann type coupling. This method provides a wide range of substrate applicability and avoids the use of a heavy metal co-catalyst and gives diaryl ethers in satisfactory yields.     

Rapid and Efficient Synthesis of Diaryl Carbazones using Microwave Technology

Diaryl carbazone is an important organic analytical reagent normally prepared by the oxidation of diaryl carbazine, but in literatures' methods, the yields were low and the procedures were trouble1,2. Recently, our laboratory reported some new methods for the preparation of diaryl carbazone from diaryl carbazine3,4. Generally, these methods have drawbacks such as tedious operation3, using large amounts of volatile and poisonous solvent which will pollute the environment inevitably3, long reaction time and complicated oxidation system4. In continuation of our studies on the synthesis of azo compounds, we decided to develop a new method to overcome the limitation.As we know, the application of microwave techniques for organic synthesis has attracted considerable interests in recent years5. Using microwave technology can enhance the selectivity and reactivity, increase the chemical yields and shorten the reaction time6. It has been widely used in a variety of organic reactions7,8. However, the synthesis of diaryl carbazones using microwave has not been reported so far.In this paper, a rapid and efficient synthesis of diaryl carbazones with NaBrO3/H2SO4 as oxidation system using microwave technology is reported for the first time. By this method, in short time (0.5 rmin), we have synthesized ten diaryl carbazones in good yields.In the oxidation study, we found that the acidic condition is necessary in these reactions.This method only needs cheap and easily available oxidants, simple instruments and easy work-up.In conclusion, It is a facile and rapid method for the preparation of diaryl carbazones from diaryl carbazines with NaBrO3/H2SO4.     

31P NMR Studies of Diethyl Phosphite Derived Nanocrystalline Hydroxyapatite

³¹P nuclear magnetic resonance (NMR) spectroscopy was used to determine the structure of the intermediate species of sol derived from triethyl phosphite, calcium diethoxide and acetic acid. NMR spectral data revealed that the reaction proceeds via a dialkyl phosphite intermediate. The use of a dialkyl phosphite precursor (diethyl phosphite) with calcium diethoxide eliminated the aging time required in triethylphosphite method and offered an effective sol-gel procedure for monophasic hydroxyapatite.     

Ullmann diaryl ether synthesis catalyzed by copper (I)/pyridine-functionalized silane

Ullmann-type diaryl ether synthesis was performed under mild conditions in DMF/K₂CO₃ using a pyridine-functionalized silane as a ligand. The products were obtained in good yields. This method tolerates a variety of functional groups and is effective in the synthesis of hindered diaryl ethers and heteroaryl ethers.