New α-Functionalized Phosphorus Acid Surfactants: Synthesis,Dissociation Constants and Molecular Aggregation

Abstract

Pursuing our investigation into h e reactivity of red phosphorus. its hydrolysis derivatives (PH₃, and H₃,PO₂).^1,2 and P-H labile compounds? we report here a convenient method for the direct synthesis of free a-hydroxyalkyl phosphinic acid surfactants from aqueous hypophosphorous acid and the long-chain aldehydes or imincs under sonication.     

REACTIONS OF DERIVATIVES OF PHOSPHORUS ACIDS WITH CARBONYL COMPOUNDS ACTIVATED BY ELECTRONEGATIVE GROUPS

Abstract

The Arbuzov reaction results in the synthesis of various phosphonic esters and is of great importance for the further development of the chemistry of organophosphorus compounds. Investigations of recent decades have shown that, besides halogen-containing organic compounds, different types of organic compounds of the electrophilic type which do not contain halogen atoms are capable of entering this reaction. Reactions with carbonyl compounds are especially interesting. This report presents the results of reactions of derivatives of tricoordinated phosphorus (trialkyl phosphites, amidophosphites, ester anhydrides, isocyanate phosphites) with carbonyl compounds. Special emphasis was placed on studying the reactions with carbonyl compounds activated by some electronegative groups. The regularities and mechanisms of these reactions were investigated depending on the structure of the carbonyl compounds, the derivatives of tricoordinated phosphorus and the reaction conditions.     

Synthesis of New Functionalized Organophosphorus Acids and their Derivatives

Abstract

Functionalized organophosphorus acids and their derivatives are of great interest as chelating ligands, bioactive substances with various properties and the key compounds for the synthesis of phosphorus containing peptides. We have developed the convenient methods of the synthesis of new functionalized organophosphorus acids and their derivatives using a series of PH-acids and their esters with highly reactive fragments PH and POSi as well as phosphorus containing arnines with fragments PCHNH and PCHNSi. These organophosphorus synthons react smoothly with α-heterosubstituted derivatives of various amines and amides, functionalized alkenes and their oxides, as well as with acyl and sulfonyl chlorides giving the perspective compounds with high yields. New available types of new functionalized organophosphorus acids and their derivatives are presented below.     

Organophosphorus Synthesis Without Phosphorus Trichloride: The Case for the Hypophosphorous Pathway

Abstract

The vast majority of organophosphorus compounds is currently synthesized from phosphorus trichloride (PCl₃), even though the final consumer products do not contain reactive phosphorus–chlorine bonds. In order to bypass phosphorus trichloride, significant interest has been devoted to functionalizing elemental phosphorus (P₄, the precursor to PCl₃), red phosphorus (P_red), or phosphine (PH₃). Yet, other industrial-scale precursors are hypophosphorous derivatives (H₃PO₂ and its alkali salts), but their use as phosphorus trichloride replacements has been completely overlooked. Here, the case is made for an alternative approach to the industrial synthesis of organophosphorus compounds based on hypophosphites.     

Heck Reaction: Stereo Selective Synthesis of Trisubstituted Olefins: Useful Intermediates for Anthraquinone Carboxylic Acid Derivatives

Palladium catalyzed arylation of dialkyl itaconate in presence of Pd(OAc)2/PPh₃ as a catalyst, afforded trisubstituted olefins stereo selectively. These alkenes are useful intermediates for the synthesis of anthraquinone carboxylic acid derivatives. A new coumarin is also synthesized using this protocol.     

New approaches towards the synthesis and characterization of alkoxy substituted spirobifluorenes and spirosilabifluorenes for organic optoelectronics

Alkoxy substituted spirobifluorene derivatives namely 2,2′,7,7′-tetrabromo-3,6-bis(methoxy)-9,9′spirobifluorene (MSBF), 2,2′,7,7′-tetrabromo-3,6-bis(ethoxy)-9,9′spirobifluorene (ESBF), 2,2′,7,7′-tetrabromo-3,6-bis(butoxy)-9,9′spirobifluorene (BSBF), 2,2′,7,7′-tetrabromo-3,3′,6,6′-tetra(methoxy)-9,9′-spiro-9-silabifluorene (MSSiBF) and their key intermediates have been synthesised successfully. All compounds have been fully characterised by ¹H and ¹³C NMR, FTIR, UV-visible spectroscopy, MS spectrometry. TGA analysis revealed good thermal stability. The systematic investigation on the solubility, thermostability and photophysical property of synthesized compound showed that alkoxy substituted spirobifluorene were unique in rigidity and have wide range of applications in molecular electronics and can be used as building units for optoelectronics material.     

Synthesis and Reactivity of the New Trimethylsilyl Esters of Aminomethylenebisorganophosphorus Acids

The interaction of trimethylsilyl esters of trivalent organophosphorus acids containing PH and POSiMe₃ fragments in the presence of trimethylsilyl trifluoromethanesulfonate as catalyst is proposed as a convenient method for the synthesis of new trimethylsilyl esters of aminomethylenebisorganophosphorus acids with three and four coordinated phosphorus. Also the new functionalized derivatives of the aminomethylenebisphosphinic acids with substituted hydroxymethyl moieties are synthesized, and some properties of the obtained compounds are presented.     

SYNTHESIS OF SYMMETRICAL AND UNSYMMETRICAL AMIDOPHOSPHITES

Abstract

A method is proposed for one-pot synthesis of either symmetrical or unsymmetrical diester amidophosphites, developed on the basis of tris-(N,N-dimethyl)-amide/or tris-(N,N-diethyl)-amide/of phosphorous acid, activated by iodine, as a new phosphorylating reagent.

Nine thiophosphate, phosphite and phosphite monoester and diester derivatives of 1-O-stearoyl-ethane-2-ol, cholesterol, β-sitosterol and R,S-α-tocopherol have been synthesized under mild conditions (20–75°C) and in high final yields (83--98%).     

Synthesis and reactivity of substituted α‐carbonylphosphonites and their derivatives

Convenient methods for the synthesis of functionalized organophosphorus compounds containing carbonyl groups as well as di‐ or trialkoxymethyl fragments attached to phosphorus, and their derivatives, starting from the available derivatives of trivalent phosphorus acids, are proposed, and some properties of the new functionalized organophosphorus compounds are presented. So, the alkylation and acylation reaction of (dialkoxymethyl) phosphonites and their analogs have been studied. It is found that the Arbuzov rearrangement of these compounds was accompanied by the phosphorus–carbon bond cleavage with unique retention of the three‐coordinate phosphorus. © 2012 Wiley Periodicals, Inc. Heteroatom Chem 23:352–372, 2012; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.21024     

Synthesis of the new adducts of imines and enamines with PH acids and their derivatives

Nucleophilic or radical addition of esters of trivalent organophosphorus acids with PH fragments to various imines and enamines is proposed as convenient methods for the synthesis of new substituted aminomethyl organophosphorus compounds with three‐, four‐, and five‐coordinated phosphorus. Also the new functionalized derivatives of these compounds with acyl and methanesulfonyl moieties are synthesized, and some properties of the obtained compounds are presented. © 2009 Wiley Periodicals, Inc. Heteroatom Chem 20:70–80, 2009; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20513     

Phosphorus Analogues of Homoproline

Abstract

Aminophosphonic and aminophosphinic acid analogs of most of the natural amino acids have been synthesized recently (1). We describe here the synthesis of phosphonic and phosphinic analogs of the natural iminocarboxylic acid homoproline. The compounds were obtained by the iminoalkylation of P(O)H-containing organophosphorus compounds with the trimer of tetrahydropyridine. This trimer adds three equivalents of dialkyl phosphite or monoalkyl alkyl(ary1) phosphonite to form the esters of piperidine-2-phosphonic or piperidine-2-alkyl (ary1)phosphinic acids. Hydrolysis of the esters in acidic medium leads to the phosphorus analogs of homoproline.     

Synthesis of new organophosphorus‐substituted derivatives of ethanesulfonic acid

Nucleophilic addition of trimethylsilyl esters of hypophosphorus acid to trimethylsilyl ester and diethylamide of vinylsulfonic acid is proposed as convenient methods for the synthesis of new 2‐sulfonylethylphosphonites and their derivatives under mild conditions. Also the new functionalized derivatives of these phosphonites, including aminomethyl fragments as well as certain properties of these compounds as important precursors of new organophosphorus‐substituted derivatives of ethanesulfonic acid, are presented. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:470–473, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20448     

Synthesis and Stereochemistry of C-Functional Derivatives of Phosphabicyclodecane

Abstract

Methods for synthesis of new phosphabicyclodecanes with substitution in a heterocycle were worked out. Configurations of individual stereoisomers of P (III) phosphabicyclodecanones, their oxides, sulfides and selenides were established by ¹H, ¹³C, ³¹P NMR spectroscopy and X-ray analysis. The results show that electron-acceptor groups (C=O, P=X) enhance mobility of hydrogen atoms in the heterocycle which leads to the increasing ability of phosphabicyclodecanones for deuteration (in a-position to C4, P=X), participation in aminomethylation reaction and to the capability to react with electrophiles. The isomerization of 5-oxo- and 5-hydroxyderivatives of P (IV) phosphahicyclodecane in presence of acid and basic catalysts was detected and studied. The mechanism of ketoenolic and thiophosphoryl-merkaptoilide (selenophosphoryl-selenoloilide) ternary prototropic tautomerism is proposed. By varying the temperature and the nature of the solvent and catalyst, it is possible to alter the direction and depth of isomeric transformations. As the result of the studies of Stereochemical directivity of reactions of nucleophile addition to double C=O and C=C bonds and of electrophile substitution in phosphabicyclodecanones, the functioning possibilities of such compounds were determined. Polyfunctional derivatives of phosphabicyclodecane, which are of interest for fine organic synthesis of new organophosphorus compounds were obtained.     

COPPER(II) COORDINATION COMPOUNDS: CLASSIFICATION AND ANALYSIS OF CRYSTALLOGRAPHIC AND STRUCTURAL DATA II. MONONUCLEAR-, HEXA-, HEPTA-AND OCTACOORDINATE COMPOUNDS

Abstract

This review summarizes the data for over five hundred and fifty six-, seven- and eight-coordinate Cu(II) coordination compounds. The six-coordinate derivatives are mostly distorted tetragonal (elongation along a single C ₄ axis). The seven-coordinate derivatives are only penta-gonal-bipyramidal with different degrees of distortion and the eight-coordinate complexes are dodecahedral. The most common ligands are O- and N-donors. There is a trend for the Cu-L distance to increase with covalent radius of the coordinated atom and also increasing coordination number. In general, Cu(II) compounds “prefer” a monoclinic class and are blue or green. Several relationships were found and discussed. The data are compared and discussed with those of four- and five-coordinate Cu(II) compounds.     

Advances in Organophosphorus Chemistry Based on Dichloro(methyl)phosphane

Besides phosphorus trichloride and phosphane, dichloro(methyl)phosphane is gaining importance as a starting material for the synthesis of organophosphorus compounds. It provides ready access to phosphonic, phosphinic and phosphonous acid derivatives, as well as their secondary products. The synthetic and application potential of organophosphorus compounds—based on industrially produced dichloro(methyl)phosphane—is illustrated by means of numerous examples.     

Thiolophosphohydrides: New Reagents in the Organo-Phosphorus Synthesis

Abstract

A simple and effective method has been developed for synthesizing a new type of organophosphorus compounds, thiolophosphohydrides, with the general formula R(R′S)PH based on the selective reduction of thioesters of P(III) acids by di- or trialkylstannanes. Stable S-alkylalkylthiophos-phonites and S-alkylalkyldithiophosphonites have been obtained for the first time by using the processes of oxidation and sulfurization. The functionally substituted phosphorus (111) thio derivatives have been obtained by the addition reactions of thiolophosphohydrides with compounds containing carbon-carbon and carbon-oxygen multiple bonds, with the cleavage of the P-H bonds and the preservation of P-S bonds. Factors affecting the rate of interaction, stability and the structure of additional products have been elucidated. Depending on the reaction conditions of thiolophosphohydrides with halogen containing electrophilic reagents and on the nature of the latter, the process can lead to the cleavage either of the P-H bond or the P-S bond. Thiolophosphohydrides as new reagents in organophosphorus synthesis open up new vistas for obtaining a variety of functionally substituted phosphor- and sulfur-containing compounds.     

Regioselective synthesis of functionalized naphtho[b]thiophenes through a ‘lactone methodology’

Benzo[b]thiophene and its benzannulated derivatives are important classes of compounds due to their unique chemical properties and biosteric relationship with indole. In this letter, we report a convenient route for the synthesis of substituted naphtho[b]thiophenes through a ring transformation reaction of suitably functionalized 2H-pyran-2-ones with 6,7-dihydro-5H-benzothiophene-4-one, in good yields.     

N′-(取代嘧啶-2-基)-N-菊酰硫脲的合成与生物活性研究

采用活性基团拼接法, 将第一菊酸构型中的最高活性组分(＋)-反式菊酸以及二氯菊酸引入到含取代嘧啶环的酰基硫脲结构中, 合成了5个未见文献报道的N′-(取代嘧啶-2-基)-N-(＋)-反式菊酰硫脲衍生物(3a～3e)和3个均未见文献报道的N′-(取代嘧啶-2-基)-N-二氯菊酰硫脲(3f～3h), 结构经元素分析、IR和¹H NMR得到确证. 初步的生物活性测试结果表明: 大部分化合物具有较好的杀菌活性, 有的化合物兼具除草和杀菌活性, 有的化合物兼具杀虫和杀菌活性.     

The Decomposition of Transition Metal Tetrafluoroborates by some strong Base Ligands

Abstract

Some transition metal complexes of triethylene-diamine (TED, I) and quinuclidine (Q, II) have been reported.^1–5 Recently we treated I and II with metal bistetrafluoroborates (M=Co²⁺, Ni²⁺, and Cu²⁺) which have not been studied yet, and postulated that pure coordination complexes might be obtained. However, evidence for the existence of 1:1 adducts such as C₆H₁₂N₂:BF₃ (III) and C₇H₁₃N:BF₂ (IV) in treatment of I and II with metal bistetrafluoroborates has now been found. We wish to describe our results concerning formation of these two new 1:1 adducts in this letter.     

Pd(0) or Pd(II)-catalyzed ring-opening reactions of benzylidene- and alkylidenecyclopropyl ketones and aldehydes

Pd(0) catalyzed reactions of methylenecyclopropyl carbonyl compounds afforded a convenient method for the synthesis of conjugate (E,E)-1,3-diene derivatives 2 in good to excellent yields. Moreover, we also found that Pd(II)-catalyzed reactions of methylenecyclopropyl carbonyl compounds with water gave 1,5-diketones in good to high yields via a carbene-palladium intermediate. The plausible reaction mechanisms have also been provided on the basis of control and ¹⁸O-labeling experiments.