- Direct18F-Labeling of Biomolecules via Spontaneous Site-Specific Nucleophilic Substitution by F-on Phosphonate Prostheses
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We describe a high radiochemical yield late-stage direct 18F-labeling of bare biomolecules containing common active groups. Spontaneity and site-selectivity are attributed to the remarkably higher rates of nucleophilic substitution reactions on phosphonates than on other electrophiles by F- at various hydrogen bond forms. Rapid access to many medicinally significant 18F-labeled biomolecules is achieved at 21-68% radiochemical yields and 35.9-55.1 GBq μmol-1 molar activities both manually or automatically.
- Wang, Chao,Zhang, Lei,Mou, Zhaobiao,Feng, Wanru,Li, Zhongjing,Yang, Hongzhang,Chen, Xueyuan,Lv, Shengji,Li, Zijing
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supporting information
p. 4261 - 4266
(2021/05/26)
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- Preparation method of phenyl phosphonate diphenyl ester (by machine translation)
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The invention belongs to the technical field of organic synthesis, and provides a preparation method of diphenyl phosphonate, wherein triphenyl phosphite is used as an initiator, and the molar ratio ?timetime? and isomerization reaction is controlled to obtain phenyl phosphonate diphenyl ester; the isomerization reaction temperature is 220 - 260 °C. the isomerization reaction temperature is controlled; 1st. In addition, both the brominated benzene and Raney nickel in the method can be recycled, the reaction cost is low, and the environmental pollution is small. (by machine translation)
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Paragraph 0045-0052; 0057-0085; 0093-0096
(2020/09/16)
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- Palladium-catalyzed solvent-free preparation of arylphosphonates Arp(O)(OAr)2 from (Aro)3p via the Michaelis-Arbuzov rearrangement
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The Pd-catalyzed Michaelis-Arbuzov rearrangement of triaryl phosphites to produce the corresponding arylphosphonates in good to excellent yields is disclosed. In comparison to the traditional methods, this new method is highly atom efficient and is general, as it can be readily extended to aryl phosphonites and phosphinites. A gram-scale reaction of (PhO)3P to PhP(O)(OPh)2 with low loading of the catalyst was also demonstrated to show its potentially practical usefulness. A plausible mechanism is proposed.
- Li, Chunya,Han, Li-Biao
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supporting information
p. 3613 - 3617
(2020/11/03)
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- Synthesis of New Chiral Crown Ethers Containing Phosphine or Secondary Phosphine Oxide Units
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The transition-metal complexes of phosphine and secondary phosphine oxide compounds can be used in various catalytic reactions. In this paper, the synthesis and characterization of eight new crown ethers containing trivalent phosphorus in their macroring are reported. These macrocycles are promising candidates as ligands for catalytic reactions.
- Szabó-Szentjóbi, Hajnalka,Majoros, István,Márton, Anna,Leveles, Ibolya,Vértessy, Beáta G.,Dékány, Miklós,Tóth, Tünde,Huszthy, Péter
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p. 2870 - 2882
(2020/10/06)
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- Cobalt catalyzed C-P bond formation by cross-coupling of boronic acids with P(O)H compounds in presence of zinc
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In our current work, we have reported the first cobalt-catalyzed cross-coupling of arylboronic acid with alkyl/aryl phosphites under mild conditions. The reaction was carried out in the presence of zinc powder as an additive and ter-pyridine as a ligand. The use of non-precious cobalt salt makes the protocol advantageous, as it is inexpensive and more abundant than the previously used methods where precious metal salts (Pd and Pt) were used. The reaction has a wide substrate scope and the products were obtained in good yields.
- Hicks, Ian,McTague, Jonathan,Hapatsha, Tatiana,Teriak, Rania,Kaur, Parminder
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- Radical arylation of triphenyl phosphite catalyzed by salicylic acid: Mechanistic investigations and synthetic applications
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A straightforward and scalable methodology to synthesize diphenyl arylphosphonates at 20 °C within 1-2 h is reported using inexpensive SA as the catalytic promoter of the reaction. Mechanistic investigations suggest that the reaction proceeds via radical-radical coupling, consistent with the so-called persistent radical effect. The reaction tolerated a wide range of functional groups and heteroaromatic moieties. The synthetic usefulness and the unique reactivity of the obtained phosphonates were demonstrated in different one-step transformations.
- Estruch-Blasco, Manel,Felipe-Blanco, Diego,Bosque, Irene,Gonzalez-Gomez, Jose C.
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supporting information
p. 14473 - 14485
(2020/12/29)
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- Visible Light-Driven, Photocatalyst-Free Arbuzov-Like Reaction via Arylazo Sulfones
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A visible light-induced formation of Aryl-Phosphorous bonds starting from arylazo sulfones and triaryl (or trialkyl)phosphites in the absence of any photoredox catalyst and any additives was developed. This reaction showed a broad substrate scope and afforded (hetero)aryl phosphonates in good yields and in up to the gram scale.
- Qiu, Di,Lian, Chang,Mao, Jinshan,Ding, Yi,Liu, Zerong,Wei, Liyan,Fagnoni, Maurizio,Protti, Stefano
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supporting information
p. 5239 - 5244
(2019/11/11)
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- Arylphosphate compound and preparation method thereof
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The invention discloses an arylphosphate compound and a preparation method thereof. The preparation method includes, with arylamine and phosphite ester as reactants and tert-butyl nitrite as an accelerator, performing stirring reaction at the temperature within 70-80 DEG C for 40-60 minutes, and separating through the column chromatography to obtain a product, namely arylphosphate compound. The preparation method is a new way of synthetizing arylphosphate target compound from low-price feasible raw materials of arylamine and phosphite ester on the acid-free and metal-free condition, has the advantages of mild reaction condition, operational simplicity and the like and overcomes the big trouble to production of medical intermediates caused by residues of metal catalysts, after-treatment ofacids in medicine synthesis, and accordingly, the simple and efficient meta-free and acid-free catalysis system has great potential application value and economic benefit.
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Paragraph 0011; 0014; 0020
(2019/04/17)
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- Avisible-light-promoted metal-free strategy towards arylphosphonates: Organic-dye-catalyzed phosphorylation of arylhydrazines with trialkylphosphites
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A visible-light-induced metal-free catalytic system was developed for the synthesis of arylphosphonates starting from arylhydrazines and trialkylphosphites. By using the inexpensive eosin B as catalyst, sub-stoichiometric amounts of DABCO, and ambient air as oxidant, diverse arylphosphonates were obtained under visible-light irradiation. Notably, this catalytic system is suitable for gram-scale reaction by utilizing sunlight as an illumination source.
- Li, Rui,Chen, Xiaolan,Wei, Shengkai,Sun, Kai,Fan, Lulu,Liu, Yan,Qu, Lingbo,Zhao, Yufen,Yu, Bing
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supporting information
p. 4807 - 4813
(2018/12/11)
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- Visible-Light-Mediated Metal-Free Synthesis of Aryl Phosphonates: Synthetic and Mechanistic Investigations
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This work describes a straightforward access to a large variety of aryl phosphonates by the simple combination of diaryliodonium salts with phosphites in the presence of a base and under visible-light illumination. The reaction proceeds smoothly, tolerates various functionalities, and was applied for the synthesis of pharmaceutically relevant compounds. Mechanistic investigations, including EPR, NMR, and DFT calculations, support the postulated reaction mechanism.
- Lecroq, William,Bazille, Pierre,Morlet-Savary, Fabrice,Breugst, Martin,Lalevée, Jacques,Gaumont, Annie-Claude,Lakhdar, Sami
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supporting information
p. 4164 - 4167
(2018/07/29)
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- Preparation method of low-triphenyl phosphate engineering plastic halogen-free flame retardant
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The invention belongs to the technical field of applied engineering plastics, and in particular, relates to a preparation method of a low-triphenyl phosphate engineering plastic halogen-free flame retardant. The method comprises the steps: under the action of a Lewis catalyst, carrying out a reaction of phenol with phosphorus oxychloride, reducing the pressure and distilling out excess phosphorusoxychloride, to obtain a mixture intermediate; carrying out a condensation reaction of the mixture intermediate and p-dihydroxybenzene, carrying out a reaction of the mixed intermediate with a properamount of p-dihydroxybenzene firstly, after a part of p-dihydroxybenzene is completely reacted, carrying out high vacuum dehydrochlorination, then adding triethylamine and the remaining p-dihydroxybenzene at relatively low temperature, and carrying out a reaction, wherein increase of the content of triphenyl phosphate is greatly reduced, toxicity to human bodies is reduced, and at the same time, the purity and the yield of the product are improved; and the preparation method has the advantages of simple process operation, short production cycle, economy and environmental protection, can satisfy the requirements of industrial scale production, and is suitable for industrialized popularization and application.
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Paragraph 0015; 0016; 0017; 0018; 0019; 0021; 0023; 0025
(2018/03/28)
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- Metal-Free Aromatic Carbon-Phosphorus Bond Formation via a Sandmeyer-Type Reaction
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An efficient metal-free phosphorylation process based on a Sandmeyer-type transformation with arylamines as the starting materials is developed. The transformation proceeds smoothly at room temperature without the exclusion of moisture or air. This phosphorylation reaction tolerates a wide range of functional groups and affords the phosphorylation products in moderate to good yields, thus providing a valuable method for the formation of aromatic carbon-phosphorus bonds.
- Wang, Shuai,Qiu, Di,Mo, Fanyang,Zhang, Yan,Wang, Jianbo
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p. 11603 - 11611
(2016/12/09)
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- Towards a characterization of the structural determinants of specificity in the macrocyclizing thioesterase for deoxyerythronolide B biosynthesis
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Type I polyketide synthases (PKSs) are giant multidomain proteins that synthesize many therapeutics and other natural products. The synthesis proceeds by a thiotemplate mechanism whereby intermediates are covalently attached to the PKS. The release of the final polyketide is catalyzed by the terminal thioesterase (TE) domain through hydrolysis, transesterification, or macrocyclization. The PKS 6-deoxyerythronolide B synthase (DEBS) produces the 14-membered macrolide core of the clinically important antibiotic erythromycin. The TE domain of DEBS (DEBS TE) has well-established, empirically-defined specificities for hydrolysis or macrocyclization of native and modified substrates. We present efforts towards understanding the structural basis for the specificity of the thioesterase reaction in DEBS TE using a set of novel diphenyl alkylphosphonates, which mimic substrates that are specifically cyclized or hydrolyzed by DEBS TE. We have determined structures of a new construct of DEBS TE alone at 1.7 ?, and DEBS TE bound with a simple allylphosphonate at 2.1 ? resolution. Other, more complex diphenyl alkylphosphonates inhibit DEBS TE, but we were unable to visualize these faithful cyclization analogs in complex with DEBS TE. This work represents a first step towards using DEBS TE complexed with sophisticated substrate analogs to decipher the specificity determinants in this important reaction.
- Argyropoulos, Panos,Bergeret, Fabien,Pardin, Christophe,Reimer, Janice M.,Pinto, Atahualpa,Boddy, Christopher N.,Schmeing, T. Martin
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p. 486 - 497
(2016/02/05)
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- A new magnetically recoverable heterogeneous palladium catalyst for phosphonation reactions in aqueous micellar solution
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A new heterogeneous palladium complex of 2-aminothiophenol supported on nanomagnetic γ-Fe2O3 was synthesized and characterized using various methods. The catalyst was used as a magnetically recoverable heterogeneous palladium catalyst for phosphonation reactions via C-P bond formation. Using this method, a wide range of electrophilic benzenes was coupled successfully with phosphite esters (triethyl/tri-isopropyl/triphenylphosphite and diethyl/di-isopropyl/diphenylphosphite) in aqueous micellar solution to generate the corresponding arylphosphonates in good to high yields. The catalyst was separated using an external magnet and reused for six consecutive cycles without any significant loss of its reactivity.
- Sobhani, Sara,Zeraatkar, Zohre
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- A Pd complex of a NNN pincer ligand supported on γ-Fe2O3@SiO2 as the first magnetically recoverable heterogeneous catalyst for C-P bond forming reactions
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A Pd complex of a NNN pincer ligand supported on γ-Fe2O3@SiO2 as a new phosphine-free Pd catalyst was synthesized and characterized by different methods such as SEM, TEM, FT-IR, TGA, ICP, XRD, XPS and elemental analysis. The synthesized catalyst was successfully used as the first magnetically recoverable heterogeneous catalyst for the synthesis of arylphosphonates via C-P bond formation by a cross-coupling reaction of different electrophilic benzenes with phosphite esters under solvent-free conditions.
- Sobhani, Sara,Vahidi, Zahra,Zeraatkar, Zohre,Khodadadi, Samaneh
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p. 36552 - 36559
(2015/05/05)
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- Direct conversion of phosphonates to phosphine oxides: An improved synthetic route to phosphines including the first synthesis of methyl JohnPhos
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The synthesis of tertiary phosphine oxides from phosphonates was achieved reliably and in good to excellent yields using stoichiometric amounts of alkyl or aryl Grignard reagents and sodium trifluoromethanesulfonate (NaOTf). In the absence of the NaOTf additive, covalent coordination oligomers of magnesium and phosphorus species dominate the reaction, producing very low yields of phosphine oxide, but high conversions of the phosphonate starting material. Mechanistic studies revealed that a five-coordinate phosphorus species - not a phosphinate - is the reaction intermediate. A diverse array of phosphonates was converted to phosphine oxides using a variety of Grignard reagents for direct carbon-phosphorus functionalization. This new methodology especially simplifies the synthesis of dimethylphosphino (RPMe2)-type phosphines by using air-, water-, and silica-stable intermediates. To highlight this reaction, a new Buchwald-type ligand ([1,1′-biphenyl]-2-yldimethylphosphine, or methyl JohnPhos) and a classic bidentate phosphine, bis(diphenylphosphino)propane (dppp), were synthesized in excellent yields.
- Kendall, Alexander J.,Salazar, Chase A.,Martino, Patrick F.,Tyler, David R.
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supporting information
p. 6171 - 6178
(2015/02/19)
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- Oxidation of phenylphosphonites with aqueous hydrogen peroxide
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An effective route to the oxidation of organic derivatives of trivalent phosphorus with an aqueous solution of hydrogen peroxide was considered. Phenylphosphonites, including those having a hydrolytically unstable phosphorus-nitrogen bond were involved into the oxidation. The identification of oxidation products, the phenylphosphonates, was carried out using the method of ion cyclotron resonance mass spectrometry with Fourier transform combined with electrospray ionization, and by 31P and 1H NMR spectroscopy. The influence of an effective antioxidant of natural origin, quercetin, on the oxidation was demonstrated. Pleiades Publishing, Ltd., 2012.
- Teleshev,Mishina,Ganin,MishinaV.Yu.,Abrashina,Nifant'ev,Kononihin,Popov,Nikolaev
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p. 1374 - 1381
(2013/01/15)
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- A concise method for synthesis of diaryl aryl- or alkylphosphonates
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A convenient method has been developed to synthesize diaryl arylphosphonates from triaryl phosphites, triethyl phosphite, and aromatic halides. The new method relies on the triethyl phosphite assisted nickel catalyzed Arbuzov reaction and can be applied to synthesize certain diaryl alkylphosphonates without catalysts.
- Yao, Qiang,Levchik, Sergei
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p. 277 - 281
(2007/10/03)
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- One-pot synthesis of unsymmetrical aryl methylphosphinates by insertion of dichlorophosphines into the O-Me bond of anisoles
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This letter describes a new one-pot method for the synthesis of unsymmetrical aryl methylphoshinates by insertion of phosphorus moiety into the O-Me bond of anisoles. These products are very difficult to obtain with other reported methods requiring several steps.
- Baccolini, Graziano,Boga, Carla
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p. 6121 - 6124
(2007/10/03)
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- Simple method for cleavage of phosphonic acid diesters to monoesters
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Phosphonic acid dialkyl or diaryl esters give, on treatment with alkali azide or alkali iodide in DMF at 100°C, quantitatively and specifically the corresponding monoesters. The reaction is applied in a series of acyclic nucleotide analogs for the preparation of PMEA monoesters and related compounds.
- Holy, Antonin
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p. 381 - 385
(2007/10/03)
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- Nonlinear Broensted Relationships in the Reaction of Phenoxide Ions with Bis(4-nitrophenyl) Phenylphosphonate in H2O-Me2SO Mixtures. Solvation Effects
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The second-order rate constants (kArO) for reaction of substituted phenoxide ions with bis(4-nitrophenyl) phenylphosphonate in aqueous as well as vatious aqueous dimethyl sulfoxide (Me2SO) mixtures are reported.Traditional Broensted plots of log kArO vs pKArOHa are linear at low pKArOHa but show very strong downward curvature at high pKArOHa.In each solvent, the break point in the Broensted plot occurs at a pKArOHa value which is much higher than that corresponding to the basicity of the leaving p-nitrophenoxide ion, suggesting that the observed levelling off does not reflect a change in the identity of the rate-determining step in a two-step process involving formation of a pentacoordinate intermediate.An analysis of the data on the basis of a novel strategy recently designed by Buncel and co-workers for the construction of Broensted plots in solvent mixtures confirms this conclusion.It is proposed that the curvature in the traditional Broensted plots is the reflection of strong imbalances in the transition states of the reactions, and it is suggested that these imbalances are essentially of solvational nature.
- Terrier, Francois,Moutiers, Gilles,Xiao, Lan,Guevel, Eric Le,Guir, Frederic
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p. 1748 - 1754
(2007/10/02)
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- The Mechanistic Diversity of the Thermal and Photochemical Decomposition of Bis(phenylphosphonoyl)Peroxides: Concerted Polar, Homolytic and Electron-Transfer Processes. On the Reactivity of (Phenylphosponoyl)oxyl Radicals
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The thermal and photochemical decomposition of the first bis(phenylphosphonoyl)peroxides, dioxybis (5), and dioxybis (6) has been studied in various solvents by 1H-, 13C-, and 31P-NMR spectroscopy, laser flash photolysis (LFP), and ESR spin-trapping experiments.Kinetic studies reveal at 20 deg C a ca. 270 times slower thermal decay for 5 than for 6, which primarily results from a lower A factor rather than differences in the activation energies.The thermal decay of 5 occurs predominantly by a novel, presumably concerted polar rearrangement with formation of a thermally unstable, mixed phosphonoyl-phosphoryl anhydride.Photolysis of 5 induces homolytical cleavage of the peroxy bond with release of oxyl radicals 7.Radical 7 is characterized by a broad, transient UV/Vis absorption spectrum in the 400 to >700 nm range (λmax ca. 580 nm), as has been demonstrated by 248-nm LFP of 5 in acetonitrile solution.The short lifetime of this absorption indicates an extremely high reactivity (in hydrogen abstraction and addition) of this electrophilic radical.The thermal and photochemical decomposition of peroxide 6 leads to a virtually identical product distribution, suggesting O-O bond cleavage to be the major initial reaction under both conditions.LFP at 248 and 308 nm of a solution of 6 in acetonitrile initially produces a weak, broad absorption at ca. 500 nm and stronger bands at 280 and 400 nm.The highly transient 500-nm absorption is assigned to the oxyl radical 8, the other bands are attributed to the phosphonoyloxy-substituted benzene radical cation 8Z.The formation of this species can be explained in terms of electron transfer in the first-formed oxyl radical 8 and/or the intact peroxide 6, followed by cleavage of the peroxy bond.The decay of 8Z is accompanied by the build-up of the absorption spectrum of a 1,4-dioxy-substituted biphenyl radical cation.Key Words: Oxyl radicals / Phosphonoyl peroxides / Laser flash photolysis /ESR-Spin trapping / Electron transfer
- Korth, Hans-Gert,Lommes, Petra
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p. 2419 - 2438
(2007/10/02)
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- Organophosphorus Antioxidants. X. The Hydroperoxide Decomposing Action of Phosphites, Phosphonites and Thiophosphites
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The kinetics and mechanism of reactions of phosphites, phosphonites, thiophosphites and hydrogenphosphites with cumyl (CHP), t-butyl (TBHP) and α-tetralyl (THP) hydrogenperoxides has been studied by means of (31)P-n.m.r. spectroscopy, high performance liquid chromatography and iodometric titration.All three valent phosphorus compounds studied initially react with hydroperoxides stoichiometrically to give the corresponding P=O products and alcohol.Some species are able to decompose cumyl hydroperoxide catalytically to form phenol and aceton.Acyloin phosphites decompose CHP catalytically after a stoichiometric reaction as thiophosphites do.Tetramethylpiperidinyl phosphites ("HALS-phosphites") react with hydroperoxides only stoichiometrically but with high velocity.Phosphonites react with hydroperoxides in the same way as the corresponding phosphites.Their reactivity, however, is much higher.Hydrogenphosphites are less reactive than phosphites in the reaction with hydroperoxides.They are able to act catalytically.
- Koenig, T.,Habicher, W. D.,Schwetlick, K.
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p. 913 - 922
(2007/10/02)
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- SYNTHESIS AND NMR SPECTROSCOPIC INVESTIGATION OF PHENYLPHOSPHORYL DERIVATIVES
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The syntheses of 16 phenyl- (1 and 3) and phenylthiophosphoryl (2) derivatives are described.The 13C and 17O NMR data sensitively reflect electron density changes in the phosphoryl substituents caused by p?-d? back-donation from X/Y to P.Taft constants ?1 and ?R0 were derived for 16 phosphoryl substituents.
- Duddeck, Helmut,Lecht, Rainer
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p. 169 - 178
(2007/10/02)
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- PHOSPHORORGANISCHE VERBINDUNGEN 96. DIE SELECTIVE VERKNUEPFUNG BIOLOGISCH WICHTIGER FUNKTIONELLER GRUPPEN MIT PHOSPHORORGANISCHEN SAEUREN
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Derivatives of phosphinic, phosphonic, and phosphoric acids of the general type R1R2P(O)X show selectivity in their reactions with nucleophiles RYH (R = n-C4H9; Y = O, NR or S) according the Eq. (1); the selectivity depends on the nature of the leaving group (X = Cl, F, CN, N3 or OC6H4NO2(p)) and the base used.The nature of the ligands R1 and R2, exert a comparatively minor influence on the reaction.Method: (a) The phosphylating agent R1R2P(O)X was allowed to react with mixture of two nucleophiles RYH and RY'H in competition (Reagent ratio 1:1:1).The product mixture (R1R2P(O)YR + R1R2P(O)Y'R was then analyzed. (b) Compounds of the type HY-CH2-CH2-Y'H (serine-n-butylamide L-cysteinmethylester) were reacted with the phosphylating agent R1R2P(O)X (reagent ratio 1:1) according the Eqs. (3) and (4) respectively.The products were isolated, identified and the yields quantitatively determined.Results: For X = F, CN, OC6H4NO2 (p), the O-ester is formed virtually exclusively.For X = Cl, only amides are formed.Azides (X = N3) show no selectivity.In competition reactions using n-butylamine and n-butylthiol, the organophosphorus chlorides (X = Cl) were found to be N-selective,, whereas the corresponding cyanides (X = CN) were S-selective.In competition reactions using n-butanol and n-butylthiol, the organophosphorus fluorides (X = F) p-nitrophenylesters (X = OC6H4NO2(p)) and cyanides (X = CN) were all O-selective.
- Horner, L,Gehring, R.
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p. 157 - 176
(2007/10/02)
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