- Nucleophilic Activation of Red Phosphorus for Controlled Synthesis of Polyphosphides
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Reactions between red phosphorus (Pred) and potassium ethoxide in various organic solvents under reflux convert this rather inert form of the element to soluble polyphosphides. The activation is hypothesized to proceed via a nucleophilic attack by ethoxide on the polymeric structure of Pred, leading to disproportionation of the latter, as judged from observation of P(OEt)3 in the reaction products. A range of solvents has been probed, revealing that different polyphosphide anions (P73-, P162-, P213-, and P5-) can be stabilized depending on the combination of the boiling point and dielectric constant (polarity) of the solvent. The effectiveness of activation also depends on the nature of nucleophile, with the rate of reaction between Pred and KOR increasing in the order t-Bu red and NaSR yielded exclusively P162- as a soluble polyphosphide product.
- Dragulescu-Andrasi, Alina,Jo, Minyoung,Miller, L. Zane,Pak, Chongin,Shatruk, Michael
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Read Online
- A simple and efficient synthesis of [2H10]deuterated bromfenvinphos by the Perkow reaction
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(E,Z)-2-bromo-1-(2,4-dichlorophenyl)vinyl bis[ethyl-2H 5] phosphate ([2H10]bromfenvinphos), a regiospecifically deuterium-labelled pesticide, was synthesized in two steps starting from [2H6]ethanol, phosphorus trichloride and 2,4-dichlorophenacylidene bromide, and fully characterized. The deuterated biologically active bromfenvinphos is an important compound for the advancement of environmental degradation testing and some mass spectrometric studies.
- Huras, Bogumiaa,Konopski, Leszek,Zakrzewski, Jerzy
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Read Online
- Autoxidation of Ethyl Phosphinite, Phosphonite, and Phosphite Esters
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The AIBN-initiated autoxidations in benzene of triethyl phosphite P(OEt)3, diethyl ethylphosphonite, EtP(OEt)2, and ethyl diethylphosphinite, Et2POEt, were studied at 50 deg C.The quantitative conversion of P(OEt)3 to triethyl phosphate obeys the rate law rate = (2.0 x 1E-4 atm-1s-1)PO2 and is zero order in phosphite.Autoxidation of EtP(OEt)2 and Et2POEt gives the complete mixture of intermediates and products predicted by Buckler's mechanism for the autoxidation of trialkylphosphines.At 1 atm of oxygen pressure and 0.02 M AIBN the pseudo-first-order rate law is rate = k', with k'= 7.49 x 1E-4 s-1 for EtP(OEt)2 and 2.37 x 1E-4 s-1 for Et2POEt.
- Hwang, Wen-Shu,Yoke, John T.
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Read Online
- Flash production of organophosphorus compounds in flow
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Flow synthesis techniques have received a significant amount of attention due to their high productivity. However, when reaction condition is heterogeneous, it is usually difficult to adapt it to flow synthesis. Herein, by selecting appropriate reagents, the synthesis of phosphate esters, which is commonly heterogeneous, was made homogeneous, enabling synthesis in flow systems. In addition, reaction rate was accelerated compared to the batch system. It was demonstrated that not only can the high productivity of flow synthesis be achieved in flow, but also high productivity can be achieved by accelerating the reaction. Finally, we demonstrated the synthesis of the Akiyama-Terada catalyst, a chiral organocatalysts, in a short period.
- Nagaki, Aiichiro,Tamaki, Takashi
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supporting information
(2021/09/09)
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- Silver-Catalyzed Regioselective Phosphorylation of para-Quinone Methides with P(III)-Nucleophiles
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A simple and efficient method for the silver-catalyzed regioselective phosphorylation of para-quinone methides (p-QMs) with P(III)-nucleophiles (P(OR)3, ArP(OR)2, Ar2P-OR) has been established via Michaelis-Arbuzov-type reaction. A broad range of P(III)-nucleophiles and para-quinone methides are well tolerated under the mild conditions, giving the expected diarylmethyl-substituted organophosphorus compounds with good to excellent yields. Moreover, a series of corresponding enantiomers can be obtained by employing dialkyl arylphosphonite (ArP(OR)2) as substrates. The control experiments and 31P NMR tracking experiments were also performed to gain insights for the plausible reaction mechanism. This protocol may have significant implications for the formation of C(sp3)-P bonds in Michaelis-Arbuzov-type reactions.
- Liu, Yu,Tang, Ke-Wen,Wong, Wai-Yeung,Xie, Jun,Xiong, Biquan,Xu, Shipan,Xu, Weifeng
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p. 14983 - 15003
(2021/11/12)
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- Preparation method of triethyl phosphite
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The invention relates to the field of production of organic chemical intermediates, and particularly discloses a preparation method of triethyl phosphite. The preparation method comprises the steps ofuniformly mixing absolute ethyl alcohol, an organic solvent, a catalyst trioctylamine and an acid-binding agent to obtain a mixed solution; cooling the mixed solution, keeping the temperature of thesystem at 0-10 DEG C, dropwise adding a phosphorus trichloride solution into the mixed solution with the molar ratio of phosphorus trichloride to absolute ethyl alcohol being 1:(3-6), continuously conducting heat preservation for 1-4h after adding is completed, and obtaining a reaction solution; and separating and purifying to obtain triethyl phosphite, wherein the molar ratio of trioctylamine tothe acid-binding agent is 2:(3-5). The preparation method has the advantages that under the condition that the product yield is not lower than 90% and the purity is not lower than 95%, the content ofammonium chloride in the reaction waste liquid is reduced, and the waste liquid treatment cost is reduced.
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Paragraph 0031-0043; 0047
(2020/12/15)
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- Synthesis process of antioxidant 618
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The invention belongs to the synthesis technology of phosphite antioxidants, in particular to a synthesis technology of antioxidant 618. Triethyl phosphite is synthesized through a microreactor, pentaerythritol diphosphite is synthesized, and the antioxidant 618 is finally synthesized. The synthesis process of the antioxidant 618 has the advantages of good sealing performance, easy control of reaction conditions, reflux utilization of solvents and products, and cost saving.
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Paragraph 0027; 0028-0041; 0047-0051; 0047-0051
(2019/08/06)
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- Continuous production method for triethyl phosphite
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The invention discloses a continuous production method for triethyl phosphite. The method comprises the steps that absolute ethyl alcohol and phosphorus trichloride are taken as reaction raw materials, dimethylaniline and o-dichlorobenzene are taken as reaction solvent, ammonia is introduced while reacting is performed, and after reacting is finished, a product is directly delivered into a continuous distillation column to be processed through reduced pressure distillation to obtain crude triethyl phosphite; the rest materials are delivered into a washing column to be washed by adding hot water and then layered, an organic layer is delivered into a distillation column to be processed through distillation dewatering to be recycled by serving as solvent, a water layer is delivered into a cooling kettle to be cooled, ammonium chloride solids are crystallized out, and mother liquor is continuously used for washing the rest materials of distillation. After the obtained triethyl phosphite is rectified through a rectifying column, the purity is 99.5%-99.9%, and the obtained ammonium chloride can serve as an ammonium fertilizer raw material. The continuous production method has the advantages that a decomposition reaction can be prevented from occurring in the process that the triethyl phosphite participates washing, dewatering can be achieved only by simply distilling the mother liquor, a salt column does not need to be introduced for dewatering, generation of secondary solid waste can be avoided, pollution to the environment is greatly reduced, the labor intensity is low, and the production cost is low.
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Paragraph 0036; 0037; 0038; 0039; 0040; 0041
(2016/10/31)
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- Method for preparing triethyl phosphite
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The invention discloses a method for preparing triethyl phosphate .The method comprises the following steps that phosphorus trichloride and absolute ethyl alcohol are adopted as raw materials, methylbenzene is adopted as a solvent, a synthetic reaction is carried out under the action of an acid absorbent, the product is subjected to filtering and vacuum distillation, and refined triethyl phosphate is obtained .Compared with the prior art, 90% or above of a byproduct hydrogen chloride can be removed under the micro-negative pressure condition, the product conversion rate is high, the quality is stable, the quantity of adopted acid absorbent can be reduced, cost can be reduced, recycled hydrogen chloride can be used for other fields, environmental pollution is reduced, and effective resources are reasonably reused; the method for preparing triethyl phosphate is simple, operate is convenient, productivity is high, and the obtained product is high in purity and yield.
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Paragraph 0043; 0044; 0045; 0046; 0047
(2017/01/26)
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- Synthesis of cyclopropane-containing phosphorus compounds by radical coupling of butenylindium with iodo phosphorus compounds
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The radical coupling of α- or β-iodo phosphorus compounds such as iodo phosphonate, iodo phosphane oxide, and iodo phosphonothioate with butenylindium species, prepared by transmetalation between a (cyclopropylmethyl)stannane and InBr3, afforded the corresponding cyclopropylmethylated products. The radical reaction was initiated by the radical species generated from butenylindium assisted by a small amount of oxygen. Butenylindium works not only as a cyclopropylmethylating reagent, but also as a radical initiator. For successful coupling, a tin/indium transmetalation was used, where it was important for the tin halide by-product to be inert to the reaction system. In addition, the transmetalation of a (cyclopropylmethyl)stannane and InBr3 provided the dibutenylindium bromide as a single product, which smoothly coupled with the unstable phosphonyl radical species from the iodo phosphorus compound. A photochemical method (UV irradiation) was also applied and accelerated the coupling reaction. The cyclopropylmethylated phosphonate produced was a good intermediate in the Horner-Wadsworth-Emmons reaction and gave functionalized olefins bearing the cyclopropane moiety. Copyright
- Kiyokawa, Kensuke,Suzuki, Itaru,Yasuda, Makoto,Baba, Akio
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supporting information; experimental part
p. 2163 - 2171
(2011/05/16)
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- Phosphorus halides complexes with 4-dimethylaminopyridine and N-methylimidazole
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Formation of complexes between phosphorus halides and 4- dimethylaminopyridine or N-methylimidazole was studied. The following phosphorus halides: trichloride, oxychloride, and sulfochloride, were found to form equilibrium mixtures of the complexes containing different numbers of the ligand molecules. Among the studied phosphorus halides only pentachloride and tribromide form stable complexes with a constant composition.
- Bezgubenko,Pipko,Sinitsa
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scheme or table
p. 911 - 918
(2011/04/15)
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- Synthesis of tervalent phosphorus esters in biphasic system using potassium phosphate as unique solid base
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The synthesis of tervalent phosphorus esters continues to be a significant area of interest, much of it again directed toward the synthesis of phosphite ligands for metal-catalyzed reactions. Typically, they were obtained through esterification of the corresponding phosphorus chlorides with the appropriate alcohols in the presence of an amine. In this paper, we present a new method for the synthesis of tervalent phosphorus esters, not yet mentioned in the literature, when potassium phosphate, as a unique base, is used in liquid-solid system. Symmetrical and unsymmetrical phosphites were obtained with good yields (65%-80%) using this method. The compounds were characterized by 31P NMR spectroscopy.
- Ilia, Gheorghe,Iliescu, Smaranda,Macarie, Lavinia,Popa, Adriana
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p. 360 - 364
(2008/09/20)
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- Selective synthesis of organophosphites
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Disclosed herein is a process for the selective synthesis of triorganophosphites intermediates, including chloridites and dichloridites, from PX3 (X=Cl, Br or I), alcoholos and triorganoamines where alcohol and triorganoamine are added either (a) separately and concurrently, or (b) alternating equimolar portions of amine and alcohol.
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- Reactions of N,N′-dialkylcyclohexane-1,2-diimines with trivalent phosphorus acid chlorides
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N,N′-Dialkylcyclohexane-1,2-diimines react with trivalent phosphorus acid chlorides to give, depending on the structure of the organophosphorus reagent and reaction conditions, either 1,3,2-diazaphospholanes (three-coordinate phosphorus) containing the cy
- Lodochnikov,Gryaznova,Gryaznov,Musin,Kibardin
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p. 437 - 442
(2007/10/03)
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- 11,12-cyclic phosphite or phosphate derivatives of erythromycin and related macrolides
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Disclosed are the antibacterial compounds having the formulas: STR1 or pharmaceutically acceptable salts and esters thereof. Also disclosed are the processes for preparing compounds of formulas (I), and II) of the invention, pharmaceutical compositions comprising a therapeutically effective amount of a compound of the invention in combination with a pharmaceutically acceptable carrier, as well as a method for treating bacterial infections by administering to a mammal a pharmaceutical composition containing a therapeutically-effective amount of a compound of the invention.
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- Preservation of the Coordination State of the Phosphorus Atoms in Tetraalkyl Pyrophosphites in Their Reaction with Tetraethylammonium Tetrafluoroborate
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Tetraalkyl pyrophosphites under mild conditions (in a polar aprotic solvent at 25-50°C or heating to 200°C without solvent) react with tetraethylammonium tetrafluoroborate to give an equimolar mixture of dialkyl phosphorofluoridite and dialkyl ethyl phosphite, i.e., both the pyrophosphite phosphorus atoms preserve their coordination number 3. A mechanism of the reaction is proposed.
- Romakhin,Nikitin
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p. 1580 - 1582
(2007/10/03)
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- Process for removal of allyl group or allyloxycarbonyl group
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This invention relates to a process for the removal of an allyl or allyloxycarbonyl group from an allyl or allyloxycarbonyl group protected compound (such as an allylic ester, carbonate, carbamate, O-allyl derivatives or N-allyl derivatives), which comprises contacting the allyl or allyloxycarbonyl group protected compound with a sulfinic acid compound, in the presence of a palladium catalyst in a reaction-inert solvent. Preferably, the sulfinic acid compound is represented by the formula: wherein X is C1-20 alkyl, substituted C1-20 alkyl (wherein the substituent(s) are independently halo, nitro, sulfo, oxo, amino, cyano, carboxy, hydroxy or moieties derived therefrom), phenyl, substituted phenyl (wherein the substituent(s) are independently C1-3 alkyl, halo nitro, sulfo, oxo, amino, cyano, carboxy, hydroxy, acetamido or moieties derived therefrom), furyl or thienyl; and M is hydrogen, an alkali metal or ammonium salt residue. Of these, most preferred sulfinic acid compound is lithium p-toluenesulfinate, sodium p-toluenesulfinate, potassium p-toluenesulfinate, p-toluenesulfinic acid, ammonium p-toluenesulfinate, lithium benzenesulfinate, sodium benzenesulfinate, potassium benzenesulfinate, benzenesulfinic acid or ammonium benzenesulfinate. This invention is well suited to a process for the conversion of an allyl ester of 5R,6S-6-(1R-hydroxyethyl)-2-(1R-oxo-3S-thiolanylthio)-2-penem-3-carboxylic acid to 5R,6S-6-(1R-hydroxyethyl)-2-(1R-oxo-3S-thiolanylthio)-2-penem-3-carboxylic acid.
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- Electrochemical Oxidation of Metal Dialkyl Phosphites and Their Reaction with Halogens
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Electrochemical oxidation of sodium dialkyl phosphites with alkyl radicals of normal structure leads to formation of tetraalkyl pyrophosphites as the main products, while electrochemical oxidation of litium dialkyl phosphites and sodium salts with branched alkyl radicals yields tetraalkyl hypophosphates. The reaction of metal dialkyl phosphites with halogens leads to analogous results.
- Romakhin,Zagumennov,Nikitin
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p. 1022 - 1026
(2007/10/03)
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- Simple and rapid determination of the activation parameters of organic reactions by temperature-dependent NMR spectroscopy II. Application to reversible reactions
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A non-isothermal (NIT) method for evaluating the activation enthalpies and entropies of reactions in solutions was applied to several reversible reactions. This was realized by a stepwise elevation of the temperature of a reaction system using a variable-temperature apparatus comprising on NMR spectrometer and a quick collection of FID (free induction decay) at every plateau of the step. The rate from NIT experiments agreed well with the previously measured rates by the conventional methods.
- Satoh, Masahiro,Hirota, Minoru
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p. 2619 - 2624
(2007/10/03)
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- Cosmetic and dermatological compositions for the protection against UV radiation containing stilbene derivatives
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Stilbene derivatives of formula (I) STR1 wherein A, R1 and R2 are as defined in the following, are useful for the protection against UV radiation.
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- Reaction of Phosphorus Acid Chlorides with Symmetric and Unsymmetric Azines
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The reaction of unsymmetric benzaldehyde isopropylidene- and isobutylidenehydrazones with o-phenylene phosphorochloridite proceeds with initial symmetrization of the azines and subsequent pyrazoline condensation of symmetric aliphatic azines with phosphorus chloride. Acetone azine reacts with diethyl chlorophosphate in the presence of triethyl phosphite, affording diethyl[1-methyl-1-(isopropylidenehydrazino)ethyl]phosphonate and l-(diethoxyphosphinoyl)-3,3,5-trimethyl-Δ2-pyrazoline. From the similar reaction with diethyl phosphorochloridite only diethyl 1-methyl-1-(isopropylidenehydrazino)ethylphosphonate was isolated.
- Gryaznov,Kurochkina,Musin,Pudovik,Kibardin
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p. 372 - 374
(2007/10/03)
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- Chemical Properties of 1,3,2-Diazaphospholines
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Δ4-1,3,2-Diazaphospholines exhibit properties typical of trivalent phosphorus derivatives: They take up sulfur, enter the Arbuzov, Perkow, and Staudinger reactions. On the other hand, these compounds show a number of peculiar features.
- Kibardin,Gryaznova,Pudovik
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p. 365 - 371
(2007/10/03)
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- Syntheses, Structures, and Reactivity of 1-Phosphanylnaphth-2-ols
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P-tertiary or amino-substituted 1-phosphanylnaphth-2-yl silyl ethers 3 are synthesized by stepwise reaction of lithium 1-lithio-2-naphtholate 1 with chlorophosphanes and ClSiMe3.The free phosphanylnaphthols 4 are prepared by alcoholysis.As established by characteristic coupling constants and X-ray structural analyses (of 3c, 4c), 3 exhibit in solution and in the solid state a cis-bisecting conformation, whereas 4 prefers the opposite trans-bisecting arrangement, allowing easy protonation and formation of chelate complexes.Substitution reactions of phosphanylnaphtholates 2 with Ph2PCl and formation of chelate complexes LNi-η5-Cp and L2Pd are described.Attempts to prepare secondary and primary phosphanylnaphthols failed because of facile cleavage of the P-C(naphthyl) bond in PH-substituted 1-phosphanyl-naphth-2-ols. - Keywords: Phosphanylnaphthol; PO ligands; Chelate complexes
- Heinicke, Joachim,Kadyrov, Renat,Kindermann, Markus K.,Kloss, Matthias,Fischer, Axel,Jones, Peter G.
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p. 1061 - 1072
(2007/10/03)
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- Phosphitylation via the Mitsunobu reaction
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Treatment of a dialkyl phosphite with triphenylphosphine and diisopropyl azodicarboxylate in toluene, followed by addition of an alcohol, results in the formation of the corresponding trialkyl phosphite. Similarly, dialkyl phosphonites can be synthesised from monoalkyl phosphites (alkyl phosphinates).
- Grice, I. Darren,Harvey, Peta J.,Jenkins, Ian D.,Gallagher, Michael J.,Ranasinghe, Millagahamada G.
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p. 1087 - 1090
(2007/10/03)
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- Process for removal of allyl group or allyloxycarbonyl group
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This invention relates to a process for the removal of an allyl or allyloxycarbonyl group from an allyl or allyloxycarbonyl group protected compound (such as an allylic ester, carbonate, carbamate, O-allyl derivatives or N-allyl derivatives), which comprises contacting the allyl or allyloxycarbonyl group protected compound with a sulfinic acid compound, in the presence of a palladium catalyst in a reaction-inert solvent. Preferably, the sulfinic acid compound is represented by the formula: X-SO2M (I)wherein X is C1 20 alkyl, substituted C1 20 alkyl (wherein the substituent(s) are independently halo, nitro, sulfo, oxo, amino, cyano, carboxy, hydroxy or moieties derived therefrom), phenyl, substituted phenyl (wherein the substituent(s) are independently C1 3 alkyl, halo nitro, sulfo, oxo, amino, cyano, carboxy, hydroxy, acetamido or moieties derived therefrom), furyl or thienyl; and M is hydrogen, an alkali metal or ammonium salt residue. Of these, most preferred sulfinic acid compound is lithium p-toluenesulfinate, sodium p-toluenesulfinate, potassium p-toluenesulfinate, p-toluenesulfinic acid, ammonium p-toluenesulfinate, lithium benzenesulfinate, sodium benzenesulfinate, potassium benzenesulfinate, benzenesulfinic acid or ammonium benzenesulfinate. This invention is well suited to a process for the conversion of an allyl ester of 5R,6S-6-(1R-hydroxyethyl)-2-(1R-oxo-3S-thiolanylthio)-2-penem-3-carboxylic acid to 5R,6S-6-(1R-hydroxyethyl)-2-(1R-oxo-3S-thiolanylthio)-2-penem-3-carboxylic acid.
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- Cosmetic and dermatological compositions for the protection against UV radiation containing stilbene derivatives
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Stilbene derivatives of formula (I) wherein A, R1 and R2 are as defined in the following, are useful for the protection against UV radiation.
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- Photochromism of Fulgides and Stereoelectronic Factors: Synthesis of (E)-4(3)-Adamantylidene-(5)-dicyanomethylene-3(4)-tetrahydrofuran-2-one 4 and 4a and (E)-4-adamantylidene-3-tetrahydrofuran-2,5-...
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In the search for fulgides with potential semiconductor laser compatibitity, 4-adamantylidene-5-dicyanomethylene-3-tetrahydrofuran-2-one (4), along with its regioisomer 4a, have been synthesized from the corresponding fulgide 6 containing a succinic anhydride ring by reaction with malononitrile in the presence of diethylamine.Upon irradiation with a uv light at λmax 350 nm, a mixture of 4 and 4a revealed a considerably enhanced bathochromic shift to the visible region , λmax 605 nm as compared with the starting fulgide 6 which, upon analogous uv irradiation, absorbed at λmax 515 nm.In the search for semiconductor-laser-compatible fulgides with increased efficiency for the reverse bleaching reaction, another fulgide (E)-4-adamantylidene-3-tetrahydrofuran-2,5-dione (10) was synthesized in seven steps starting from 2-bromo-m-xylene.However, 10 failed to undergo electrocyclic ring-closure upon irradiation with a uv light at λmax 350 nm.The analogous fulgide 8, which contains an isopropylidene functionality in place of the adamantyl group of 10, was resynthesized for comparison, and showed two absorption maxima, one at 545 nm and the other at 620 nm.The missing physico-chemical data for 8 have also been provided.
- Sun, Zhiyuan,Hosmane, Ramachandra S.,Tadros, Maher,Guha, Shekhar,Chen, Wenpeng,Chen, Jar-Mo
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p. 1819 - 1828
(2007/10/03)
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- [(SUBSTITUTED) PHENYALKYL]FURYLALKYNYL-AND [SUBSTITUTED)PHENYALKYL]THIENYLALKYNYL-N-HYDROXYUREA INHIBITORS OR LEUKOTRIENE BIOSYNTHESIS
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The present invention relates to compounds of the formula and the pharmaceutically acceptable salts thereof wherein Z is selected from optionally substituted phenyl, furyl, thienyl or thiazolyl; which inhibits leukotriene biosynthesis and is useful in the treatment of inflammatory disease states; also disclosed are leukotriene biosynthesis inhibiting compositions and a method for inhibiting 5-lipoxygenase activity and leukotriene biosynthesis
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- REACTION OF TRIETHYLALUMINUM WITH SECONDARY PHOSPHITES
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The reaction of triethylaluminum with secondary esters of phosphorous acid (diethyl phosphite, diphenyl phosphite, and neopentylene phosphite) has been considered.In all cases phosphoryl complexes are formed at first.These complexes may then undergo transformations determined by the nature of the phosphite taken- the transformation of the hydrophosphoryl group, or the nucleophilic replacement of organoxyl groups on the phosphorus atom.An analysis of the transformations observed was carried out in terms of stereoelectronic concepts.
- Nifant'ev, E. E.,Chechegova, E. V.,Trofimtsova, I. A.,Chekulaeva, L. A.,Gavrilenko, V. V.,Ruchkina, N. G.
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p. 541 - 546
(2007/10/02)
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- OXIDATIVE ALKOXYLATION OF PHOSPHINE IN ALCOHOLIC SOLUTIONS OF PLATINUM(IV) HALIDE COMPLEXES
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Platinum(IV) halide complexes are shown for the first time to undergo fast reduction in alcohols (MeOH, EtOH, PrOH, BuOH, and i-AmOH) at 298-323 K under the action of PH3 to Pt(II)halide complexes with the highly selective formation of the corresponding trialkyl phosphites.The products of O-phosphorylation of the alcohols are studied by GLC and 31P NMR and IR spectroscopy.The intermediate compounds were studied by x-ray microanalyses and x-ray photoelectron and UV spectroscopy.The reaction is promoted by Pt(II) compounds and retarded by H2O and acids.The complex Pt(IV) chlorides are reduced more slowly than the mixed chloride bromide and especially chloride complexes.The kinetics and mechanism of this new reaction are discussed.
- Dorfman, Ya. A.,Levina, L. V.,Aibasov, E. Zh.
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p. 1847 - 1859
(2007/10/02)
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- PHOSPHORYLATED ALKOXYACETYLENES. VIII. SYNTHESIS AND PROPERTIES OF (ALKOXYETHYNYL)PHOSPHONITES
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(Alkoxyethynyl)phosphonites, which have not been known previously, are stable only in solution, are capable of undergoing isomerization into (carbonylmethylene)phosphoranes, readily disproportionate with the formation of trialkyl phosphites, and take up nucleophilic reagents at the triple bond.
- Lukashev, N. V.,Fil'chikov, A. A.,Kozlov, A. I.,Luzikow, Yu. N.,Kazankova, M. A.
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p. 1600 - 1603
(2007/10/02)
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- Unsaturated amino acids
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The invention relates to unsaturated amino acids of the formula I STR1 in which R1 represents hydroxy or etherified hydroxy, R2 represents hydrogen, alkyl, hydroxy or etherified hydroxy, R3 represents hydrogen, alkyl, haloalkyl, hydroxyalkyl, lower alkoxyalkyl, arylalkyl, lower alkenyl, halogen or aryl, R4 represents hydrogen, alkyl or aryl, R5 represents hydrogen or alkyl, R6 represents carboxy or esterified or amidated carboxy, R7 represents amino or amino substituted by alkyl or acyl, A represents unsubstituted or alkyl-substituted α,ω-alkylene having from 1 to 3 carbon atoms or represents a bond, and B represents methylene or a bond, with the proviso that A is other than a bond when B represents a bond, and salts thereof. They can be manufactured, for example, in accordance with the Michaelis-Arbuzov reaction and can be used as pharmacologically active substances.
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- Studies on the Activation Pathway of Phosphonic acid using Acyl Chlorides as Activators
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The activation pathway of phosphonic acid with acyl chlorides has been investigated with the aim of evaluating the synthetic utility of the intermediates involved for the preparation of hydrogen-phosphonate (H-phosphonate) monoesters.It is found that, depending on the amount of condensing reagent used, three distinctive intermediates are potentially formed, namely the pyrophosphonate (2), the phosphono-acyl mixed anhydride (3a), and the triacyl phosphite (4a).Their chemical reactivities towards oxygen nucleophiles indicate that the most suitable intermediate for H-phosphonate monoester synthesis is the pyrophosphonate (2).
- Stawinski, Jacek,Thelin, Mats
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p. 849 - 853
(2007/10/02)
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- Deoxyribonucleoside Phosphorodithioates. Preparation of Dinucleoside Phosphorodithioates from Nucleoside Thiophosphoramidites
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A series of protected thymidine thiophosphoramidites have been prepared and their properties evaluated.Although less reactive than phosphoramidites, thiophosphoramidites with small N-substituents (methyl) are useful synthons for the preparation of nucleoside phosphorodithioates, as demonstrated by the preparation of a thymidine dimer.The coupling reactions are not as clean as those of the analogous phosphoramidites since the alkylthio group is somewhat labile.
- Dahl, Bjarne H.,Bjergarde, Kirsten,Sommer, Vibeke B.,Dahl, Otto
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p. 896 - 901
(2007/10/02)
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- Reactions of η2-Acyl Ligands in Tp'(CO)2Mo2-C(O)R> Complexes To Form Complexed Enolates and Enones, Allyls, and Alkyne Insertion Products
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Elaboration of the η2-acyl ligand in hydridotris(3,5-dimethylpyrazolyl)borate (Tp') complexes of the type Tp'(CO)2Mo2-C(O)R> (R=Me, Et) has been accomplished by deprotonation to form enolates which react with electrophiles such as MeI, PhCH2Br, and PhCHO.Two enolate complexes, K and K, have been characterized by NMR spectroscopy.Photolysis of an acetonitrile solution of the achiral dicarbonyl reagent, Tp'(CO)2Mo2-C(O)R>, followed by addition of triphenyl phosphite forms racemic Tp'(CO)Mo.Excellent diastereoselectivity characterizes the addition of benzyl bromide (BzBr) to the enolate of Tp'(CO)Mo2-C(O)CH2CH3>; the Tp'(CO)Mo(η2-C(O)CHMeBz) product has been structurally characterized.Condensation of enolate complexes with benzaldehyde or benzophenone produces unsaturated η2-enone complexes.The structure of Tp'(CO)2Mo2-C(O)CH=CPh2> is reported.The η2-enone complexes undergo conjugate addition reactions to form saturated η2-acyl products, e.g., nucleophilic addition of MeLi to Tp'(CO)2Mo(η2-C(O)CH=CHPh) followed by acidification yields Tp'(CO)2Mo2-C(O)CH2CHMePh>.Heating Tp'(CO)2Mo(η2-C(O)CMe=CHPh) in toluene yields a ?-allyl complex, Tp'(CO)2Mo(η3-CH2CHCHPh).Insertion of alkynes (RCCR, R = Et or Ph) into the metal-carbon bond of the η2-acyl ligand in Tp'(CO)(CH3CN)Mo(η2-C(O)Et) under carbon monoxide forms oxametallacycles of the Tp'(CO)2Mo(CRCRC(O)Et) (R = Et or Ph).The structure of Tp'(CO)2Mo(CEtCEt(O)Et) has been determined.
- Rusik, C.A.,Collins, M.A.,Gamble, A.S.,Tonker, T.L.,Templeton, J.L.
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p. 2550 - 2560
(2007/10/02)
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- Anomalous Michaelis-Becker Reaction: 1-Phenylethan-1,2,2-triphosphonic Acid and their Esters
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Sodium dialkylphosphite reacts with trichlorovinylbenzene to yield in an one-batch procedure 1-phenyl-1,2,2-ethanetriphosphonic acid hexaalkyl esters.A carbanionic intermediate of an "anomalous Michaelis-Becker reaction" is deduced.Acidolysis of esters leads to the parent triphosphonic acids.NMR parameters of this acid are strongly influenced by protolytic equilibrium. - Key words: One-batch synthesis, Oligophosphonic Acid, NMR Spectra
- Fischer, Ulrich,Haegele, Gerhard
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p. 1152 - 1156
(2007/10/02)
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- Herbicidally active 2-substituted 5-phenoxyphenylphosphonic acid esters
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The present invention relates to novel herbicidal and plant growth-inhibiting 2-substituted 5-phenoxyphenylphosphonic acid derivatives of the formula STR1 wherein each of R1 and R2 independently is hydroxyl, lower alkoxy, lower alkylthio, alkylamino, dialkylamino, chlorine, benzyloxy or benzylthio, X is halogen or a --CF3, --NO2, --CN, --CONH2 or --CSNH2 group, n is 0 to 3, and Y is --OH, halogen, NO2, --CN, NH2, --NHCO--R, --NHCOOR or --NH--SO2 --R, wherein R is an unsubstituted or halogenated lower alkyl radical. Preferred compounds are 2-nitro-5-(2'-chloro-4'-trifluoromethylphenoxy)-phenylphosphonic acid and the lower dialkyl esters thereof. The invention also relates to the production of the novel phosphonic acid derivatives, starting from a 3,4-dinitrodiphenyl ether and reacting it with a trialkylphosphite as first step. The invention further relates to herbicidal and plant growth-regulating compositions which contain one of the novel compounds as active component, and also to the use of these compounds and compositions for controlling weeds (also selectively), for inhibiting plant growth and desiccating parts of plants above the soil, as well as for totally destroying existing plant growth.
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