- Reactions of Ferrocenium Hexafluorophosphate with P?OR Nucleophiles Give Ring C?H Functionalization or Ring Replacement Products Depending on the Phosphorus Reagent
-
Ferrocenium hexafluorophosphate reacts with different P?OR nucleophiles (PR3) in CH2Cl2 at room temperature to give either half-sandwich complexes [CpFe(PR3)3](PF6) (PR3=P(OMe)3, P(OEt)3, PhP(OMe)2) or ferrocenylphosphonium salts [CpFe(C5H4PR3)](PF6) (PR3=iPr2P(OMe), iPr2P(OEt)). Mixtures of both products are formed for some other nucleophiles (PR3=Ph2P(OMe), Ph2P(OEt), PhP(OiPr)2). The mechanism of the former reaction was established using DFT calculations. This reaction pathway is especially characteristic of π-acceptor nucleophiles, which is presumably explained by their ability to stabilize the 19e intermediates. The result of the reaction with tertiary phosphines, aminophosphines, and P?OR nucleophiles can be reliably predicted based on the values of the Tolman electronic parameter (below 2070 cm?1 – only ferrocenylphosphonium salt, in between 2073 cm?1 and 2080 cm?1 – only half-sandwich complex, and in the range from 2070 cm?1 to 2073 cm?1 – mixtures of both products).
- Chamkin, Aleksandr A.,Krivykh, Vasily V.,Kreindlin, Arkady Z.,Dolgushin, Fedor M.,Ustynyuk, Nikolai A.
-
p. 1601 - 1610
(2021/04/16)
-
- Monoacylphosphine oxides with substituents in the phosphonyl moiety as Norrish I photoinitiators: Synthesis, photoinitiattion properties and mechanism
-
In order to study the effect of the substituents in the phosphonyl moiety of monoacylphosphine oxide (MAPO) on its stability and initiation performance, (2,4,6-trimethylphenyl)(phenyl)(benzoyl)phosphine oxide (TMBPO), (4-tolyl)(phenyl)(2,4,6-trimethylbenzoyl)phosphine oxide (4-MTPO) and (2,4-xylyl)(phenyl)(2,4,6-trimethylbenzoyl)phosphine oxide (2,4-DMTPO) were designed and prepared. Studies on TMBPO showed that the introduction of methyl groups into the phosphonyl moiety of MAPO significantly enhanced its stability and light absorption abilities. The photopolymerization of trimethylolpropane triacrylate (TMPTA) showed that the initiation efficiency of 4-MTPO and 2,4-DMTPO were higher than that of TPO, regardless of whether it was initiated upon LED at 385 nm or 420 nm. In addition, the migration rates of 4-MTPO and 2,4-DMTPO in cured TMPTA were approximately 1/2 and 1/4 that of TPO, respectively.
- Duan, Haodong,Gao, Jun,Han, Yuxi,Leng, Kangwei,Li, Qianmin,Liu, Dayong,Wang, Zhongwei,Xu, Xiaolei,Yu, Qing
-
-
- Silver-Catalyzed Regioselective Phosphorylation of para-Quinone Methides with P(III)-Nucleophiles
-
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
-
p. 14983 - 15003
(2021/11/12)
-
- Preparation method of material compound
-
The invention provides a preparation method of a diarylphosphonate compound, which comprises the following steps: in a protective gas atmosphere, taking diarylphosphonic acid and halogenated alkane as raw materials, taking heteropoly acid as a catalyst and taking an organic solvent as a solvent, and conducting reacting to obtain the diarylphosphonate compound. According to the preparation method disclosed by the invention, only an extremely small amount of catalyst is needed, the reaction temperature is relatively mild, the reaction time can be obviously shortened, the yield and purity are relatively high, and an unexpected technical effect is achieved.
- -
-
Paragraph 0050-0055; 0064-0065
(2021/04/10)
-
- Synthesis method of diphenyl hypophosphite
-
The invention discloses a synthesis method of diphenyl hypophosphite, which belongs to the technical field of organic synthesis. The method comprises: by adopting N-methylimidazole as an acid-bindingagent, carrying out a reaction on diphenyl phosphorus chloride and an alcohol to obtain diphenyl hypophosphite and N-methylimidazole hydrochloride, carrying out standing and layering to remove the N-methylimidazole hydrochloride, and rectifying to obtain a finished product. The synthesis process does not need to add any solvent, is safe and environment-friendly, can remove the N-methylimidazole hydrochloride through layering, is simple to operate, mild in reaction condition, simple in wastewater and waste gas treatment, and easy to realize industrialization.
- -
-
Paragraph 0033-0040
(2020/10/04)
-
- New preparation method of first-class phenyl phosphine oxide initiator
-
The invention provides a new preparation method of a first-class phenyl phosphine oxide initiator. The method comprises the steps that (1) benzene and aluminum trichloride are added into a reaction vessel and stirred uniformly, then phosphorus trichloride is added, the temperature is slowly increased, and after a complete reaction, the temperature is reduced to room temperature; (2) a reaction mixture obtained in the step (1) is slowly added dropwise into a solvent containing a decomplexing agent, and the temperature is controlled for decomplexing; (3) a decomplexing product obtained in the step (2) is filtered to separate solids, and filtrate is subjected to pressure reduction distillation to obtain phenyl dialkoxy phosphine or diphenyl alkoxy phosphine; (4) a product obtained in the step(3) is dissolved in a benzene or methylbenzene solvent, and a trichloromethyl acetyl compound is added dropwise for a reaction; and (5) a solution obtained after the complete reaction in the step (4)is subjected to low-pressure desolvation, and light-yellow liquid or solid, namely the phenyl phosphine oxide initiator, is obtained through crystallization, suction filtering and drying. The methodhas the advantages that raw materials are easy to obtain, cost is low, operation is easy to perform, and mass production can be realized.
- -
-
Paragraph 0041-0043
(2020/03/05)
-
- Adaptive Behavior of a Ditopic Phosphine Ligand
-
Synthetic, structural and computational studies have been performed to investigate ligand interchange in the fluxional chelate complex [RhCl3{Ph2PACH2C(OA)OEt-κ2POA}{Ph2PBCH2C(OB)OEt-κP}], which contains two hybrid phosphine-ester ligands, one acting as P,O chelator, the other as a P-monodentate ligand. The observed ligand exchange may occur according to two pathways which both involve four elementary movements: a) oxygen dissociation with formation of a lacunary octahedral RhCl3P2 intermediate; b) migration of the Cl atom trans to PA towards the position trans to PB; c) rotations of the phosphine moieties about the Rh–P bonds, these occurring either concomitantly with the Cl displacement or in a separate step; d) coordination of an oxygen atom of the second phosphine. The two pathways thus differ by conformational changes within two distinct steps. In each pathway the rate-limiting step is the one involving a movement of the two phosphines, which generates steric frictions between the two PPh2 groups. The calculated theoretical energetic spans of both pathways (ΔG≠ ≈ 17 kcal mol–1) is close to the energy barrier obtained from a variable temperature NMR study carried out in C2D2Cl4 (ΔG≠ = 15.5 kcal mol–1). While one of the pathways leads to an isomer with a Rh-bound ethoxy O atom, the other results in the isomer having the metal coordinated to the adjacent C=O group. Exchange between the two O atoms of the coordinated ester group occurs readily (ΔGTS = 12.5 kcal mol–1).
- Renard, Nicolas,Brenner, Eric,Matt, Dominique,Gourlaouen, Christophe
-
p. 2996 - 3004
(2019/07/05)
-
- Palladium-Catalyzed Stereoselective Cyclization of in Situ Formed Allenyl Hemiacetals: Synthesis of Rosuvastatin and Pitavastatin
-
A diastereoselective palladium-catalyzed cyclization of allenyl hemiacetals is described. It permits the selective synthesis of 1,3-dioxane derivatives, precursors for syn-configured 1,3-diols which make an appearance in all of the statin representatives. The reaction allows the total synthesis of Rosuvastatin and Pitavastatin in a straightforward fashion.
- Spreider, Pierre A.,Breit, Bernhard
-
supporting information
p. 3286 - 3290
(2018/06/11)
-
- Exploring the Reactivity of Donor-Stabilized Phosphenium Cations: Lewis Acid-Catalyzed Reduction of Chlorophosphanes by Silanes
-
Phosphane-stabilized phosphenium cations react with silanes to effect either reduction to primary or secondary phosphanes, or formation of P-P bonded species depending upon counteranion. This operates for in situ generated phosphenium cations, allowing catalytic reduction of P(III)-Cl bonds in the absence of strong reducing agents. Anion and substituent dependence studies have allowed insight into the competing mechanisms involved.
- Pearce, Kyle G.,Borys, Andryj M.,Clark, Ewan R.,Shepherd, Helena J.
-
supporting information
p. 11530 - 11536
(2018/09/21)
-
- Chemoselective reduction of the phosphoryl bond of O-alkyl phosphinates and related compounds: An apparently impossible transformation
-
A method is reported for the phosphoryl bond cleavage of O-alkyl phosphinates, phosphinothioates and certain phosphonamidates to furnish the corresponding P(iii) borane adducts. The two-step procedure relies upon initial activation of the phosphoryl bond with an alkyl triflate, followed by reduction of the resulting intermediate using lithium borohydride.
- Kenny, Niall P.,Rajendran, Kamalraj V.,Gilheany, Declan G.
-
supporting information
p. 16561 - 16564
(2015/11/18)
-
- Revisited synthesis of aryl-H-phosphinates
-
A systematic study of the reaction conditions for the preparation of pure aryl-H-phosphinate esters, originally developed by Sander and optimized by Petnehazy, is reported. The influence of the reaction concentration has been investigated for the formation of phosphonite intermediates via direct addition of triethyl phosphite to the appropriate Grignard reagent. Subsequent hydrolysis of the phosphonites under acidic conditions gives various aryl-H-phosphinates in high yields and purities. Georg Thieme Verlag Stuttgart, New York.
- Volle, Jean-Noel,Filippini, Damien,Midrier, Camille,Sobecki, Michal,Drag, Marcin,Virieux, David,Pirat, Jean-Luc
-
body text
p. 2490 - 2494
(2011/09/20)
-
- Advantages of organophosphorus synthesis in ionic liquids: "Green" approaches to useful phosphorus-substituted building blocks
-
Novel examples concerning the application of ionic liquids as a promoting reaction media in organophosphorus chemistry are discussed. Imidazolium ionic liquids were found to accelerate the Michaelis-Arbuzov reaction allowing to perform it under very mild conditions. Both phosphonium and imidazolium ILs give the possibility to perform easily direct amidation of phosphoryl acetic acids by various amines. Nucleophilic displacement reactionin a series of bromoalkylphosphonates was carried out in quantitative yield to afford azidoalkylphosphonates using the [bmim][PF6]/H2O system. Copyright Taylor & Francis Group, LLC.
- Odinets,Matveeva,Sharova,Artyushin,Kozlov,Vorob'eva,Osipov,Roeschenthaler
-
scheme or table
p. 383 - 388
(2009/04/04)
-
- Structural studies of PdCl2L2 complexes with fluorinated phosphines, phosphites, and phosphinites as precursors of benzyl bromide carbonylation catalysts, and and X-ray crystal structure of cis-PdCl2[PPh2 (OEt)]2
-
PdCl2L2-type complexes with phosphines (L = PPhx(C6F5)3-x (x = 0-3)), phosphites (L = P(OMe)3, P(OPh)3, P(OEt)3), and phosphinites (L = PPh2 (OC6F5), PPh2(O-3,5-F2 C6H3), PPh2(OEt), PPh2 (O-n-Bu), PPh2(O-t-Bu)) were synthesized and characterized by UV-vis and 31P NMR methods. PdCl2L2 complexes with less sterically demanding phosphines (Θ 2[PPh2(OEt)]2. These complexes react with CO in the presence of NEt3 forming Pd(CO)xLy (x + y = 4) type carbonyls characterized by IR spectra. All PdCl2L2 complexes studied are active as precursors of benzyl bromide carbonylation catalysts at 40°C and 1 atm CO; however, the activity of the cis isomers is higher than that of the trans isomers. The highest yields of the carbonylation product, phenylacetic acid methyl ester, were obtained using cis-PdCl2[P(OMe)3]2 (92%), cis-PdCl2[P(OPh)3]2 (89%), and cis-PdCl2[PPh2(O-n-Bu)]2 (78%) as catalyst precursors.
- Trzeciak,Bartosz-Bechowski,Ciunik,Niesyty,Ziolkowski
-
p. 752 - 759
(2007/10/03)
-
- Alkyl arylphosphinites
-
A process for the preparation of alkyl arylphosphinites of the formula (I) STR1 in which R1 is (C1 -C16)-alkyl, cyclohexyl, cyclopentyl, aryl which can also be substituted by halogen, (C1 -C6)-alkoxy groups R2 is aryl which can also be substituted by halogen, (C1 -C6)-alkyl, (C1 -C6)-alkoxy groups, where R1 and R2 together with the phosphorous atom can also form a ring and R3 is (C1 -C4)-alkyl, which comprises reacting halo(aryl) phosphines of the formula (II) STR2 in which R1, R2 have the meaning given above and X is halogen, with ammonia-containing alcohols of the formula (III) in which R3 has the meaning given above.
- -
-
-
- Selective conversion of acrylonitrile into 1,4-dicyano-1-butene catalyzed by polymer-bound alkyl diarylphosphinites
-
Selective conversion of acrylonitrile into 1,4-dicyano-1-butene by contacting a liquid phase comprising acrylonitrile with an effective amount of a polymer-bound alkyl diarylphosphinite catalyst having the formula I: STR1 wherein the trivalent phosphorus is substituted by one alkoxy group and one aryl group and wherein the third bond of phosphorus is a P--C bond to a pendant aryl group of the polymer matrix, such as polystyrene cross-linked with divinylbenzene is disclosed. Treatment of the liquid phase, prior to contacting same with the polymer-bound catalyst, with a drying agent comprising a polymer-bound dialkyl arylphosphonite and regeneration of the drying agent are also disclosed.
- -
-
-
- PENTACO-ORDINATE PHOSPHORUS COMPOUNDS BY NUCLEOPHILIC ADDITION TO ACTIVATED ALKENES AND ALKYNES IN THE PRESENCE OF ALCOHOLS AND PHENOLS
-
The reactions of a variety of trico-ordinate phosphorus compounds, ArnP(OR)3-n (n= 1 or 2), and cyclic analogues, with acrylonitrile, ethyl acrylate or ethyl phenylpropiolate and alcohols or phenols in low polarity media gives rise to a wide range of pentaco-ordinate phosphorus compounds.Attempts to extend this synthetic route to phosphoranes containing P-N or P-S bonds met with no success.
- Beer, Paul D.,Edwards, Robert C.,Hall, C. Dennis,Jennings, J. R.,Cozens, R. J.
-
p. 283 - 296
(2007/10/02)
-
