- Long sought synthesis of quaternary phosphonium salts from phosphine oxides: Inverse reactivity approach
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Quaternary phosphonium salts (QPS), a key class of organophosphorus compounds, have previously only been available by routes involving nucleophilic phosphorus. We report the realisation of the opposite approach to QPS utilising phosphine oxides as the electrophilic partner and Grignard reagents as nucleophiles. The process is enabled through the crucial intermediacy of the derived halophosphonium salts. The route does not suffer from the slow kinetics and limited availability of many parent phosphines and a broad range of QPS were prepared in excellent yields.
- Vetter, Anna C.,Nikitin, Kirill,Gilheany, Declan G.
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- METALLORGANISCHE VERBINDUNGEN DER LANTHANOIDE. X. BIS(η5-CYCLOPENTADIENYL)CHLOROLUTETINYLMETHYLENTRIPHENYLPHOSPHORAN: EIN ZWITTERIONISCHES METALLORGANYL DER LANTHANOIDENREIHE
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Bis(η5-cyclopentadienyl)chlorolutetium reacts with methylenetriphenylphosphorane yielding a stable 1/1 complex, which was proved to be a zwitterionic organometallic compound having a Lu-CH2 ?-bond by NMR spectroscopy.
- Schumann, Herbert,Reier, Friedrich Wilhelm
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- Exploring an Umpolung strategy for quaternization of phosphorus
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We propose a new, potentially widely-applicable, Umpolung approach for the synthesis of quaternary phosphonium salts R3PR1 X (X = Cl, Br) from phosphine oxides R3PO. The new organic group R1 is introduced via nucleophilic attack on an intermediate halophosphonium salt using a Grignard reagent R1MgX and replaces the traditional phosphine quaternization approach. Consequently, the new method does not suffer from the limited availability of many parent phosphines and is much faster than standard quaternization.
- Vetter, Anna C.,Nikitin, Kirill,Gilheany, Declan G.
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- Unveiling Extreme Photoreduction Potentials of Donor-Acceptor Cyanoarenes to Access Aryl Radicals from Aryl Chlorides
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Since the seminal work of Zhang in 2016, donor-acceptor cyanoarene-based fluorophores, such as 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN), have been widely applied in photoredox catalysis and used as excellent metal-free alternatives to noble metal Ir- and Ru-based photocatalysts. However, all the reported photoredox reactions involving this chromophore family are based on harnessing the energy from a single visible light photon, with a limited range of redox potentials from -1.92 to +1.79 V vs SCE. Here, we document the unprecedented discovery that this family of fluorophores can undergo consecutive photoinduced electron transfer (ConPET) to achieve very high reduction potentials. One of the newly synthesized catalysts, 2,4,5-tri(9H-carbazol-9-yl)-6-(ethyl(phenyl)amino)isophthalonitrile (3CzEPAIPN), possesses a long-lived (12.95 ns) excited radical anion form, 3CzEPAIPN?-*, which can be used to activate reductively recalcitrant aryl chlorides (Ered ≈ -1.9 to -2.9 V vs SCE) under mild conditions. The resultant aryl radicals can be engaged in synthetically valuable aromatic C-B, C-P, and C-C bond formation to furnish arylboronates, arylphosphonium salts, arylphosphonates, and spirocyclic cyclohexadienes.
- Cao, Jilei,Tang, Xinxin,Toh, Ren Wei,Wang, Han,Wu, Jie,Wu, Xiangyang,Xu, Jinhui,Yang, Xiaona,Yeow, Edwin K. L.,Zhou, Rong
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supporting information
p. 13266 - 13273
(2021/09/07)
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- Practical synthesis of phosphonium salts with orthoformates and their application as flame retardants in polycarbonate
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An efficient and practical approach to phosphonium salts has been developed. By the reaction of phosphines and different acid sources with orthoformates in one-step operation, the process allowed rapid access to phosphonium salts with diverse counterions in high yield after the purification by recrystallization. The flame retardant performance in PC has also been examined by blending several phosphonium salts to PC respectively. Phosphonium phosphates showed excellent flame retardancy in PC with only 2 phr blending.
- Jiang, Pingkai,Li, Tao,Xu, Chencong,Zhang, Yong Jian
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- Quaternary phosphonium salt flame retardant and synthesis method and application thereof
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The invention provides a quaternary phosphonium salt flame retardant and a synthesis method and application thereof, and the method comprises the following steps: by taking an acidic compound, ortho-formic acid trisubstituted ester and an organic phosphine compound III or IV as raw materials, carrying out a one-step reaction process to prepare the quaternary phosphonium salt flame retardant I or II. The flame retardant disclosed by the invention has good thermal stability and has an excellent flame-retardant effect when being applied to various polymers. The method is simple and convenient insynthesis operation, low in raw material price, mild in synthesis condition and high in yield. According to the synthesis method, introduction of halogen ions is avoided, and dozens of anions are successfully introduced. By adding a small amount of the flame retardant, the obtained PC flame-retardant composite material UL-94 can reach the V-0 grade.
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Paragraph 0210-0214
(2020/06/20)
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- A three phenyl methyl chloride [...] method for the preparation of
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The invention discloses a preparation method of triphenylmethylphosphonium chloride. The triphenylmethylphosphonium chloride is prepared by using methanol as a solvent and triphenylphosphonium and methyl chloride as reactants. The reaction formula is as follows: (C6H5)3P+CH3Cl-->(C6H5)3CH3PCl. In the formula, the mol ratio of the triphenylphosphonium to the methyl chloride is 1:1-1:2. After the reaction, the process of reflux, distillation and recrystallization is carried out. By controlling the time, temperature, pressure and reactant mol ratio in the reaction process and carrying out the process of reflux, distillation and recrystallization after the reaction, the invention enhances the yield of the product triphenylmethylphosphonium chloride, and the product triphenylmethylphosphonium chloride has the advantages of fewer impurities and high purity (higher than 99%). Besides, the solvent used in the reaction process can be recycled, thereby saving the cost and being more environment-friendly.
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Paragraph 0031 - 0040
(2016/10/09)
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- A direct synthesis of vinylphosphonium salts from α-trimethylsilyl ylides and non-enolizable aldehydes
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A direct synthesis of vinylphosphonium salts from α-trimethylsilyl ylides and non-enolizable aldehydes was reported. The vinylphosphonium salt was isolated in 90% yield and with high stereoselectivity favoring the (E)-olefin. High chemoselectivity observed favoring Peterson elimination over Wittig-type elimination and general stereoselectivity favoring (E)-vinylphosphonium salts require free-rotation about the central C-C bond of a betaine intermediate. The results show that the clean synthesis of the stable silylphosphonium iodide salt, subsequent generation of its yield derivative, and stoichiometric reaction with aldehydes at low temperature allows highly selective vinylphosphonium salt formation. It is also seen that the (E)-vinylphosphonium stereoselectivity is due to kinetic control involving Peterson syn-elimination from the erythro betaine.
- McNulty, James,Das, Priyabrata
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scheme or table
p. 8469 - 8472
(2009/10/23)
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- Synthesis and Properties of Phosphabetaine Structures. I. Reactions of Triphenylphosphine and Triphenyl Phosphite with Unsaturated Carboxylic Acids and Their Derivatives
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Reactions of triphenylphosphine and triphenyl phosphite with unsaturated carboxylic acids and their derivatives yield, depending on the nature of the reactants, phosphobetaine carboxylates, phosphonium salts, functionally substituted phosphonates, and als
- Galkin,Bakhtiyarova,Polezhaeva,Shaikhutdinov,Klochkov,Cherkasov
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p. 1052 - 1056
(2007/10/03)
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- Modified borohydride agents; Efficient reduction of azides with (1,4- diazabicyclo[2.2.2]octane) (tetrahydroborato)zinc complex [Zn(BH4)2(dabco)] and methyltriphenylphosphonium tetrahydroborate [MePh3P+BH-4]
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(1,4-Diazabicyclo[2.2.2]octane)(tetrahydroborato)zinc complex and methyltriphenylphosphonium tetrahydroborate are stable modified borohydrides which are used for the efficient reduction of aryl, alkyl, and aroyl azides with excellent yields in THF or CH2Cl2 at room temperature or under reflux conditions.
- Firouzabadi,Adibi,Zeynizadeh
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p. 1257 - 1273
(2007/10/03)
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- Synthesis of new organophosphorus derivatives of acylureas and acylsemicarbazides
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A convenient route to phosphorus acylureas and acylsemicarbazides is reported. The syntheses of the new compounds involve the reaction between a chloroacetyl compound and various phosphorus starting materials (dithiophosphate, phosphine, phosphite and phosphinite).
- Plenat, Francoise,Cassagne, Murielle,Cristau, Henri Jean
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p. 2941 - 2955
(2007/10/03)
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- Silylated Aminophosphonium Salts and Aminophosphonium Methylides
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The reaction of the aminophosphonium methylides (Et2N)3P=CH2, Me(Et2N)2P=CH2, (Me2N)3P=CH2, or Me(Me2N)2P=CH2 (1a-d) with the chlorosilanes Me3SiCl and (t-Bu)2SiCl2, resp., yield silylated phosphonium salts 2a-d (Scheme 1).Treatment of these with strong b
- Schmidbaur, Hubert,Pichl, Reinhard,Mueller, Gerhard
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p. 789 - 794
(2007/10/02)
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- 1,3-Ambident Nucleophilic Phosphorus Ylides, V. (2-Iminoethylidene)phosphoranes
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The title compounds 8 undergo α,γ-reaction with dicarbonyl dichlorides (4, 5), mono- (9) and dicarboximidoyl chlorides (7) and N,N-bis(chloroformyl)amines (12) to give five- and six-membered N-heterocyclic phoshonium salts (1, 3, 6, 10, 14). - The 1,3-dipolar cycloaddition with N-phenylbenzonitrile imide (11) opens the way to a new one-step synthesis of 1,3,4,5-tetraaryl-1,2,4-triazolium salts 17.The structure of pyrrole derivative 2 is elucidated by X-ray analysis.
- Capuano, Lilly,Dahm, Birgit,Schramm, Volker
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p. 3536 - 3543
(2007/10/02)
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- Synthesis, Structure and Conformation of Triphenylphosphonium-bis(diphenylarsino)methylide
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Triphenylphosphonium-diphenylarsino-methylide (1) and -bis-(diphenylarsino)methylide (2) are easily available through transylidation processes using Ph3P=CH2 and Ph2AsCl as the starting materials in the appropriate molar ratio.Analytical and spectroscopic
- Schmidbaur, Hubert,Nussstein, Peter,Mueller, Gerhard
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p. 1456 - 1462
(2007/10/02)
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- Reactions with Phosphine Alkylenes, XLV. Reactions of Alkylidenetriphenylphosphoranes with Tetramethylformamidinium Chloride. Synthesis of triphenylphosphonium Chloride and (Formylalkylidene)triphenylphosphoranes
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Phosphonium ylides 1 react with tetramethylformamidinium chloride (2) to form enamine phosphonium chlorides 8 and the formic orthoamide 7.The salts 8 show temperature depending 1H NMR spectra with respect to the protons of the dimethylamino group (hindered rotation around the C - N(CH3)2 bond).Treatment of 8 with acids and subsequently with bases gives rise to the formation of the formyl ylides 19. 8a is deprotonated with sodium amide to give the phosphaallene ylide 20, which reacts with water to yield the phosphane oxide 21, and with methyl iodide stereospecifically to form 8b.
- Bestmann, Hans Juergen,Schmid, Guenter,Oechsner, Helmut,Ermann, Peter
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p. 1561 - 1571
(2007/10/02)
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- Reactions with Organophosphorus Compounds, XLVI. Reactivity Umpolung of 1,3-Dioxo Compounds through Introduction of a Triphenylphosphonio Group. - Regioselective Syntheses of Isoxazoles and Pyrazoles from (2,4-Dioxoalkyl)triphenylphosphonium Salts
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Phosphonium salts 2 and 6, upon deprotonation with BuLi and subsequent reaction with acyl halides, yield the γ-acyl derivatives 3 and 7, respectively, which on treatment with hydrochloric acid afford the corresponding (dioxoalkyl)phosphonium salts 4 and 8.Isoxazole derivatives 9 and 10 are formed regioselectivly from 4 and 8 with NH2OH*HCl, while with R-NH-NH2*HCl (R = H or C6H5) the pyrazole-containing phosphonium salts 14 and 15 are obtained in an analogous reaction.In each case the direction of cyclisation is different to the reactions of the corresponding non-phosphorus substituted 1,3-dioxo compounds.On treatment with aqueous NaOH 9 and 10 are cleaved to triphenylphosphane oxide and isoxazoles 11 and 12, while 14 and 15 yield the pyrazoles 16 and 17.Wittig reaction of 9a or 14a with aldehydes or ketones leads to the isoxazole olefins 13 or the pyrazole olefins 18, respectively.
- Oehler, Elisabeth,Zbiral, Erich
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p. 2852 - 2867
(2007/10/02)
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- 3,5-Bisoxygenated 2-(ω-halo-3-oxygenated-1-alkenyl)-cyclopentane-1-heptanoic acids and derivatives thereof
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3,5-Bisoxygenated 2-(ω-halo-3-oxygenated-1-alkenyl)-cyclopentane-1-heptanoic acids and derivatives thereof, conveniently obtained by processes utilizing 2-formyl-3-hydroxy-5-oxycyclopent-1-eneheptanoic acids as the starting materials, display valuable pharmacological properties, e.g. anti-fertility, bronchodilating, anti-secretory, smooth muscle stimulatory, and blood platelet aggregation-inhibiting.
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