- Synthesis of flame-retardant phosphaphenanthrene derivatives with high phosphorus contents
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Two novel types of phosphate derivatives of phosphaphenanthrene with a high phosphorus content were prepared by phosphorylation reaction between either 2-(6-oxido-6H-dibenzc,e1,2oxaphosphorin-6-yl)-methanol (ODOPM) or 2-(6-oxido-6H-dibenzc,e1,2.oxaphosphorin-6-yl)-1,4-benzenediol (ODOPB) and dialkyl phosphoryl chloride. The structures of all compounds were characterised by 1H NMR, 13C NMR, 31P NMR, Fourier transform infrared spectroscopy, and high-resolution mass spectrometry. The thermal stability of representative compounds was determined by thermal gravimetric analysis and differential scanning calorimetry. The results showed that the compounds have excellent resistance to oxidation, high thermal stability with an onset decomposition temperature above 200°C, and a high char yield over 25 %, owing to the high P content. The representative compound was added to conventional electrolytes of lithium-ion batteries as flame retardant additive, and the self-extinguishing time and ionic conductivity were measured. The result showed that the compounds have effective flame retardant properties.
- Zheng, Jinyun,Yu, Yujian,Zhang, Lulu,Zhen, Xiaomin,Zhao, Yufen
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Read Online
- Zinc-catalyzed transformation of diarylphosphoryl azides to diarylphosphate esters and amides
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We have developed a facile and efficient procedure for the synthesis of diarylphosphate esters and amides. Using Zn(acac)2 as the catalyst, the reaction of diarylphosphoryl azides with aliphatic alcohols and phenols through an unusual P?N bond cleavage provided a number of diarylphosphate esters in good yields (22 examples, up to 94%). Additionally, various diarylphosphate amides were obtained from the corresponding amines in excellent yields as well (8 examples, up to 96%).
- Ying, Jun,Gao, Qian,Wu, Xiao-Feng
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supporting information
p. 1540 - 1543
(2020/04/15)
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- Preparation method of cresyl diphenyl phosphate
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The invention relates to a preparation method of cresyl diphenyl phosphate. The method includes the steps of: 1) esterification reaction: mixing phosphorus oxychloride with a catalyst, then adding phenol dropwise, and at the end of the reaction, conducting reduced pressure distillation to obtain diphenoxy phosphoryl chloride; 2) reduced pressure reaction: reacting the intermediate diphenoxy phosphoryl chloride obtain in step 1) with m, p-cresol under a reduced pressure, and removing the reacted hydrogen chloride gas to obtain a cresyl diphenyl phosphate crude product; and 3) refining: carryingout alkali washing, washing and reduced pressure distillation on the cresyl diphenyl phosphate crude product obtained in step 2) to obtain cresyl diphenyl phosphate. Phosphorus oxychloride and phenolare employed for reaction to prepare the diphenoxy phosphoryl chloride intermediate, the generated intermediate reacts with m, p-cresol to prepare the product, the synthetic route reduces the impurities phenyl xylylphosphate, tricresyl phosphate and triphenyl phosphate, thus improving the purity.
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Paragraph 0037; 0049-0050; 0054-0055; 0059-0064
(2019/11/21)
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- Chemical synthesis method of diphenyl chlorophosphate
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The invention relates to a synthesis method of diphenyl chlorophosphate. The method comprises the following steps: by taking certain amount of organic ammonia as a catalyst, mixing certain amount of diphenyl phosphate or diphenyl phosphate salt or mixing both at any proportion, and reacting with certain amount of bis(trichloromethyl)carbonate ester in an organic solvent for 1-10h, wherein the reaction temperature is 0-60 DEG C, and the diphenyl phosphate salt is sodium diphenyl phosphate or potassium diphenyl phosphate; after the reaction in the step 1) is over, cooling, washing and drying the product drying; performing normal-pressure or reduced-pressure recovery of solvent; cooling to filter out insolubles to obtain diphenyl chlorophosphate. The method provided by the invention has the following beneficial effects: the process line is simple, the reaction conditions are mild, the aftertreatment energy consumption is low, high-vacuum and high-temperature distillation is not needed, the production cost is low, and the product yield and quality are both relatively high; meanwhile, the problem of generation of much phosphorous-containing wastewater and solid waste is avoided.
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Paragraph 0021
(2019/10/01)
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- Exploration of chiral Lewis acid Mg2+ catalysts in the synthesis of aryl organophosphate triesters from phosphorus oxychloride through a three-step, two-pot substitution sequence
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A variety of nucleophilic and Lewis acid catalysts were examined for use in promoting the synthesis of organophosphate triesters. Eight novel organophosphate triesters are reported here for the first time. MgSO4 was discovered as an inexpensive catalyst capable of improving the synthesis of a variety of aryl organophosphate triesters from the readily available and low cost precursor phosphorus oxychloride in a three-step, two-pot sequence. Yields for this method improve upon the uncatalyzed method by 8–36%. Several chiral catalysts were tested, but none were able to induce enantioselectivity in the reaction.
- Granger, Emily,Solomianko, Katarzyna,Young, Cori,Erb, Jeremy
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p. 1404 - 1408
(2018/03/13)
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- A preparation method of chlorinated diphenyl phosphate (by machine translation)
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The invention relates to a chlorinated diphenyl phosphate preparation method, its characteristic is that the phenol and phosphorus oxychloride into reactor, adding catalyst, by 2.5 - 5.5 hours heated to 130 - 150 °C, thermal insulation reaction, in the GC-phenol content of less than 0.5% completion of the reaction, the reaction liquid after the reaction and get the finished product chlorinated diphenyl phosphate; wherein the catalyst is a triphenylphosphine and triphenyl phosphine oxide; phenol with phosphorus oxychloride in a molar ratio of 1:1 - 3:1, triphenylphosphine consumption is phenol weight of 0.5 - 5%, triphenyl phosphine oxide consumption is phenol weight of 0.5 - 8%; the reaction temperature is 50 - 150 °C. The present invention does not need to use the advantages of the solvent. (by machine translation)
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Paragraph 0014
(2017/08/29)
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- Reactivity of Ferrocenyl Phosphates Bearing (Hetero-)Aromatics and [3]Ferrocenophanes toward Anionic Phospho-Fries Rearrangements
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The temperature-dependent behavior within anionic phospho-Fries rearrangements (apFr) of P(O)(OFc)n(EAr)3-n (Fc = Fe(η5-C5H5)(η5-C5H4); E = O; Ar = phenyl, naphthyls, (R)-BINOL, [3]ferrocenophanyl; E = N, 1H-pyrrolyl, 1H-indolyl, 9H-carbazolyl; n = 1-3) is reported. While Fc undergoes one, the Ph-based apFr depends on temperature. First, the aryls are lithiated and rearranged, followed by Fc and N-heterocycles. Addition of Me2SO4 thus gave methylated Fc, contrary to non-organometallic aromatics giving mixtures of HO and MeO derivatives. The (R)-BINOL Fc phosphate gave Fc-rearranged phosphonate in 91% de. Exchanging O- with N-aliphatics prevented apFr, due to higher electron density at P. Also 1,2-N→C migrations were observed. X-ray analysis confirms 1D H bridge bonds for OH and NH derivatives. The differences in reactivity between N-aliphatic and N-aromatic phosphoramidates were verified by electrochemistry. The redox potentials revealed lower values for the electron-rich aliphatics, showing no apFr, preventing a nucleophilic attack at P after lithiation. Redox separations for multiple Fc molecules are based on electrostatic interactions.
- Korb, Marcus,Lehrich, Steve W.,Lang, Heinrich
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p. 3102 - 3124
(2017/03/23)
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- A preparation method of chlorinated diphenyl phosphate
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The invention provides a method for preparing diphenyl phosphorochloridate. The method is characterized in that a proper catalyst and a reactant of phosphorus oxychloride are used and form a stable complex at a certain temperature, so that a chlorine atom in the phosphorus oxychloride is protected, and accordingly generation of a by-product of triphenyl phosphate in the reaction process is inhibited. Thus, the yield of diphenyl phosphorochloridate is increased. Besides, the dissociation temperature of the formed complex and the boiling point of the catalyst are lower than the rectification temperature of a principal product, the catalyst can be firstly removed in the rectification process, and the principal product is not affected. Besides, the catalyst obtained through rectification can be repeatedly used. The method for preparing the diphenyl phosphorochloridate has a series of advantages of being high in yield, safe, clean, low in cost and the like.
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Paragraph 0019; 0020; 0021; 0022; 0023; 0024; 0025; 0026
(2017/10/06)
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- FLAME RETARDANT COMPRISING AROMATIC PHOSPHATE ESTER-BASED COMPOUND, AND METHOD FOR PREPARING SAME
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A method for preparing a novel aromatic phosphate ester-based compound, including: (a) reacting a compound expressed by chemical formula 1 (i) and a C6-10 aryl compound substituted with hydroxy or C1-6 alkoxy, or a C6-20 arylalkyl compound substituted with hydroxy or C1-6 alkoxy (ii), which are used as reaction materials by gradually heating to the temperature levels of 90-125° C., 125-180° C., 180-210° C. and 210-240° C.; (b) separating an aromatic phosphate ester-based compound from the resultant product in step (a) under the condition of a pressure of 0.01 mmHg-50 mmHg and a temperature of 50° C.-300° C. using fractional distillation; and (c) reacting the aromatic phosphate ester-based compound separated in step (b) (i) and C1-10 alcohol or a nitrogen compound (ii) at a temperature of 10-70° C.
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Paragraph 0149-0158
(2015/11/10)
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- Neodymium tris-diarylphosphates: Systematic study of the structure-reactivity relationship in butadiene and isoprene polymerisation
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The catalytic properties of neodymium tris-phosphates with various diarylphosphate ligands in the stereoregular 1,4-cis-polymerisation of butadiene and isoprene were studied. The considerable variability of the diaryl phosphate structure allowed for the systematic investigation of the dependence of the catalytic properties of neodymium tris-diarylphosphates on the electronic and steric properties of the ligand. Electron-withdrawing substituents (F, Cl, Br) in the aryl moiety increased the catalyst activity of tris-diarylphosphate. Neodymium aryl phosphates containing lipophilic bulky ligands provided the synthesis of polydienes with a monomodal molecular-weight distribution. The optimal catalytic properties demonstrated that the neodymium aryl phosphate prepared from bis(2,6-dimethyl-4-tert-butylphenyl)-phosphoric acid showed high activity and ensured a monomodal MWD of polydienes (Mw/Mn ~ 2 for polybutadiene and Mw/Mn ~ 3 for polyisoprene) in various conditions.
- Nifant'Ev, Ilya E.,Tavtorkin, Alexander N.,Korchagina, Sof'Ya A.,Gavrilenko, Inna F.,Glebova, Nataliya N.,Kostitsyna, Nataliya N.,Yakovlev, Vladimir A.,Bondarenko, Galina N.,Filatova, Marina P.
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p. 219 - 277
(2014/05/20)
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- Synthesis of phosphoramidates: A facile approach based on the C-N bond formation via Ir-catalyzed direct C-H amidation
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A new synthetic route to phosphoramidates by intermolecular C-H amidation is presented. Substrates with assorted directing groups were activated by an iridium-based catalyst system and reacted with a number of phosphoryl azides, executing efficient phosphoramidate synthesis via C-N bond formations. (Chemical Equation Presented).
- Kim, Hyunwoo,Park, Juhyeon,Kim, Jeung Gon,Chang, Sukbok
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supporting information
p. 5466 - 5469
(2015/01/09)
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- Highly Z-selective synthesis of a,b-unsaturated nitriles using the Horner-Wadsworth-Emmons reaction
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A new HWE reagent, (o-tBuC6H4O)2P(O)CH2CN (2e), reacts with various types of aldehydes to give Z-a,bunsaturated nitriles with 86% to >99% Z-selectivity. Especially, the reaction of 2e with bulkier aldehydes, both aromatic and aliphatic, gave the Z-olefins with extremely high selectivity. The combination of t-BuOK and 18-crown-6 (1 equiv) is the base of choice for aromatic aldehydes and t-BuOK is generally the base of choice for aliphatic aldehydes.
- Ando, Kaori,Okumura, Miho,Nagaya, Shigeo
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p. 2026 - 2028
(2013/04/23)
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- N,N-Dichloro poly(styrene-co-divinyl benzene) sulfonamide polymeric beads: an efficient and recyclable reagent for the synthesis of dialkyl chlorophosphates from dialkylphosphites at room temperature
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An efficient and operationally simple method is developed for the synthesis of dialkyl chlorophosphates from dialkylphosphites using a new chlorine bearing reagent, N,N-dichloro poly(styrene-co-divinyl benzene) sulfonamide in the form of polymeric beads. The reagent afforded dialkyl chlorophosphates at room temperature, and is recyclable.
- Gupta, Hemendra K.,Mazumder, Avik,Garg, Prabhat,Gutch, Pranav K.,Dubey, Devendra K.
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scheme or table
p. 6704 - 6706
(2009/04/07)
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- Trichlorocyanuric acid: An efficient reagent for one-pot synthesis of Ptychodiscus brevis (PB-1) toxin and its derivatives
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Trichlorocyanuric acid is an efficient regent for simple and one-pot synthesis of dialkyl, N-cycloctylphosphoraamidates (PB-1) and its various derivatives in excellent yields. The procedure is operationally simple and involves the reaction of various dialkylphosphites with trichloroisocyanuric acid in acetonitrile and subsequent treatment with amines in presence KF-celite to give PB-1 and derivatives.
- Gupta, Arvind K.,Acharya, Jyotiranjan,Dubey, Devendra K.,Kaushik, Mahabir P.
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- Efficient and convenient one-pot synthesis of phosphoramidates and phosphates
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A simple and efficient one-pot method is described for the synthesis of phosphoramidates/phosphates in excellent yields from dialkylphosphites and trichloroisocyanuric acid in acetonitrile and subsequent treatment with dialkyl amines/alcohols. The procedure is operationally simple, has reduced reaction times, and uses a one-pot procedure. Copyright Taylor & Francis Group, LLC.
- Gupta,Acharya,Dubey,Kaushik
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p. 3403 - 3407
(2008/02/13)
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- N-tert-butyl-N-chlorocyanamide: A mild and efficient chlorinating agent for the synthesis of dialkyl/diaryl chlorophosphates
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An efficient reagent for the synthesis of dialkyl/diaryl chlorophosphates has been developed. N-tert-Butyl-N-chlorocyanamide acts as a chlorinating agent both in polar as well in non-polar medium and the transformation of dialkyl/diaryl phosphites to the dialkyl/diaryl chlorophosphates takes place rapidly under mild conditions in quantitative yields. Copyright
- Kumar, Vinod,Kaushik, Mahabir Parshad
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p. 312 - 313
(2007/10/03)
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- Trichloroisocyanuric acid: An efficient reagent for the synthesis of dialkyl chlorophosphates from dialkyl phosphites
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A mild and operationally simple method for the synthesis of dialkyl chlorophosphates is described. Trichloroisocyanuric acid is used as an effective reagent for the rapid conversion of dialkyl phosphites to their corresponding dialkyl chlorophosphates under mild conditions.
- Acharya,Gupta,Shakya,Kaushik
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p. 5293 - 5295
(2007/10/03)
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- N, N′-Dichloro bis(2,4,6-trichlorophenyl) urea (CC-2): An efficient reagent for synthesis of dialkyl chlorophosphates
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An efficient and simple method is described for the preparation of dialkyl chlorophosphates by the use of new positive chlorine bearing reagent namely N,N′-dichloro bis(2,4,6-trichlorophenyl) urea.
- Shakya,Dubey,Pardasani, Deepak,Palit, Meehir,Gupta
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p. 821 - 823
(2007/10/03)
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- α-haloenamines as reagents for the conversion of phosphorus oxyacids to their halogenated analogues
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Phosphorus oxyacids are converted to their halogenated analogues under mild conditions. α-Haloenamines are shown to be effective halogen transfer reagents affording good to high yields of the desired products at reaction times, in some cases, less than one minute. Georg Thieme Verlag Stuttgart.
- Norlin, Rikard,Juhlin, Lars,Lind, Per,Trogen, Lars
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p. 1765 - 1770
(2007/10/03)
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- Reaction of chlorides of phosphoric, sulfonic, and carboxylic acids on solid potassium carbonate surface under PTC circumstances
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Simple syntheses of phosphoric (4) and carboxylic (6) acid anhydrides have been elaborated by means of solid potassium carbonate in phase-transfer catalytic acylation. Behavior of various acid chlorides, phosphoric (1), sulfonic (2), and carboxylic (8), have also been studied toward potassium carbonate in the presence of lipophilic quaternary ammonium salt.
- Jaszay, Zsuzsa M.,Petnehazy, Imre,Toe, Laszlo
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p. 447 - 450
(2007/10/03)
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- Phosphorus-containing phenolic, thiophenolic or aminophenyl flame-retardant hardener, and epoxy resins cured thereby
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A hardener for an epoxy resin comprises a phenolic, thiophenolic, aminophenyl, tris-phenolic, tris-thiophenolic, tris-aminophenyl, tetrakis-phenolic, tetrakis-thiophenolic, or tetrakis-aminophenyl compounds; or phenol-formaldehyde or phenol-formaldehyde/melamine-formaldehyde resins wherein the phenyl rings are substituted with at least one of the structures wherein R1and R2independently are H, C1-C18alkyl, C6-C18aryl, C6-C18substituted aryl, C6-C18aryl methylene, or C6-C18substituted aryl methylene; X is O, S or NH and Ar is wherein R is C1-C4alkyl and n=0-5.
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- Alpha- haloenamine reagents
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The present invention describes immobilized haloenamine reagents, immobilized tertiary amides, methods for their preparation, and methods of use.
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- Reductive cleavage of the halogen-phosphorus, oxygen-phosphorus and phosphorus-phosphorus bonds with alkali metals
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The reduction of phosphorus acid chlorides as well as hypophosphates, pyrophosphates and mixed P(III)-P(V) anhydrides with alkali metals (Li, Na, K) in NH3 liq. / THF solution and potassium naphthalenide was investigated. It was found that this type of phosphorus compounds easily undergo reduction: a) >P(O)Cl to >P(O)H; b) >P(O)P(O)P(O)H; c) >P(O)-O-P(O)P(O)OH and >P(O)H; d) >P(O)-O-PP(O)O- and >P-. The results of our experiments strongly suggest that the mixed P(III)-P(V) anhydride is reduced by potassium naphthalenide in THF with the cleavage of the P(III)-oxygen bond.
- Nycz, Jacek,Rachon, Janusz
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- Phosphorylation of phosphazenes
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Incorporation of phosphate and phosphonate units into the side groups of aryloxyphosphazenes, at both the polymer and cyclic trimer levels, is disclosed. Phosphorylated cyclic trimers are utilized as flame-retardant additives to polystyrene.
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- Electron Demand in the Transition State of the Cyclopropylidene to Allene Ring Opening
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The electronic structure of the transition state for the cyclopropylidene to allene conversion has been probed.The methodology involved the relative rates of ring opening vs trapping by MeOH for a series of variously substituted 2,3-diarylcyclopropylidenes.With the assumption that the rate of trapping was unaffected by substituents, a Hammett correlation was constructed.The negative value (-0.72) for ρ indicated that the carbenic center attracts electron density in the ring-opening transition state, much like the cyclopropyl cation to allyl cation transition state.Temperature-dependent studies showed that the observed preference for ring opening was driven by entropy factors.Also, using reasonable estimates for the close to diffusion-controlled trapping activation enthalpies, the derived enthalpies for ring opening were in close agreement with the best theoretical values.
- Warner, Philip,Sutherland, Robert
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p. 6294 - 6300
(2007/10/02)
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- Crystalline powders of aromatic diphosphates, their preparation and use
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Crystalline powders of an aromatic diphosphate of the formula (I): wherein R1 and R2 are, the same or different, a lower alkyl group, R3 is a hydrogen atom or a lower alkyl group, R4 is a hydrogen atom or a lower alkyl group, Y is a bonding arm, -CH2-, -C(CH3)2-, -S-, -SO2-, -CO-, -O- or -N=N-, k is 0 or 1 and m is an integer of 0 to 4.
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- ESTERIFICATION KINETICS OF PHENOL WITH PHOSPHORYL TRICHLORIDE
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The liquid-phase esterification kinetics of phenol with POCl3 has been studied at isothermal conditions within the temperature interval from 90 to 110 deg C.The esterification rate constants of the first, second, and third esterification steps and the activation energies of these steps have been calculated.The given system of competitive consecutive reactions can be described by a system of differential equations which has been solved by the Gauss-Newton optimization method of non-linear regression in the Marquardt modification.In the sequence of the first, second, and third step the esterification rate constants have been found to gradually decrease, whereas the activation energies increase in the same sequence.
- Magura, Miroslav,Vojtko, Jan,Zemanova, Eva,Kaszonyi, Alexander,Ilavsky, Jan
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p. 608 - 615
(2007/10/02)
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- Synthesis of Some New Aryl Phosphates
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Eight new triaryl phosphates (1-8) were synthesized by phosphorylation of the corresponding phenol with phosphorus oxychloride for evaluation as stationary phases in gas chromatography.They were duly characterized by infrared, proton magnetic resonance, and mass spectral techniques after their purity was established by HPLC.
- Bhagat, Shib D.,Mathur, Raj K.
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p. 131 - 133
(2007/10/02)
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- STUDIES ON THE REACTION OF NUCLEOSIDE PHOSPHORODIESTERS WITH ARYL SULFONYL CHLORIDES
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It was found that activation of phosphorodiesters by aryl sulfonyl chlorides does not stop at the stage of symmetrical pyrophosphates I but proceeds further with the formation of diester chlorophosphates II.
- Garegg, Per J.,Regberg, Tor,Stawinski, Jacek,Stroemberg, Roger
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p. 2665 - 2666
(2007/10/02)
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- Reactions of Phosphodiester Anions with Phosgene
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The mechanisms of reactions of phosgene with the N-methylpyridinium salts of diphenyl phosphate and 1,2-dimethylethenylene phosphate (or 4,5-dimethyl-2-oxido-2-oxo-1,3,2-dioxaphosphole) have been studied by 31P NMR spectrometry in dichloromethane at various temperatures and molar ratios of reactants.The products are mixtures of pyrophosphates and phosphorochloridates in proportions that vary with the structure of the phosphodiester and the experimental conditions.The reactions have also been carried out in benzene suspension.The conditions can be adjusted to give exclusively and in high yields (over 85percent) either bis(1,2-dimethylethenylene)pyrophosphate or 1,2-dimethylethenylene phosphorochloridate (or 2-chloro-4,5-dimethyl-2-oxo-1,3,2-dioxaphosphole).These cyclic enediol phosphoryl derivatives are excellent reagents for the synthesis of complex biological phosphodiesters.
- Ramirez, Fausto,Marecek, James F.
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p. 847 - 850
(2007/10/02)
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- CATALYTIC EFFECT OF SUBSTITUTED DIPHENYLPHOSPHORIC ACIDS ON THE FORMATION OF ESTERS
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The catalytic effect of substituted diphenylphosphoric acids on the rate of the reaction of butyryl chloride with 1-butanol in toluene was investigated.It was shown that the effect of the nature of the substituent in the acid molecule has little effect on its catalytic activity.This indicates a bifunctional mechanism of catalysis in the reaction.
- Zhil'tsov, N. P.,Semenyuk, G. V.,Korzhenevskaya, N. G.
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p. 825 - 828
(2007/10/02)
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- Phosphate-carboxylate compounds
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Compounds of the following formula: STR1 wherein R is selected from the group consisting of hydrogen and an alkyl group containing from 1 to 4 carbon atoms, R' is selected from the group consisting of --OB and halogen, B is alkali metal, ammonium or trialkanolammonium, and M is selected from B or alkyl having up to 20 carbon atoms, Are provided. The salts are useful as detergent builders, and the esters are useful intermediates to make the salts.
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- Preparation of esters of phosphorus acids
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Esters of phosphorus acids are prepared by an improved process whereby aromatic alcohols and phosphorus halides are reacted at specified temperatures in the presence of amine catalysts thereby providing high yields of substantially pure esters and allowing preparation of selected halogen-containing mono- and di-esters of phosphorus acids wherein halogen is directly bonded to phosphorus having substantially no side reactant contamination. The phosphorus esters are useful as intermediates in the preparation of plasticizers, oil additives and functional fluids.
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