2524-64-3Relevant articles and documents
Synthesis of flame-retardant phosphaphenanthrene derivatives with high phosphorus contents
Zheng, Jinyun,Yu, Yujian,Zhang, Lulu,Zhen, Xiaomin,Zhao, Yufen
, p. 1688 - 1692 (2014)
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.
Zinc-catalyzed transformation of diarylphosphoryl azides to diarylphosphate esters and amides
Ying, Jun,Gao, Qian,Wu, Xiao-Feng
supporting information, p. 1540 - 1543 (2020/04/15)
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%).
Chemical synthesis method of diphenyl chlorophosphate
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Paragraph 0019; 0020, (2019/10/01)
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.
Preparation method of cresyl diphenyl phosphate
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Paragraph 0037; 0049-0050; 0054-0055; 0059-0064, (2019/11/21)
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.
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
Granger, Emily,Solomianko, Katarzyna,Young, Cori,Erb, Jeremy
, p. 1404 - 1408 (2018/03/13)
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.
A preparation method of chlorinated diphenyl phosphate (by machine translation)
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Paragraph 0014, (2017/08/29)
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)
Reactivity of Ferrocenyl Phosphates Bearing (Hetero-)Aromatics and [3]Ferrocenophanes toward Anionic Phospho-Fries Rearrangements
Korb, Marcus,Lehrich, Steve W.,Lang, Heinrich
, p. 3102 - 3124 (2017/03/23)
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.
A preparation method of chlorinated diphenyl phosphate
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Paragraph 0019; 0020; 0021; 0022; 0023; 0024; 0025; 0026, (2017/10/06)
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.
FLAME RETARDANT COMPRISING AROMATIC PHOSPHATE ESTER-BASED COMPOUND, AND METHOD FOR PREPARING SAME
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Paragraph 0149-0158, (2015/11/10)
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.
Neodymium tris-diarylphosphates: Systematic study of the structure-reactivity relationship in butadiene and isoprene polymerisation
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.
, p. 219 - 277 (2014/05/20)
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.
