- Nano-silica?PVC-bonded N-ethyl sulfamic acid as a recyclable solid catalyst for the hydroxyalkylation of phenol with formaldehyde to bisphenol F
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Sulfamic acid functionalized PVC-coated nano-silica (NS) catalyst (NS?PVC-EDA-SO3H) was prepared via multi-step treatment processes and characterized by FT-IR, N2 adsorption-desorption, TGA/DTG, XRD, TEM, STEM-EDS, as well as acid-base back-titration. The hydroxyalkylation of phenol with formaldehyde to bisphenol F was employed to evaluate in detail its acid catalysis performances. The results indicated that the newly constructed NS?PVC-EDA-SO3H possessed richer short mesoporous to macroporous channels and highly exposed sulfamic acids and could exhibit excellent hydroxyalkylation activity and reusability owing to fast mass transfer and reaction rates for the conversion of substrates, as well as excellent structural and chemical stabilities. This new solid acid was obviously superior to the conventional homogeneous concentrated sulfuric acid and heterogeneous sulfonated resin catalysts in catalytic activity and reusability, which could achieve a remarkable formaldehyde conversion (99.9%) and selectivity of bisphenol F (94.5%) under optimal hydroxyalkylation conditions. Furthermore, it could also be recovered easily and used repeatedly at least nine times without an obvious decrease in activity.
- Jiang, Dabo,Zhou, Shuolin,Fu, Zaihui,Xu, Qiong,Xiao, Jiafu,Zheng, Min,Zhong, Wenzhou,Liu, Xianxiang,Kirk, Steven Robert,Yin, Dulin
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- The hydroxyalkylation of phenol with formaldehyde over mesoporous M(Al, Zr, Al-Zr)-SBA-15 catalysts: The effect on the isomer distribution of bisphenol F
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Mesoporous M(Al, Zr, Al-Zr)-SBA-15 catalysts prepared by a direct method were used for the hydroxyalkylation of phenol with formaldehyde to bisphenol F in the presence of water. The results showed that M(20)-SBA-15 with the Si/M molar ratio of 20 exhibited higher catalytic activity. The isomer distribution of bisphenol F could be regulated in the hydroxyalkylation of phenol with formaldehyde by changing the Al/Zr ratio in M(20)-SBA-15 catalysts. Al(20)-SBA-15 was in favor of the formation of 4,4′-isomer, whereas Zr(20)-SBA-15 was in favor of the formation of 2,4′- and 2,2′-isomers.
- Tan, Ying,Li, Yongfei,Wei, Yuanfeng,Wu, Zhimin,Yan, Jiaqi,Pan, Langsheng,Liu, Yuejin
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- Hydroxyalkylation of phenol to bisphenol F over Al-pillared clay
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Hydroxyalkylation of phenol to bisphenol F over the intercalation of aluminum hydroxy oligomeric into layered montmorillonite K10 was investigated. A remarkably high product yield (89.2%) and selectivity to bisphenol F (92.7%) has been achieved at a 110 °C reaction temperature and reaction time of 80 min with a Al-MMT(6) catalyst. A series of catalysts were prepared and characterized by FT-IR, XRD, BET, NH3-TPD and Py-IR. Characterization results showed that the catalytic performance of these catalysts depended on weak and moderate acidity and the textural properties (specific surface areas). The effect of the catalyst calcination temperature to this reaction was also studied. Moreover, the influences of various reaction parameters like mole ratio, catalyst concentration, reaction temperature and reaction time on the product yield and selectivity to bisphenol F were investigated. Finally, the reusability of the catalyst was studied and a plausible mechanistic pathway was proposed.
- Wu, Xianzhang,Xia, Xinnian,Liu, Ran,Chen, You
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- ION CHANNEL ANTAGONISTS/BLOCKERS AND USES THEREOF
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Provided are ion channel antagonists/blockers and uses thereof. Specifically, it provides the compounds of formula (I) or pharmaceutically acceptable salts, stereoisomers, solvates or prodrugs, preparation method therefor and application thereof. Definition of each group in the formula can be found in the specification for details. Provided is also pharmaceutical composition useful for treatment of heart disease and other ion channel related diseases.
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- Method for preparing bisphenol F with high 2,2'-isomer content
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The invention discloses a method for preparing bisphenol F with high 2,2'-isomer content. The method for preparing bisphenol F with high 2,2'-isomer content, disclosed by the invention, comprises thefollowing steps: by taking a calcium magnesium silicate compound as a catalyst, taking phenol and formaldehyde as raw materials, carrying out a condensation reaction, thereby obtaining the bisphenol Fwith high 2,2'-isomer content. The adopted calcium magnesium silicate compound catalyst is prepared by the following sub-steps: taking silica, a calcium salt and a magnesium salt as raw materials, calcining at a high temperature, and thus obtaining the product by a hydrothermal method. When the catalyst is used for synthesis of the bisphenol F, the bisphenol F with high 2,2'-isomer content is obtained. In the whole technical preparation process, the cost of the raw materials and operating equipment is low, the operating procedures are simple, the corrosivity is low, and the method is green and environment-friendly.
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Paragraph 0019; 0024; 0029; 0034; 0036; 0038; 0040; 0042
(2018/12/14)
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- The invention relates to a multi-polyoxymethylene dimethyl ether as raw materials for preparing bisphenol F method
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The invention relates to a method for preparing bisphenol F by adopting polyoxymethylene dimethyl ethers (PODEn; n is larger than or equal to 2 and smaller than or equal to 8) as a raw material. The method comprises the main step of carrying out a hydroxyl alkylation reaction between phenyl hydroxide and PODEn under the condition of acid catalysis, so as to obtain a target product, wherein the hydroxyl alkylation reaction can be performed in the absence of water or in the presence of water. The method has the advantages that the solubility of PODEn in phenyl hydroxide and water is high, so that a bisphenol F synthesis system serves as a homogeneous-phase system, and is conducive to heat and mass transfer; besides, PODEn has an effect of quantitatively and slowly releasing formaldehyde, so that the hydroxyl alkylation reaction is mild and easy to control, side reactions are less, such by-products as triphenol and phenolic resin are unlikely to generate, and the advantages of high yield and selectivity are achieved.
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Paragraph 0031; 0034
(2017/08/25)
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- For simultaneous preparation14 C mark F isomer of bisphenol (by machine translation)
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The invention discloses a method for simultaneous preparation of14 C mark bisphenol F isomer, which belongs to the radioactive isotope14 C mark in the field of compound. The trace of the present invention synthetic method is by formaldehyde and14 C benzene ring mark of the phenol in phosphate under catalysis of condensation reaction, after the reaction, through separation and purification, to obtain14 C mark bisphenol F three kinds of isomers of 4, 4 '- dihydroxy diphenyl methane (4, 4' - BPF), 2, 4 '- dihydroxy diphenyl methane (2, 4' - BPF) and 2, 2 '- dihydroxy diphenyl methane (2, 2' - BPF). The invention has the following advantages: available reaction raw materials, the reaction phenolic ratio is low, the unreacted phenol get good recovery. The method for preparing bisphenol F isomer chemical purity is greater than 99%, radioactive purity are 2, 2 '- BPF 99.2%, 2, 4' - BPF 99.0%, 4, 4' - BPF 99.5%, can meet the follow-up study of the purity requirement for the material. (by machine translation)
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Paragraph 0038-0039
(2017/08/29)
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- A modified metal organic framework of phosphotungstic acid to bisphenol F catalytic synthesis method
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The invention discloses a method for synthesizing bisphenol F from phenol and formaldehyde with a phosphotungstic acid modified metal organic frame catalyst. In the method, through selection of different metal source and modification amount of phosphotungstic acid, the phosphotungstic acid modified metal organic frame catalyst is prepared in a one-step manner. The catalyst is simple in preparation method, is convenient to separate and recycle and can be reused and is free of corrosion to devices. When being used for catalyzing the phenol and the formaldehyde to synthesizing the bisphenol F, the catalyst can regulating distributions of three isomers of a product of the bisphenol F. The invention provides a new method for catalytically synthesizing the bisphenol F.
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Paragraph 0028; 0041; 0042; 0045; 0046; 0047; 0048
(2016/10/20)
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- Highly efficient and recyclable alkylammonium hydrosulfate catalyst for formation of bisphenol F by condensation of phenol with formaldehyde
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Several C1-C4 alkylammonium hydrosulfates [R3NH][HSO4] have been conveniently prepared from the cheap raw materials sulfuric acid and alkylamines. Their acidities were measured by chemical titration and determined using UV-vis spectroscopy with a basic indicator 4-nitroaniline. The catalytic performance of these hydrosulfates for the condensation of phenol with formaldehyde to bisphenol F (BPF) was evaluated in detail on a batch reactor. The results indicated that the proposed catalysts are very active for such condensation due to its homogeneous catalysis characteristics in reaction conditions. Among the catalysts examined, [H3NCH2CH2NH3][HSO4]2 shows the best catalytic performance and it can achieve a complete conversion of formaldehyde, providing a higher than 90% selectivity for BPF under the optimal conditions. Furthermore, the catalyst can be recovered from the reaction mixture via an azeotropic distillation with cyclohexane to remove water and then filtration and used repeatedly six times almost without loss of activity, showing an excellent reusability. It is suggested that the present catalytic process combines the characteristics of a homogenized reaction and heterogenized recovery so might provide a highly-efficient, environmentally-friendly and low-cost route for synthesis of bisphenol F.
- Xiao, Jiafu,Huang, Hua,Xiang, Weijian,Liao, Wei,Liu, Junyi,She, Xichun,Xu, Qiong,Fu, Zaihui,Kirk, Steven Robert,Yin, Dulin
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p. 92716 - 92722
(2016/10/11)
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- IMPROVED MANUFACTURING PROCESS FOR DIHYDROXYDIPHENYLMETHANE WITH HIGH SELECTIVITY FOR 2,4'- DIHYDROXYDIPHENYLMETHANE
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The invention relates to an improved manufacturing process for the preparation of high 2, 4 '-dihydroxydiphenylmethane, by a process involving reaction of phenol and formaldehyde, in the presence of an inorganic polyprotic acid. According to this process, the reaction conditions are selected to favour a high yield of dihydroxydiphenylmethane, with a relatively high concentration of the 2,4'-isomer, by using a relatively low molar excess of phenol than conventional methods.
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Page/Page column 15
(2015/04/15)
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- Development of chemical probes: Toward the mode of action of a methylene-linked di(aryl acetate) E1
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Analogues of the novel inhibitor of the PI3-K/PKB pathway, 2-[5-(2-chloroethyl)-2-acetoxy-benzyl]-4-(2-chloroethyl)-phenyl acetate (E1), have been prepared and preliminary SAR performed. This established that at least one of the chloroethyl para-substituents could be removed or modified and the ability to inhibit PKB/Akt activation retained. Synthetic methodologies were then developed to methylene-linked aryl acetates for use as molecular probes to identify the target of compound E1.
- Smith, Mark E.B.,Gunn, Richard M.,Rosivatz, Evelyn,Mak, Lok H.,Woscholski, Ruediger,Hailes, Helen C.
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experimental part
p. 4917 - 4927
(2010/09/10)
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- Method for producing diarylmethane or its derivatives
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A method to produce diarylmethane or its derivatives by condensation reaction can be carried out without difficulty and without the deterioration of catalyst, and the intended product can be produced inexpensively by recovering and recycling used alcohol. In the method, dimethoxymethane and an aromatic compound are reacted at a temperature of 80 to 400° C. with an acid catalyst. Further, the method comprises the steps of (1) reacting alcohol with formaldehyde using an acid catalyst to obtain acetal; (2) reacting the acetal and an aromatic compound using an acid catalyst to obtain a reaction mixture containing diarylmethane or its derivatives and alcohol; (3) separating and recovering diarylmethane or its derivatives and alcohol from the reaction mixture, and (4) recycling at least a portion of the recovered alcohol to the step (1).
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- The reactivity of o-hydroxybenzyl alcohol and derivatives in solution at elevated temperatures
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The reactivity of o-hydroxybenzyl alcohol (o-HBA, 1), as a model compound for lignin, has been studied in various solvents between 390 and 560 K. Both in polar and apolar solvents the benzylic cation is the reactive intermediate. In alcoholic solvents, the benzylic cation reacts with the solvent to give the corresponding ethers. Relative reaction rates have been determined for different alcohols; a factor of 14 is encountered between the most (methanol) and least (tert-butyl alcohol) reactive ones. The etherification is reversible, in contrast to the electrophilic aromatic substitution with phenol and anisole, for which k(PhOH) = 1 X 105 M-1 s- 1 and k(anisole) = 1 x 104 M-1 s-1, at 424 K. In apolar hydroaromatic solvents, 7H-benz[de]anthracene, 9,10-dihydroanthracene, and 9,10- dihydrophenanthrene, the formation of o-cresol proceeds via hydride transfer from the solvent to the benzylic cation; rate constants at 555 K are 2 x 106, 5 x 104, and 5 x 103 M-1 s-1, respectively.
- Dorrestijn, Edwin,Kranenburg, Marieke,Ciriano, Maria Victoria,Mulder, Peter
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p. 3012 - 3018
(2007/10/03)
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- Process for making polyphenols from ketones or aldehydes and phenols
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A process for the condensation of an aldehyde or ketone starting material with a phenol, unsubstituted in the 4-position, comprises reacting the aldehyde or ketone starting material with the phenol in a reaction mixture in the presence of a soluble or insoluble mercaptosulfonic acid compound under conditions sufficient to bring about formation of a geminal bisphenolic moiety at each aldehyde or ketone moiety in the starting material. A miscible mercaptosulfonic acid compound is characterized by the formula or a precursor thereof, wherein θ is an alkylene, cycloaliphatic, arylene, alkylenearylene, alkylenecycloaliphatic, alkylenearyl, heterocyclic or alkyleneheterocyclic residue. Heterogeneous catalysts comprise insoluble materials comprising catalytically-active species represented by the formula: STR1 L is an optional linking group and -- is a bond, which catalytically-active species is attached by the bond -- to an insoluble organic or inorganic support; or a catalytically-active species represented by the formula: STR2 wherein L' is an optional linking group, -- is a bond and θ' and θ" are residues of θ, and a and b are independently selected from integers equal to or greater than 1.
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- o-(α-Benzotriazolylalkyl)phenols: Novel Precursors for the Preparation of 1,1-Bis(2-hydroxyaryl)alkanes
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Reactions of o-(α-benzotriazolylalkyl)phenols with a variety of substituted phenols and naphthols in the presence of a base provide efficient access to symmetrical and more importantly to unsymmetrical 1,1-bis(2-hydroxyaryl)alkanes.
- Katritzky, Alan R.,Zhang, Zhongxing,Lang, Hengyuan,Lan, Xiangfu
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p. 7209 - 7213
(2007/10/02)
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- Magnesium-mediated ortho-Specific Formylation and Formaldoximation of Phenols
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Deprotonation of phenols using magnesium methoxide, followed by distillative removal of free methanol and addition of paraformaldehyde results in ortho-specific magnesium mediated formylation to give the corresponding salicyladehyde magnesium salts, from which the salicylaldehydes can be isolated by acidic work-up.Addition of aq. hydroxylamine sulfate to the salicylaldehyde magnesium salt, in place of the acid work-up, gives the corresponding salicylaldoximes.
- Aldred, Robert,Johnston, Robert,Levin, Daniel,Neilan, James
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p. 1823 - 1832
(2007/10/02)
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- Reactions of 2-phenyl-4H-1,3,2-benzodioxaborin, a stable ortho-quinone methide precursor
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Thermolysis of 1-phenyl-4H-1,3,2-benzodioxaborins generated the corresponding ortho-quinone methides, which were found to undergo intermolecular cycloaddition reactions with ethyl vinyl ether, dihydropyran, β-methylstyrene, cyclohexene, and 1-ethoxy-1-trimethylsiloxy-1-propenes to give various substituted chromans.Intramolecular trapping of the quinone methides with an olefin led to the syntheses of several analogs of tetrahydrocannabinols. ortho-Quinone methides, generated by treatment of the 2-phenyl-4H-1,3,2-benzodioxaborins with a Lewis acid, react with various nucleophiles to give the corresponding 1,4-addition products.Thus, alkyl and aryl thiols, alcohols, amine, hydride, allyl trimethylsilane, acetophenone, and diethyl malonate as well as some aryl compounds react with the quinone methide to give various 2-substituted phenols.Intramolecular reaction of the quinone methide with an aryl group led to the preparation of some 4-phenylchromans and tetralins.
- Chambers, Jeffrey D.,Crawford, Jason,Williams, Haydn W. R.,Dufresne, Claude,Scheigetz, John,et al.
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p. 1717 - 1732
(2007/10/02)
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- Carbonates of acetylenic alcohols
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Polymerizable carbonate compounds of the formula: wherein A is an aromatic polycycle, R1 and R2 are independently hydrogen atom or alkyl, and n is 1, 2 or 3, are disclosed. They are useful as a component of nonemanating, self-curing and heat resistant resin compositions.
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- PHENOLIC RESINS MANUFACTURED BY POLYCONDENSATION IN THE SOLID STATE FROM PURE PRECURSORS; CRYSTALLOGRAPHIC AND 13C NMR INVESTIGATIONS
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Two important precursors of phenolic resins manufactured from phenol are studied.Crystal stuctures and 13C NMR spectra in solide state are determined for these pure compounds.The thermal polycondensation of one precursor is monitored by 13C NMR.
- Perrin, Robert,Bertholon, Guy,Grenier-Loustalot, M. F.,Lamartine, Roger,Perrin, Monique,Thozet, Alain
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p. 155 - 162
(2007/10/02)
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- CONDENSATION OF PHENOL WITH ALDEHYDES IN THE PRESENCE OF ALUMINUM PHENOLATE
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The reaction of phenol with aldehydes in the presence of aluminum phenolate leads to mixtures of the corresponding 1,1-bis(hydroxyphenyl)alkanes.The 2,2' or 2,4' isomers predominate, depending on the structure of initial aldehyde.
- Kozlikovskii, Ya. B.,Chernyaev, B. V.
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p. 2198 - 2201
(2007/10/02)
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- The Synthesis of 4,11,18,25-Tetrachloro4>metacyclophane-7,14,21,28-tetrol. Structural Analogues of Phloroglucides
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The synthesis of the title compounds is described.Some of the compounds prepared exhibited antimicrobial activity in vitro.Structure-activity relationship is briefly discussed.
- Moshfegh, Ali A.,Badri, Rashid,Hojjatie, Massoud,Kaviani, Mehrangiz,Naderi, Basirat,et al.
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p. 1221 - 1228
(2007/10/02)
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