- The Reaction of 2,4,6-Trihalophenols with Tropylium Perchlorate. A New Route for Triphenylmethane-Type Pigments
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The reaction of 2,4,6-tribromo- and triiodophenols with tropylium perchlorate in the presence of triethylamine gave 4-(3,5-dihalo-4-hydroxy-α-phenylbenzylidene)-2,6-dihalo-2,5-cyclohexadien-1-ones, respectively.
- Morita, Tadayoshi,Takahashi, Kazuko,Nozoe, Tetsuo
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- Metal- And solvent-free synthesis of aniline- And phenol-based triarylmethanes: Via Br?nsted acidic ionic liquid catalyzed Friedel-Crafts reaction
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A beneficial, scalable and efficient methodology for the synthesis of aniline-based triarylmethanes has been established through the double Friedel-Crafts reaction of commercial aldehydes and primary, secondary or tertiary anilines using Br?nsted acidic ionic liquid as a powerful catalyst, namely [bsmim][NTf2]. This protocol was successfully performed under metal- and solvent-free conditions with a broad range of substrates, giving the corresponding aniline-based triarylmethane products in good to excellent yields (up to 99%). In addition, alternative aromatic nucleophiles such as phenols and electron-rich arenes were also studied using this useful approach to achieve a diversity of triarylmethane derivatives in high to excellent yields. This journal is
- Jaratjaroonphong, Jaray,Saeeng, Rungnapha,Senapak, Warapong,Sirion, Uthaiwan,ponpao, nipaphorn
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p. 22692 - 22709
(2021/07/21)
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- METHOD FOR PRODUCING BISPHENOL COMPOUND
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PROBLEM TO BE SOLVED: To provide a method for producing an aldehyde bisphenol compound, where, a specific catalyst and a second component are combined, to efficiently and easily obtain a 4,4'-substituted body with a significantly high regioselectivity. SOLUTION: When an aldehyde bisphenol compound is produced from a phenol and an aldehyde, the production is conducted in coexistence with a heteropoly acid as an acid catalyst and a specific mercapto compound. SELECTED DRAWING: None COPYRIGHT: (C)2019,JPOandINPIT
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Paragraph 0185
(2019/06/26)
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- METHOD FOR PRODUCING BISPHENOL COMPOUND
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PROBLEM TO BE SOLVED: To provide a method for producing an aldehyde bisphenol compound, wherein a 4,4'-substituted body is obtained efficiently and easily with significantly high regioselectivity. SOLUTION: When producing an aldehyde bisphenol compound from a phenol and an aldehyde, a heteropoly acid is used as an acid catalyst. The heteropoly acid has: a hydrogen atom; an oxygen atom; an atom of Groups 5 to 6 in the periodic table; and an atom of Groups 7 to 16 in the periodic table, excluding the oxygen atom, as constituent atoms, respectively, with the ratio between the number of hydrogen atoms/the number of anions being 0.080 or more. SELECTED DRAWING: None COPYRIGHT: (C)2020,JPOandINPIT
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Paragraph 0193-0194; 0196; 0198; 0200-0205
(2019/12/25)
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- METHOD FOR PRODUCING BISPHENOL COMPOUND
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PROBLEM TO BE SOLVED: To provide a method for producing an aldehyde bisphenol compound, wherein a 4,4'-substituted body is obtained efficiently and easily with significantly high regioselectivity. SOLUTION: When producing an aldehyde bisphenol compound from a phenol and an aldehyde, a heteropoly acid is used as an acid catalyst, the heteropoly acid represented by the following formula (I): Hn(X2Y18O62) [where, n is an integer of 1 or greater, represented by the following formula (II), X is a p-valent atom of Groups 7 to 16 in the periodic table, excluding the oxygen atom, Y is a p-valent atom of Groups 5 to 6 in the periodic table, where p and q are valences of X and Y and represented by the number of 1 or more]. The formula (II): n=124-2p-18q [where, n, p and q are the same as described in the formula (I)]. SELECTED DRAWING: None COPYRIGHT: (C)2020,JPOandINPIT
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Paragraph 0191; 0194
(2019/12/31)
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- Solventless triarylmethane synthesis via hydroxyalkylation of anisole with benzaldehyde by modified heteropoly acid on mesocellular foam silica (MCF)
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Triarylmethane (TRAM) compounds have wide applications such as leuco dyes for sensing tumors and other biological activities. Hydroxyalkylation of arenes with benzaldehyde results in formation of triarylmethane compounds. In the present study, 20 (wt.%) Cs2.5H0.5PW12O40 (Cs-DTP) supported on mesocellular foam (MCF) silica was prepared, characterized and tested for its activity in hydroxyalkylation reaction of anisole with benzaldehyde. Its activity was compared with commercial catalysts like Amberlyst-15, montmorillonite clay K-10, H3PW12O40 and unsupported Cs2.5H0.5PW12O40.The prepared catalyst showed the best activity compared to others with advantage of separation of catalyst and reusability. Reaction parameters were studied in detail and kinetic study was carried out for the said reaction. 20 (wt. %) Cs-DTP/MCF was found to be the best, robust and reusable catalyst. Reaction mechanism and kinetics were also studied. The results are new.
- Bhadra, Kalpesh H.,Yadav, Ganapati D.
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p. 150 - 158
(2018/06/18)
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- Br?nsted acid ionic liquids catalyzed Friedel-Crafts Alkylations of electron-rich arenes with aldehydes
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Triarylmethanes (TRAMs) and diarylalkanes (DIAAs) are valuable intermediates with wide applications in many fields. TRAMs are usually obtained from the acid-catalysed bisarylation of activated aryl aldehydes. However, the synthesis poses many problems, such as harsh reaction conditions, and the disposal of the excess solvents and/or toxic metal waste. In this study, some functionalized ionic liquids including Br?nsted acid ionic liquids (BAILs) and traditional ionic liquids were designed and synthesized. BAILs catalyzed Friedel-Crafts (F-C) alkylation was applied in this specific reaction for the first time. And the BAILs showed bifunctional properties acting as catalyst and solvent. Research shows that BAILs can be used for catalyzing F-C alkylations of electron-rich arenes with aromatic or aliphatic aldehydes successfully under mild reaction conditions. Furthermore, BAILs containing triflic anion has higher activity than other BAILs and traditional ionic liquids. [HSO 3-pmim][OTf] gets the highest yields in the presence of 20 mol% of BAILs at 40 °C to give the corresponding TRAMs derivatives. After five cycles, the yields remain about 93-97%. Finally, according to IR spectrum and the experimental validation, the aromatic electrophilic substitution reaction was considered to be the possible catalysis mechanisms.
- Wang, Ailing,Zheng, Xueliang,Zhao, Zhuangzhi,Li, Changping,Cui, Yingna,Zheng, Xuefang,Yin, Jingmei,Yang, Guang
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p. 198 - 204
(2014/07/08)
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- Room-temperature bismuth-catalyzed bis-arylation of carbonyl compounds with aryl ethers and phenols
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Using Bi2(SO4)3 as the catalyst and TMSCl as the additive, a wide variety of aldehydes, ketones, and acetals were smoothly condensed with aryl ethers at room temperature to provide the corresponding diarylmethanes and triarylmethanes selectively in good to excellent yields. Using Bi2(SO4)3 as the catalyst and TMSCl as the additive, a wide variety of aldehydes, ketones, and acetals were smoothly condensed with aryl ethers at room temperature to selectively provide the corresponding diarylmethanes and triarylmethanes in good to excellent yields. Copyright
- Liu, Congrong,Li, Manbo
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p. 1274 - 1278
(2013/11/06)
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- Linear free-energy relationship analysis of a catalytic desymmetrization reaction of a diarylmethane-bis(phenol)
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(Figure presented) Linear free-energy relationships have been found for enantioselectivity and various steric parameters in an enantioselective desymmetrization of symmetrical bis(phenol) substrates. The potential origin of this observation and the role of different steric parameters are discussed.
- Gustafson, Jeffrey L.,Sigman, Matthew S.,Miller, Scott J.
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supporting information; experimental part
p. 2794 - 2797
(2010/09/04)
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- A case of remote asymmetric induction in the peptide-catalyzed desymmetrization of a bis(phenol)
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We report a catalytic approach to the synthesis of a key intermediate on the synthetic route to a pharmaceutical drug candidate in single enantiomer form. In particular, we illustrate the discovery process employed to arrive at a powerful, peptide-based asymmetric acylation catalyst. The substrate this catalyst modifies represents a remarkable case of desymmetrization, wherein the enantiotopic groups are separated by nearly a full nanometer, and the distance between the reactive site and the pro-stereogenic element is nearly 6 A. Differentiation of enantiotopic sites within molecules that are removed from the prochiral centers by long distances presents special challenges to the field of asymmetric catalysis. As the distance between enantiotopic sites increases within a substrate, so too may the requirements for size and complexity of the catalyst. The approach presented herein contrasts enzymatic catalysts and small-molecule catalysts for this challenge. Ultimately, we report here a synthetic, miniaturized enzyme mimic that catalyzes a desymmetrization reaction over a substantial distance. In addition, studies relevant to mechanism are presented, including (a) the delineation of structure-selectivity relationships through the use of substrate analogs, (b) NMR experiments documenting catalyst-substrate interactions, and (c) the use of isotopically labeled substrates to illustrate unequivocally an asymmetric catalyst-substrate binding event.
- Lewis, Chad A.,Gustafson, Jeffrey L.,Chiu, Anna,Balsells, Jaume,Pollard, David,Murry, Jerry,Reamer, Robert A.,Hansen, Karl B.,Miller, Scott J.
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supporting information; experimental part
p. 16358 - 16365
(2009/05/09)
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- Catalytic selective bis-arylation of imines with anisole, phenol, thioanisole and analogues
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The first highly efficient double Friedel-Crafts reaction of N-tosyl imines with anisole, phenol, thioanisole and analogues has been developed to produce the corresponding symmetric diarylmethanes and triarylmethanes with high regioselectivity in the presence of a catalytic amount of Bi2(SO 4)3-TMSCl at room temperature. The Royal Society of Chemistry.
- Liu, Cong-Rong,Li, Man-Bo,Yang, Cui-Feng,Tian, Shi-Kai
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p. 1249 - 1251
(2008/12/21)
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- Dual-reagent catalysis within Ir-Sn domain: Highly selective alkylation of arenes and heteroarenes with aromatic aldehydes
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(Chemical Equation Presented) Reactions of arenes and heteroarenes with aromatic aldehydes proceeded smoothly in the presence of a catalytic combination of [Ir(COD)Cl]2-SnCl4 to afford the corresponding triarylmethane derivatives (TRAMs) in high yields. This 100% TRAM selective transformation is clean and eliminates the use of acid systems.
- Podder, Susmita,Choudhury, Joyanta,Roy, Ujjal Kanti,Roy, Sujit
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p. 3100 - 3103
(2008/02/05)
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- Synthesis and sulfonation of poly(aryl ethers) containing triphenyl methane and tetraphenyl methane moieties from isocynate-masked bisphenols
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Wholly aromatic poly(aryl ethers) containing triphenylmethane and tetraphenylmethane moieties were successfully synthesized by aromatic nucleophilic substituting polycondensation from masked bisphenols and decafluorobiphenyl followed by sulfonation with chlorosulfonic acid. The sulfonation took place only at the para positions on the pendant phenyl rings due to the novel biphenol structures designed. For the synthesized polymers, the sulfonation content can be easily controlled and the water-takeup can be conveniently tailored by changing the amount of sulfonation agent. These sulfonated polymers are soluble in polar organic solvents, such as NMP, dimethylacetamide, dimethyl sulfoxide, dimethylformamide, and ethylene glycol monomethyl ether and can be readily cast into tough and smooth films from solutions. The films exhibited very high water absorption ability and superior mechanical strength. These polymers also showed high glass transition temperatures ranging from 176 to 203°C compared with Nafion. The sulfonated polymers can be potentially used as the proton-exchange membranes for fuel cells.
- Wang,Meng,Wang,Shang,Li,Hay
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p. 3151 - 3158
(2007/10/03)
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- MANUFACTURING METHOD FOR POLYCARBONATE
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A method for manufacturing polycarbonate by melt-polycondensing bisphenol and carbonic acid diester uses as catalyst an alkali metal compound and/or alkaline earth metal compound (a). The catalyst is added to the bisphenol prior to the melt polycondensation, in an effective amount, i.e., the amount of alkali metal compound and/or alkaline earth metal compound (a) that acts effectively as a catalyst, is contained in said bisphenol, and is controlled to have the same catalytic activity as 1×10?8 to 1×10?6 mole of bisphenol disodium salt per mole of pure bisphenol A. The method conducts the reaction efficiently from the initial stage in a stable manner to obtain polycarbonate with good color, good heat stability and color stability during molding and the like.
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- Method for manufacturing bisphenol
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A method for manufacturing bisphenol by reacting phenols and ketones, characterized (1) in that an alkali metal compound and/or alkaline earth metal compound is added to bisphenol obtained by reacting a phenol and a ketone, and (2) in that the basicity of the bisphenol is adjusted so as to be equivalent to an amount of 1 × 10-8to 1 × 10-6moles of bisphenol as disodium salt with respect to 1 mole of bisphenol provides a bisphenol in which there is no residue of the organic catalysts ordinarily used in manufacturing bisphenol, so that byproducts are not produced during purification, allowing bisphenol with outstanding color tone, thermal resistance, etc., to be obtained.
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- Process for the purification of bisphenols and preparation of polycarbonates therefrom
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A phenol and a ketone are reacted to form bisphenol, and the liquid bisphenol obtained or a mixed solution of said solution and a phenol is filtered through a calcined metal filter to obtain bisphenol which makes it possible to efficiently obtain bisphenol which either does not contain fine particulate impurities or contains such impurities only in minute amounts, and a method for manufacturing polycarbonate using bisphenol obtained bythis method. The filtration grade of the calcined metal filter should be 1.0 μm or less. After filtering, the calcined metal filter can be backwashed or chemically washed and then reused. The bisphenol should preferably be bisphenol A.
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- Metal cation-exchanged montmorillonite (Mn+-mont)-catalysed aromatic alkylation with aldehydes and ketones
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The alkylation of aromatic compounds with aldehydes and ketones in the presence of a variety of metal cation-exchanged montmorillonites (Mn+-mont; Mn+ = Zr4+, Al3+, Fe3+, Zn2+, H+, Na+) has been investigated. Al3+- and Zr4+-Monts are revealed to be effective as catalysts, while no reaction takes place with Na+-mont. Al3+-Mont-catalysed alkylation of phenol with several aldehydes produces mainly or almost solely the corresponding gem-bis(hydroxyphenyl)alkanes (bisphenols) in good yields, while that with several ketones affords selectively the corresponding alkylphenols in moderate to good yields. The alkylation always occurs at the carbonyl carbon without any skeletal rearrangement and the kind of products depends much on the steric hindrance of an electrophilic intermediary carbocation. The alkylation of anisole, veratrole and p-cresol proceeds well, while that of toluene, benzene, chlorobenzene and nitrobenzene scarcely occurs.
- Tateiwa, Jun-Ichi,Hayama, Ei,Nishimura, Takahiro,Uemura, Sakae
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p. 1923 - 1928
(2007/10/03)
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- Processes for producing aromatic polycarbonate oligomer and aromatic polycarbonate
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A process for producing continuously an aromatic polycarbonate oligomer by reacting an aromatic dihydroxy compound and an alkali metal base or an alkaline earth metal base with a carbonyl halide compound comprises: (1) feeding continuously to a tank reactor an aromatic dihydroxy compound, water, a molecular weight controlling agent, a polymerization catalyst, a carbonyl halide compound, and an organic solvent, and an alkali metal base or an alkaline earth metal base in an amount of 1.15-1.6 equivalents based on the aromatic dihydroxy compound, (2) carrying out the reaction with a residence time as defined by the following formula, where X is an amount of the polymerization catalyst in terms of mole % based on the amount of mole of the aromatic dihydroxy compound fed per unit time, and Y is a residence time (min.), and (3) continuously withdrawing the reaction mixture from the tank reactor to obtain an aromatic polycarbonate oligomer having a number average molecular weight of 1,000-10,000. An aromatic polycarbonate is produced by polycondensation of the aromatic polycarbonate oligomer.
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- Method for preparing aromatic bischloroformate compositions
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Bischloroformate oligomer compositions are prepared by passing phosgene into a heterogeneous aqueous-organic mixture containing at least one dihydroxyaromatic compound, with simultaneous introduction of a base at a rate to maintain a specific pH range and to produce a specific volume ratio of aqueous to organic phase. By this method, it is possible to employ a minimum amount of phosgene. The reaction may be conducted batchwise or continuously. The bischloroformate composition may be employed for the preparation of cyclic polycarbonate oligomers or linear polycarbonate, and linear polycarbonate formation may be integrated with bischloroformate composition formation in a batch or continuous process.
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- Bischoloroformate preparation method with phosgene removal and monochloroformate conversion
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Aqueous bischloroformates are prepared by the reaction of a dihydroxyaromatic compound (e.g., bisphenol A) with phosgene in a substantially inert organic liquid (e.g., methylene chloride) and in the presence of an aqueous alkali metal or alkaline earth metal base, at a pH below about 8. After all solid dihydroxyaromatic compound has been consumed, the pH is raised to a higher value in the range of about 7-12, preferably 9-11, and maintained in said range until a major proportion of the unreacted phosgene has been hydrolyzed. At the same time, any monochloroformate in the product may be converted to bischloroformate.
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- Cyclic monocarbonate bishaloformates
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Cyclic monocarbonate bischloroformates are prepared by the reaction of a carbonyl halide such as phosgene with a bridged substituted resorcinol or hydroquinone such as bis(2,4-dihydroxy-3-methylphenyl)methane or bis(2,5-dihydroxy-3,4,6-trimethylphenyl)methane in the presence of aqueous alkali metal hydroxide. The cyclic monocarbonate bischloroformates may be used for the preparation of linear or cyclic polycarbonates containing cyclic carbonate structural units, which may in turn be converted to crosslinked polycarbonates.
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- Polyetherimide bisphenol compositions
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Polyetherimide bisphenols and bischloroformates are prepared by the reaction of dianhydrides or certain bisimides with aminophenols or mixtures thereof with diamines. They are useful as intermediates for the preparation of cyclic heterocarbonates, which may in turn be converted to linear copolycarbonates. The bisphenols can also be converted to salts which react with cyclic polycarbonate oligomers to form block copolyetherimidecarbonates.
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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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