- Homocoupling of a Grignard Reagent toward the Synthesis of 2,2′-Bis(trifluoromethyl)-4,4′-diaminobiphenyl
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A new process for the synthesis of 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl (TFMB) comprising three steps has been industrially developed. The first step is the homocoupling of the Grignard reagent derived from 1-chloro-2-(trifluoromethyl)benzene with iron chloride(III) in the presence of an oxidizing agent to afford 2,2′-bis(trifluoromethyl)biphenyl. The second step is the nitration of this biphenyl to 2,2′-bis(trifluoromethyl)-4,4′-dinitrobiphenyl, and the third step is the reduction of this dinitrobiphenyl using hydrogen over Pd/C to afford TFMB. This process has been demonstrated on an industrial scale.
- Nakatani, Jiro,Nozoe, Tatsuhiro
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supporting information
p. 2442 - 2446
(2021/11/13)
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- METHOD OF MANUFACTURING BIS(TRIFLUOROMEHTYL)DIAMINOBIPHENYL COMPOUND
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To exemplary embodiments of the present invention, a bis dinitrobiphenyl compound is prepared. On the solution the bis dinitrobiphenyl based compound is reacted with an alkali sulfide. The productivity of bis diaminobiphenyl compounds can be improved.
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Paragraph 0056-0089
(2021/09/21)
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- Synthesis method of 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl
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The invention discloses a synthesis method of 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl. The method comprises the following steps: subjecting 2-chloro-5-aminobenzotrifluoride serving as a starting raw material and acyclic anhydride in a formula I to amidation to obtain an intermediate II, then carrying out reductive coupling reaction on the intermediate II to obtain an intermediate III, and finally carrying out deamidation reaction on the intermediate III to obtain the 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, wherein the cyclic anhydride in the formula I is succinic anhydride, glutaric anhydride, adipic anhydride or maleic anhydride. The starting material 2-chloro-5-aminobenzotrifluoride is an important farm chemical and medical intermediate, and is low in price, convenient and easy to obtain; the synthesis route is short, the reaction condition is mild, and the method is environment-friendly; the total yield of the synthetic route can reach 60-80%, and compared with the prior art, the synthetic route has obvious advantages and is suitable for industrial mass production.
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- Preparation method of 2,2'-bis (trifluoromethyl)-4,4'-diaminobiphenyl
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The invention discloses a preparation method of 2,2'-bis (trifluoromethyl)-4,4'-diaminobiphenyl. The method comprises the following steps: S1, preparing 3,3'-bis (trifluoromethyl) diphenylhydrazine through catalytic reduction reaction by taking m-nitrobenzotrifluoride and hydrazine hydrate as raw materials and taking low-boiling-point alcohol as a solvent under the catalysis of inorganic base and palladium carbon at 40-76 DEG C; and S2, in a protective gas atmosphere, adding the 3,3'-bis (trifluoromethyl) diphenylhydrazine prepared in the step S1 into inorganic acid, and preparing 2,2'-bis (trifluoromethyl)-4,4'-diaminobiphenyl through a rearrangement reaction at a temperature of -10 DEG C to 20 DEG C. According to the invention, hydrazine hydrate is used as a reducing agent instead of hydrogen, the use amount of the hydrazine hydrate is small, the reaction condition is mild, the requirement on equipment is low, and the catalyst is small in use amount, reusable and low in cost.
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Paragraph 0027; 0031-0033; 0037-0039; 0043-0045; 0049; ...
(2021/06/26)
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- Preparation Method for 2,2'-Bis(Trifluoromethyl)-4,4'-Diaminobiphenyl
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The present invention relates to a method for producing 3,3 '- bis 2,2 - diaminobiphenyl by a benzidine rearrangement reaction from' -4 bis hydrazinobenzene in high yield, and more specifically, to dissolve 4 3,3 '-' - bis hydrazinobenzene in (A) organic solvent. (B) The solution prepared in (A) is added dropwise to an inorganic acid solution while maintaining a temperature below 0 °C.30°C. When the (C) titration is completed, less than 0 °C -30°C or less is reacted. 2,2 '- Bis -4, 4' - diaminobiphenyl, which is characterized in that it comprises.
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Paragraph 0026-0037
(2021/07/20)
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- Method for preparing polyimide monomer having low yellow index
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The present invention chemically synthesizes a polyimide monomer. 10. The synthesized polyimide monomer is introduced into the loading area of the sublimation purification apparatus. - 3 TTTorr under vacuum above sublimation temperature of the synthesized polyimide monomer, followed by recrystallization. Provided is a method for preparing a polyimide monomer having improved yellowness index.
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Paragraph 0039; 0050-0051
(2021/11/02)
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- DIAMINE COMPOUND, POLYIMIDE PRECURSOR AND POLYIMIDE FILM PREPARED BY USING SAME
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The present invention discloses a novel diamine having a structure including an intramolecular imide group while having an aromatic ring group with a rigid structure. In addition, and by comprising the novel diamine as a polymerization component, the present invention can provide a polyimide film having improved mechanical and thermal properties while maintaining optical properties of polyimide.
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Paragraph 0250-0251; 0253; 0258-0259; 0261
(2020/09/26)
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- Preparation method of 2,2'-bis(trifluoromethyl)-4,4'-biphenyldiamine
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The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of 2,2'-bis(trifluoromethyl)-4,4'-biphenyldiamine. The preparation method comprisesthe following steps of coupled reaction: in a polar aprotic solvent, under the catalysis effect of a main catalyst and a cocatalyst and the activation effect of ligands, 2-bromine-5-nitrobenzotrifluoride takes coupled reaction to generate 2,2'-bis(trifluoromethyl)-4,4'-dinitrobipheny; (2) hydrogenation reaction: the 2,2'-bis(trifluoromethyl)-4,4'-dinitrobipheny prepared in the first step, catalysts and solvents are mixed, and react with hydrogen gas in a microchannel for hydrogenation reaction; the 2,2'-bis(trifluoromethyl)-4,4'-biphenyldiamine is obtained. The preparation method has the advantages that the operation is simple; the catalyst consumption is little; the reaction energy consumption is low; the yield and the purity of the product are improved; the method is applicable to continuous production.
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Paragraph 5-7
(2019/04/10)
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- Preparation method of 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl
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The invention relates to a preparation method of 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl. The preparation method comprises the following steps: synthesizing 3,3'-bis(trifluoromethyl)hydrazo-benzene in an inorganic alkaline aqueous solution by adopting nitrobenzotrifluoride as a raw material, adopting a phase transfer catalyst, a co-catalyst and Pd/C as a catalytic system and adopting aromatic hydrocarbon as a solvent, and performing the re-arrangement reaction on the 3,3'-bis(trifluoromethyl)hydrazo-benzene in an inorganic acid aqueous solution, thus obtaining 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl, wherein the phase transfer catalyst is one or a mixture of more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and cetyl trimethyl ammonium bromide, and the co-catalyst is one or a mixture of more of 2,3-dichloro-1,4-naphthoquinone, 2-hydroxyanthraquinone and 2,6-dioxyanthraquinone. The preparation method has the advantages of mild reaction condition, simple process, high product quality and yield, low production cost, environmental friendliness, suitability for continuous production and the like.
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Paragraph 0029; 0031; 0032; 0034; 0035; 0037; 0038; 0040
(2019/02/04)
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- Preparation method of 2,2'-bis-trifluoromethyl-4,4'-diaminodiphenyl
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The invention relates to a preparation method of 2,2'-bis-trifluoromethyl-4,4'-diaminodiphenyl. The preparation method includes the steps that 2,2'-bis-trifluoromethyl-4,4'-diaminodiphenyl is dissolved in polar proton solvent methyl alcohol, reducing agent anhydrous ammonium formate and catalyst zinc powder are added, the temperature is raised to 30-50 DEG C for a reaction till the raw material 2,2'-bis-trifluoromethyl-4,4'-diaminodiphenyl completely reacts, heat filtration is conducted, a filter cake is washed with methyl alcohol, filter liquor is decompressed, the solvent is recovered, after crystals are separated out, cooling and filtering are conducted, and off-white crystals, namely, 2,2'-bis-trifluoromethyl-4,4'-diaminodiphenyl are obtained. According to 2,2'-bis-trifluoromethyl-4,4'-diaminodiphenyl, the ratio of anhydrous ammonium formate to the zinc powder to methyl alcohol is 1:(4-8):(0.1-0.2):(30-40). Ammonium formate is adopted for reducing, the zinc powder is adopted as the catalyst, and the advantages of being high in reaction yield, mild in condition, low in cost, simple in after-treatment, environmentally friendly and the like are achieved.
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Paragraph 0017; 0018
(2016/11/21)
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- PROCESS FOR PRODUCTION OF 2,2'-BIS(TRIFLUOROMETHYL)- 4,4'-DIAMINOBIPHENYL
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The present invention is a method for producing of 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, wherein 2,2'-bis(trifluoromethyl)biphenyl is produced from o-chlorobenzotrifluoride, further, 2,2'-bis(trifluoromethyl)biphenyl is dinitrated in 1,2-dichloropropane solution, and 2,2'-bis(trifluoromethyl)-4,4'-dinitrobiphenyl is isolated and reduced. The method for producing of 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl of the present invention is an industrially excellent method for producing with high safety and high production efficiency.
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Page/Page column 7
(2009/09/28)
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- Process for Producing 2,2'-Bis(Trifluoromethyl)-4,4'-Diaminobiphenyl
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A process for producing 2,2′-bis (trifluoromethyl)-4,4′-diaminobiphenyl which is useful as a raw material for polyimide resin, etc. In benzidine rearrangement of 3,3′-bis(trifluoromethyl) hydrazobenzene in the presence of an inorganic acid such as sulfuric acid aqueous solution or concentrated hydrochloric acid, use of a water-immiscible organic solvent such as toluene as reaction solvent can increase the yield of the product. 3,3′-bis(trifluoromethyl) hydrazobenzene can be synthesized by reduction of m-nitrobenzotrifluoride.
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Page/Page column 2
(2009/04/24)
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- Functionalized Photoreactive Compounds
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The present invention concerns functionalized photoreactive compounds of formula (I), that are particularly useful in materials for the alignment of liquid crystals. Due to the adjunction of an electron withdrawing group to specific molecular systems bearing an unsaturation directly attached to two unsaturated ring systems, exceptionally high photosensitivities, excellent alignment properties as well as good mechanical robustness could be achieved in materials comprising said functionalized photoreactive compounds of the invention.
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- PROCESS FOR PRODUCING 2,2'-BIS(TRIFLUOROMETHYL)-4,4'-DIAMINOBIPHENYL
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A process for producing 2,2'-bis (trifluoromethyl)-4,4'-diaminobiphenyl which is useful as a raw material for polyimide resin, etc.. In benzidine rearragement of 3,3'-bis(trifluoromethyl) hydrazobenzene in the presence of an inorganic acid such as sulfuric acid aqueous solution or concentrated hydrochloric acid, use of a water-immiscible organic solvent such as toluene as reaction solvent can increase the yield of the product. 3,3'-bis(trifluoromethyl) hydrazobenzene can be synthesized by reduction of m-nitrobenzotrifluoride.
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- PROCESS FOR PRODUCING 2,2'-BIS(TRIFLUOROMETHYL)-4,4'-DIAMINOBIPHENYL
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A process for producing 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, which is useful as a material for polyimide resins, etc. It comprises using a water-immiscible organic solvent, such as toluene, as a reaction solvent to conduct the benzidine rearrangement of 3,3'-bis(trifluoromethyl)hydrazobenzene in the presence of an inorganic acid such as an aqueous sulfuric acid solution or concentrated hydrochloric acid. Thus, the rearrangement yield is heightened. The 3,3'-bis(trifluoromethyl)hydrazobenzene can be synthesized by the reduction of m-nitrobenzotrifluoride.
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Page/Page column 5; 6
(2008/06/13)
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- DICARBOXYLIC ACID DERIVATIVES AS PPAR-AGONISTS
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A novel class of dicarboxylic acid derivatives, the use of these compounds as phar-maceutical compositions, pharmaceutical compositions comprising the compounds and meth-ods of treatment employing these compounds and compositions. The present compounds may be useful in the treatment and/or prevention of conditions mediated by Peroxisome Prolifera-tor-Activated Receptors (PPAR).
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