- Mechanism study on Raney nickel-catalyzed amination of resorcinol
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Amination of resorcinol catalyzed by Raney nickel has been examined with good yield. Using the first principle density functional theory, some detailed mechanism of the amination of resorcinol on the Ni(111) surface is explored. The resorcinol is adsorbed on the Ni surface at the hollow site to form ketone by isomerization. The isomerization has a barrier of 122.1 kJ/mol. Ketone can couple with secondary amine mediated by resorcinol to afford hemiaminal. For the formation of hemiaminal, the steric effect of the alkyl group of secondary amine is obvious. Hemiaminal undergoes dehydration to get final product, which occurs by the preferred adsorption in the bridge site, cleavage of CO bond initially, followed by subsequent cleavage of CH bond.
- Ge, Xin,Pan, Jiong-Bin,Qian, Chao,Feng, Lie,Chen, Yun-Bin,Chen, Xin-Zhi
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Read Online
- Method for synthesizing M-diethylaminophenol
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The invention provides a method for synthesizing m-diethylaminophenol. The method comprises the following steps: mixing potassium hydroxide and magnesium oxide, and calcining at 700-800 DEG C to obtain a solid super base catalyst; adding sodium amide and the solid super base catalyst into diethylamine, stirring, keeping the temperature at 3-8 DEG C, dropwise adding o-chlorophenol within 20 minutes, stirring for 10-20 minutes after dropwise adding is finished, starting ultrasonic oscillation, heating, carrying out reflux reaction for 10-30 minutes, carrying out reduced pressure rotary evaporation to recover diethylamine, adding xylene, stirring, cooling to 5 DEG C or below, and adding water to quench the catalyst; and adjusting the pH value of a water layer to be neutral or weakly acidic, and recovering xylene to obtain the m-diethylaminophenol finished product. The method disclosed by the invention not only is short in time and high in efficiency, but also does not use expensive m-aminophenol raw materials, so that the problem of troublesome post-treatment is solved; meanwhile, potential safety hazards caused by using unsafe catalysts can be avoided, so that m-diethylaminophenol production is safer, more economical and more efficient, and industrialization is better facilitated.
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Paragraph 0016-0020
(2021/01/15)
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- A inter-b-aminophenol preparation method
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The invention belongs to organic synthesis and chemical raw material preparation technical field, and in particular relates to inter-b-aminophenol and intermediate preparation method, inter-b-aminophenol of the preparation method, comprises the steps of: (1) dinitrobenzene substituted benzyl alcohol generated by the reaction with 1 - benzyloxy - 3 - nitrophenyl; (2) 1 - benzyloxy - 3 - nitrobenzene with acetaldehyde in the foaming PH to acid substituted in the reaction solution, or 1 - benzyloxy - 3 - nitrobenzene with acetaldehyde to replace after the recovery of the solvent of the reaction solution dissolved in the dissolving of the re-dissolved solution in organic solvent, by reducing amination and catalytic debenzylation of hydrogenation generating inter-b-aminophenol. 1 - Benzyloxy - 3 - nitrophenyl without separation and purification, directly with the aldehyde and hydrogen reduction amination and debenzylation of hydrogenation reaction. The method is simple, mild condition, equipment strength requirement is low, not produce waste, environment friendly, easily available raw materials, high yield, is suitable for the large-scale generation.
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Paragraph 0036-0051; 0055-0063
(2019/07/01)
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- Synthesis process of sulfonic-group rhodamine compound
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The invention discloses a synthesis process of a sulfonic-group rhodamine compound. The process comprises the steps: mixing saccharin and a protonic acid catalyst, performing heating for a reaction soas to obtain a compound shown in a formula (I), performing a reaction between a compound shown in a formula (II) and resorcinol through heating under the action of the protonic acid catalyst so as toobtain a compound shown in a formula (III), performing a reaction between the compound of the formula (I) and the compound in the formula (III) through heating under the action of a Lewis acid catalyst under the conditions of nitrogen protection and light shielding so as to obtain the sulfonic-group rhodamine compound shown in a formula (IV). Through the synthesis process, the use of thionyl chloride in a conventional process is avoided, the operation is simplified, the production safety is improved, the pollution to the environment is little, the reaction can be carried out under normal pressure, and the reaction has a high selectivity; and the chemical structural formulas of the compounds represented separately by the formula (I), the formula (II), the formula (III) and the formula (IV)are shown.
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Paragraph 0027; 0030; 0033; 0035; 0038; 0040
(2019/04/26)
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- Inter-alkane amidogen phenolic synthetic method (by machine translation)
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Inter-alkane amidogen phenolic synthetic method, its characteristic is: 1st step, between the two alkane amidogen acyl aniline and sulfuric acid aqueous solution mixing and heating to 50 - 110 °C, thermal insulation reaction of aniline [...] sulfuric acid aqueous solution; 2nd step, continue to drip the sodium nitrite aqueous solution, sodium nitrite aqueous solution for dropping temperature of - 10 - 20 °C, drop bi yu 5 - 30 °C insulation, [...] aniline obtained diazonium salt of the sulfuric acid aqueous solution; 3rd step, [...] aniline diazonium salt of the sulfuric acid aqueous solution is directly heated to 45 - 110 °C, thermal insulation, in the hydrolysis reaction of the diazonium salt, cooling after treatment, to obtain the product between two alkane amidogen phenol; three-step required by the reaction of sulfuric acid in the 1st step reaction in the finished disposable adding; a three-step reaction in a finish step by step in the pot. The method of the invention with raw materials are cheap, abundant, synthetic high security of the process, the product yield is high, the three waste less pollution and the like, has high industrial value. (by machine translation)
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Paragraph 0020
(2019/01/23)
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- Method for continuously synthesizing meta-di-alkane aminophenol
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The invention discloses a method for continuously synthesizing meta-di-alkane aminophenol. The technical scheme includes that continuous diazotization or continuous diazonium salt hydrolysis or continuous diazotization and diazonium salt hydrolysis is carried on raw materials such as di-alkane aminophenol, sodium nitrite and sulfuric acid, and after-treatment such as extraction is carried out to obtain the meta-di-alkane aminophenol which is a product. The method has the advantages that the raw materials can come from sufficient sources and are low in cost, processes for synthesizing the meta-di-alkane aminophenol are high in safety, products are high in yield, the method is little in waste gas, wastewater and industrial residue pollution, is green and environmental friendly and has a highindustrialization value, and the like.
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Paragraph 0020; 0032
(2019/01/23)
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- A benzothiazole-rhodol based luminophor: ESIPT-induced AIE and an application for detecting Fe2+ ion
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Herein, we designed and synthesized a luminophor, Rh-F, which is an intergrant of rhodol and 2-hydroxy benzothiazole by introducing a benzothiazole unit onto the ortho-position of the phenolic hydroxy of rhodol. Rh-F exhibited excellent fluorescence properties such as a large Stokes shift (>180 nm) and the synergistic effect of aggregation-induced emission (AIE) and an excited state intramolecular proton transfer (ESIPT) feature. The AIE/ESIPT mechanism was thoroughly explored using X-ray single-crystal structures and photophysical determinations. Furthermore, Rh-F showed a sensitive fluorescence response to Fe2+ with low detection limits of 115.2 nM and high selectivity. Studies of its sensing mechanism indicated that the Fe2+-induced blue-green fluorescence-quenched at 525 nm originates from an irreversible Fe2+ chelate with the oxygen atom of the hydroxyl group and the N atom of the benzothiazole moiety. This blocked the ESIPT process of Rh-F which resulted in the quenching of the fluorescence sensor for Rh-F.
- Guan, Jianping,Tu, Qin,Chen, Long,Yuan, Mao-Sen,Wang, Jinyi
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supporting information
(2019/06/03)
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- Synthetic method for m-dialkylaminophenol
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The invention provides a synthetic method for m-dialkylaminophenol. The synthetic method is characterized by comprising the following steps: step 1, adding an aqueous solution of sodium nitrite into an aqueous solution of sulfuric acid containing m-dialkylaminoaniline drop by drop at a temperature of -10 to 20 DEG C, and maintaining the obtained solution at a temperature of 5 to 30 DEG C for 1 to10 h after completion of the addition so as to obtain an aqueous solution of sulfuric acid containing m-dialkylaminoaniline diazohydrosulfate; and step 2, directly heating aqueous solution of sulfuricacid containing m-dialkylaminoaniline diazohydrosulfate to 45-110 DEG C, maintaining the solution at the temperature for 1-18 h, allowing m-dialkylaminoaniline diazohydrosulfate to undergo the hydrolysis reaction of a diazonium salt, and successively carrying out cooling and post-treatment so as to obtain the product dialkylaminophenol, wherein sulfuric acid needed in the first step and the second step is totally added in one shot in a first-step reaction, and the first-step diazotization reaction and the second-step hydrolysis reaction of the diazonium salt are carried out step by step in one pot. The method of the invention has the characteristics of low raw material price, sufficient raw material sources, high safety, high product yield, less three-wastes pollution and the like, and has high industrialization value.
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Paragraph 0019
(2019/01/08)
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- An asymmetric near red foreign acid dye and its preparation method and application
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The invention discloses an asymmetric near-infrared squaraine dye, a preparation method thereof and an application thereof. According to the invention, an m-aminophenol derivative and the squaric acid are mixed to dissolve in an appropriate solvent, and then are subjected to the backflow water-diversion treatment in the nitrogen protection environment. After that, the resultant obtained reaction mixture is cooled to be at the room temperature and subjected to the decompression treatment to remove the solvent. The resultant crude product is purified through the silica gel column chromatography process to prepare the asymmetric near-infrared squaraine dye. According to the technical scheme of the invention, through introducing an oxygen-ether chain, the dissolvability of the squaraine dye in an aqueous solution can be effectively improved. The obtained asymmetric near-infrared squaraine dye is good in stability and excellent in optical performance, which can be used as a protein biomarker for dual responses of fluorescence reaction and colorimetric reaction. The asymmetric near-infrared squaraine dye can be applied in multiple fields of biological molecule marking, analyzing, separating, and the like.
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Paragraph 0035; 0036; 0037
(2018/02/04)
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- Synthesis and photophysical studies of new benzo[a]phenoxazinium chlorides as potential antifungal agents
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A set of four new benzo[a]phenoxazinium chlorides possessing ethyl, propyl, decyl and tetradecyl groups at the 9-amino function of the heterocycle along with a propyl group at the 5-amino position was efficiently synthesized. These compounds displayed fluorescence with maximum emission wavelengths of 673 and 685?nm, in anhydrous ethanol and water. All the benzo[a]phenoxazines were evaluated against the yeast Saccharomyces cerevisiae in a broth microdilution assay. It was found that their antifungal activity depended on the variation in the lengths of the aliphatic chains. The highest MIC activity of 1.56?μM was obtained for compound 7 comprising a di-alkylated propyl substituent at 9-amino position and a propyl chain at the 5-amino position of the heterocycle core.
- Leit?o, M. Inês P.S.,Raju, B. Rama,Naik, Sarala,Coutinho, Paulo J.G.,Sousa, Maria Jo?o,Gon?alves, M. Sameiro T.
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supporting information
p. 3936 - 3941
(2016/08/09)
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- Novel Potent Orthosteric Antagonist of ASIC1a Prevents NMDAR-Dependent LTP Induction
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Acid sensing ion channels 1a (ASIC1a) are of crucial importance in numerous physiological and pathological processes in the brain. Here we demonstrate that novel 2-oxo-2H-chromene-3-carboxamidine derivative 5b, designed with molecular modeling approach, inhibits ASIC1a currents with an apparent IC50 of 27 nM when measured at pH 6.7. Acidification to 5.0 decreases the inhibition efficacy by up to 3 orders of magnitude. The 5b molecule not only shifts pH dependence of ASIC1a activation but also inhibits its maximal evoked response. These findings suggest that compound 5b binds to pH sensor of ASIC1a acting as orthosteric noncompetitive antagonist. At 100 nM, compound 5b completely inhibits induction of long-term potentiation (LTP) in CA3-CA1 but not in MF-CA3 synapses. These findings support the knockout data indicating the crucial modulatory role of ASIC1a channels in the NMDAR-dependent LTP and introduce a novel type of ASIC1a antagonists (Chemical Equation).
- Buta, Andriy,Maximyuk, Oleksandr,Kovalskyy, Dmytro,Sukach, Volodymyr,Vovk, Mykhailo,Ievglevskyi, Oleksandr,Isaeva, Elena,Isaev, Dmytro,Savotchenko, Alina,Krishtal, Oleg
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p. 4449 - 4461
(2015/06/25)
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- Preparation of carbocylic M-aminohydroxyaromatics
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A process for preparing carbocyclic m-aminohydroxyaromatics comprises reacting the corresponding o-- or m-halohydroxyaromatics or metal salts thereof with primary or secondary amines in the presence of a base and in the presence or absence of a diluent.
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- 1:2 chromium complex dyestuffs
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1:2 chromium complex dyestuffs of the formula (I) STR1 in which A, B, R1, R2, R3, R4, p, m, n, n' and Cat(+) have the meaning given in the description, are suitable for dyeing and printing amido-containing materials.
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- Hydroxylation directe d'anilines en aminophenols
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Anilines react with hydrogen peroxide in SbF5-HF to give aminophenols.The formation of the products can be accounted for by the reaction of the electrophile H3O2+ on the anilinium ions.For compounds 1a-4a, the reaction yields three possible aminophenols, the meta isomer being the major product.The process is more selective with ortho toluidine 5a and para toluidine 6a, giving aminophenol(s) 5c (42percent)) and 5e (21percent), and 6c (71percent), respectively.With meta toluidine 7a, only aminophenol 7d (35percent) can be isolated from the complex reaction mixture, ring substitution pattern of the substrate favoring para hydroxylation.
- Jacquesy, Jean-Claude,Jouannetaud, Marie-Paule,Morellet, Guy,Vidal, Yves
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p. 625 - 629
(2007/10/02)
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- DIRECT CONVERSION OF ANILINES INTO AMINOPHENOLS
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Hydroxylation of anilines by hydrogen peroxide in SbF5-HF yields the three possible aminophenols, the meta isomer being the major product.The reaction implies attack of protonated hydrogen peroxide H3O2(1+) on the N-protonated substrate.
- Jacquesy, Jean-Claude,Jouannetaud, Marie-Paule,Morellet, Guy,Vidal, Yves
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p. 1479 - 1482
(2007/10/02)
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- Indolyl phthalide compounds
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3-Aryl-3-indolylphthalides, 3-aryl-3-pyrrolylphthalides and 3-aryl-3-carbazolylphthalides prepared by interaction of the appropriate 2-(heteroaryl)carbonylbenzoic acid and the appropriate phenylamine, and 3,3-bis(indolyl)phthalides prepared by the interaction of the appropriate 2-(indolyl)carbonylbenzoic acid and the appropriate indole are useful as color formers in pressure-sensitive carbonless duplicating systems, thermal marking systems and hectographic copying systems.
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- Phthalide compounds, processes and marking systems
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3-Aryl-3-indolylphthalides, 3-aryl-3-pyrrolylphthalides and 3-aryl-3-carbazolylphthalides prepared by interaction of the appropriate 2-(heteroaryl)carbonylbenzoic acid and the appropriate phenylamine, and 3,3-bis(indolyl)phthalides prepared by the interaction of the appropriate 2-(indolyl)carbonylbenzoic acid and the appropriate indole are useful as color formers in pressure-sensitive carbonless duplicating systems, thermal marking systems and hectographic copying systems.
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- Heteroarylphthalides
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3-Aryl-3-indolylphthalides, 3-aryl-3-pyrrolylphthalides and 3-aryl-3-carbazolylphthalides prepared by interaction of the appropriate 2-(heteroaryl)carbonylbenzoic acid and the appropriate phenylamine, and 3,3-bis(indolyl)-phthalides prepared by the interaction of the appropriate 2-(indolyl)carbonylbenzoic acid and the appropriate indole are useful as color formers in pressure-sensitive carbonless duplicating systems, thermal marking systems and hectographic copying systems.
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