1073-69-4Relevant academic research and scientific papers
Solid-supported sulfonylhydroxylamine as an effective N-animating agent of anilines
Ohno, Hiroshi,Tanaka, Hiroshi,Takahashi, Takashi
, p. 1191 - 1194 (2005)
An effective method for the synthesis of aryl hydrazines by amination of anilines using the solid-supported phenylsulfonylhydroxylamine was described. Treatment of aniline with the solid-supported aminating agent, followed by removal of the resin, provided the corresponding hydrazine in 21% yield. The resulting hydrazines were directly adapted to the solid-phase synthesis of indoles, providing nine naltrindole derivatives varying the substituents on the aromatic rings.
Synthesis of benzofuro[3,2-b] indoline amines via deamination-interrupted Fischer indolization and their unexpected reactivity towards nucleophiles
Tomakinian, Terry,Guillot, Régis,Kouklovsky, Cyrille,Vincent, Guillaume
, p. 5443 - 5446 (2016)
We report the access to the benzofuro[3,2-b]indoline framework of phalarine from benzofuran-2-ones via the Fischer indolization reaction which was interrupted at the deamination step. Unexpectedly, allyl nucleophiles did not add to the aminal position of these benzofuro[3,2-b]indoline amines but to the adjacent ring junction center in the presence of trifluoroborane to deliver 3,3-disubstituted indolines containing a difluoroboron-containing six-membered ring with fluorescence properties.
Discovery of novel inhibitors of human phosphoglycerate dehydrogenase by activity-directed combinatorial chemical synthesis strategy
Gou, Kun,Luo, Youfu,Luo, Yuan,Sun, Qingxiang,Tan, Yuping,Tao, Lei,Zhao, Yinglan,Zhou, Xia,Zhou, Yue,Zuo, Zeping
, (2021/07/26)
Serine, the source of the one-carbon units essential for de novo purine and deoxythymidine synthesis plays a crucial role in the growth of cancer cells. Phosphoglycerate dehydrogenase (PHGDH) which catalyzes the first, rate-limiting step in de novo serine biosynthesis has become a promising target for the cancer treatment. Here we identified H-G6 as a potential PHGDH inhibitor from the screening of an in-house small molecule library based on the enzymatic assay. We adopted activity-directed combinatorial chemical synthesis strategy to optimize this hit compound. Compound b36 was found to be the noncompetitive and the most promising one with IC50 values of 5.96 ± 0.61 μM against PHGDH. Compound b36 inhibited the proliferation of human breast cancer and ovarian cancer cells, reduced intracellular serine synthesis, damaged DNA synthesis, and induced cell cycle arrest. Collectively, our results suggest that b36 is a novel PHGDH inhibitor, which could be a promising modulator to reprogram the serine synthesis pathway and might be a potential anticancer lead worth further exploration.
Cross-Coupling between Hydrazine and Aryl Halides with Hydroxide Base at Low Loadings of Palladium by Rate-Determining Deprotonation of Bound Hydrazine
Borate, Kailaskumar,Choi, Kyoungmin,Goetz, Roland,Hartwig, John F.,Shinde, Harish,Wang, Justin Y.,Zuend, Stephan J.
supporting information, p. 399 - 408 (2020/10/29)
Reported here is the Pd-catalyzed C–N coupling of hydrazine with (hetero)aryl chlorides and bromides to form aryl hydrazines with catalyst loadings as low as 100 ppm of Pd and KOH as base. Mechanistic studies revealed two catalyst resting states: an arylpalladium(II) hydroxide and arylpalladium(II) chloride. These compounds are present in two interconnected catalytic cycles and react with hydrazine and base or hydrazine alone to give the product. The selectivity of the hydroxide complex with hydrazine to form aryl over diaryl hydrazine was lower than that of the chloride complex, as well as the catalytic reaction. In contrast, the selectivity of the chloride complex closely matched that of the catalytic reaction, indicating that the aryl hydrazine is derived from this complex. Kinetic studies showed that the coupling process occurs by rate-limiting deprotonation of a hydrazine-bound arylpalladium(II) chloride complex to give an arylpalladium(II) hydrazido complex.
PROCESS FOR THE SYNTHESIS OF ARYL HYDRAZINES
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Page/Page column 21-23; 25; 26; 30; 31; 34; 35, (2020/06/01)
The invention relates to a process for the synthesis of aryl hydrazinesof formula I or a salt thereof, which process comprises subjecting an arene of formula II to a coupling reaction with hydrazine or a derivative thereof, wherein the coupling reaction is conducted in the presence of a catalyst comprising palladium and a diphosphine ligand, wherein the phosphorus atoms are connected through two, three, four, or five atoms selected from car- bon, nitrogen, oxygen or iron, and in which the non-connecting phosphorus substituents are C1- C 10-alkyl or C3-C10-cycloalkyl, wherein the amount of Pd used is up to 0.5 mol-% relative to the amount of arene of formula II; and a base.
Method for synthesizing 1-(2,4-dichlorophenyl)-3-methyl-4-difluoromethyl-1,2,4-triazole-5-ketone
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Paragraph 0056; 0057, (2018/03/28)
The invention discloses a method for synthesizing 1-(2,4-dichlorophenyl)-3-methyl-4-difluoromethyl-1,2,4-triazole-5-ketone. The method takes p-chloroaniline as a raw material, through diazotization, reduction, and salt forming, p-chlorophenylhydrazine hydrochloride is synthesized, p-chlorophenylhydrazine is obtained through alkali neutralization, under condition that tert-butyl alcohol is taken asa solvent, chlorophenylhydrazine, acetaldehyde, sodium cyanate and sodium hypochlorite are subjected to condensation, cyclisation and an oxidation reaction to generate 1-p-chlorophenyl-3-methyl-1H-1,2,4-triazole-5-ketone, and the 1-p-chlorophenyl-3-methyl-1H-1,2,4-triazole-5-ketone is subjected to salt forming, reaction with chlorodifluoromethane, and chlorination to obtain the 1-(2,4-dichlorophenyl)-3-methyl-4-difluoromethyl-1,2,4-triazole-5-ketone (a sulfentrazone intermediate). The synthetic method takes p-chloroanniline as the raw material, the synthetic method is realized by only one-time chlorination, steric hindrance for intermediate synthesis is small, and the impurity is low, so that the yield is increased; in addition, the raw materials required by the synthesis route are easilyacquired, the cost is low, the condition is mild, operation is simple, security is high, and the synthesis method is in favor of realizing industrial production.
Lewis Acid Catalyzed Annulation of Cyclopropane Carbaldehydes and Aryl Hydrazines: Construction of Tetrahydropyridazines and Application Toward a One-Pot Synthesis of Hexahydropyrrolo[1,2- b]pyridazines
Dey, Raghunath,Kumar, Pankaj,Banerjee, Prabal
, p. 5438 - 5449 (2018/05/28)
In this report, a facile synthesis of tetrahydropyridazines via a Lewis acid catalyzed annulation reaction of cyclopropane carbaldehydes and aryl hydrazines has been demonstrated. Moreover, the generated tetrahydropyridazine further participated in a cycloaddition reaction with donor-acceptor cyclopropanes to furnish hexahydropyrrolo[1,2-b]pyridazines. We also performed these two steps in one pot in a consecutive manner. In addition, a monodecarboxylation reaction of hexahydropyrrolo[1,2-b]pyridazine was achieved with a good yield.
Synthesis method of p-chlorophenyl hydrazine
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Paragraph 0013-0022, (2017/05/19)
The invention discloses a synthesis method of p-chlorophenyl hydrazine. The method comprises the following steps: (1) adding hydrazine hydrate into a four-neck flask, starting to stir and adding a hydrochloric acid solution dropwise at a certain reaction temperature to obtain a hydrazine hydrochloride solution; (2) adding p-chloroaniline into the four-neck flask, starting to stir by using glycol as a solvent, adding the hydrazine hydrochloride solution obtained in the step (1) dropwise at the reaction temperature of 100 to 120 DEG C, performing heat-insulating reflux reaction for 2 to 6 hours, and filtering, washing and drying after the reaction is finished to obtain the p-chlorophenyl hydrazine. By the method, one-step synthesis of the p-chlorophenyl hydrazine is realized by using the p-chloroaniline and the hydrazine hydrate, the yield can reach more than 85%, and the method is suitable for enterprise large-scale production; by the method provided by the invention, the tedious operation steps, such as diazotization, reduction and acidolysis, in the traditional method are avoided, and the process safety is improved; by the method, the use amount of water can be reduced, the discharge quantity of waste water is greatly reduced, waste water treatment in the later period is avoided, and the cost is reduced.
Method for preparing p-chlorophenylhydrazine
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Paragraph 0010, (2017/08/29)
The invention discloses a method for preparing p-chlorophenylhydrazine. According to the method, p-chloroaniline, methyl ethyl ketazine and water are taken as raw materials, p-chlorophenylhydrazine is synthesized by reaction at a certain temperature, and ammonia and butanone generated in the reaction process can be recycled to be used for synthesizing methyl ethyl ketazine. Compared with a conventional process for preparing p-chlorophenylhydrazine through diazotization reaction, the method is mild in reaction condition, not higher in requirements for devices, fewer in reaction steps, high in yield and simple in aftertreatment, product impurities are fewer, the purity is high, the production cost is low, the process is free of generation of waste water and waste gas, and the method is a green environment-friendly novel process.
P-chlorophenylhydrazine synthesis method
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Paragraph 0007; 0008; 0009, (2017/07/21)
The invention discloses a p-chlorophenylhydrazine synthesis method. The technical scheme comprises the following steps: reacting sodium hypochlorite and p-chloroaniline to prepare p-chlorphenyl monochloroamine, and reacting the p-chlorphenyl monochloroamine and ammonia to obtain p-chlorophenylhydrazine. Compared with the traditional diazo-reaction process for preparing p-chlorophenylhydrazine, the method disclosed by the invention has the advantages of mild reaction conditions, low requirements for equipment, less reaction steps, simple synthesis method, low by-product and wastewater output, low energy consumption, high yield and low production cost, thereby being an energy-saving environment-friendly new process.
