- Visible-light-mediated phosphonylation reaction: formation of phosphonates from alkyl/arylhydrazines and trialkylphosphites using zinc phthalocyanine
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In this work, we developed a ligand- and base-free visible-light-mediated protocol for the photoredox syntheses of arylphosphonates and, for the first time, alkyl phosphonates. Zinc phthalocyanine-photocatalyzed Csp2-P and Csp3-P bond formations were efficiently achieved by reacting aryl/alkylhydrazines with trialkylphosphites in the presence of air serving as an abundant oxidant. The reaction conditions tolerated a wide variety of functional groups.
- Hosseini-Sarvari, Mona,Koohgard, Mehdi
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supporting information
p. 5905 - 5911
(2021/07/12)
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- Cross-Coupling between Hydrazine and Aryl Halides with Hydroxide Base at Low Loadings of Palladium by Rate-Determining Deprotonation of Bound Hydrazine
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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.
- Borate, Kailaskumar,Choi, Kyoungmin,Goetz, Roland,Hartwig, John F.,Shinde, Harish,Wang, Justin Y.,Zuend, Stephan J.
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supporting information
p. 399 - 408
(2020/10/29)
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- 1, 3, 4-oxadiazole hydrazide compound as well as preparation method and application thereof
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The invention relates to a 1, 3, 4-oxadiazole hydrazide compound as well as a preparation method and application thereof. The compound has a structure as shown in a general formula (I), according to the invention, the method includes taking a 1, 3, 4-oxadiazole compound as a basis and introducing hydrazide into the system; the compound has a good inhibition effect on plant pathogenic bacteria, fungi and oomycetes, and has a good inhibition effect on pathogenic bacteria such as rice bacterial leaf blight, wheat scab, pepper fusarium wilt, sclerotinia sclerotiorum, colletotrichum gloeosporioides, phytophthora infestans, blueberry root rot and the like.
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Paragraph 0062-0063
(2020/09/02)
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- Synthesis method of oxalyl hydrazine ligands and application of oxalyl hydrazine ligands in C-N bond coupling reaction
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The invention belongs to the technical field of organic chemical synthesis, and particularly relates to a synthesis method of oxalyl hydrazine ligands and application of the oxalyl hydrazine ligands to C-N coupling reaction. The invention provides a method for synthesizing oxalyl hydrazine ligands by taking hydrazine compounds and oxalyl chloride as raw materials. The method has the advantages that the raw materials are easy to obtain, the operation is simple, the post-treatment is easy, and the method is suitable for industrial large-scale production; furthermore, coupling of aryl iodide andhydrazine hydrate is realized by utilizing oxalyl hydrazine ligands, and aryl hydrazine is synthesized. The method is mild in reaction condition, safe, efficient and suitable for industrial production.
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Paragraph 0020; 0024-0029
(2020/11/02)
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- 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
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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.
- Dey, Raghunath,Kumar, Pankaj,Banerjee, Prabal
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p. 5438 - 5449
(2018/05/28)
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- Preparation method of 4-methyl phenylhydrazine hydrochloride
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The invention relates to a preparation method of 4-methyl phenylhydrazine hydrochloride. The preparation method comprises the following steps: diazotization, reduction, purification and salt formation. In the diazotization and reduction steps, reaction liquid is kept with high acidity by means of concentrated hydrochloric acid, so that the reaction is smoothly and fully carried out. In the reduction step, zinc powder-concentrated hydrochloric acid is taken as a reducing agent to replace sodium thiosulfate, sodium hydrogen sulfite, stannous chloride-hydrochloric and the like, the reducing property is good, the yield is high, the reaction time is shortened, impurities such as zinc hydroxide generated by the reaction are conveniently removed, and the product is few in impurity and high in purity. In the salt formation step, acetone is used to wash, so that the purity of the product is improved, and the appearance of the product is ensured. According to the preparation method, the processis stable and reliable, the operation is easy, the product purity is high (the content of the product detected by high performance liquid chromatography is greater than or equal to 99%), the yield isgreater than or equal to 39%, and the demand on 4-methyl phenylhydrazine hydrochloride in the market is fully met.
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Paragraph 0017-0024; 0030; 0032; 0034; 0040; 0042; 0044
(2018/07/30)
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- Preparation method of 4-methyl phenylhydrazine oxalate
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The invention relates to a preparation method of 4-methyl phenylhydrazine oxalate. The preparation method comprises the following steps: diazotization, reduction, purification and salt formation. In the diazotization and reduction steps, reaction liquid is kept with high acidity by means of concentrated hydrochloric acid, so that the reaction is smoothly and fully carried out. In the reduction step, zinc powder-concentrated hydrochloric acid is taken as a reducing agent to replace sodium thiosulfate, sodium hydrogen sulfite, stannous chloride-hydrochloric and the like, the reducing property isgood, the yield is high, the reaction time is shortened, impurities such as zinc hydroxide generated by the reaction are conveniently removed, and the product is few in impurity and high in purity. In the salt formation step, acetone is used to wash, so that the purity of the product is improved, and the appearance of the product is ensured. According to the preparation method, the process is stable and reliable, the operation is easy, the product purity is high (the content of the product detected by high performance liquid chromatography is greater than or equal to 99.2%), the yield is greater than or equal to 42%, and the demand on 4-methyl phenylhydrazine oxalate in the market is fully met.
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Paragraph 0020; 0022; 0024; 0030; 0032; 0034; 0037-0044
(2018/07/30)
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- Preparation method of 4-methyl phenylhydrazine phosphate
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The invention relates to a preparation method of 4-methyl phenylhydrazine phosphate. The preparation method comprises the following steps: diazotization, reduction, purification and salt formation. Inthe diazotization and reduction steps, reaction liquid is kept with high acidity by means of concentrated hydrochloric acid, so that the reaction is smoothly and fully carried out. In the reduction step, zinc powder-concentrated hydrochloric acid is taken as a reducing agent to replace sodium thiosulfate, sodium hydrogen sulfite, stannous chloride-hydrochloric and the like, the reducing propertyis good, the yield is high, the reaction time is shortened, impurities such as zinc hydroxide generated by the reaction are conveniently removed, and the product is few in impurity and high in purity.In the salt formation step, acetone is used to wash, so that the purity of the product is improved, and the appearance of the product is ensured. According to the preparation method, the process is stable and reliable, the operation is easy, the product purity is high (the content of the product detected by high performance liquid chromatography is greater than or equal to 99.2%), the yield is greater than or equal to 42%, and the demand on 4-methyl phenylhydrazine phosphate in the market is fully met.
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Paragraph 0020-0024; 0030-0034; 0039-0044
(2018/07/30)
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- Diaza [1,4] Wittig-type rearrangement of N-allylic-N-Boc-hydrazines into γ-amino- N -Boc-enamines
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Diaza [1,4] Wittig-type rearrangement of N-allylic-N-Boc-hydrazines into γ-amino-N-Boc-enamines was demonstrated. The scope and limitation, experimental mechanistic studies, and a proposed reaction mechanism were also described.
- Tayama, Eiji,Kobayashi, Yoshiaki,Toma, Yuka
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supporting information
p. 10570 - 10573
(2016/09/02)
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- Synthesis of benzofuro[3,2-b] indoline amines via deamination-interrupted Fischer indolization and their unexpected reactivity towards nucleophiles
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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.
- Tomakinian, Terry,Guillot, Régis,Kouklovsky, Cyrille,Vincent, Guillaume
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supporting information
p. 5443 - 5446
(2016/05/09)
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- Diversification of edaravone via palladium-catalyzed hydrazine cross-coupling: Applications against protein misfolding and oligomerization of beta-amyloid
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N-Aryl derivatives of edaravone were identified as potentially effective small molecule inhibitors of tau and beta-amyloid aggregation in the context of developing disease-modifying therapeutics for Alzheimer's disease (AD). Palladium-catalyzed hydrazine monoarylation protocols were then employed as an expedient means of preparing a focused library of 21 edaravone derivatives featuring varied N-aryl substitution, thereby enabling structure-activity relationship (SAR) studies. On the basis of data obtained from two functional biochemical assays examining the effect of edaravone derivatives on both fibril and oligomer formation, it was determined that derivatives featuring an N-biaryl motif were four-fold more potent than edaravone.
- Maclean, Mark A.,Diez-Cecilia, Elena,Lavery, Christopher B.,Reed, Mark A.,Wang, Yanfei,Weaver, Donald F.,Stradiotto, Mark
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supporting information
p. 100 - 104
(2015/12/18)
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- Remazol-Catalyzed Hydroperoxyarylation of Styrenes
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A mild photocatalytic hydroperoxyarylation of styrenes has been developed, in which a novel photocatalyst, remazol brilliant blue R (RBBR), is employed at low catalytic loading (1 mol%). The operationally easy procedure uses air as the dioxygen source. Simple mono-substituted styrenes react with aryl hydrazines in moderate-to-good yields. RBBR is proposed to act as a photosensitizer for the generation of singlet oxygen.
- Chen, Ying-Ho,Lee, Ming,Lin, Yi-Zhen,Leow, Dasheng
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supporting information
p. 1618 - 1621
(2015/08/06)
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- Synthesis and Site-Specific Incorporation of Red-Shifted Azobenzene Amino Acids into Proteins
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A series of red-shifted azobenzene amino acids were synthesized in moderate-to-excellent yields via a two-step procedure in which tyrosine derivatives were first oxidized to the corresponding quinonoidal spirolactones followed by ceric ammonium nitrate-catalyzed azo formation with the substituted phenylhydrazines. The resulting azobenzene-alanine derivatives exhibited efficient trans/cis photoswitching upon irradiation with a blue (448 nm) or green (530 nm) LED light. Moreover, nine superfolder green fluorescent protein (sfGFP) mutants carrying the azobenzene-alanine analogues were expressed in E. coli in good yields via amber codon suppression with an orthogonal tRNA/PylRS pair, and one of the mutants showed durable photoswitching with the LED light.
- John, Alford A.,Ramil, Carlo P.,Tian, Yulin,Cheng, Gang,Lin, Qing
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supporting information
p. 6258 - 6261
(2016/01/09)
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- Synthesis of 1-(1-aryl-1H-1,2,3-triazol-4-yl)-β-carboline derivatives
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Reaction of 5-methyl-1-aryl-1H-1,2,3-triazole-4-carbocylic acid chlorides with tryptamine derivatives afforded substituted 1-aryl-N-[2-(1H-indol-3-yl) ethyl]-5-methyl-1H-1,2,3-triazole-4-carboxamides. At heating these compounds in toluene in the presence of POCl3 and P2O5 Bischler-Napieralski cyclization occurs giving 1-(1-aryl-5-methyl-1H-1,2,3- triazol-4-yl)-4,9-dihydro-3H-β-carbolines that can be transformed into β-carboline and tetrahydro-β-carboline derivatives.
- Pohodylo,Matiichuk,Obushak
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p. 275 - 279
(2014/04/17)
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- Efficient synthesis of aryl hydrazines using copper-catalyzed cross-coupling of aryl halides with hydrazine in PEG-400
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An efficient and convenient method for the synthesis of aryl hydrazines is described via copper-catalyzed cross-coupling of aryl halides with aqueous hydrazine in PEG-400. This protocol is applicable to both electron-deficient and electron-rich aryl iodides and bromides, and even to sterically hindered substrates, giving aryl hydrazines in good to excellent yields.
- Chen, Junmin,Zhang, Yimin,Hao, Wenyan,Zhang, Rongli,Yi, Fei
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p. 613 - 617
(2013/07/25)
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- Mild and rapid Pd-catalyzed cross-coupling with hydrazine in continuous flow: Application to the synthesis of functionalized heterocycles
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Minimizing risk: The synthesis of arylhydrazines through C?£?N cross-coupling of aryl chlorides with hydrazine is described. Through the use of continuous flow, the hazards associated with the use of hydrazine in the presence of transition metals are decreased. In addition, multistep flow sequences have also been developed for the generation of functionalized heterocycles utilizing the arylhydrazine intermediates.
- Deangelis, Andrew,Wang, Dong-Hui,Buchwald, Stephen L.
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supporting information
p. 3434 - 3437
(2013/05/09)
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- TETRAZOLE COMPOUNDS AS OREXIN RECEPTOR ANTAGONISTS
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The invention relates to tetrazole compounds of formula (I) wherein X, Y, Z, R1, R2 and R3 are as described in the description; to pharmaceutically acceptable salts thereof, and to the use of such compounds use as medicaments, especially as orexin receptor antagonists.
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Page/Page column 33
(2011/04/25)
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- Palladium-catalyzed cross-coupling of aryl chlorides and tosylates with hydrazine
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Hydrazine is not a problem anymore: The title transformation is the first reaction to yield aryl hydrazines through the cross-coupling of aryl chlorides and tosylates with hydrazine. An appropriately designed palladium catalyst allows this reaction to proceed rapidly under mild conditions, and with excellent chemoselectivity (see scheme; Ad=adamantyl, Ts=4-toluenesulfonyl).
- Lundgren, Rylan J.,Stradiotto, Mark
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supporting information; experimental part
p. 8686 - 8690
(2011/01/08)
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- TETRAZOLE COMPOUNDS AS OREXIN RECEPTOR ANTAGONISTS
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The invention relates to tetrazole compounds of formula (I) wherein X, Y, Z, R1, R2 and R3 are as described in the description; to pharmaceutically acceptable salts thereof, and to the use of such compounds use as medicaments, especially as orexin receptor antagonists.
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Page/Page column 79
(2010/01/07)
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- Pyrazolones as inhibitors of 11B-hydroxysteroid dehydrogenase
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Provided herein are compounds of the formula (I): as well as pharmaceutically acceptable salts thereof, wherein the substituents are as those disclosed in the specification. These compounds, and the pharmaceutical compositions containing them, are useful for the treatment of diseases such as, for example, type II diabetes mellitus and metabolic syndrome.
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Page/Page column 15
(2008/06/13)
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- Solid-supported sulfonylhydroxylamine as an effective N-animating agent of anilines
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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.
- Ohno, Hiroshi,Tanaka, Hiroshi,Takahashi, Takashi
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p. 1191 - 1194
(2007/10/03)
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- Thrombopoietin mimetics
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Non-peptide TPO mimetics are disclosed, as well as a method of treating thrombocytopenia, in a mammal, including a human, in need thereof, which comprises administering to such mammal an effective amount of a selected hydroxy-1-azo-naphthalene derivative.
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Page column 12
(2008/06/13)
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- Novel Synthesis of Agaritine, a 4-Hydrazinobenzyl-Alcohol Derivative Occuring in Agaricaceae
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The 4-hydrazinobenzyl alcohol (3) was prepared (58percent) by diisobutylaluminiumhydride reduction of methyl 4-hydrazinobenzoate (4), whereas LiAlH4 of LiBH4 reduction of 4 proceeded further to yield (via intermediate 3) (4-tolylhydrazine (5).The alcohol 3 was stable under O2-free conditions and exhibited no tendency to eliminate H2O, neither thermally nor with H+ catalysis.Oxidation of 3 with SeO2 yielded 4-(hydroxymethyl)benzenediazonium ion (8), identified by its azo coupling product 9 with 2-naphthol.Condensation of 3 with 1-benzyl 5-hydrogen N-(benzyloxycarbonyl)-L-glutamate (1) in presence of dicyclohexylcarbodiimide afforded 82percent of N2-(benzyloxycarbonyl)-L-glutamic acid 1-(benzyl-ester) 5-(2-hydrazide) (11) which upon controlled hydrogenolysis (quinoline-sulfur-poisoned Pd/C catalyst) gave 82percent of L-glutamic acid 5-(2-hydrazide) (1), i.e. agaritine, a metabolite of Agaricus bisporus.Without poisoning of the catalyst, hydrogenolysis of (11) yielded L-glutamic acid 5-2-(4-tolyl)hydrazide) (12).
- Datta, Subir,Hoesch, Lienhard
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p. 1261 - 1267
(2007/10/02)
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- Reduction electrochimique des sels d'aryldiazonium en milieu aqueux: II. Effet de substituants sur la stabilisation du radical libre intermediaire de reduction et sur le rendement de la synthese d'arylhydrazines primaires
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The polarographic behaviour of a series of aromatic diazonium salts , BF4- in aqueous media is reported and discussed.The half-wave potentials corresponding to the first reduction step have been correlated to Hammett substituent constant ? and are defined by the equation : E=0.14?-0.015+/-0.01 V vs SCE.Substituent effects on the yield of electrochemical synthesis on a mercury pool of by electrochemical reduction of aryldiazoniums salts 10E-3 mol.l-1 at 0 1,1 V vs.SCE are also investigated at low temperature.The best yield (70percent) are obtained with the electron donating substituents on the phenyl ring.Unfortunately, large scale electrolytic reduction of aromatic diazoniums 10E-2 mol.l-1 at -1,1 V vs SCE results in the formation of primary hydrazines in poor yields.On such a large scale, it no longer seems possible to minimize the competitive chemical side reactions.
- Hamet-Elfakir, Claire,Caullet, ClAude
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p. 687 - 692
(2007/10/02)
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- MECHANISM OF THE FISCHER INDOLE SYNTHESIS. QUANTUM-CHEMICAL INTERPRETATION OF THE REARRANGEMENT OF SUBSTITUTED CYCLOHEXANONE ARYLHYDRAZONES TO TETRAHYDROCARBAZOLES
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Calculations of a number of model structures within the scheme of Fischer indole synthesis were made on the basis of a bonding variant of perturbation theory in the self-consistent-field (SCF) MO LCAO method.A quantum-chemical interpretation of the effect of substituents on the course of the thermal process is given.The kinetics of the thermal and acid-catalyzed indolization of substituted cyclohexanone arylhydrazones to tetrahydrocarbazoles were studied by spectrophotometry.It was shown that the experimental data are in satisfactory agreement with the calculated values. It was concluded that a concerted mechanism ( a -sigma-tropic shift) for the step involving the formation of a carbon-carbon bond in the Fischer reaction is preferred.
- Visotskii, Yu. B.,Przheval'skii, N. M.,Zemskii, B. P.,Grandberg, I. I.,Kostromina, L. Yu.
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p. 713 - 722
(2007/10/02)
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- Isoxazolyl indolamines
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This disclosure describes compounds of the formula STR1 wherein R1 represents hydrogen, fluoro, chloro, lower alkyl having 1 to 4 carbon atoms, or lower alkoxy having 1 to 4 carbon atoms, and R2 represents lower alkyl or STR2 where R5 represents hydrogen, fluoro, chloro, lower alkyl or lower alkoxy, and R3 and R4 each independently represent lower alkyl as defined above, and R3 and R4 together with N represent STR3 or pharmaceutically acceptable acid addition salts thereof, which are useful as anti-diabetic agents.
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- Phenyl-1,2,3,4-tetrahydrocarbazoles and use thereof
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This application relates to phenyl-substituted 1,2,3,4-tetrahydrocarbazoles and to their use as anti-depressant agents useful in the treatment of mental depression of either endogenous or reactive nature.
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- Carbazole methyl malonates
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A process for the preparation of α-methyl-carbazole-2-acetic acids, which comprises reacting an α-methyl-3-oxocyclohexane malonic acid di-lower alkyl ester with a substituted phenylhydrazine, and thereafter sequentially oxidizing and hydrolyzing the reaction product to obtain the desired acid, is described.
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- Pyrazol-4-acetic acid compounds
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Pyrazol-4-acetic acid compounds, such as substituted pyrazol-4-acetic acid, its esters, amides, nitriles and their pharamaceutically acceptable salts and method for the preparation of these compounds are disclosed. The novel compounds are useful analgesics, anti-inflammatory, and antipyretics.
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