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A five-step, atom-efficient synthesis of the Galanthan tetracyclic skeleton has been developed. The key step is an unusual intramolecular de Mayo reaction using an isocarbostyril substrate with a functionalized tether on nitrogen. The target molecule is produced in 35% overall yield from isocarbostyril. 相似文献
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《Comptes Rendus Chimie》2015,18(7):776-784
Synthesis of transition metal–dinitrogen complexes and stoichiometric transformations of their coordinated dinitrogen into ammonia and hydrazine have so far been well investigated in order to achieve a novel nitrogen fixation under ambient conditions. As an extension of our study, the dimolybdenum–dinitrogen complex bearing PNP pincer ligands has been found to work as an effective catalyst for the formation of ammonia from dinitrogen, where 52 equiv of ammonia are produced based on the catalyst (26 equiv of ammonia are produced based on the molybdenum atom of the catalyst). This is the most effective catalytic reaction system for the formation of ammonia from molecular dinitrogen catalyzed by transition metal–dinitrogen complexes as catalysts under ambient reaction conditions. Herein, we describe recent results concerning the catalytic reaction, including the proposed reaction pathway. 相似文献
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V. R. Akhmetova G. R. Nadyrgulova T. V. Tyumkina Z. A. Starikova D. G. Golovanov M. Yu. Antipin R. V. Kunakova U. M. Dzhemilev 《Russian Chemical Bulletin》2006,55(10):1824-1834
Cyclothiomethylation of phenyl hydrazine with CH2O and H2S in a ratio of 1: 3: 2 in an acidic medium (HCl) afforded previously unknown 3-phenyl-1,3,4-thiadiazolidine (35% yield) and
N-phenyl(perhydro-1,3,5-dithiazin-5-yl)amine (35% yield). The analogous reaction in an alkaline medium (BuONa) produced N-phenyl(perhydro-1,3-thiazetidin-3-yl)amine (22% yield). The reaction of 1,2-diphenyl hydrazine with CH2O and H2S in an alkaline medium gave 1,2,4,5-tetraphenylhexahydro-1,2,4,5-tetrazine and previously unknown 3,4-diphenyl-1,3,4-thiadiazolidine
and 5,6-diphenyltetrahydro-1,3,5,6-dithiadiazepine in 39 and 22% yields, respectively. Cyclothiomethylation of benzyl hydrazine
afforded previously unknown bis[(6-benzyl-4,2,6-thiadiazolidin-2-yl)methyl] sulfide (60% yield) and N-benzyl(perhydro-1,3,5-dithiazin-5-yl)amine (19% yield). The reaction of tosyl hydrazine produced 3-[(p-tolyl)sulfonyl]-1,3,4-thiadiazolidine, N-(perhydro-1,3,5-dithiazin-5-yl)-p-tolylsulfonamide, and 3,7-bis(p-tolylsulfonylamino)-1,5-dithia-3,7-diazacyclooctane in 21, 38, and 41% yields, respectively.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1758–1767, October, 2006. 相似文献
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E. P. Levanova A. I. Vilms V. A. Bezborodov I. A. Babenko N. G. Sosnovskaya N. V. Istomina A. I. Albanov N. V. Russavskaya I. B. Rozentsveig 《Russian Journal of General Chemistry》2017,87(3):396-401
The reaction of dichlorodiethyl ether or dichlorodiethylamine hydrochloride with potassium or ethanolammonium dichalcogenides prepared in situ from elemental sulfur or selenium in the system hydrazine hydrate–alkali results in oligomeric dichalcogenides, whose further splitting at the chalcogen–chalcogen bond in the same system and subsequent alkylation affords bis(organylsulfanyl)- or bis(organylselanyl)-substituted derivatives of diethyl ether or diethylamine. Ligands with aryl substituents at the chalcogens have been prepared in 48-59% yield by splitting of diaryldichalcogenides in the system hydrazine hydrate–alkali and subsequent reaction with dichlorodiethyl ether or dichlorodiethylamine. A ditopic tetradentate ligand has been synthesized by the use of dichlorodiethylformal. 相似文献
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1,2-二氯乙烷裂解反应是一个自由基链反应。在热反应中,为了克服引发自由基反应所需要的能量,反应必须在较高温度下进行。但是在光化学反应中,特别是应用了激光引发自由基,使得这一裂解反应可以在较低的温度下进行。因此利用激光引发的自由基链反应,不仅在理论上有浓厚的兴趣,并且在工业上有广阔的应用前景。Wolfrum曾详细地研究过利用准分子激光(KrF激光)裂解1,2-二氯乙烷的反应。由于1,2-二氯乙烷对KrF激光有较强的吸收,容易产生氯自由基,使整个链反应速率决定步骤由链的引发变为链的传递,而降低反应温度。因为光化学反应温度低,抑止了很多副反应,从而提高反应的选择性。 相似文献
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Domingos JB Longhinotti E Brandão TA Santos LS Eberlin MN Bunton CA Nome F 《The Journal of organic chemistry》2004,69(23):7898-7905
Nonionic hydrazine reacts with anionic bis(2,4-dinitrophenyl) phosphate (BDNPP), giving 2,4-dinitrophenyl hydrazine and dianionic 2,4-dinitrophenyl phosphate by an S(N)2(Ar) reaction, and at the phosphoryl center, giving 2,4-dinitrophenoxide ion and a transient phosphorylated hydrazine that rearranges intramolecularly to N-(2,4-dinitrophenyl)-N-phosphonohydrazine. Approximately 58% of the reaction at pD = 10 occurs by N-phosphorylation, as shown by (31)P NMR spectroscopy. Reaction of HO(2)(-) is wholly at phosphorus, and the intermediate peroxophosphate reacts intramolecularly, displacing a second 2,4-dinitrophenoxide ion, or with H(2)O(2), giving 2,4-dinitrophenyl phosphate and O(2). Rate constants of O- and N-phosphorylation in reactions at phosphorus of NH(2)NH(2), HO(2)(-), and NH(2)OH and its methyl derivatives follow Bronsted relationships with similar slopes, but plots differ for oxygen and nitrogen nucleophiles. The reaction with NH(2)NH(2) has been probed by using both NMR spectroscopy and electrospray ionization mass and tandem mass spectrometry, with the novel interception of key reaction intermediates in the course of reaction. 相似文献
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Mitsuru Ueda Hiroya Sugita 《Journal of polymer science. Part A, Polymer chemistry》1988,26(1):159-166
A convenient method for the synthesis of poly(1,3,4-oxadiazole)s of high molecular weights has been developed. These polymers were prepared readily by the direct polycondensation of dicarboxylic acids with hydrazine sulfate ( 1 ) using phosphorus pentoxide/methanesulfonic acid (PPMA) as both a condensing agent and solvent. Polycondensation of aliphatic dicarboxylic acids with 1 proceeded even at room temperature and produced poly(1,3,4-oxadiazole)s with inherent viscosities up to 1.4 dL/g. The synthesis of aromatic poly(1,3,4-oxadiazole)s from aromatic dicarboxylic acids containing phenyl ether structures was carried out by a one-pot procedure because the preactivation of dicarboxylic acids was required. The synthesis of 2,5-disubstituted-1,3,4-oxadiazoles by the reaction of carboxylic acids with 1 in PPMA was studied to demonstrate the feasibility of the reaction for polymer formation. The thermogravimetry of the aromatic poly(1,3,4-oxadiazole)s showed 10% weight loss both in air and in nitrogen at 440–490°C. 相似文献
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Palumbo Piccionello A Guarcello A Buscemi S Vivona N Pace A 《The Journal of organic chemistry》2010,75(24):8724-8727
The reaction of various 1,2,4-oxadiazoles with an excess of hydrazine in DMF has been investigated. 3-Amino-1,2,4-triazoles are produced through a reductive ANRORC pathway consisting of the addition of hydrazine to the 1,2,4-oxadiazole followed by ring-opening, ring-closure, and final reduction of the 3-hydroxylamino-1,2,4-triazole intermediate. The general applicability of 1,2,4-oxadiazoles ANRORC reactivity is demonstrated also in the absence of C(5)-linked electron-withdrawing groups. 相似文献
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Kazutake Hagiya 《Tetrahedron》2009,65(31):6109-1096
Di-2-methoxyethyl azodicarboxylate (DMEAD) is prepared in 65% yield in two steps as a crystalline solid. Use of DMEAD in the Mitsunobu reaction of a variety of alcohols with pronucleophiles results in good yields of the products under sufficient stereospecificity of inversion, as conventional diisopropyl azodicarboxylate (DIAD) does. Isolation of the product is, however, much easier with DMEAD than that with DIAD, because the hydrazine produced from DMEAD is highly hydrophilic and is completely separable by a simple extraction into neutral water. Purification of the organic layer, after separation of the other by-product, triphenylphosphane oxide, by filtration, easily provides high purity of the product in a good yield. Concentration of the water layer yields the hydrazine, which can be reused for the preparation of DMEAD. One-step removal of the two by-products by the aqueous extraction was also possible when trimethylphosphane and DMEAD were employed. 相似文献
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Buscemi S Pace A Palumbo Piccionello A Macaluso G Vivona N Spinelli D Giorgi G 《The Journal of organic chemistry》2005,70(8):3288-3291
The reaction of 3-benzoyl-5-perfluoroalkyl-1,2,4-oxadiazoles with hydrazine has been investigated, evidencing the possibility of competitive reaction paths. Nucleophilic addition of the hydrazine to the electrophilic C(5) of the 1,2,4-oxadiazole ring, followed by ring opening and ring closure with enlargement, leads with high yield and in very mild experimental conditions to the formation of Z-oximes of 3-perfluoroalkyl-6-phenyl-2H-1,2,4-triazin-5-ones (11a-c) as major products of the reaction. In turn, the hydrazine can attack the electrophilic carbonyl carbon giving 4-perfluoroacylamino-5-phenyl-2H-1,2,3-triazoles (13a-c) through the well-known Boulton-Katritzky rearrangement of the intermediate hydrazones. 相似文献
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Fouad Bentiss Michel Lagrene Michel Traisnel Bouchaib Mernari Hassan Elattari 《Journal of heterocyclic chemistry》1999,36(1):149-152
A number of symmetrically 3,5-disubstituted 4-amino-1,2,4-triazoles have been prepared by the reaction of aromatic nitriles with hydrazine dihydrochloride or sulfate with an excess of hydrazine hydrate in ethyl ene or diethylene glycol under a nitrogen atmosphere. The structures of the new triazoles derivatives were confirmed by analytical and spectral data. 相似文献
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Interaction of hydrazine or dimethylhydrazine with 5-diazoimidazole-4-carboxamide produced, presumably via tetrazenes, high yields of 5-azidoimidazole-4-carboxamide. In contrast, when semicarbazide reacted with either the diazoimidazole or the analogous diazo-1,2,3-triazole, the yield of the azidoheterocycle was low, and the yield of biurea, and presumably the aminoheterocycle, was high. 3-Azidopyrazole-4-carboxamide was obtained from a reaction of hydrazine with the diazopyrazole. Both azido and amino derivatives were formed from reactions of diazo-imidazole esters with hydrazine or thiosemicarbazide. 相似文献
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Di-p-nitrobenzyl azodicarboxylate is prepared in 83.6% yield in two steps as a bright yellow solid, which can be used as an azo-reagent in the Mitsunobu reaction. When a chiral secondary alcohol was used, sufficient configurational inversion of alcohol occurred under Mitsunobu conditions. That the hydrazine produced from DNAD is semisoluble in some solvents such as THF and CH2Cl2 makes it separated easily from the reaction mixture just via filtration. Then the recovered hydrazine compound can be re-exposed to oxidant to produce DNAD. Because DNAD is more stable than DIAD at ambient temperatures and allows easy separation, it is a good alternative azo-reagent for the Mitsunobu reaction. 相似文献
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Electrocatalytic oxidation of hydrazine at cobalt hexacyanoferrate- modified glassy carbon, Pt and Au electrodes 总被引:1,自引:0,他引:1
The electrocatalytic oxidation of hydrazine has been studied on glassy carbon, Pt and Au electrodes modified by cobalt hexacyanoferrate
(CoHCF) using cyclic voltammetry and rotating disc techniques. It has been shown that the oxidation of hydrazine to nitrogen
occurs at the potential coinciding with that of Co(II) to Co(III) transformation in a CoHCF film, where no oxidation signal
is observed at a bare glassy carbon electrode. A Tafel plot, derived from RDE voltammograms, exhibits a slope of 150 mV, indicating
a one-electron charge transfer process to be the rate-limiting step. The electrocatalytic efficiency of the modified electrode
towards hydrazine oxidation depends on solution pH, and the optimum range was found to be located between pH 5 and pH 7. The
kinetic behaviour and location of the electrocatalytic process were examined using the W.J. Albery diagnosis table, and it
was concluded that the reaction has either a “surface” or a “layer” reaction mechanism. Pt- and Au-CoHCF-modified electrodes
show no significant electrocatalytic activity towards hydrazine oxidation.
Received: 25 April 1997 / Accepted: 12 August 1997 相似文献
16.
Burwell F. Powell C. G. Overberger J.-P. Anselme 《Journal of heterocyclic chemistry》1983,20(1):121-128
The sodium hydrosulfite reduction of N-nitroso-1,2,3,4-tetrahydroisoquinoline ( 5 ) does not result in the loss of nitrogen and leads to the corresponding hydrazine 6 which upon oxidation with mercuric oxide in ethanol at 62° gives the hexahydrotetrazine 7 in 39% yield. Treatment of the N-tosyl derivative of 6 with base affords 7 in nearly quanitative yield. Oxidation of 6 in 1-butanol at 95° results in the formation of a complex product mixture from which only one component, 1,1′-azobis-3,4-dihydroisoquinoline ( 8 ) could be isolated. Surprisingly the sodium hydrosulfite reduction of 2-nitroso-3-phenyl-1,2,3,4-tetrahydroisoquinoline ( 15 ) also failed to proceed with loss of nitrogen and yields the corresponding hydrazine 16 . However, 16 was cleanly oxidized by mercuric oxide in ethanol at 62° with concurrent elimination of nitrogen to afford 2-phenylindane in 75% yield. Possible rationalizations for these results are presented. 相似文献
17.
Direct Transformation of Molecular Dinitrogen into Ammonia Catalyzed by Cobalt Dinitrogen Complexes Bearing Anionic PNP Pincer Ligands
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Dr. Shogo Kuriyama Dr. Kazuya Arashiba Prof. Dr. Hiromasa Tanaka Yuki Matsuo Dr. Kazunari Nakajima Prof. Dr. Kazunari Yoshizawa Prof. Dr. Yoshiaki Nishibayashi 《Angewandte Chemie (International ed. in English)》2016,55(46):14291-14295
The direct formation of ammonia from molecular dinitrogen under mild reaction conditions was achieved by using new cobalt dinitrogen complexes bearing an anionic PNP‐type pincer ligand. Up to 15.9 equivalents of ammonia were produced based on the amount of catalyst together with 1.0 equivalent of hydrazine (17.9 equiv of fixed nitrogen atoms). 相似文献
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The reaction of hydroxylamine and hydrazine on γ pyrones was generally reported to yield various heterocycles in which nitrogen is incorporated. More recently, several authors have reported that γ-pyrones oximes and hydrazone derivatives can be obtained and have settled some controversial previous results. This report presents a review of this question. 相似文献
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This paper describes the electrochemical properties of reduced graphene sheets (RGSs) for the electrocatalytic properties towards the hydrazine oxidation in alkaline media. The RGSs have been produced in high yield by a soft chemistry route involving graphite oxidation, ultrasonic exfoliation, and chemical reduction. The RGSs possess excellent electrocatalytic activity towards the hydrazine oxidation. In our opinion, RGSs are a potential electrode material for direct hydrazine fuel cells and electrochemical sensors for hydrazine detection. 相似文献