- Towards a Nitrogen-fixing Cycle: Electrochemical Reduction of a Hydrazido-complex of Molybdenum(IV) under N2 to Yield the Dialkylhydrazine and a Molybdenum(0) Dinitrogen Complex
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Electrochemical reduction of trans-3CH2>)(dppe)2>+, (5) (dppe = Ph2PCH2CH2PPh2) at a Pt electrode in tetrahydrofuran-0.2 M under N2 yields the free organohydrazine and trans-, (1), under CO yields cis- and trans- and N-aminopiperidine, and under Ar yields the reduction product trans-II-(cyclo-3CH2>)(dppe)2>; the product (1) is readily converted into (5), thus a cycle for the fixation of N2 as an organohydrazine is plausible.
- Pickett, Christopher J.,Leigh, G. Jeffery
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- Synthesis of N-aminopyrrolidine by the raschig process: Kinetic and mechanistic study of the monochloramine-pyrrolidine interaction
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1-Pyrrolidinamine (NAPY) belongs to a family of large compounds, namely the alkylhydrazines, used as precursors for different targets in fine chemicals, such as pharmaceuticals and cosmetics. Different synthetic methods are described in the literature; however, many of them are not adaptable on a large scale. The Raschig process appears to be the most relevant method for preparing hydrazines at the industrial scale: hydrazines are obtained by two successive reactions. The first involves the formation of monochloramine from sodium hypochlorite and excess ammonia. The second consists of reacting, in a basic medium, the monochloramine previously synthesized with excess amine to provide the corresponding hydrazine. It is a clean and selective method, distinguished by its nonpolluting aspect, its low cost, and the feasibility of continuous transposition to industrial scale. However, it presents some disadvantages linked to the low hydrazine concentrations in the synthesis solutions. The optimization of the synthesis parameters is therefore essential and requires a detailed kinetic and mechanistic study of the reaction of NAPY formation by the chloramine/pyrrolidine interaction. The kinetics of the NAPY formation reaction were studied in alkaline medium, at first at a temperature of 25°C. Excess pyrrolidine was used with respect to NH2Cl, in order to minimize the influence of side reactions. Owing to the high reaction rates, the essays were carried out in a dilute medium, using reagent concentrations ranging between 1 × 10-3 and 4 × 10-2 M. The ionic strength of the medium was established by NaOH concentration (0.1 M). Then, the influence of the temperature was studied between 15 and 45°C for NH2Cl and PY concentrations, respectively, equal to 2 × 10-3 and 0.01 M, in order to check the conformance to the Arrhenius law. Finally, the characterization of the reaction mixture permitted establishment of a global reaction scheme, including two main secondary reactions.
- Dhenain,Darwich,Frangieh,Goutal,Delalu
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- Synthesis of Novel Saccharide Hydrazones
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Synthesis of important heterocyclic hydrazine derivatives N-aminopyrrolidine, N-aminopiperidine, and N-aminoazepane from hydrazine hydrate and dihalogenides were examined and optimized. These heterocyclic hydrazine derivatives were used in condensation reactions with six different monosaccharides to form corresponding hydrazones. Biological evaluations of these novel compounds, which are simple acyclic nucleoside analogs, were done. L-Arabinose N-aminoazepane hydrazone showed minor anti-HIV activity, giving a starting point for further structural modifications. (Chemical Equation Presented).
- Ilisson, Mihkel,Tomson, Kristjan,Selyutina, Anastasia,Türk, Silver,M?eorg, Uno
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- N-Amino-1,8-Naphthalimide is a Regenerated Protecting Group for Selective Synthesis of Mono-N-Substituted Hydrazines and Hydrazides
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A new route to synthesis of various mono-N-substituted hydrazines and hydrazides by involving in a new C?N bond formation by using N-amino-1,8-naphthalimide as a regenerated precursor was invented. Aniline and phenylhydrazines are reproduced upon reacting these individually with 1,8-naphthalic anhydride followed by hydrazinolysis. The practicality and simplicity of this C?N dihalo alkanes; developed a synthon for bond formation protocol was exemplified to various hydrazines and hydrazides. N-amino-1,8-naphthalimide is suitable synthon for transformation for selective formation of mono-substituted hydrazine and hydrazide derivatives. Those are selective mono-amidation of hydrazine with acid halides; mono-N-substituted hydrazones from aldehydes; synthesis of N-aminoazacycloalkanes from acetohydrazide scaffold and inserted to hydroxy derivatives; distinct synthesis of N,N-dibenzylhydrazines and N-benzylhydrazines from benzyl halides; synthesis of N-amino-amino acids from α-halo esters. Ecofriendly reagent N-amino-1,8-naphthalimide was regenerated with good yields by the hydrazinolysis in all procedures.
- Manoj Kumar, Mesram,Venkataramana, Parikibanda,Yadagiri Swamy, Parikibanda,Chityala, Yadaiah
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supporting information
p. 17713 - 17721
(2021/11/10)
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- Selective reduction of N-nitroso aza-aliphatic cyclic compounds to the corresponding N-amino products using zinc dust in CO2–H2O medium
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[Figure not available: see fulltext.] A new method for reduction of N-nitroso aza-aliphatic cyclic compounds employing zinc in pressurized CO2–H2O medium has been developed. H2O and NH4Cl were used as hydrogen donors, and reduction was performed under environmentally benign conditions. The presented approach allowed to obtain the respective N-amino products selectively and in excellent yields (up to 97%).
- Yang, Weiqing,Lu, Xiang,Zhou, Tingting,Cao, Yongjing,Zhang, Yuanyuan,Ma, Menglin
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p. 780 - 783
(2018/10/20)
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- Novel route to the synthesis of chalcogenolanes, chalcogenanes, and 1,2-dichalcogenaepanes
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The saturated heterocyclic compounds C4H8Y, C 5H10Y, and C5H10Y2 (Y = Se or Te) have been prepared by the reaction of 1,4-dibromobutane or 1,5-dibromopentane with potassium chalcogenides. The novelty of the route consists of the use of the hydrazine hydrate-KOH system for the reductive generation of potassium selenide, telluride, diselenide or ditelluride from elemental chalcogens.
- Levanova,Grabel'Nykh,Elaev,Russavskaya,Klyba,Albanov,Korchevin
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p. 1345 - 1352
(2014/07/21)
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- METHOD FOR ISOMERIZING ORGANIC COMPOUND
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PROBLEM TO BE SOLVED: To provide a method for isomerizing a compound bearing a hydrocarbon group having a carbon-carbon double bond which permits transfer of the carbon-carbon double bond of the compound without using a catalyst or an organic solvent. SOLUTION: The method for isomerizing the compound comprises transferring the position of the carbon-carbon double bond by causing the compound bearing the hydrocarbon group having the carbon-carbon double bond to non-catalytically react in a reaction medium in a high-temperature and high-pressure state. Thus, the isomer having the double bond transferred is obtained in a short time in one step by pressing the compound bearing the hydrocarbon group having the carbon-carbon double bond into high-temperature high-pressure water as a reaction site at a high speed. Neither waste nor wastewater to dispose of is discharged from the manufacturing processes.
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Page/Page column 5; 12
(2008/06/13)
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- MANUFACTURING METHOD OF ISOMERIZED PRODUCT OF ETHYLENICALLY UNSATURATED CARBOXYLIC ACID OR ESTER THEREOF
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PROBLEM TO BE SOLVED: To provide a method for selectively manufacturing an isomerized product of an ethylenically unsaturated monocarboxylic acid or esters thereof from the ethylenically unsaturated monocarboxylic acid or esters thereof without using a catalyst or an organic solvent. SOLUTION: The manufacturing method of the isomerized product of the ethylenically unsaturated monocarboxylic acid or esters thereof comprises transferring a double bond and selectively synthesizing a stereoisomer by causing the ethylenically unsaturated monocarboxylic acid or esters thereof to non-catalytically react in a reaction medium in a high temperature and high pressure state (a subcritical state or a supercritical state). Thus, the desired isomer is selectively manufactured in a short time in a one-step process without using the organic solvent. Moreover, waste or wastewater is hardly generated in the manufacturing processes.
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Page/Page column 5-6; 11
(2008/06/13)
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- N-heterocyclic inhibitors of TNF-α expression
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N-heterocyclic compounds that block cytokine production via inhibition of p38 kinase are disclosed. In one embodiment, compounds of the present invention are represented by Formula I: Methods of production, pharmaceutical compositions and methods of treating conditions associated with inappropriate p38 kinase activity or TNF-α expression utilizing compounds of the present invention are also disclosed.
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- Non-metallocene compounds, method for the production thereof and use of the same for the polymerisation of olefins
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The invention relates to a method for producing special transition metal compounds, to novel transition metal compounds and to the use of the same for the polymerisation of olefins.
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- Methods of treating insulin resistance syndrome and diabetes
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This invention is directed to methods of treating insulin resistance syndrome and diabetes in a patient in need thereof, comprising administering to said patient a pharmaceutically effective amount of a compound derived from adenosine and analogues thereof, or a pharmaceutically acceptable salt thereof, a pharmaceutically acceptable prodrug thereof, an N-oxide thereof, a hydrate thereof or a solvate thereof, or a pharmaceutical composition comprising such compound.
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- N-heterocyclic inhibitors of TNF-alpha expression
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N-heterocyclic compounds that block cytokine production via inhibition of p38 kinase are disclosed. In one embodiment, compounds of the present invention are represented by Formula I: Methods of production, pharmaceutical compositions and methods of treating conditions associated with inappropriate p38 kinase activity or TNF-α expression utilizing compounds of the present invention are also disclosed.
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- Compounds having antihypertensive, cardioprotective, anti-ischemic and antilipolytic properties
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A compound of the formula wherein K is N; Q is CH2or O; R6is hydrogen, alkyl, allyl, 2-methylallyl, 2-butenyl, or cycloalkyl where the nitrogen of the ring of X is substituted by Y; E is O or S; Y is hydrogen, alkyl, aralkyl, substituted aralkyl, aryl, substituted aryl, heterocyclyl, substituted heterocyclyl, heterocyclylalkyl, or substituted heterocyclylalkyl; and n and p are independently 0, 1, 2, or 3, provided that n+p is at least 1; T is hydrogen, alkyl, alkylcarbonyl, alkylthiocarbonyl, halo, carboxyl, A and B are independently hydrogen, alkyl, hydroxyalkyl, alkoxyalkyl, or OR′; or a pharmaceutically acceptable salt thereof, a pharmaceutic-ally acceptable prodrug thereof, an N-oxide thereof, a hydrate thereof or a solvate thereof.
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- N- heterocyclic inhibitors of TNF-alpha expression
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N-heterocyclic compounds that block cytokine production via inhibition of p38 kinase are disclosed. In one embodiment, compounds of the present invention are represented by Formula I: Methods of production, pharmaceutical compositions and methods of treating conditions associated with inappropriate p38 kinase activity or TNF-α expression utilizing compounds of the present invention are also disclosed.
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- Succinate derivative compounds useful as cysteine protease inhibitors
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Disclosed are novel succinate derivative compounds of the formula(I)/(Ia): wherein R1, R2, R3, R4, R5, R6, R7, X and A are defined herein. The compounds are useful as inhibitors of cysteine proteases. Also disclosed are methods of using and methods of making such compounds.
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- Stereoselective Synthesis of Trifluoromethylated Compounds: Nucleophilic Addition of Formaldehyde N,N-Dialkylhydrazones to Trifluoromethyl Ketones
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The nucleophilic 1,2-addition of formaldehyde N,N-dialkylhydrazones 1, 2, and 7-10 to trifluoromethyl ketones 3a-e takes place in the absence of any catalyst or promoter to afford a series of α-hydroxy-α-trifluoromethylhydrazones (4, 5, and 11-14) in good-to-excellent yields. From the several reagents studied, optimal results were achieved using 1-(methyleneamino)pyrrolidine (2) for the synthesis of racemic adducts and (S)-l-(methyleneamino)-2-[1-(methoxy)diphenyl-methyl]-pyrrolidine (10) for the asymmetric version of the reaction. The resolving properties of the chiral auxiliary carried by 10 allowed an easy Chromatographic (flash) separation of any obtained diastereomeric mixture. Thus, a single operation rendered moderate-to-good amounts (42-75%) of optically pure adducts (S,S)-14 (de > 98%) by combining excellent chemical (82-92%) and moderate optical (51-81%) yields. Hydrazones 5 and (S,S)-14 were protected by benzylation [→ 16 and (SJS)-18] and then transformed into benzyl-protected α-trifluoromethyl cyanohydrins 21 by MMPP oxidative cleavage and into α-benzyloxy-a-trifluoromethyl aldehydes 22 by ozonolysis. Alternatively, adducts 5 and (S,S)-14 were methylated [→ 19 and (S,S)-20] and transformed into the corresponding α-methoxy-α-trifluoromethyl carboxylic acids 24 by successive ozonolysis and in situ oxidation (NaClO2, tBuOH, isobutene) of the crude a-methoxyaldehydes.
- Pareja, Carmen,Martin-Zamora, Eloisa,Fernandez, Rosario,Lassaletta, Jose M.
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p. 8846 - 8854
(2007/10/03)
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- Process for producing 1-aminopyrrolidine, and 1-aminopyrrolidine according to the process
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1-Aminopyrrolidine which is obtained by reacting hydrazine hydrate with a compound represented by the following formula (I): wherein X1 and X2 are the same or different, and each represents a leaving group, in methanol; and a process for producing 1-aminopyrrolidine, comprising the step of reacting hydrazine hydrate with the above compound represented by formula (I) in methanol.
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- Process for producing cyclic hydrazine derivatives, tetra-hydropyridazine and hexahydropyridazine
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The present invention relates to a process for producing alicyclic hydrazine derivatives, tetrahydropyridazine and hexahydropyridazine which are useful as intermediate starting materials such as medicines and agricultural chemicals. Especially, the present invention provides; a process for producing an alicyclic hydrazine derivative or its hydrohalogenic acid salt, which comprises reacting a hydrazine hydrohalogenic acid salt with a diol compound or an alicyclic ether compound in the presence of an excessive inorganic acid existing in a free form or in the form of an acid addition salt; a process for producing tetrahydropyridazine from 1-aminopyrrolidine, which comprises oxidizing 1-aminopyrrolidine with an oxidizing agent to form tetrahydropyridazine; and a process for producing hexahydropyridazine, which comprises oxidizing 1-aminopyrrolidine with an oxidizing agent, synthesizing tetrahydropyridazine, and thereafter, hydrogenating the tetrahydropyridazine in the presence of a base.
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- Nodulisporic acid derivatives
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The present invention relates to novel nodulosporic acid derivatives, which are acaricidal, antiparasitic, insecticidal and anthelmintic agents.
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- Aminooxypyrrolidinylthiocarbapenem compounds
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An antibacterial aminooxypyrrolidinylthiocarbapenem I, its production from the corresponding carbapenem V and thiol VI, its pharmaceutical formulation, and its use or combating bacteria are presented. STR1 (wherein R is optionally substituted amino; Rsup
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- Condensed heterocyclic derivatives and herbicides
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A condensed heterocyclic derivative having the formula: STR1 wherein X is an oxygen atom or a sulfur atom; and Z is STR2
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- 3-aryl-7-chloro-3,4-dihydroacridine-1,9(2H,10H)-dione 1-oximes and 1-hydrazone derivatives, their salts, a process for their preparation, agents containing them and their use
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3-Aryl-7-chloro-3,4-dihydroacridine-1,9(2H,10H)-dione 1-oximes and 1-hydrazone derivatives of the formula I STR1 and their physiologically tolerated acid addition and ammonium salts are described, as is a process for their preparation. The new compounds are chemotherapeutic agents and are active against protozoa, especially malaria plasmodia.
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- Reduction of Nitrosamines with Aqueous Titanium Trichloride: Convenient Preparation of Aliphatic Hydrazines
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The reduction of selected nitrosamines by aqueous TiCl3 has been investigated.In general, aliphatic nitrosamines were converted in good yield to the corresponding hydrazines, with little overreduction to the amines.Reaction proceeded rapidly at room temperature in both alkaline and acidic media.A variety of N,N-dialkylhydrazines have been isolated by using the TiCl3 method, which compares favorably with previously reported procedures for preparatively converting nitrosamines to hydrazines.In the reduction of N-nitroso-N-methylaniline, the proportion of amine in the product increased significantly as the pH of the reaction mixture was lowered, presumably reflecting the known instability of arylalkylnitrosamines in strong acid, coupled with a ready reducibility of the corresponding Fischer-Hepp intermediates; some tendency toward reductive cleavage of the N-aryl-N-alkylhydrazine's N-N-bond was also noted.Reduction of an α-nitrosamino ether gave the monoalkylhydrazine as the major product, while all other reducing agents studied converted this starting material chiefly to a mixture of primary and secondary amines.
- Lunn, George,Sansone, Eric B.,Keefer, Larry K.
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p. 3470 - 3473
(2007/10/02)
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