- 1,2-Bis(N-fluoro-p-toluenesulfon-amido)ethane chloroform solvate
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The title compound, N,N′-difluoro-N,N′-ethylenedi-p-toluenesulfonamide, C16H18F2N2O4S2 ·CHCl3, is a novel stable compound of the N-F class of reagents containing two R2/sub
- Ardeshir,Banks,Besheesh,Brisdon,Pritchard
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Read Online
- Synthesis and Evaluation of a Macrocyclic Actinium-225 Chelator, Quality Control and In Vivo Evaluation of 225Ac-crown-αMSH Peptide
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Targeted alpha-therapy (TAT) has great potential for treating a broad range of late-stage cancers by delivering a focused and lethal radiation dose to tumors. Actinium-225 (225Ac) is an emerging alpha emitter suitable for TAT; however, the avai
- Bénard, Fran?ois,Causey, Patrick,Gao, Feng,Gendron, Denise,Perron, Randy,Radchenko, Valery,Robertson, Andrew,Rodriguez-Rodriguez, Cristina,Schaffer, Paul,Yang, Hua,Yuan, Zheliang,Zhang, Chengcheng
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Read Online
- Ligand-Controlled Regiodivergence for Catalytic Stereoselective Semireduction of Allenamides
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Ligand-controlled regiodivergence has been developed for catalytic semireduction of allenamides with excellent chemo- and stereocontrol. This system also provides an example of catalytic regiodivergent semireduction of allenes for the first time. The divergence of the semireduction is enabled by ligand switch with the same palladium pre-catalyst under operationally simple and mild conditions. Monodentate ligand XPhos exclusively promotes selective 1,2-semireduction to afford allylic amides, while bidentate ligand BINAP completely switched the regioselectivity to 2,3-semireduction, producing (E)-enamide derivatives.
- Hajiloo Shayegan, Mojtaba,Li, Zhong-Yuan,Cui, Xin
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supporting information
(2021/12/02)
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- Unconventional Synthetic Process of Fasudil Hydrochloride: Costly Homopiperazine Was Avoided
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An efficient, robust, and cost-effective synthetic process of fasudil hydrochloride 1 was developed. Starting from readily available ethylenediamine and 5-isoquinoline sulfonyl chloride, the target product 1 was prepared through a six-step reaction, including sulfonamidation, protection, nucleophilic substitution, deprotection, cyclization, and salification. The process afforded 1 in 67.1% overall yield (based on 5-isoquinoline sulfonyl chloride) with 99.94% purity. Compared to the earlier published methodologies, the use of homopiperazine or its derivatives as intermediates was avoided. The salient features of this environmentally friendly synthetic route include easily available starting materials and operational simplicity, which could be suitable for large-scale industrial production.
- Zhao, Jianhong,Wang, Dingding,Yang, Wu-Lin,Niu, Jinming,Wu, Weiting
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- CHELATOR COMPOSITIONS FOR RADIOMETALS AND METHODS OF USING SAME
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A chelator having the general structure (I) for chelating radiometals such as 225Ac under mild conditions is provided. (I) The chelator can be coupled to a biological targeting moiety to facilitate targeted delivery of the chelated radiometal i
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Paragraph 0088; 0090
(2021/09/04)
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- A Versatile Synthesis of Vinyl-Substituted Heterocycles via Regio- And Enantioselective Pd-Catalyzed Tandem Allylic Substitution
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We herein report a versatile, regio- and enantioselective palladium-catalyzed tandem allylic substitution powered by a chiral bisphosphorus ligand WingPhos with the palladium loading as low as 0.1 mol %, forming a series of chiral vinyl-substituted heterocycles, including tetrahydroquinoxalines, piperazines, dihydro-2H-benzo[b][1,4]-oxazines, and morpholines, in exellent ee's and yields. The protocol features readily available starting materials, mild reaction conditions, and a broad substrate scope. Mechanistic investigation supports a tandem allylic substitution process.
- Qian, Chao,Tang, Wenjun,Tang, Wenjun
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supporting information
p. 4483 - 4488
(2020/06/05)
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- Identification of 2,4-Disubstituted Imidazopyridines as Hemozoin Formation Inhibitors with Fast-Killing Kinetics and in Vivo Efficacy in the Plasmodium falciparum NSG Mouse Model
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A series of 2,4-disubstituted imidazopyridines, originating from a SoftFocus Kinase library, was identified from a high throughput phenotypic screen against the human malaria parasite Plasmodium falciparum. Hit compounds showed moderate asexual blood stage activity. During lead optimization, several issues were flagged such as cross-resistance against the multidrug-resistant K1 strain, in vitro cytotoxicity, and cardiotoxicity and were addressed through structure-Activity and structure-property relationship studies. Pharmacokinetic properties were assessed in mice for compounds showing desirable in vitro activity, a selectivity window over cytotoxicity, and microsomal metabolic stability. Frontrunner compound 37 showed good exposure in mice combined with good in vitro activity against the malaria parasite, which translated into in vivo efficacy in the P. falciparum NOD-scid IL-2Rnull (NSG) mouse model. Preliminary mechanistic studies suggest inhibition of hemozoin formation as a contributing mode of action.
- Horatscheck, André,Andrijevic, Ana,Nchinda, Aloysius T.,Le Manach, Claire,Paquet, Tanya,Khonde, Lutete Peguy,Dam, Jean,Pawar, Kailash,Taylor, Dale,Lawrence, Nina,Brunschwig, Christel,Gibhard, Liezl,Njoroge, Mathew,Reader, Janette,Van Der Watt, Mari?tte,Wicht, Kathryn,De Sousa, Ana Carolina C.,Okombo, John,Maepa, Keletso,Egan, Timothy J.,Birkholtz, Lyn-Marie,Basarab, Gregory S.,Wittlin, Sergio,Fish, Paul V.,Street, Leslie J.,Duffy, James,Chibale, Kelly
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supporting information
p. 13013 - 13030
(2020/11/13)
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- Reagent-switch controlled metal-free intermolecular geminal diamination and aminooxygenation of vinylarenes
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We report here the first general method for the geminal diamination and an intermolecular metal-free, geminal aminooxygenation of vinylarenes using hypervalent iodine reagent. A new m-CPBA mediated geminal aminooxygenation is also reported. A novel reagent-switch for the control of migrating group by controlling the two independent geminal addition paths is developed. Deuterium labelling studies and the control studies have provided unambiguous evidences for the phenyl migration and hydride migration in the oxidative geminal difunctionalization process mediated by PhI(OCOCF3)2and m-CPBA, respectively through a semi-pinacol rearrangement.
- Venkatesan Balaji, Pandur,Chandrasekaran, Srinivasan
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supporting information
p. 1095 - 1104
(2016/07/06)
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- Palladium-Catalyzed Modular Synthesis of Substituted Piperazines and Related Nitrogen Heterocycles
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We report here a novel method for the modular synthesis of highly substituted piperazines and related bis-nitrogen heterocycles via a palladium-catalyzed cyclization reaction. The process couples two of the carbons of a propargyl unit with various diamine components to provide nitrogen heterocycles in generally good to excellent yields and high regio- and stereochemical control. (Chemical Equation Presented).
- Montgomery, Thomas D.,Rawal, Viresh H.
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supporting information
p. 740 - 743
(2016/03/01)
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- PYRAZOLOPYRIMIDINE INHIBITORS OF IRAK4 ACTIVITY
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The present invention relates to pyrazolopyrimidine inhibitors of IRAK4 of formula (I) and provides compositions comprising such inhibitors, as well as methods therewith for treating IRAK4-mediated or -associated conditions or diseases.
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Page/Page column 76
(2016/09/26)
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- THIENOPYRAZINE INHIBITORS OF IRAK4 ACTIVITY
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The present invention relates to thienopyrazine inhibitors of IRAK4 of formula (I) and provides compositions comprising such inhibitors, as well as methods therewith for treating IRAK4-mediated or -associated conditions or diseases.
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Page/Page column 41
(2016/09/26)
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- PYRROLOPYRIDAZINE INHIBITORS OF IRAK4 ACTIVITY
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The present invention relates to pyrrolopyridazine inhibitors of IRAK4 of formula (I) and provides compositions comprising such inhibitors, as well as methods therewith for treating IRAK4-mediated or -associated conditions or diseases.
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Page/Page column 44; 45
(2016/09/26)
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- A rare earth europium complex and its synthetic method
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The embodiment of the invention discloses a rare earth europium complex and a synthetic method thereof. The method comprises the following steps: dispersing ligands L in ethyl alcohol to form a suspension liquid of the ligands L; adding NaOH into the susp
- -
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Paragraph 0059-0062
(2016/12/01)
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- PYRROLOTRIAZINE INHIBITORS OF IRAK4 ACTIVITY
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The present invention relates to pyrrolotriazine inhibitors of IRAK4 of formula (I) and provides compositions comprising such inhibitors, as well as methods therewith for treating IRAK4-mediated or -associated conditions or diseases.
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Page/Page column 51
(2016/09/26)
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- Zinc-Catalyzed Alkyne Oxidation/C-H Functionalization: Highly Site-Selective Synthesis of Versatile Isoquinolones and β-Carbolines
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An efficient zinc(II)-catalyzed alkyne oxidation/C£H functionalization sequence was developed, thus leading to highly site-selective synthesis of a variety of isoquinolones and β-carbolines. Importantly, in contrast to the well-established gold-catalyzed intermolecular alkyne oxidation, over-oxidation can be completely suppressed in this system and the reaction most likely proceeds by a Friedel-Crafts-type pathway. Mechanistic studies and theoretical calculations are described.
- Li, Long,Zhou, Bo,Wang, Yong-Heng,Shu, Chao,Pan, Yi-Fei,Lu, Xin,Ye, Long-Wu
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supporting information
p. 8245 - 8249
(2015/07/07)
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- A convenient and benign synthesis of sulphonamides in PEG-400
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A simple and convenient method is reported for the synthesis of a series of sulphonamides in PEG-400 using potassium carbonate as the base. The reaction is carried out in a heterogeneous medium and consequently product recovery is simple. The desired products with a variety of aromatic amines could be synthesized in a short reaction time in good yield. The PEG could be recovered for reuse.
- Das, Pranab Jyoti,Sarmah, Bhaskar
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p. 189 - 191
(2015/02/19)
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- From Cyclen to 12-Crown-4 Copper(II) Complexes: Exchange of Donor Atoms Improves DNA Cleavage Activity
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Macrocyclic CuII complexes with [NXOY] donor sets of different N/O ratios were synthesised resulting in a series ranging from cyclen (X = 4, Y = 0: 1) to 12-crown-4 (X = 0, Y = 4: 6) complexes. In order to elucidate the structure of the complexes UV/Vis spectroscopy and X-ray crystallography were applied, focusing especially on the literature-unknown compounds with regioisomeric [N2O2] and [NONO] donor sets (3, 4). The complexes were subjected to DNA cleavage experiments under reducing conditions and were also tested in the absence of a reducing agent. Although 3 and 6 were the most active DNA cleavers in the presence of reducing ascorbate, both of them and 4 also cleaved DNA (not hydrolytically) in its absence. This brings up questions regarding the cleavage mechanism. The present study is an expansion of our previously reported finding that heterosubstitution in macrocyclic ligands leads to changes in oxidative DNA cleavage activity of CuII complexes.
- Hormann, Jan,Van Der Meer, Margarethe,Sarkar, Biprajit,Kulak, Nora
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p. 4722 - 4730
(2015/10/19)
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- Identifying the roles of amino acids, alcohols and 1,2-diamines as mediators in coupling of haloarenes to arenes
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Coupling of haloarenes to arenes has been facilitated by a diverse range of organic additives in the presence of KOtBu or NaOtBu since the first report in 2008. Very recently, we showed that the reactivity of some of these additives (e.g., compounds 6 and 7) could be explained by the formation of organic electron donors in situ, but the role of other additives was not addressed. The simplest of these, alcohols, including 1,2-diols, 1,2-diamines, and amino acids are the most intriguing, and we now report experiments that support their roles as precursors of organic electron donors, underlining the importance of this mode of initiation in these coupling reactions.
- Zhou, Shengze,Doni, Eswararao,Anderson, Greg M.,Kane, Ryan G.,Macdougall, Scott W.,Ironmonger, Victoria M.,Tuttle, Tell,Murphy, John A.
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supporting information
p. 17818 - 17826
(2015/02/19)
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- Nitric oxide reactivity of copper(ii) complexes of bidentate amine ligands: Effect of substitution on ligand nitrosation
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Three copper(ii) complexes with bidentate ligands L1, L 2 and L3 [L1, N,N/- dimethylethylenediamine; L2, N,N/-diethylethylenediamine and L3, N,N/-diisobutylethylenediamine], respectively, were synthesized as their perchlorate salts. The single crystal structures for all the complexes were determined. The nitric oxide reactivity of the complexes was studied in acetonitrile solvent. The formation of thermally unstable [CuII-NO] intermediate on reaction of the complexes with nitric oxide in acetonitrile solution was observed prior to the reduction of copper(ii) centres to copper(i). The reduction was found to result with a simultaneous mono- and di-nitrosation at the secondary amine sites of the ligand. All the nitrosation products were isolated and characterized. The ratio of the yield of mono- and di-nitrosation product was found to be dependent on the N-substitution present in the ligand framework.
- Sarma, Moushumi,Mondal, Biplab
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supporting information; experimental part
p. 2927 - 2934
(2012/04/10)
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- Quantitative structure-activity relationships studies for prediction of antimicrobial activity of synthesized disulfonamide derivatives
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A new series of disulfonamides were synthesized and assayed as antimicrobial agents against Staphylococcus aureus, Bacillus cereus, and Escherichia coli. The quantitative structure-activity relationship analysis (QSAR) was applied to find out the correlat
- Alyar, Saliha,?zbek, Neslihan,Kuzuk?ran, Ku?bra,Karacan, Nurcan
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experimental part
p. 175 - 183
(2012/02/04)
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- ZnO and ZnO-nanoparticles: Efficient and reusable heterogeneous catalysts for one-pot synthesis of N-acylsulfonamides and sulfonate esters
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Commercially available and preparative ZnO nanoparticles are reported as efficient and reusable catalysts for the chemoselective synthesis of N-acylsulfonamides and sulfonate esters. A one-pot sequential sulfonylation and acylation of amines took place to afford the N-acylsulfonamides in excellent yields under solvent-free conditions. The ZnO catalyst can be reused for without significant loss of catalytic activity.
- Tamaddon, Fatemeh,Sabeti, Mohammad Reza,Jafari, Abbas Ali,Tirgir, Farhang,Keshavarz, Elham
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experimental part
p. 41 - 45
(2012/01/12)
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- A novel and efficient solvent-free and heterogeneous method for the synthesis of primary, secondary and bis-N-acylsulfonamides using metal hydrogen sulfate catalysts
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Some metal hydrogen sulfates were used as acid catalysts in the N-acylation of different sulfonamides using carboxylic acid chlorides and anhydrides as acylating agents under both heterogeneous and solvent-free conditions. Al(HSO4)3
- Massah, Ahmad Reza,Asadi, Beheshteh,Hoseinpour, Mahdieh,Molseghi, Azadeh,Kalbasi, Roozbeh Javad,Javaherian Naghash, Hamid
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body text
p. 7696 - 7705
(2009/12/04)
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- Copper-catalyzed 1,2-double amination of 1-halo-1-alkynes. Concise synthesis of protected tetrahydropyrazines and related heterocyclic compounds
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Reaction of N,N′-di(p-toluenesulfonyl)-1,2-diamine, 1-bromo-1-alkyne, K3PO4, and a catalytic amount of CuI in hot DMF afforded N,N′-di(p-toluenesulfonyl)-1,2,3,4-tetrahydropyrazines in good yields. The reaction most likely involves (i) monoalkynylation of the diamine derivative with 1-bromo-1-alkyne, and (ii) 6-endo-dig ring closure between the acetylenic bond and another sulfonylamine moiety of the diamine. When the starting 1,2-diamine derivative was replaced with N,N′-di(p-toluenesulfonyl)-1,3-diamine or N-(p-toluenesulfonyl)-2-amino-1-ethanol, the corresponding seven-membered diazacycle or six-membered N,O-heterocycle was produced. In addition, 1,1-dibromo-1-alkene could be used in place of 1-bromo-1-alkyne. Copyright
- Fukudome, Yasuhiro,Naito, Hiroyuki,Hata, Takeshi,Urabe, Hirokazu
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p. 1820 - 1821
(2008/09/18)
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- Investigation of macrocyclisation routes to 1,4,7-triazacyclononanes: Efficient syntheses from 1,2-ditosylamides
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Two routes to the synthesis of a cyclohexyl-fused 1,4,7-triazacyclononane involving macrocyclisations of tosamides have been investigated. In the first approach, using a classic Richman-Atkins-type cyclisation of a cyclohexyl-substituted 1,4,7-tritosamide
- Stones, Graham,Tripoli, Regis,McDavid, Colin L.,Roux-Duplgtre, Kewin,Kennedy, Alan R.,Sherrington, David C.,Gibson, Colin L.
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p. 374 - 384
(2008/10/09)
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- The coordination chemistry of 1,4-diazepan-6-amine
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The new, tridentate, facially coordinating ligand 1,4-diazepan-6-amine (daza) has been prepared from ethane-1,2-diamine and 2,3-dibromo-1-propanol in a seven-step procedure with an overall yield of 22%. The conformation of the free ligand has been elucida
- Romba, Jens,Kuppert, Dirk,Morgenstern, Bernd,Neis, Christian,Steinhauser, Stefan,Weyhermueller, Thomas,Hegetschweiler, Kaspar
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p. 314 - 328
(2007/10/03)
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- Diepoxide derivatives of N, N*-disubstituted disulfonamides
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The present invention relates to novel diepoxides having the formulas I. and II. [in-line-formulae]R*N(A)SO2RSO2N(A)R*??I[/in-line-formulae][in-line-formulae]R*SO2N(A)RN(A)SO2R*??II[/in-line-formulae] where A=2,3-epoxypropyl, R* is a monovalent hydrocarbon alkyl aryl, aryl-alkyl, alkyl-aryl radical of 1-20 carbon atoms or a monovalent inertly substituted hydrocarbon aryl, alkyl, alkyl-aryl or aryl-alkyl radical of 1-20 carbons atoms and R is a divalent hydrocarbon arylene, alkylene, alkylene-aryl, arylene-alkyl radical or combinations thereof of 2-20 carbon atoms or an inertly substituted divalent hydrocarbon alkylene, arylene, arylene-alkyl, or alkylene-aryl radical or combinations thereof of 2-20 carbon atoms. The epoxides are useful in preparing novel epoxide resins.
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Page/Page column 3
(2008/06/13)
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- N,N′-Diiodo-N,N′-1,2-ethanediylbis(p-toluenesulfonamide) as a reagent for conversion of aldehydes to methyl esters
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N,N′-Diiodo-N,N′-1,2-ethanediylbis(p-toluenesulfonamide) (NIBTS) can be used for the oxidation of aldehydes to the corresponding methyl esters with high efficiency in a single step.
- Ghorbani-Vaghei, Ramin,Shahbazee, Elham,Veisi, Hojat
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p. 207 - 208
(2007/10/03)
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- Design and synthesis of pyrrolo[2,1-c][1,4]benzodiazepine (PBD)- polyaminoalkyl conjugates by the use of SNAr reaction of 2-nitro-5-fluorobenzoate precursor as key reaction
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The design and synthesis of a series of pyrrolo[2,1-c][1,4]benzodiazepine (PBD)- polyaminoalkyl conjugates as DNA minor groove binders are described. To introduce polyaminoalkyl groups to the pyrrolo[2,1-c][1,4]benzodiazepine pharmacophore, SNA
- Iida, Hirokazu,Hayashi, Naoto,Lown, J. William,Matsumoto, Kiyoshi
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p. 693 - 711
(2007/10/03)
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- PIPERAZINE SUBSTITUTED ARYL BENZODIAZEPINES AND THEIR USE AS DOPAMINE RECEPTOR ANTAGONISTS FOR THE TREATMENT OF PSYCHOTIC DISORDERS
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Described herein are antipyschotic compounds of formula (I) wherein, A is an optionally benzo-fused five or six member aromatic ring having zero to three hetero atoms independently selected from N, O, and S; Alk is (C1-4) alkylene optionally substituted w
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Page/Page column 75
(2010/02/07)
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- The application of N,N′-dibromo-N,N′-1,2-ethanediylbis (p-toluenesulphonamide) as a powerful reagent for deoximation of various oximes
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N,N′-Dibromo-N,N′-1,2-ethanediylbis (p-toluenesulphonamide) [BNBTS] 2 was reacted with oximes and converts them to their corresponding carbonyl compounds in good yields under mild conditions.
- Khazaei, Ardeshir,Ghorbani Vaghei, Ramin,Tajbakhsh, Mahmoud
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p. 5099 - 5100
(2007/10/03)
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- Synthesis of polyaminoalkyl substituted conjugates of pyrrolo[2,1- c][1,4]benzodiazepine involving S(N)Ar reaction of 2-nitro-5-fluorobenzoate precursors
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A synthetic procedure is described for conjugating polyaminoalkyl groups to the pyrrolo[2,1-c][1,4]benzodiazepine pharmacophore in order to alter its characteristic DNA sequence binding preference. To this end S(N)Ar reactions of 2-nitro-5-fluorobenzoate
- Matsumoto, Kiyoshi,Iida, Hirokazu,Lown, J. William
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p. 1015 - 1020
(2007/10/03)
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- Photodegradation of aryl sulfonamides: N-tosylglycine
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Continuing uncertainty about pathways and consequences of the photolability of aryl sulfonamides is partly resolved by the results of comprehensive product analysis in the photolysis of aqueous N-tosylglycine, which indicate that intramolecular electron or hydrogen transfer (according to conditions) promote the widely reported S-N cleavage and reveal the nature of subsequent and competing processes.
- Hill, Roger R.,Jeffs, Graham E.,Roberts, David R.,Wood, Sharon A.
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p. 1735 - 1736
(2007/10/03)
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- Functionalized macrocyclic ligands for imaging applications
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The present invention provides new and structurally diverse compositions comprising compounds of the general formula: STR1 Wherein U is --(CH2)n X or --(CH2)n NR1 (CH2)X; R1 is h
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- Design and synthesis of calcium and magnesium ionophores based on double-armed diazacrown ether compounds and their application to an ion-sensing component for an ion-selective electrode
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The double-armed diazacrown ethers, which have a base diazacrown ether ring with two diamide-type side chains, were designed and synthesized on the basis of the proposed molecular model for the novel neutral Ca2+ and Mg2+ ionophores. The potentiometric ion-selective electrodes were prepared with over 20 kinds of systematically synthesized diazacrown ether derivatives. The relationship between the molecular structures of the ionophores and the ion selectivities was fully discussed. The electrodes based on the 21- and 18-membered diazacrown ether derivatives possessing a glycolic diamide and malonic diamide in their side chains (K23E1 and K22B5) exhibited excellent Ca2+ and Mg2+ selectivities, respectively. The ion-selectivity features of the novel Ca2+ and Mg2+ ionophores supply important structural information about the design of host molecules for alkaline earth metal cations.
- Suzuki, Koji,Watanabe, Kazuhiko,Matsumoto, Yukihiro,Kobayashi, Mitsuru,Sato, Sayaka,Siswanta, Dwi,Hisamoto, Hideaki
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p. 324 - 334
(2007/10/02)
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- N,N'-Doacylated imidazolidines and hexahydropyrimidines
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A method for the preparation of N-monoacyl imidazolidines and hexahydropyrimidines (as hydrochlorides) by interaction of monoacylated derivatives of ethylenediamine and trimethylethylenediamine with chloromethyl methyl ether was developed.Also a method for the preparation of N,N'-diacylimidazolidines and hexahydropyrimidines either by acylation of their monoacyl derivatives or by reaction of the corresponding N,N'-diacyl alkylenediamine derivatives with dimethoxymethane, diacetoxymethane, 1,3,5-trioxane or chloromethyl methyl ether was designed. - Key words: N-mono- and N,N'-diacylated imidazolidines, N-mono- and N,N'-diacylated hexahydropyrimidines, N,N'-diacylated alkylenediamines, acylation, methylation, cyclization.
- Luk'yanov, O. A.,Pokhvisneva, G. V.,Ternikova, T. V.
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p. 1376 - 1380
(2007/10/02)
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- Condensation of Alkanediamines with Formaldehyde; Intramolecular Disproportionation of N-Hydroxymethyl Groups into N-Methyl and N-Formyl Groups
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The condensation of α,ω-alkanediamines NH2(CN2)nNH2 with aqueous formaldehyde has been studied by NMR spectroscopy of isolated products and of product mixtures.The condensation was reversible and gave products of widely different types depending on alkane chain length: bicyclic oxadiaza compounds (n = 2, 3, 4), a tricyclic tetraaza compound (n = 2), a quinquecyclic octaaza compound (n = 3), two-dimensional polymers (n = 4, 5).A slow irreversible rearrangement gave in two cases (n = 3, 4), unicyclic 1-formyl-3-methyl-1,3-diaza compounds.The condensation of N,N'-dimethyl-α,ω-alkandediamines CH3NH(CH2)nNHCH3 with aqueous formaldehyde was also studied.The reversible formation of simple unicyclic diaza compounds was observed in all cases (n = 2, 3, 4), but in one case (n = 2) there was again a slow irreversible rearrangement to the N-formyl-N,N'N'-trimethyl derivative.The rearrangement reaction involves a hydride shift and is strictly intramolecular.The conditions for its occurrence can be understood on a conformational basis.
- Dale, Johannes,Sigvartsen, Turid
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p. 1064 - 1070
(2007/10/02)
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- Photochemistry of Amino Ketones, 14. - Synthesis and Transannular Photocyclisation of 2-Benzoyl-1,4-bis-(tosyl)piperazines
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1,1-Dialkyl-1,2-bis(tosylamino)ethanes 4 are prepared in a three-step reaction starting with dialkyl ketones 1.With strong bases in dimethylformamide compounds 4 react regioselectively with 1,2-dibromoalkyl phenyl ketones 5 to afford the 2-benzoyl-1,4-bis
- Wessig, Pablo,Legart, Frank,Hoffmann, Berit,Henning, Hans-Georg
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p. 979 - 982
(2007/10/02)
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- MACROHETEROCYCES. XXXVI. A CONVENIENT METHOD FOR SYNTHESIS OF DI- AND POLYAZACROWN ETHERS
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A method is proposed for the production of di- and polyazacrown ethers by the condensation of bissulfonamides with dibromides or ditosyloxy derivatives in a two-phase aqueous alkali-toluene (benzene) system.The optimum concentration range for the substrate and the alkylating agent is 0.017-0.1 M.The catalytic activity of the quaternary ammonium salts decreases in the order (Bu)4NI > (Bu4)NBr > (Bu4)NCl > (Bu4)NHSO4 > (C2H5)3C6H5CH2NCl >> (Et)4NI > (Et)4NBr.The highest yields of te 12-membered azacrown ethers are obtained in the presence of lithium hyroxide, and the largest yields of the crown ethers with larger ring sizes are obtained in the presence of sodium or potassium hydroxide, and this is probably due to the matrix effects of the cation.
- Luk'yanenko, N.G.,Basok, S.S.,Filonova, L.K.
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p. 1562 - 1571
(2007/10/02)
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- Chemistry of N-Nitrososulfonamides. Substitution Reaction by the Acetyl Group
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The N-nitroso group on N-nitrososulfonamides was substituted for the acetyl group in chloroform to give N-acetylsulfonamides in moderate qields.
- Iwata, Masaaki,Kuzuhara, Hiroyoshi
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p. 3395 - 3396
(2007/10/02)
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- A THERMOMETRIC TITRIMETRIC STUDY OF THE COMPLEXATION OF ALKALINE-EARTH METALS BY MACROCYCLIC POLY(AMINOCARBOXYLIC) ACIDS
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Thermometric titrimetry has been employed to determine K, ΔH and ΔS data for the complexation reaction in aqueous solution of 1,4-piperazine-N,N'-diacetic acid, 1,5-diazacyclooctane-N,N'-diacetic acid, 1-oxa-4,7-diazacyclononane-N,N'-diacetic acid, 4-oxa-1,7-diazacyclodecane-N,N'-diacetic acid and 1,11-dioxa-4,8-diazacyclotridecane-N,N'-diacetic acid with alkaline earth metal cations.Factors influencing the thermodynamic stability of these complexes are discussed.
- Ewin, Gavin,Hill, John O.
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p. 3501 - 3519
(2007/10/02)
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- Improved Richman-Atkins Syntheses of Cyclic Polyamines Particularly 1,4,7-Triazacyclononane (tacn) and 1,4,7-Triazacyclodecane (tacd), with the Aid of Cation-Exchange in Purification and Isolation
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Richman-Atkins cyclization syntheses for the cyclic triamines 1,4,7-triazacyclononane (tacn) and 1,4,7-triazacyclodecane (tacd) with the alternative possible sets of reagents asd tosyl derivatives have been examined in detail and compared.The cyclizations from the tritosyl derivative of diethylenetriamine (dientt) and the appropriate diols as ditosylates proceeded relatively cleanly, although there were small amounts of higher products and some carry through of dientt for tacn.The alternative cyclizations, from 2,2'-(tosylimino)bisethyl ditosylate and a ditosyl diamine, gave little reaction to form tacn as the tritosyl derivative.The reaction to form tritosyl tacd proceeded further, but was accompanied by significant formation of higher condensation products, particularly the hexamines 1,4,7,11,14,17-hexaazacycloeicosane (2:2 cyclic dimer) and 3,7,10,13-tetraazahexadecane-1,16-diamine.A cation-exchange procedure, applied after the detosylation stage, is described for obtaining the required pure 1 : 1 cyclic polyamines as their hydrochloride salts with high recovery.This is an effective method for removing higher co-products.These may be recovered, and by this means the above hexamines were isolated in admixture.
- Searle, Graeme H.,Geue, Rodney J.
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p. 959 - 970
(2007/10/02)
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- Dynamic Protection of Amines using 18-Crown-6
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The regioselectivity of diamine monoacylation has been controlled by selective complexation with 18-crown-6 and a proton source.
- Barrett, Anthony G. M.,Lana, J. Carlos A.,Tograie, Shahrzad
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p. 300 - 301
(2007/10/02)
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- Complexes of macrocyclic compounds
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Novel macrocyclic (monocyclic and bicyclic) compounds having nitrogen bridgehead atoms and having in the hydrocarbon bridging chains at least two additional hetero atoms selected from the group consisting of sulfur, oxygen, and nitrogen, when admixed with a compatible cation-donor compound form stable cation-containing macrocyclic complexes which, in turn, can be conveniently dissociated by addition of acid or a quaternizing agent. The novel macrocyclics are valuable for use in the same way and for the same purposes as chelating agents.
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- Monocyclic macrocyclic compounds and complexes thereof
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Novel monocyclic macrocyclic compounds having nitrogen bridgehead atoms and having in the hydrocarbon bridging chains at least two additional hetero atoms selected from the group consisting of sulfur, oxygen, and nitrogen, when admixed with a compatible cation-donor compound form stable cation-containing macrocyclic complexes which, in turn, can be conveniently dissociated by addition of acid or a quaternizing agent. The novel macrocyclics are valuable for use in the same way and for the same purposes as chelating agents.
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