- Synthesis of the carbon framework of scholarisine a by intramolecular oxidative coupling
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Scholarisine A, isolated from the leaves of Alstonia scholaris, is a monoterpene indole alkaloid with an unprecedented cage-like structure. In this paper, preparation of the distinctive cage-like core skeleton of scholarisine A is described. The key feature of this synthetic strategy is an intramolecular oxidative coupling reaction at the late stage to construct a 10-oxa-tricyclo[5.3.1.03, 8]undecan-9-one structure fused with indolenine. Intramolecular oxidative coupling by using N-iodosuccinimide gave the carbon framework of scholarisine A in moderate yield, which is the first example of intramolecular oxidative-coupling reaction between non-activated enolate and indole. This study lays the foundation for continued investigations towards the total synthesis of scholarisine A. Copyright
- Watanabe, Tsugunori,Kato, Nobuki,Umezawa, Naoki,Higuchi, Tsunehiko
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- Equilibrium constants and alkylation kinetics of two lithium enolates/LiHMDS mixed aggregates in THF
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LiEn + LiHMDS ?Kagg Li2EnHMDS (Formula Presented) Products Products Mixed aggregates between lithium enolates and lithium hexamethyldisilazide (LiHMDS) have been studied in THF using UV-vis spectroscopy. The equillibrium constants (K
- Kim, Yeong-Joon,Streitwieser, Andrew
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- The synthesis of pentadienylium salts via reactions of (5-ethoxy-1,5-diaryl-2,4-pentadienylidene)ethyloxonium perchlorate with hydrazines
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Reaction of the readily available (5-ethoxy-1,5-diaryl-2,4-pentadienylidene)ethyloxonium perchlorate 1 with hydrazines, R2NNH2 or RNHNH2, provides a simple and efficient synthesis of previously unknown (5-ethoxy-1,5-diaryl-2,4-pentadienylidene)hydrazinium salts 2a-d. Application of this method to the synthesis of the highly conjugated pentadienylium salt from terephthalic dihydrazide is reported.
- Riviere, Francois,Romanenko, Vadim D.,Mazieres, Marie-Rose,Sanchez, Michel,Wolf, Jean-Gerard
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- Divergent Kinetic and Theromodynamic Acidity in Organotransition-Metal Hydride Complexes: Synthesis, Structure, and Reactivity of the Rhenium Anion of Li+5-C5H5)Re(NO)(PPh3)>-
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Reaction of hydride complex (η5-C5H5)Re(NO)(PPh3)(H) (1) and n-BuLi/TMEDA (THF, -78 deg C) gives (η5-C5H4Li)Re(NO)(PPh3)(H) (Li+-8), as shown by 31P NMR monitoring, deuterium labeling, and methylation (CH3OSO2CF3, -78 deg C) to (η5-C5H4CH3)Re(NO)(PPh3)(H) (9, 52 percent).Complex Li+-8 rearranges to the rhenium anion of Li+5-C5H5)Re(NO)(PPh3)>- (Li+-3; -32 deg C, 0.5 h) with ΔH* = 11.3 +/- 0.5 kcal/mol, ΔS* = -26.2 +/- 1.4 eu, and kH/kD (-22.4 deg C) = 1.16 +/- 0.08.Crossover experiments show hydrogen migration to be intramolecular, and K+-8 rearranges ca. 104 faster than Li+-8 at -91.6 deg C.Equilibration experiments show the η5-C5H5 and ReH proton pKa's (THF) in 1 to be ca. 36 and 26 - 30, respectively.Thus, the less acidic proton is abstracted kinetically, and a rationale is proposed.Reactions of Li+-3 with alkylating agents (CH3I, n-C4H9I, ClCH2CH=CH2, ClCH2COPh), benzoic anhydride, and D2O give the corresponding alkyl, acyl, and deuteride complexes (56 - 90 percent).IR data show Li+-3 to be a mixture of three ion pairs in THF.Pentamethyl analogue (η5-C5Me5)Re(NO)(PPh3)(H) (13) is prepared from methyl complex (η5-C5Me5)Re(NO)(PPh3)(CH3) (11; HCOOH, then 110 deg C; 43 percent).Reaction of 13 and n-BuLi/K+-t-BuO- gives principally K+5-C5Me5)Re(NO)(PPh3)>-, as assayed by 31P NMR and methylation (CH3I) to 11.
- Crocco, Guy L.,Gladysz, J. A.
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- Synthesis and grafting of CAN-derived tetravalent cerium alkoxide silylamide precursors onto mesoporous silica MCM-41
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The heteroleptic tetravalent cerium complex [Ce(OiPr) 3{N(SiMe3)2}]2 was synthesised by treating ceric ammonium nitrate (CAN) sequentially with sodium isopropoxide and lithium bis(trimethylsilyl)amide in THF. The trivalent ate complex [Ce(OiPr)2{N(SiMe3)2]2}][Li(thf) 2] was also isolated from these reaction mixtures. A transsilylamination reaction of [Ce(OiPr)3{N(SiMe3) 2}]2 with tetramethyldisilazane produced a considerable amount of homoleptic Ce[N(SiHMe2)2]4. The polymeric complex [Li2Ce2(OiPr)10(1,4-dioxane)] n was isolated as an additional ligand redistribution product. When tetravalent complexes Ce[N(SiHMe2)2]4, Ce[N(SiMe3)2]3Cl and Cp3CeCl were allowed to react with samples of periodic mesoporous silica MCM-41, Ce(iv) hybrid materials were produced. All hybrid materials were characterised via N2 physisorption, elemental analysis and DRIFT spectroscopy.
- Crozier, Alan R.,Schaedle, Christoph,Maichle-Moessmer, Caecilia,Toernroos, Karl W.,Anwander, Reiner
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- Synthesis and structural elucidation of solvent-free and solvated lithium dimethyl (HMDS) zincates
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Using a co-complexation methodology the unsolvated lithium zincate [LiZn(HMDS)Me2] (4, HMDS = 1,1,1,3,3,3-hexamethyldisilazide) was prepared by reaction of an equimolar amount of LiHMDS with Me2Zn in a non-polar toluene-hexane solvent mixture. X-Ray crystallographic studies reveal that the asymmetric unit of 4 has a dinuclear arrangement, based on a planar LiNZnC four-membered ring. As a result of intermolecular interactions between the lithium centre of one asymmetric unit and a terminal methyl group of another, 4 presents a polymeric chain array in the solid state. DFT calculations revealed that the formation of the polymer is the driving force for the success of co-complexation of LiHMDS and Me2Zn to yield the unsolvated zincate 4. The reaction of 4 with PMDETA (N,N,N′,N″,N″- pentamethyldiethylenetriamine) afforded the new solvated zincate [(PMDETA)Li(μ-Me)Zn(HMDS)Me] (5). X-Ray crystallographic studies show that the asymmetric unit of 5 consists of an open, dinuclear LiCZnC arrangement rather than a closed cyclic one, in which the HMDS ligand unusually occupies a terminal position on Zn. DFT computational studies showed that the structure found for 5 was energetically preferred to the expected HMDS-bridging isomer due to the steric hindrance imposed by the tridentate PMDETA ligand. The reaction of 4 with the neutral nitrogen donors 4-tert-butylpyridine and tert-butylcyanide afforded the homometallic compounds [(tBu-pyr)Li(HMDS)] (6) and [(tBuCN)Li(HMDS)] (7) respectively as a result of disproportionation reactions. Compounds 6 and 7 were characterized by NMR (1H, 13C and 7Li) spectroscopy. The Royal Society of Chemistry.
- Armstrong, David R.,Herd, Emma,Graham, David V.,Hevia, Eva,Kennedy, Alan R.,Clegg, William,Russo, Luca
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- A trigonal-pyramidal Erbium(III) single-molecule magnet
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Given the recent advent of mononuclear single-molecule magnets (SMMs), a rational approach based on lanthanides with axially elongated f-electron charge cloud (prolate) has only recently received attention. We report herein a new SMM, [Li(THF)4[Er{N(SiMe3)2}3Cl] 2 THF, which exhibits slow relaxation of the magnetization under zero dc field with an effective barrier to the reversal of magnetization (ΔEeff/kB=63.3 K) and magnetic hysteresis up to 3 K at a magnetic field sweep rate of 34.6 Oe s-1. This work questions the theory that oblate or prolate lanthanides must be stabilized with the appropriate ligand framework in order for SMM behavior to be favored.
- Brown, Andrew J.,Pinkowicz, Dawid,Saber, Mohamed R.,Dunbar, Kim R.
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- Structural Similarity in a Series of Alkali Metal Aluminates with Heteroleptic tert-Butoxide–Isobutyl Ligand Sets
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With the aim of increasing the number of well-defined alkali metal aluminates, six new crystalline examples containing heteroleptic tert-butoxide – isobutyl ligand sets are reported. NMR spectroscopic studies in C6D6 solution have determined their common general formula [(iBu)2Al(OtBu)2AM·(D)], where AM = Li, D = 2 THF, TMEDA or PMDETA; AM = Na, D = TMEDA or PMDETA; and AM = K, D = PMDETA. X-ray crystallographic studies show that despite the different sized alkali metals involved all six complexes adopt a common dinuclear motif with [AlO(AM)O] ring cores. Though Al–OtBu–Li linkages are common, the heavier alkali metal examples reported here are exceptionally rare. These structures could be interpreted as co-complexes between monomeric forms of tBuO(AM) and (iBu)2Al(OtBu).
- Whitelaw, Michael T.,Kennedy, Alan R.,Mulvey
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- An Efficient Directed Claisen Reaction Allows for Rapid Construction of 5,6-Disubstituted 1,3-Dioxin-4-ones
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An efficient directed Claisen reaction between tert-butyl propionate and phenyl propionate is described. This enables a practical synthesis of 6-ethyl-2,2,5-trimethyl-4H-1,3-dioxin-4-one and thereby (Z)-[(4-ethylidene-2,2,5-trimethyl-4H-1,3-dioxin-6-yl)oxy]trimethylsilane, a key building block in our synthesis of macrolide antibiotics. The three-step route elaborated for the preparation of the latter substance requires no chromatography and is amenable to large-scale synthesis.
- Zhang, Ziyang,Kitamura, Yoshiaki,Myers, Andrew G.
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- NMR spectroscopic study of the adduct formation and reactivity of homoleptic rare earth amides with alkali metal benzyl compounds, and the crystal structures of [Li(TMEDA)2][Nd{N(SiMe3)2}3(CH2Ph)] and [{Li(TMP)}2{Li(Ph)}]2
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An NMR spectroscopic study has been conducted into the reactivity of alkali metal benzyls [M(CH2Ph)], (M = Li, Na, K) with lanthanide tris(amide) complexes [Ln(N″)3] (Ln = Y, Ce, Nd; N″ = N(SiMe3)2) and [Ce(TMP)3] (TMP = 2,2,6,6-tetramethylpiperidide). It was found that for [Ln(N″)3], benzyl adducts [M][Ln(N″)3(CH2Ph)] were initially formed, and the molecular structure for M = Li(TMEDA)2 and Ln = Nd was determined revealing a distorted tetrahedral [Nd(N″)3(CH2Ph)] anion. In all cases, these adduct complexes were unstable, intramolecularly deprotonating a methyl arm of a N″ ligand via benzyl basicity and eliminating toluene to prepare cyclometallated complexes of the form [M][Ln(N″)2{κ2-CH2Si(Me)2N(SiMe3)}]. In parallel studies, reactions of [Li(Ph)] with [Ln(N″)3] (Ln = Ce, Nd) afforded [Li(N″)], whilst for (Ln = Y) adduct formation was observed. [Ce(TMP)3] did not generate any characterisable bimetallic adducts. The reaction of [Li(Ph)] with [Li(TMP)] afforded the hexanuclear [{Li(TMP)}2{Li(μ-Ph)}]2, which features lithium in three different coordination environments.
- Rachor, Simon G.,Cleaves, Peter A.,Robertson, Stuart D.,Mansell, Stephen M.
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- Shape-and size-controlled Ag nanoparticles stabilized by in situ generated secondary amines
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Silver amides such as AgNiPr2 and AgN(SiMe3)2 have been employed successfully as precursors for the yield synthesis of silver nanoparticles under mild conditions of dihydrogen gas reduction (2 atm) in organic media. Transmission electron microscopy (TEM) showed the formation of silver nanoparticles with FCC structure, variously sized from 26 to 35 nm for AgNiPr2 and from 14 to 86 nm for AgN(SiMe3)2, the synthesis could take place in absence of added stabilizers due to the in situ formation of secondary amines from the reaction of dihydrogen gas with the amide ligands of the silver precursor. Indeed, the presence of HNR2 (R = iPr2, N(SiMe3)2) on the surface of the nanoparticle was confirmed by spectroscopic means. Finally, the addition of ethylenediamine as additional capping agent allowed not only the control of the structural characteristics of the resulting Ag nanoparticles (well-dispersed with spherical shape), but that regarding the nanoparticle size as it inhibited overgrowth, limiting it to ca. 25 nm.
- Ramírez-Meneses,Montiel-Palma,Domínguez-Crespo,Izaguirre-López,Palacios-Gonzalez,Dorantes-Rosales
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- TITRATION OF ORGANIC COMPOUNDS AS VERY WEAK ACIDS WITH LITHIUM SILANAMIDE
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Numerous organic compounds, such as alcohols, acetophenones, esters, anilides, carbamates, and lactams, can be titrated as very weak acids in tetrahydrofuran.End points were determined by potentiometry and by color change of N-phenyl-p-aminoazobenzene.Relative percent errors for the determination of approximately 1.00-mmol amounts of sample generally ranged from 2 to 6percent.Examples of compounds which did not react quantitatively with the lithium silylamide reagent were benzophenone, benzylbenzoate, and N-phenylbenzylamine.
- Clyde, Dale D.
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- Process for preparing lithium bis (trimethyldisilyl) amide
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The invention provides a process for preparing lithium bis (trimethyldisilyl) amide, which comprises the following steps of: under the protection of inert gas, adding lithium, isoprene, hexamethyldisilazane and tetrahydrofuran into a reaction vessel, carrying out one-step synthesis reaction, and preparing to obtain the finished product. The product is directly synthesized by adopting a one-step method, the link of producing the n-butyllithium product is omitted, the utilization rate of metal lithium is improved, the solvent component of the product is single and only tetrahydrofuran is contained, and the solvent is simple and easy to recover; and meanwhile, the manufacturing cost is greatly saved, and the market competitiveness of the product is greatly improved.
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Paragraph 0020-0022
(2021/04/28)
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- Accessing Photoredox Transformations with an Iron(III) Photosensitizer and Green Light
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Efficient excited-state electron transfer between an iron(III) photosensitizer and organic electron donors was realized with green light irradiation. This advance was enabled by the use of the previously reported iron photosensitizer, [Fe(phtmeimb)2]+ (phtmeimb = {phenyl[tris(3-methyl-imidazolin-2-ylidene)]borate}, that exhibited long-lived and luminescent ligand-to-metal charge-transfer (LMCT) excited states. A benchmark dehalogenation reaction was investigated with yields that exceed 90% and an enhanced stability relative to the prototypical photosensitizer [Ru(bpy)3]2+. The initial catalytic step is electron transfer from an amine to the photoexcited iron sensitizer, which is shown to occur with a large cage-escape yield. For LMCT excited states, this reductive electron transfer is vectorial and may be a general advantage of Fe(III) photosensitizers. In-depth time-resolved spectroscopic methods, including transient absorption characterization from the ultraviolet to the infrared regions, provided a quantitative description of the catalytic mechanism with associated rate constants and yields.
- Aydogan, Akin,Bangle, Rachel E.,Cadranel, Alejandro,Turlington, Michael D.,Conroy, Daniel T.,Cau?t, Emilie,Singleton, Michael L.,Meyer, Gerald J.,Sampaio, Renato N.,Elias, Benjamin,Troian-Gautier, Ludovic
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supporting information
p. 15661 - 15673
(2021/10/01)
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- Expanding the Library of Uranyl Amide Derivatives: New Complexes Featuring the tert -Butyldimethylsilylamide Ligand
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New uranyl derivatives featuring the amide ligand, -N(SiHMe2)tBu, were synthesized and characterized by X-ray crystallography, multinuclear NMR spectroscopy, and absorption spectroscopies. Steric properties of these complexes were also quantified using the computational program Solid-G. The increased basicity of the free ligand -N(SiHMe2)tBu was demonstrated by direct comparison to -N(SiMe3)2, a popular supporting ligand for uranyl. Substitutional lability on a uranyl center was also demonstrated by exchange with the -N(SiMe3)2 ligand. The increased basicity of this ligand and diverse characterization handles discussed here will make these compounds useful synthons for future reactivity.
- Pattenaude, Scott A.,Coughlin, Ezra J.,Collins, Tyler S.,Zeller, Matthias,Bart, Suzanne C.
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p. 4543 - 4549
(2018/04/23)
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- Designing Stability into Thermally Reactive Plumbylenes
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Lead analogues of N-heterocyclic carbenes (NHPbs) are the least understood members of this increasingly important class of compounds. Here we report the design, preparation, isolation, structure, volatility, and decomposition pathways of a novel aliphatic NHPb: rac-N 2,N 3-di-tert-butylbutane-2,3-diamido lead(II) (1Pb). The large steric bulk of the tert-butylamido moieties and rac-butane backbone successfully hinder redox decomposition pathways observed for diamidoethylene and -ethane backbone analogues, pushing the onset of thermal decomposition from below 0 °C to above 150 °C. With an exceptionally high vapor pressure of 1 Torr at 94 ± 2 °C and excellent thermal stability among Pb(II) complexes, 1Pb is a promising precursor for the chemical vapor deposition (CVD) and atomic layer deposition (ALD) of functional lead-containing materials.
- Ba?i?, Goran,Zanders, David,Mallick, Bert,Devi, Anjana,Barry, Seán T.
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p. 8218 - 8226
(2018/07/25)
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- Compound double volute phosphinylidyne nitrogen silane and its preparation method
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The invention relates to a novel spirophosphoryl compound and particularly relates to a compound bis-spirophosphoryl nitrogen silane and a preparation method thereof. The preparation method comprises the following steps: S1, at a temperature of 0 DEG C and under a nitrogen atmosphere, dissolving hexamethyl bisilazane in tetrahydrofuran, uniformly stirring and dropwise adding n-butyllithium, and after dropwise adding n-butyllithium, recovering to room temperature and reacting for 1-1.5 hours; after reaction, obtaining a tetrahydrofuran solution of hexamethyl silylamino lithium for later use; S2, at a temperature of minus 20 DEG C and under a nitrogen atmosphere, adding the tetrahydrofuran solution of hexamethyl silylamino lithium and 3,9-dichloro-2,4,8,10-tetrahydro-3,9-diphosphorus spiro[5, 5]-3,9-dioxy undecane into the solvent, reacting for 1-6 hours under a condition that the temperature ranges from minus 20 DEG C to 0 DEG C, recovering to room temperature and reacting for 12 hours, filtering, spirally steaming the filtrate to obtain a solid initial product, washing respectively by normal hexane and anhydrous acetonitrile, and drying to obtain the compound bis-spirophosphoryl nitrogen silane.
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Paragraph 0028
(2016/12/01)
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- Templating Influence of Molecular Precursors on Pr(OH)3 Nanostructures
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Four new praseodymium alkoxo and amido compounds ([Pr3(μ3-OtBu)2(μ2-OtBu)3(OtBu)4(HOtBu)2] (1), [Pr{OC(tBu)3}3(THF)] (2), [PrCl{N(SiMe3)2}2(THF)]2 (3), and [PrCl{OC(tBu)3}2(THF)]2 (4)) were synthesized and structurally characterized by single-crystal X-ray diffraction analysis. Application of these compounds in solvothermal synthesis of praseodymium oxide/hydroxide nanostructures showed their templating influence on the morphology and phase composition of the resulting solid-state materials. Differential reactivity of the chosen alkoxide ligands toward water and the different arrangements of metal-oxygen units in the studied precursor compounds strongly influenced the kinetics of hydrolysis and cross-condensation reactions as manifested in the morphological changes and phase composition of the final products. Thermal decomposition studies of 1-4 confirmed their conversion into the corresponding oxide phases. Activation of compounds 1, 2, and 4 by either a base or a stoichiometric amount of water showed the distinct influence of their chemical configuration on the obtained nanopowders: whereas 1 solely produced nanorods of Pr(OH)3, 2 predominantly formed a mixture of rod-shaped and spherical particles. The solvothermal decomposition of 4 resulted in Pr(OH)2Cl or PrOCl due to the presence of Cl ligands in the molecular precursor. The resultant materials were thoroughly characterized to demonstrate the relationship between precursor chemistry and the processing parameters that are clearly manifested in the morphology and phase of the final ceramics. (Chemical Equation Presented).
- Hemmer, Eva,Cavelius, Christian,Huch, Volker,Mathur, Sanjay
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p. 6267 - 6280
(2015/07/15)
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- Alternative synthetic routes to hydrofluoroolefins
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A series of hydrofluoroolefins with -CF=CH2, -CH=CHF and -CH=CF2 groups were designed and prepared via various synthetic routes, including HX or BrF elimination, Wittig-type olefination or fluorination using SF4.
- Yagupolskii, Yu. L.,Pavlenko,Shelyazhenko,Filatov,Kremlev,Mushta,Gerus,Peng, Sheng,Petrov,Nappa, Mario
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p. 134 - 141
(2015/11/10)
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- Ion pair pKs of some amines: Extension of the computed lithium pK scale
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The pK of p-(methylamino)biphenyl, 1, on our Li scale, pK(Li) = 22.09, compared to the cesium scale, pK(Cs) = 28.60. For hexamethyldisilazane, HMDS, pK(Li) = 23.05, pK(Cs) = 29.26. These results are those for the monomers in THF; corrections were made for dimers present in some cases. The pK(Li) of these two amines fit well the previously found correlation with Hartree-Fock calculations at 6-31+g(d) using RLi coordinated with three dimethyl ethers as a computational model for RLi in THF. The results are also compared with earlier pK(Li)s reported from equilibria with lithium amides in which aggregation was not considered.
- Streitwieser, Andrew,Facchetti, Antonio,Xie, Linfeng,Zhang, Xingyue,Wu, Eric C.
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supporting information; scheme or table
p. 985 - 990
(2012/03/26)
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- Synthesis of symmetrical dinitro-and diamino-substituted Troeger's base analogues
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This report describes a new synthetic approach to symmetrical diamino-substituted Troeger's base analogues, allowing the synthesis of 1,7-, and 4,10-diamino derivatives with no additional substituents and of 3,9-diamino derivative with methyl groups in the 1-, 4-, 7-and 10-positions. The synthesis uses regioselective nitration of dihalo-substituted-or tetrahalo-substituted Troeger's bases followed either by hydrogenation of the nitro functions accompanied by removal of halogen atoms or alternatively by chemoselective reduction of nitro groups to obtain the dihalo-diamino- substituted Troeger's base analogues. The 2,8-diamino derivatives, not accessible by this approach, can be prepared by Buchwald-Hartwig amination of the 2,8-dibromo-substituted Troeger's bases.
- Sturala, Jiri,Cibulka, Radek
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p. 7066 - 7074
(2013/02/21)
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- SYNTHESIS OF BICYCLIC COMPOUNDS AND METHOD FOR THEIR USE AS THERAPEUTIC AGENTS
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Disclosed embodiments concern the synthesis and use of therapeutic compounds that for treating emerging flu strains and minimizing resistance to such strains. Methods for making the disclosed compounds concern using a base-mediated addition/cyclization sequence followed by functional group manipulation to develop functionalized compounds that can target neuraminidase, which makes them ideal candidates for treating influenza. Pharmaceutical compositions comprising the therapeutic compounds and biologically-acceptable materials are also described. Methods of inhibiting neuraminidase in subjects that are suspected of containing neuraminidase are also described. The use of metabolites of the disclosed compounds can also be used in diagnostic assays for therapeutic dosing of the disclosed compounds.
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Page/Page column 40; 41
(2011/09/15)
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- PROTEIN PHOSPHATASE INHIBITOR
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Provided is a novel protein phosphatase inhibitor. The protein phosphatase inhibitor contains, as an active ingredient, a silicon compound represented by the following general formula (1) or a salt thereof, wherein R1, R2 and R3 are the same or different and represent a hydrocarbon group having 1 to 12 carbon atoms; X represents an optionally substituted hydrocarbon group having 3 to 36 carbon atoms or an optionally substituted heterocyclic group; and n represents an integer of 0 or 1.
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Page/Page column 14
(2011/08/08)
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- DESAZADESFERROTHIOCIN AND DESAZADESFERROTHIOCIN POLYETHER ANALOGUES AS METAL CHELATION AGENTS
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Disclosed herein are new compounds of desazadesferrothiocin polyether (DADFT-PE) analogues, as well as pharmaceutical compositions comprising them and their application as metal chelation agents for the treatment of disease. Methods of chelation of iron and other metals in a human or animal subject are also provided for the treatment of metal overload and toxicity.
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Page/Page column 26
(2011/11/13)
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- One-step process for preparing paliperidone and its oxalate salt
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The present invention relates to a one-step process for the preparation of the antipsychotic agent Paliperidone by oxidation of Risperidone, and to Paliperidone oxalate or a hydrate, solvate or polymorph thereof.
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Page/Page column 6
(2010/07/06)
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- Ge precursor, GST thin layer formed using the same, phase-change memory device including the GST thin layer, and method of manufacturing the GST thin layer
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Provided are a Ge precursor for low temperature deposition containing Ge, N, and Si, a GST thin layer doped with N and Si formed using the same, a memory device including the GST thin layer doped with N and Si, and a method of manufacturing the GST thin layer. The Ge precursor for low temperature deposition contains N and Si such that the temperature at which the Ge precursor is deposited to form a thin layer, particularly, the GST thin layer doped with N and Si, can be low. In addition, during the low temperature deposition, H2 plasma can be used. The GST phase-change layer doped with N and Si formed from the Ge precursor for low temperature deposition has a low reset current. Therefore, a memory device including the GST phase-change layer doped with N and Si can be highly integrated, have a high capacity, and can be operated at a high speed.
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Page/Page column 7-8
(2009/04/24)
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- SPIROINDOLINONE DERIVATIVES
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There are provided spiroindolinone derivatives of the formula and pharmaceutically acceptable salts and esters thereof wherein R1, R2, R3, R4 and R are as herein described. The compounds exhibit anticancer activity.
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Page/Page column 9
(2009/01/20)
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- RENIN INHIBITORS
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Described are compounds that bind to aspartic proteases to inhibit their activity. They are useful in the treatment or amelioration of diseases associated with aspartic protease activity. Also described are methods of use of the compounds described herein in ameliorating or treating aspartic protease related disorders in a subject in need thereof.
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Page/Page column 88-89
(2009/01/23)
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- PROCESSES FOR THE PREPARATION OF PENEMS AND ITS INTERMEDIATE
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The present invention relates to a process for the preparation of 4-acetoxy azetidinone of Formula I, wherein R2 is hydrogen or a suitable amino protecting group and P is suitable hydroxy protecting group, and to the use of these compounds as intermediates for the preparation of ?-lactam antibiotics that possess the carbapenem and penem ring systems. 4-acetoxy azetidinone of Formula I is a key intermediate in the synthesis of ?-lactam antibiotics which are commonly prescribed antimicrobial agents having activity against a wide range of both Gram-positive and Gram-negative bacteria.
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Page/Page column 20
(2008/06/13)
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- CHIRAL AMINE-CATALYZED ASYMMETRIC ADDITION OF CARBON-CENTERED NUCLEOPHILES TO IMINES
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The present invention relates to an asymmetric synthesis useful for preparing compounds useful for the treatment of cardiovascular diseases and for studying the role of motor proteins in cell cycle progression.
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Page/Page column 62
(2010/11/25)
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- N-SUBSTITUTED-1H-QUINOLINE-2, 4-DIONES, PREPARATION METHOD THEREOF, AND PHARMACEUTICAL COMPOSITION CONTAINING THE SAME
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The present invention relates to compounds of N-substituted-1H-quinoline-2,4-diones acting as a 5HT6 receptor antagonist, a preparation method thereof, and a pharmaceutical composition containing the same for treatment of the central nervous system disorders. The compounds of N-substituted-1H-quinoline-2,4-diones according to the present invention have excellent binding affinity for the 5HT6 receptor and excellent selectivity for the 5HT6 receptor over other receptors. Also, the compounds reverse a disruption of PPI by methamphetamine and don't show rotatod deficit in mice. Therefore the compounds according to the present invention may be valuably used for treatment of a 5HT6 receptor relating disorders.
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Page/Page column 20
(2010/11/26)
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- 3-aryl-3-methyl-quinoline-2,4-diones, preparation method thereof and pharmaceutical composition containing same
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The present invention relates to compounds of 3-aryl-3-methyl-quinoline-2,4-diones , or a pharmaceutically acceptable salt thereof acting as a 5HT6 receptor antagonist, a preparation method thereof, and a pharmaceutical composition containing the same for treatment of the central nervous system disorders. The compounds of 3-aryl-3-methyl-quinoline-2,4-diones according to the present invention may be valuably used for treatment of a 5HT6 receptor relating disorders because of its excellent binding affinity for the 5HT6 receptor and excellent selectivity for the 5HT6 receptor over other receptors.
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Page/Page column 14-15
(2008/06/13)
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- SYNTHESIS OF AVRAINVILLAMIDE, STEPHACIDIN B, AND ANALOGUES THEREOF
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The syntheses of the natural products, avrainvillamide and stephacidin B, are provided. The α,β-unsaturated nitrone functionality of avrainvillamide and its 3- alkylidene-3H-indole 1 -oxide core is shown to covalently and reversibly bond to heteroatom-based nucleophiles. This capability may allow these molecules to bind active site nucleophiles and may provide the basis for designing potent and selective enayme inhibitors. Both avrainvillamide and its dimer stephacidin B have been reported to exhibit antiproliferative activity, and avrainvillamide has been reported to exhibit antimicrobial activity against multi-drug resistant bacteria. Avrainvillamide has been found to target cytoskeleton-linking membrane protein (CLIMP-63) thereby preventing cells from undergoing mitosis. The invention provides syntheses of these natural products as well as analogs of these natural products and their functional cores. The compounds of the invention may be used in the treatment of diseases such as cancer, autoimmune diseases, and bacterial infection.
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Page/Page column 129-130
(2008/06/13)
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- NOVEL PYRIMIDINE COMPOUNDS, PROCESS FOR THEIR PREPARATION AND COMPOSITIONS CONTAINING THEM
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The present invention provides new heterocyclic compounds, particularly substituted pyrimidines, methods and compositions for making and using these heterocyclic compounds, and methods for treating a variety of diseases and disease states, including atherosclerosis, arthritis, restenosis, diabetic nephropathy, or dyslipidemia, or disease states mediated by the low expression of Perlecan.
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Page/Page column 280-281
(2008/06/13)
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- Beta-lactam synthesis
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The present invention is directed to a process for the preparation of β-lactams. Generally, an imine is cyclocondensed with a ketene acetal or enolate to form the β-lactam product in a "one pot" synthesis, this process is generally performed at a higher temperature than conventional processes.
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Page/Page column 13; 14
(2008/06/13)
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- 7Li, 31P, and1H pulsed Gradient Spin-Echo (PGSE) diffusion NMR spectroscopy and ion pairing: On the temperature dependence of the ion pairing in Li(CPh3), fluorenyllithium, and Li[N(SiMe 3)2] amongst other salts
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7Li, 31P, and 1H variable-temperature pulsed gradient spin-echo (PGSE) diffusion methods have been used to study ion pairing and aggregation states for a range of lithium salts such as lithium halides, lithium carbanions, and a lithium amide in THF solutions. For trityllithium (2) and fluorenyllithium (9), it is shown that ion pairing is favored at 299 K but the ions are well separated at 155 K. For 2-lithio-1,3-dithiane (13) and lithium hexamethyldisilazane (LiHMDS 16), low-temperature data show that the ions remain together. For the dithio anion 13, a mononuclear species has been established, whereas for the lithium amide 16, the PGSE results allow two different aggregation states to be readily recognized. For the lithium halides LiX (X = Br, Cl, I) in THF, the 7Li PGSE data show that all three salts can be described as well-separated ions at ambient temperature. The solid state structure of trityllithium (2) is described and reveals a solvent-separated ion pair formed by a [Li(thf)4]+ ion and a bare triphenylmethide anion.
- Fernandez, Ignacio,Martinez-Viviente, Eloisa,Breher, Frank,Pregosin, Paul S.
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p. 1495 - 1506
(2007/10/03)
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- Anti-infective agents
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Compounds having the formula are hepatitis C (HCV) polymerase inhibitors. Also disclosed are a composition and method for inhibiting hepatitis C (HCV) polymerase, processes for making the compounds, and synthetic intermediates employed in the processes.
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Page/Page column 78 -79
(2008/06/13)
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- Methods for treating autoimmune disorders, and reagents related thereto
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The invention generally relates to improved methods for treatment or prophylaxis in animal subjects (including humans) of autoimmune disorders including Type I diabetes, septic shock, multiple sclerosis, inflammatory bowel disease (IBD) and Crohn's disease.
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Page/Page column 23; 24
(2010/02/11)
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- Method of perfluoroalkylated trisphenols phosphine oxide (perfluoroalkyl)
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The invention relates to a method for perfluoroalkylation by means of tris(perfluoroalkyl)phosphine oxides.
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Page/Page column 5
(2010/02/13)
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- INDOLYLMALEIMIDE DERIVATIVES
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Provided are compounds of formula (I) which have interesting pharmacological properties.
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- Cephalotaxane derivatives and process for their preparation
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The present invention concerns a new general process for asymetric hemisynthesis of harringtonines and their analogs, that are alcaloids used in chimiotherapy. This process comprises direct esterification of a natural cephalotaxine with an acylating compound constituted of a side chain precursor which backbone and fonctionalization are entirely preformed.
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- Bicyclic compounds and pharmaceutical composition containing tricyclic compound for treating or preventing sleep disorders
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A compound having the following general fomula: wherein R1 is an optionally substituted hydrocarbon, amino or heterocyclic group; R2 is H or an optionally substituted hydrocarbon group; R3 is H or an optionally substituted hydrocarbon or heterocyclic group; X is CHR4, NR4, O or S in which R4 is H or an optionally substituted hydrocarbon group; R5 is H, a halogen atom, C1-6 alkyl group, a C1-6 alkoxy group, a hydroxy group, a nitro group, a cyano group or an amino group wherein the C1-6 alkyl group, the C1-6 alkoxy group and the amino group may be substituted by 1 to 5 substituents, Y is C or N; ring B is an optionally substituted benzene ring; m = 1 to 4 and n = 0 to 2; L represents a leaving group such as a halogen atom, an alkylsulfonyl group, an alkylsulfonlyoxy group and arylsulfonyloxy group; or a salt thereof.
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Referential example 81
(2010/11/29)
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- Sub room temperature differential vapor pressure osmometry: A method for the determination of the aggregation number of α-heterosubstituted organolithium compounds and lithium amides in solution
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The aggregation number of α-Selenium- and α-Sulfur-substituted organolithium compounds, lithium amides, and transition metal complexes in solution has been determined by sub room temperature differential vapor pressure osmometry. This novel method allows measurements of oxygen, moisture, and temperature sensitive compounds. The aggregation number of these compounds can be determined in THF solutions at 0°C and in diethyl ether solutions at -35°C. by Oldenbourg Wissenschaftsverlag, Muenchen.
- Dress,Roelle,Wenzel,Boesherz,Frommknecht,Merkel,Sauer
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- Pyridazinone derivatives and processes for preparing the same
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Disclosed are a pyridazinone compound represented by the formula: STR1 wherein (1) R1 is a substituted or unsubstituted C1-10 alkyl, a C3-6 cycloalkyl, a lower alkenyl, a heterocyclic group having N, O or S atom or camphor-10-yl; R3 is hydrogen, a substituted or unsubstituted lower alkyl or a lower alkenyl; or R1 and R3 are bonded at terminal ends thereof to form a lower alkylene; and Z is a group represented by the formula: STR2 where n is 1 or 2; and D is hydrogen or a halogen; or (2) R1 is a substituted or unsubstituted C1-10 alkyl, a substituted or unsubstituted phenyl, a C3-6 cycloalkyl, a lower alkenyl, a heterocyclic group having N, O or S atom or camphor-10-yl; R3 is hydrogen, a substituted or unsubstituted lower alkyl or a lower alkenyl; or R1 and R3 are bonded at terminal ends thereof to form a lower alkylene; and Z is a group represented by the formula: STR3 and R2 is hydrogen, a substituted or unsubstituted lower alkyl, an aryl or a lower alkenyl; and --A--B-- is an ethylene or vinylene each of which may be substituted by 1 or 2 groups selected from the group consisting of a lower alkyl and phenyl group, or a pharmaceutically acceptable salt thereof, and processes for preparing the same.
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- High purity formulations of highly substituted lithium amide bases
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A process for preparing high purity solutions of highly substituted lithium amide bases by direct reaction of lithium metal with highly substituted amine bases alone or in an ether solvent, a hydrocarbon solvent or in a mixed ether/hydrocarbon solvent mixture, optionally in the presence of a catalyst selected from tin salts and transition metal salts of Groups 4B, 5B, 6B, 7B, and 8 of the Periodic Table.
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- Alkylation process for preparing azetidinone compound and starting compound therefor
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Novel process for preparing azetidinone compound of the formula [III]: STR1 wherein R1 is H or lower alkyl, R2 and R3 combine together with the adjacent nitrogen to form heterocyclic group, and R4 is protected or unprotected hydroxy-substituted lower alkyl, which comprises reacting an alkanamide compound of the formula [I]: STR2 wherein R1, R2 and R3 are the same as defined above, with a compound of the formula [II]: STR3 wherein L1 is a leaving group and R4 is the same as defined above, in the presence of a base, said compound [III] being useful as synthetic intermediate for 1-methylcarbapenem derivative having excellent antibacterial activity.
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- Method of preparation of lithium alkylamides
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A process for quickly preparing easily separable solutions of lithium alkylamides, as exemplified by the formula wherein M is silicon or carbon, R and R1 are C1 -C8 alkyl, cycloalkyl or alkylene groups, LB is a Lewis base, x and y are integers equaling 2, and z is greater than 1, comprising the steps of reacting lithium metal in bulk form with an alkylamine in mole ratios of metal to alkylamine ranging from 2 to 1 to 10 to 1 in a solvent selected from ethereal or selected from the group consisting of conjugated dienes, vinyl aromatic and polycyclic aromatic compounds, under an inert atmosphere at elevated temperatures for 1 to 10 hours, cooling the product and separating the product solution from the unreacted lithium metal in the reactor.
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- Difluoroprostacyclins
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A difluoroprostacyclin of the following formula (V), its lower alkanol ester or its pharmaceutically acceptable salt: STR1 wherein A is an ethylene group, a vinylene group or an ethynylene group, R is a substituted or unsubstituted C1-10 alkyl group, a substituted or unsubstituted C1-10 alkenyl group, a substituted or unsubstituted C1-10 alkynyl group, a substituted or unsubstituted C3-8 cycloalkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryloxy group, Q is a substituted or unsubstituted C1-10 alkyl group, a substituted or unsubstituted C1-10 alkenyl group, a substituted or unsubstituted C1-10 alkynyl group, a substituted or unsubstituted C3-8 cycloalkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group.
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- Lipopeptide derivatives
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There are disclosed lipopeptide derviatives of the general formula: STR1 where the substituents are defined herein which have antifungal and antiprotozoal activity. There are also disclosed pharmaceutical compositions containing these compounds.
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- Monospecific antibodies useful in evaluating inhibition of polymorphonuclear leukocyte elastase by N-substituted azetidinones
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Inhibitors of human leukocytes elastase are known to be useful in the treatment of a wide variety of antiinflammatory and antidegenerative diseases. In inhibiting elastase, the therapeutic agents are shown to form a characteristic stable complex with the enzyme. In the radioimmunoassay disclosed herein, the inhibitor-enzyme complex is advantageously hydrolyzed and specific product(s) of the hydrolysis are measured utilizing polyclonal antibodies capable of binding to one or more haptens of formula II STR1 wherein M is allyl or n-propyl, Z1 is (a) 5-benzofuranyl or (b) substituted phenyl wherein the substituent is methyl or ethyloxy. The assays utilizing these antibodies are useful in a clinical setting, for determining appropriate dosage and assessing the effectiveness of treatment.
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