- Synthesis in solution of peptoids using Fmoc-protected N-substituted glycines
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A convenient synthesis of Fmoc-protected N-substituted glycine derivatives starting from ethyl bromoacetate is described. As an illustration of the use of these building blocks for the preparation of peptoids, the synthesis of the C-terminal penta retropeptoid of Substance P (SP) is shown.
- Kruijtzer, John A. W.,Liskamp, Rob M. J.
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- Synthesis and optical properties of sulfur-containing monomers and cyclomatrix polyphosphazenes
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Novel cyclotriphosphazenes with sulfur-containing spirocyclic side groups were synthesized and polymerized to cyclomatrix materials for potential optical applications. The cyclotriphosphazenes were designed to give a high content of the phosphazene unit and sulfur atoms, as well as the capability for polymerization by ring- opening of the side groups. The chemical structures of the monomers were confirmed by NMR spectrometry, mass spectrometry, and single-crystal X-ray diffraction. Transparent solids were obtained by thermal bulk polymerization, and these were analyzed by the use of DSC, infrared spectroscopy, and mass spectrometry. One of the resultant cyclomatrix polyphosphazenes had a refractive index at 589 nm of 1.6465 and an Abbe number of 39. The contribution of the phosphazene unit to the refractive index is discussed.
- Fushimi, Toshiki,Allcock, Harry R.
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- The chemistry of methyltitanium trichloride. II. Variable-temperature nuclear magnetic resonance and infrared spectra of some complexes of methyltitanium trichloride and of titanium tetrachloride with unsymmetrical bidentate ligands
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The pseudooctahedral complexes of methyltitanium trichloride with the unsymmetrical bidentate ligands methyl β-dimethylaminoethyl ether, methyl β-methylthioethyl ether, and methyl β-dimethylaminoethyl sulfide are precipitated on mixing hexane solutions of methyltitanium trichloride and the appropriate ligand. They are intensely colored solids, extremely sensitive to atmospheric oxygen and moisture and thermally unstable, decomposing gradually on storage in vacuo at room temperature. The nmr spectra of the complexes show that, in solution, they prefer to adopt that meridional configuration in which the harder ligand atom lies trans to the titanium-methyl group. In their ir spectra, the complexes all show bands in the 450-490-cm-1 region, which are assigned to v(Ti-C). These bands are absent from the ir spectra of the corresponding complexes of titanium tetrachloride, which we have also prepared and characterized (mainly to assist in the assignment of nmr data). By contrast to the foregoing, the product isolated from the reaction of methyltitanium trichloride with N,N,N′,-N′-tetramethyl-o-aminobenzylamine (B) is a titanium(III) derivative which can be formulated as TiCl3 · B.
- Clark,McAlees
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- Application of sulforaphane and derivatives thereof as bacterial effector protein transcription inhibitor
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The invention discloses application of sulforaphane and derivatives thereof as a bacterial effector protein transcription inhibitor. The invention provides an application of sulforaphane and derivatives thereof in any one of application of the following 1) and 7): 1) prevention and treatment of pathogenic bacteria; 2) improvement of the resistance of plants to pathogenic bacteria; 3) inhibiting ofpathogenicity of pathogenic bacteria; 4) inhibiting of the function of a pathogenic bacterium III type secretion system; 5) inhibiting of the expression of effector protein related genes of a pathogenic bacterium type III secretion system; 6) inhibiting of the expression of a pathogenic bacteria transcription factor hrpL; and 7) using as a pathogenic bacteria effector protein transcription inhibitor. Experiments prove that the sulforaphane and the derivatives thereof can inhibit the function of a pathogenic bacteria type III secretion system by specifically inhibiting transcription of the pathogenic bacteria type III secretion system, can resist invasion of pathogenic bacteria without destroying interaction between plants and beneficial microorganisms, and have a wide application prospectin prevention and treatment of plant pathogenic bacteria.
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Paragraph 0073; 0075-0077
(2021/03/31)
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- Engineering Catalysts for Selective Ester Hydrogenation
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The development of efficient catalysts and processes for synthesizing functionalized (olefinic and/or chiral) primary alcohols and fluoral hemiacetals is currently needed. These are valuable building blocks for pharmaceuticals, agrochemicals, perfumes, and so forth. From an economic standpoint, bench-stable Takasago Int. Corp.'s Ru-PNP, more commonly known as Ru-MACHO, and Gusev's Ru-SNS complexes are arguably the most appealing molecular catalysts to access primary alcohols from esters and H2 (Waser, M. et al. Org. Proc. Res. Dev. 2018, 22, 862). This work introduces economically competitive Ru-SNP(O)z complexes (z = 0, 1), which combine key structural elements of both of these catalysts. In particular, the incorporation of SNP heteroatoms into the ligand skeleton was found to be crucial for the design of a more product-selective catalyst in the synthesis of fluoral hemiacetals under kinetically controlled conditions. Based on experimental observations and computational analysis, this paper further extends the current state-of-the-art understanding of the accelerative role of KO-t-C4H9 in ester hydrogenation. It attempts to explain why a maximum turnover is seen to occur starting at 25 mol % base, in contrast to only 10 mol % with ketones as substrates.
- Dub, Pavel A.,Batrice, Rami J.,Gordon, John C.,Scott, Brian L.,Minko, Yury,Schmidt, Jurgen G.,Williams, Robert F.
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p. 415 - 442
(2020/03/04)
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- SYNTHESIS OF FLUORO HEMIACETALS VIA TRANSITION METAL-CATALYZED FLUORO ESTER AND CARBOXAMIDE HYDROGENATION
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This application is directed to use of transition metal-ligand complexes to hydrogenate fluorinated esters and carboxamides into fluorinated hemiacetals. Methods for synthesis of certain ligands are also provided.
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Paragraph 0194
(2020/11/24)
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- Preparation method of indoleamine 2,3-dioxygenase inhibitor and intermediates thereof
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The invention relates to a preparation method of an indoleamine 2,3-dioxygenase inhibitor and intermediates thereof. The invention discloses a preparation method capable of industrialization. By the method, problems of long synthetic route, low yield and unsuitable industrialization in the prior art are solved. The invention also relates to some intermediates for generating the indoleamine 2,3-dioxygenase inhibitor, especially an intermediate as shown in the general formula (I).
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Paragraph 0195-0201
(2019/07/16)
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- Preparation method of lapatinib intermediate 2-(methanesulfonyl)ethylamine hydrochloride
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The invention discloses a preparation method of lapatinib intermediate 2-(methanesulfonyl)ethylamine hydrochloride. The preparation method comprises the steps of adopting 2-chloroethylamine hydrochloride (Compound 2) as a starting material, and under an alkaline condition, carrying out dimolecular substitution reaction on the starting material and sodium methyl mercaptide to prepare 2-methylmercapto ethylamine (Compound 3); then adopting water as a solvent, adding hydrochloric acid for salifying, and directly using hydrogen peroxide for oxidizing to obtain the 2-(methanesulfonyl)ethylamine hydrochloride (Compound 1). According to the preparation method provided by the invention, a synthetic route is short, the raw materials are simple and easy to get, the water is adopted as the solvent, the reaction condition is moderate, the after-treatment is simple, and the obtained product is good in quality and high in yield. The method can cause less three wastes, and is environmentally friendly and suitable for industrial production. The formula is shown in the specification.
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Paragraph 0011; 0038-0040
(2017/10/13)
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- Kengreal intermediates as well as preparation methods and application thereof
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The invention discloses Kengreal intermediates as well as preparation methods and an application thereof. The intermediates respectively comprise chemical structures as shown in formula VI and formula VII. The intermediates can be applied to synthesis of a known key intermediate TEPAD of Kengreal, and the method has advantages of high total molar yield, simple operation without special requirements for equipment, safety without pollution, low cost, and the like; the method has extremely high practical value for industrialization of Kengreal, and compared with the prior art, the method has significant progress.
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Paragraph 0085; 0086; 0087; 0088
(2017/08/27)
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- PROCESS FOR HOMOGENEOUSLY CATALYZED, HIGHLY SELECTIVE DIRECT AMINATION OF PRIMARY ALCOHOLS WITH AMMONIA TO PRIMARY AMINES WITH A HIGH VOLUME RATIO OF LIQUID PHASE TO GAS PHASE AND/OR HIGH PRESSURES
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The present invention relates to a process for preparing primary amines comprising the process steps A) provision of a solution of a primary alcohol in a fluid, nongaseous phase,B) contacting of the phase with free ammonia and/or at least one ammonia-releasing compound and a homogeneous catalyst and optionallyC) isolation of the primary amine formed in process step B), characterized in that the volume ratio of the volume of the liquid phase to the volume of the gas phase in process step B is greater than 0.05 and/or in that process step B is carried out at pressures greater than 10 bar.
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Paragraph 0075
(2013/09/26)
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- Copper(II) complexes of aliphatic tridentate amine/dithioether ligands - Synthesis and molecular structures
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Three new tridentate ligands (1-3) featuring a central secondary amine linked by ethylene bridges to two thioether donor functions with S-methyl or S-benzyl substituents have been synthesized and reacted with copper(II) chloride or copper(II) nitrate. The resulting complexes of type [CuX2(L)] (L = amine-dithioether ligand) 6, 7, and 9 exhibit a square-pyramidal coordination geometry with the nitrogen and sulfur donor groups of the tridentate ligand occupying three of the basal binding sites at the metal ion. Two chloro (6 and 7) or a nitrato ligand (9) originating from the metal precursor salt complete the coordination sphere of the copper(II) ion. The apical donors are bonded with significantly longer bond distances compared to identical donors in the basal plane. The weakly bound apical chloro ligand of 6 can be abstracted with silver(I) nitrate effecting the formation of the dinuclear complex 10 featuring a nitrato ligand coordinated to two copper(II) centers in a bridging fashion. For all copper(II) complexes the observed Cu-S bond distances are very similar and not significantly influenced by alteration of the alkyl group at the thioether donor function.
- Blomenkemper, Marc,Schr?der, Henning,Pape, Tania,Hahn, F. Ekkehardt
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experimental part
p. 143 - 147
(2012/07/27)
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- A sulfoximine-based inhibitor of human asparagine synthetase kills l-asparaginase-resistant leukemia cells
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An adenylated sulfoximine transition-state analogue 1, which inhibits human asparagine synthetase (hASNS) with nanomolar potency, has been reported to suppress the proliferation of an l-asparagine amidohydrolase (ASNase)-resistant MOLT-4 leukemia cell line (MOLT-4R) when l-asparagine is depleted in the medium. We now report the synthesis and biological activity of two new sulfoximine analogues of 1 that have been studied as part of systematic efforts to identify compounds with improved cell permeability and/or metabolic stability. One of these new analogues, an amino sulfoximine 5 having no net charge at cellular pH, is a better hASNS inhibitor (KI= 8 nM) than 1 and suppresses proliferation of MOLT-4R cells at 10-fold lower concentration (IC50 = 0.1 mM). More importantly, and in contrast to the lead compound 1, the presence of sulfoximine 5 at concentrations above 0.25 mM causes the death of MOLT-4R cells even when ASNase is absent in the culture medium. The amino sulfoximine 5 exhibits different dose-response behavior when incubated with an ASNase-sensitive MOLT-4 cell line (MOLT-4S), supporting the hypothesis that sulfoximine 5 exerts its effect by inhibiting hASNS in the cell. Our work provides further evidence for the idea that hASNS represents a chemotherapeutic target for the treatment of leukemia, and perhaps other cancers, including those of the prostate.
- Ikeuchi, Hideyuki,Ahn, Yong-Mo,Otokawa, Takuya,Watanabe, Bunta,Hegazy, Lamees,Hiratake, Jun,Richards, Nigel G.J.
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p. 5915 - 5927
(2012/11/06)
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- Reversible inactivation of bovine plasma amine oxidase by cysteamine and related analogs
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Cysteamine (1) was reported many years ago to reversibly inhibit lentil seedling amine oxidase, through the formation of a complex with thioacetaldehyde, the turnover product of 1. Herein, cysteamine (1) and its analogs 2-(methylamino)ethanethiol (3) and 3-aminopropanethiol (6) were found to be reversible inhibitors of bovine plasma amine oxidase (BPAO), but 2-(methylthio)ethylamine (7) was determined to be a weak irreversible inhibitor of BPAO. Based on our results, indicating the necessity of a sulfhydryl-amine for reversible inactivation of BPAO, the failure of inhibited BPAO to recover activity after gel filtration, the first-order kinetics of activity recovery upon dialysis, and 2,4,6-trihydroxyphenylalanine quinine (TPQ) cofactor transformation which indicated from the results of phenylhydrazine titration and substrate protection, we propose a mechanism for the reversible inactivation of BPAO by 1 involving the formation of a cofactor adduct, thiazolidine, between BPAO and 1.
- Jeon, Heung Bae,Jang, Yujin
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experimental part
p. 442 - 446
(2011/10/12)
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- Complexes of titanium and zirconium containing a tridentate linked amido-cyclopentadienyl ligand with a soft donor group: Synthesis, structure, and ethylene polymerization catalysis
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Group 4 metal complexes M(η5:η1-C5R4SiMe 2NCH2CH2SMe)Cl2 (R=H, M=Ti; R=Me, M=Ti, Zr) containing the thioether-functionalized linked amido-cyclopentadienyl ligand were synthesized and characterized by 1H- and 13C-NMR spectroscopy, mass spectrometry, and elemental analysis. The crystal structures of the complexes Ti(η5:η1-C5H4SiMe 2NCH2CH2SMe)Cl2 and Zr(η5:η1:η1-C5Me 4SiMe2NCH2CH2SMe)Cl2 were determined by single-crystal X-ray diffraction studies. The titanium complex is a conventional three-legged piano-stool molecule without an intramolecular interaction between the sulfur donor group and the titanium center, whereas the zirconium complex adopts a trigonal bipyramidal structure, with the five-membered ring and the coordinating methylthio group in the apical positions. Reaction between the titanium dibenzyl Ti(η5:η1-C5Me4ZNCH 2CH2SMe)(CH2Ph)2 (Z=SiMe2, CH2SiMe2) and B(C6F5)3 in C6D5Br resulted in the clean formation of the solvent-separated ion pair [Ti(η5:η1-C5Me4ZNCH 2CH2SMe)(η2-CH2Ph)] +[(PhCH2)B(C6F5)3] -. The dichloro complexes M(η5:η1-C5Me4SiMe 2NCH2CH2SMe)Cl2, when activated with methylaluminoxane, catalyzed the polymerization of ethylene with moderate activities. The phosphino-functionalized ligand C5Me4SiMe2NC6H4(PPh 2)-2 was also coordinated at titanium and zirconium centers; NMR spectroscopic data inferred an intramolecular metal-phosphine interaction for these M{η5:η1-C5Me4SiMe 2NC6H4(PPh2)-2}Cl2 complexes.
- Okuda, Jun,Eberle, Thomas,Spaniol, Thomas P.,Piquet-Faure, Valerie
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p. 127 - 137
(2007/10/03)
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- Solid-phase syntheses of peptoids using Fmoc-protected N-substituted glycines: The synthesis of (retro)peptoids of leu-enkephalin and substance P
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A particularly interesting class of oligomeric peptidomimetics is formed by the peptoids, which consist of N-substituted glycine residues. A solid- phase synthesis method for peptoids is presented in which these residues are introduced using their Fmoc derivatives. This 'monomer' method allowed the monitored synthesis of relatively large quantities of pure peptoids as well as the translation of, in principle, any peptide into the corresponding peptoid. The required Fmoc-substituted glycines were accessible by convenient synthesis, and a number of monomers including those containing side chains with functional groups have been synthesized. The use of Fmoc monomers also allowed implementation of a solid-phase synthesis protocol on a commercial peptide synthesizer. The method was exempli- fled by the solid-phase syntheses of the (retro)peptoids of Leu-enkephalin and substance P. Mass spectrometric studies of (retro)peptoids were essential for their characterization, and the presence of the B- and Y'- type ions allows sequence analysis. Substance P (retro)peptoids were biologically active. HPLC analysis showed an increased hydrophobicity, and pepsin treatment resulted in greatly reduced degradation compared with the corresponding peptide.
- Kruijtzer, John A.W.,Hofmeyer, Lovina J.F.,Heerma, Wigger,Versluis, Cornelis,Liskamp, Rob M.J.
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p. 1570 - 1580
(2007/10/03)
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- Synthesis of New Glycopeptidomimetics Based on N-Substituted Oligoglycine bearing an N-Linked Lactoside Side-chain
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A new family of model N-substituted oligoglycines (peptoids) containing an N-linked lactoside side-chain was synthesized by a convergent and a reiterative strategy using tert-butyl bromoacetate and primary amines as building blocks.
- Saha, Uttam K.,Roy, Rene
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p. 2571 - 2574
(2007/10/03)
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- SYNTHESIS AND CORRECTED STRUCTURES OF SULPHUR-CONTAINING AMIDES FROM GLYCOSMIS SPECIES: SINHARINES, PENIMIDES, AND ILLUKUMBINS
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The structures of sinharine and methylsinharine isolated from Glycosmic cyanocarpa, penimide A and penimide B from G. chlorosperma, and methylillukumbin A, illukumbin B and methylillukumbin B from G. mauritiana were revised on the basis of synthesis and additional spectroscopic evidence.The methylthio group and the aromatic moiety have to change their positions in the molecules.Thus the compounds represent amides of 3-(methylthio)-propenoic acid and not cinnamides as described previously.
- Hinterberger, Sabine,Hofer, Otmar,Greger, Harald
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p. 6279 - 6286
(2007/10/02)
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