- Synthesis of 13C-labelled cutin and suberin monomeric dicarboxylic acids of the general formula HO213C-(CH2)n-13CO2H (n = 10, 12, 14, 16, 18, 20, 22, 24, 26, 28)
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13C-labeled dicarboxylic acids HO213C-(CH2)n-13CO2H (n = 10, 12, 14, 16, 18, 20, 22, 24, 26, 28) have been synthesized as internal standards for LC-MS and GC-MS analysis of cutin and suberin monomer degradation by soil-based microorganisms. Different synthetic strategies had to be applied depending on the chain length of the respective synthetic target and because of economic considerations. 13C-labels were introduced by nucleophilic substitution of a suitable leaving group with labelled potassium cyanide and subsequent hydrolysis of the nitriles to produce the corresponding dicarboxylic acids. All new compounds are characterized by GC/MS, IR, and NMR methods as well as by elemental analysis.
- Schink, Carina,Spielvogel, Sandra,Imhof, Wolfgang
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- Inhibition of bacterial growth and galactosyltransferase activity of WbwC by α, ω-bis(3-alkyl-1H-imidazolium)alkane salts: Effect of varying carbon content
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A series of compounds was designed and synthesized having two imidazolium rings separated by a polymethylene spacer and having alkyl substituents on each of the imidazolium rings. The compounds were assayed for their effects on the activity of galactosyltransferase WbwC, and also on the growth of Gram-negative and Gram-positive bacteria, as well as human cells. The inhibition observed on enzyme activities and cell growth was dependent on the total number of carbons in the spacer and the alkyl substituents on the imidazolium rings. These readily synthesized, achiral compounds have potential as antimicrobial and antiseptic agents.
- Brockhausen, Inka,Kocev, Alexander,Kong, Xianqi,Melamed, Jacob,Szarek, Walter A.,Vlahakis, Jason Z.,Wang, Shuo,Xu, Yaozu
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- At Long Last: Olefin Metathesis Macrocyclization at High Concentration
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Macrocyclic lactones, ketones, and ethers can be obtained in the High-Concentration Ring-Closing Metathesis (HC-RCM) reaction in high yield and selectivity at concentrations 40 to 380 times higher than those typically used by organic chemists for similar macrocyclizations. The new method consists of using tailored ruthenium catalysts together with applying vacuum to distill off the macrocyclic product as it is formed by the metathetical backbiting of oligomers. Unlike classical RCM, no large quantities of organic solvents are used, but rather inexpensive nonvolatile diluents, such as natural or synthetic paraffin oils. Moreover, use of a protecting atmosphere or a glovebox is not needed, as the new catalysts are perfectly moisture and air stable. In addition, some other cyclic compounds previously reported as unobtainable by RCM in neat conditions, or in high dilutions even, can be formed with the help of the HC-RCM method.
- Sytniczuk, Adrian,Dabrowski, Micha?,Banach, ?ukasz,Urban, Mateusz,Czarnocka-?niada?a, Sylwia,Milewski, Mariusz,Kajetanowicz, Anna,Grela, Karol
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supporting information
p. 8895 - 8901
(2018/07/05)
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- METHOD OF CYCLIC COMPOUNDS PRODUCTION IN OLEFINE METATHESIS REACTION AND USE OF RUTHENIUM CATALYSTS IN PRODUCTION OF CYCLIC OLEFINS IN OLEFINE METATHESIS REACTION
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The invention relates to a method for the preparation of cyclic compounds in the metathesis of olefins from acyclic dienes comprising terminal and/or non-terminal C=C double bonds; the invention also relates to the use of homogeneous ruthenium complexes and homogeneous ruthenium complexes deposited on a solid support as catalysts and/or pre-catalysts for the preparation of cyclic olefins in olefin metathesis reactions. Formula (I)
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Page/Page column 70
(2018/11/22)
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- METHOD FOR MANUFACTURING ALCOHOL BY HYDROGENATION OF CARBOXYLIC ACID COMPOUND AND ESTER COMPOUND
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PROBLEM TO BE SOLVED: To provide a method for obtaining alcohol by hydrogenation of carboxylic acid compound efficiently by using a homogeneous system catalyst, especially a method for obtaining alcohol by hydrogenation of various carboxylic acid compound and ester compound by the homogeneous system catalyst efficiently even under alleviation condition. SOLUTION: A carboxylic acid compound and/or an ester compound is hydrogenated in a presence of a rhenium complex represented by ReXmYnZp, where X is a halogen atom, Y is same or different and each a ligand containing one or more phosphorus atom, Z is a ligand other than X and Y, m is an integer of 1 to 6, p is an integer of 0 to 2 and the sum of m, n and p is an integer of 2 to 6, and a specific alkali metal salt. COPYRIGHT: (C)2015,JPOandINPIT
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Paragraph 0117; 0118; 0127; 0129; 0130
(2016/10/10)
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- NEW LIGANDS FOR TARGETING OF S1P RECEPTORS FOR IN VIVO IMAGING AND TREATMENT OF DISEASES
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The present invention relates to novel compounds of formulae (I) and (II) which are useful in the prevention, treatment and diagnosis, in vivo diagnosis of diseases or disorders related to S1P receptors, in particular, in diseases which are connected to the regulatory function of sphingosine-1-phosphate (S1P) and its analogues, such as inflammation, pain, autoimmune diseases and cardiovascular diseases.
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Paragraph 0209; 0210; 0211; 0212; 0213; 0214
(2014/06/25)
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- Total synthesis and absolute configuration of epicoccamide D, a naturally occurring mannosylated 3-acyltetramic acid
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The endofungal metabolite epicoccamide D was synthesised in eighteen steps and 17 % yield as the first member of the family of natural glycotetramic acids. The modular character of the synthesis opens access also to analogues featuring different sugars and spacers. It comprises several high-yielding key steps. The β-D-mannosyl group was introduced by using an α-D-glucosyl imidate donor with subsequent oxidative-reductive epimerisation at C-2′. The pyrrolidine ring was closed quantitatively by a Lacey-Dieckmann condensation of an N-(β-ketoacyl)-N-methyl alaninate. The resulting 3-[ω-(β-D- mannosyl)octadec-2-enoyl]tetramic acid was hydrogenated in the presence of the rhodium catalyst (R,R)-[Rh(Et-DUPHOS)][BF4] to establish the (7S)-stereocentre. This was possible only after blocking the acyltetramic acid as a BF2-chelate to prevent capture of the metal catalyst. We also assigned the hitherto unknown configuration of the natural product as being 5S,7S by comparison of its 13C NMR spectroscopic and optical rotation data with those of our two synthetic 5S,7R/S-diasteromers. Copyright
- Loscher, Sebastian,Schobert, Rainer
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supporting information
p. 10619 - 10624
(2013/08/23)
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- NEW LIGANDS FOR TARGETING OF S1P RECEPTORS FOR IN VIVO IMAGING AND TREATMENT OF DISEASES
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The present invention relates to novel compounds of formulae (I) and (II) which are useful in the prevention, treatment and diagnosis, in vivo diagnosis of diseases or disorders related to S1P receptors, in particular, in diseases which are connected to the regulatory function of sphingosine-1-phosphate (S1P) and its analogues, such as inflammation, pain, autoimmune diseases and cardiovascular diseases.
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Page/Page column 25-26
(2013/03/26)
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- The anti-malarial activity of bivalent imidazolium salts
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A series of compounds containing bivalent imidazolium rings and one triazolium analog were synthesized and evaluated for their ability to inhibit the replication of Plasmodium falciparum cultures. The activity and selectivity of the compounds for P. falciparum cultures were found to depend on the presence of electron-deficient rings that were spaced an appropriate distance apart. The activity of the compounds was not critically dependent on the nature of the linker between the electron-deficient rings, an observation that suggests that the rings were responsible for the primary interaction with the molecular target of the compounds in the parasite. The bivalent imidazolium and triazolium compounds disrupted the process whereby merozoites gain entry into erythrocytes, however, they did not appear to prevent merozoites from forming. The compounds were also found to be active in a murine Plasmodium berghei infection, a result consistent with the compounds specifically interacting with a parasite component that is required for replication and is conserved between two Plasmodium species.
- Vlahakis, Jason Z.,Mitu, Simona,Roman, Gheorghe,Rodriguez, E. Patricia,Crandall, Ian E.,Szarek, Walter A.
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experimental part
p. 6525 - 6542
(2011/12/02)
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- Solid-phase synthesis of quinol fatty alcohols, design of N/O-substituted quinol fatty alcohols and comparative activities on axonal growth
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Following the promising activity of Q2FA15 on axonal growth, two new series of N/O-substituted QFAs were synthesized, based on a SN2-type reaction. O-alkylated QFA bearing 14 carbon atoms on the side chain (n = 14) shows a very potent activity on axonal growth though lowered when compared to Q2FA15. While O-alkylation allows good retention of the biological activity, N-alkylation abolishes it nonetheless. A solid-phase-supported synthesis of Q2FA15 allowing the conception of new hybrid compounds is also described.
- Hanbali, Mazen,Bagnard, Dominique,Luu, Bang
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p. 3917 - 3920
(2007/10/03)
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- Tocopherol long chain fatty alcohols decrease the production of TNF-α and NO radicals by activated microglial cells
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Tocopherol derivatives were found to strongly modulate microglial activation induced by lipopolysaccharide. The synthesis of a series of Tocopherol long chain Fatty Alcohols (TFA) and their biological activities on the modulation of microglial activation are described. Specifically, the 2-(12-hydroxy-dodecyl)-2,5,7,8-tetramethyl-chroman-6-ol, the TFA bearing 12 carbon atoms on the side chain (n = 12), shows the most potent inhibition of secretion on nitric oxide (NO) and tumour necrosis factor-α (TNF-α) by lipopolysaccharide (LPS)-activated microglia.
- Muller, Thierry,Grandbarbe, Luc,Morga, Eleonora,Heuschling, Paul,Luu, Bang
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p. 6023 - 6026
(2007/10/03)
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- The first examples of a Meta-benzannulation from the reaction of Fischer carbene complexes with alkynes
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The intramolecular benzannulations of carbene complexes with alkynes are examined where the alkyne is tethered to the α-carbon of the vinyl carbene complex. These reactions are sensitive to the length of the tether and to the nature of the solvent. With a tether length of 16 methylenes, the reaction occurs in the same fashion as the intermolecular reactions to give a p-cyclophane. With intermediate tether lengths (n = 10, 13), the reaction gives an additional p-cyclophane in which the two oxygen substituents are meta on the arene ring. This type of product is unprecedented from the reaction of carbene complexes and alkynes and is quite surprising because the formation of this product requires that the carbon-carbon bond between the α- and β-carbons of the vinyl carbene complex is broken. A mechanism is proposed to account for this process which involves the crossed intramolecular [2 + 2] cycloaddition of the alkene and a ketene in a conjugated dienyl ketene to give a benzvalenone paddalane intermediate. Copyright
- Wang, Huan,Huang, Jie,Wulff, William D.,Rheingold, Arnold L.
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p. 8980 - 8981
(2007/10/03)
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- DERMATOLOGICAL COMPOSITIONS AND METHODS
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Disclosed are methods and compositions for regulating the melanin content of mammalian melanocytes; regulating pigmentation in mammalian skin, hair, wool or fur; treating or preventing various skin and proliferative disorders; by administration of various compounds, including alcohols, diols and/or triols and their analogues.
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- Novel chemistry of abdominal defensive glands of nymphalid butterfly Agraulis vanillae
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Abdominal defensive glands of both sexes of the Gulf fritillary butterfly, Agraulis vanillae (Linnaeus) (Nymphalidae:Heliconiinae) emit a pronounced odor when disturbed. We have identified 6-methyl-5-hepten-2-one; oleic, palmitic, and stearic esters of the corresponding alcohol 6-methyl-5-hepten-2-ol; hexadecyl acetate; 1,16-hexadecanediol diacetate; and 1,15-hexadecanediol diacetate in the glandular exudate. Since we have determined that free-flying birds or birds in a butterfly conservatory discriminate against A. vanillae as prey, we suggest that the constituents in the glands may play a defensive role against potential avian predators.
- Ross, Gary N.,Fales, Henry M.,Lloyd, Helen A.,Jones, Tappey,Sokoloski, Edward A.,Marshall-Batty, Kimberly,Blum, Murray S.
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p. 1219 - 1228
(2007/10/03)
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- Treatment of neurodegenerative diseases
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Disclosed are methods for increasing the differentiation of mammalian neuronal cells for purposes of treating neurodegenerative diseases or nerve damage by administration of various compounds including alcohols, diols and/or triols and their analogues.
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- Synthesis of a biotinated lipofullerene as a new type of transmembrane anchor
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As a prototype for a new class of lipid membrane components, the lipophilic fullerene derivative (so-called lipofullerene) 1 was synthesized and characterized. This mixed [1:5]hexakisadduct consists of ten long alkyl chains within five didodecyl malonate addends and a linker malonate carrying a (+)-biotin unit as part of an amphiphilic spacer. The malonates are attached to the fullerene core in an octahedral addition pattern, which was achieved by two successive cyclopropanation sequences with the functional precursor malonate 8 and dodecyl malonate 10. The final step of the synthesis of 1 was the attachment of activated biotin 5 with the deprotected precursor 11. Binding experiments followed by reflectometric interference spectroscopy [RIfS] proved the capability of 1 to bind specifically the protein streptavidin (SA) through the biotin unit. The amphiphilic behavior of 1 was demonstrated by Langmuir Blodgett (LB) film investigations.
- Braun, Martin,Camps,Vostrowsky, Otto,Hirsch, Andreas,Endress, Emil,Bayerl, Thomas M.,Birkert, Oliver,Gauglitz, Guenter
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p. 1173 - 1181
(2007/10/03)
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- Pyridinecarboxamide derivatives
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Pyridinecarboxamide derivatives of the formula STR1 (wherein n represents an integer of 14-18, and R represents a hydrogen atom or a straight or branched C1 -C4 alkyl group) or physiologically acceptable salts thereof. The compounds have excellent inhibiting activity of cerebral edema, especially ischemic cerebral edema, and inhibiting activity of delayed death of neuronal cells (an inhibiting activity of Ca-influx in neuronal cells). Cerebral edema is a pathologic condition accompanying cerebrovascular disorders, especially the acute stage of cerebrovascular disorders and then the compounds are useful as an agent for inhibiting cerebral edema or a therapeutic agent for cerebrovascular disorders. Moreover, the compounds have no hypotensive action which is considered to be side-effect in treating the acute stage cerebrovascular disorders and hardly show a behavior suppressing action so that they are an excellent therapeutic agent for, in particular, the acute stage cerebrovascular disorders. Moreover, the compounds show a cerebral protective activity (an anti-anoxic activity), an increasing activity of cerebral blood flow, and an inhibiting activity of lipid peroxidation and these activities may lead to the increased utility as a therapeutic agent for cerebrovascular disorders.
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- Treatment of diseases mediated by the nitric oxide/cGMP/protein kinase G pathway
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Disclosed are methods and compositions for stimulating cellular nitric oxide (NO) synthesis, cyclic guanosine monophosphate levels (cGMP), and protein kinase G (PKG) activity for purposes of treating diseases mediated by deficiencies in the NO/cGMP/PKG signal transduction pathway, by administration of various compounds including alcohols, diols and/or triols and their analogues.
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- Effect of cyclohexenonic long chain fatty alcohols on neurite outgrowth. Study on structure-activity relationship
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Four series of long chain fatty alcohols bearing a cyclohexenone moiety in addition to a ω-alkanol side chain were synthesized using 'Umpolung' reactivity strategy. Their effect on neurite outgrowth was evaluated by means of fetal rat neurons in culture. The length of the ω-hydroxy side chain is a crucial factor for biological activity.
- Girlanda-Junges, Celine,Keyling-Bilger, Florence,Schmitt, Gaby,Luu, Bang
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p. 7735 - 7748
(2007/10/03)
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- Multiple Electron Tunneling Paths across Self-Assembled Monolayers of Alkanethiols with Attached Ruthenium(II/III) Redox Centers
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Alkanethiol monolayers with pendant redox centers are deposited on gold electrodes by selfassembly.The monolayers are composed of both an electroactive thiol, HS(CH2)nC(O)NHCH2pyRu(NH3)5(2+/3+), with 10-15 methylene groups, and a diluent thiol, HS(CH2)mCOOH, also with 10-15 methylene groups.The monolayers are classified as "matched" (n = m), "exposed" ( n = 15, m = 10-14), and "buried" (n = 10, m = 11-15) according to the relative position of the redox center.Cyclic voltammograms in aqueous Na2SO4 indicate that the monolayers are close-packed with the redox centers residing in the aqueous phase in all but the most buried cases.Measurements of electron transfer kinetics by several methods (cyclic voltammetry, ac impedance spectroscopy, chronoamperometry) yield an internally consistent set of kinetic parameters, the standard rate constant ko, and the reorganization energy λ of the redox centers.The reorganization energies are in good agreement with the theoretically predicted value of 1.0 eV for the pyRu(NH3)5 redox centers.Plots of ln(ko) vs m are linear in all three cases.The slopes of the linear regression fit provide tunneling parameters (β, where ko ca. e-βm) of 0.97 +/- 0.03 (matched cases), 0,83 +/- 0.03 (exposed cases) and 0.16 +/- 0.02 (buried cases) per methylene.This pattern of β's is interpreted in terms of electronic coupling between the redox center and the electrode via both the redox thiol and the proximate diluent thiols, with the coupling via the diluent thiols dominating in the exposed cases.
- Finklea, Harry O.,Liu, Luna,Ravenscroft Melissa S.,Punturi, Sesto
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p. 18852 - 18858
(2007/10/03)
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- Hydrogenation of carboxylic acids using bimetallic catalysts consisting of Group 8 to 10, and Group 6 or 7 metals
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Hydrogenation of carboxylic acids to alcohols was effectively catalyzed by bimetallic systems consisting of Group 8 to 10 late transition-metals, and Group 6 or 7 early transition-metal carbonyls. These catalysts easily converted α,ω-dicarboxylic acid monoesters into ω-hydroxyalkanoic esters in good yields.
- He, De-Hua,Wakasa, Noriko,Fuchikami, Takamasa
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p. 1059 - 1062
(2007/10/02)
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- The Thermodynamics of the Micelle Formation of Sodium α,ω-Alkanediyl Disulfate
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The critical micelle concentrations of a α,ω-type surfactant: (sodium α,ω-alkanediyl disulfate: n=12, 14, 16) in an aqueous solution have been determined by studying the electrical conductivity, and the free energies of the micelle formation have then been estimated from these data.The free energy of micelle formation of a α,ω-type surfactant was smaller than that of a normal-type surfactant with the same alkyl chain length as the α,ω-type one.The free-energy changes per -(CH2)-segment was also calculated from these data.It is found that the free-energy change per -(CH2)-segment of the α,ω-type surfactant is -11.1 -1>.
- Ikeda, Kenji,Nakasima, Tomoko,Esumi, Kunio,Meguro, Kenjiro
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p. 578 - 580
(2007/10/02)
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- Process for preparing olefins by metathesis of cyclic olefins with acyclic olefins
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A process for preparing esters and halides is disclosed comprising the step of reacting a cyclic olefin having the formula I STR1 wherein R1 and R4 are the same or different from each other and each represents hydrogen, methyl, or ethyl; R2 and R3 are the same or different from each other and each represents hydrogen or alkyl containing 1 to 5 carbon atoms; and n represents a whole number from 2 to 12, with an acyclic olefin having the formula II STR2 wherein R5 represents hydrogen, methyl, ethyl or the group STR3 wherein R12 and R13 are the same or different from each other and each represents hydrogen or alkyl containing 1 to 5 carbon atoms; Y represents halogen; an acyloxy group R14 --CO--O wherein R14 represents alkyl containing 1-12 carbon atoms, phenyl or phenyl alkyl containing 7-12 carbon atoms, or an oxycarbonyl group R15 --O--CO wherein R15 represents alkyl containing 1-12 carbon atoms, phenyl or phenyl alkyl containing 7-12 carbon atoms; p represents a whole number from 1-12 except when Y is an R14 CO--O group wherein p is from 2 to 12. R6 and R7 are the same or different from each other and each represents hydrogen, methyl, or ethyl; R8 and R9 are the same or different from each other and each represents hydrogen or alkyl containing 1 to 5 carbon atoms; X represents halogen; an acyloxy group R10 --CO--O--, wherein R10 represents alkyl containing 1-12 carbon atoms, phenyl, or phenylalkyl containing 7-12 carbon atoms, or an oxycarbonyl group R11 --O--CO, wherein R11 represents alkyl containing 1-12 carbon atoms, phenyl, or phenylalkyl containing 7-12 carbon atoms, m represents a whole number from 1-12 except when X is an R10 --CO--O-- group wherein m is from 2 to 12 in the presence of a catalytic composition comprising a halogen-tungsten salt and a reducing agent which is an organic tin compound.
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