- Cyanidation of halogen compounds and esters catalyzed by PEG400 without solvent
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Primary aliphatic and aromatic nitriles were synthesized in excellent yields (84-96%) and purity by the cyanidation of halogen compounds and esters with dry powdered sodium cyanide catalysed by phase transfer catalyst PEG400 under solvent-free conditions.
- Cao,Chen,Pei
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- An acidic layered clay is combined with a basic layered clay for one-pot sequential reactions
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A Ti4+-exchanged montmorillonite (Ti4+-mont) and a hydrotalcite (HT) are strong solid Bronsted acid and base, and these two clay catalysts could be used in a single reactor without neutralization of active sites. Because the Ti4+-mont have active acid site in the narrow interlayers, the base sites of large HT particles show no interaction with the acid sites. A variety of acid and base reactions, such as esterification, acetalization, deacetalization, aldol reaction, Michael reaction, and epoxidation, proceeded using both the Ti4+-mont and the HT in a single reactor. Copyright
- Motokura, Ken,Fujita, Noriaki,Mori, Kohsuke,Mizugaki, Tomoo,Ebitani, Kohki,Kaneda, Kiyotomi
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- 1,3-Dibromo-5,5-dimethylhydantoin as a Precatalyst for Activation of Carbonyl Functionality
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Activation of carbonyl moiety is one of the most rudimentary approaches in organic synthesis and is crucial for a plethora of industrial-scale condensation reactions. In esterification and aldol condensation, which represent two of the most important reactions, the susceptibility of the carbonyl group to nucleophile attack allows the construction of a variety of useful organic compounds. In this context, there is a constant need for development of and improvement in the methods for addition-elimination reactions via activation of carbonyl functionality. In this paper, an advanced methodology for the direct esterification of carboxylic acids and alcohols, and for aldol condensation of aldehydes using widely available, inexpensive, and metal-free 1,3-dibromo-5,5-dimethylhydantoin under neat reaction conditions is reported. The method is air- and moisture-tolerant, allowing simple synthetic and isolation procedures for both reactions presented in this paper. The reaction pathway for esterification is proposed and a scale-up of certain industrially important derivatives is performed.
- ?ebular, Klara,Bo?i?, Bojan ?.,Stavber, Stojan
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- Organic-inorganic hybrid supermicroporous iron(III) phosphonate nanoparticles as an efficient catalyst for the synthesis of biofuels
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Here we report a novel family of crystalline, supermicroporous iron(III) phosphonate nanomaterials (HFeP-1-3, HFeP-1-2, and HFeP-1-4) with different FeIII-to-organophosphonate ligand mole ratios. The materials were synthesized by using a hydrothermal reaction between benzene-1,3,5-triphosphonic acid and iron(III) chloride under acidic conditions (pH≈4.0). Powder X-ray diffraction, N2 sorption, transmission and scanning electron microscopy (TEM and SEM) image analysis, thermogravimetric and differential thermal analysis (TGA-DTA), and FTIR spectroscopic tools were used to characterize the materials. The triclinic crystal phase [P1(2) space group] of the hybrid iron phosphonate was established by a Rietveld refinement of the PXRD analysis of HFeP-1-3 by using the MAUD program. The unit cell parameters are a=8.749(1), b=8.578(1), c=17.725(3) ?; α=104.47(3), β=97.64(1), γ=113.56(3)°; and V=1013.41 ?3. With these crystal parameters, we proposed an 24-membered-ring open framework structure for HFeP-1. Compound HFeP-1-3, with an starting Fe/ligand molar ratio of 3.0, shows the highest Brunauer-Emmett-Telller (BET) surface area of 556 m2g -1 and uniform supermicropores of approximately 1.1 nm. The acidic surface of the porous iron(III) phosphonate nanoparticles was used in a highly efficient and recyclable catalytic transesterification reaction for the synthesis of biofuels under mild reaction conditions. Iron brews biofuels: Highly crystalline, supermicroporous iron(III) phosphonate nanoparticles have been synthesized through a hydrothermal reaction between benzene-1,3,5- triphosphonic acid and FeCl3. The resulting material was used as an efficient and recyclable catalyst for the synthesis of biofuels under mild reaction conditions (see scheme). Copyright
- Pramanik, Malay,Bhaumik, Asim
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- Borontrifluoride etherate promoted one-pot conversion of nitriles to esters
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One-pot borontrifluoride etherate promoted transformation of nitriles to esters was achieved by heating in corresponding alcohol as a reactant and solvent.
- Jayachitra,Yasmeen,Srinivasa Rao,Ralte, Samuel L.,Srinivasan,Singh
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- Esterification of aryl/alkyl acids catalysed by n-bromosuccinimide under mild reaction conditions
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N-halosuccinimides (NXSs) are well-known to be convenient, easily manipulable and low-priced halogenation reagents in organic synthesis. In the present work, N-bromosuccinimide (NBS) has been promoted as the most efficient and selective catalyst among the NXSs in the reaction of direct esterification of aryl and alkyl carboxylic acids. Comprehensive esterification of substituted benzoic acids, mono-, di- and tri-carboxy alkyl derivatives has been performed under neat reaction conditions. The method is metal-free, air- and moisture-tolerant, allowing for a simple synthetic and isolation procedure as well as the large-scale synthesis of aromatic and alkyl esters with yields up to 100%. Protocol for the recycling of the catalyst has been proposed.
- ?ebular, Klara,Bo?i?, Bojan ?.,Stavber, Stojan
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- Iron(III) chloride-promoted direct conversion of aryl/alkyl cyanides to esters
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Aryl/alkyl cyanides were quickly converted into the corresponding esters in the presence of iron(III) chloride in refluxing alcohols with very good yields. Copyright Taylor & Francis Group, LLC.
- Srinivasan,Rao, K. Srinivasa,Jayachitra,Ralte, Samuel L.
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- Hydrophilic molecular rotor derivatives - Synthesis and characterization
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Recent research shows high potential for some p-N,N- dialkylaminobenzylidenecyanoacetates, part of a group known as fluorescent molecular rotors, to serve as fluorescent, non-mechanical viscosity sensors. Of particular interest are molecules compatible with aqueous environments. In this study, we present the synthesis and physical characterization of derivatives from 9-(2-carboxy-2-cyanovinyl)-julolidine and related molecules. All compounds show a power-law relationship of fluorescence emission with the viscosity of the solvent, different mixtures of ethylene glycol and glycerol to modulate viscosity. Compounds with high water solubility exhibit the same behavior in aqueous solutions of dextran, where the dextran concentration was varied to modulate viscosity. In addition, some compounds have been found to have low sensitivity towards changes in the pH in the physiological range. The compounds presented show promise to be used in biofluids, such as blood plasma or lymphatic fluid, to rapidly and non-mechanically determine viscosity.
- Haidekker, Mark A.,Brady, Thomas P.,Chalian, Sevag H.,Akers, Walter,Lichlyter, Darcy,Theodorakis, Emmanuel A.
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- Organic-inorganic hybrid porous sulfonated zinc phosphonate material: Efficient catalyst for biodiesel synthesis at room temperature
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A new porous zinc phosphonate material (HZnP-1) has been synthesized via the reaction between p-xylenediphosphonic acid and anhydrous ZnCl2 under hydrothermal and mildly acidic conditions (pH ～ 5) in the absence of any structure directing agent. The phenyl group of this material has been sulfonated with concentrated sulfuric acid to obtain sulfonic acid functionalized material HZnPS-1. Powder X-ray diffraction (XRD), field emission scanning electron microscopy (FE SEM), N2 sorption, solid state 13C CP MAS and 31P MAS NMR, and FT IR spectroscopic tools are employed to characterize these materials. The crystal structures of both the materials are indexed corresponding to the new orthorhombic phases with unit cell parameters a = 11.00, b = 8.74, c = 14.62 A, α = β = γ = 90° for HZnP-1, and a = 10.65, b = 13.52, c = 15.30 A and α = β = γ = 90° for HZnPS-1. HZnPS-1 showed outstanding catalytic activity and high recycling efficiency for the synthesis of different biodiesel compounds via esterification of long chain fatty acids by using methanol as both reactant and solvent at room temperature. The green and eco-friendly catalytic system described herein can overcome the problem faced by the existing catalytic systems known in biodiesel synthesis, such as drastic conditions (high reaction temperature) and requirement of hazardous organic solvents.
- Pramanik, Malay,Nandi, Mahasweta,Uyama, Hiroshi,Bhaumik, Asim
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- Facile dehydration of primary amides to nitriles catalyzed by lead salts: The anionic ligand matters
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The synthesis of nitrile under mild conditions was achieved via dehydration of primary amide using lead salts as catalyst. The reaction processes were intensified by not only adding surfactant but also continuously removing the only by-product, water from the system. Both aliphatic and aromatic nitriles can be prepared in this manner with moderate to excellent yields. The reaction mechanisms were obtained with high-level quantum chemical calculations, and the crucial role the anionic ligand plays in the transformations were revealed.
- Ruan, Shixiang,Ruan, Jiancheng,Chen, Xinzhi,Zhou, Shaodong
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- BTK Inhibitors and uses thereof
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The invention discloses a bruton's tyrosine kinase (BTK) inhibitor and use thereof. Specifically, the invention provides heteroaromatic compounds or stereoisomers, geometrical isomers, tautomers, racemates, nitrogen oxides, hydrates, solvates, metabolites and pharmaceutically acceptable salts or prodrugs thereof, and pharmaceutical compositions containing the heteroaromatic compounds; the invention also discloses use of the heteroaromatic compounds or the pharmaceutical compositions containing the heteroaromatic compounds in preparation of medicines; the medicines can be used for treating autoimmune diseases, inflammatory diseases or proliferative diseases.
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Paragraph 1771-1776
(2020/05/02)
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- Green synthesis method of methyl cyanoacetate
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The invention discloses a green synthesis method of methyl cyanoacetate. The preparation process comprises the following steps: heating methyl chloroacetate and acetone cyanohydrin to 40-100 DEG C inthe absence of a catalyst and a solvent, and reacting to obtain methyl cyanoacetate. Acetone cyanohydrin serves as a cyaniding reagent and directly reacts with methyl chloroacetate to generate methylcyanoacetate, no other solvent or catalyst is needed, the yield is high, and the production cost is greatly reduced.
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Paragraph 0029-0045
(2020/10/30)
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- A cyanoacetic acid methyl ester (by machine translation)
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The invention belongs to the field of organic synthetic technology, in particular to a process for synthesis of methyl cyanoacetate, is divided into two steps: cyanoacetate acetic acid synthesis and cyanoacetic acid synthesis of methyl. The invention through in the esterification reaction process slow access sulfur trioxide, sulfur trioxide with the water generated by the esterification reaction to produce sulfuric acid, as a catalyst in the catalytic reaction carried out to the right, on the other hand the consumption of water in the product preventing the generation of side reaction, raise the product yield while reducing the occurrence of side reactions. (by machine translation)
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Paragraph 0011-0019
(2019/01/14)
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- BORON CONTAINING POLYBASIC BACTERIAL EFFLUX PUMP INHIBITORS AND THERAPEUTICS USES THEREOF
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Disclosed herein are polybasic bacterial efflux pump inhibitors containing boronic acid functionality and theft methods of synthesis, methods of use, and pharmaceutical compositions. Some embodiments include methods of treating or preventing a bacterial infection by co-administering to a subject infected with bacteria or at risk of infection with bacteria the efflux pump inhibitor with another anti-bacterial agent
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Page/Page column 56
(2012/08/28)
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- A practical system to synthesize the multiple-substituted 2,5-dihydrofuran by the intermolecular dipolar cycloaddition reactions involving acceptor/acceptor-substituted diazo reagents
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A practical system for synthesizing the multiple-substituted 2,5-dihydrofuran through intermolecular dipolar cycloaddition reactions of acceptor/acceptor diazo reagents, aldehydes, and acetylenedicarboxylate was developed. The reactions proceeded effectively under ambient temperature with low reactant ratios. The control reactions revealed that there are two competitive paths: one forms 1,3-dioxolane and the other forms 2,5-dihydrofuran. These two paths could be controlled by modifying the steric hindrance of the diazo reagents.
- Zhu, Shifa,Chen, Lijuan,Wang, Chao,Liang, Renxiao,Wang, Xiujun,Ren, Yanwei,Jiang, Huanfeng
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experimental part
p. 5507 - 5515
(2011/08/06)
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- Novel Platensimycin Derivatives, Their Intermediates, and Process for Preparing the Same, and New Process for Preparing Platensimycin
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The present invention relates to novel platensimycin derivatives, their intermediates and preparing methods of the same. Platensimycin is known as an effective antibiotic material having a broad antimicrobial spectrum and its derivatives are also expected to be effective antibiotic candidates. The present invention also relates to a novel preparing method of platensimycin. The intermediates used for the production of platensimycin and its derivatives of the present invention are tricyclo ketone derivatives and tetracyclo derivatives. Tetracyclo derivatives are prepared from tricyclo ketone derivatives prepared by carbonyl ylide [3+2] cycloaddition of dia-zoketone derivative.
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Page/Page column 35
(2011/02/25)
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- Synthesis and antiviral bioactivities of 2-cyano-3-substitutedamino(phenyl) methylphosphonylacrylates (Acrylamides) containing alkoxyethyl moieties
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An efficient reaction under microwave irradiation has been developed for the synthesis of a series of novel 2-cyano-3-substituted-amino(phenyl) methylphosphonylacrylates (acrylamides) II. The products obtained in shorter reaction time with moderate yields are fully characterized by elemental analysis, IR, 1H, 13C, and 31P NMR spectral data. The role of introducing various substituents and the effect of incorporating a-aminophosphonates with an alkoxyethyl moiety into the parent cyanoacrylate (acrylamide) structure are investigated. Among the studied compounds, both II-17 and II-24 displayed good in vivo curative, protection, and inactivation effects, which were comparable to those of the commercial reference ningnanmycin (inhibitory rates of 58.8, 60.2, 78.9% and 60.0, 58.9, 85.5%, respectively, at 500 mg/L against TMV). To the best of the authors' knowledge, this is the first report on the synthesis and antiviral activity of the title compounds II.
- Yang, Jia-Qiang,Song, Bao-An,Bhadury, Pinaki S.,Chen, Zhuo,Yang, Song,Xue-Jian, Cai,Hu, De-Yu,Xue, Wei
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experimental part
p. 2730 - 2735
(2011/07/31)
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- Synthesis and antiviral activities of cyanoacrylate derivatives containing an α-aminophosphonate moiety
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Target compounds 8 were obtained by the reaction of alkyl 2-cyano-3,3-dimethylthioacrylate or cyarylamide (7a-7e) and α- aminobenzylphosphonate (5a-5e) under reflux condition using ethanol as solvent. Their structures were clearly verified by spectroscopic data (IR and 1H, 13C, and 31P NMR) and elemental analysis. These compounds were shown to be antivirally active in the bioassay. It was found that title compounds 8d and 8e had the same inactivation effect against tobacco mosaic virus (EC50 = 55.5 and 55.3 μg/mL) as the commercial product ningnanmycin (EC50 = 50.9 μg/mL). To the best of our knowledge, this is the first report on the synthesis and antiviral activity of cyanoacrylate derivatives containing an α-aminophosphonate moiety.
- Long, Ning,Cai, Xue-Jian,Song, Bao-An,Yang, Song,Chen, Zhuo,Bhadury, Pinaki S.,Hu, De-Yu,Jin, Lin-Hong,Xue, Wei
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body text
p. 5242 - 5246
(2010/04/06)
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- Scandium triflate catalyzed transesterification of carboxylic esters
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The direct transesterification of carboxylic esters is efficiently catalyzed with Sc(OTf)3 (10 mol%) in boiling alcoholic solvent. Methyl, ethyl, isopropyl, and allyl esters were prepared from a broad range of different substrates in high yields. The application of microwave irradiation led to significantly reduced reaction times. Georg Thieme Verlag Stuttgart.
- Remme, Nicole,Koschek, Katharina,Schneider, Christoph
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p. 491 - 493
(2007/12/27)
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- Method for producing cyanoacetic acid esters
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A method for producing cyanoacetic acid esters of general formula (I): wherein R represents on optionally substituted linear or branched C1-8 alkyl group or an aryl C1-4 alkyl group. According to the method, an alkoxypropionitrile of the general formula (II): wherein R is defined above, is oxidized to form the desired product in the presence of a catalyst, based on lead or on one of the transition metals, using oxygen or an oxygen-forming reagent.
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Page column 2
(2008/06/13)
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- Process for preparing cyanoacetic esters
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Cyanoacetic esters of the general formula: in which R is C1-10-alkyl, C3-10-alkenyl or aryl-C1-4alkyl, are prepared by the reaction of alkali metal cyanoacetates with the corresponding halides R—X, in which X is chlorine, bromine or iodine, in an aqueous/organic two-phase system in the presence of a phase-transfer catalyst.
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- Method for the continuous production of esters of thermally unstable acids
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A method for the continuous production of esters of thermally unstable acids by the esterification, with or without a catalyst, of the acids with alcohols is provided. The method involves esterification at temperatures of approximately 80° C. to approximately 130° C., essentially in a single reaction zone, to which the acid and an excess of alcohol are continuously supplied and from which a vapor stream containing alcohol and water produced by the esterification reaction are removed, while at the same time removing an ester-rich liquid reaction mixture from the single reaction zone, from which the ester is obtained.
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- Indanylidene compounds, a process for their preparation and their use as UV absorbers
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Compounds of the formula I according to claim 1 are excellently suitable as UV absorbers for use in cosmetic products, in particular sunscreen compositions, daytime care products and hair care products. They are furthermore suitable for protection of products.
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- A selective method for the preparation of aliphatic methyl esters in the presence of aromatic carboxylic acids
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2,2-Dimethoxypropane, methanol and a catalytic amount of HCl selectively esterify aliphatic carboxylic acids, in the presence of aromatic carboxylic acids, at room temperature and in high yields.
- Rodriguez,Nomen,Spur,Godfroid
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p. 8563 - 8566
(2007/10/03)
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- AMBERLYST 15: A PRACTICAL, MILD AND SELECTIVE CATALYST FOR METHYL ESTERIFICATON OF CARBOXYLIC ACIDS
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Mild and selective methyl esterification of carboxylic acids are realized using Amberlyst 15 as acid catalyst in methanol.No racemization, epimerization or ketalization products have been observed with this method.Excellent results are obtained in the esterifications of bile acids.
- Petrini, Marino,Ballini, Roberto,Marcantoni, Enrico
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p. 847 - 854
(2007/10/02)
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- The Synthetic Potential of the Isocyanide-Cyanide Rearrangement
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Excellent chemical and optical yields (>96percent retention) of cyanides are achieved by vapor phase thermolysis or short contact flow thermolysis of isocyanides. trans-2-Butenyl isocyanide rearranges without concomitant allylic isomerization to trans-2-butenyl cyanide.Optically active 1-(formyloxymethyl)-2-phenylethyl cyanide is obtained from optically active L-phenylalanine as a new type of chiral pool synthon.
- Meier, Michael,Ruechardt, Christoph
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- The Isonitrile-Nitrile Rearrangement. A Reaction without a Structure-Reactivity Relationship
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Reproducible rates of isomerisation of aliphatic isonitriles to nitriles in solution can be measured by GLC or IR when free-radical inhibitors are added to suppress a competing radical chain reaction.The reactivities of 19 primary, secondary, tertiary, cyclic, bicyclic, bridgehead, benzyl, substituted-benzyl, α-carbomethoxymethyl, and triphenylmethyl isocyanides in this rearrangement reaction vary by only a factor of 67 in rate or by +/- 2 kcal mol-1 in ΔG(excit.).This is explained by a tight hypervalent three-membered cyclic transition state in agreement with a previous prediction by ab initio calculation.The slower rate of 9-triptycyl isocyanide is proposed to be due to steric hindrance by the three peri hydrogens.Aromatic isocyanides isomerize about 10 times faster independent of polar para substituents and bulky ortho substituents.A hypervalent orthogonal transition state with retention of the aromatic sextet is proposed in contrast to the popular phenonium-type transition states for aryl migration in other 1,2-rearrangements.The reactivity data and the transition-state structures are discussed in context with other cationotropic 1,2-shifts.
- Meier, Michael,Mueller, Barbara,Ruechardt, Christoph
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p. 648 - 652
(2007/10/02)
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- Synthesis of Methyl Esters by Titanate-catalyzed Transesterifications
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The low solubility of tetramethyl titanate has so far prevented the laboratory use of titanate-catalyzed transesterifications with formation of methyl esters.Two procedures are described here, which allow the application of this exceedingly mild method to the synthesis of methyl esters: one uses methyl propionate/Ti(OEt)4, the other one uses methanol/Gly-Ti, a new type of catalyst, prepared from Ti(OEt)4/ethylene glycol 2:1.
- Schnurrenberger, Peter,Zueger, Max F.,Seebach, Dietrich
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p. 1197 - 1201
(2007/10/02)
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- Mild Conversion of Carboxamides and Carboxylic Acid Hydrazides to Acids and Esters
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A mild and selective conversion of unsubstituted carboxamides and carboxylic acid hydrazides to the corresponding acids and esters is brought about by the use of acidic resins.Application of the procedure to several carboxamides and carboxylic acid hydrazides is described.
- Greenlee, William J.,Thorsett, Eugene D.
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p. 5351 - 5353
(2007/10/02)
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- A FACILE METHOD OF TRANSESTERIFICATION USING PHOSPHORUS YLID
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The transesterification of carboxylic esters catalysed with phosphorus ylid under neutral and mild conditions has been investigated.The reactions of esters having an electron withdrawing group with methanol proceeded rapidly and with high yield, whereas the reverse reactions proceeded slowly or not at all.
- Hashimoto, Shizunobu,Furukawa, Isao,Kuroda, Tomoyuki
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p. 2857 - 2860
(2007/10/02)
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