- Ammonium Tungstate as an Effective Catalyst for Selective Oxidation of Alcohols to Aldehydes or Ketones with Hydrogen Peroxide under Water - A Synergy of Graphene Oxide
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Ammonium tungstate was found to be a facile and efficient catalyst for selective oxidation of alcohols to the corresponding carbonyl compounds with hydrogen peroxide as oxidant. Heterogeneous graphene oxide as acid effectively intensified the transformations and resulted in excellent yields. The use of water as solvent rendered the reactions promising both economically and environmentally.
- Fu, Huihui,Hu, Chuanfeng,Huang, Zhida,Zhou, Jianhao,Peng, Xinhua
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Read Online
- POLITAG-Pd(0) catalyzed continuous flow hydrogenation of lignin-derived phenolic compounds using sodium formate as a safe H-source
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Phenols are aromatic biobased compounds and as they are accessible from lignin depolymerization, they can be a useful platform chemicals to produce value-added products. Herein we report our recent investigations on the definition of an approach to the efficient continuous flow selective hydrogenation of phenols in water. Our protocol is based on the use of sodium formate as a clean and safe hydrogen source in combination with our newly defined heterogeneous POLITAG-Pd(0) catalytic system. POLITAG is a polymeric heterogeneous support decorated with pincer-type ionic ligands proven to be highly efficient for the stabilization of Pd(0) nanoparticles. The results obtained are remarkable in comparison with other protocols that employ sodium formate as H-source. Indeed, our investigation has been extended to a variety of differently substituted phenolic compounds that have been hydrogenated with excellent to good selectivity in continuous flow conditions. Durability of the catalyst has been also tested with a representative continuous processing of over 100 mmol that showed no loss in efficiency and minimal metal leaching.
- Campana, Filippo,Ferlin, Francesco,Silvetti, Matteo,Trombettoni, Valeria,Vaccaro, Luigi,Valentini, Federica
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- Highly Selective Hydrogenation of Phenols to Cyclohexanone Derivatives Using a Palladium@N-Doped Carbon/SiO2Catalyst
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A new palladium-based heterogeneous material was synthesized by means of immobilization of Pd(OAc)2/1,10-phenanthroline on commercially available SiO2and subsequent pyrolysis at 600 °C for 2 h in air, namely, a Pd@N-doped carbon/SiO2catalyst. The obtained catalyst was studied by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), and X-ray photoelectron spectroscopy (XPS) techniques, and was effectively applied in the highly selective hydrogenation of phenols to give the corresponding cyclohexanone derivatives with 93-98% yields at 100 °C under 0.4 MPa H2in EtOH. It was demonstrated that introducing nitrogen could effectively promote the Pd dispersion and enhance the electronic interaction of Pd, both of which facilitate the improvement of the catalytic activity and selectivity. The likely reaction pathway was outlined to elucidate the selective hydrogenation mechanism according to experimental results.
- Sheng, Xueru,Wang, Chao,Wang, Wentao
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supporting information
p. 2425 - 2431
(2021/11/16)
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- Synthesis method of 4-substituent cyclohexanone
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The invention discloses a synthesis method of 4-substituent cyclohexanone, which comprises the following steps: by taking a 4-substituent phenol compound as a raw material, carrying out catalytic hydrogenation on 4-substituent phenol to obtain 4-substituent cyclohexanol, and then oxidizing the 4-substituent cyclohexanol by taking oxygen-containing gas as an oxidant to prepare the 4-substituent cyclohexanone. The oxygen-containing gas is used as the oxidizing agent, the oxygen-containing gas is low in price, good in reaction selectivity, high in oxidation reaction yield and environment-friendly, and is an ideal clean oxidizing agent; in addition, the whole synthesis process is simple, mild in condition, simple in post-treatment, green, environment-friendly and suitable for large-scale industrial production.
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- Synthesis method of 4-substituent cyclohexanone liquid crystal intermediate
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The invention discloses a synthesis method of a 4-substituent cyclohexanone liquid crystal intermediate, which comprises the following step: carrying out oxidation catalytic reaction on 4-substituent cyclohexanol under the action of trichloroisocyanide urea to obtain the 4-substituent cyclohexanone liquid crystal intermediate. The method is high in reaction selectivity, high in yield, environment-friendly, simple in post-treatment and suitable for industrial production.
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- A New Route to Cyclohexanone using H2CO3 as a Molecular Catalytic Ligand to Boost the Thorough Hydrogenation of Nitroarenes over Pd Nanocatalysts
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Carbon dioxide has been important in green chemistry, especially in catalytic and chemical engineering applications. While exploring CO2 to produce cyclohexanone for nylon or nylon 66 that is currently produced with low yields using harsh catalytic methods, we made the exciting discovery that carbonic acid, generated from dissolved CO2 in water, was utilized as molecular catalytic ligand to produce cyclohexanone via the hydrogenation of nitrobenzene in aqueous solution that uses Pd catalysts with a total yield higher than 90 %. Importantly, the gaseous nature of catalytic ligand H2CO3 profoundly simplifies post-catalysis cleanup unlike liquid or solid catalysts. This new green catalysis strategy demonstrated the universality for hydrogenation of aromatic compounds like aniline and N-methylaniline and could be broadly applicable in other catalytic field like artificial photosynthesis and electrocatalytic organic synthesis.
- Zhao, Tian-Jian,Zhang, Jun-Jun,Zhang, Bing,Liu, Yong-Xing,Lin, Yun-Xiao,Wang, Hong-Hui,Su, Hui,Li, Xin-Hao,Chen, Jie-Sheng
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p. 2837 - 2842
(2019/05/27)
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- Synthetic method of cis-4-methoxycyclohexyl-1-carbamic acid
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The invention provides a synthetic method of cis-4-methoxycyclohexyl-1-carbamic acid. The synthetic method includes the steps of catalytic hydrogenation, oxidative reaction, replacement reaction and hydrolytic reaction; the hydrolytic reaction is carried out in a microreactor, with a Jones reagent acting as an oxidant; barium hydroxide octahydrate is used as an alkaline material in the hydrolyticreaction. The synthetic method has few steps and shorter reaction time; the salt content in reaction wastewater is low, the content of heavy metals is low, and discharged waste is little; the finishedproduct has the content of 98% and above; the total reaction yield is 45% and above.
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- Novel spirodecenol compound and preparation method thereof
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The invention discloses a novel spirodecenol compound and a preparation method thereof, and belongs to the technical field of pesticide synthesis. The invention adopts the key point that the novel spirodecenol compound has a structure as described in the specification. The invention also discloses a novel spirodecenol compound and a preparation method thereof. According to the invention, a novel spirodecenol compound is synthesized by a new method, a reaction process is simple and easy to operate, raw materials are cheap and easy to obtain, the reaction efficiency is high, the repeatability isgood, the insecticidal activity effect is obvious, and the spirodecenol compound has a good application prospect.
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Paragraph 0034; 0035
(2018/05/16)
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- PROCESS FOR THE PREPARATION OF CYCLIC KETONES
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The present invention provides a process for the preparation of compound of formula II.
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Page/Page column 5
(2018/03/25)
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- Selective hydrogenation of phenol to cyclohexanone by SiO2-supported rhodium nanoparticles under mild conditions
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A silica-supported rhodium catalyst for the selective hydrogenation of phenol to cyclohexanone under mild conditions has been developed. As the Rh concentration on the catalyst increased from 0.5 to 15 wt%, the conversion (at phenol/Rh mole ratio 100/1) dropped whereas the initial selectivity to cyclohexanone increased. The direct hydrogenation to cyclohexanol occurred in parallel with partial hydrogenation to cyclohexanone. The negative correlation between selectivity and Rh dispersion suggests that direct hydrogenation occurs at low coordination sites whereas dissociation of phenol to phenoxy followed by hydrogenation to cyclohexanone takes place at higher coordinated terrace sites. DFT calculations revealed that the activation barrier for O–H bond cleavage is lower for phenol adsorbed on a Rh(1 1 1) flat surface than on small particles. By blocking the low coordination edge and step sites through grafting with (3-mercaptopropyl)trimethoxysilane, the cyclohexanone selectivity was improved from 82 to 93% at 100% conversion. The catalyst is active at room temperature and 1 atm H2 pressure and can be easily activated by in-situ reduction.
- Zhang, Hongwei,Han, Aijuan,Okumura, Kazu,Zhong, Lixiang,Li, Shuzhou,Jaenicke, Stephan,Chuah, Gaik-Khuan
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p. 354 - 365
(2018/06/26)
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- Ductile Pd-Catalysed Hydrodearomatization of Phenol-Containing Bio-Oils Into Either Ketones or Alcohols using PMHS and H2O as Hydrogen Source
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A series of phenolic bio-oil components were selectively hydrodearomatized by palladium on carbon into the corresponding ketones or alcohols in excellent yields using polymethylhydrosiloxane and water as reducing agent. The selectivity of the reaction was governed by the water concentration where selectivity to alcohol was favoured at higher water concentrations. As phenolic bio-oil examples cardanol and beech wood tar creosote were studied as substrate to the developed reaction conditions. Cardanol was hydrodearomatized into 3-pentadecylcyclohexanone in excellent yield. From beech wood tar creosote, a mixture of cyclohexanols was produced. No hydrodeoxygenation occurred, suggesting the applicability of the reported method for the production of ketone-alcohol oil from biomass. (Figure presented.).
- Di Francesco, Davide,Subbotina, Elena,Rautiainen, Sari,Samec, Joseph S. M.
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supporting information
p. 3924 - 3929
(2018/09/14)
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- PYRIMIDINE-BASED ANTIPROLIFERATIVE AGENTS
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This invention is in the area of pyrimidine-based compounds for the treatment of disorders involving abnormal cellular proliferation, including but not limited to tumors and cancers.
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- Preparation method of p-methoxycyclohexanone
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The invention discloses a preparation method of p-methoxycyclohexanone. The preparation method comprises the steps that p-methoxyphenol is subjected to a hydrogenation reduction reaction under existence of a catalyst and a solvent to prepare p-methoxycyclohexanol; and p-methoxycyclohexanol is subjected to an oxidation reaction under existence of an oxidizing agent and a solvent to prepare p-methoxycyclohexanone. The target product can be obtained only by conducting reduction and oxidation reactions on p-methoxyphenol, p-methoxycyclohexanol obtained through the reduction reaction does not needto be purified and is directly used in the oxidation reaction, the technology is simple and easy to operate, the raw materials are wide in source, the production cost is low, and the preparation method is suitable for industrialized production.
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Paragraph 0023; 0025; 0028; 0030; 0032; 0035
(2018/09/11)
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- Oxidation of Secondary Methyl Ethers to Ketones
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We present a mild way of converting secondary methyl ethers into ketones using calcium hypochlorite in aqueous acetonitrile with acetic acid as activator. The reaction is compatible with various oxygen- and nitrogen-containing functional groups and afforded the corresponding ketones in up to 98% yield. The use of this methodology could expand the application of the methyl group as a useful protecting group.
- Gilissen, Pieter J.,Blanco-Ania, Daniel,Rutjes, Floris P. J. T.
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p. 6671 - 6679
(2017/07/15)
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- A 4 - methoxy cyclohexanone preparation method
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The invention discloses a preparation method of 4-methoxycyclohexanon. According to the preparation method, hydrogen peroxide is taken as an oxidizing agent, a molecular sieve supported phosphotungstic acid is taken as a catalyst, a 4-methoxycyclohexanon reaction solution is obtained through continuous catalytic oxidation by a tubular reactor, and a target object 4-methoxycyclohexanon with a reaction formula shown in the specification is obtained through solvent extraction and desolvation. According to the preparation method, hydrogen peroxide is taken as the oxidizing agent, the cost of raw materials is low, the raw materials are environment-friendly, no three wastes are generated, and the problems of high cost of other raw materials, high COD (chemical oxygen demand) of wastewater, high salt content of the wastewater, heavy metal chromium pollution and the like are solved. With the adoption of a continuous catalytic oxidation process, the condition that generated targets stay in a reaction system for a long time and have a polymerization reaction is effectively avoided, and danger of potential explosion caused by the fact that hydrogen peroxide accumulates, is not stable at the high temperature and easily decomposes to produce a large amount of oxygen is avoided. A supported phosphotungstic acidmolecular sieve is adopted for catalysis, the reaction yield is greatly improved, the aftertreatment is simple, filtration and separation are not required, and lossless and repeated use of the catalyst is realized.
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Paragraph 0022; 0026; 0030; 0034; 0038; 0039-0042; 0046
(2017/08/25)
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- ARGININE METHYLTRANSFERASE INHIBITORS AND USES THEREOF
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Described herein are compounds of Formula (S-I), pharmaceutically acceptable salts thereof, and pharmaceutical compositions thereof. Compounds described herein are useful for inhibiting arginine methyltransferase activity. Methods of using the compounds for treating arginine methyltransferase-mediated disorders are also described.
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- Robustly supported rhodium nanoclusters: Synthesis and application in selective hydrogenation of lignin derived phenolic compounds
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The stabilization of small rhodium nanoclusters (NCs) in a polymer derived silicon carbonitride (SiCN) matrix has been reported to generate highly robust and active solid catalysts for the selective hydrogenation of phenolic compounds. An aminopyridinato Rh complex was used to modify a preceramic polymer (HTT 1800) followed by its pyrolysis at 1100 °C to afford small Rh NCs nicely dispersed over dense SiCN ceramic. For the synthesis of porous catalysts containing Rh NCs, microphase separation (followed by pyrolysis) of a diblock copolymer of HTT 1800 with hydroxy-polyethylene (PE-OH) was used. Both catalysts exhibit high activity in the hydrogenation of substituted phenols at room temperature and under low hydrogen pressure. The catalysts remained highly active and selective for six consecutive catalytic runs.
- Fehn, Sonja,Zaheer, Muhammad,Denner, Christine E.,Friedrich, Martin,Kempe, Rhett
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p. 9252 - 9256
(2016/11/11)
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- Highly Selective Hydrogenation of Aromatic Ketones and Phenols Enabled by Cyclic (Amino)(alkyl)carbene Rhodium Complexes
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Air-stable Rh complexes ligated by strongly σ-donating cyclic (amino)(alkyl)carbenes (CAACs) show unique catalytic activity for the selective hydrogenation of aromatic ketones and phenols by reducing the aryl groups. The use of CAAC ligands is essential for achieving high selectivity and conversion. This method is characterized by its good compatibility with unsaturated ketones, esters, carboxylic acids, amides, and amino acids and is scalable without detriment to its efficiency.
- Wei, Yu,Rao, Bin,Cong, Xuefeng,Zeng, Xiaoming
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supporting information
p. 9250 - 9253
(2015/08/11)
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- Selective Hydrogenation of Phenol to Cyclohexanone over Pd-HAP Catalyst in Aqueous Media
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The production of pure cyclohexanone under mild conditions over catalysts with high reactivity, selectivity, compatibility, stability, and low cost is still a great challenge. Here we report a hydroxyapatite-bound palladium catalyst (Pd-HAP) to demonstrate its excellent performance on phenol hydrogenation to cyclohexanone. Based on catalyst characterization, the Pd nanoclusters (≈0.9 nm) are highly dispersed and bound to phosphate in HAP. Only basic active sites on HAP surface are detected. At 25°C and ambient H2 pressure in water, phenol can be 100% converted into cyclohexanone with 100% selectivity. This system shows a universal applicability to temperature, pH, solvent, low H2 purity, and pressure. The catalyst reveals high stability to be recycled without deactivation or morphology change; and Pd nano-clusters barely aggregate even at 400°C. During the reaction, HAP adsorbs phenol, and Pd nanoclusters activate and spillover H2. The mechanism is also investigated, proposed, and verified.
- Xu, Guangyue,Guo, Jianhua,Zhang, Ying,Fu, Yao,Chen, Jinzhu,Ma, Longlong,Guo, Qingxiang
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p. 2485 - 2492
(2015/08/24)
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- Development and evaluation of ST-1829 based on 5-benzylidene-2-phenylthiazolones as promising agent for anti-leukotriene therapy
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Different inflammatory diseases and allergic reactions are mediated by leukotrienes, which arise from the oxygenation of arachidonic acid catalyzed by 5-lipoxygenase (5-LO). One promising approach for an effective anti-leukotriene therapy is the inhibition of this key enzyme. This study presents the synthesis and development of a potent and direct 5-LO inhibitor based on the well characterized 5-benzylidene-2-phenylthiazolone C06, whose further pharmacological investigation was precluded due to its low solubility. Through optimization of C06, evaluation of structure-activity relationships including profound assessment of the thiazolone core and consideration of the solubility, the 5-benzyl-2-phenyl-4-hydroxythiazoles represented by 46 (ST-1829, 5-(4-chlorobenzyl)-2-p-tolylthiazol-4-ol) were developed. Compound 46 showed an improved 5-LO inhibitory activity in cell-based (ICinf50/inf values 0.141/4M) and cell-free assays (ICinf50/inf values 0.03 1/4M) as well as a prominent enhanced solubility. Furthermore, it kept its promising inhibitory potency in the presence of blood serum, excluding excessive binding to serum proteins. These facts combined with the non-cytotoxic profile mark a major step towards an effective anti-inflammatory therapy.
- Lill, Andreas P.,R?dl, Carmen B.,Steinhilber, Dieter,Stark, Holger,Hofmann, Bettina
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p. 503 - 523
(2014/12/11)
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- BET BROMODOMAIN INHIBITORS AND THERAPEUTIC METHODS USING THE SAME
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Inhibitors of BET bromodomains and compositions containing the same are disclosed. Methods of using the BET bromodomain inhibitors in the treatment of diseases and conditions wherein inhibition of BET bromodomain provides a benefit, like cancers, also are disclosed.
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- 4-Benzamido-TEMPO catalyzed oxidation of a broad range of alcohols to the carbonyl compounds with NaBrO3 under mild conditions
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4-Benzamido-TEMPO catalyzed oxidation system for conversion of a wide range of alcohols to the aldehydes or ketones with NaBrO3 under room temperature conditions has been developed. The credible, operationally convenient and economical, and condition mild oxidation protocol is particularly of interest in laboratory and in fine chemicals manufacture. 4-Benzamido-TEMPO catalyzed oxidation system for conversion of a wide range of alcohols to the aldehydes or ketones with NaBrO3 as oxidant under room temperature conditions has been developed. Copyright
- Shen, Jiaxuan,Sun, Jiangkai,Qin, Shuangshuang,Chu, Changhu,Liu, Renhua
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p. 405 - 409
(2014/06/10)
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- Selective hydrogenation of phenol and derivatives over an ionic liquid-like copolymer stabilized palladium catalyst in aqueous media
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A combination of "water soluble" palladium nanoparticles stabilized by an ionic liquid-like copolymer and phosphotungstic acid synergistically promotes selective hydrogenation of phenol to cyclohexanone. The nanocatalyst preparation and selective phenol hydrogenation are successfully combined into a one-pot process in this research. Conversion exceeding 99% was achieved with >99% selectivity under an atmospheric pressure of hydrogen in aqueous media. Moreover, even at room temperature, >99% conversion and >99% selectivity could still be obtained. The generality of the catalyst system for this reaction was demonstrated by selective hydrogenation of other hydroxylated aromatic compounds with similar performance. The Royal Society of Chemistry 2013.
- Chen, Aibing,Zhao, Guoying,Chen, Jinzhu,Chen, Limin,Yu, Yifeng
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p. 4171 - 4175
(2013/05/09)
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- Selective hydrogenation of phenol and derivatives over polymer- functionalized carbon-nanofiber-supported palladium using sodium formate as the hydrogen source
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Selective hydrogenation of phenol to cyclohexanone over a catalyst of polyaniline-functionalized carbon-nanofiber-supported palladium (Pd-PANI/CNF) with sodium formate as the hydrogen source has been studied. Phenol conversion exceeding 99 % was achieved with a cyclohexanone selectivity of >99 % in aqueous media. In an extension to Pd-PANI/CNF, polymers such as polypyrrole (PPY), poly(4-vinylpyridine) (PVP), and poly(1-vinylimidazole) (PVI) were further applied to a catalyst of Pd-polymer/CNF for selective phenol hydrogenation. All of the Pd-polymer/CNF catalysts showed excellent to good performance toward selective phenol hydrogenation. However, Pd-PANI/CNF was considerably more active and selective to afford the desired cyclohexanone than Pd-PPY/CNF, Pd-PVP/CNF, and Pd-PVI/CNF. Moreover, a series of phenol-derived compounds were selectively hydrogenated in high yields under the investigated aqueous conditions. The research highlights an environmentally benign and effective process for the selective reduction of phenol derivatives with sodium formate as an alternative hydrogen source. Source material: Palladium supported on nitrogen-containing-polymer-functionalized carbon nanofibers was used as the catalyst for selective hydrogenation of phenol to cyclohexanone using sodium formate as the hydrogen source in aqueous media (see figure). The hydrogenation involved a hydrogen-transfer reaction pathway with cyclohexanone as the "intermediate". Copyright
- Chen, Aibing,Li, Yonglei,Chen, Jinzhu,Zhao, Guoying,Ma, Longlong,Yu, Yifeng
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p. 1370 - 1378
(2013/12/04)
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- Direct selective hydrogenation of phenol and derivatives over polyaniline-functionalized carbon-nanotube-supported palladium
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Cyclohexanone is an industrially important intermediate in the synthesis of materials such as nylon and polyamides, but direct selective hydrogenation of phenol to cyclohexanone under green conditions is a challenge owing to the over-reduction of cyclohexanone to cyclohexanol. A catalyst made of palladium nanoparticles supported on polyaniline-functionalized carbon nanotubes, Pd-PANI/CNT, which was shown to be highly active towards the direct hydrogenation of phenol to cyclohexanone, is reported. Phenol conversion exceeding 99 % was achieved with a cyclohexanone selectivity of >99 % under atmospheric pressure of hydrogen in aqueous media. The generality of the catalyst for this reaction was demonstrated by selective hydrogenation of other hydroxylated aromatic compounds with similar performance, again under green and mild conditions. It is suggested the Pd-N interactions and polymeric stabilization play a key role in the formation of stable and highly dispersed palladium nanoparticles on the conducting composite material PANI/CNT. The results also indicate that the phenol conversion is related presumably to the conductive property of PANI/CNT, whereas the cyclohexanone selectivity is attributed to the nitrogen-containing nature of PANI/CNT. Support group: Direct selective hydrogenation of phenol to cyclohexanone was achieved over a polyaniline (PANI)-functionalized carbon-nanotube (CNT)-supported palladium catalyst under atmospheric hydrogen pressure in aqueous media (see scheme). The results indicate that the phenol conversion is related to the conductive property of composite material PANI/CNT, whereas the cyclohexanone selectivity is attributed to the nitrogen-containing nature of PANI/CNT.
- Chen, Jinzhu,Zhang, Wei,Chen, Limin,Ma, Longlong,Gao, Hui,Wang, Tiejun
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p. 142 - 148
(2013/04/10)
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- Method for Preparing Cyclic Ketones
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A method for hydrogenating optionally substituted phenols with one hydroxyl group to cyclohexanones over modified, palladium-comprising supported catalysts. This is possible surprisingly in selected alcoholic solvents with high selectivity. Here it is even possible to recycle the catalysts employed, which hitherto has only been possible with considerable loss of selectivity.
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Paragraph 0061
(2013/07/05)
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- Selective reduction of phenol derivatives to cyclohexanones in water under microwave irradiation
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Selective reduction of phenol to cyclohexanone over the Pd/C catalyst in the presence of a hydrogen source of HCOONa/H2O has been studied. Surprisingly, phenol was transformed efficiently to cyclohexanone in an excellent yield of above 98% under microwave irradiation. The influence of some parameters like reaction temperature, time and amount of hydrogen donor, as well as the reaction pathway has been discussed. The combination of microwave irradiation and HCOONa/H2O was certified to be effective for the reduction of phenol as well as its derivatives to their corresponding cyclohexanones. The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2012.
- Cheng, Haiyang,Liu, Ruixia,Wang, Qiang,Wu, Chaoyong,Yu, Yancun,Zhao, Fengyu
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experimental part
p. 1085 - 1090
(2012/07/13)
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- Spectroscopic and X-ray crystallographic evidence for electrostatic effects in 4-substituted cyclohexanone-derived hydrazones, imines, and corresponding salts
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The axial conformer of several 4-substituted cyclo-hexanone hydrazone salts was found to predominate in solution. Changes in the charge of the molecule and the polarity of the solvent led to changes in the conformational preference of each molecule that were consistent with electrostatic stabilization of the axial conformer. H NMR spectroscopic analysis was utilized to determine the structure of cyclohexanone-derived substrates by comparison to conformationally restricted trans-decalone derivatives and computational models. X-ray crystallography demonstrated that the axial configuration of a pendant benzyloxy group is the preferred conformation of an iminium ion in the solid state. The structure of a neutral hydrazone was also determined to favor the axial configuration for a pendant benzyloxy group in the solid state.
- Dibble, David J.,Ziller, Joseph W.,Woerpef
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p. 7706 - 7719
(2011/12/02)
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- Novel Compounds for the Treatment of Diseases Associated with Amyloid or Amyloid-Like Proteins
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The present invention relates to novel compounds that can be employed in the treatment of a group of disorders and abnormalities associated with amyloid protein, such as Alzheimer's disease, and of diseases or conditions associated with amyloid-like proteins. The compounds of the present invention can also be used in the treatment of ocular diseases associated with pathological abnormalities/changes in the tissues of the visual system. The present invention further relates to pharmaceutical compositions comprising these compounds and to the use of these compounds for the preparation of medicaments for treating or preventing diseases or conditions associated with amyloid and/or amyloid-like proteins. A method of treating or preventing diseases or conditions associated with amyloid and/or amyloid-like proteins is also disclosed.
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- PYRAZINE COMPOUNDS AS PHOSPHODIESTERASE 10 INHIBITORS
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Pyrazine compounds, and compositions containing them, and processes for preparing such compounds. Provided herein also are methods of treating disorders or diseases treatable by inhibition of PDE10, such as obesity, non-insulin dependent diabetes, schizophrenia, bipolar disorder, obsessive-compulsive disorder, and the like.
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Page/Page column 144
(2010/06/15)
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- NEW GALLIUM BISAMINOTHIOLATE COMPLEXES FOR MYOCARDIAL IMAGING
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The present invention is directed to compounds of Formula I: and pharmaceutically acceptable salts thereof; wherein A1, A2 and A3 are the same or different cycloalkyl, wherein at least one of A1, A2 or A3 is substituted. R1 through R6 are independently hydrogen or alkyl, R7 and R8 are independently hydrogen or alkyl and RP is hydrogen or sulfhydryl protecting group. This invention is also directed to complexes, wherein said compounds chelate radioactive metal ions, such as Gallium. The complexes of the rpesent invention are useful as myocardial perfusion imaging agents.
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- BENZIMIDAZOLES WHICH HAVE ACTIVITY AT M1 RECEPTOR AND THEIR USES IN MEDICINE
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Compounds of formula (I), salts and solvates are provided: formula (I), wherein Q, R and R6 are as defined in the claims. Uses of the compounds for therapy, for example in the treatment of psychotic disorders and cognitive impairment, are also disclosed.
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- BENZIMIDAZOLES WHICH HAVE ACTIVITY AT M1 RECEPTOR AND THEIR USES IN MEDICINE
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Compounds of Formula (I) and salts and solvates are provided; wherein R, R5, R6 and Q are defined as in the claims. Uses of the compounds for therapy, for example in the treatment of psychotic disorders and cognitive impairment, are also disclosed.
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- BENZIMIDAZOLES WHICH HAVE ACTIVITY AT M1 RECEPTOR AND THEIR USES IN MEDICINE
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Compounds of formula (I), salts and solvates are provided, wherein Q, R, R4 - R6 are as def ined in the Claims. Uses of the Compounds for therapy, for example in the treatment of psychotic disorders and cognitive impairment, are also disclosed.
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- Synthesis of 5-substituted 4,5,6,7-tetrahydroindoles from cyclohexanones
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5-Substituted 4,5,6,7-tetrahydroindoles were prepared from 4-substituted cyclohexanones in three steps: conversion to an enol silyl ether, introduction of a formylmethyl group at 2-C, and the Paal-Knorr pyrrole synthesis by reacting the 1,4-dicarbonyl compounds with ammonia. The substituents are H, methyl, ethyl, tert-butyl, methoxy, and phenyl.
- Lee, Chang Kiu,Lee, In-Sook Han,Noland, Wayland
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p. 419 - 428
(2008/02/09)
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- New bioorganic reagents: Evolved cyclohexanone monooxygenase - Why is it more selective?
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Four mutants of the cyclohexanone monooxygenase (CHMO) evolved as catalysts for Baeyer-Villiger oxidation of 4-hydroxycyclohexanone were investigated as catalysts for a variety of 4-substituted and 4,4-disubstituted cyclohexanones. Several excellent catalytic matches (mutant/substrate) were identified. The most important, however, is the finding that, in a number of cases, a mutant with a single exchange, Phe432Ser, was shown to be as robust and more selective as a catalyst than the wild-type CHMO. All biotransformations were performed on a laboratory scale, allowing full characterization of the products. The absolute configurations of two products were established. A model suggesting a possible role of the 432 serine residue in enantioselectivity control is proposed.
- Kayser, Margaret M.,Clouthier, Christopher M.
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p. 8424 - 8430
(2007/10/03)
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- D-xylopyranosyl-phenyl-substituted cycles, medicaments containing such compounds, their use and process for their manufacture
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D-Glucopyranosyl-phenyl-substituted cycles of general formula I wherein the groups R1 to R6, Z, Cy and R7a, R7b, R7c, R7d are defined as in claim 1, have an inhibiting effect on the sodium-dependent glucose cotransporter SGLT. The present invention also relates to pharmaceutical compositions for the treatment of metabolic disorders.
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Page/Page column 21
(2010/02/15)
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- METHODS OF TREATMENT OF AMYLOIDOSIS USING ASPARTYL-PROTEASE INHIBITORS
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The invention relates to acetyl 2-hydroxy-1,3-diaminospirocyclohexanes and derivatives thereof that are useful in treating diseases, disorders, and conditions associated with amyloidosis. Amyloidosis refers to a collection of diseases, disorders, and conditions associated with abnormal deposition of A-beta protein.
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Page/Page column 251
(2010/02/13)
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- Process for preparing cyclohexanones by hydrogenation of the corresponding phenols (II)
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Substituted or unsubstituted cyclohexanones are advantageously prepared by hydrogenation of the corresponding phenols in the presence of a palladium-on-carbon catalyst at from 100 to 250 DEG C. and from 1 to 20 bar of hydrogen pressure if the reaction is carried out in the presence of straight-chain, branched or cyclic alkanes having a boiling point at atmospheric pressure of over 70 DEG C. as solvents. This makes it possible to obtain substituted or unsubstituted cyclohexanones in short hydrogenation times and in high yields using low-toxicity, physically problem-free solvents which are easy to handle from a safety point of view.
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- Process for preparing substituted cyclohexanones
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Substituted cyclohexanones of the formula STR1 where R1 to R5 are as defined in the description, can be obtained by catalytic hydrogenation of phenols of the formula STR2 where R1 to R5 are as defined in the description. The reaction is carried out at from 20° to 250° C., from 1 to 200 bar and in an ether as solvent. If desired, an alkaline alkali metal, alkaline earth metal or ammonium compound is used as additive.
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- Direct evidence for anchimeric assistance in alcohol elimination from gas-phase MH+ ions of 1,4-dialkoxycyclohexanes under chemical ionisation. Experiment and theory
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trans-1,4-Dialkoxycyclohexanes afford very abundant [MH - ROH]+ ions upon chemical ionisation (CI), in contrast to the cis-isomers, suggesting anchimeric assistance in the alcohol elimination from the MH+ ions of the trans-diethers. Collision induced dissociation (CID) measurements of the [MH - ROH]+ ions, obtained from various suitably deuterium labelled stereoisomeric 1-ethoxy-4-methoxycyclohexanes, indicated fromation of symmetrical bicyclic ethyl and methyl oxonium ions by an anchimerically assisted alcohol elimination from the trans-diethers. On the other hand these measurements suggest that the cis-isomers afford isomeric monocyclic O-protonated 4-alkoxycyclohexene cations, in which the hydrogens at positions 2 and 3 (as well as those at positions 5 and 6, and 1 and 4) are not equivalent. The two results, namely the symmetrical bicyclic structure and the high abundance of the [MH - ROH]+ ions in the CI mass spectra of the trans-diethers, in contrast to the non-symmetrical monocyclic structure and low abundance of these ions in the cis-isomers, are suggested to be direct evidence for anchimeric assistance in a gas-phase ion dissociation process. Ab initio calculations at the MP3/6-31G*//6-31G* level support the anchimerically assisted elimination mechanism observed in trans-1-ethoxy-4-methoxycyclohexane, but also show that the energy difference between the anchimerically assisted and non-assisted elimination mechanisms is small (ca. 2-3 kcal mol-1)(1 cal = 4.184 J).
- Shvily, Ronit,Mueller, Thomas,Apeloig, Yitzhak,Mandelbaum, Asher
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p. 1221 - 1234
(2007/10/03)
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- Method for preparing aromatic secondary amino compound
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Disclosed are (1) a method for preparing an aromatic secondary amino compound which comprises reacting an N-cyclohexylideneamino compound in the presence of a hydrogen moving catalyst and a hydrogen acceptor by the use of a sulfur-free polar solvent and/or a cocatalyst, and (2) a method for preparing an aromatic secondary amino compound which comprises reacting cyclohexanone or a nucleus-substituted cyclohexanone, an amine and a nitro compound corresponding to the amine in a sulfur-free polar solvent in the presence of a hydrogen moving catalyst, a cocatalyst being added or not added. In a further aspect, a method is provided for the preparation of aminodiphenylamine by reacting phenylenediamine and cyclohexanone in the presence of a hydrogen transfer catalyst in a sulfur-free polar solvent while using nitroaniline as a hydrogen acceptor.
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- Method for preparing aromatic secondary amino compound
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Disclosed are (1) a method for preparing an aromatic secondary amino compound which comprises reacting an N-cyclohexylideneamino compound in the presence of a hydrogen moving catalyst and a hydrogen acceptor by the use of a sulfur-free polar solvent and/or a cocatalyst, and (2) a method for preparing an aromatic secondary amino compound which comprises reacting cyclohexanone or a nucleus-substituted cyclohexanone, an amine and a nitro compound corresponding to the amine in a sulfur-free polar solvent in the presence of a hydrogen moving catalyst, a cocatalyst being added or not added.
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- Improvements in the synthesis of adamantane-2,6-dione and preparation of the novel adamantane-2,6-dione mono-ketal
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A facile seven-step synthesis of adamantane-2,6-dione is presented that involves minimal purification, provides multigram quantities of product, and proceeds in an overall yield of 21%. The mono-ketal of adamantane-2,6-dione is obtained in 18% overall yield.
- Ayres, Fred D.
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p. 7151 - 7154
(2007/10/02)
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- Enantioselective deprotonation of protected 4-hydroxycyclohexanones
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A series of derivatives of 4-hydroxycyclohexanone (1a-g) with the hydroxy group protected as a silyl ether (1a,b), ether (1d,g), an acetal (1c), or an ester (1e,f) were deprotonated with chiral, optically pure, lithium amides 3-9. The resulting non-racemic enolates were trapped as enol acetates. The enantioselectivity of deprotonation was up to 74percent ee.
- Majewski, Marek,Mackinnon, John
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p. 1699 - 1704
(2007/10/02)
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- Cardiotonic Agents. 1-Methyl-7-(4-pyridyl)-5,6,7,8-tetrahydro-3(2H)-isoquinolinones and Related Compounds. Synthesis and Activity
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A series of 1-methyl-7-(4-pyridyl)-5,6,7,8-tetrahydro-3(2H)-isoquinolinones and related compounds were synthesized and evaluated for positive inotropic activity.Most members of this series exerted a dose-dependent increase in myocardial contractility in the dog acute heart failure model, whereas they caused only slight changes in heart rate and blood pressure.Several derivatives, especially those with cyano, acetyl, and ethyl substituents at the 4-position, were more potent than milrinone, which was used as a reference. 4-Acetyl-1-methyl-7-(4-pyridyl)-5,6,7,8-tetrahydro-3(2H)-isoquinolinone (MS-857) is one of the most potent positive inotropic agents in this series.
- Kaiho, Tatsuo,San-nohe, Kunio,Kajiya, Seitaro,Suzuki, Tsuneji,Otsuka, Kengo,et al.
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p. 351 - 357
(2007/10/02)
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- Isoquinoline derivatives
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Isoquinoline derivatives represented by the general formula (I): STR1 wherein R1 denotes a hydrogen or halogen atom, or a nitro or acetyl group, and R2 denotes a hydrogen atom, or a methyl, methoxy, phenyl, 4-pyridyl or 2-pyridyl group, and therapeutically acceptable salts thereof have high cardiotonic activity and low toxicity.
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- 2-Cyanoaziridinyl-(1)-2-substituted-aziridinyl-(1)-methanes
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A 2-cyanoaziridinyl-(1)-2-substituted-aziridinyl-(1)-methane STR1 wherein R is a nitrile or carbamoyl group, and R1 and R2 each independently is a hydrogen atom, an aliphatic hydrocarbon radical containing up to 10 carbon atoms optionally substituted by hydroxyl, alkoxy, amino, alkylamino, dialkylamino, alkoxycarbonyl, cyano, 1, 2 or 3 halogens, cycloalkyl, phenyl or phenoxy; nitrile, carboxyl, alkoxycarbonyl or optionally hydrogenated monocyclic heteroaryl or phenyl optionally substituted by alkyl, alkoxy, hydroxy, alkoxcarbonyl, dialkylamino, alkylthio, trifluoromethyl, nitro, carbamoyl, nitrile, sulphonamido, hydroxyalkyl, methylenedioxy, or halogen; or R1 and R2, together with the carbon atom to which they are attached, form a ring containing up to 8 ring members of which at least one may be oxygen, sulphur, SO, SO2 NH, N-alkyl, N-acyl or N-alkoxycarbonylalkyl, and which can be substituted by alkyl, alkoxy, hydroxyl, alkylenedioxy, alkoxycarbonyl, hydroxyalkyl, alkoxycarbonylalkyl, dialkylamino, oxo or 2-cyanoaziridino groups, or can be fused to 1 or 2 benzene rings or can be bridged by alkylene radicals containing up to 3 carbon atoms. The compounds are characterized by cytostatic and immune response-stimulating activity.
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- Synthesis of analogues of N (2 chloroethyl) N' trans 4 methylcyclohexyl) N nitrosourea for evaluation as anticancer agents
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The superior activity of N (2 chloroethyl) N' (trans 4 methylcyclohexyl) N nitrosourea (MeCCNU) against advanced murine Lewis lung carcinoma in comparisons with the cis form and other nitrosoureas prompted the synthesis of a number of MeCCNU analogues, including several cis trans pairs. The methyl group was replaced by a variety of substituents (CO2H, CH2CO2H, CO2Me, CH2OAc, CH2Cl, OMe); the trans 3 methylcyclohexyl, cis 2 methyl 1,3 dithian 5 yl, cis and trans 2 methyl 1,3 dithian 5 yl tetraoxide, and 1 methylhexyl (open chain) analogues were also prepared. Preliminary tests against murine leukemia L1210 revealed therapeutic indices (ED50/LD10) ranging from 0.26 to 0.79; all but 3 analogues effected 50% cure rates at nontoxic doses, the open chain analogue being one of the least active. In terms of therapeutic index, diequatorial (trans 4) isomers were, with one exception, as active as or, in 4 of the 8 examples, somewhat more active than the corresponding axial equatorial (cis 4) isomers. In this series, 4 of the 5 2-fluoroethyl analogues prepared were clearly inferior to the corresponding 2 chloroethyl analogues.
- Johnston,McCaleb,Clayton,Frye,Krauth,Montgomery
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p. 279 - 290
(2007/10/04)
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