- Magnetic Fe3O4@chitosan nanoparticle: Synthesis, characterization and application as catalyst carrier
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A novel method was developed to prepare Fe3O4@CS beads with core-shell structure using a double-crosslinking process. Before the coating process, an unique crosslinking agent, glutaraldehyde (GA), was adsorbed onto the surface of Fe3O4 in advance, so the subsequent CS can uniformly coat around the magnetic core processed from the strong interaction between GA and CS, forming a perfect core-shell structure. The obtained Fe3O4@CS beads were followed by the Pd deposition through in-situ reduction method, and the prepared composite catalyst was applied exemplarily in synthesizing nabumetone to check its reusing property. The nanoparticles were characterized by transmission electron microscopy (TEM), X-ray powder diffraction (XRD), Fourier transformation infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and the magnetic hysteresis loop determination method. This novel composite catalyst showed admirable potential in reusable catalysis. Copyright
- He, Linghao,Yao, Lu,Liu, Fujun,Qin, Bing,Song, Rui,Huang, Wei
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Read Online
- MgO nanoparticle-based multifunctional catalysts in the cascade reaction allows the green synthesis of anti-inflammatory agents
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Up to now, the anti-inflammatory agent nabumetone has been synthesized by a two-step process involving either a Heck reaction between 6-bromo-2-methoxynaphthalene and methyl vinyl ketone or a condensation between 6-methoxy-2 naphthaldehyde and acetone to give an intermediate that is separated, purified, and hydrogenated in a second and separate process to give the final product, while producing a large amount of waste products. Here we report a residue-free catalytic process for the production of nabumetone with ≥ 98 % yield and 100% selectivity achieved through a cascade reaction system involving a multifunctional base/acid/hydrogenation catalyst based on nanocrystalline (~3 nm) MgO.
- Climent, Maria Jose,Corma, Avelino,Iborra, Sara,Mifsud, Maria
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Read Online
- A Low Rhodium Content Smart Catalyst for Hydrogenation and Hydroformylation Reactions
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Abstract: This paper describes the preparation, broad characterization and study of activity in hydrogenation and hydroformylation reactions of an easily produced 0.18% Rh/Al2O3. Analytical studies on fresh and recycled samples shed light on the smart properties of such catalyst. Results showed high activity as well as fine/excellent chemoselectivity or regioselectivity, characteristics that may suggest a wide range of applicability. Graphic Abstract: The low metal content catalyst 0.18% Rh/Al2O3 was very active in both hydrogenation and hydroformylation reactions so providing intermediates for valuable APIs, as Nabumetone and Eletriptan, and a fragrance with a fresh, green-floral smell, that recalls scent of lily of the valley.[Figure not available: see fulltext.]
- Paganelli, Stefano,Tassini, Riccardo,Rathod, Vikas D.,Onida, Barbara,Fiorilli, Sonia,Piccolo, Oreste
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p. 1508 - 1521
(2020/10/15)
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- Direct Access to Isotopically Labeled Aliphatic Ketones Mediated by Nickel(I) Activation
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An extensive range of functionalized aliphatic ketones with good functional-group tolerance has been prepared by a NiI-promoted coupling of either primary or secondary alkyl iodides with NN2 pincer NiII-acyl complexes. The latter were easily accessed from the corresponding NiII-alkyl complexes with stoichiometric CO. This Ni-mediated carbonylative coupling is adaptable to late-stage carbon isotope labeling, as illustrated by the preparation of isotopically labelled pharmaceuticals. Preliminary investigations suggest the intermediacy of carbon-centered radicals.
- Donslund, Aske S.,Pedersen, Simon S.,Gaardbo, Cecilie,Neumann, Karoline T.,Kingston, Lee,Elmore, Charles S.,Skrydstrup, Troels
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supporting information
p. 8099 - 8103
(2020/03/16)
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- Environmentally responsible, safe, and chemoselective catalytic hydrogenation of olefins: ppm level Pd catalysis in recyclable water at room temperature
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Textbook catalytic hydrogenations are typically presented as reactions done in organic solvents and oftentimes under varying pressures of hydrogen using specialized equipment. Catalysts new and old are all used under similar conditions that no longer reflect the times. By definition, such reactions are both environmentally irresponsible and dangerous, especially at industrial scales. We now report on a general method for chemoselective and safe hydrogenation of olefins in water using ppm loadings of palladium from commercially available, inexpensive, and recyclable Pd/C, together with hydrogen gas utilized at 1 atmosphere. A variety of alkenes is amenable to reduction, including terminal, highly substituted internal, and variously conjugated arrays. In most cases, only 500 ppm of heterogeneous Pd/C is sufficient, enabled by micellar catalysis used in recyclable water at room temperature. Comparison with several newly introduced catalysts featuring base metals illustrates the superiority of chemistry in water.
- Gallou, Fabrice,Gao, Eugene S.,Lipshutz, Bruce H.,Takale, Balaram S.,Thakore, Ruchita R.
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supporting information
p. 6055 - 6061
(2020/10/14)
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- A CATALYST FOR ONE POT SYNTHESIS OF NABUMETONE AND PROCESS OF PREPARATION THEREOF
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The present invention relates to novel heterogeneous catalyst composition for selective synthesis of Nabumetone in one pot process and process to prepare the catalyst. The present invention provides a novel catalyst comprises of Lanthanum, Magnesium, and Nickel particles doped on specific type of silica support, preferably that the support is in amorphous nature. The catalyst is having bifunctional condensation and hydrogenation properties for one pot synthesis of Nabumetone comprising of: Nickel and Lanthanum-magnesium mixed oxide on support of mesoporous silica; Wherein 25 to 30 % w/w of Lanthanum-magnesium mixed oxide are entrapped in pores and surface of support is coated with 3 to 5% w/w Nickel with the result that it prevent the leaching of Lanthanum-magnesium mixed oxide in reaction medium and provides reusability of catalyst.
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Page/Page column 2; 13-17
(2020/11/30)
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- Aldehydes as Alkylating Agents for Ketones
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Common and non-toxic aldehydes are proposed as reagents for alkylation of ketones instead of carcinogenic alkyl halides. The developed reductive alkylation reaction proceeds in the presence of the commercially available ruthenium catalyst [(cymene)RuCl2]2 (as low as 250 ppm) and carbon monoxide as the reducing agent. The reaction works well for a broad substrate scope, including aromatic and aliphatic aldehydes and ketones. It can be carried out without a solvent and often gives nearly quantitative yields of the products. This straightforward and cost-effective method is promising not only for laboratory application but also for industry, which produces carbon monoxide as a large-scale waste product.
- Runikhina, Sofiya A.,Afanasyev, Oleg I.,Biriukov, Klim,Perekalin, Dmitry S.,Klussmann, Martin,Chusov, Denis
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supporting information
p. 16225 - 16229
(2019/11/22)
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- From Alkyl Halides to Ketones: Nickel-Catalyzed Reductive Carbonylation Utilizing Ethyl Chloroformate as the Carbonyl Source
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Ketones are an important class of molecules in synthetic and medicinal chemistry. Rapid and modular synthesis of ketones remains in high demand. Described here is a nickel-catalyzed three-component reductive carbonylation method for the synthesis of dialkyl ketones. A wide range of both symmetric and asymmetric dialkyl ketones can be accessed from alkyl halides and a safe CO source, ethyl chloroformate. The approach offers complementary substrate scope to existing carbonylation methods while avoiding the use of either toxic CO or metal carbonyl reagents.
- Shi, Renyi,Hu, Xile
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supporting information
p. 7454 - 7458
(2019/04/30)
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- Application of Silicon-Initiated Water Splitting for the Reduction of Organic Substrates
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The use of water as a donor for hydrogen suitable for the reduction of several important classes of organic compounds is described. It is found that the reductive water splitting can be promoted by several metalloids among which silicon shows the best efficiency. The developed methodologies were applied for the reduction of nitro compounds, N-oxides, sulfoxides, alkenes, alkynes, hydrodehalogenation as well as for the gram-scale synthesis of several substrates of industrial importance.
- Gevorgyan, Ashot,Mkrtchyan, Satenik,Grigoryan, Tatevik,Iaroshenko, Viktor O.
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p. 375 - 382
(2018/06/04)
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- An easily recoverable and recyclable homogeneous polyester-based Pd catalytic system for the hydrogenation of α,β-unsaturated carbonyl compounds
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Abstract Homogeneous catalysis is an efficient tool to carry out hydrogenation processes but the major drawback is represented by the separation of the expensive catalyst from the product mixture. In this view we prepared a polyester-based Pd catalytic system that offers the advantages of both homogenous and heterogeneous catalyses: efficacy, selectivity and recyclability. Here its application in the hydrogenation of selected α,β-unsaturated carbonyl compounds is described.
- Bartoli, Mattia,Rosi, Luca,Petrucci, Giorgio,Armelao, Lidia,Oberhauser, Werner,Frediani, Marco,Piccolo, Oreste,Rathod, Vikas Damu,Paganelli, Stefano
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p. 228 - 233
(2015/07/20)
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- A scalable two-step continuous flow synthesis of nabumetone and related 4-aryl-2-butanones
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Three different continuous flow strategies for the generation of important 4-aryl-2-butanone derivatives including the anti-inflammatory drug nabumetone [4-(6-methoxy-2-naphthalenyl)-2-butanone] and the aroma compounds raspberry ketone [4-(4-hydroxyphenyl)-2-butanone] and its methyl ether [4-(4-methoxyphenyl)-2-butanone] were evaluated. All three protocols involve the initial preparation of the corresponding 4-aryl-3-buten-2-ones via Mizoroki-Heck, Wittig, or aldol strategies, which is then followed by selective hydrogenation of the C=C double bond to the desired 4-aryl-2-butanones. The synthetic routes to 4-aryl-3-buten-2-ones were first optimized/intensified on small scale to reaction times of 1-10 min using batch microwave heating technology and then translated to a scalable continuous flow process employing commercially available stainless steel capillary tube reactors. For the synthesis of 4-(4-methoxyphenyl)-3-buten-2-one a further scale-up using a custom-built mesofluidic mini-plant flow system capable of processing several liters per hour was designed to further expand the scale of the process. The final hydrogenation step was performed using a fixed-bed continuous flow hydrogenator employing Ra/Ni as a catalyst.
- Viviano, Monica,Glasnov, Toma N.,Reichart, Benedik,Tekautz, Guenter,Kappe, C. Oliver
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p. 858 - 870
(2012/06/30)
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- A PRODRUG COMPRISING BETA-KETO CARBOXYLIC ACID, BETA-KETO CARBOXYLIC ACID SALT OR BETA-KETO CARBOXYLIC ACID ESTER FOR DRUG DELIVERY
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There is provided a prodrug of a pharmaceutically active agent, said prodrug comprising a beta-keto carboxylic acid, a beta-keto carboxylic acid salt or a beta-keto carboxylic acid ester functional group, to a pharmaceutical composition comprising the prodrug, and to the use of the prodrug or composition for treatment of a mammalian subject suffering from a condition which can be cured or alleviated by administration of said pharmaceutically active agent. There is further provided a method of inhibiting decarboxylation of a compound comprising a beta-keto carboxylic acid or a salt thereof with a monovalent cation, characterized in that a dry salt of said beta-keto carboxylic acid with a divalent or polyvalent cation is prepared.
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Page/Page column 68-88
(2010/11/04)
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- Direct cobalt-catalyzed conjugate addition of functionalized aryl halides and triflates: A new strategy for the conjugate addition onto methyl vinyl ketone
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An efficient cobalt-catalyzed method for the direct conjugate addition of functionalized aryl halides or triflates onto methyl vinyl ketone is described. The experimentally simple procedure relies on the use of a catalytic system consisting of CoBr2(Bpy) and zinc and does not require the preformation of a stoichiometric organometallic species. The approach described herein displays considerable functional-group compatibility at good to excellent yields. Georg Thieme Verlag Stuttgart.
- Amatore, Muriel,Gosmini, Corinne
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experimental part
p. 1073 - 1076
(2009/10/10)
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- Arylation of allyl alcohols in organic and aqueous media catalyzed by oxime-derived palladacycles: Synthesis of β-arylated carbonyl compounds
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A 4-hydroxyacetophenone oxime-derived palladacycle catalyzes the Mizoroki-Heck reaction of allyl alcohols with aryl iodides, bromides, and chlorides in aqueous and organic solvents. The reaction takes place in the presence of dicyclohexylmethylamine or cesium carbonate as bases, the addition of tetrabutylammonium bromide (TBAB) as additive for aryl bromides and chlorides being necessary. Under these reaction conditions, β-arylated aldehydes and ketones are mainly obtained using a rather low loading of palladium (0.1-1 mol%). Similar catalytic activity is shown by a Kaiser oxime resin-derived palladacycle, which allows one to perform recycling and reusing experiments with low Pd leaching. The high regio- and chemoselectivity observed supported that these palladacycles, working as a source of Pd(0) species, operates mainly through a neutral mechanism. This methodology has been applied to the synthesis of important β-arylated carbonyl compounds, such as 4-phenylbutan-2-one, 4-(4-hydroxyphenyl)butan-2-one, dihydrochalcones, the anti-inflamatory nabumetone, and the fragance β-lilial. γ-Arylation is observed in the reactions of allyl alcohol and but-3-en-2-ol with 2-iodoaniline giving mainly the corresponding quinolines. The same tendency is observed in the case of 1,1-dimethylallyl alcohol affording either γ-arylated alcohols or (E)-1-arylisoprenes.
- Alacid, Emilio,Najera, Carmen
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p. 2572 - 2584
(2008/09/19)
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- A convenient synthesis of Nabumetone - An anti-inflammatory drug candidate
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A facile and industrially viable approach to Nabumetone (an ami-inflammatory agent) is reported.
- Srinivasulu,Reddy, A. Raghupathi,Nagaraju,Reddy, P. Pratap,Reddy, M. Satyanarayana
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p. 207 - 208
(2007/10/03)
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- A facile direct conversion of aldehydes to esters and amides using acetone cyanohydrin
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Aromatic aldehydes with electron-withdrawing groups undergo rapid reactions with a variety of alcohols and secondary amines to afford the corresponding esters and amides, respectively, in high yields, when treated with NaCN or acetone cyanohydrin and base under ambient reaction conditions. In case of α,β-unsaturated aldehydes, simultaneous reduction of the CC bond along with esterification occurred to produce the saturated esters in high yields.
- Raj, I. Victor Paul,Sudalai
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p. 8303 - 8306
(2007/10/03)
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- Arylation of allylic alcohols in ionic liquids catalysed by a Pd-benzothiazole carbene complex
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The reaction of aryl bromides with allylic alcohols catalysed by a Pd-benzothiazole carbene complex, in tetrabutylammonium bromide as solvent, leads principally to β-arylated carbonyl compounds. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.
- Calo, Vincenzo,Nacci, Angelo,Monopoli, Antonio,Spinelli, Michele
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p. 1382 - 1385
(2007/10/03)
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- Nickel-catalyzed electrochemical arylation of activated olefins
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Nickel-catalyzed electrochemical conjugate additions of substituted aryl bromides to activated olefins under recently optimized reaction conditions are reported. Good to high yields were obtained, whatever the nature of substituents in the meta- and para-positions of the benzene ring. In the ortho-substituted series, yields were good with electron-donating substituents, but low with electron-withdrawing groups. The activation of aryl chlorides and the sequential functionalization of aryl dihalides were also investigated.
- Condon, Sylvie,Dupre, Daniel,Falgayrac, Gilles,Nedelec, Jean-Yves
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p. 105 - 111
(2007/10/03)
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- Heck arylation of allylic alcohols in molten salts
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The Heck coupling of ArX (X=I, Br) with allylic alcohols, carried out at 80-120°C in molten n-Bu4NBr using NaHCO3 as base and PdCl2 as catalyst without extra ligands, leads to the corresponding β-arylated carbonyl compounds. After extraction of the organic materials with diethyl ether, the ionic layer can be reused directly.
- Bouquillon, Sandrine,Ganchegui, Benjamin,Estrine, Boris,Hénin, Fran?oise,Muzart, Jacques
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p. 153 - 156
(2007/10/03)
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- Process research and structural studies on nabumetone
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A short, simple and economical process for large-scale preparation of nabumetone has been developed. The single-crystal structures of nabumetone and one of its key intermediates have been determined by X-ray diffraction studies. Two impurities have been isolated and characterised.
- Prabhakar,Reddy, C. Bakki,Reddy, Ch. Maheedhara,Nageshwar,Devi, A. Sivalakshmi,Babu, J. Moses,Vyas,Sarma,Reddy
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p. 121 - 125
(2013/09/08)
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- Process for the synthesis of nabumetone
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New process for the synthesis of the antiinflammatory drug known as nabumetone that consists in reacting 2-acetyl-5-bromo-6-methoxynaphthalene with an alkyl acetate in presence of an alkaline alcoholate to get 4-(5-bromo-6-methoxy-2-naphthyl)-4-hydroxybut-3-en-2-one that by catalytic hydrogenation in a polar solvent and in presence of a base gives 4-(6-methoxy-2-naphthyl)butan-2-one known as nabumetone.
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- Production of nabumetone or precursors thereof
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In producing nabumetone or precursor thereof, use is made of 2-bromo-6-methoxynaphthalene formed by (a) methylating 6-bromo-2-naphthol with methyl bromide or methyl chloride, in a halogen-free liquid solvent comprising at least about 40% by weight of one or more compounds of the formula RZ where R is a hydrogen atom or an alkyl group, and Z is a hydroxyl group or a cyanide group with the proviso that if Z is a cyanide group, R is an alkyl group, and in the presence of at least one strong base; and (b) recovering and purifying 2-bromo-6-methoxynaphthalene so formed. The 6-bromo-2-naphthol in turn is preferably formed by reacting 1,6-dibromo-2-naphthol with hydrogen in a halogen-containing liquid solvent comprising at least about 50% by weight of (A) at least one liquid organic halide solvent in which the halogen content has an atomic number of 35 or less or (B) a mixture of water and at least one such liquid organic halide solvent, and in the presence of catalytic amounts of (i) a tungsten carbide-based catalyst, and (ii) at least one phase transfer catalyst, most preferably while purging HBr from the reaction mixture as it is formed. In this way, the quantities of by-products formed in the overall operation are reduced, the need for use of excess iron and/or dimethyl sulfate as reaction components is avoided, and the overall efficiency of plant operation is improved especially when conducted on a large scale.
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- Process for the preparation of a naphthylbutanone
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An expedient synthesis of 4-(6-methoxynaphth-2-yl)-2-butanone is carried out by reacting 2-bromo-6-methoxynaphthalene with 3-ethylenedioxybutene in the presence of PdCl2 and triphenylphosphine, hydrogenating the 6-methoxy-2-(3-ethylene-dioxybuten-1-yl)naphthalene obtained and then hydrolysing the latter with an acid.
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- Process for the preparation of a naphthylbutanone
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An expedient synthesis of 4-(6-methoxynaphth-2-yl)-2-butanone is carried out by reacting 2-bromo-6-methoxynaphthalene with 3-ethylenedioxybutene in the presence of PdCl2and triphenylphosphine, hydrogenating the 6-methoxy-2-(3-ethylene-dioxybuten-1-yl)naphthalene obtained and then hydrolysing the latter with an acid.
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- Process for the synthesis of nabumetone
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New process for the synthesis of the antiinflammatory drug known as nabumetonethat consists in reacting 2-acetyl-5-bromo-6-methoxynaphthalene with an alkyl acetate in presence of an alkaline alcoholate to get 4-(5-bromo-6-methoxy-2-naphthyl)-4-hydroxybut-3-en-2-one that by catalytic hydrogenation in a polar solvent and in presence of a base gives 4-(6-methoxy-2-naphthyl)butan-2-one known as nabumetone.
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- Palladium(II)-Catalyzed Conjugate Addition of Aromatics to α,β-Unsaturated Ketones and Aldehydes with Arylantimony Compounds
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Triarylstibines react with α,β-unsaturated ketones and aldehydes in acetic acid at room temperature in the presence of AgOAc and a catalytic amount of Pd(OAc)2 to afford the conjugate addition products (the formal hydroarylated compounds to an olefinic part) in good yields. In contrast, diarylantimony chlorides, arylantimony dichlorides, and diphenylantimony acetate react with the enones and enals even in the absence of AgOAc to afford the same products in higher yields compared with those from triarylstibines. These are new C-C bond-forming reactions using arylantimony(III) compounds in which the formation of a palladium enolate or a trivalent antimony enolate is proposed as an intermediate.
- Cho, Chan Sik,Motofusa, Shin-Ichi,Ohe, Kouichi,Uemura, Sakae
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p. 2341 - 2348
(2007/10/03)
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- Chemical Process
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The present invention relates to a process for the preparation of 4-(61 -methoxy-21 -naphthyl)butan-2-one and to certain compounds for use in that process. British Pat. Spec. No. 1,474,377 discloses inter alia that 4-(61 -methoxy-21 -naphthyl) butan-2-one possesses useful anti-inflammatory activity. A particularly favored process has now been discovered that can be used to produce 4-(61 -methoxy-21 -naphthyl) butan-2-one in particularly good yield. The present invention provides a process for the preparation of 4-(61 -methoxy-21 -naphthyl)butan-2-one which process comprises the hydrogenation of a compound of the formula (I): STR1 wherein Ar is a 6-methoxy-2-naphthyl group; X and Y are each hydrogen atoms or together represent a second bond between the carbon atoms to which they are attached; and R is a group such that --CO2 R represents an ester group convertible by hydrogenation to a CO2 H group.
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- Preparation of 4(6'-methoxy-2'-naphthyl)butan-2-one
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This invention provides a process for the preparation of 4-(6'-methoxy-2'naphthyl)-butan-2-one, which process comprises the hydrogenation of 4-(6' methoxy-2'-naphthyl)-4-hydroxy-but-3-en-2-one.
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