- Cobalt-catalyzed addition of arylzinc reagents to norbornene derivatives through 1,4-cobalt migration
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A cobalt-diphosphine catalyst promotes the addition of an arylzinc reagent to a norbornene derivative to afford o-(2-exo-norbornyl)arylzinc species. This migratory arylzincation reaction is considered to involve insertion of norbornene into an arylcobalt species, alkyl-to-aryl 1,4-cobalt migration, and transmetalation between the resulting o-(2-exo-norbornyl)arylcobalt species and the arylzinc reagent. The o-(2-exo-norbornyl)arylzinc species can be intercepted by common organic electrophiles under copper or palladium catalysis.
- Tan, Boon-Hong,Yoshikai, Naohiko
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Read Online
- Transition metal catalyzed preparation of Grignard compounds
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The "inorganic Grignard reagents", in particular those of 1, have surprisingly been shown to be efficient homogeneous catalysts for the conversion of inactive chloroarenes and heteroarenes (via the aryl-iron intermediate 2) into the corresponding Grignard
- Bogdanovi, Borislav,Schwickardi, Manfred
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Read Online
- Mechanistic studies into visible light-driven carboxylation of aryl halides/triflates by the combined use of palladium and photoredox catalysts
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The reaction mechanism of palladium-catalyzed visible light-driven carboxylation of aryl halides and triflates with a photoredox catalyst was examined in detail. Experimental and theoretical studies indicated that the active species for photoredox- catalyzed reduction was cationic ArPd(II)+ species to generate nucleophilic ArPd(I) or its further reduced ArPd(0)- species, which reacted with CO2 to give carboxylic acids. Hydrodehalogenated compounds, main byproducts in this carboxylation, were thought to be generated by protonation of these reduced species.
- Caner, Joaquim,Iwasawa, Nobuharu,Martin, Ruben,Murata, Kei,Shimomaki, Katsuya,Toriumi, Naoyuki
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supporting information
p. 1846 - 1853
(2021/08/13)
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- Photo-induced thiolate catalytic activation of inert Caryl-hetero bonds for radical borylation
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Substantial effort is currently being devoted to obtaining photoredox catalysts with high redox power. Yet, it remains challenging to apply the currently established methods to the activation of bonds with high bond dissociation energy and to substrates with high reduction potentials. Herein, we introduce a novel photocatalytic strategy for the activation of inert substituted arenes for aryl borylation by using thiolate as a catalyst. This catalytic system exhibits strong reducing ability and engages non-activated Caryl–F, Caryl–X, Caryl–O, Caryl–N, and Caryl–S bonds in productive radical borylation reactions, thus expanding the available aryl radical precursor scope. Despite its high reducing power, the method has a broad substrate scope and good functional-group tolerance. Spectroscopic investigations and control experiments suggest the formation of a charge-transfer complex as the key step to activate the substrates.
- K?nig, Burkhard,Wang, Hua,Wang, Shun
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p. 1653 - 1665
(2021/06/17)
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- H2-Free Selective Dehydroxymethylation of Primary Alcohols over Palladium Nanoparticle Catalysts
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The dehydroxymethylation of primary alcohols is a promising strategy to transform biomass-derived oxygenates into hydrocarbon fuels. In this study, a novel, highly efficient, and reusable heterogeneous catalyst system was established for the H2-free dehydroxymethylation of primary alcohol using cerium oxide-supported palladium nanoparticles (Pd/CeO2). A wide range of aliphatic and aromatic alcohols including biomass-derived alcohols were converted into the corresponding one-carbon shorter hydrocarbons in high yields in the absence of any additives, accompanied by the production of H2 and CO. Pd/CeO2 was easily recovered from the reaction mixture and reused, retaining its high activity, thus, providing a simple and sustainable methodology to produce hydrocarbon fuels from biomass-derived oxygenates.
- Yamaguchi, Sho,Kondo, Hiroki,Uesugi, Kohei,Sakoda, Katsumasa,Jitsukawa, Koichiro,Mitsudome, Takato,Mizugaki, Tomoo
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p. 1135 - 1139
(2020/12/29)
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- Efficient base-free hydrodehalogenation of organic halides catalyzed by a well-defined diphosphine-ruthenium(II) complex
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A base-free, robust catalytic system based on the diphosphine-ruthenium(II) complex cation has been developed for the hydrodehalogenation of a wide range of aryl- and alkyl-chlorides/bromides (27 examples) with molecule hydrogen. Notably, the reaction proceeds at 120 °C with low catalyst loading (0.1 mol%) and exhibits a good tolerance toward functional groups, such as amido, carboxyl, sulfonyl, methoxyl, ester groups. All dehalogenation products are confirmed by GC, GC–MS and NMR spectroscopy. Moreover, a mechanism for the diphosphine-ruthenium(II) complex cation catalyzed dehalogenation process has been proposed. This hydrodehalogenation methodology shows a potential application for the organic transformation and degradation of organic halides.
- Gao, Pengxiang,Liu, Qingbin,Liu, Yahuan,Ma, Ning,Wang, Zheng,Zhao, Ziwei
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- A method of synthesis of piperonolamine
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The present invention belongs to the field of organic chemical synthesis, specifically relates to a synthesis method of piperine, comprising: using catechol as a raw material to prepare piperonaldehyde; β - nitro-3,4-dioxenosylstyrene prepared with piperonaldehyde; β - nitro -3,4-dioxenesimethylenestyrene to obtain piperine ethylamine. Among them, the preparation of piperaldehyde from catechol as raw materials includes two ways: (1) catechol→3,4-dihydroxymandelic acid→3,4-dihydroxybenzaldehyde→ piperaldehyde; (2) catechol→ piperine ring → piperine. The raw materials used in the present invention are safe and readily available, low cost; the reaction conditions are mild, the operation is simple, the chemical yield is high, and the intermediate reagents are easy to recover; suitable for industrial production.
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Paragraph 0144-0147; 0157-0160
(2022/01/07)
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- Catalytic Reductions Without External Hydrogen Gas: Broad Scope Hydrogenations with Tetrahydroxydiboron and a Tertiary Amine
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Facile reduction of aryl halides with a combination of 5% Pd/C, B2(OH)4, and 4-methylmorpholine is reported. Aryl bromides, iodides, and chlorides were efficiently reduced. Aryl dihalides containing two different halogen atoms underwent selective reduction: I over Br and Cl, and Br over Cl. Beyond these, aryl triflates were efficiently reduced. This combination was broadly general, effectuating reductions of benzylic halides and ethers, alkenes, alkynes, aldehydes, and azides, as well as for N-Cbz deprotection. A cyano group was unaffected, but a nitro group and a ketone underwent reduction to a low extent. When B2(OD)4 was used for aryl halide reduction, a significant amount of deuteriation occurred. However, H atom incorporation competed and increased in slower reactions. 4-Methylmorpholine was identified as a possible source of H atoms in this, but a combination of only 4-methylmorpholine and Pd/C did not result in reduction. Hydrogen gas has been observed to form with this reagent combination. Experiments aimed at understanding the chemistry led to the proposal of a plausible mechanism and to the identification of N,N-bis(methyl-d3)pyridin-4-amine (DMAP-d6) and B2(OD)4 as an effective combination for full aromatic deuteriation. (Figure presented.).
- Korvinson, Kirill A.,Akula, Hari K.,Malinchak, Casina T.,Sebastian, Dellamol,Wei, Wei,Khandaker, Tashrique A.,Andrzejewska, Magdalena R.,Zajc, Barbara,Lakshman, Mahesh K.
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supporting information
p. 166 - 176
(2020/01/02)
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- PROCESS FOR THE PREPARATION OF 2,2-DIFLUORO-1,3-BENZODIOXOLE AND INTERMEDIATES THEREOF
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The present invention relates to a process for preparing 2,2-difluoro-1,3-benzodioxole. The process comprises a step of reacting 1,3-benzodioxole with chlorine in benzotrifluoride in the present of a radical initiator. The present invention also relates to the process for preparing 2,2-dichloro-1,3-benzodioxole which is used as an intermediate in preparation of 2,2-difluoro-1,3-benzodioxole.
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Page/Page column 5
(2020/05/15)
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- Synthetic method for preparing benzodioxole under catalysis of composite alkali
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The invention discloses a synthetic method for preparing benzodioxole under the catalysis of a composite alkali. According to the method, in a weakly alkaline environment subjected to nitrogen replacement or protection, N-methyl pyrrolidone is used as a solvent medium, catechol and dihaloalkane are used as raw materials, dichloromethane continuously added in a synthesis process is azeotropic withwater generated in a reaction, and dichloromethane refluxes into a reaction container again after water separation, so that benzodioxole is synthesized.
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Paragraph 0023-0030
(2020/04/22)
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- RhI-Catalyzed PIII-Directed C?H Bond Alkylation: Design of Multifunctional Phosphines for Carboxylation of Aryl Bromides with Carbon Dioxide
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We report the C?H alkylation of biarylphosphines at the ortho′ position(s) with alkenes by using rhodium(I) catalysis, which provides straightforward access to a large library of multifunctionalized phosphines. Some of these modified ligands outperformed commercially available phosphines in the Pd-catalyzed carboxylation of aryl bromides with carbon dioxide in the presence of a photoredox catalyst.
- Zhang, Zhuan,Roisnel, Thierry,Dixneuf, Pierre H.,Soulé, Jean-Fran?ois
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supporting information
p. 14110 - 14114
(2019/08/30)
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- Palladium-Catalyzed Visible-Light-Driven Carboxylation of Aryl and Alkenyl Triflates by Using Photoredox Catalysts
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A visible-light-driven carboxylation of aryl and alkenyl triflates with CO2 is developed by using a combination of Pd and photoredox catalysts. This reaction proceeds under mild conditions and can be applied to a wide range of substrates including acyclic alkenyl triflates.
- Shimomaki, Katsuya,Nakajima, Tomoya,Caner, Joaquim,Toriumi, Naoyuki,Iwasawa, Nobuharu
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supporting information
p. 4486 - 4489
(2019/06/24)
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- Synthesis of Arylacetaldehydes by Iridium-Catalyzed Arylation of Vinylene Carbonate with Arylboronic Acids
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The one-step synthesis of arylacetaldehydes by carbon–carbon bond formation between formylmethyl and aryl groups has been realized by the reaction of vinylene carbonate with arylboronic acids in the presence of an iridium/bisphosphine catalyst and a catalytic amount of tetrahydroxydiboron.
- Wang, Zhe,Xue, Fei,Hayashi, Tamio
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supporting information
p. 11054 - 11057
(2019/07/17)
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- Preparation method of benzodioxole
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The invention discloses a preparation method of benzodioxole. The preparation method comprises the following steps: with DMSO, dichloromethane and sodium hydroxide as base materials, controlling a temperature to be not higher than 100 DEG C in a microwave heating manner, dropwise adding a DMSO solution of catechol, and separating out the product benzodioxole and dichloromethane after a reaction isfinished. The preparation method is low in price, mild in reaction conditions, low in the generation amount of wastewater and good in process safety, can realize green recycling of an organic solvent, and reduces production cost.
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Paragraph 0014; 0016-0022
(2019/12/25)
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- Method for total synthesis of berberine with guaiacol as raw material
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The invention discloses a method for total synthesis of berberine with guaiacol as a raw material. According to a drug synthesis method, guaiacol serves as the raw material, 2-hydroxy-3-methoxybenzaldehyde is obtained through a selective formylation reaction, 2,3-dimethoxybenzaldehyde is obtained through a methylation reaction, pentamethyleneamine is obtained through a methylenenation reaction with catechol as a raw material, and homopiperony lamine is obtained through a one-step catalytic addition reaction; 2,3-dimethoxybenzaldehyde and homopiperony lamine are subjected to a one-pot condensation hydrogenation reaction under the condition of a nickel-based catalyst, hydrochloric acid is added to a reaction product, a crystal substance is cooled, after the reaction product is refined, hydrochloric acid is added, and cooling crystallization and filtration washing are conducted to obtain the product berberine. According to the method, the technology is simplified, and the use of toxic cyanide is avoided; 2,3-dimethoxybenzaldehyde and homopiperony lamine are subjected to a one-pot condensation hydrogenation and salifying technology, the time is saved, the energy is saved, and the costis lowered; in the technological process, solvents are recycled.
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Paragraph 0015; 0016
(2019/04/26)
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- Method for preparing homopiperonyl amine by taking pyrocatechol as raw material
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A method for preparing homopiperonyl amine by taking pyrocatechol as the raw material relates to medicine preparing methods. The method comprises, firstly, taking the pyrocatechol with a purity degreeof 99 w% as the raw material, dimethyl sulfoxide as solvent and potassium carbonate as acid-binding agent to have methylenenation reaction with dichloromethane at 130 DEG C to obtain benzodioxole; secondly, taking ethyl acetate as solvent to perform one-step addition reaction on the benzodioxole and home-made 2-chlorethamin at 65 DEG C and with existence of catalysts to obtain homopiperonyl amine, and performing alkali neutralization; thirdly, evaporating the ethyl acetate from the reaction liquid, cooling down the reaction liquid for crystallization, and vacuumizing, filtering and drying crystals; fourthly, recrystallizing the initial product in absolute ethyl alcohol to obtain the finished homopiperonyl amine. The method for preparing the homopiperonyl amine by taking pyrocatechol as the raw material is simple in process, reduces the cost, avoids application of toxic cyanides and achieves green and sustainable processes as well as significant economic and social benefits.
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Paragraph 0010; 0012
(2019/05/02)
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- Method for fully synthesizing berberine
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The invention discloses a method for fully synthesizing berberine, and relates to a drug synthesis method. The method realizes the industrial full synthesis production of the berberine and is made from a bulk organic raw material catechol, the raw material is easily available, and the price is low; 2,3-dimethoxybenzaldehyde is obtained through selective formylation and methylation of the catechol;after a piperonyl ring is obtained through a catechol methylenenation reaction, piperonyl amine is synthesized through a one-step catalytic addition reaction, so that the synthesis steps of the piperonyl amine are shortened, the use of toxic cyanide is avoided, and the process is green and sustainable; condensation hydrogenation and salification reactions adopt a 'one-pot method', and thus the time and the energy are saved, and the cost is decreased. Industrialized full synthesis production of the berberine opens up large-scale production of the berberine, meets the clinical and research needs of the berberine in current anti-tumor, anti-blood pressure, anti-heart rhythm, blood sugar reduction, treatment of Alzheimer's disease and the like, provides effective drugs for reducing pain of patients, and has remarkable economic and social benefits.
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Paragraph 0013; 0015
(2019/04/17)
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- The invention relates to a catechol is raw material of synthetic small bo hong alkali method (by machine translation)
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The invention relates to a catechol is raw material of synthetic small bo hong alkali method, relates to a method for drug synthesis, in order to catechol as raw materials, with the catechol 2 - methyl chloride selective methylation reaction get O-methoxyphenol, continue to selective hydroformylation reaction to obtain the 2 - hydroxy - 3 - methoxybenzaldehyde; with the catechol 2 - methyl chloride methylene compounds obtained by reaction of pepper link, to continue to work with 2 - chloroethylamine catalytic addition reaction pepper ethylamine; the pepper ethylamine with 2 - hydroxy - 3 - methoxybenzaldehyde in a nickel-based catalyst "one-pot" condensation under the conditions of the hydrogenation reaction, the reaction product is hydrochloric acid, cooling of the crystal, and filtering to obtain the hydrochloride condensate; will be hydrochloride compression compound refined, continue to work with the glyoxal, under the condition of a copper-based catalyst, a cyclization reaction is carried out, the reaction product after passing through the refining process, hydrochloric acid, cooling crystallization, filtration washing to obtain the product of the ABS red alkali. The industrialization of this invention fully synthetic production of the ABS red alkali, to create a small bo hong alkali drug chemical synthesis method. (by machine translation)
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Paragraph 0023
(2019/05/15)
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- The invention relates to a raw material for the preparation of the ABS guaiacol red alkali method (by machine translation)
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The invention relates to a raw material for the preparation of the ABS guaiacol red alkali method, relates to a pharmaceutical preparation method, the present invention in order to guaiacol as raw materials, through the selective hydroformylation reaction to obtain the 2 - hydroxy - 3 - methoxybenzaldehyde; to catechol as raw materials, the reaction methylene compounds pepper link, catalytic addition a footwork of to the pepper ethylamine; 2 - hydroxy - 3 - methoxy benzaldehyde with pepper ethylamine in a nickel-based catalyst "one-pot" condensation under the conditions of the hydrogenation reaction, the reaction product is hydrochloric acid, cooling of the crystal, the hydrochloride compression compound crystal refined, continue to work with the glyoxal, under the condition of a copper-based catalyst, a cyclization reaction is carried out, the reaction product after passing through the refining process, hydrochloric acid, cooling crystallization, filtration washing to obtain the product of the ABS red alkali. The invention catechol as raw materials, the reaction process for preparing methylene compounds after the pepper link, one-step catalytic addition reaction pepper ethylamine, shorten the technological process, overcomes the use of toxic cyanide, process green; process solvent recycling. (by machine translation)
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Paragraph 0016
(2019/05/15)
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- Cyclotriol derivative and production method and application thereof
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The invention discloses a cyclotriol derivative and a production method and application thereof. The cyclotriol derivative is of a structure as shown in a general formula I, wherein R1, R2 and R3 areOH or AcNH; R1=OH, and R2=R3=AcNH or R2=OH, and R1=R3=AcNH or R3=OH, and R1=R2=AcNH; * stands for R configuration or S configuration; and Ac stands for caffeoyl CAc or derivatives caffesulfonyl SAc and caffe(mono-methyl ester)phosphonyl PAc of the caffeoyl CAc. According to the production method of the cyclotriol derivative, conditions are mild, automatic and industrial production are easy to achieve, operation is simple, convenient and safe, and the obtained cyclotriol derivative can act on anti-respiratory syncytial virus F protein, has high anti-RSV activity, low cell toxicity and high stability, can be used for producing medicines for treating virus infection, and is especially used for producing medicines for treating respiratory syncytial virus infection.
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Paragraph 0138-0141
(2019/09/13)
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- Quinic acid derivative and preparation method and application thereof
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The invention discloses a quinic acid derivative and a preparation method and application thereof. The quinic acid derivative has a structure represented by a formula I, wherein R1, R2 and R3 are OH or AcNH; R1 = OH, R2 = R3 = AcNH, or R2 = OH, R1 = R3 = AcNH, or R3 = OH, R1 = R2 = AcNH; * represents an R configuration or an S configuration; and Ac represents caffeoyl CAc or a derivative caffesulfonyl SAc, and coffee(mono-methyl ester)phosphonyl PAc. The quinic acid derivative has the advantages of mild preparation conditions, simple and safe operation, high product purity and relatively hightotal yield, and the obtained quinic acid derivative can be used for preparing medicaments for treating viral infections, especially for preparing medicaments for treating influenza virus, parainfluenza virus and respiratory syncytial virus infections.
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Paragraph 0138-0141
(2019/10/01)
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- Degradation of lignin with aqueous ammonium-based ionic liquid solutions under milder conditions
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This study investigates the performance of two aqueous ionic liquids (ILs), dimethylbutylammonium acetate ([DMBA][Ac]) and dimethylbutylammonium butanoate ([DMBA][B]), solutions for depolymerizing alkali lignin into valuable phenolic compounds. The favorable operation conditions, including reaction temperature and reaction time, are explored. The extent of depolymerization of the lignin is evaluated by analysis with gel permeation chromatography (GPC). The results show that the average molecular weights of the depolymerized lignin samples can be reduced by as high as 93.8% and 86.8% after treating with the aqueous [DMBA][Ac] and [DMBA][B], respectively. Moreover, the aromatic chemical species in the depolymerized solutions are identified by using gas chromatography?mass spectrophotometry (GC-MS). The confirmation of the chemical species is further made by using a series of spectroscopic techniques, such as FT-IR, and 1H NMR and 13C NMR spectroscopy. Promising results have been achieved for the depolymerization of the lignin into valuable chemicals by using the proposed green media, aqueous solutions of ionic liquids [DMBA][Ac] and [DMBA][B], under milder conditions.
- Gupta, Bhupender S.,Lee, Ming-Jer,Tolesa, Leta Deressa
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p. 3357 - 3365
(2019/02/25)
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- Electron transfer-induced reduction of organic halides with amines
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Reduction of a variety of organo halides was examined by using amines as a sacrificial hydrogen source. UV light-induced reduction of vinyl and aryl halides with triethylamine proceeded smoothly to give the corresponding reduced products. High temperature heating also caused the reduction and DABCO (1,4-diazabicyclo[2.2.2]octane) also served as a good reducing reagent.
- Fukuyama, Takahide,Fujita, Yuki,Miyoshi, Hayato,Ryu, Ilhyong,Kao, Shih-Chieh,Wu, Yen-Ku
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supporting information
p. 5582 - 5585
(2018/06/04)
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- Novel synthesis method of sesamol
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The invention discloses a novel synthesis method of sesamol. The method specifically comprises the following steps: first, gamma-glycidyl oxypropyl trimethoxysilane is used as a dispersing agent to prepare modified mullite powder; then, the modified mullite powder is used as a carrier to prepare a supported catalyst; catechol and dichloromethane are used as raw materials to prepare 1,3-benzodioxole under the catalysis of the supported catalyst; glyoxylic acid, a sulfuric acid solution and 1,3-benzodioxole are used as raw materials to obtain 3,4-methylenedioxy phenyl glycolic acid; the 3,4-methylenedioxy phenyl glycolic acid reacts with a nitric acid solution to prepare piperonal; finally, the piperonal and MCPBA react to prepare the sesamol. The method disclosed in the invention is simpleto operate, low in preparation cost and high in product yield.
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Paragraph 0026-0029
(2018/11/22)
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- Green synthesis process of berberine
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The invention discloses a green synthesis process of berberine. The synthesis process comprises the following steps: firstly, introducing dichloromethane into N,N-dimethylformamide by adopting catechol under the alkaline condition and reacting to synthesize benzodioxole; secondly, preparing pepper propionitrile by utilizing the obtained benzodioxole, preparing pepper propionamide by utilizing obtained pepper propionitrile, preparing homopiperony lamine by utilizing pepper propionamide and then synthesizing N-2,3-dimethoxybenzyl homopiperony lamine hydrochloride; finally, synthesizing berberinehydrochloride by utilizing the N-2,3-dimethoxybenzyl homopiperony lamine hydrochloride under the condition of glyoxal, formic acid and copper sulfate. The green synthesis process of the berberine, disclosed by the invention, has the advantages that the formation of black polymers is reduced, the reaction yield is improved, the problem that environmental pollution caused by a large amount of the black polymers produced in the original process production is solved and the requirements of green chemical synthesis required by China are met.
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Paragraph 0026; 0027; 0028
(2018/09/08)
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- Visible-Light-Driven Carboxylation of Aryl Halides by the Combined Use of Palladium and Photoredox Catalysts
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A highly useful, visible-light-driven carboxylation of aryl bromides and chlorides with CO2 was realized using a combination of Pd(OAc)2 as a carboxylation catalyst and Ir(ppy)2(dtbpy)(PF6) as a photoredox catalyst. This carboxylation reaction proceeded in high yields under 1 atm of CO2 with a variety of functionalized aryl bromides and chlorides without the necessity of using stoichiometric metallic reductants.
- Shimomaki, Katsuya,Murata, Kei,Martin, Ruben,Iwasawa, Nobuharu
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supporting information
p. 9467 - 9470
(2017/07/24)
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- A facile and mild Pd-catalyzed one-pot process for direct hydrodeoxygenation (HDO) phenols to arenes through a ArOSO2F intermediates transformation
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A practical one-pot process for hydrodeoxygenation (HDO) of phenolic derivatives to their corresponding arenes was developed. This method provided a facile route to upgrading bio-oil. The substrate scope of this protocol was wide, complicated and multi-phenolic compounds were also smoothly hydrodeoxygenated to their corresponding arenes.
- Wang, Xiao-Yan,Leng, Jing,Wang, Shi-Meng,Asiri, Abdullah M.,Marwani, Hadi M.,Qin, Hua-Li
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supporting information
p. 2340 - 2343
(2017/05/29)
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- Nickel-catalyzed reductive defunctionalization of esters and amides to aromatic hydrocarbons
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The removal of ester and amide groups is of fundamental significance in organic syntheses. Under non-catalytic conditions, hydride sources are chiefly used for their reduction. Recently developed Ni-catalyzed one-pot reductive activation of esters and ami
- Mondal, Manoj,Bharali, Pankaj
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p. 13211 - 13214
(2017/11/27)
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- Selective Reductive Removal of Ester and Amide Groups from Arenes and Heteroarenes through Nickel-Catalyzed C?O and C?N Bond Activation
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An inexpensive nickel(II) catalyst and a hydrosilane were used for the efficient reductive defunctionalization of aryl and heteroaryl esters through a decarbonylative pathway. This versatile method could be used for the removal of ester and amide functional groups from various organic molecules. Moreover, a scale-up experiment and a synthetic application based on the use of a removable carboxylic acid directing group highlight the usefulness of this reaction.
- Yue, Huifeng,Guo, Lin,Lee, Shao-Chi,Liu, Xiangqian,Rueping, Magnus
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supporting information
p. 3972 - 3976
(2017/03/27)
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- Transfer Hydro-dehalogenation of Organic Halides Catalyzed by Ruthenium(II) Complex
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A simple and efficient Ru(II)-catalyzed transfer hydro-dehalogenation of organic halides using 2-propanol solvent as the hydride source was reported. This methodology is applicable for hydro-dehalogenation of a variety of aromatic halides and α-haloesters and amides without additional ligand, and quantitative yields were achieved in many cases. The potential synthetic application of this method was demonstrated by efficient gram-scale transformation with catalyst loading as low as 0.5 mol %.
- You, Tingjie,Wang, Zhenrong,Chen, Jiajia,Xia, Yuanzhi
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p. 1340 - 1346
(2017/02/10)
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- Method for preparing pepper ring
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The invention discloses a price relatively inexpensive, reaction condition mild synthetic pepper ring process method that adopts DMSO, methylene chloride and sodium hydroxide as the base material, drips with DMSO solution of catechol, regulates reaction temperature at 120 DEG C or below, cuts down solvent decomposition phenomenon caused by high temperature, takes separation means of oil-water separator instead of hydraulic steam distillation to extract products during post processing, reduces greatly the amount of resulted waste water, gives better process safety. The method recycles and reuses the disengaged water, and reduces the amount of waste water to the minimum. The method recycles and reapplies dichloromethane and DMSO recovered by distillation, which is shown by study result produces no effect on reaction, achieving the green recycled use of organic solvent, the method cuts down production cost.
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Paragraph 0018; 0019; 0020; 0021; 0022; 0023; 0024
(2017/03/08)
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- Aryloxyphenoxies propionate compound and its preparation method and application
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The invention discloses a piperonyl-containing aryloxyphenoxies propionate compound, which has the following structure: the formula is shown in the specification. The specific preparation method includes steps of taking catechol as raw material, and compounding heliotropin through two-step reaction; performing reduction reaction with NaBH4 to prepare 3, 4- methylenedioxy phemethylol; reacting 2-(4-aryloxyphenoxies) propionyl chloride with prepare 3, 4- methylenedioxy phemethylol to prepare two piperonyl-containing aryloxyphenoxies propionate compounds. The compound has good weeding activity; especially, the weeding activity of monocotyledon weed is better than that of dicotyledonous weed; the preparation method is simple to operate, and the yield is high.
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Paragraph 0028; 0035; 0036
(2017/09/29)
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- Aryloxy-phenoxy propionate compounds and preparation method and application thereof
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The invention discloses aryloxy-phenoxy propionate compounds containing piperonyl. The compounds have a following structure. The preparation method specifically includes following preparation steps: using catechol as a raw material; synthesizing heliotropin through two-step reaction; enabling heliotropin to be in reductive reaction with NaBH4 to prepare 3, 4-methylene dioxybenzyl alcohol; enabling 2-(4-aromatic oxygen phenyl) propionyl chloride to react with 3, 4-methylene dioxybenzyl alcohol to prepare two aryloxy-phenoxy propionate compounds containing piperonyl. The compounds have higher weeding activity, especially for monocotyledon weed than dicotyledon weed. The preparation method is simple to operate and high in yield.
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Paragraph 0035; 0036
(2017/08/29)
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- Synthetic process of berberine
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The invention discloses a synthetic process of berberine. The synthetic process comprises the following synthetic route: pyrocatechol and dichloromethane are taken as raw materials and dimethyl sulphoxide is taken as a solvent to synthesize 1,3-benzodioxole; 1,3-benzodioxole is subjected to ViLsmeiar formylation to synthesize heliotropin; heliotropin undergoes nitration through a Henry reaction to generate beta-nitro-3,4-dioxomethenyl styrene; beta-nitro-3,4-dioxomethenyl styrene is subjected to Clemmensen reduction to generate 3,4-(methylenedioxyphenyl)ethylamine; and 3,4-(methylenedioxyphenyl)ethylamine and 2,3-dimethoxy benzaldehyde condense, and the obtained product is reduced to generate N-2,3-dimethoxybenzyl [3,4-(methylenedioxy)phenyl]ethylamine hydrochloride. N-2,3-dimethoxybenzyl [3,4-(methylenedioxy)phenyl]ethylamine hydrochloride is cyclized in a condition of glyoxal, formic acid and copper sulphate to generate berberine hydrochloride. According to the synthetic route, cyanation is avoided and toxicity is reduced. Zinc amalgam is adopted to replace H2Ni and LiAlH4, so that the cost is greatly reduced, the process difficulty is reduced, and the product yield is increased.
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Paragraph 0029
(2017/04/22)
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- AN IMPROVED METHOD FOR THE PREPARATION OF ALKYLENEDIOXYBENZENE COMPOUNDS
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This invention relates to an improved method for preparing alkylenedioxybenzene compounds of Formula I, from the corresponding ortho-dihydroxy aromatic compound of Formula II wherein n is 0, 1, 2 or 3; and R1 and R2 independently represent H, linear or branched C1 – C10 alkyl or alkenyl group, cycloalkyl group, halogen selected from C1, Br, I, nitro (-NO2), alkoxy (-OR) or SR thioether (-SR), wherein R is linear or branched alkyl group comprising C1-C6 carbon atoms.
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Page/Page column 13; 14
(2017/10/13)
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- Synthesis of crescent shaped heterocycle-fused aromatics via Garratt-Braverman cyclization and their DNA-binding studies
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Three crescent shaped heterocycle-fused phenanthrene based systems 1–3 have been synthesized starting from benzene (or substituted benzene) 1,2-bis-propargyl alcohols. Bis-alkylation with propargylic bromides provided the key intermediate, the bis-propargyl bis-ethers. In spite of the possibility of many competing reactions, the latter underwent facile double Garratt-Braverman cyclization to provide compounds 1–3 in near quantitative yield, in a striking reaction involving the formation of four C–C bonds in a single step. Compounds 1–3 showed binding interaction with DNA, predominantly, via groove binding along with partial intercalation (combilexins). Molecular docking study supported the proposed binding modes.
- Ghosh, Debaki,Basu, Souradeep,Singha, Monisha,Das, Joyee,Bhattacharya, Prabuddha,Basak, Amit
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supporting information
p. 2014 - 2018
(2017/05/04)
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- Flow Metal-Free Ar-C Bond Formation via Photogenerated Phenyl Cations
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A convenient photochemical flow protocol for the formation of aryl-carbon bonds via photogenerated phenyl cations has been developed. A wide range of phenylated products, including biaryls, allylarenes, 2-arylacetals and benzyl γ-lactones, was smoothly synthesized in satisfactory yields under metal-free conditions. The adoption of a flow reactor often allowed us to adopt higher concentrations of substrates and shorter irradiation times compared to those usually employed in batch systems.
- Bergami, Matteo,Protti, Stefano,Ravelli, Davide,Fagnoni, Maurizio
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supporting information
p. 1164 - 1172
(2016/04/19)
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- Radical Hydrodeiodination of Aryl, Alkenyl, Alkynyl, and Alkyl Iodides with an Alcoholate as Organic Chain Reductant through Electron Catalysis
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A simple and efficient method for radical hydrodeiodination is reported. The novel approach uses electron catalysis. In situ generated Na-alcoholates are introduced as radical chain reducing reagents and reactions work with O2as cheap initiator. Hydrodeiodination works on aryl, alkenyl, alkynyl iodides and a tert-alkyl iodide also gets reduced applying the method. Albeit less general, the method is also applicable to the reduction of aryl bromides. The novel reagent is successfully used to conduct typical reductive radical cyclization reactions and mechanistic studies are reported.
- Dewanji, Abhishek,Mück-Lichtenfeld, Christian,Studer, Armido
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supporting information
p. 6749 - 6752
(2016/06/09)
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- An efficient method for the preparation of dialkoxymethanes from dichloromethane with alcohols catalyzed by a Cu-NHC complex
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A facile, rapid and efficient method for the preparation of dialkoxymethanes from dichloromethane with alcohols catalyzed by a Cu-NHC complex is reported. A variety of symmetrical dialkoxymethanes can be prepared under mild condition in excellent yields (up to 98%). The unsymmetrical ether is also obtained in 89% yield from the etherification of p-tolylmethanol and n-butyl chloride catalyzed by ICyCuCl complex at 80?°C. The reaction provides a new method for the preparation of dialkoxymethanes under mild conditions in excellent yields.
- Zhan, Lewu,Pan, Renming,Xing, Ping,Jiang, Biao
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supporting information
p. 4036 - 4038
(2016/08/18)
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- Gold-Catalyzed Proto- and Deuterodeboronation
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A mild gold-catalyzed protodeboronation reaction, which does not require acid or base additives and can be carried out in "green" solvents, is described. As a result, the reaction is very functional-group-tolerant, even to acid- and base-sensitive functional groups, and should allow for the boronic acid group to be used as an effective traceless directing or blocking group. The reaction has also been extended to deuterodeboronations for regiospecific ipso-deuterations of aryls and heteroaryls from the corresponding organoboronic acid. Based on density functional theory calculations, a mechanism is proposed that involves nucleophilic attack of water at boron followed by rate-limiting B-C bond cleavage and facile protonolysis of a Au-σ-phenyl intermediate.
- Barker, Graeme,Webster, Stacey,Johnson, David G.,Curley, Rachel,Andrews, Matthew,Young, Paul C.,MacGregor, Stuart A.,Lee, Ai-Lan
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p. 9807 - 9816
(2015/11/03)
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- Preparation of polymer-bound palladium catalyst and its application to the reduction of nitro arenes and the hydrodehalogenation of aryl halides
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Polymer-bound palladium catalyst was prepared as PdO nanoparticles bound on the surface of polystyrene beads. This catalytic system showed good activities in the reduction of nitro arenes and the hydrodehalogenation of aryl halides. When the nitro arenes were reacted with 10 mol% PdO and K3PO 4 (1.5 equiv.) in DMF/cyclohexanol at 110 C, the corresponding amino arenes were formed in good yields. In addition, these reaction conditions afforded hydrodehalogenated products from aryl iodides, bromides, and chlorides.
- Min, Hongkeun,Lee, Sunyoung,Park, Minhan,Hwang, Jinil,Jung, Hyun Min,Lee, Sunwoo
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- Nickel-catalyzed reductive conjugate addition to enones via allylnickel intermediates
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An alternative method to copper-catalyzed conjugate addition followed by enolate silylation for the synthesis of β-disubstituted silyl enol ether products (R1(R2)HCCH=C(OSiR43)R 3) is presented. This method uses haloarenes instead of nucleophilic aryl reagents. Nickel ligated to either neocuproine or bipyridine couples an α,β-unsaturated ketone or aldehyde (R2HC=CHC(O)R 3) with an organic halide (R1-X) in the presence of a trialkylchlorosilane reagent (Cl-SiR43). Reactions are assembled on the benchtop and tolerate a variety of functional groups (aldehyde, ketone, nitrile, sulfone, pentafluorosulfur, and N-aryltrifluoroacetamide), electron-rich iodoarenes, and electron-poor haloarenes. Mechanistic studies have confirmed the first example of a catalytic reductive conjugate addition of organic halides that proceeds via an allylnickel intermediate. Selectivity is attributed to (1) rapid, selective reaction of LNi0 with chlorotriethylsilane and enone in the presence of other organic electrophiles, and (2) minimization of enone dimerization by ligand steric effects.
- Shrestha, Ruja,Dorn, Stephanie C. M.,Weix, Daniel J.
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supporting information
p. 751 - 762
(2013/03/14)
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- Nickel-catalyzed Kumada cross-coupling reactions of tertiary alkylmagnesium halides and aryl bromides/triflates
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We report a Ni-catalyzed process for the cross-coupling of tertiary alkyl nucleophiles and aryl bromides. This process is extremely general for a wide range of electrophiles and generally occurs with a ratio of retention to isomerization >30:1. The same procedure also accommodates the use of aryl triflates, vinyl chlorides, and vinyl bromides as the electrophilic component.
- Joshi-Pangu, Amruta,Wang, Chao-Yuan,Biscoe, Mark R.
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supporting information; experimental part
p. 8478 - 8481
(2011/06/25)
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- Rhodium(I)-catalyzed synthesis of aryltriethoxysilanes from arenediazonium tosylate salts with triethoxysilane
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An efficient method for the preparation of aryltriethoxy-silanes from arenediazonium tosylate salts has been developed, which expands the substrates of rhodium-catalyzed silylation from iodides, bromides, and triflates to diazonium salts. A new method for hydrodediazoniation has also been explored.
- Tang, Zhi Yong,Zhang, Yuan,Wang, Tao,Wang, Wei
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supporting information; experimental part
p. 804 - 808
(2010/06/14)
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- SUBSTITUTED AROMATIC CARBOXAMIDE AND UREA DERIVATIVES AS VANILLOID RECEPTOR LIGANDS
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The invention relates to substituted aromatic carboxamide and urea derivatives, to processes for the preparation thereof, to pharmaceutical compositions containing these compounds and also to the use of these compounds for preparing pharmaceutical compositions (formula (I)).
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Page/Page column 114
(2010/11/18)
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- Eco-friendly hydrodehalogenation of electron-rich aryl chlorides and fluorides by photochemical reaction
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Aryl chlorides and fluorides are smoothly hydrodehalogenated by irradiation either in neat i-PrOH or in a polar solution in the presence of hypophosphorous acid or triethylsilane. The procedure gives the halogen-free products in good to excellent yields under mild eco-friendly conditions and avoids the recourse to toxic metal catalysts.
- Dichiarante, Valentina,Fagnoni, Maurizio,Albini, Angelo
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experimental part
p. 942 - 945
(2010/04/23)
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- Palladium catalyzed-dehalogenation of aryl chlorides and bromides using phosphite ligands
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The catalytic system based on Pd-phosphite for the dehalogenation reactions of aryl chlorides and bromides is described. The Pd-phosphite catalyst effectively promoted the dehalogenation of aryl halides to give dehalogenated products in moderate to excellent yields. The aryl chlorides required strong bases such as NaOtBu for this transformation, whereas the aryl bromides were dehalogenated in the presence of weak bases such as Cs2CO3. This catalytic system exhibited tolerance to functional groups such as methoxy, amine, hydroxyl, ether, amide, benzyl and ketone groups. It also demonstrated chemoselectivity in that bromochlorobenzene was converted only to chlorobenzene.
- Moon, Jeongju,Lee, Sunwoo
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scheme or table
p. 473 - 477
(2009/04/14)
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- Method For Producing Optionally Substituted Methylenedioxybenzene
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The invention relates to a method for producing optionally substituted methylenedioxybenzene. The invention particularly relates to the production of methylenedioxybenzene. The inventive production method is characterized by the fact that it involves the reaction of an optionally substituted catechol with an aldehyde in the presence of a solid acid catalyst selected among: a titanium silicalite and a zeolite that is doped with tin and/or titanium.
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Page/Page column 5
(2008/06/13)
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- Metal-free synthesis of sterically crowded biphenyls by direct Ar-H substitution in alkyl benzenes
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(Chemical Equation Presented) Four's definitely a crowd: The chemoselective activation of Ar-H bonds in methylbenzenes by treatment with photogenerated phenyl cations allowed the synthesis of sterically crowded biphenyl compounds, including tetra-ortho-substituted biphenyls, by intermolecular cross-coupling (see scheme). This method is an appealing metal-free alternative to widely used transition-metal catalysis. TFE = 2,2,2-trifluoroethanol.
- Dichiarante, Valentina,Fagnoni, Maurizio,Albini, Angelo
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p. 6495 - 6498
(2008/09/16)
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- A re-examination of the methylenation reaction
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A re-examination of the methylenation reaction of 1-hydroxy-2-mercapto-, 1,2-dihydroxy- and 1,2-dimercapto-substituted benzenes by bromochloromethane with cesium carbonate shows that these substrates give mixtures of five- and ten-membered benzocondensed heterocyclic compounds and in some cases even dibenzodioxines.
- Cabiddu, Maria Grazia,Cadoni, Enzo,De Montis, Stefania,Fattuoni, Claudia,Melis, Stefana,Usai, Michele
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p. 4383 - 4387
(2007/10/03)
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- Tetralone acids as intermediates for the synthesis of podophyllotoxin analogues
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Tetralone acids 6, 7 and 8 have been synthesised as intermediates for the synthesis of podophyllotoxin analogues 3, 4 and 5. The possible steric hindrance of cyclohexyl group on the intramolecular Friedel-Crafts acylation reaction of anhydrides 15 b,c to tetralone acids 7 and 8 is also discussed here.
- Basavaraju,Anjanamurthy
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p. 876 - 880
(2007/10/03)
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