- Copper-catalyzed aerobic alcohol oxidation under air in neat water by using a water-soluble ligand
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A copper-catalyzed primary benzylic and allylic alcohols oxidation system has been developed under air in neat water by use of a water-soluble ligand (pytl-β-CD). The ligand was designed and synthesized via a click conjunction between functionalized β-cyclodextrin (β-CD) and 2-ethinylpyridine.
- Zhang, Guofu,Han, Xingwang,Luan, Yuxin,Wang, Yong,Wen, Xin,Xu, Li,Ding, Chengrong,Gao, Jianrong
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Read Online
- Organic Electrochemistry: Expanding the Scope of Paired Reactions
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Paired electrochemical reactions allow the optimization of both atom and energy economy of oxidation and reduction reactions. While many paired electrochemical reactions take advantage of perfectly matched reactions at the anode and cathode, this matching of substrates is not necessary. In constant current electrolysis, the potential at both electrodes adjusts to the substrates in solution. In principle, any oxidation reaction can be paired with any reduction reaction. Various oxidation reactions conducted on the anodic side of the electrolysis were paired with the generation and use of hydrogen gas at the cathode, showing the generality of the anodic process in a paired electrolysis and how the auxiliary reaction required for the oxidation could be used to generate a substrate for a non-electrolysis reaction. This is combined with variations on the cathodic side of the electrolysis to complete the picture and illustrate how oxidation and reduction reactions can be combined.
- Moeller, Kevin D.,Wu, Tiandi
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supporting information
p. 12883 - 12890
(2021/05/07)
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- A metal-free heterogeneous photocatalyst for the selective oxidative cleavage of CC bonds in aryl olefins: via harvesting direct solar energy
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Selective cleavage of CC bonds is highly important for the synthesis of carbonyl containing fine chemicals and pharmaceuticals. Novel methodologies such as ozonolysis reactions, Lemieux-Johnson oxidation reaction etc. already exist. Parallel to these, catalytic methods using homogeneous catalysts also have been discovered. Considering the various advantages of heterogeneous catalysts such as recyclability and stability, couple of transition metal-based heterogeneous catalysts have been applied for this reaction. However, the pharmaceutical industries prefer to use metal-free catalysts (especially transition metal-free) to avoid further leaching in the final products. This is for sure a big challenge to an organic chemist and to the pharmaceutical industries. To make this feasible, a mild and efficient protocol has been developed using polymeric carbon nitrides (PCN) as metal-free heterogeneous photocatalysts to convert various olefins into the corresponding carbonyls. Later, this catalyst has been applied in the gram scale synthesis of pharmaceutical drugs using direct solar energy. Detailed mechanistic studies revealed the actual role of oxygen, the catalyst, and the light source.
- Das, Shoubhik,Hatami, Nareh,Jooss, Christian,Lange, Niklas Simon,Ronge, Emanuel,Schilling, Waldemar,Zhang, Yu
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supporting information
p. 4516 - 4522
(2020/08/10)
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- Method for preparing 3,4-dimethyl benzaldehyde by efficiently catalyzing pseudocumene
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The invention belongs to the technical field of polyoxometallate catalysts, and relates to a method for preparing 3,4-dimethyl benzaldehyde by catalytically oxidizing pseudocumene with a polyoxometallate (Keggin type, Dawson type, Silverton type, Waugh type, Lindquist type, Anderson type and the like) catalyst. The polyoxometallate is adopted as the catalyst, and placed in a reactor, then an organic solvent and the pseudocumene are added in sequence, finally an oxidizing agent is added, stirring and reacting are carried out for 12-48 hours at the temperature of 50 DEG C to 80 DEG C, separationis carried out, and the 3,4-dimethyl benzaldehyde is obtained. Compared with the prior art, the method is easy to operate and mild in condition, the method for preparing the 3,4-dimethyl benzaldehydehas atom economy and environmental friendliness, the conversion rate of the pseudocumene and the selectivity of the 3,4-dimethyl benzaldehyde are high, the catalyst has the advantages of being green,efficient, easy to recycle and the like, and application and popularization value is achieved.
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Paragraph 0023-0056
(2019/08/20)
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- A method for preparation of aromatic aldehydes (by machine translation)
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The invention provides a process for preparing aromatic aldehydes method, comprises the following steps: alkyl substituted benzene and carbon monoxide in the catalyst under catalysis of carbonylation reaction, to obtain the aromatic aldehyde; the catalyst is hydrogen chloride or concentrated hydrochloric acid. The present invention provides a preparation method is simple, solved in the prior art to aluminum chloride as the catalyst, aluminum chloride with an aromatic aldehyde complex problems; and the present invention provides prepared by the preparation method of the aromatic aldehyde high purity, can reach 97.89% -99.12%; in addition, the present invention provides a preparation method can be continuous reaction, it is suitable for industrial large-scale production. (by machine translation)
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Paragraph 0044-0046
(2019/03/15)
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- 3. 4 - Dimethyl benzaldehyde preparation method
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The present invention relates to the technical field of fine organic synthesis, in particular to 3, 4 - dimethyl benzaldehyde preparation method, comprising the steps of: 1) acylate: will be 100 parts by weight of ortho-xylene and 150 parts by weight of 1, 3 - dioxa cyclohexane for acidification under acidic conditions, inject the nitrogen used as a ventilation; adding 220 parts by weight of aluminum trichloride with 100 parts by weight of a mixed Lewis acid catalytic, access 120 parts by weight of carbon monoxide, acylation reaction temperature is lower than 5 °C, time is at least 12 hours; 2) water washing: washing solution after the acylate, washing temperature 0 - 5 °C; 3) distillation: oil phase distillation, the distillation temperature in the 145 °C - 225 °C between, sneaking object O-xylene condensed into liquid and enters the tank; 4) re-distillation. The present invention relates to 1, 3 - dioxa cyclohexane as solvent can be better dissolved gaseous carbon monoxide, into the special catalyst reaction can be carried out under the atmospheric pressure, to reduce the requirement of reaction equipment; accelerate the reaction speed and selective, in the product less geometric isomer, the prepared 3, 4 - dimethyl benzaldehyde high purity.
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Paragraph 0023-0027
(2019/05/15)
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- Fe(NO3)3·9H2O-catalyzed aerobic oxidative deoximation of ketoximes and aldoximes under mild conditions
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A mild, simple process for the effective aerobic oxidative deoximation of a wide range of ketoximes and aldoximes has been developed that utilizes Fe(NO3)3·9H2O as the single catalyst and molecular oxygen as the green oxidant. The environmentally benign protocol provides moderate to excellent yield and broad functional groups tolerance and is a valuable synthetic method for practical applications. According the relevant verification experiment, a plausible mechanism has been proposed.
- Li, Yongshu,Xu, Nizhou,Mei, Guangyao,Zhao, Yun,Zhao, Yiyong,Lyu, Jinghui,Zhang, Guofu,Ding, Chengrong
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supporting information
p. 810 - 814
(2018/08/09)
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- Fe(NO3)3/2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ): An efficient catalyst system for selective oxidation of alcohols under aerobic conditions
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A practical and efficient catalyst system for the oxidation of alcohols to carbonyl compounds using catalytic amounts of DDQ and Fe(NO3)3 with air as the environmentally benign oxidant has been developed. A variety of benzylic, heterocyclic, allylic and propargylic alcohols were smoothly converted into aldehydes or ketones in good to excellent yields. In case of large-scale reaction for the oxidation of benzyl alcohol, benzaldehyde was obtained in 93% isolated yield. Moreover, a possible reaction mechanism was proposed.
- Hu, Yongke,Chen, Lei,Li, Bindong
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- NH3?H2O: The Simplest Nitrogen-Containing Ligand for Selective Aerobic Alcohol Oxidation to Aldehydes or Nitriles in Neat Water
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Aqueous ammonia (NH3?H2O) has been shown to serve as the simplest nitrogen-containing ligand to effectively promote copper-catalyzed selective alcohol oxidation under air in water. A series of alcohols with varying electronic and steric properties were selectively oxidized to aldehydes with up to 95 % yield. Notably, by increasing the amount of aqueous ammonia in neat water, the exclusive formation of aryl nitriles was also accomplished with good-to-excellent yields. Additionally, the catalytic system exhibits a high level of functional group tolerance with ?OH, ?NO2, esters, and heteroaryl groups all being amenable to the reaction conditions. This one-pot and green oxidation protocol provides an important synthetic route for the selective preparation of either aldehydes or nitriles from commercially available alcohols.
- Zhang, Guofu,Ma, Danting,Zhao, Yiyong,Zhang, Guihua,Mei, Guangyao,Lyu, Jinghui,Ding, Chengrong,Shan, Shang
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p. 885 - 889
(2018/12/10)
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- Method for preparing aromatic aldehydes by using graphene oxide-titanium sulfate nano composite
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The invention discloses a method for preparing aromatic aldehydes by using a graphene oxide-titanium sulfate nano composite (GO-Ti), and belongs to the technical field of fine chemical product preparation. According to the method, aromatic benzyl alcohols with different structures are taken as reaction substrates, tetrahydrofuran and the like are used as solvents, a hydrogen peroxide solution is used as an oxidizing agent, an oxidation reaction is carried out under the action of a GO-Ti nano composite catalyst, and the aromatic aldehydes are obtained by column chromatography or reduced pressure distillation after the reaction is finished, wherein the reaction temperature is 50-70 DEG C and the reaction time is 3-12 hours. The synthesis method provided by the invention is simple, the used solvents all can be recycled, the oxidation also can be carried out without solvents, the operation is convenient, the reaction conditions are mild, the economic benefit is high, and the environment isfree from pollution. The catalyst still has high conversion rate and selectivity after being recycled and used for 10 times.
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Paragraph 0055-0057
(2018/09/08)
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- Co-immobilization of Laccase and TEMPO in the Compartments of Mesoporous Silica for a Green and One-Pot Cascade Synthesis of Coumarins by Knoevenagel Condensation
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Co-immobilization of bio- and chemocatalysts produces sustainable, recyclable hybrid systems that open new horizons for green cascade approaches in organic synthesis. Here, the co-immobilization of laccase and 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) in mesoporous silica was used for the one-pot aqueous synthesis of 30 coumarin-3-carboxylate derivatives under mild conditions through the condensation of in situ oxidized 2-hydroxybenzyl alcohols and malonate derivatives. A maximum yield was obtained after incubating at pH 6.0 and 45 °C for 24 h. An efficient organic synthesis was catalyzed by the hybrid catalyst in 10 % organic solvent. More than 95 % of the initial activity of the enzyme was preserved after 10 cycles, and no significant catalyst deactivation occurred after 10 runs. This new system efficiently catalyzed the in situ aerobic oxidation of salicyl alcohols, followed by Knoevenagel condensation, which confirmed the possibility of producing efficient hybrid catalysts by co-immobilization of catalytic species in mesoporous materials.
- Mogharabi-Manzari, Mehdi,Amini, Mohsen,Abdollahi, Mohammad,Khoobi, Mehdi,Bagherzadeh, Ghodsieh,Faramarzi, Mohammad Ali
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p. 1542 - 1546
(2018/02/28)
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- Supported palladium nanoparticles as switchable catalyst for aldehyde conjugate/s and acetate ester syntheses from alcohols
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Polymer-supported Pd(0) (Pd@PS) nanoparticles (NPs) were explored as a switchable catalyst for oxidative aldehyde conjugate/s (AC/s) and acetate esters (AEs) syntheses from alcohols. Using the same substrates, the catalyst in the presence of oxygen and K2CO3 participated in AC/s synthesis, and in the presence of traces of air and NaOtBu, unusual AEs products were obtained.
- Kumar, Sandeep,Chaudhary, Abha,Bandna,Bhattacherjee, Dhananjay,Thakur, Vandna,Das, Pralay
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supporting information
p. 3242 - 3245
(2017/07/12)
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- Simple formylation of aromatic compounds using a sodium formate/triphenylphosphine ditriflate system
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A new procedure was developed for formylation of arenes to produce aromatic aldehydes using a sodium formate/triphenylphosphine ditriflate system in ethanol at room temperature in good yields. The simplicity of the procedure, short reaction times, and mild reaction conditions are the other advantages of this metal- and carbon monoxide-free protocol.
- Khodaei, Mohammad M.,Alizadeh, Abdolhamid,Hezarkhani, Hadis Afshar
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supporting information
p. 840 - 843
(2017/06/13)
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- Method for preparing aldehyde by oxidizing primary alcohol
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The invention discloses a method for preparing aldehyde by catalytic oxidation of primary alcohol. The method comprises the steps that the primary alcohol as shown in a formula (I) or (III) is taken as a raw material, copper salt is taken as a catalyst, air is taken as an oxidizing agent, TEMPO (2,2,6,6-tetramethyl-1-piperidine-N-oxyl compound) is taken as a pro-oxygenic agent, ammonium hydroxide is taken as a co-catalyst and solvent, the primary alcohol, the copper salt, the air, the TEMPO and the ammonium hydroxide are mixed uniformly and react for 9 to 24 hours at the temperature of 60 to 120 DEG C; after the reaction, reaction liquid is subjected to aftertreatment to obtain aldehyde as shown in a formula (II) or (IV). The method has the advantages of high reaction rate and yield, low cost, convenience in operation and safety in reaction. The whole process is environmental friendly and free of pollution.
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Paragraph 0026; 0027; 0028; 0029; 0030; 0106; 0107-0110
(2017/07/21)
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- Efficient and Highly Selective Solvent-Free Oxidation of Primary Alcohols to Aldehydes Using Bucky Nanodiamond
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Selective oxidation of alcohols to aldehydes is widely applicable to the synthesis of various green chemicals. The poor chemoselectivity for complicated primary aldehydes over state-of-the-art metal-free or metal-based catalysts represents a major obstacle for industrial application. Bucky nanodiamond is a potential green catalyst that exhibits excellent chemoselectivity and cycling stability for the selective oxidation of primary alcohols in diverse structures (22 examples, including aromatic, substituted aromatic, unsaturated, heterocyclic, and linear chain alcohols) to their corresponding aldehydes. The results are comparable to reported transition-metal catalysts including conventional Pt/C and Ru/C catalysts for certain substrates under solvent-free conditions. The possible activation process of the oxidant and substrates by the surface oxygen groups and defect species are revealed with model catalysts, ex situ electrochemical measurements, and ex situ attenuated total reflectance. The zigzag edges of sp2 carbon planes are shown to play a key role in these reactions.
- Lin, Yangming,Wu, Kuang-Hsu Tim,Yu, Linhui,Heumann, Saskia,Su, Dang Sheng
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p. 3497 - 3505
(2017/09/15)
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- A NOVEL ROUTE FOR PREPARATION OF L,3:2,4-BIS-(3,4- D IM ETH YLB ENZYLIDENE)SO RB ITO L
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A new route for preparation of 3:2,4-bis-(3,4- dimethylbenzylidene) sorbitol [DMDBS] has been disclosed which is comprising: bromination of o-xylene to obtain a mixture of 4-bromo- o-xylene as a major product and 3-bromo-o-xylene; conversion of bromo-o-xylenes into corresponding dimethylbenzaldehyde by Grignard reaction; and reaction of 3,4-dimethylbenzaldehyde with sorbitol in presence of catalyst and solvent to obtain DMDBS. The invented route is cost-effective and it obviates the need to separate 3,4-dimethylbenzaldehyde from its 2,3-isomer.
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Page/Page column 6; 7
(2016/06/01)
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- A PROCESS FOR PREPARATION OF 3,4-DIMETHYLBENZALDEHYDE
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A novel process for preparation of 3,4-dimethylbenzaldehyde has been disclosed. The process is comprising steps of (i) reacting 4- bromo-o-xylene with magnesium metal to obtain Grignard compound of formula 1; (ii) formylating the compound of formula 1 by reaction with N,N-dimethylformamide to form compound of formula 2; (iii) treating compound of formula 2 with aqueous HC1 to obtain 3,4- dimethylbenzaldehyde.
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Page/Page column 6
(2016/06/01)
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- Formylation of electron-rich aromatic rings mediated by dichloromethyl methyl ether and TiCl4: Scope and limitations
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Here the aromatic formylation mediated by TiCl4 and dichloromethyl methyl ether previously described by our group has been explored for a wide range of aromatic rings, including phenols, methoxy- and methylbenzenes, as an excellent way to produce aromatic aldehydes. Here we determine that the regioselectivity of this process is highly promoted by the coordination between the atoms present in the aromatic moiety and those in the metal core.
- Ramos-Tomillero, Iván,Paradís-Bas, Marta,De Pinho Ribeiro Moreira, Ibério,Bofill, Josep María,Nicolás, Ernesto,Albericio, Fernando
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supporting information
p. 5409 - 5422
(2015/05/13)
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- Oxygenation of Methylarenes to Benzaldehyde Derivatives by a Polyoxometalate Mediated Electron Transfer-Oxygen Transfer Reaction in Aqueous Sulfuric Acid
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The synthesis of benzaldehyde derivatives by oxygenation of methylarenes is of significant conceptual and practical interest because these compounds are important chemical intermediates whose synthesis is still carried out by nonsustainable methods with very low atom economy and formation of copious amounts of waste. Now an oxygenation reaction with a 100% theoretical atom economy using a polyoxometalate oxygen donor has been found. The product yield is typically above 95% with no "overoxidation" to benzoic acids; H2 is released by electrolysis, enabling additional reaction cycles. An electrocatalytic cycle is also feasible. This reaction is possible through the use of an aqueous sulfuric acid solvent, in an aqueous biphasic reaction mode that also allows simple catalyst recycling and recovery. The solvent plays a key role in the reaction mechanism by protonating the polyoxometalate thereby enabling the activation of the methylarenes by an electron transfer process. After additional proton transfer and oxygen transfer steps, benzylic alcohols are formed that further react by an electron transfer-proton transfer sequence forming benzaldehyde derivatives. (Chemical Equation Presented).
- Sarma, Bidyut Bikash,Efremenko, Irena,Neumann, Ronny
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p. 5916 - 5922
(2015/05/27)
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- A highly efficient heterogeneous aerobic alcohol oxidation catalyzed by immobilization of bipyridine copper(I) complex in MCM-41
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A heterogeneous copper(I)-catalyzed aerobic oxidation of primary benzylic and allylic alcohols to aldehydes was achieved under air in EtOH at 50°C in the presence of 5 mol % of MCM-41-immobilized bipyridine copper(I) complex [MCM-41-bpy-CuI] and 5 mol % of 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) using aqueous ammonia as base, yielding a variety of aromatic and α,β-unsaturated aldehydes in good to excellent yields. This heterogeneous copper catalyst can be easily recovered by a simple filtration of reaction solution and reused for at least 10 consecutive trials without any decreases in activity. The use of recyclable heterogeneous copper catalyst and green reagents, such as air as oxidant and ethanol as solvent, made the system attractive for environmentally sustainable processes.
- Zhao, Hong,Chen, Qiurong,Wei, Li,Jiang, Yuanyuan,Cai, Mingzhong
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p. 8725 - 8731
(2015/10/20)
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- N-Functionalized Amino Acids Promoted Aerobic Copper-Catalyzed Oxidation of Benzylic Alcohols in Water
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Instead of traditional N,N-bidentate ligands, N-functionlized amino acids were used as powerful N,O-bidentate ligands in aerobic copper/TEMPO-catalyzed system for promoting oxidation of benzylic alcohols. Under the optimized reaction conditions, a wide range of primary and secondary benzylic alcohols have been efficiently converted into aldehydes and ketones with good to excellent yields in water.
- Zhang, Guofu,Lei, Jie,Han, Xingwang,Luan, Yuxin,Ding, Chengrong,Shan, Shang
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p. 779 - 784
(2015/03/30)
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- L-Proline: An efficient N,O-bidentate ligand for copper-catalyzed aerobic oxidation of primary and secondary benzylic alcohols at room temperature
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A novel and highly practical copper-catalyzed aerobic alcohol oxidation system with l-proline as the ligand at room temperature has been developed. A wide range of primary and secondary benzylic alcohols tested have been smoothly transformed into corresponding aldehydes and ketones with high yields and selectivities.
- Zhang, Guofu,Han, Xingwang,Luan, Yuxin,Wang, Yong,Wen, Xin,Ding, Chengrong
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supporting information
p. 7908 - 7910
(2013/09/02)
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- Aerobic oxidation of benzylic halides to carbonyl compounds with molecular oxygen catalyzed by tempo/kno2 in aqueous media
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Benzylic halides were successfully oxidized to the corresponding aldehydes and ketones in good to excellent yields in aqueous media with molecular oxygen as oxidant in the presence of catalytic amounts of TEMPO (2,2,6,6- tetramethylpiperidyl-1-oxy) and potassium nitrite (KNO2).
- Liu, Qifa,Lu, Ming,Yang, Fei,Wei, Wei,Sun, Feng,Yang, Zhenbang,Huang, Sufeng
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scheme or table
p. 1106 - 1114
(2010/04/29)
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- A highly efficient synthetic method for the preparation of 3,4-dimethylbenzaldehyde from o-xylene in aqueous media
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In this study, 3,4-dimethylbenzaldehyde was obtained in 82.3% total yield by oxidation of 3,4-dimethylbenzyl chloride with NaNO3/AcOH catalyzed by PEG-600 in aqueous media. The starting material 3,4-dimethylbenzyl chloride was prepared by chloromethylation of o-xylene in CTAB micellar catalytic system. Compared with other synthetic methods, this method not only enhanced the yield, but also afforded an efficient work-up procedure. The structures of the products were confirmed by Elemental analysis,1H NMR and 13C NMR or compared with authentic samples.
- Hu,Lu,Liu,Wei,Liu
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experimental part
p. 487 - 494
(2010/08/20)
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- Biooxidation of Primary Alcohols to Aldehydes through Hydrogen Transfer Employing Janibacter terrae
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Chemoselective oxidations still represent a challenge for chemists. Lyophilized cells of Janibacter terrae were employed for the chemoselective oxidation of primary alcohols to the corresponding aldehydes by hydrogen transfer with the use of acetaldehyde as the hydrogen acceptor. Secondary alcohol moieties were transformed at a much slower rate. The substrate spectrum encompasses substituted benzyl alcohols, whereby substrates with a substituent in the meta position were well tolerated, whereas only very small substituants were tolerated in the ortho position. Furthermore, nalkanols and allylic alcohols were transformed with good conversions. The biocatalyst was compatible with DMSO as a water miscible organic solvent up to 30 % v/v.
- Orbegozo, Thomas,De Vries, Johannes G.,Kroutil, Wolfgang
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experimental part
p. 3445 - 3448
(2010/09/05)
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- Oxidation of benzyl halides to aldehydes and ketones with potassium nitrate catalyzed by phase-transfer catalyst in aqueous media
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The catalytic oxidation of benzyl halides to aldehydes and ketones in aqueous media was studied under relatively mild reaction conditions by using phase-transfer catalyst combined with potassium nitrate and 10% aqueous potassium hydroxide solution. As a result, a simple high-yield procedure has been developed. Copyright Taylor & Francis Group, LLC.
- Liu, Qifa,Lu, Ming,Sun, Feng,Li, Jiang,Zhao, Yuebing
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experimental part
p. 4188 - 4197
(2009/04/11)
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- Orthoamides, LXVII [1]. Bis(diformylamino)methane - A new efficient formylating reagent for aromatic compounds
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Formaldehyde reacts with diformamide (10) to give N-(hydroxymethyl) diformamide (11), which upon treatment with thionylchloride yields N-(chlormethyl)diformamide (12) together with small amounts of oxydimethylenebis(diformamide) (13). Various diformylamine derivatives, such as diformylaminomethyl formiate (14), diformylaminomethylisothiocyanate (15) and the N-diformylaminomethylated guanidinium salt 16, can be prepared from 12. Bis(diformylamino) methane (7) can be obtained by the reaction of sodium diformamide (8) with either 1-(chloromethyl)pyridinium chloride (9) or N-(chloromethyl)diformamide (12) in acetonitrile. The action of tris(chloromethyl) amine (18) on sodium diformamide (8) affords tris(diformylaminomethyl)amine (19). The constitution of the compounds 7,11 and 19 was confirmed by crystal structure determination. The nature of the products from the reactions of aromatic compounds with 12 depends on the Lewis acid which is used as activator. Thus the N-benzylformamides 20a, b can be obtained from toluene and mesitylene and 12/BF3-ether, whereas 1,2,4- trimethoxybenzene is formylated by 12/AlCl3 to give the aldehyde 22. Interestingly enough, a novel and efficient formylating reagent resulted from these investigations: bis(diformylamino)methane (7), which can be activated by Lewis acids, e. g. AlCl3. The scope of this procedure is comparable with that of the Olah-formylation method (formylfluoride/BF3).
- Kantlehner, Willi,Anders, Ernst,Mezger, Jochen,Stoyanov, Edmont V.,Kre?, Ralf,Wermann, Kurt,Frey, Wolfgang,G?rls, Helmar
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experimental part
p. 395 - 406
(2009/01/31)
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- Orthoamide, LX [1]. N,N,N',N'-Tetraformylhydrazine- a Formylation Agent for Aromatic Compounds of Wide Scope
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The reagent system formed from N,N,N',N'-tetraformylhydrazine (3) and aluminum chloride allows the formylation of aromatic compounds. The scope of the method is comparable with the Olah formylation and the Gross-Rieche procedure, since benzene and fluorobenzene can be formylated. Two formyl groups are transferred from 3 to the aromatic nuclei when a molar ratio 4:1:4 (aluminum chloride/3/aromatic compound) is chosen.
- Kantlehner, Willi,Haug, Erwin,Scherr, Oliver,Stoyanov, Edmont V.,Mezger, Jochen,Ziegler, Georg
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p. 355 - 365
(2007/10/03)
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- Micelle-enhancing effect on a flavin-photosensitized reaction of benzyl alcohols in aqueous solution
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The tetra-O-acetylriboflavin (Fl)-photosensitized dehydrogenation of benzyl alcohols 1 proceeded more efficiently in aqueous solutions in the presence of sodium dodecyl sulfate (H2O/SDS) than acetonitrile solutions. The fluorescence quenching of Fl with 1 occurred efficiently in H2O/SDS. The apparent rate constants (kQ) for the fluorescence quenching were determined by Stern-Volmer plots. The plots of kQ vs the free-energy changes for the electron transfer from 1 to the excited singlet of Fl showed the Rehm-Weller-type correlation. However, plots for H2/SDS were deviated from a curve calculated by the Rehm-Weller equation, although plots for MeCN were fitted to the calculated curve. The deviation in H2O/SDS is attributable to the incorporation of Fl and 1 into the hydrophobic domain of the SDS micelle, where the condensation, less-polar medium, and exteior negative charge operate favorably for efficient electron transfer.
- Yasuda, Masahide,Nakai, Takuya,Kawahito, Yasumasa,Shiragami, Tsutomu
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p. 601 - 605
(2007/10/03)
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- Inhibitors of phenylalanine ammonialyase: 1-aminobenzylphosphonic acids substituted in the benzene ring
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Dextrorotatory 1-amino-3′,4′-dichlorobenzylphosphonic acid was found to be a potent inhibitor of the plant enzyme phenylalanine ammonia-lyase both in vitro and in vivo from among the ring-substituted 1-aminobenzylphosphonic acids and other analogues of phenylglycine. A structure activity relationship analysis of the results obtained permits predictions on the geometry of the pocket of the enzyme and is a basis in the strategy of better inhibitor synthesis.
- Zoń, Jerzy,Amrhein, Nikolaus,Gancarz, Roman
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- Orthoamides, LIX [1]. Formyl-aalen [tris(diformylamino)methane] - A new formylating reagent for activated aromatic compounds
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In the presence of strong Lewis acids such as aluminum chloride or boron trichloride, formyl-aalen [tris(diformylamino)methane] (3) acts as a formylating reagent for aromatic alkane compounds and aromatic ethers. The orthoamide 3 delivers three formyl groups for the formylation process. Thus toluene, cumene, tert-butylbenzene, hexylbenzene, o-xylene, p-cymene, biphenyl, anisole, diphenylether and 1,3-dimethoxybenzene can be formylated in 1,2-dichloroethane. In these reactions, 3 and aluminum chloride should be used in a molar ratio of 1:6 to 1:9.
- Kantlehner, Willi,Haug, Erwin,Scherr, Oliver,Ziegler, Georg
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p. 1295 - 1304
(2007/10/03)
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- Benzylic biooxidation of various toluenes to aldehydes by peroxidase
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A catalytic method is described for the oxidation of toluene and substituted derivatives to the corresponding benzaldehydes by hydrogen peroxide, using peroxidase. In most cases the respective benzoic acid was produced as a byproduct. The reaction proceeds under mild conditions in an aqueous medium.
- Russ, Rainer,Zelinski, Thomas,Anke, Timm
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p. 791 - 793
(2007/10/03)
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- New formylating agents - Preparative procedures and mechanistic investigations
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The reactivity of new formylating agents related to formamide has been investigated both experimentally and theoretically. The reaction in 1,2-dichloroethane between tris(diformylamino)methane (2) and several arenes, catalyzed by AlCl3 or BCl3, was shown to proceed in good yields to afford the corresponding para-substituted aldehydes. The nature of the active electrophilic species was also investigated theoretically. Thus, the relative stability of the O- and N-protonated forms, as well as those of AlCl3 adducts, of several formylating agents - diformamide, triformamide, N,N,N′,N′-tetraformylhydrazine, and tris(diformylamino)methane - were determined in the gas phase and in water or DCE by means of DFT calculations at the B3LYP/6-311++G(d,p) level, the solvents being modeled with the IPCM method. The amide oxygen atom in all cases appeared to be the most basic site, both in the Bronsted and Lewis sense, constituting a first step towards the understanding of the mechanism of this reaction.
- Bagno, Alessandro,Kantlehner, Willi,Scherr, Oliver,Vetter, Jens,Ziegler, Georg
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p. 2947 - 2954
(2007/10/03)
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- Reactions of (Aryl)(chloro)methyl p-tolyl sulfoxides with tetrasulfur tetranitride (S4N4): Formation and characterization of 3,5-diaryl-1,2,4,6-thiatriazine 1-oxides
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The reactions of (aryl)(chloro)methyl p-tolyl sulfoxides 2 with tetrasulfur tetranitride (S4N4) in p-dioxane at reflux gave 3,5-diaryl-1,2,4,6-thiatriazine 1-oxides, 3,5-diaryl-1,2,4-thiadiazoles, and 1-amino-3,5-diaryl-1,2,4,6-thiat
- Kong, Yung Cheol,Kim, Kyongtae,Ja Park, Yung
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p. 7153 - 7161
(2007/10/03)
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- Orthoamides. LIII. A New Synthesis for Aromatic Aldehydes of Wide Scope
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Diformamide (1) reacts with activated aromatic compounds like toluene, anisole, m-xylene, 1,2-dimethoxybenzene in the presence of AlCl3 to give N-(diarylmethyl)-formamides 2a-d, the corresponding aromatic aldehydes 3-6 are formed as by-products in low yields. From N,N-dimethylaniline and 1/AlCl3 the triphenylmethane derivative 7 can be obtained. The reaction of anisole with N-methyl-diformamide (9) affords the formamide 10. The mixture of formamide, P4O10 and AlCl3 reveals to be a reagent which is capable to formylate toluene and anisole, resp. Triformamide (14)/AlCl3 is an effective formylating system which allows the preparation of aromatic aldehydes (e.g. 3,4,17-32) from the corresponding aromatic hydrocarbons. Aluminiumchloride can be replaced by borontrichloride. The yields of the formylation reactions depend strongly from the reaction conditions (molar ratio: aromatic hydrocarbon/ AlCl3/14; solvent, reaction temperature). The scope of the reaction covers nearly complete those of the Gattermann-Koch-, Gattermann- and Vilsmeier-Haack-reaction.
- Kantlehner, Willi,Vettel, Markus,Gissel, Alexander,Haug, Erwin,Ziegler, Georg,Ciesielski, Michael,Scherr, Oliver,Haas, Richard
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p. 297 - 310
(2007/10/03)
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- Electrosynthesis of aromatic aldehydes by palladium-catalyzed carbonylation of aryl iodides in the presence of formic acid
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The palladium-catalyzed electrocarbonylation of aryl halides performed in the presence of formic acid under one atmosphere of carbon monoxide affords aromatic aldehydes in good to high yields.
- Carelli, Italo,Chiarotto, Isabella,Cacchi, Sandro,Pace, Paola,Amatore, Christian,Jutand, Anny,Meyer, Gilbert
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p. 1471 - 1473
(2007/10/03)
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- Use of polymer supported reagents for clean multi-step organic synthesis: Preparation of amines and amine derivatives from alcohols for use in compound library generation
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The automated sequential application of polymer supported perruthenate (PSP) and polymer supported cyanoborohydride (PSCBH) in an oxidation-reductive amination procedure allowed the efficient transformation of simple alcohols into more complex amines which can be further derivatised by the use of polymer bound amino sulfonylpyridinium chlorides.
- Ley, Steven V.,Bolli, Martin H.,Hinzen, Berthold,Gervois, Anne-Geraldine,Hall, Beverley J.
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p. 2239 - 2241
(2007/10/03)
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- Oxidation of 1,2,4- and 1,3,5-Trimethylbenzenes with Cerium(IV) Ions in Perchloric Acid Solutions
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The reaction stoichiometry and the influence of certain reagents on the rate of reduction of cerium(IV) ions with 1,2,4- and 1,3,5-trimethylbenzenes are examined. Permanently formed intermediates are identified, and conditions for their isolation are developed. The most probable oxidation mechanisms are proposed.
- Deka,Dziegiec
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p. 1896 - 1901
(2007/10/03)
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- Aromatic Spiranes XX [1]: Syntheses of Dimethylsubstituted 2-Carboxymethyl-indan-1-ones and Benzylchlorides as Synthones for Syntheses of di- to tetramethylsubstituted Spirobiindandiones
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The isomeric dimethyl methylbenzoates 5, obtained from the bromides via Grignard reactions with dimethylcarbonate, were reduced with LiAlH4 to the hydroxymethyl derivatives 6. The latter were then transformed both to the benzylchlorides 7 (with SOCl2) and to the aldehydes 8 (with pyridinium chlorochromate). Knoevenagel-Doebner reaction of 8 afforded the acrylic acids 9 which (after hydrogenation to 11) were cyclized to the desired indanones 12 with polyphosphoric acid. On the other hand, 12c and 12e were prepared from dimethyl 3-chloropropiophenone (14) by warming with sulfuric acid. After NaH-catalyzed reaction with dimethylcarbonate, the indanones 12 gave the ketoesters 15 which then could be hydrogenated to the indanes 16. All reactions proceeded with satisfactory to excellent yields (60-90%).
- Neudeck
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p. 185 - 200
(2007/10/03)
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- Formylation of Aromatic Compounds with CO in HSO3F-SbF5 under Atmospheric Pressure
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The formylation of aromatic compounds such as benzene, toluene, xylenes, mesitylene, indan, tetralin, fluorobenzene, chlorobenzene, and bromobenzene was carried out in HSO3F-SbF5 under atmospheric CO pressure at 0 deg C.In HSO3F-SbF5, both formylation and sulfonation took place to give formyl and sulfonyl compounds.In the case of alkylbenzenes, including toluene, xylenes, mesitylene, and tetralin, formylalkylbenzenesulfonyl fluorides, new compounds, were obtained by a one-pot reaction as well as alkylbenzaldehydes, alkylbenzenesulfonyl fluorides, and bis(alkylphenyl) sulfones.The direct introduction of a formyl and sulfonyl group was achieved in alkylbenzenes.The reaction path of the new compounds is a two-step reaction comprised of formylation as the first step and sulfonation as the second step.The product composition was strongly dependent on the acid strength of the HSO3F-SbF5 systems.The formyl compounds became predominant with increasing acidity of the HSO3F-SbF5 system.On the other hand, only sulfonyl compounds were produced when the acidity of the HSO3F-SbF5 system was low.
- Tanaka, Mutsuo,Iyoda, Jun,Souma, Yoshie
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p. 2677 - 2680
(2007/10/02)
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- Enantioselective Synthesis of Cyclohexene Nitro Aldehydes via Diels-Alder Reactions with Sugar Nitroolefins
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Uncatalysed Diels-Alder reactions between (E)-1-deoxy-1-nitroalkenes derived from sugars and 2,3-dimethylbuta-1,3-diene yielded an easily separable mixture of the two possible diastereoisomeric adducts with good diastereofacial selectivity.In each case, preponderance of the major adduct has been rationalized in terms of the configuration of the chiral centre adjacent to the dienophilic double bond.Acid or alkaline deacetylation of the adducts, followed by degradative oxidation of the sugar side-chains, led to enantiomerically pure trans- or cis-cyclohexene nitro aldehydes.We also report on the easy elimination of the nitro group in nitro aldehydes, leading to cyclohexa-1,4-diene 11 or the aromatic aldehyde 12.
- Serrano, Jose A.,Moreno, Maria Ch.,Roman, Emilio,Arjona, Odon,Plumet, Joaquin,Jimenez, Jesus
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p. 3207 - 3212
(2007/10/02)
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- Process for continuous production of alkylbenzaldehydes
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Alkylbenzaldehyde is continuously produced in high yield from alkylbenzene by formylation with carbon monoxide in the presence of HF--BF3, where the alkylbenzene, HF--BF3 and carbon monoxide under a carbon monoxide partial pressure of at least 5 kg/cm2 absolute are introduced into the reactor to continuously carry out complexing of the alkylbenzene with HF--BF3 and formylation with the carbon monoxide successively in one and same reactor.
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- Substituted imidazo thiazoles thiazines, thiazepines and thiazocines
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Disclosed herein are novel tetrahydro imidazo thiazoles, tetrahydro imidazo thiazines, hexahydro imidazo thiazepines and hexahydro imidazo thiazocines, intermediates for the preparation thereof, methods of using the compounds as anti-inflammatory agents and methods of using an intermediate thereof as anti-secretory agents to relieve the symptoms of gastric distress.
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