- Method for synthesizing ether by catalyzing alcohol through trimethyl halosilane
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The invention discloses a method for synthesizing ether by catalyzing alcohol through trimethyl halosilane. According to the method, under the conditions of air or nitrogen atmosphere, no solvent andno transition metal catalyst, an alcohol compound is directly used as a raw material, trimethyl halosilane is used as a catalyst, and symmetric or asymmetric ether is synthesized through one-step selective dehydration reaction. According to the method, the use of strong acid, strong base and organic primary halides with high toxicity, instability and higher price is avoided, the synthesis steps are shortened, the synthesis efficiency is improved, the reaction has good selectivity, and a target ether product can be obtained preferentially.
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Paragraph 0055-0058
(2020/12/29)
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- Breaking C-O Bonds with Uranium: Uranyl Complexes as Selective Catalysts in the Hydrosilylation of Aldehydes
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We report herein the possibility to perform the hydrosilylation of carbonyls using actinide complexes as catalysts. While complexes of the uranyl ion [UO2]2+ have been poorly considered in catalysis, we show the potentialities of the Lewis acid [UO2(OTf)2] (1) in the catalytic hydrosilylation of a series of aldehydes. [UO2(OTf)2] proved to be a very active catalyst affording distinct reduction products depending on the nature of the reductant. With Et3SiH, a number of aliphatic and aromatic aldehydes are reduced into symmetric ethers, while iPr3SiH yielded silylated alcohols. Studies of the reaction mechanism led to the isolation of aldehyde/uranyl complexes, [UO2(OTf)2(4-Me2N-PhCHO)3], [UO2(μ-κ2-OTf)2(PhCHO)]n, and [UO2(μ-κ2-OTf)(κ1-OTf)(PhCHO)2]2, which have been fully characterized by NMR, IR, and single-crystal X-ray diffraction.
- Monsigny, Louis,Thuéry, Pierre,Berthet, Jean-Claude,Cantat, Thibault
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p. 9025 - 9033
(2019/10/02)
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- Aryl Boronic Acid Catalysed Dehydrative Substitution of Benzylic Alcohols for C?O Bond Formation
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A combination of pentafluorophenylboronic acid and oxalic acid catalyses the dehydrative substitution of benzylic alcohols with a second alcohol to form new C?O bonds. This method has been applied to the intermolecular substitution of benzylic alcohols to form symmetrical ethers, intramolecular cyclisations of diols to form aryl-substituted tetrahydrofuran and tetrahydropyran derivatives, and intermolecular crossed-etherification reactions between two different alcohols. Mechanistic control experiments have identified a potential catalytic intermediate formed between the aryl boronic acid and oxalic acid.
- Estopi?á-Durán, Susana,Donnelly, Liam J.,Mclean, Euan B.,Hockin, Bryony M.,Slawin, Alexandra M. Z.,Taylor, James E.
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supporting information
p. 3950 - 3956
(2019/02/16)
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- Silver/NBS-Catalyzed Synthesis of α-Alkylated Aryl Ketones from Internal Alkynes and Benzyl Alcohols via Ether Intermediates
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The silver hexafluoroantimonate/N-bromosuccinimide (NBS)-catalyzed synthesis of α-alkylated aryl ketones with a tertiary carbon center from internal alkynes and benzyl alcohols is reported. This reaction proceeds via the etherification of benzyl alcohols with an in situ generated benzyl bromide, formed by the reaction of benzyl alcohol with a catalytic amount of NBS and AgSbF6. Ag-catalyzed C-O cleavage of the ether leads to a tolyl radical, which undergoes addition to the alkyne, ultimately leading to the α-alkylated aryl ketone products.
- Chun, Supill,Chung, Young Keun
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supporting information
p. 5583 - 5586
(2018/09/21)
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- An ether compound of green high-efficient synthetic method (by machine translation)
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The invention discloses an ether compound of green high-efficient synthetic method, energy-saving environmental protection, comprising: mild reaction system, uses aldehyde, silane as the starting material, under the action of the silver salt in a price, for in solvent-free conditions, through reducing the - coupling - cheng mi reaction, realization of high efficiency alcohol of preparation. Synthesis method of the invention has the advantages of low dosage of catalyst, solvent-free, conversion and high yield, the reaction time is short, safe and stable, easy to operate, the product only distillation purification without any additional organic solvent, the whole range of green, environmental protection, high efficiency and the like, can overcome the defects of the prior art, it has very good industrial application value. (by machine translation)
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Paragraph 0049
(2018/07/07)
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- Efficient carbon-supported heterogeneous molybdenum-dioxo catalyst for chemoselective reductive carbonyl coupling
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Reductive coupling of various carbonyl compounds to the corresponding symmetric ethers with dimethylphenylsilane is reported using a carbon-supported dioxo-molybdenum catalyst. The catalyst is air- and moisture-stable and can be easily separated from the reaction mixture for recycling. In addition, the catalyst is chemoselective, thus enabling the synthesis of functionalized ethers without requiring sacrificial ligands or protecting groups.
- Liu, Shengsi,Li, Jiaqi,Jurca, Titel,Stair, Peter C.,Lohr, Tracy L.,Marks, Tobin J.
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p. 2165 - 2169
(2017/07/22)
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- Direct halogenation of alcohols with halosilanes under catalyst- and organic solvent-free reaction conditions
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A chemoselective method for the direct halogenation of different types of alcohols with halosilanes under catalyst- and solvent-free reaction conditions (SFRC) is reported. Various primary, secondary and tertiary benzyl alcohols and tertiary alkyl alcohols were directly transformed to the corresponding benzyl and alkyl halides, respectively, using chlorotrimethylsilane (TMSCl) and bromotrimethylsilane (TMSBr).
- Ajvazi, Njomza,Stavber, Stojan
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supporting information
p. 2430 - 2433
(2016/05/19)
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- Selective synthesis of thioethers in the presence of a transition-metal-free solid Lewis acid
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The synthesis of thioethers starting from alcohols and thiols in the presence of amorphous solid acid catalysts is reported. A silica alumina catalyst with a very low content in alumina gave excellent results in terms of both activity and selectivity also under solvent-free conditions. The reaction rate follows the electron density of the carbinol atom in the substrate alcohol and yields up to 99% and can be obtained for a wide range of substrates under mild reaction conditions.
- Santoro, Federica,Mariani, Matteo,Zaccheria, Federica,Psaro, Rinaldo,Ravasio, Nicoletta
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supporting information
p. 2627 - 2635
(2017/01/09)
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- Synthesis of ethers from carbonyl compounds by reductive etherification catalyzed by iron(III) and silyl chloride
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A simple iron- and silyl chloride catalyzed method for the preparation of symmetrical and nonsymmetrical ethers is presented. Various aldehydes and ketones were reductively etherified by using triethylsilane as a reducing agent in the presence of 2 mol% of iron(III) oxo acetate and 8 mol% of chloro(trimethyl)silane. The reactions can be carried out at ambient temperatures and pressures with ethyl acetate as the solvent.
- Savela, Risto,Leino, Reko
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p. 1749 - 1760
(2015/06/16)
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- Reductive coupling reaction of aldehydes using indium(III) triflate as the catalyst
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A reductive coupling reaction was effectively developed to convert an aldehyde to its symmetrical ether. The successful reactions required Et 3SiH and CH2Cl2 as the suitable solvent in the presence of a catalytic amount of In(OTf)3. Various aldehydes were subjected to the method, and each afforded the expected ethers in good to excellent yields.
- Mineno, Tomoko,Tsukagoshi, Rie,Iijima, Tsubasa,Watanabe, Kazuki,Miyashita, Hiroyuki,Yoshimitsu, Hitoshi
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p. 3765 - 3767
(2014/07/07)
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- Zinc-catalyzed reduction of aldehydes with a hydrosilane leading to symmetric ethers and silyl ethers
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The efficient reductive etherification of aromatic or aliphatic aldehydes using a reducing system that combines Zn(OTf)2 with either TMDS or Et3SiH is described. The present reducing system can also be applied to the hydrosilylation of aromatic aldehydes having either a strong electron-withdrawing group or a pyridine ring.
- Sakai, Norio,Nonomura, Yoshifumi,Ikeda, Reiko,Konakahara, Takeo
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p. 489 - 491
(2013/06/26)
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- TiCl4-mediated direct N-alkylation of sulfonamides with inactive ethers
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A TiCl4-mediated intermolecular or intramolecular direct N-alkylation reaction of sulfonamides with inactive ethers as alkylating agents was successfully achieved. This method provides a novel approach towards N-alkyl sulfonamides from inactive ethers via an easy workup procedure. Georg Thieme Verlag Stuttgart · New York.
- Chen, Jiayan,Dang, Ling,Li, Qiang,Ye, Yong,Fu, Shaomin,Zeng, Wei
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supporting information; experimental part
p. 595 - 600
(2012/03/27)
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- Photolytic decomposition of dibenzylic sulfites
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The photolytic decay of a library of para-substituted dibenzylic sulfites has been evaluated by UV radiation in a Srinivasan-Griffin-Rayonet photochemical reactor in various deuterated solvents. The decay for each dibenzylic sulfite was examined with respect to Swain and Lupton's field constant, F. The rate of photolytic decay varies depending on the identity of the benzyl substituents. Furthermore, it has been observed that the solvent affects both the rate of sulfite photolytic decay as well as final product distribution.
- Grenga, Paolo N.,Stoutenburg, Eric G.,Priefer, Ronny
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p. 4933 - 4937
(2012/11/13)
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- H5CoW12O40 supported on nano silica from rice husk ash: A green bifunctional catalyst for the reaction of alcohols with cyclic and acyclic 1,3-dicarbonyl compounds
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Rice husk ash (RHA) is an abundant agricultural by-product. The present research work deals with the production of nano silica powders, with high surface area and in amorphous form, from RHA using optimized technique. 12-Tungestocobaltic acid, H5CoW12O40 (CoW), was supported on silica from RHA to produce silica supported CoW (CoW/NSiO 2) as a nano catalyst. The characterization data derived from FT-IR reveal that the Keggin structure of CoW remains intact in CoW/NSiO2. TEM image showed that the catalyst had spherical shape with an average particle size of 10 nm. The acidity of the catalyst was measured by potentiometric titration with n-butylamine. To our surprise, this very strong solid acid catalyst showed an excellent distribution of acid sites, suggesting that the catalyst possesses a higher number of surface active sites compared to CoW supported on commercial silica (CoW/SiO2), CoW and K 5CoW12O40. A high catalytic activity was found over CoW/NSiO2. Finally, CoW/NSiO2 has been used as a highly effective catalyst for benzylation of linear 1,3-dicarbonyl compounds with benzylic alcohols and synthesis of β-keto enol ethers from cyclic 1,3-dicarbonyl compounds. The present methodology offers a practical, simple, mild, environmentally friendly, and timesaving method under solvent-free conditions.
- Rafiee, Ezzat,Khodayari, Maryam,Kahrizi, Masoud,Tayebee, Reza
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experimental part
p. 121 - 128
(2012/06/01)
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- Dehydration of benzyl alcohols in phosphonium ionic liquids: Synthesis of ethers and alkenes
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The dehydration of benzylic alcohols has been studied in several phosphonium ionic liquids in the absence of any metal catalysts. Benzyl ethers and alkenes were obtained from primary and secondary benzylic alcohols in good to excellent yields for these reactions. Commercially available hydrophobic phosphonium ionic liquids containing the trihexyl(tetradecyl)phosphonium cation paired with six different anions were used for the reactions under microwave irradiation. The interaction of the substrate with the ionic liquid was investigated using different NMR techniques, such as NOESY NMR. The effects of cation and anions on the behaviour of these ionic liquids in the reactions were studied in order to understand the mechanism. A catalytic cycle is proposed involving activation of the benzyl alcohol by the phosphonium cation. Copyright
- Kalviri, Hassan A.,Kerton, Francesca M.
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experimental part
p. 3178 - 3186
(2012/01/03)
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- The reductive etherification of carbonyl compounds using polymethylhydrosiloxane activated by molecular iodine
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Aldehydes and ketones undergo a smooth reductive etherification by polymethylhydrosiloxane (PMHS) in the presence of a catalytic amount of molecular iodine under mild conditions to afford the corresponding symmetrical ethers in excellent yields. This new reagent system (PMHS/I2) provides a simple and convenient route for the preparation of symmetrical ethers from carbonyl compounds.
- Yadav,Subba Reddy,Shiva Shankar,Swamy
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experimental part
p. 46 - 48
(2010/03/24)
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- Influence of lewis acid and solvent in the hydrosiylation of aldehydes and ketones with Et3SiH; Tris(pentafluorophenyl)borane B(C 6F5)3 versus Metal inflates [M(OTf) 3; M = Sc, Bi, Ga, and Al] - Mecha
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The scope of the B(C6F5)3-catalyzed hydrosilylation of (X)Ph- CH=O and (X)Ph-C(R)=O was expanded to include a large set of subslitulents (X =H, p-Me, o-Me, p-F, o-F, p-Cl, p-Br, p-NO2m, m-NO2, p-Et; R
- Bach, Peter,Albright, Andrea,Laali, Kenneth K.
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experimental part
p. 1961 - 1966
(2009/09/06)
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- Catalytic dehydrative etherification and chlorination of benzyl alcohols in ionic liquids
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Dibenzyl ethers and benzyl chloride can be obtained in moderate to excellent yields through Pd-catalysed reactions in hydrophobic ionic liquids using microwave or conventional heating. The Royal Society of Chemistry 2009.
- Kalviri, Hassan A.,Petten, Chad F.,Kerton, Francesca M.
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scheme or table
p. 5171 - 5173
(2009/12/08)
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- Chlorine borrowing: An efficient method for an easier use of alcohols as alkylation agents
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Chlorine functionalised tin dioxide nanoparticles proved able to partially convert alcohols into the corresponding chlorides, which act as alkylation agents with an increased electrophilicity, as evidenced on ether formation and Friedel-Crafts reactions.
- Makowski, Philippe,Rothe, Regina,Thomas, Arne,Niederberger, Markus,Goettmann, Frederic
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scheme or table
p. 34 - 37
(2010/04/22)
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- High-efficiency conversion of trimethylsilyl ethers to their corresponding ethers using carbon-based solid acid as a new catalyst in heterogeneous mixtures
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Carbon-based solid acid was used as a new catalyst for conversion of trimethylsilyl ethers to their corresponding ethers in heterogeneous mixtures. The experiments were done moderately at room temperature, and high yields in suitable times were obtained under these conditions. Copyright Taylor & Francis Group, LLC.
- Shokrollahi, Arash,Zali, Abbas,Pouretedal, Hamid Reza
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p. 371 - 375
(2008/04/01)
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- An efficient synthesis of unsymmetrical diarylmethanes from the dehydration of arenes with benzyl alcohols using InCl3·4H2O/acetylacetone catalyst system
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An efficient and practical synthesis of unsymmetrical diarylmethanes has been achieved from the dehydration of arenes with benzyl alcohols in the presence of catalytic amount of InCl3·4H2O/acetylacetone.
- Sun, Hong-Bin,Li, Biao,Chen, Songjie,Li, Jie,Hua, Ruimao
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p. 10185 - 10188
(2008/02/13)
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- Borrowing hydrogen: Indirect "Wittig" olefination for the formation of C-C bonds from alcohols
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The successful development of an indirect three-step domino sequence for the formation of C-C bonds from alcohol substrates is described. An iridium-catalysed dehydrogenation of alcohol 1 affords the intermediate aldehyde 2. The desired C-C bond can then be formed by a facile Wittig olefination, yielding the intermediate alkene 3. In the final step the alkene is hydrogenated to afford the indirect Wittig product, the alkane 4. The key to this process is the concept of borrowing hydrogen; hydrogen removed in the initial dehydrogenation step is simply borrowed by the iridium catalyst. Functioning as a hydrogen reservoir, the catalyst facilitates C-C bond formation before subsequently returning the borrowed hydrogen in the final step. Herein we present full details of our examination into both the substrate and reaction scope and the limitations of the catalytic cycle. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.
- Black, Phillip J.,Edwards, Michael G.,Williams, Jonathan M. J.
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p. 4367 - 4378
(2007/10/03)
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- Silica Sulfuric Acid: An Efficient Catalyst for the Direct Conversion of Primary and Secondary Trimethylsilyl Ethers to their Corresponding Ethers under Mild and Heterogeneous Conditions
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Primary and secondary trimethylsilyl ethers were converted to their corresponding ethers in the presence silica sulfuric acid with good to excellent yields under mild and heterogeneous conditions.
- Zolfigol, Mohammad Ali,Mohammadpoor-Baltork, Iraj,Mirjalili, Bibi Fatemeh,Bamoniri, Abdolhamid
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p. 1877 - 1879
(2007/10/03)
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- The use of Nafion-H as an efficient catalyst for the direct conversion of primary and secondary trimethylsilyl ethers to their corresponding ethers under mild and heterogeneous conditions
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Primary and secondary trimethylsilyl ethers were converted to their corresponding ethers in the presence Nafion-H with good to excellent yields under mild and heterogeneous conditions.
- Zolfigol, Mohammad Ali,Mohammadpoor-Baltork, Iraj,Habibi, Davood,Mirjalili, BiBi Fatemeh,Bamoniri, Abdolhamid
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p. 8165 - 8167
(2007/10/03)
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- Silica sulfuric acid as an efficient reagent for the synthesis of symmetrical ethers under mild and heterogeneous conditions
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A mild and efficient method for the synthesis of symmetrical ethers using silica sulfuric acid is reported. All reactions are performed under compeletly heterogeneous conditions in good to high yields.
- Shirini, Farhad,Zolfigol, Mohammad Ali,Mohammadi, Kamal
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p. 2357 - 2361
(2007/10/03)
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- Oxidation of dibenzyl ethers by dilute nitric acid
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A simple process for the manufacture of benzaldehyde (BzH) by oxidation of dibenzyl ether (DBE) has been reported in this paper. Two-phase reaction between dibenzyl ether and aqueous dilute nitric acid in the presence of catalytic amount of sodium nitrite has been investigated. Effect of stirring speed, concentration of nitric acid in the aqueous phase, mole ratio of reactants, sodium nitrite concentration, and reaction temperature on the conversion of DBE and yield of BzH has been investigated. 80% yield of BzH with 95% conversion of DBE has been reported. Oxidation of bis(chlorobenzyl) ethers to corresponding aldehydes is difficult compared to oxidation of DBE under otherwise identical conditions. Initial concentration of sodium nitrite does not affect the overall progress of the reaction.
- Joshi,Sawant,Joshi
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p. 152 - 157
(2013/09/07)
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- Bismuth Bromide-Catalyzed reductive coupling of carbonyl compounds and its application to the synthesis of novel crownophanes
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The reductive homocoupling of carbonyl compounds and heterocoupling of a carbonyl compound with an alkoxysilane were both effected smoothly with triethylsilane in the presence of a catalytic amount of bismuth bromide (1-3 mol%) under mild conditions. This ether-forming reaction was successfully applied to the single-step preparation of novel crownophanes with olefinic or acetylenic linkages.
- Komatsu, Naoki,Ishida, Jun-Ya,Suzuki, Hitomi
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p. 7219 - 7222
(2007/10/03)
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- Reactivities of Carbonyl Compounds in Acid-Catalyzed Hydride Transfer vs. Electron Transfer
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Rate constants for acid-catalyzed hydride-transfer reactions from triethylsilane to a series of carbonyl compounds are compared with those for acid-catalyzed electron transfer from the excited state of 2+ to the same series of carbonyl compounds in the presence of HClO4 in acetonitrile at 298 K.
- Fukuzumi, Shunichi,Fujita, Morifumi
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p. 2059 - 2062
(2007/10/02)
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- Electrogenerated Acid-Assisted Preparation of Ethers from Aldehydes and Ketones
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Symmetrical and unsymmetrical ethers are prepared from carbonyl compounds and alkoxytrimethylsilanes in the presence of hydrosilane by using an electrogenerated acid catalyst.
- Torii, Sigeru,Takagishi, Sadahito,Inokuchi, Tsutomu,Okumoto, Hiroshi
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p. 775 - 776
(2007/10/02)
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- Reduction of carbonyl compounds promoted by silicon hydrides under the influence of trimethylsilyl-based reagents
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The synthetic utility of hydrosilanes under the influence of trimethylsilyl-based reagents as new reducing systems is described. 1,1,3,3-Tetramethyldisiloxane (TMDS) reagent in combination with iodotrimethylsilane or bromotrimethylsilane produces alkyl halides from aldehydes in good to excellent yields.Polymethylhydrosiloxane (PMS) in the presence of iodotrimethylsilane also produces benzyl iodides in excellent yields.On the contrary, PMS reagent was found unsuitable for the synthesis of benzyl bromides.Similary, TMDS reagent in combination with trimethylsilyl triflate produces symmetrical ethers from aldehydes without concomitant formation of competitive products.Under similar conditions, PMS reagent failed to provide the expected symmetrical ethers and Friedel-Crafts products were formed.Reduction of quinones to hydroquinones is also described.
- Aizpurua, Jesus M.,Lecea, Begona,Palomo, Claudio
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p. 2342 - 2347
(2007/10/02)
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- Selective Reduction by 2-Amino-4-methylpyridine Borane and 2-Aminopyrimidine Borane
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Stereo- and chemoselective reductions and synthetic utility of the title compounds are described.
- Okamoto, Yoshihisa,Osawa, Toshimitsu,Kurasawa, Yoshihisa,Kinoshita, Toshio,Takagi, Kaname
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p. 1383 - 1385
(2007/10/02)
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- ZEOLITE-CuNaY CATALYZED DECOMPOSITION OF ARYLDIAZOMETHANE
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Decomposition of aryldiazomethanes is catalyzed by copper ion-exchanged Y-type zeolite to afford cis-1,2-diarylethylenes in high selectivity.The catalytic activity and selectivity are found to be affected by the exchange level of copper ions in zeolite and the solvent used.
- Onaka, Makoto,Kita, Hiroshi,Izumi, Yusuke
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p. 1895 - 1898
(2007/10/02)
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- New Olefin and Oxiran Syntheses from Carbonyl Compounds, and Diethyl Sodiophosphonate Anions and 1-Aminophosphonate Amino-anions
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Reaction of aromatic aldehydes, and phthalic and thiophthalic anhydrides, with diethyl sodiophosphonate (1) gives the trans-stilbenes (3), 3,3'-biphthalidylidene (30), and 3,3'-bis-(2-thiophthalidylidene) (33).Similar treatment of fluorenone (8) and xanthone (17) with (1) leads to 9,9'-bis(fluororenylidene) (9) and 9,10-dihydro-9-oxophenanthrene-10-spiro-9'-fluorene (10), and to 9,9'-bixanthenylidene (18) and 9,9'-bixanthenyl (19), respectively, but the reaction using anthrone (11) as a carbonyl reagent yields only anthraquinone (12) and anthracene (13).Similar treatment using N-methylisatoic anhydride (34) and N-methylisatin (36) produces NN'-dimethylisoindigo (35).Reaction of benzaldehyde and p-chlorobenzaldehyde with diethyl 1--cyclohexylphosphonate (40) gives mainly corresponding mixtures of trans- (41a,b) and cis-stilbene epoxides (42a,b), while similar treatment of p-nitrobenzaldehyde with (40) produces 4,4'-dinitrostilbene (3e).Reaction of (8) with (40), as well as with (1), gives (9) and (10).The mechanism of formation of these products is discussed.
- Minami, Toru,Matsuzaki, Narihide,Ohshiro, Yoshiki,Agawa, Toshio
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p. 1731 - 1738
(2007/10/02)
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