- Influence of Protonation on Gattermann-Koch Formylation Rate of Alkylbenzene in CF3SO3H-SbF5
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The influence of the protonation on Gattermann-Koch formylation rate of alkylbenzenes was studied in CF3SO3H-SbF5.From the kinetic study of m-xylene formylation using various SbF5:m-xylene molar ratios in CF3SO3H, it is revealed that the formylation rate is explained with the equations which take into account the protonation equilibrium of m-xylene, and the apparent formylation rate is decreased by the protonation.The decrease of the apparent formylation rate by the protonation is proportional to the ratio of protonated alkylbenzene to form the ?-complex; therefore, the apparent relative formylation rate of alkylbenzenes is not consistent with their relative basicity under strong acidic conditions such as in CF3SO3H-SbF5.
- Tanaka, Mutsuo,Fujiwara, Masahiro,Ando, Hisanori
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Read Online
- A Simple, Mild and General Oxidation of Alcohols to Aldehydes or Ketones by SO2F2/K2CO3 Using DMSO as Solvent and Oxidant
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A practical, general and mild oxidation of primary and secondary alcohols to carbonyl compounds proceeds in yields of up to 99% using SO2F2 as electrophile in DMSO as both the oxidant and the solvent at ambient temperature. No moisture- and oxygen-free conditions are required. Stoichiometric amount of inexpensive K2CO3, which generates easy to separate by-products, is used as the base. Thus, 5-gram scale runs proceeded in nearly quantitative yields by a simple filtration as the work-up. The use of a polar solvent such as DMSO, which usually promotes competing Pummerer rearrangement, is also noteworthy. This protocol is compatible with a variety of common N-, O-, and S-functional groups on (hetero)arene, alkene and alkyne substrates (68 examples). The protocol was applied (99% yield) to a formal synthesis of the important cholesterol-lowering drug Rosuvastatin. (Figure presented.).
- Zha, Gao-Feng,Fang, Wan-Yin,Leng, Jing,Qin, Hua-Li
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supporting information
p. 2262 - 2267
(2019/04/17)
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- A Transition-Metal-Free One-Pot Cascade Process for Transformation of Primary Alcohols (RCH2OH) to Nitriles (RCN) Mediated by SO2F2
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A new transition-metal-free one-pot cascade process for the direct conversion of alcohols to nitriles was developed without introducing an “additional carbon atom”. This protocol allows transformations of readily available, inexpensive, and abundant alcohols to highly valuable nitriles.
- Jiang, Ying,Sun, Bing,Fang, Wan-Yin,Qin, Hua-Li
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supporting information
p. 3190 - 3194
(2019/05/21)
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- Magnetic crosslinked copoly(ionic liquid) nanohydrogel supported palladium nanoparticles as efficient catalysts for the selective aerobic oxidation of alcohols
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Nowadays it is still a great sustainable processes challenge to produce efficient, selective and easy magnetic recovery and recycling catalysts for oxidation of alcohols using air as the oxidant. In this work, a new magnetic nanohydrogel comprising [DABCO-allyl][Br] ionic liquid, allyl alcohol and N,N’-methylenebis(acrylamide) is used for stabilization of small and highly uniform palladium nanoparticles of 3–4 nm size MXCPILNHG@Pd. This material has been characterized by Fourier-transform infrared spectroscopy (FTIR), atomic adsorption spectroscopy (AAS), thermogravimetric analysis (TGA), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), SEM-Map, energy-dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectra (XPS), vibrating-sample magnetometer (VSM) and dynamic light scattering (DLS). According to optimization of cross-linking degree and ratio of DABCO-IL, MXCPILNHG-2@Pd is found as a highly selective catalyst in oxidations of primary alcohols to the corresponding aldehydes in toluene and to acids in water. Furthermore, secondary alcohols were reacted efficiently to the corresponding ketones in both toluene and water. Catalyst is magnetically recovered and recycled for several times in both toluene and water and the reused catalysts are characterized by TEM and XPS.
- Gholinejad, Mohammad,Afrasi, Mahmoud,Nikfarjam, Nasser,Nájera, Carmen
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p. 185 - 195
(2018/07/14)
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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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- 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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- 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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- Photooxidative cleavage of aromatic alkenes into aldehydes using catalytic iodine and molecular oxygen under visible light irradiation
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We report a method for the photooxidative cleavage of aromatic alkenes to give aldehydes using molecular oxygen as the terminal oxidant, visible light, a catalytic amount of iodine and trifluoroacetic acid.
- Fujiya, Akitoshi,Kariya, Atsumasa,Nobuta, Tomoya,Tada, Norihiro,Miura, Tsuyoshi,Itoh, Akichika
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p. 884 - 888
(2014/04/03)
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- Morphology dependant oxidation of aromatic alcohols by new symmetrical copper(II) metallatriangles formed by self-assembly of a shared bis-benzimidazolyl diamide ligand
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A new bis-benzimidazole-based diamide ligand N2,N 2′-bis((1H-benzo[d]imidazol-2-yl)methyl)-[1,1′-biphenyl] -2,2′-dicarboxamide, L and its three Cu(II) metallatriangles of general formula [Cu3(L)3X3]·3X·nH 2O (where X = Cl, Br, NO3) have been synthesized and one of them is structurally characterized. X-ray diffraction work reveals that the metallatriangle [Cu3(L)3Cl3] ·3Cl·15H2O crystallizes in trigonal R3? space group with two independent molecules in the asymmetric unit. The asymmetric unit contains only one-third of the molecules and the rest are generated by the crystallographic 3? axis. Each copper(II) ion adopts a highly distorted square pyramidal geometry. The copper(II) metallatriangles are used as catalyst to carry out the oxidation of substituted benzyl alcohols heterogeneously, in the presence of tert-butyl hydroperoxide. Interestingly, the ratio of product profile and the percentage conversion of the products changes with the surface morphology of the metallatriangle employed as a catalyst. A kite type morphology is found to be highly selective to the formation of acid product over the aldehyde, while a hexagonal type morphology results in a mixed acid + aldehyde product. The initial rate of formation of the aldehyde is found to be almost independent of the amount of catalyst employed.
- Mahiya, Kuldeep,Mathur, Pavan
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- Oxidative cleavage of C=C bond of styrene and its derivatives with H 2O2 using vanadyl (IV) acetylacetonate anchored SBA-15 catalyst
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Cleavage of C=C bond of styrene and its derivatives into two carbonyl compounds with H2O2 is accomplished at mild conditions using Vanadyl(IV) acetylacetonate anchored SBA-15 catalyst, which is prepared and characterized by BET surface area, low angle XRD and FT-IR. It is a highly efficient, recyclable and reusable catalyst.
- Anand, Narani,Reddy, Kannapu Hari Prasad,Rao, Kamaraju Seetha Rama,Burri, David Raju
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experimental part
p. 1355 - 1363
(2012/02/01)
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- Synthesis of aromatic aldehydes by organocatalytic [4+2] and [3+3] cycloaddition of α,β-unsaturated aldehydes
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Organocatalytic inter- and intramolecular [4+2] and [3+3] cycloadditions of α,β-unsaturated aldehydes to give polysubstituted aromatic aldehydes are described. High periselectivity for the cycloadditions, with catalyst effects exerted by l-proline and pyrrolidine-HOAc, as well as cocatalyst, additive effects, has been observed.
- Hong, Bor-Cherng,Tseng, Hsing-Chang,Chen, Shang-Hung
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p. 2840 - 2850
(2007/10/03)
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- Efficient and convenient procedure for protection of hydroxyl groups to the THP, THF and TMS ethers and oxidation of these ethers to their aldehydes or ketones in [BPy]FeCl4 as a low cost room temperature ionic liquid
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Alcohols were converted to the corresponding THP, THF or TMS ethers in high to excellent yields in 1-n-butylpyridinium chloroferrate media as a stable and low cost room temperature ionic liquid. In addition, oxidation of these ethers to their aldehydes or ketones without any overoxidation reactions in this ionic liquid was also performed.
- Khosropour, Ahmad R.,Khodaei, Mohammad M.,Ghaderi, Sattar
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p. 326 - 330
(2007/10/03)
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- Orthoamides, LXIII [1]. Tris(dichloromethyl)amine, a new formylating reagent for aromatic compounds of wide scope
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The reagent system formed from tris(dichloromethyl)amine (5) and aluminium chloride allows the formylation of aromatic compounds. The scope of the method is comparable with that of the Olah formylation and the Gro?-Rieche procedure, since benzene and even chlorobenzene can be formylated. One formyl group is transferred from 5 to the aromatic nucleus. In order to find optimal reaction conditions, the molar amounts of aromatic compounds, 5 and aluminum chloride were varied as well as reaction temperatures and solvents. The activation of 5 with other Lewis acids is also described.
- Kantlehner, Willi,Wezstein, Markus,Kre?, Ralf,Zschach, Franziska,Vetter, Jens,Ziegler, Georg,Mezger, Jochen,Stoyanov, Edmont V.,Goeppert, Alain,Sommer, Jean
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p. 448 - 463
(2007/10/03)
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- TEMPO-derived task-specific ionic liquids for oxidation of alcohols
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A novel 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) radical bearing an ionic liquid-type appendage has been prepared, and its catalytic activity for the selective oxidation of alcohols to the corresponding carbonyl compounds in ionic liquid-aqueous biphasic conditions has been investigated. The ionic liquid-supported TEMPO radical shows catalyst properties similar to those of nonsupported counterpart in terms of activity and selectivity, and can be easily recycled and reused without loss of activity and selectivity.
- Wu, Xue-E.,Ma, Li,Ding, Meng-Xian,Gao, Lian-Xun
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p. 607 - 610
(2007/10/03)
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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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- N-chloro-3-methyl-2,6-diphenylpiperidin-4-one (NCP) - An efficient, mild, stable oxidant for cleavage of carbon-nitrogen double bonds of oximes
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Aldoximes and ketoximes are effectively deoximated to regenerate the carbonyl compound by an efficient, mild, stable oxidant N-chloro-3-methyl-2,6-diphenylpiperidin-4-one (NCP).
- Balasubramanian,Ramalingan,Kabilan
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p. 2979 - 2984
(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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- Method of producing phenol compound
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A method of producing a phenol compound comprising a step of oxidizing an aromatic aldehyde to an aryl formate and an aromatic carboxylic acid with an oxygen-containing gas, and a step of decomposing the aryl formate to the phenol compound. To facilitate the separation of the aryl formate and the unreacted aromatic aldehyde, a mixture of the aryl formate and the unreacted aromatic aldehyde is recycled to the oxidation process to concentrate the aryl formate in the oxidation mixture. Alternatively, the oxidation process is carried out in an organic solvent having substantially no ability of dissolving water to increase the conversion of the aromatic aldehyde and the selectivity of the aryl formate, thereby producing the aryl formate in a high yield. In another method, the aryl formate is produced by oxidizing the aromatic aldehyde in the organic solvent having substantially no ability of dissolving water with performic acid generated in situ in the reaction system from the reaction between formic acid and hydrogen peroxide. Since the oxidation proceeds in the organic solvent, hydrogen peroxide in aqueous phase contact the aromatic aldehyde. This significantly reduces the amount of explosive cyclic perther and a high-boiling product.
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- Highly efficient aerobic oxidation of benzylic and allylic alcohols by a simple catalyst system of [RuCl2(p-cymene)]2/Cs2CO3
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A new catalyst system of [RuCl2(p-cymene)]2/Cs2CO3 has been disclosed for highly efficient aerobic oxidation of activated alcohols to the corresponding carbonyl compounds, which is characterized by its high selectivity and activity, operational simplicity, and low air and moisture sensitivity. (C) 2000 Elsevier Science Ltd.
- Lee,Chang
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p. 7507 - 7510
(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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- 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 and dichloromethylation as alternative directions of rieche reaction. A novel to the synthesis of sterically hindered aromatic dialdhydes
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A previously unknown direction of Rieche reaction has been found: formylation of mesitylene, m-xylene, and durene with dichloromethyl methyl ether in the presence of aluminium trichloride and, to lesser extent, of titanium tetrachloride give the respective benzylidene dichlorides besides aldehydes. A novel approach to the synthesis of sterically hindered aromatic dialdehydes has been offered which involves the transformation of a monoaldehyde into the corresponding benzylidene dichloride, Rieche formylation of the latter, and hydrolysis of dichloromethyl aldehyde formed.
- Yakubov, Alexander P.,Tsyganov, Dmitry V.,Belen'kii, Leonid I.,Krayushkin, Mikhail M.
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p. 3397 - 3404
(2007/10/02)
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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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- Process for nucleophilic fluoroalkylation of aldehydes
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Aryl difluoromethyl sulfone adds to alkehydes under phase transfer conditions to give novel substituted alcohols of the general formula wherein R is an aryl, cycloaliphatic, sec- or tert-aliphatic, or heterocyclic group and Ar is an aryl group. The substituted alcohols of formula I are of particular utility as intermediates in the synthesis of a variety of useful end products. For example, the products of formula I may be utilized in desulfonylation reactions, oxidation reactions and fluorination reactions.
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- Ortho Metalation Directed by α-Amino Alkoxides
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The addition of aromatic aldehydes to certain lithium dialkylamides in benzene or tetrahydrofuran gave α-amino alkoxides which were ortho lithiated with excess n-butyllithium.Subsequent alkylation and hydrolysis provided ortho-substituted aromatic aldehydes via a one-pot reaction.The ortho metalation of α-amino alkoxides derived from 1- and 2-naphthaldehyde and various substituted benzaldehydes was examined.When N,N,N'-trimethylethylenediamine was used as the amine component of the α-amino alkoxide, metalation could be carried out at lower temperatures.This rate increase is due to an intramolecular TMEDA-like assisted metalation.The synthetic utility of this ortho metalation, including how varying the amine component of the α-amino alkoxide affects the regiochemistry and metalation rate, is discussed.
- Comins, Daniel L.,Brown, Jack D.
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p. 1078 - 1083
(2007/10/02)
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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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- Formylation and Acylation Reactions Catalysed by Trifluoromethanesulphonic Acid
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Regioselective formylation of toluene, m- and p-xylene, and mesitylene has been achieved by carbonylation in trifluoromethanesulphonic acid at CO pressures of 90-125 atm.In the case of cumene, the formylation reaction is in competition with disproportionation to form di- and tri-isopropylbenzenes, leading to a complex product mixture.Slow addition of cyclohexene or cyclopentene to a mixture of benzene and CF3SO3H under a high CO pressure affords 4-cyclohexylbenzaldehyde and 4-cyclopentylbenzaldehyde in 34percent and 33percent yieds, respectively, while 2-methylbut-1-ene gives 2,2,3-trimethylindanone (39percent) under similar conditions.When cyclohexene is mixed with the acid under carbon monoxide (120 atm) before addition of benzene the major products are cyclohexyl phenyl ketone and cyclohexenyl cyclohexyl ketones.
- Booth, Brian L.,El-Fekky, Teymour A.,Noori, Ghazi F. M.
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p. 181 - 186
(2007/10/02)
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