- Rapid, chemoselective and mild oxidation protocol for alcohols and ethers with recyclable N-chloro-N-(phenylsulfonyl)benzenesulfonamide
-
Chlorine is the 20th most abundant element on the earth compared to bromine, iodine, and fluorine, a sulfonimide reagent, N-chloro-N-(phenylsulfonyl)benzenesulfonamide (NCBSI) was identified as a mild and selective oxidant. Without activation, the reagent was proved to oxidize primary and secondary alcohols as well as their symmetrical and mixed ethers to corresponding aldehydes and ketones. With recoverable PS-TEMPO catalyst, selective oxidation over chlorination of primary and secondary alcohols and their ethers with electron-donating substituents was achieved. The reagent precursor of NCBSI was recovered quantitatively and can be reused for synthesizing NCBSI.
- Badani, Purav,Chaturbhuj, Ganesh,Ganwir, Prerna,Misal, Balu,Palav, Amey
-
supporting information
(2021/06/03)
-
- carba Nicotinamide Adenine Dinucleotide Phosphate: Robust Cofactor for Redox Biocatalysis
-
Here we report a new robust nicotinamide dinucleotide phosphate cofactor analog (carba-NADP+) and its acceptance by many enzymes in the class of oxidoreductases. Replacing one ribose oxygen with a methylene group of the natural NADP+ was found to enhance stability dramatically. Decomposition experiments at moderate and high temperatures with the cofactors showed a drastic increase in half-life time at elevated temperatures since it significantly disfavors hydrolysis of the pyridinium-N?glycoside bond. Overall, more than 27 different oxidoreductases were successfully tested, and a thorough analytical characterization and comparison is given. The cofactor carba-NADP+ opens up the field of redox-biocatalysis under harsh conditions.
- D?ring, Manuel,Sieber, Volker,Simon, Robert C.,Tafertshofer, Georg,Zachos, Ioannis
-
supporting information
p. 14701 - 14706
(2021/05/13)
-
- Method for hydrogenolysis of halides
-
The invention discloses a method for hydrogenolysis of halides. The invention discloses a preparation method of a compound represented by a formula I. The preparation method comprises the following step: in a polar aprotic solvent, zinc, H2O and a compound represented by a formula II are subjected to a reaction as shown in the specification, wherein X is halogen; Y is -CHRR or R; hydrogenin H2O exists in the form of natural abundance or non-natural abundance. According to the preparation method, halide hydrogenolysis can be simply, conveniently and efficiently achieved through a simple and mild reaction system, and good functional group compatibility and substrate universality are achieved.
- -
-
Paragraph 0232; 0269-0271
(2021/01/11)
-
- Aerobic oxidation of alcohols catalyzed by in situ generated gold nanoparticles inside the channels of periodic mesoporous organosilica with ionic liquid framework
-
In situ generated gold nanoparticles inside the nanospaces of periodic mesoporous organosilica with an imidazolium framework (Au?PMO-IL) were found to be highly active, selective, and reusable catalysts for the aerobic oxidation of activated and nonactivated alcohols under mild reaction conditions. The catalyst was characterized by nitrogen adsorption-desorption measurement, thermogravimetric analysis (TGA), transmission electron microscopy (TEM), elemental analysis (EA), diffuse reflectance infrared Fourier transform spectroscopy (DRIFT), X-ray photoelectron spectroscopy (XPS), and inductively coupled plasma atomic emission spectroscopy (ICP-AES). The catalyst exhibited excellent catalytic activity in the presence of either Cs2CO3 (35 °C) or K2CO3 (60 °C) as reaction bases in toluene as a reaction solvent. Under both reaction conditions, various types of alcohols (up to 35 examples) including activated benzylic, primary and secondary aliphatic, heterocyclic, and challenging cyclic aliphatic alcohols converted to the expected carbonyl compounds in good to excellent yields and selectivity. The catalyst was also recovered and reused for at least seven reaction cycles. Data from three independent leaching tests indicated that amounts of leached gold particles were negligible (0.2 ppm). It is believed that the combination of bridged imidazolium groups and confined nanospaces of PMO-IL might be a major reason explaining the remarkable stabilization and homogeneous distribution of in situ generated gold nanoparticles, thus resulting in the highly active and recyclable catalyst system.
- Bigdeli, Akram,Karimi, Babak,Khodadadi Karimvand, Somaiyeh,Khorasani, Mojtaba,Safari, Ali Asghar,Vali, Hojatollah
-
supporting information
p. 70 - 79
(2020/06/08)
-
- Dehalogenative Deuteration of Unactivated Alkyl Halides Using D2O as the Deuterium Source
-
The general dehalogenation of alkyl halides with zinc using D2O or H2O as a deuterium or hydrogen donor has been developed. The method provides an efficient and economic protocol for deuterium-labeled derivatives with a wide substrate scope under mild reaction conditions. Mechanistic studies indicated that a radical process is involved for the formation of organozinc intermediates. The facile hydrolysis of the organozinc intermediates provides the driving force for this transformation.
- Xia, Aiyou,Xie, Xin,Hu, Xiaoping,Xu, Wei,Liu, Yuanhong
-
p. 13841 - 13857
(2019/10/17)
-
- Method for preparing camphor through continuous dehydrogenation of isoborneol
-
The invention relates to a method for preparing camphor through continuous dehydrogenation of isoborneol.In the camphor synthetizing industry at present, the step of preparing camphor through dehydrogenation of isoborneol is critical.The method for preparing camphor through isoborneol overcomes the defects that the conversion rate is low, products are difficultly purified, a catalyst is likely to be inactivated, and hydrogen cannot be recycled due to batch operation.By adopting continuous operation, the camphor yield is high, and obtained hydrogen can be recycled; due to tubular reactors connected in series, the reaction temperature and pressure are controllable, materials are subjected to a reaction on the liquid phase condition, the conversion rate of the reversible reaction is increased, the product purification difficulty is lowered, the catalysis efficiency of the selected catalyst is high on the condition, the service life is long, the product is reproducible, and defects existing in original technologies are overcome to a large extent.
- -
-
Paragraph 0033-0034
(2017/05/20)
-
- Ultrasmall Platinum Nanoparticles Supported Inside the Nanospaces of Periodic Mesoporous Organosilica with an Imidazolium Network: An Efficient Catalyst for the Aerobic Oxidation of Unactivated Alcohols in Water
-
The imidazolium group inside the wall of a periodic mesoporous organosilica provides an excellent environment for the stabilization of ultrasmall Pt nanoparticles ((NP)@PMO-IL) with significant activity and recyclability in the selective aerobic oxidation of various alcohols in water at ambient pressure of oxygen. In particular, the catalyst exhibited high activity in the oxidation of unactivated primary alcohols and sterically encumbered secondary aliphatic alcohols, which remain challenging substrates for many catalytic aerobic protocols.
- Karimi, Babak,Naderi, Zahra,Khorasani, Mojtaba,Mirzaei, Hamid M.,Vali, Hojatollah
-
p. 906 - 910
(2016/03/15)
-
- Nitrite-containing resin as an efficient and recyclable catalyst for aerobic oxidation of oximes to carbonyl compounds
-
Using novel nitrite-containing resin as an NO source and Amberlyst-15 as cocatalyst, we developed aerobic oxidation of oximes to corresponding carbonyl compounds with molecular oxygen as a clean oxidant reagent. It was distinguished from the previous related reports, and the experimental results indicated that additional water obviously decreased the yield. This process provides a better choice for oxidative deoximation with many advantages, such as high yield, simple procedure, high catalytic performance, and recyclable catalyst.
- Guo, Shu,Zeng, Renyou,Li, Caiye
-
supporting information
p. 1446 - 1453
(2016/09/14)
-
- A highly efficient palladium(ii)/polyoxometalate catalyst system for aerobic oxidation of alcohols
-
A simple catalyst system composed of Pd(OAc)2, phosphomolybdic acid and tetrabutylammonium acetate oxidises a range of alcohols efficiently, with turnover numbers (TONs) of up to 10000.
- Dornan, Laura M.,Muldoon, Mark J.
-
p. 1428 - 1432
(2015/04/14)
-
- Reactions of hydroxyl-containing compounds with tert-butyl hydroperoxide in the presence of chromium tetra-tert-butoxide
-
Primary and secondary aliphatic, alkylaromatic, cyclic, and organoelement alcohols are efficiently oxidized by tert-butyl hydroperoxide in the presence of both equimolar and catalytic quantities of chromium tetra-tert-butoxide (C6H6, 20°C). α-Diols containing tertiary hydroxyl groups interact with this system via oxidative splitting of the carbon scaffold. The oxidation includes the stages of formation and decomposition of chromium-containing peroxy compounds. Further transformations of the carbonyl compounds depend on the structure of radicals in the molecules.
- Stepovik,Zaburdaeva,Fukin,Karaghiosoff
-
p. 2547 - 2559
(2015/12/30)
-
- Mn(ii) acetate: An efficient and versatile oxidation catalyst for alcohols
-
A homogeneous catalytic system consisting of Mn(ii) acetate (18 μmol), tert-butylhydroperoxide (2.5 mmol), acetonitrile (1.5 mL) and trifluoroacetic acid (91 μmol) was developed for efficient and selective oxidation of various alcohols (1 mmol). The system yielded good to quantitative conversions (42-100%) of various secondary alcohols, such as 2-octanol, fenchyl alcohol and borneol, to their corresponding ketones. Primary alcohols, for example 1-octanol and differently substituted benzyl alcohols, were mainly converted to their corresponding carboxylic acids. Studies with a selection of hydrocarbons, tertiary amines and a cyclic ether isochroman showed that besides alcohols, other substrates can be oxidised as well.
- Raeisaenen, Minna T.,Al-Hunaiti, Afnan,Atosuo, Elisa,Kemell, Marianna,Leskelae, Markku,Repo, Timo
-
p. 2564 - 2573
(2014/07/22)
-
- Copper(I)/ABNO-catalyzed aerobic alcohol oxidation: Alleviating steric and electronic constraints of Cu/TEMPO catalyst systems
-
Cu/TEMPO catalyst systems promote efficient aerobic oxidation of sterically unhindered primary alcohols and electronically activated substrates, but they show reduced reactivity with aliphatic and secondary alcohols. Here, we report a catalyst system, consisting of (MeObpy)CuI(OTf) and ABNO (MeObpy =4,4′-dimethoxy-2,2′-bipyridine; ABNO = 9-azabicyclo[3.3.1]nonane N-oxyl), that mediates aerobic oxidation of all classes of alcohols, including primary and secondary allylic, benzylic, and aliphatic alcohols with nearly equal efficiency. The catalyst exhibits broad functional group compatibility, and most reactions are complete within 1 h at room temperature using ambient air as the source of oxidant.
- Steves, Janelle E.,Stahl, Shannon S.
-
supporting information
p. 15742 - 15745
(2013/11/06)
-
- C-H modification of 2-azaadamantane: Synthesis of C5-functionalized AZADOs for advanced use
-
Regioselective C-H functionalization of N-protected 2-azaadamantane was achieved via a radical-induced bromination. The obtained 5-bromo-2-azaadamantane is readily transformed to arylated/alkylated 2-azaadamantane N-oxyls [AZADOs], which exhibit high catalytic activities for alcohol oxidation. The Japan Institute of Heterocyclic Chemistry.
- Sasano, Yusuke,Nishiyama, Tomohiro,Tomizawa, Masaki,Shibuya, Masatoshi,Iwabuchi, Yoshiharu
-
p. 2109 - 2118
(2013/10/22)
-
- TEMPO-mediated oxidation of alcohols with ion-supported (diacetoxyiodo)benzenes
-
The oxidation of secondary alcohols and primary alcohols with novel ion-supported (diacetoxyiodo)benzenes (IS-DIB) in the presence of a catalytic amount of 2,2,6,6-tetramethylpiperidine-1-oxy radical (TEMPO) in dichloromethane at room temperature proceeded efficiently to provide the corresponding ketones and aldehydes, respectively, in good yields with high purity. Isolation of the product was easily accomplished by simple diethyl ether extraction of the reaction mixture and subsequent removal of the solvent from the extract. Moreover, ion-supported iodobenzenes, which were co-products derived from IS-DIB in the present oxidation, were recovered in good yields and could be re-oxidized to IS-DIB for reuse in the same oxidation. Georg Thieme Verlag Stuttgart · New York.
- Suzuki, Yusuke,Iinuma, Masataka,Moriyama, Katsuhiko,Togo, Hideo
-
experimental part
p. 1250 - 1256
(2012/06/04)
-
- Aqueous hydrogen peroxide and 2,4,4,6-tetrabromo-2,5-cyclohexadienone catalyst: An efficient mild ecofriendly cleaving reagent of thioacetals and thioketals
-
A clean mild efficient dethioacetalization protocol is revealed utilizing a catalytic combination of 2,4,4,6-tetrabromo-2,5-cyclohexadienone (TBCHD) (20 mol%) with 30% hydrogen peroxide as a terminal oxidizer in aqueous acetonitrile at room temperature. High yields of carbonyl compounds without overoxidation for oxidation-prone aromatic and furyl aldehydes, simple work-up, use of cost-compatible readily accessible reagents, tolerance of a wide range of common functional and protecting groups including phenolic hydroxy, methylenedioxy, acetoxy, aromatic amino, carbon-carbon double bond, allyl, benzyl, TBDPS ethers, NHBoc, NHBz are the key attractive features of the method.
- Ganguly, Nemai C.,Nayek, Subhasis,Barik, Sujoy Kumar
-
scheme or table
p. 251 - 256
(2012/03/11)
-
- A convenient method for deoximation of oximes by using N-iodosuccinimide under microwave irradiation
-
A rapid and selective method for the cleavage of oximes has been achieved by a simple reaction of a ketoxime or an aldoxime with N-iodosuccinimide in acetone under microwave irradiations.
- Manesh, Abbas Amini,Khazaei, Ardeshir
-
experimental part
p. 762 - 764
(2011/12/16)
-
- Mild, Efficient, and greener dethioacetalization protocol using 30% hydrogen peroxide in catalytic combination with ammonium iodide
-
A simple, mild, efficient, and expedient greener dethioacetalization protocol employing a catalytic amount of nontoxic ammonium iodide (10mol%) in combination with 30% hydrogen peroxide as terminal oxidizer is revealed. The reagent accomplished facile deprotection of 1,3-dithianes and dithiolanes of activated aromatic substrates in an aqueous medium in the presence of sodium dodecylsulfate (SDS) at room temperature under virtually neutral conditions. Deactivated and sterically encumbered substrates, which are otherwise reluctant to cleave under aqueous micellar conditions, were expeditiously cleaved in good to excellent yields in acetic acid. The method is tolerant, with several acid-sensitive protecting groups, such as tert-butyldiphenylsilyl (TBDPS) ether, aryl acetate, NHBoc, and NHBn, and with further oxidation of oxidation-prone activated benzaldehydes and furyl aldehydes. A tentative mechanism of hypoiodous acid-mediated catalytic cleavage is proposed.
- Ganguly, Nemai C.,Mondal, Pallab
-
experimental part
p. 2374 - 2384
(2011/08/05)
-
- Oxidation studies on some natural monoterpenes: Citral, pulegone, and camphene
-
Citral extracted from Cymbopogon citratus (Gramineae) was subjected to photochemical epoxidation with hydrogen peroxide to obtain a mixture of epoxy derivatives at the C2=C3 and C6=C7 double bonds. The thermal oxidation of citral with m-chloroperoxybenzoic acid at room temperature gave only the corresponding 6,7-epoxy derivative as a mixture of E and Z isomers with respect to the C2=C3 double bond. Photosensitized oxygenation of citral in the presence of tetraphenylporphyrin, Rose Bengal, or chlorophyll lead to a mixture of two isomeric hydroperoxides, (2E)-6-hydroperoxy-3,7-dimethylocta-2,7-dienal and (2E,5E)-7-hydroperoxy-3,7- dimethylocta-2,5-dienal. Epoxidation of pulegone isolated from Penny royal oil (Mentha pulegium, Lamiaceae) with hydrogen peroxide under irradiation with a sodium lamp lead to a mixture of cis- and trans-isomeric 2,2,6-trimethyl-1- oxaspiro[2.5]octan-4-ones, whereas under conditions of photosensitized oxygenation two hydroperoxide derivatives, 2-(1-hydroperoxy-1-methylethyl)-5- methylcyclohex-2-en-1-one and 2-hydroperoxy-5-methyl-2-(1-methylethenyl) cyclohexan-1-one, were also formed. Camphene reacted with hydrogen peroxide under irradiation to give a mixture of the corresponding endo- and exo-epoxy derivatives and camphor, while its thermal oxidation with m-chloroperoxybenzoic produced only the two former.
- Elgendy,Khayyat
-
experimental part
p. 814 - 822
(2009/07/05)
-
- Highly efficient and selective oxidation of secondary alcohols to ketones under organic solvent and transition metal free conditions
-
The aqueous HBr/H2O2 was found to be highly efficient and green catalytic system for the selective oxidation of the secondary alcohols to ketones in excellent yields under organic solvent free conditions. The results of the oxidation of the secondary alcohols with solid alternatives of the aqueous hydrogen peroxide like SPC or SPB are also described.
- Jain, Suman L.,Sharma, Vishal B.,Sain, Bir
-
p. 6841 - 6847
(2007/10/03)
-
- Regeneration of the carbonyl compounds from their semicarbazones using tetra-n-alkylammonium bromates
-
Tetra alkyl ammonium bromates are prepared by a simple procedure and used for the oxidative regeneration of the parent carbonyl compound from their semicarbazones. Reaction conditions are simple and the deprotection gives satisfactory yield of the carbonyl compound.
- Baruah, Akashi,Nath, Utpal,Das, Satya Sandhya,Das, Pranab Jyoti
-
p. 2157 - 2160
(2007/10/03)
-
- Silicon-catalyzed conversion of nitro compounds into ketones and poly(1,3-diketones)
-
The reaction of various secondary nitro compounds with 1.1 equivalents of potassium hydride in 1,4-dioxane and then with 0.10 equivalent of chlorotrimethylsilane gave the corresponding ketones in 62-90% yields. By a similar strategy, poly(1,3-diketones) were synthesized directly from nitroalkenes with sodium ethoxide, potassium hydride, and chlorotrimethylsilane in 1,4-dioxane. The use of chlorotrimethylsilane in a catalytic amount was the key to the success of this transformation; the use of an excess of chlorotrimethylsilane led to poor yields for the same reactions. Georg Thieme Verlag Stuttgart.
- Hwu, Jih Ru,Josephrajan, Thainashmuthu,Tsay, Shwu-Chen
-
p. 3305 - 3308
(2008/09/17)
-
- A simple and highly selective biomimetic oxidation of alcohols and epoxides with N-bromosuccinimide in the presence of β-cyclodextrin in water
-
A simple, mild and highly efficient biomimetic oxidation of various alcohols and epoxides with N-bromosuccinimide (NBS) catalyzed by β-cyclodextrin in water has been developed. A series of alcohols and epoxides were oxidized selectively at room temperature in excellent yields. This method is a direct one-pot synthesis under mild conditions using water as solvent and has many advantages over the existing methodologies.
- Krishnaveni, N. Srilakshmi,Surendra,Rao, K. Rama
-
p. 346 - 350
(2007/10/03)
-
- Aerobic oxidation of cycloalkanes, alcohols and ethylbenzene catalyzed by the novel carbon radical chain promoter NHS (N-hydroxysaccharin)
-
Replacement of Ishii's N-hydroxyphthalimide (NHPI) with the novel carbon radical chain promoter N-hydroxysaccharin (NHS) affords, in combination with metal salts, notably Co, or other additives, selective catalytic autoxidation of hydrocarbons, alcohols and alkylbenzenes under mild conditions (25-100°C, O2 1 atm). The effects of solvent, temperature and the nature of the additives were investigated to give an optimised oxidation protocol for the various systems. The NHS/Co combination was more reactive than NHPI/Co in the autoxidation of cycloalkanes. In contrast, the opposite order of reactivity was observed in the autoxidation of ethylbenzene and alcohols. It is suggested, on the basis of bond dissociation energy (BDE) considerations, that this is a result of a change in the rate-limiting step with the more reactive ethylbenzene and alcohol substrates. In the autoxidation of the model cycloalkane, cyclododecane, the best results (90% selectivity to a 4:1 mixture of alcohol and ketone at 24% conversion) were obtained with NHS/Co(acac)3 in PhCF3 at 80°C. Competition experiments revealed that, in contrast to what is commonly believed, formation of the dicarboxylic acid by ring opening is not a result of further oxidation of the ketone product. It is suggested that ring opened products are a result of β-scission of the cycloalkoxy radical formed via (metal-catalysed) decomposition of the hydroperoxide. This is suppressed in the presence of NHS (or NHPI) which efficiently scavenge the alkoxy radicals.
- Baucherel, Xavier,Gonsalvi, Luca,Arends, Isabel W. C. E.,Ellwood, Simon,Sheldon, Roger A.
-
p. 286 - 296
(2007/10/03)
-
- Hydrolysis of Alkenyl Esters and Ethers Catalyzed by Metal Complexes
-
(Equation presented) Various kinds of transition metals catalyzed the hydrolysis of alkenyl esters and ethers under buffer-free, high concentration conditions compared to usual biocatalysts. Hydrolytic kinetic resolution of cis-2-tert-butylcyclohexyl vinyl ether was achieved by chiral (salen)Co complexes with good selectivity (krel = 10.0).
- Aoyama, Hiroshi,Tokunaga, Makoto,Hiraiwa, Shin-Ichiro,Shirogane, Yuki,Obora, Yasushi,Tsuji, Yasushi
-
p. 509 - 512
(2007/10/03)
-
- Cobalt phthalocyanine catalyzed aerobic oxidation of secondary alcohols: An efficient and simple synthesis of ketones
-
A variety of activated and non-activated secondary alcohols have been efficiently oxidized to their corresponding ketones in excellent yields with molecular oxygen using cobalt phthalocyanine as catalyst in the presence of powdered potassium hydroxide.
- Sharma, Vishal B.,Jain, Suman L.,Sain, Bir
-
p. 383 - 386
(2007/10/03)
-
- Wet silica-supported permanganate for the cleavage of semicarbazones and phenylhydrazones under solvent-free conditions
-
Wet silica-supported potassium permanganate was used as an inexpensive and efficient reagent for conversion of semicarbazones and phenylhydrazones to the corresponding carbonyl compounds under solid-state conditions.
- Hajipour, Abdol R.,Adibi, Hadi,Ruoho, Arnold E.
-
p. 4553 - 4555
(2007/10/03)
-
- New odorless protocols for the Swern and Corey-Kim oxidations
-
New odorless protocols for the Swern oxidation as well as the Corey-Kim oxidation using dodecyl methyl sulfoxide (1) or dodecyl methyl sulfide (3) are described.
- Nishide, Kiyoharu,Ohsugi, Shin-Ichi,Fudesaka, Masato,Kodama, Sumiaki,Node, Manabu
-
p. 5177 - 5179
(2007/10/03)
-
- The fluorous Swern and Corey-Kim reactions: Scope and mechanism
-
Protocols for the efficient preparation of 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-8-methanesulfenyloctane and 1,1,1,2,2,3,3,4,4-nonafluoro-6-methanesulfenylhexane (fluorous dimethyl sulfide) and for their oxidation to the corresponding sulfoxides (fluorous dimethyl sulfoxide) are reported. The lower molecular weight sulfoxide, in conjunction with oxalyl chloride and Hunig's base, brings about the oxidation of diversely functionalized primary and secondary alcohols to aldehydes and ketones in excellent yield. The fluorous sulfoxide is efficiently recovered for reuse by a simple continuous fluorous extraction and hydrogen peroxide oxidation protocol. The whole process is odor-free. A deuterium-labeling experiment is used to demonstrate that the oxidations take place via the classical Swern mechanism, i.e. by intramolecular hydride abstraction from a sulfur ylid. Corey-Kim oxidations may be performed with the higher molecular weight fluorous sulfide, although recycling is not as efficient.
- Crich, David,Neelamkavil, Santhosh
-
p. 3865 - 3870
(2007/10/03)
-
- NaBrO3-FeCl3 as a new reagent for oxidation of benzylic and secondary alcohols to carbonyl compounds
-
NaBrO3 combined with FeCl3 is found to be an efficient reagent for the conversion of benzylic and secondary alcohols into aldehydes and ketones, respectively.
- Shaabani,Ajabi
-
p. 148 - 151
(2007/10/03)
-
- Caro's acid supported on silica gel. Part 3: A mild and selective reagent for regeneration of carbonyl compounds from oximes
-
Various oximes were converted into the corresponding carbonyl compounds in high yields with Caro's acid supported on silica gel in acetic acid at room temperature.
- Movassagh,Lakouraj,Ghodrati
-
p. 4501 - 4506
(2007/10/03)
-
- Oxidation of Organic Substrates with Potassium Ferrate(VI) in the Presence of the K10 Montmorillonite
-
Among various aluminosilicate supports, the K10 montmorillonite clay was the best catalyst for the oxidation of organic substrates with potassium ferrate(VI).Thus, a solid mixture of K2FeO4 and K10 has been used for the efficient oxidation of selected alcohols, benzylamine, thiophenol, and aniline in hydrocarbon solvents at room temperature.Somewhat humid clay performs best, and it is important to control the amount of water associated to the solid support.
- Delaude, Lionel,Laszlo, Pierre,Lehance, Pascal
-
p. 8505 - 8508
(2007/10/02)
-
- Electrochemical Oxidation of Secondary Alcohols Using Thioanisole as an Oraganic Mediator in the Presence of 2,2,2-Trifluoroethanol
-
Electrochemical oxidation of secondary alcohols gave the corresponding ketones in good yields when 2,2,2-trifluoroethanol was used as a solvent or a co-solvent of MeCN containing Et4NBF4 as a supporting electrolyte.
- Matsumura, Yoshihiro,Yamada, Masaki,Kise, Naoki,Fujiwara, Mitchitake
-
p. 6411 - 6418
(2007/10/02)
-
- Selective Oxidation of Alcohols and Aldehydes with Hydrogen Peroxide Catalyzed by Methyltrioctylammonium Tetrakis(oxodiperoxotungsto)phosphate(3-) under Two-Phase Conditions
-
The use of methyltrioctylammonium tetrakis(oxodiperoxotungsto)phosphate(3-) (1c) in combination with hydrogen peroxide as the primary oxidant in an aqueous/organic biphase system provides a cheap, efficient, and versatile catalytic method for alcohol and aldehyde oxidation.By this method, a variety of water-insoluble primary and secondary alcohols and aldehydes were oxidized to carboxylic acids and ketones in good yields under mild conditions and after relatively short reaction times.
- Venturello, Carlo,Gambaro, Mario
-
p. 5924 - 5931
(2007/10/02)
-
- READY OXIDATION OF ALCOHOLS TO CARBONYL COMPOUNDS BY SODIUM BROMITE IN METHYLENE DICHLORIDE IN THE PRESENCE OF ALUMINIUM OXIDE
-
Aliphatic secondary alcohols and aromatic alcohols were oxidized by sodium bromite in an inert solvent in the presence of aluminium oxide under mild conditions to give the corresponding carbonyl compounds in good yields.
- Morimoto, Takashi,Hirano, Masao,Aikawa, Yumiko,Zhang, Xiumin
-
p. 2423 - 2424
(2007/10/02)
-
- OXIDATION OF ALCOHOLS USING DIMETHYL SULFOXIDE AND TRICHLORMETHYL CHLOROFORMATE
-
Treatment of structurally diverse alcohols with dimethyl sulfoxide in the presence of trichloromethyl chloroformate (phosgene dimer) and triethylamine efficiently afforded the corresponding aldehydes or ketones in excellent yields.
- Takano, Seiichi,Inomata, Kohei,Tomita, Shun'ichi,Yanase, Masashi,Samizu, Kyiohiro,Ogasawara, Kunio
-
p. 6619 - 6620
(2007/10/02)
-
- Chromium(VI) or Ruthenium(II) Complex Catalysis in Oxidation of Alcohols to Aldehydes and Ketones by Means of Bis(trimethylsilyl) Peroxide
-
Bis(trimethylsilyl) peroxide (BTSP) serves as an effective oxidant of alcohols in the presence of chromium(VI) or ruthenium(II) complexes as catalysts in dichloromethane.Selective oxidation of primary alcohols in preference to secondary ones using RuCl2(PPh3)3 as a catalyst is also described.
- Kanemoto, Shigekazu,Matsubara, Seijiro,Takai, Kazuhiko,Oshimara, Koichiro,Utimoto, Kiitiro,Nozaki, Hitosi
-
p. 3607 - 3612
(2007/10/02)
-
- A DERIVATIVE OF AZEPINE AND ITS APPLICATION AS A SPECIFIC OPTICAL RESOLUTION AGENT
-
The synthesis of (-)-(2S,trans)-perhydro-2-isopropyl-5-methyl-azepin-1-amine (1) and its use as a specific optical resolution agent of ketones is described.A method for the resolution of ketones and its application to three ketones is described.This method also involves the synthesis and separation of the pairs of hydrazones diastereomers followed by removal of hydrazines by hydrolysis to give the individual enantiomers of II, III and IV with high chiral purities.
- Fernandez, Franco,Perez, Cristina
-
p. 2411 - 2417
(2007/10/02)
-
- THIOCARBONYLS INTO CARBONYLS: EFFICIENT CONVERSION BY CLAY-SUPPORTED FERRIC NITRATE
-
A simple and inexpensive procedure is proposed for achieving the title transformation.The method works best with thiobenzophenones (60-100percent yields.
- Chalais, Stephane,Cornelis, Andre,Laszlo, Pierre,Mathy, Arthur
-
p. 2327 - 2328
(2007/10/02)
-
- Kinetics of Dehydration of Camphor and Fenchone over Alumina Catalysts
-
Kinetics of dehydration of camphor and fenchone to aromatics have been investigated over alumina of different acid strength in a flow reactor in the temperature range 300-405 deg.The dehydration activity increases with decreasing acid strength and fenchone is more reactive than camphor over all the three catalysts under the experimental conditions.The reactions follow first order kinetics.Energy of activation and other thermodynamic parameters are calculated.A linear regression analysis has been carried out to obtain isokinetic relationship which holds good for dehydration of camphor and fenchone with correlation coefficient of 0.98 and 0.96, respectively.
- Krishnasamy, V.,Balasubramanian, K.
-
p. 213 - 215
(2007/10/02)
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- A NEW Cr(VI) REAGENT FOR THE CATALYTIC OXIDATION OF SECONDARY ALCOHOLS TO KETONES
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A new process is described for the oxidation of secondary alcohols to ketones using peroxyacetic acid in the presence of a catalytic amount of 2,4-dimethylpentane-2,4-diol cyclic chromate.
- Corey, E. J.,Barrette, Ernie-Paul,Magriotis, Plato A.
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p. 5855 - 5858
(2007/10/02)
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- RUTHENIUM-CATALYZED OXIDATION OF ALCOHOLS WITH SODIUM BROMATE
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Ruthenium trichloride-catalyzed oxidation of secondary alcohols with sodium bromate under basic conditions affords ketones in the excellent yields.
- Yamamoto, Yasuo,Suzuki, Hiroharu,Moro-oka, Yoshihiko
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p. 2107 - 2108
(2007/10/02)
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- CHEMOSELECTIVE OXIDATION WITH MOLYBDENIUM CATALYST-t-BUTYL HYDROPEROXIDE
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Benzyltrimethylammonium tetrabromooxomolybdate is an excellent chemoselective catalyst to oxidize secondary alcohols to ketones, primary alcohols to esters, and aldehydes to acids or esters with t-butyl hydroperoxide.
- Masuyama, Yoshiro,Takahashi, Masato,Kurusu, Yasuhiko
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p. 4417 - 4420
(2007/10/02)
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- Pyridinium Fluorochromate or benzyltrimethylammonium Chlorochromate for selective Oxidation of Alcohols.
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Selective oxidation of secondary alcohols in the presence of primary ones has been achieved by the following sequences, (1) selective protection of primary alcohols with t-BuMe2SiCl, (2) oxidation of secondary alcohols with title reagents, and (3) deprotection of primary hydroxyls.
- Nonaka, Tsuyoshi,Kanemoto, Shigekazu,Oshima, Koichiro,Nozaki, Hitosi
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p. 2019 - 2020
(2007/10/02)
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- Synthetic Methods and Reactions. 112. Synthetic Transformations with Trichloromethylsilane/Sodium Iodide Reagent
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A new, convenient, and inexpensive alternative to the in situ equivalent of iodotrimethylsilane was developed.A mixture of trichloromethylsilane/sodium iodide in dry acetonitrile is found to be a more selective reagent than chlorotrimethylsilane/sodium iodide for the cleavage of ethers, esters, and lactones.Ethers are cleaved regioselectively by this reagent.Cleavage of esters and lactones also occured more readily with the present system.Conversion of alcohols, particularly tertiary and benzylic alcohols, to corresponding iodides is achieved in very short times at ambient temperatures.Deoxygenation of sulfoxides to sulfides is found to be instantaneous.Reductive dehalogenation of alicyclic α-halo ketones to the corresponding ketones has also been studied.The reagent is also used for the deprotection of acetals to carbonyl compounds.
- Olah, George A.,Husain, Altaf,Singh, Brij P.,Mehrotra, Ashok K.
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p. 3667 - 3672
(2007/10/02)
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- REDUCTION OF α-HALOCARBONYL COMPOUNDS WITH SODIUM HYDROGEN TELLURIDE
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Sodium hydrogen telluride is an efficient reagent for dehalogenation os α-halocarbonyl compounds
- Osuka, Atsuhiro,Suzuki, Hitomi
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p. 119 - 120
(2007/10/02)
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- STERIC ASPECTS OF THE OXIDATION OF THIOKETONES BY SINGLET OXYGEN
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Singlet oxygen oxidation of dialkyl thioketones yields the corresponding ketones and in some cases sulfoxides in varying amounts.Steric considerations on the reactive zwitterionic/diradical intermediates have been invoked to rationalise the product distribution.
- Ramnath, Narayan,Jayathertha, Vaidhya Rao,Ramesh, Varadaraj,Ramamurthy, Vaidhyanathan
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