- Chemoselective Electrochemical Oxidation of Secondary Alcohols Using a Recyclable Chloride-Based Mediator
-
Selective anodic oxidation of alcohols in the presence of other functional groups can be accomplished by using nitroxyl radical mediators. However, the electrochemical chemoselective oxidation of secondary alcohols in the presence of primary alcohols is a
- Sommer, Florian,Kappe, C. Oliver,Cantillo, David
-
supporting information
p. 166 - 170
(2021/06/16)
-
- A Convenient Protocol for the Oxidation of Benzyl and Secondary Alcohols to Carbonyl Compounds by Trichoroisocyanuric Acid
-
A very convenient methodology to oxidize benzyl alcohols to benzaldehydes (9 examples, up to 95%) and secondary alcohols to ketones (8 examples, up to 99%) using trichloroisocyanuric acid in CH2Cl2/MeCN (1:1) as co-solvent in the presence of water at room temperature is presented in this study.
- De Mattos, Marcio C. S.,Dos Santos, Carlos Vinicius P.
-
p. 854 - 861
(2022/03/01)
-
- Transition Metal-Substituted Potassium Silicotungstate Salts as Catalysts for Oxidation of Terpene Alcohols with Hydrogen Peroxide
-
Abstract: In this work, the catalytic activity of the transition metal-substituted potassium silicotungstate salts (i.e. K8-nSiMn+W11O39 (Mn+ = Cu2+, Co2+, Ni2+, Zn2+ and Fe3+) was investigated on the oxidation reactions of the terpene alcohols with H2O2 aqueous solution. The metal-substituted silicotungstate salts were easily synthesized in one-pot reactions of the precursor metal solutions (i.e. Na2WO4, Na2SiO3 and MCln) with KCl added in stoichiometric amount; after this precipitation step, the solid heteropoly salts were filtered and dried in an oven. This procedure of synthesis avoids multi-step processes that starts from the pristine heteropolyacid. The substituted metal heteropoly salts were characterized by infrared spectroscopy, measurements of the specific surface area (BET) and porosimetry by isotherms of adsorption/desorption of N2, X-rays diffraction, thermal analyses, dispersive X-rays spectroscopy, scanning electronic microscopy. The acidity strength was estimated by potentiometric titration with n-butylamine. All the salts were evaluated as catalysts in terpenic alcohols oxidation reactions with H2O2. The K5SiFeW11O39 was the most active and selective catalyst toward oxidation products. The impacts of the main reaction variables such as catalyst concentration, temperature, oxidant load, and nature of the terpene substrate were assessed. The highest activity of the K5SiFeW11O39 catalyst was assigned to the highest Lewis acidity. Graphic Abstract: [Figure not available: see fulltext.].
- da Silva, Marcio Jose,da Silva Andrade, Pedro Henrique,Sampaio, Vinicius Fernando Coelho
-
p. 2094 - 2106
(2020/11/13)
-
- Photochemical oxidation of benzylic primary and secondary alcohols utilizing air as the oxidant
-
A mild and green photochemical protocol for the oxidation of alcohols to aldehydes and ketones was developed. Utilizing thioxanthenone as the photocatalyst, molecular oxygen from air as the oxidant and cheap household lamps or sunlight as the light source, a variety of primary and secondary alcohols were converted into the corresponding aldehydes or ketones in low to excellent yields. The reaction mechanism was extensively studied.
- Nikitas, Nikolaos F.,Tzaras, Dimitrios Ioannis,Triandafillidi, Ierasia,Kokotos, Christoforos G.
-
supporting information
p. 471 - 477
(2020/02/13)
-
- Direct Oxidation of Csp3?H bonds using in Situ Generated Trifluoromethylated Dioxirane in Flow
-
A fast, scalable, and safer Csp3?H oxidation of activated and un-activated aliphatic chains can be enabled by methyl(trifluoromethyl)dioxirane (TFDO). The continuous flow platform allows the in situ generation of TFDO gas and its rapid reactivity toward tertiary and benzylic Csp3?H bonds. The process exhibits a broad scope and good functional group compatibility (28 examples, 8–99 %). The scalability of this methodology is demonstrated on 2.5 g scale oxidation of adamantane.
- Lesieur, Mathieu,Battilocchio, Claudio,Labes, Ricardo,Jacq, Jér?me,Genicot, Christophe,Ley, Steven V.,Pasau, Patrick
-
supporting information
p. 1203 - 1207
(2019/01/04)
-
- METHOD FOR PRODUCING CARBONYL COMPOUND
-
PROBLEM TO BE SOLVED: To provide a method for producing a carbonyl compound, allowing for improvement of ease of production and furthermore allowing for reduction of production cost, by positively utilizing inexpensive iodine. SOLUTION: A carbonyl compound is produced by mixing primary alcohol or secondary alcohol, and iodic acid (HIO3) in a non-solvent or an aprotic polar solvent based on the following general formula (1), where R1 is an optionally substituted linear- or branched 1-12C aliphatic group, or an optionally substituted aromatic group; R2 is a hydrogen atom, an optionally substituted linear- or branched 1-12C alkyl group, or an optionally substituted aromatic group; R1 and R2 each may be coupled with each other to form a ring of aromatic group or a non-aromatic group. SELECTED DRAWING: None COPYRIGHT: (C)2018,JPOandINPIT
- -
-
Paragraph 0032-0035; 0037-0040
(2018/03/23)
-
- Solventless, selective and catalytic oxidation of primary, secondary and benzylic alcohols by a Merrifield resin supported molybdenum(vi) complex with H2O2 as an oxidant
-
Here, we have described the synthesis, characterization and catalytic activity of a dioxo-molybdenum(vi) complex supported on functionalized Merrifield resin (MR-SB-Mo). The functionalization of Merrifield resin (MR) was achieved in two-steps viz. carbonylation (MR-C) and Schiff base formation (MR-SB). The compounds, MR-C, MR-SB and MR-SB-Mo, were characterized at each step of the synthesis by elemental, SEM, EDX, thermal, BET and different spectroscopic analysis. The catalyst, MR-SB-Mo, efficiently and selectively oxidized a wide variety of alcohols to aldehydes or ketones using 30% H2O2 as an oxidant with reasonably good TOF (660 h-1 in case of benzyl alcohol). The catalyst acted heterogeneously under solventless reaction conditions and did not lead to over oxidized products under optimized conditions. The catalyst afforded regeneration and can be reused for at least five reaction cycles without loss of efficiency and product selectivity. A reaction mechanism for the catalytic activity of MR-SB-Mo was proposed and a probable reactive intermediate species isolated.
- Boruah, Jeena Jyoti,Das, Siva Prasad
-
p. 34491 - 34504
(2018/10/21)
-
- Revisiting Sodium Hypochlorite Pentahydrate (NaOCl·5H 2 O) for the Oxidation of Alcohols in Acetonitrile without Nitroxyl Radicals
-
Sodium hypochlorite pentahydrate (NaOCl·5H 2 O) is capable of oxidizing alcohols in acetonitrile at 20 °C without the use of catalysts. The oxidation is selective to allylic, benzylic, and secondary alcohols. Aliphatic primary alcohols are not oxidized.
- Hirashita, Tsunehisa,Sugihara, Yuto,Ishikawa, Shota,Naito, Yohei,Matsukawa, Yuta,Araki, Shuki
-
p. 2404 - 2407
(2018/11/23)
-
- Polyethylene Glycols as Efficient Catalysts for the Oxidation of Bicyclic Monoterpenes by Ceric Ammonium Nitrate in Acetonitrile under Acid-Free Conditions: Kinetic and Mechanistic Approach
-
Polyethylene glycols (PEG) acts as efficient catalysts for the oxidation of bicyclic monoterpenes such as borneol, isoborneol, and camphor by ceric ammonium nitrate (CAN), a laboratory desktop reagent, in acetonitrile medium under mineral acid-free conditions. The kinetics of the reactions revealed first-order dependence on in both [CAN] and [bicyclic terpene]. The rate of oxidation is accelerated with an increase in [PEG] linearly, which could be explained by considering PEG-bound oxidant (PEG-CAN) as more reactive species than (CAN) itself. The mechanism of oxidation in PEG media has been explained through the participation of PEG-bound oxidant (PEG-CAN) and bicyclic monoterpene in the slow step.
- Rajitha,Shylaja,Rajanna,Yadagiri
-
p. 383 - 396
(2018/03/30)
-
- Addition of tris(trimethylsilyl) phosphite to quinuclidin-3-one and its carbocyclic analogs
-
Convenient methods of synthesis of functionalized phosphonic acids and their trimethylsilyl esters containing quinuclidine, adamantine, and bornane (camphane) moieties, involving reactions of tris(trimethylsilyl) phosphite with quinuclidin-3-one and its c
- Prishchenko,Livantsov,Novikova,Meleshonkova,Livantsova,Petrosyan
-
p. 1879 - 1881
(2017/09/25)
-
- A TEMPO-like nitroxide combined with an alkyl-substituted pyridine: An efficient catalytic system for the selective oxidation of alcohols with iodine
-
An efficient method for the oxidation of alcohols to aldehydes or ketones in a two-phase CH2Cl2/NaHCO3 (aq.) system, using iodine and catalytic amounts of 4-acetylamino-2,2,6,6-tetramethylpiperidine-1-oxyl and 2,4,6-trimethylpyridine, was developed. The performance of the method was demonstrated by the selective oxidation of 37 variously substituted alcohols in ≥90% yield, including the gram-scale synthesis of the important chemical 2,5-diformylfuran from biomass-derived 5-hydroxylmethylfurfural.
- Kashparova, Vera P.,Klushin, Victor A.,Zhukova, Irina Yu.,Kashparov, Igor S.,Chernysheva, Daria V.,Il'chibaeva, Irina B.,Smirnova, Nina V.,Kagan, Efim Sh.,Chernyshev, Victor M.
-
supporting information
p. 3517 - 3521
(2017/10/05)
-
- Molybdenum complexes with a μ-O{MoO2}2 core: their synthesis, crystal structure and application as catalysts for the oxidation of bicyclic alcohols using N-based additives
-
Three binuclear μ-oxidobis{dioxidomolybdenum(vi)} complexes, [(μ-O){MoVIO2(MeOH)}2(L1)] 1, [(μ-O){MoVIO2(MeOH)}2(L2)] 2, and [(μ-O){MoVIO2(MeOH)}2(L3)] 3 with potential dibasic tetradentate azine ligands [H2L1 = azine of salicylaldehyde, H2L2 = azine of 3-methoxysalicyaldehyde and H2L3 = azine of 3,5-ditertiarybutylsalicylaldehyde] are reported. The complexes are characterized via elemental analysis, various spectroscopic techniques (FT-IR, UV-Vis, 1H and13C NMR), thermogravimetric analysis and single-crystal X-ray diffraction (2 and 3) studies. These complexes are binuclear having a μ-O{MoO2}2 core where ligands coordinate through a set of phenolic oxygen and azine nitrogen to each molybdenum, thus behaving as bis(bidentate). These complexes are investigated as catalysts for the oxidation of two bicyclic alcohols (fenchyl alcohol and isoborneol) using 30% H2O2 as the oxidant in the presence of NEt3 as the additive. The conversion of bicyclic alcohols within the additives follows the order: NEt3 > py > NH3 > K2CO3 > KOH. In the presence of an N-based additive, fenchyl alcohol and isoborneol selectively give high yields of fenchone and camphor, respectively, while in the absence of the additive the conversion is relatively low.
- Maurya, Mannar R.,Rana, Lata,Avecilla, Fernando
-
p. 724 - 734
(2017/02/05)
-
- An alkoxyamine compound, alkoxy alcohol oxidation catalyst and method of using the alcohol oxidation
-
PROBLEM TO BE SOLVED: To provide a novel alkoxyamine compound which can be easily manufactured and applied suitably as an alcohol oxidation catalyst capable of exerting sufficiently high catalytic activity in oxidation of primary and secondary alcohols.SOLUTION: There is provided an alkoxyamine compound with a homoadamantane skeleton represented by the general formula (1) in the figure. [In the formula (1), Rand Rare each independently any one selected from the group consisting of a hydrogen atom and alkyl groups that may be substituted.
- -
-
Paragraph 0096; 0099-0100
(2017/02/02)
-
- Copper(ii) and iron(iii) complexes with arylhydrazone of ethyl 2-cyanoacetate or formazan ligands as catalysts for oxidation of alcohols
-
The aquasoluble [Cu(1κN,O2:2κO-HL1)(S)]2 [S = CH3OH (1), (CH3)2NCHO (2)] and [Cu(κN-HL1)(en)2]·CH3OH·H2O (3) CuII complexes were prepared by the reaction of CuII nitrate hydrate with the new ligand (E/Z)-4-(2-(1-cyano-2-ethoxy-2-oxoethylidene)hydrazinyl)-3-hydroxybenzoic acid (H3L1), in the presence (for 3) or absence (for 1 and 2) of ethylenediamine (en), while the FeIII complex [Fe(κN3-HL2)2] (4) was isolated by treatment of iron(III) chloride hexahydrate with the new ligand (1E,1E)-N′,2-di(1H-1,2,4-triazol-3-yl)diazenecarbohydrazonoyl cyanide (H3L2), and characterized by elemental analysis, IR spectroscopy and single crystal X-ray diffraction. Cooperative E,Z → E isomerization of H3L1, induced by coordination and ionic interactions, occurs upon interaction with CuII in the presence of en. Complexes 1-4 act as catalyst precursors for the solvent-free microwave (MW) assisted selective oxidation of primary or secondary alcohols and diols to the corresponding aldehydes, ketones and diketones, respectively, with yields in the 5-99% range (TONs up to 4.96 × 102) after 60 min of MW irradiation at 120 °C. The influence of temperature, time and organic radicals was studied and also the regioselective oxidation of the catalytic systems involving the primary and secondary alcohols.
- Martins, Nuno M. R.,Mahmudov, Kamran T.,Guedes Da Silva, M. Fátima C.,Martins, Luísa M. D. R. S.,Pombeiro, Armando J. L.
-
supporting information
p. 10071 - 10083
(2016/12/07)
-
- Synthetic utility of iodic acid in the oxidation of benzylic alcohols to aromatic aldehydes and ketones
-
Various primary and secondary benzylic alcohols were efficiently oxidized to aromatic aldehydes and aromatic ketones with iodic acid in DMF at 60?°C for 2?h and with iodic acid in the presence of TEMPO (5?mol?%) in DMF at room temperature, respectively. The former method was effective for the oxidation of sterically hindered alcohols at 60?°C and the latter method was effective for the oxidation of less sterically hindered alcohols at room temperature.
- Imai, Sho,Togo, Hideo
-
p. 6948 - 6954
(2016/10/13)
-
- Method to oxidize alcohols selectively to aldehydes and ketones with heterogeneous supported ruthenium catalyst at room temperature in air and catalyst thereof
-
The present invention relates to a method for selectively oxidizing alcohol by using a heterogeneous catalyst for producing aldehyde and ketone in an organic synthesis process used in the laboratory and chemical industries, and a catalytic system thereof. The method can be used as an intermediate product for synthesizing medicine, scent, fragrance, and precise chemical products, and can use a heterogeneous catalyst at room temperature in air by using the catalytic system and producing alcohol and ketone.COPYRIGHT KIPO 2016
- -
-
Paragraph 0021; 0022
(2016/10/07)
-
- Organic inorganic hybrid cobalt phthalocyanine/polyaniline as efficient catalyst for aerobic oxidation of alcohols in liquid phase
-
Organic inorganic hybrid catalyst synthesized by doping of cobalt phthalocyanine (CoPc) on polyaniline support (CoPc/PANI) exhibited higher activity for the oxidation of various alcohols to the corresponding carbonyl compounds in high to excellent yield using molecular oxygen as oxidant and isobutyraldehyde as a sacrificial agent. Notably, the synthesized catalyst was found to be truly heterogeneous in nature and could be easily recovered, recycled for several recycling runs without loss of catalytic activity.
- Panwar, Vineeta,Kumar, Pawan,Ray, Siddharth S.,Jain, Suman L.
-
p. 3948 - 3953
(2015/06/08)
-
- N,O-ligated Pd(ii) complexes for catalytic alcohol oxidation
-
N,O-ligated Pd(ii) complexes show considerable promise for the oxidation of challenging secondary aliphatic alcohols. The crystal structures of the highly active complexes containing the 8-hydroxyquinoline-2-carboxylic acid (HCA) and 8-hydroxyquinoline-2-sulfonic acid (HSA) ligands have been obtained. The (HSA)Pd(OAc)2 system can effectively oxidise a range of secondary alcohols, including unactivated alcohols, within 4-6 h using loadings of 0.5 mol%, while lower loadings (0.2 mol%) can be employed with extended reaction times. The influence of reaction conditions on catalyst degradation was also examined in these studies.
- Dornan, Laura M.,Clendenning, Grainne M. A.,Pitak, Mateusz B.,Coles, Simon J.,Muldoon, Mark J.
-
p. 2526 - 2534
(2014/07/22)
-
- Oxidation of Alcohols to Aldehydes or Ketones with 1-Acetoxy-1,2-benziodoxole-3(1H)-one Derivatives
-
Various benzylic and aliphatic alcohols were smoothly oxidized to the corresponding aromatic aldehydes and ketones as well as aliphatic ketones by treatment with 1-acetoxy-5-nitro-1,2-benziodoxole-3(1H)-one (ANBX), 1-acetoxy-5-bromo-1,2-benziodoxole-3(1H)-one (ABBX), 1-acetoxy-5-chloro-1,2-benziodoxole-3(1H)-one (ACBX), and 1-acetoxy-5-fluoro-1,2-benziodoxole-3(1H)-one (AFBX). These new trivalent iodine compounds were prepared from 5-substituted 2-iodobenzoic acids and meta-chloroperoxybenzoic acid (m-CPBA). ANBX and ABBX were the most effective reagents for this oxidation of alcohols, and this present reaction is very attractive because of the ease of product isolation and the reusability of the reagents.
- Iinuma, Masataka,Moriyama, Katsuhiko,Togo, Hideo
-
p. 772 - 780
(2015/10/05)
-
- Reaction of seleno- or thiofenchone with propiolic acid: Wagner-meerwein rearrangement
-
A reaction of selenofenchone with propiolic acid in refluxing chloroform produced 1,3-oxaselenin-6-one, which further reacted with acid to afford the ring-opened product. A reaction of 1,3-oxathiin-6-one prepared from thiofenchone with trifluoroacetic acid gave a Wagner-Meerwein rearranged product. In the presence of AlCl3, thiofenchone reacted with methyl propiolate to afford the corresponding rearranged ester.
- Okuma, Kentaro,Matsui, Hiroyuki,Mori, Yuichi
-
p. 578 - 583
(2015/02/18)
-
- ALPHA-HYDROGEN SUBSTITUTED NITROXYLS AND DERIVATIVES THEREOF AS CATALYSTS
-
The present invention relates to novel alpha-hydrogen substituted nitroxyl compounds and their corresponding oxidized (oxoammonium cations) and reduced (hydroxylamine) forms, and to the use of such compounds, inter alia, for (1) oxidation of primary and secondary alcohols to aldehydes and ketones, respectively; (2) resolution of racemic alcohols; (3) desymmetrization of meso-alcohol; (4) as radicals and spin trapping reagents; and (5) as polymerization agents. The present invention further relates to processes for preparing the novel nitroxyl/oxoammonium/ hydroxylamine compounds from the corresponding amines, and to certain novel amine derivatives and their uses. The compounds of the invention as well as the amine precursors are also useful as ligands for transition metals and as organocatalysts in e.g., aldol reactions.
- -
-
Page/Page column 37
(2013/08/28)
-
- Various oxidative reactions with novel ion-supported (diacetoxyiodo) benzenes
-
The oxidation of secondary alcohols and primary alcohols with two novel ion-supported (diacetoxyiodo)benzenes (IS-DIBs) A and B in the presence of a catalytic amount of 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO) in dichloromethane at room temperature proceeded efficiently to provide the corresponding ketones and aldehydes, respectively, in good yields. The oxidative reaction of N,N-diisopropylbenzylamines with those IS-DIBs was also carried out to generate the corresponding aromatic aldehydes in good yields. In addition, the Hofmann rearrangement of primary amides in methanol under basic conditions and the oxidative 1,2-rearrangement of propiophenones in trimethyl orthoformate under acidic conditions with those IS-DIBs provided the corresponding methyl carbamates and methyl 2-arylpropanoates, respectively, in good yields. Moreover, treatment of acetophenones with those IS-DIBs in the presence of trifluoromethanesulfonic acid in acetonitrile generated the corresponding 5-aryl-2-methyloxazoles in good yields. In those five reactions, the desired products were obtained in good yields with high purity by simple extraction of the reaction mixture with diethyl ether and subsequent removal of the solvent from the extract. Moreover, ion-supported iodobenzenes, which were the co-products derived from IS-DIBs in the present oxidative reactions, were recovered in good yields and could be re-oxidized to IS-DIBs A and B for reuse in the same oxidative reactions.
- Iinuma, Masataka,Moriyama, Katsuhiko,Togo, Hideo
-
p. 2961 - 2970
(2013/04/10)
-
- Manganese-catalyzed selective oxidation of aliphatic C-H groups and secondary alcohols to ketones with hydrogen peroxide
-
An efficient and simple method for selective oxidation of secondary alcohols and oxidation of alkanes to ketones is reported. An in situ prepared catalyst is employed based on manganese(II) salts, pyridine-2-carboxylic acid, and butanedione, which provides good-to-excellent conversions and yields with high turnover numbers (up to 10 000) with H2O2 as oxidant at ambient temperatures. In substrates bearing multiple alcohol groups, secondary alcohols are converted to ketones selectively and, in general, benzyl C-H oxidation proceeds in preference to aliphatic C-H oxidation. Manganeasy! MnII, picolinic acid, and butanedione make a smart mix for oxidation of secondary alcohols and alkanes and especially benzylic groups to ketones at room temperature with near stoichiometric amounts of hydrogen peroxide, low catalyst loadings, and high turn-over numbers. Copyright
- Dong, Jia Jia,Unjaroen, Duenpen,Mecozzi, Francesco,Harvey, Emma C.,Saisaha, Pattama,Pijper, Dirk,De Boer, Johannes W.,Alsters, Paul,Feringa, Ben L.,Browne, Wesley R.
-
p. 1774 - 1778
(2013/10/21)
-
- Catalyst-free selective oxidation of alcohols to carbonyls using trans-3,5-dihydroperoxy-3,5-dimethyl-1,2-dioxolane as an efficient oxidant
-
A simple and efficient method for the selective oxidation of alcohols to ketones using trans-3,5-dihydroperoxy-3,5-dimethyl-1,2-dioxolane at room temperature is developed. The reactions were smoothly proceeded under catalyst-free conditions to provide ketones in quantitative yields within short reaction times. Also, this method is compatible with many functional groups including aldehydes, olefins, halogens, amines and esters. Graphical Abstract: [Figure not available: see fulltext.]
- Azarifar, Davood,Najminejad, Zohreh,Khosravi, Kaveh
-
p. 979 - 983
(2013/09/23)
-
- Selective catalytic oxidation of alcohols, aldehydes, alkanes and alkenes employing manganese catalysts and hydrogen peroxide
-
The manganese-containing catalytic system [MnIV,IV 2O3(tmtacn)2]2+ (1)/carboxylic acid (where tmtacn=N,N′,N′′-trimethyl-1,4,7-triazacyclononane), initially identified for the cis-dihydroxylation and epoxidation of alkenes, is applied for a wide range of oxidative transformations, including oxidation of alkanes, alcohols and aldehydes employing H2O2 as oxidant. The substrate classes examined include primary and secondary aliphatic and aromatic alcohols, aldehydes, and alkenes. The emphasis is not primarily on identifying optimum conditions for each individual substrate, but understanding the various factors that affect the reactivity of the Mn-tmtacn catalytic system and to explore which functional groups are oxidised preferentially. This catalytic system, of which the reactivity can be tuned by variation of the carboxylato ligands of the in situ formed [MnIII,III 2(O)(RCO2)2(tmtacn)2]2+ dimers, employs H2O2 in a highly atom efficient manner. In addition, several substrates containing more than one oxidation sensitive group could be oxidised selectively, in certain cases even in the absence of protecting groups. Copyright
- Saisaha, Pattama,Buettner, Lea,Van Der Meer, Margarethe,Hage, Ronald,Feringa, Ben L.,Browne, Wesley R.,De Boer, Johannes W.
-
supporting information
p. 2591 - 2603
(2013/10/21)
-
- On the key role of hydroxyl groups in platinum-catalysed alcohol oxidation in aqueous medium
-
In the aerobic selective oxidation of alcohols in aqueous medium in a batch reactor, it was observed that the addition of water to dioxane solvent (10-50 vol%) substantially increased the activity of a Pt/C catalyst. Periodic density functional theory (DFT) calculations were carried out to compare the reactivity of alcohols on the bare Pt(111) surface and in the presence of adsorbed water or hydroxyl groups, to explain the effect of water. The calculations indicate that the presence of adsorbed hydroxyl groups promotes the catalytic activity by participating directly in the catalytic pathways and reducing the activation barrier. Good agreement was found between the experiments in aqueous phase and these calculations. Further, decarbonylation of the aldehyde may be involved in the deactivation during oxidation of a primary alcohol. The Royal Society of Chemistry 2013.
- Chibani, Siwar,Michel, Carine,Delbecq, Francoise,Pinel, Catherine,Besson, Michele
-
p. 339 - 350
(2013/03/28)
-
- Immobilization of Ru(III) complex on silica: A heterogenized catalyst for selective oxidation of alcohols in water at room temperature
-
We have developed a heterogenized catalyst ('SiO2'-NH 2-RuIII) by the immobilization of [Ru(acac) 2(CH3CN)2]PF6 on SiO2. The catalyst was characterized by SEM, solid state NMR, EPR, FT-IR, ICP, and BET surface area analyses. 'SiO2'-NH2-RuIII catalyzed the selective oxidation of alcohols with periodic acid in water at room temperature. This protocol was applicable to the controlled oxidation of structurally diverse primary and secondary alcohols. The catalyst could be quantitatively recovered and reused up to six cycles without significant loss of catalytic activity.
- Ganesamoorthy,Muthu Tamizh,Shanmugasundaram,Karvembu
-
p. 7035 - 7039
(2013/12/04)
-
- TiCl4 hiocarbonyls and oxidation of sulfides in the presence of H2O2
-
H2O2 in combination with TiCl4 proved to be a highly reactive reagent system for the desulfurization of thioamide and thioketone derivatives in excellent yields and short reaction times with high purity. Sulfides were also found to undergo oxidation to sulfones under similar reaction conditions. In most cases, these reactions are highly selective, simple, and clean, affording products in high yields and purity.
- Bahrami, Kiumars,Khodaei, Mohammad M.,Shakibaian, Vida,Khaledian, Donya,Yousefi, Behrooz H.
-
experimental part
p. 155 - 163
(2012/06/01)
-
- Efficient Swern oxidation and Corey-Kim oxidation with ion-supported methyl sulfoxides and methyl sulfides
-
The Swern oxidation of various benzylic and allylic alcohols, primary alcohols, and secondary alcohols with two ion-supported methyl sulfoxides A-1 (C6) and B-1 (C10), and oxalyl chloride in the presence of triethylamine in dichloromethane, followed by simple diethyl ether extraction of the reaction mixture, gave the corresponding aldehydes and ketones, respectively, in good yields with high purity. Similarly, the Corey-Kim oxidation of various benzylic and allylic alcohols, primary alcohols, and secondary alcohols with two ion-supported methyl sulfides A-2 (C6) and B-2 (C10), and N-chlorosuccinimide in the presence of triethylamine in dichloromethane, followed by simple diethyl ether extraction of the reaction mixture, furnished the corresponding aldehydes and ketones, respectively, in good yields with high purity. Both reactions did not produce any unpleasant odor at all. In the Swern oxidation, ion-supported methyl sulfides were recovered in high yields and could be re-oxidized to produce ion-supported methyl sulfoxides A-1 (C6) and B-1 (C10), for reuse in the same oxidation. In the Corey-Kim oxidation, ion-supported methyl sulfides A-2 (C6) and B-2 (C10) were recovered in high yields and could be also reused for the same oxidation.
- Tsuchiya, Daisuke,Tabata, Masayuki,Moriyama, Katsuhiko,Togo, Hideo
-
experimental part
p. 6849 - 6855
(2012/08/28)
-
- Modified Marko's aerobic oxidation of alcohols under atmospheric pressure with air or molecular oxygen at room temperature
-
A modified version of Marko's aerobic oxidation procedure, using highly pure (99.995+%) CuCl with 4,7-diphenyl-1,10-phenanthroline (dpPhen), DBAD, and Cs2CO3 (98% purity) successfully oxidized primary and secondary alcohols to the corresponding aldehydes and ketones in excellent yield at room temperature with either air or molecular oxygen under atmospheric pressure.
- Nishii, Takeshi,Ouchi, Tomomi,Matsuda, Aya,Matsubara, Yuka,Haraguchi, Yuuko,Kawano, Tomomi,Kaku, Hiroto,Horikawa, Mitsuyo,Tsunoda, Tetsuto
-
p. 5880 - 5882,3
(2020/07/31)
-
- 3,5-dimethylpyrazolium chlorochromate(VI): An efficient reagent for solvent-free oxidation of organic substrates
-
A new chromium(VI) reagent 3,5-dimethylpyrazolium chlorochromate, C 5H8N2H[CrO3Cl] (DmpzHCC), was synthesized and used for the selective oxidation of various organic compounds under solvent-free conditions with high efficiency. This new compound has certain advantages over its companion analogues in terms of controlled acidity, amount of oxidant, lack of solvent, short reaction times, and high yields.
- Canbulat, Melek,Oezguen, Beytiye
-
experimental part
p. 634 - 637
(2012/08/29)
-
- Oxidation of alcohols to aldehydes and ketones using TBHP as an oxidant over LaMO3 (M = Cr, Mn, Co, Ni, Fe) perovskites
-
Oxidation of a wide variety of structurally and electronically diverse primary and secondary alcohols to aldehydes and ketones was carried out using a novel catalytic system of LaCrO3 and tert-butyl hydroperoxide (TBHP) under solvent-free conditions. The methodology afforded the desired carbonyl compounds in good to excellent yields, and the catalyst can be reused several times with no significant loss in activity. Copyright Taylor & Francis Group, LLC.
- Singh, Savita J.,Jayaram, Radha V.
-
experimental part
p. 299 - 308
(2011/11/13)
-
- Ruthenium(II) carbonyl complexes containing 'pincer like' ONS donor Schiff base and triphenylphosphine as catalyst for selective oxidation of alcohols at room temperature
-
Reactions of H2L with [RuHCl(CO)(PPh3)3] in toluene gives [Ru(L)(CO)(PPh3)2] (L = binegative tridentate ONS donor ligand derived from salicylaldehyde/4-substituted salicylaldehyde/2-hydroxy-1-naphthaldehyde and o-aminothiophenol) at room temperature. All the complexes were characterized by elemental analyses and UV-Visible, FT-IR, 1H, 13C and 31P NMR spectroscopic methods. 1H-1H COSY and 1H-31P HMBC spectra of [Ru(L4)(CO)(PPh3) 2] have been studied. 1H-31P HMBC spectrum established the coupling of phosphorus atoms with azomethine proton. The single crystal X-ray analysis of [Ru(L5)(CO)(PPh3)2] revealed that Schiff base ligand is coordinated to the metal center, via dissociation of the two acidic protons, as a dianionic tridentate ONS donor and that ruthenium(II) ion adopts octahedral coordination with the phosphorus atoms in trans-disposition. Ruthenium complexes have been used in conjunction with N-methylmorpholine-N-oxide (NMO) for the catalytic oxidation of various alcohols at room temperature. Benzylic primary and secondary alcohols are oxidized in good to excellent yields, and aliphatic and cyclic alcohols give carbonyl compounds in moderate yields.
- Muthu Tamizh,Mereiter,Kirchner,Karvembu
-
experimental part
p. 194 - 201
(2012/03/11)
-
- Kinetics and mechanisms of the tropospheric reactions of menthol, borneol, fenchol, camphor, and fenchone with hydroxyl radicals (OH) and chlorine atoms (Cl)
-
Relative kinetic techniques have been used to measure the rate coefficients for the reactions of oxygenated terpenes (menthol, borneol, fenchol, camphor, and fenchone) and cyclohexanol with hydroxyl radicals (OH) and chlorine atoms (Cl) at 298 ± 2 K and atmospheric pressure. The rate coefficients obtained for the reactions of the title compounds with OH are the following (in units of 10-11 cm3 molecule-1 s-1): (1.48 ± 0.31), (2.65 ± 0.32), (2.49 ± 0.30), (0.38 ± 0.08), (0.39 ± 0.09) for menthol, borneol, fenchol, camphor, and fenchone, respectively. For the corresponding reactions with Cl atoms the rate coefficients are as follows (in units of 10-10 cm3 molecule-1 s-1): (3.21 ± 0.26), (3.40 ± 0.28), (2.72 ± 0.13), (2.93 ± 0.17), (1.59 ± 0.10), and (1.86 ± 0.29) for cyclohexanol, menthol, borneol, fenchol, camphor, and fenchone, respectively. The reported error is twice the standard deviation. Product studies of the reactions were performed using multipass in situ FTIR (Fourier transform infrared spectroscopy) and solid-phase microextraction (SPME) with analysis by GC-MS (gas chromatography-mass spectrometry). A detailed mechanism is proposed to justify the observed reaction products.
- Ceacero-Vega, Antonio A.,Ballesteros, Bernabe,Bejan, Iustinian,Barnes, Ian,Jimenez, Elena,Albaladejo, Jose
-
experimental part
p. 4097 - 4107
(2012/06/30)
-
- Application and mechanistic studies of a water-oxidation catalyst in alcohol oxidation by employing oxygen-transfer reagents
-
By using a dimeric ruthenium complex in combination with tert-butyl hydrogen peroxide (TBHP) as stoichiometric oxidant, a mild and efficient protocol for the oxidation of secondary benzylic alcohols was obtained, thereby giving the corresponding ketones in high yields within 4 h. However, in the oxidation of aliphatic alcohols, the TBHP protocol suffered from low conversions owing to a competing Ru-catalyzed disproportionation of the oxidant. Gratifyingly, by switching to Oxone (2 KHSO5×KHSO 4×K2SO4 triple salt) as stoichiometric oxidant, a more efficient and robust system was obtained that allowed for the oxidation of a wide range of aliphatic and benzylic secondary alcohols, giving the corresponding ketones in excellent yields. The mechanism for these reactions is believed to involve a high-valent RuV-oxo species. We provide support for such an intermediate by means of mechanistic studies. Biphasinating: The use of a dimeric ruthenium complex in the oxidation of alcohols to their corresponding carbonyl compounds in high yields with various oxygen-transfer reagents is reported. This provides support for a mechanism that involves a high-valent RuV-oxo species (see scheme). Copyright
- Verho, Oscar,Dilenstam, Marléne D. V.,K?rk?s, Markus D.,Johnston, Eric V.,?kermark, Torbj?rn,B?ckvall, Jan-E.,?kermark, Bj?rn
-
p. 16947 - 16954
(2013/03/28)
-
- Swern oxidation of alcohols with ion-supported methyl sulfoxide and oxalyl chloride
-
The oxidation of primary and secondary alcohols with ion-supported methyl sulfoxide and oxalyl chloride in the presence of triethylamine in dichloromethane efficiently proceeded to give the corresponding aldehydes and ketones, respectively, in good yields with high purity. Isolation of the product was achieved very easily by simple diethyl ether extraction of the reaction mixture and subsequent removal of solvent from the extract. The reaction did not produce any unpleasant odor. Furthermore, ion-supported methyl sulfide was recovered in good yield and could be re-oxidized to ion-supported methyl sulfoxide for reuse in the same oxidation. Georg Thieme Verlag Stuttgart · New York.
- Tsuchiya, Daisuke,Moriyama, Katsuhiko,Togo, Hideo
-
experimental part
p. 2701 - 2704
(2012/01/03)
-
- Twist does a twist to the reactivity: Stoichiometric and catalytic oxidations with twisted tetramethyl-IBX
-
The methyl groups in TetMe-IBX lower the activation energy corresponding to the rate-determining hypervalent twisting (theoretical calculations), and the steric relay between successive methyl groups twists the structure, which manifests in significant solubility in common organic solvents. Consequently, oxidations of alcohols and sulfides occur at room temperature in common organic solvents. In situ generation of the reactive TetMe-IBX from its precursor iodo-acid, i.e., 3,4,5,6-tetramethyl-2-iodobenzoic acid, in the presence of oxone as a co-oxidant facilitates the oxidation of diverse alcohols at room temperature.
- Moorthy, Jarugu Narasimha,Senapati, Kalyan,Parida, Keshaba Nanda,Jhulki, Samik,Sooraj, Kunnikuruvan,Nair, Nisanth N.
-
experimental part
p. 9593 - 9601
(2012/01/03)
-
- Oxidation of primary and secondary alcohols by 4-acetylamino-2,2,6,6- tetramethylpiperidine-1-oxoammonium tetrafluoroborate in aqueous media
-
water soluble oxidant 4-acetylamino-2,2,6,6-tetramethylpiperidine-1- oxoammonium tetrafluoroborate 1 oxidizes primary and secondary aliphatic, primary allylic, and primary and secondary benzylic alcohols to their corresponding aldehydes and ketones in aqueous media in good to excellent yields. ARKAT-USA, Inc.
- Mamros, Audrey N.,Sharrow, Phillip R.,Weller, William E.,Luderer, Mark R.,Fair, Justin D.,Pazehoski, Kristina O.,Luderer, Matthew R.
-
experimental part
p. 23 - 33
(2011/06/20)
-
- N-bromo-(4-methylphenyl) sulfonimide: A mild and efficient reagent for oxidative deoximation of oximes under microwave irradiations
-
Aldoximes and ketoximes are converted to the parent carbonyl compounds in good yields when treated with N-bromo-(4-methylphenyl) sulfonimide (2), under microwave irradiations. The simple work-up minimizes the loss of product and oximes have been selectively oxidized in the presence of alcohols and alkenes.
- Manesh, Abbas Amini,Khazaei, Ardeshir
-
experimental part
p. 624 - 626
(2012/01/03)
-
- Microwave promoted regeneration of carbonyl compounds from oximes using N, N-dichloro poly(styrene-co-divinylbenzene)sulphonamide resin
-
An efficient, economically viable and operationally simple method was developed for deoximation of oximes (of ketones and aldehydes) to their corresponding carbonyl compounds using polymer beads of N, N-dichloro poly(styrene-co-divinylbenzene)sulphonamide resin. Polymeric reagent offered speedy conversion and substantial yields of products under mild condition and is recyclable. Deoximation was monitored by the use of 13C NMR.
- Beldar,Sharma, Mamta
-
experimental part
p. 288 - 292
(2012/02/01)
-
- Trimethylsilyl chloride promoted selective desulfurization of thiocarbonyls to carbonyls with hydrogen peroxide
-
In the presence of hydrogen peroxide and trimethylsilyl chloride, thiocarbonyls desulfurize to the corresponding carbonyls. The safe, operationally simple, general reaction gives excellent yields in short reaction times with no side reactions and excellent regioselectivity, which makes this process an attractive, environmentally benign alternative for the desulfurization of thiocarbonyls
- Bahrami, Kiumars,Khodaei, Mohammad Mehdi,Tajik, Maryam
-
experimental part
p. 4282 - 4286
(2011/02/25)
-
- 6-membered pseudocyclic IBX acids: Syntheses, X-ray structural characterizations, and oxidation reactivities in common organic solvents
-
We designed and synthesized λ5-cyclic periodinanes 1 and 2, which are homologous to IBX (1-hydroxy-1-oxo-1H-1λ5- benzo[d][1,2]iodoxol-3-one) by one carbon, to thwart close packing of molecules in the crystal lattice to permit solubility in common organic solvents and to facilitate oxidations with enhanced reactivity. The X-ray crystal structures revealed that both 1 and 2 exist in the solid state as pseudocyclic (PC) acids, i.e., 1PC and 2PC, and that the molecules in the lattice are less weakly associated as compared to those in the parent IBX due to the twisting introduced via the sp3 benzylic carbon. Both 1PC and 2PC are found to dissolve in palpable amounts in DCM and acetonitrile to allow oxidation of a variety of alcohols and sulfides to carbonyl compounds and sulfoxides in a facile manner. The subtle differences in the sterics due to methyl and ethyl substituents in 1PC and 2PC are found to manifest in contrasting reactivities in that the oxidations of alcohols occur faster with 2PC, while those of sulfides to sulfoxides occur more rapidly with 1PC.
- Moorthy, Jarugu Narasimha,Senapati, Kalyan,Parida, Keshaba Nanda
-
supporting information; experimental part
p. 8416 - 8421
(2011/03/20)
-
- Solvent free oxidation of primary alcohols and diols using thymine iron(iii) catalyst
-
In this study, we developed an efficient and selective iron-based catalyst system for the synthesis of ketones from secondary alcohols and carboxylic acids from primary alcohol. In situ generated iron catalyst of thymine-1-acetate (THA) and FeCl3 under solvent-free condition exhibits high activity. As an example, 1-octanol and 2-octanol were oxidized to 1-octanoic acid and 2-octanone with 89% and 98% yields respectively.
- Al-Hunaiti, Afnan,Niemi, Teemu,Sibaouih, Ahlam,Pihko, Petri,Leskelae, Markku,Repo, Timo
-
supporting information; experimental part
p. 9250 - 9252
(2011/02/22)
-
- Synthesis, structural characterization and alcohol oxidation activity of a new mononuclear manganese(II) complex
-
A manganese(II) complex of 2,4,6-tris(2-pyridyl)-1,3,5-triazine (tptz) has been synthesized and characterized by single-crystal X-ray diffraction, elemental analyses, IR, and UV-Vis spectroscopic techniques. Oxidation of alcohols to their corresponding aldehydes and ketones was conducted by this catalyst using oxone (2KHSO5KH-SO4K2SO4) as an oxidant under biphasic reaction conditions (CH2Cl2/H 2O) and tetra-n-butylammonium bromide as phase transfer agent under air at room temperature. Easy preparation, mild reaction conditions, high yields of the products, short reaction times, no further oxidation to the corresponding carboxylic acids, high selectivity and inexpensive reagents make this catalytic system a useful oxidation method for aliphatic and benzylic alcohols. Springer Science+Business Media B.V. 2010.
- Najafpour, Mohammad Mahdi,Amini, Mojtaba,Bagherzadeh, Mojtaba,Boghaei, Davar M.,McKee, Vickie
-
experimental part
p. 297 - 303
(2011/11/06)
-
- Reactions of halonorbornane and oxo-substituted derivatives with different anions by the electron transfer mechanism; Redox catalysis in stabilized radicals
-
Reactions of 2-bromo-, 2-chloronorbornane, 3-chloronorbornan-2-one and 3-bromocamphor with Me3Sn-, Ph2P- or PhS- ions were studied by an SRN1 mechanism in liquid ammonia or DMSO. The results show that substrates having a carbonyl group facilitate electron transfer reactions, which are impeded in the absence of such a group. However, when the free radical formed is stabilized by conjugation, the coupling reaction decreases, causing a concomitant increase in the reduction product. Theoretical studies explain the observed reactivity on the basis of a mechanism involving reductive cleavage as a function of the π-σ interactions.
- Uranga, Jorge G.,Santiago, Ana N.
-
experimental part
p. 2006 - 2012
(2011/01/10)
-
- One-pot synthesis of carbamoyl azides directly from primary alcohols and oxidation of secondary alcohols to ketones using iodobenzene dichloride in combination with sodium azide
-
An effective synthesis of carbamoyl azides directly from primary alcohols using iodobenzene dichloride in combination with sodium azide has been developed. Moreover, the same regent combination was also efficient for the oxidation of secondary alcohols to the corresponding ketones.
- Li, Xiao-Qiang,Wang, Wei-Kun,Zhang, Chi
-
scheme or table
p. 2342 - 2350
(2009/12/27)
-
- Expedient method for oxidation of alcohol by hydrogen peroxide in the presence of amberlite IRA 400 resin (basic) as phase-transfer catalyst
-
Amberlite IRA 400 (strongly basic), a classical polymer imparts phase-transfer catalysis in the oxidation of primary and secondary alcohols by hydrogen peroxide to give excellent yields of the corresponding carbonyl compounds or carboxylic acids in acetonitrile solvent at reflux temperature in 4-6 h. The catalytic system is inert to other susceptible oxidation sites such as carbon-carbon double bonds. Copyright Taylor & Francis Group, LLC.
- Bhati, Nishi,Sarma, Kuladip,Goswami, Amrit
-
p. 1416 - 1424
(2008/09/20)
-
- Oxidation of alcohols by chlorine dioxide in organic solvents
-
The kinetics of oxidation of a series of alcohols (propan-2-ol, 2-methylpropan-1-ol, butan-1-ol, butan-2-ol, 3-methylpentan-1-ol, heptan-4-ol, decan-2-ol, cyclohexanol, borneol) by chlorine dioxide in organic solvents was studied using spectrophotometry. The reaction is described by the second-order rate equation w = k[ROH][ClO2]. The rate constants were measured in the range of 10-60 °C, and the activation parameters of the processes were calculated. The products were identified, and the yields were determined.
- Ganieva,Ganiev,Grabovskiy,Kabalnova
-
body text
p. 2328 - 2331
(2010/02/15)
-
- Heteropoly acid-based supported ionic liquid-phase catalyst for the selective oxidation of alcohols
-
A supported ionic liquid strategy has been applied for the immobilization of a heteropolyacid, molybdovanadophosphoric acid, onto ionic liquid-modified mesoporous silica SBA-15. The immobilized catalyst demonstrated high activity in the aerobic oxidation of primary and secondary alcohols to aldehydes and ketones, respectively. No overoxidation of the primary alcohols to carboxylic acids was observed. Secondary alcohols were chemoselectively oxidized to ketones in the presence of primary alcohol, hetero atom, and allyl groups. This catalyst could be recycled five times without obvious loss of activity.
- Bordoloi, Ankur,Sahoo, Suman,Lefebvre,Halligudi
-
experimental part
p. 232 - 239
(2009/03/11)
-
- A facile, catalytic deoximation method using potassium bromide and ammonium heptamolybdate in the presence of hydrogen peroxide in an aqueous medium
-
A simple, mild and efficient procedure for the cleavage of a wide range of ketoximes and aldoximes to the corresponding carbonyl compounds in an aqueous medium using catalytic amounts of potassium bromide and ammonium heptamolybdate tetrahydrate in combination with 30% hydrogen peroxide is described. Georg Thieme Verlag Stuttgart.
- Ganguly, Nemai C.,Barik, Sujoy Kumar
-
p. 425 - 428
(2008/09/20)
-