- EFFECT OF RING SIZE ON THE ACID-CATALYSED HYDROLYSIS OF CYCLIC α,β-EPOXYSILANES
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Acid-catalysed hydrolysis of epoxysilanes derived from common-, medium- and large-ring vinylsilanes is described.Whereas the large epoxysilanes give ketones, the medium-ring epoxysilanes give transannular products and the common-ring epoxysilanes provide α,β-dihydroxysilanes.The results are explained as due to the conformational rigidity in the common-ring silyldiols and the conformational freedom in the large-ring silyldiols to achive antiperiplanar geometry for 1,2-elimination of trimethylsilanol.
- Nagendrappa, Gopalpur,Vidyapati, T. J.
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Read Online
- The effect of ligand variation on the rate of cyclododecane oxidation under modified GoAgg(II) conditions
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The effect of various ligands on the GoAgg(II) oxidation of cyclododecane to cyclododecanone has been investigated. The addition of picolinic acid and a number of its congeners increases the rate of oxidation up to fiftyfold. On the other hand, the addition of pyridine-2-phosphonic acid stops oxidation completely.
- About-Jaudet,Barton,Csuhai,Ozbalik
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Read Online
- Oxidation of Ethers by Nitrogen Dioxide in the Presence of Silica Gel
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Ethers are efficiently oxidized by nitrogen dioxide to give the corresponding aldehydes or ketones in the presence of silica gel under mild conditions.
- Nishiguchi, Takeshi,Okamoto, Hiroaki
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Read Online
- Oxidative Cleavage of Alkenes by O2with a Non-Heme Manganese Catalyst
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The oxidative cleavage of C═C double bonds with molecular oxygen to produce carbonyl compounds is an important transformation in chemical and pharmaceutical synthesis. In nature, enzymes containing the first-row transition metals, particularly heme and non-heme iron-dependent enzymes, readily activate O2 and oxidatively cleave C═C bonds with exquisite precision under ambient conditions. The reaction remains challenging for synthetic chemists, however. There are only a small number of known synthetic metal catalysts that allow for the oxidative cleavage of alkenes at an atmospheric pressure of O2, with very few known to catalyze the cleavage of nonactivated alkenes. In this work, we describe a light-driven, Mn-catalyzed protocol for the selective oxidation of alkenes to carbonyls under 1 atm of O2. For the first time, aromatic as well as various nonactivated aliphatic alkenes could be oxidized to afford ketones and aldehydes under clean, mild conditions with a first row, biorelevant metal catalyst. Moreover, the protocol shows a very good functional group tolerance. Mechanistic investigation suggests that Mn-oxo species, including an asymmetric, mixed-valent bis(μ-oxo)-Mn(III,IV) complex, are involved in the oxidation, and the solvent methanol participates in O2 activation that leads to the formation of the oxo species.
- Bennett, Elliot L.,Brookfield, Adam,Guan, Renpeng,Huang, Zhiliang,Mcinnes, Eric J. L.,Robertson, Craig M.,Shanmugam, Muralidharan,Xiao, Jianliang
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supporting information
p. 10005 - 10013
(2021/07/19)
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- Method for the continuous production of ketones from epoxides in a fixed bed
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A method is useful for the continuous production of ketones from a compound with at least one epoxide group in at least one fixed bed reactor. A catalyst composition is used with at least one noble metal and at least one metal oxide. To reduce the proportions of high-boilers which form in the reaction, an inert gas is introduced so that a carbon monoxide partial pressure of 50 mbar or less is set in the reactor.
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Paragraph 0076-0096
(2021/06/04)
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- Efficient oxidation of cycloalkanes with simultaneously increased conversion and selectivity using O2 catalyzed by metalloporphyrins and boosted by Zn(AcO)2: A practical strategy to inhibit the formation of aliphatic diacids
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The direct sources of aliphatic acids in cycloalkanes oxidation were investigated, and a strategy to suppress the formation of aliphatic acids was adopted through enhancing the catalytic transformation of oxidation intermediates cycloalkyl hydroperoxides to cycloalkanols by Zn(II) and delaying the emergence of cycloalkanones. Benefitted from the delayed formation of cycloalkanones and suppressed non-selective thermal decomposition of cycloalkyl hydroperoxides, the conversion of cycloalkanes and selectivity towards cycloalkanols and cycloalkanones were increased simultaneously with satisfying tolerance to both of metalloporphyrins and substrates. For cyclohexane, the selectivity towards KA-oil was increased from 80.1% to 96.9% meanwhile the conversion was increased from 3.83 % to 6.53 %, a very competitive conversion level with higher selectivity compared with current industrial process. This protocol is not only a valuable strategy to overcome the problems of low conversion and low selectivity lying in front of current cyclohexane oxidation in industry, but also an important reference to other alkanes oxidation.
- Shen, Hai-Min,Wang, Xiong,Ning, Lei,Guo, A-Bing,Deng, Jin-Hui,She, Yuan-Bin
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- Three metal centers (Co _AOMARKENCODEAMPX0AOA) Cu _AOMARKENCODEAMPX0AOA Method using Zn) 2D MOFs/ultraviolet light to catalyze oxidation of cycloalkane
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The invention relates to a three-metal center (Co _AOMARKENCODEAMPX0AOA). Cu _AOMARKENCODEAMPX0AOA The method comprises Zn) 2D MOFs/ultraviolet light catalytic oxidation of cycloalkane to synthesize cycloalkyl alcohol and cycloalkanone, and belongs to the field of industrial catalysis and fine organic synthesis. To the application method, metalloporphyrin three-metal center (Co _AOMARKENCODEAMPX0AOA) is used. Cu _AOMARKENCODEAMPX0AOA Zn) 2D MOFs dispersed in cycloalkane, wherein metalloporphyrin three-metal center (Co _AOMARKENCODEAMPX0AOA) Cu _AOMARKENCODEAMPX0AOA Zn) 2D MOFs mass is 0.01% - 20%, g / mol of the substance of the cycloalkane, and the reaction system is sealed. An oxidant is introduced, the ultraviolet lamp is a light source, and the reaction liquid of the stirring reaction 2.0-24 . 0h. is subjected to post-treatment to obtain the product cycloalkyl alcohol and cycloalkyl ketone. The method provided by the invention has the advantages of low reaction temperature, mild reaction conditions, high reaction efficiency, high selectivity of cycloalkyl alcohol and cycloalkyl ketone, less byproducts and small environmental impact. The invention provides a high efficiency. Available, safe cycloalkanes selectively catalyze the oxidative synthesis of cycloalkyl alcohols and cycloalkyl ketones.
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Paragraph 0028; 0081-0082
(2021/11/06)
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- Electrochemically driven desaturation of carbonyl compounds
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Electrochemical techniques have long been heralded for their innate sustainability as efficient methods to achieve redox reactions. Carbonyl desaturation, as a fundamental organic oxidation, is an oft-employed transformation to unlock adjacent reactivity through the formal removal of two hydrogen atoms. To date, the most reliable methods to achieve this seemingly trivial reaction rely on transition metals (Pd or Cu) or stoichiometric reagents based on I, Br, Se or S. Here we report an operationally simple pathway to access such structures from enol silanes and phosphates using electrons as the primary reagent. This electrochemically driven desaturation exhibits a broad scope across an array of carbonyl derivatives, is easily scalable (1–100 g) and can be predictably implemented into synthetic pathways using experimentally or computationally derived NMR shifts. Systematic comparisons to state-of-the-art techniques reveal that this method can uniquely desaturate a wide array of carbonyl groups. Mechanistic interrogation suggests a radical-based reaction pathway. [Figure not available: see fulltext.]
- Gnaim, Samer,Takahira, Yusuke,Wilke, Henrik R.,Yao, Zhen,Li, Jinjun,Delbrayelle, Dominique,Echeverria, Pierre-Georges,Vantourout, Julien C.,Baran, Phil S.
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p. 367 - 372
(2021/03/31)
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- Sulfonium ion-promoted traceless Schmidt reaction of alkyl azides
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Schmidt reaction by sulfonium ions is described. General primary, secondary, and tertiary alkyl azides were converted to the corresponding carbonyl or imine compounds without any trace of the activators. This bond scission reaction through 1,2-migration of C-H and C-C bonds was accessible to the one-pot substitution reaction.
- Ardiansah, Bayu,Kakiuchi, Kiyomi,Morimoto, Tsumoru,Tanimoto, Hiroki,Tomohiro, Takenori
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p. 8738 - 8741
(2021/09/08)
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- Visible light photoredox catalyzed deprotection of 1,3-oxathiolanes
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An efficient visible light photoredox catalyzed aerobic deprotection of 1,3-oxathiolanes using organic dye Eosin Y as a photocatalyst is disclosed. The deprotection procedure features the use of a metal-free catalyst, mild conditions, a broad range of substrate scope, and good functional group tolerance. 35 examples were tested under the standard conditions and most of them afforded the deprotected products in modest to high yields.
- Yang, Mingyang,Xing, Zhimin,Fang, Bowen,Xie, Xingang,She, Xuegong
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supporting information
p. 288 - 291
(2020/01/13)
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- Method for catalytic oxidation of cycloalkane by confinement porphyrin Co (II)
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The invention relates to a method for catalytic oxidation of cycloalkane by confinement porphyrin Co (II). The method comprises the following steps: dispersing confinement cobalt porphyrin (II) in cycloalkane, sealing the reaction system, heating to 100-130 DEG C while stirring, introducing oxygen to 0.2-3.0 MPa, keeping the set temperature and oxygen pressure, stirring to react for 3.0-24.0 h, and carrying out post-treatment on a reaction solution to obtain products naphthenic alcohol and naphthenic ketone. The method achieves high selectivity of naphthenic alcohol and naphthenic ketone, andeffectively inhibits the generation of aliphatic diacid. The aliphatic diacid is low in selectivity, so that the continuity of the cycloalkane oxidation process and the separation of the products arefacilitated; the method has the potential of solving the problem that naphthenic alcohol and naphthenic ketone are easily and deeply oxidized to generate aliphatic diacid in the industrial cycloalkanecatalytic oxidation process; and the method is a novel efficient and feasible method for selective catalytic oxidation of cycloalkane.
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Paragraph 0073; 0074
(2020/05/01)
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- Confinement porphyrin Co (II), and preparation method and application thereof
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Confinement porphyrin Co (II). A preparation method includes: under acidic condition, performing condensation on aromatic aldehyde and pyrrole in equal molar ratio to obtain a phenylporphyrin compound, and carrying out metallization in a chloroform-methanol solution to obtain porphyrin Cu (II), performing bromination and demetalization by perchloric acid to obtain confinement porphyrin, performingstirring reflux on the confinement porphyrin in a methanol solution for 12.0-24.0 h to obtain confinement porphyrin Co (II). An application includes: dissolving the confinement porphyrin Co (II) in naphthenic hydrocarbon and sealing the reaction system, stirring and heating the reaction system to 100-130 DEG C and feeding oxygen to 0.2-3.0 MPa; maintaining the set temperature and oxygen pressureand performing a stirring reaction for 3.0-24.0 h; performing after treatment on the reaction liquid to prepare the product. In the invention, generation of fatty diacid is effectively inhibited, andcontinuity of a naphthenic hydrocarbon oxidization process and product separation is facilitated. The invention has the potential of solving the problem that naphthene alcohols and naphthene ketones are liable to undergo deep oxidization and form the fatty diacid in an industrial naphthenic hydrocarbon catalytic oxidation process.
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Paragraph 0105-0106
(2020/04/17)
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- Method for synergistically catalyzing and oxidizing cycloparaffin through confined metalloporphyrin cobalt (II)/Cu (II) salt
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The invention discloses a method for synergistically catalyzing and oxidizing cycloparaffin through confined metalloporphyrin cobalt (II)/Cu (II) salt. The preparation method comprises the following steps: dispersing confined metalloporphyrin cobalt (II) (0.001%-5%, g/mol) and Cu (II) salt (0.01%-10%, mol/mol) into cycloparaffin; and sealing the reaction system, heating the temperature to 90-150 DEG C while stirring, introducing an oxidant, keeping the set temperature and pressure, carrying out stirring and reacting for 2.0-24.0 hours, and carrying out after-treatment on the reaction solutionto obtain the products cycloalkyl alcohol and cycloalkyl ketone. The method disclosed by the invention has the advantages of high cycloalkyl alcohol and cycloalkyl ketone selectivity, low reaction temperature, few byproducts, small environmental influence and the like. In addition, the content of cycloalkyl hydroperoxide is low, and the safety coefficient is high. The invention provides an efficient, feasible and safe method for synthesizing cycloalkyl alcohol and cycloalkyl ketone through selective catalytic oxidation of cycloparaffin.
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Paragraph 0047-0048
(2020/12/10)
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- Ruthenium Trichloride Catalyst in Water: Ru Colloids versus Ru Dimer Characterization Investigations
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An easy-to-prepare ruthenium catalyst obtained from ruthenium(III) trichloride in water demonstrates efficient performances in the oxidation of several cycloalkanes with high selectivity toward the ketone. In this work, several physicochemical techniques were used to demonstrate the real nature of the ruthenium salt still unknown in water and to define the active species for this Csp3-H bond functionalization. From transmission electron microscopy analyses corroborated by SAXS analyses, spherical nanoobjects were observed with an average diameter of 1.75 nm, thus being in favor of the formation of reduced species. However, further investigations, based on X-ray scattering and absorption analyses, showed no evidence of the presence of a metallic Ru-Ru bond, proof of zerovalent nanoparticles, but the existence of Ru-O and Ru-Cl bonds, and thus the formation of a water-soluble complex. The EXAFS (extended X-ray absorption fine structure) spectra revealed the presence of an oxygen-bridged diruthenium complex [Ru(OH)xCl3-x]2(μ-O) with a high oxidation state in agreement with catalytic results. This study constitutes a significant advance to determine the true nature of the RuCl3·3H2O salt in water and proves once again the invasive nature of the electron beam in microscopy experiments, routinely used in nanochemistry.
- Lebedeva, Anastasia,Albuquerque, Brunno L.,Domingos, Josiel B.,Lamonier, Jean-Fran?ois,Giraudon, Jean-Marc,Lecante, Pierre,Denicourt-Nowicki, Audrey,Roucoux, Alain
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p. 4141 - 4151
(2019/03/26)
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- Efficient Palladium(0) supported on reduced graphene oxide for selective oxidation of olefins using graphene oxide as a ‘solid weak acid’
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Selective oxidation of olefin derivatives to ketones has made innovative development over palladium(0) supported on reduced graphene oxide. Compared to traditional Wacker oxidation, the novel method offers an economical and environment-friendly option by using graphene oxide (GO) as a ‘solid weak acid’ instead of classical homogeneous catalysts like H2SO4 and CF3COOH. X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscope and transmission electron microscopy images of Pd0/RGO showed that the nanoscaled Pd particles generated at the flake structure of reduced graphene oxide. Under optimized condition, up to 44 kinds of ketones with different structures can be prepared with excellent yields.
- Gao, Xi,Zhou, Jianhao,Peng, Xinhua
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- Process for producing laurolactam and its synthesis apparatus
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A method for manufacturing laurolactam and a synthesis apparatus thereof according to the present invention have a remarkably high conversion rate of raw materials and selectivity of a target compound, have an effect of synthesizing the target compound with a high yield and high purity, can minimize costs used for equipment and processes, are practical, and have an advantage of being more simplified compared to the prior art.COPYRIGHT KIPO 2019
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Paragraph 0085-0088
(2020/05/14)
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- METHOD FOR MANUFACTURING CYCLODODECANONE AND APPARATUS FOR MANUFACTURING THE SAME
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A method for manufacturing cyclododecanone according to the present invention has an effect of having a significantly high conversion rate of cyclododecene and selectivity of cyclododecanone, can minimize the cost used for equipment and processes, is practical, and has an advantageous effect on industrial mass production compared to the prior art by significantly reducing a reaction residence time and a required reaction volume of a reactor.COPYRIGHT KIPO 2019
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Paragraph 0051-0080
(2020/05/14)
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- Purification and Characterization of an Enone Reductase from Sporidiobolus salmonicolor TPU 2001 Reacting with Large Monocyclic Enones
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We discovered a novel enone reductase from Sporidiobolus salmonicolor TPU 2001 (SsERD) and expressed the gene in Escherichia coli. The enzyme catalyzed the reduction of (E)-3-methylcyclopentadec-2-en-1-one (E-2), cyclopentadec-2-en-1-one (3), and cyclododec-2-en-1-one (4) to (S)-muscone (S-1), cyclopentadecan-1-one (5), and cyclododecan-1-one (6), respectively. The apparent Km and Vmax values for E-2 were estimated to be 4.9±0.4 μm and 100±1.4 nmol min?1 mg?1, respectively. The enzyme was specific to NADPH, and cysteine residues strongly affected the enzyme activity. The enzyme exhibited the highest activity at pH 8.0 and high stability in the pH range from 4.5 to 11.0. Using 10 mU of the enzyme, S-1 was synthesized from 0.1 mm E-2 with 94.8 % yield and 100 % enantiomeric excess by incubation at pH 7.0 and 30 °C for 60 min. We further successfully constructed an enone reductase with high specific activity by mutation of SsERD. The Y67A variant from SsERD exhibited 4.5 times higher specific activity and 3 times higher catalytic efficiency toward E-2. This is the first report of an enzyme catalyzing the reduction of carbon–carbon double bond of large monocyclic enones.
- Yamamoto, Kazunori,Oku, Yuko,Ina, Atsutoshi,Izumi, Atsushi,Doya, Masaharu,Ebata, Syuji,Asano, Yasuhisa
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p. 3697 - 3704
(2017/10/16)
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- CATALYST SYSTEM FOR PRODUCING KETONES FROM EPOXIDES
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A catalyst composition is useful for producing a ketone from a compound containing at least one epoxide group, and the catalyst composition contains at least one precious metal; and at least one mixed oxide; wherein the mixed oxide contains zirconium dioxide and silicon dioxide; wherein the precious metal is supported and the support is not entirely made of the mixed oxide; and wherein a mass ratio of zirconium dioxide to silicon dioxide in the mixed oxide is 86:14 to 99.9:0.1.
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Paragraph 0138; 0139
(2016/05/02)
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- PROCESS FOR PREPARING CYCLODODECANONE
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Cyclododecanone (CDON) is prepared by epoxidizing cyclododecene (CDEN) to epoxycyclododecane (CDAN epoxide), and rearranging the CDAN epoxide to CDON to obtain a mixture comprising said CDON and CDEN, wherein CDEN is separated from the CDON-containing mixture and sent to the epoxidation to CDAN epoxide in step a.
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Paragraph 0091-0099
(2016/02/20)
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- NOVEL HYPERVALENT IODINE COMPOUND HAVING 5-X(X=F,Cl,Br)-1,2-BENZIODOXOL-3-(1H)-ON PART
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PROBLEM TO BE SOLVED: To provide a novel trivalent hypervalent iodine compound which has excellent reactivity in an oxidation reaction using a trivalent hypervalent iodine compound and which enables easy removal and isolation of a monovalent iodine compound produced as a byproduct by an extraction operation. SOLUTION: Provided is a novel trivalent hypervalent iodine compound having a 5-X(X=F, Cl, or Br)-1,2-benziodoxol-3-(1H)-on part. This compound enables oxidation of a compound which has not been able to be oxidized by a conventional trivalent hypervalent iodine compound. Further, a monovalent iodine compound produced as a byproduct after completion of the oxidation reaction has become able to be removed and isolated by washing and extraction operations. COPYRIGHT: (C)2015,JPO&INPIT
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Paragraph 0027
(2016/12/16)
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- Oxidative debenzylation of N-benzyl amides and O-benzyl ethers using alkali metal bromide
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The oxidative debenzylation of N-benzyl amides and O-benzyl ethers was promoted with high efficiency by a bromo radical formed through the oxidation of bromide from alkali metal bromide under mild conditions. This reaction provided the corresponding amides from N-benzyl amides and carbonyl compounds from O-benzyl ethers in high yields.
- Moriyama, Katsuhiko,Nakamura, Yu,Togo, Hideo
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supporting information
p. 3812 - 3815
(2014/08/05)
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- N-alkylation of ammonia and amines with alcohols catalyzed by Ni-loaded CaSiO3
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Nickel nanoparticles loaded onto calcium silicate (Ni/CaSiO3) have been prepared by ion-exchange method followed by in situ H 2-reduction of the calcined precursor. Ni/CaSiO3 was found to be effective for the catalytic direct synthesis of primary amines from alcohols and NH3 under relatively mild conditions. Various aliphatic alcohols are tolerated, and the turnover number (TON) was higher than those of Ru-based homogeneous catalysts. The catalyst was recoverable and was reused. Effects of the surface oxidation states and particle size of Ni on the catalytic activity were studied by infrared (IR) investigation of the states of adsorbed CO and transmission electron microscopy (TEM). It is clarified that the surface Ni0 sites on small (3 nm) sized Ni nanoparticles are the catalytically active species. Ni/CaSiO3 was also effective for the alkylation of anilines and aliphatic amines with various alcohols (benzyl and aliphatic alcohols) under additive free conditions; primary amines were converted into secondary amines and secondary amines into tertiary amines.
- Shimizu, Ken-Ichi,Kanno, Shota,Kon, Kenichi,Hakim Siddiki,Tanaka, Hideyuki,Sakata, Yoshihisa
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p. 134 - 138
(2014/06/09)
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- Synthesis of alkyl hydroperoxides via alkylation of gem -dihydroperoxides
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2-Fold alkylation of 1,1-dihydroperoxides, followed by hydrolysis of the resulting bisperoxyacetals, provides a convenient method for synthesis of primary and secondary alkyl hydroperoxides.
- Kyasa, Shivakumar,Puffer, Benjamin W.,Dussault, Patrick H.
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p. 3452 - 3456
(2013/06/26)
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- METHOD FOR PRODUCING AMIDE COMPOUND
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The present invention relates to a method for producing a high purity, high quality amide compound, particularly, lactam. A first embodiment of the present invention is characterized in that an amount of each of a halide, an aldehyde compound, an alcohol compound and a nitrile compound contained in a solution recycled into an oxime-forming step is controlled to an amount of 0.4 mol % or less based on the ketone as a starting material. A second embodiment of the present invention is characterized in that one or more compounds selected from the group consisting of a ketone, an oxime and an amide compound are purified by hydrogenation and/or crystallization for eliminating impurities containing a double bond. A third embodiment of the present invention is characterized in that a content of impurities having a cyclic bridge structure is controlled by using a cycloalkanone purified by recrystallization.
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Page/Page column 25-26
(2013/02/28)
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- Environmentally benign deprotection of dithioacetals using 30% hydrogen peroxide catalyzed by Fe(acac)3 and sodium iodide
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The reaction of dithioacetals with 30% hydrogen peroxide in the presence of catalytic amounts of iron(III) acetylacetonate and sodium iodide efficiently produced the corresponding carbonyl compounds in high yields.
- Kirihara, Masayuki,Suzuki, Satoshi,Ishizuka, Yuki,Yamazaki, Kento,Matsushima, Ryoji,Suzuki, Takaya,Iwai, Toshiaki
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p. 5477 - 5480
(2013/09/23)
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- Wacker-type oxidation of internal alkenes using Pd(Quinox) and TBHP
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The Pd-catalyzed TBHP-mediated Wacker-type oxidation of internal alkenes is reported. The reaction uses 2-(4,5-dihydro-2-oxazolyl)quinoline (Quinox) as ligand and TBHP(aq) as oxidant to deliver single ketone constitutional isomer products in a predictable fashion from electronically biased olefins. This methodology is showcased through its application on an advanced intermediate in the total synthesis of the antimalarial drug artemisinin.
- Deluca, Ryan J.,Edwards, Jennifer L.,Steffens, Laura D.,Michel, Brian W.,Qiao, Xiaoxiao,Zhu, Chunyin,Cook, Silas P.,Sigman, Matthew S.
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p. 1682 - 1686
(2013/04/10)
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- Heterogeneous Ni catalyst for direct synthesis of primary amines from alcohols and ammonia
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This paper reports the synthesis of primary amines from alcohols and NH3 by an Al2O3-supported Ni nanoparticle catalyst as the first example of heterogeneous and noble-metal-free catalytic system for this reaction without additional hydrogen sources under relatively mild conditions. Various aliphatic alcohols are tolerated, and turnover numbers were higher than those of Ru-based homogeneous catalysts. The catalyst was recoverable and was reused. The effects of the Ni oxidation states and the acid-base nature of support oxides on the catalytic activity are studied. It is clarified that the surface metallic Ni sites are the catalytically active species, and the copresence of acidic and basic sites on the support surface is also indispensable for this catalytic system.
- Shimizu, Ken-Ichi,Kon, Kenichi,Onodera, Wataru,Yamazaki, Hiroshi,Kondo, Junko N.
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p. 112 - 117
(2013/03/29)
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- Hydrocarbon oxidation catalyzed by self-folded metal-coordinated cavitands
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Functionalized cavitands have been shown to self-fold via coordination of Fe(ii) salts and effect catalytic C-H oxidation reactions of unfunctionalized alkanes under mild aqueous conditions in the presence of tert-butyl hydroperoxide as co-oxidant. Secondary and tertiary C-H bonds can be converted to ketones and alcohols, respectively, and ethers can be converted to esters. The cavitands retain the catalytic metal throughout the reaction, and can be recovered by filtration. The Royal Society of Chemistry 2012.
- Djernes, Katherine E.,Padilla, Melissa,Mettry, Magi,Young, Michael C.,Hooley, Richard J.
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supporting information
p. 11576 - 11578
(2013/01/15)
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- Exaltone (=Cyclopentadecanone) from Isomuscone (=Cyclohexadecanone), a one-C-atom ring-contraction methodology via a stereospecific favorskii rearrangement: Regioselective application to (-)-(R)-muscone
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Treatment of cyclohexadecanone (1g; with I2 (2.2 mol-euqiv.) and KOH in MeOH) furnished the unsaturated (Z)-ester 2g in 83% yield, via a stereospecific Favorskii rearrangement (Scheme 1). Further treatment with 3-chloroperbenzoic acid (m-CPBA) afforded the unreported epoxy ester 3g (88% yield), which was cleaved in 33% yield to Exaltone (=cyclopentadecanone; 1f) with NaOH in MeOH/H2O and then HCl at 65°. This methodology was similarly extended to higher (C17) and lower (C15 to C11) cyclic ketone analogues, as well as regioselectively to (-)-(R)-muscone (5c) and homomuscone (5f) (Scheme 2). Olfactive properties of the corresponding macrocyclic 1-oxaspiro[2,n]alkanes and -alkenes 4 and 8, resulting from a Coreyi-Chaykovsky oxiranylation, are also presented. Copyright
- Chapuis, Christian,Robvieux, Fabrice,Cantatore, Carole,Saint-Leger, Christine,Maggi, Laurent
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p. 428 - 447
(2012/05/07)
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- Deprotection of dithioacetals with 30% hydrogen peroxide catalyzed by tantalum(V) chloride-sodium iodide or niobium(V) chloride-sodium iodide
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The reaction of dithioacetals with 30% hydrogen peroxide in the presence of catalytic amounts of tantalum(V) and iodide ion effectively produced carbonyl compounds in high yields. Dithioacetals also can be deprotected using the niobium(V) catalyzed oxidation of iodide ion by hydrogen peroxide under mild conditions.
- Kirihara, Masayuki,Noguchi, Takuya,Okajima, Nobuhiro,Naito, Sayuri,Ishizuka, Yuki,Harano, Aiko,Tsukiji, Hiroyuki,Takizawa, Ryu
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experimental part
p. 1515 - 1520
(2012/03/07)
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- Structure-reactivity relationship for alcohol oxidations via hydride transfer to a carbocationic oxidizing agent
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Second-order rate constants were determined for the oxidation of 27 alcohols (R1R2CHOH) by a carbocationic oxidizing agent, 9-phenylxanthylium ion, in acetontrile at 60°C. Alcohols include open-chain alkyl, cycloalkyl, and unsaturated alcohols. Kinetic isotope effects for the reaction of 1-phenylethanol were determined at three H/D positions of the alcohol (KIEα-D=3.9, KIEβ-D3=1.03, KIE OD=1.10). These KIE results are consistent with those we previously reported for the 2-propanol reaction, suggesting that these reactions follow a hydride-proton sequential transfer mechanism that involves a rate-limiting formation of the α-hydroxy carbocation intermediate. Structure-reactivity relationship for alcohol oxidations was deeply discussed on the basis of the observed structural effects on the formation of the carbocationic transition state (Cδ+-OH). Efficiencies of alcohol oxidations are largely dependent upon the alcohol structures. Steric hindrance effect and ring strain relief effect win over the electronic effect in determining the rates of the oxidations of open-chain alkyl and cycloalkyl alcohols. Unhindered secondary alkyl alcohols would be selectively oxidized in the presence of primary and hindered secondary alkyl alcohols. Strained C7-C11 cycloalkyl alcohols react faster than cyclohexyl alcohol, whereas the strained C5 and C12 alcohols react slower. Aromatic alcohols would be efficiently and selectively oxidized in the presence of aliphatic alcohols of comparable steric requirements. This structure-reactivity relationship for alcohol oxidations via hydride-transfer mechanism is hoped to provide a useful guidance for the selective oxidation of certain alcohol functional groups in organic synthesis. Copyright
- Lu, Yun,Bradshaw, Joshua,Zhao, Yu,Kuester, William,Kabotso, Daniel
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p. 1172 - 1178
(2013/01/12)
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- CCl3CN: A crucial promoter of M CPBA-mediated direct ether oxidation
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The direct oxidation of ether sp3 C-H bonds using the new reagent system mCPBA/CCl3CN/MeCN has been developed. CCl 3CN in MeCN drastically alters the reactivity of m-chloroperbenzoic acid (mCPBA), and chemoselective transformation of methyl ethers to ketones was realized under mild conditions. Radical-based mCPBA-mediated oxidation was suggested as the reaction mechanism. The present new reaction expands the utility of methyl ethers as stable synthetic precursors of carbonyl compounds and of mCPBA as a radical-based C-H oxidizing agent.
- Kamijo, Shin,Matsumura, Shoko,Inoue, Masayuki
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supporting information; experimental part
p. 4195 - 4197
(2010/11/17)
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- Manganese-catalyzed direct oxidation of methyl ethers to ketones
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Direct C-H oxidation of alkyl ethers into ketones was achieved using 0.1 mol % of MnCl2 and 4, 4′, 4″-tri(tert-butyl)-2, 2′:6′, 2″-terpyridine (tBu-terpy) in the presence of mCPBA. Conversion of methyl ethers into ketones was particularly efficient and chemoselective. Electron-deficient oxygen functionalities survived under the reaction conditions. The present method broadens the utility of methyl ethers as stable protective groups for hydroxy functionalities and as precursors to carbonyl compounds. (Chemical equation presented).
- Kamijo, Shin,Amaoka, Yuuki,Inoue, Masayuki
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supporting information; experimental part
p. 486 - 489
(2010/09/04)
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- Unified oxidation protocol for the synthesis of carbonyl compounds using a manganese catalyst
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We have developed a unified protocol for the oxidation of ethers, benzylic compounds, and alcohols to carbonyl compounds. The protocol uses catalytic amounts of manganese(II) chloride tetrahydrate and tri(t-butyl)-2,2':6',2Prime;- terpyridine in combination with a stoichiometric amount of either m-chloroperbenzoic acid (MCPBA) or potassium hydrogen peroxysulfate (KHSO 5). A reagent system consisting of the Mn catalyst and MCPBA permitted the chemoselective sp3 C-H oxidation of alkyl ethers and benzylic compounds to generate the corresponding ketones. Alternatively, the water-soluble inorganic salt KHSO5 in combination with the Mn catalyst was used to oxidize alcohols to ketones or carboxylic acids. Importantly, the Mn catalyst/KHSO5 system eliminates technical difficulties associated with the isolation of carboxylic acid products. All the oxidations presented in this feature article proceed at sup-ambient temperature in an aerobic atmosphere, and can therefore be used in practical syntheses of complex organic molecules. Georg Thieme Verlag Stuttgart · New York.
- Kamijo, Shin,Amaoka, Yuuki,Inoue, Masayuki
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experimental part
p. 2475 - 2489
(2010/09/06)
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- Iodine-alumina as an efficient and useful catalyst for the regeneration of carbonyl functionality from the corresponding 1,3-oxathiolanes and 1,3-dithiolanes in aqueous system
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A simple and useful method has been demonstrated for the deprotection of 1,3-oxathiolanes and 1,3-dithiolanes to the corresponding carbonyl compounds in excellent yield by employing catalytic amount (30 mol %) of iodine supported on neutral alumina in ethanol-water or water. The major advantages of this protocol are mild reaction conditions, less reaction time, easy to handle, high yields, inexpensive reagent and environmentally benign.
- Rohman, Md. Rumum,Rajbangshi, Mantu,Laloo, Badaker M.,Sahu, Priti R.,Myrboh, Bekington
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experimental part
p. 2862 - 2864
(2010/07/06)
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- Highly selective synthesis of cyclododecanone over mesostructured VSBA-15 catalysts
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Highly ordered VSBA-15 mesoporous catalysts have been synthesized under pH-adjusting direct hydrothermal (pH-aDH) method using vanadyl sulphate hydrate and Pluronic P123 as the sources of vanadium and template, respectively. The mesoporous catalysts characterized by sophisticated instrumental techniques, viz. ICP-AES, XRD, N2 adsorption, ESR, UV-vis DRS, 51V MAS NMR, 29Si MAS NMR and TEM show their two-dimensional mesostructures with tetrahedral vanadium species on the silica surface. The well ordered VSBA-15 catalysts have been used in the oxidation of cyclododecane (CDD) with hydrogen peroxide (H2O2, 30%) to find their catalytic activities. The regenerated VSBA-15 catalysts have been examined to find their catalytic stabilities. VSBA-15(5) catalyst has been washed with ammonium acetate solution to investigate the leaching of vanadium species in the framework of silica network of SBA-15, and the catalytic activity of washed VSBA-15(5) has also been examined in the catalytic reactions. Moreover, the hydrothermally stable VSBA-15(5) catalyst has also been examined in the catalytic reaction to find the effect of its catalytic activity. Additionally, the influences of various reaction parameters such as temperature, time, ratios of reactant and solvents on the oxidation of CDD have been investigated. Based on the catalytic results, VSBA-15(5) catalyst is found to be a highly active, recyclable and promising heterogeneous catalyst for selective synthesis of cyclododecanone (CDDO).
- Selvaraj,Park
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experimental part
p. 22 - 30
(2011/01/12)
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- PROCESS FOR PREPARING PURE CYCLODODECANONE
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The present invention relates to a process for preparing at least one cyclic compound with Z cycles and 7 to 16 carbon atoms with a keto group, at least comprising the stages: (a1) oxidation of a composition (A), at least comprising one cyclic olefin with Z cycles and 7 to 16 carbon atoms and at least two C—C double bonds, by means of dinitrogen monoxide to give a composition (A1),(a2) separating off the at least one cyclic olefin with Z cycles and 7 to 16 carbon atoms with at least two C—C double bonds from the composition (A1) in order to obtain a composition (A2), and(b) distillative treatment of the composition (A2) from step (a2) in order to obtain a composition (B), comprising the at least one cyclic compound with Z cycles and 7 to 16 carbon atoms with a keto group andless than 1.0% by weight of the at least one compound with Z?1 cycles and 7 to 16 carbon atoms with at least one aldehyde group, where Z can be 1, 2, 3 or 4.
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Page/Page column 18-19
(2010/08/07)
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- A new property of geminal bishydroperoxides: Hydrolysis with the removal of hydroperoxide groups to form a ketone
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A new property of geminal bishydroperoxide was discovered: the ability to hydrolyze in acid medium in the presence of hydrogen peroxide with the formation of ketones. The most resistant to hydrolysis are the cyclic C 6-bishydroperoxydes: at room temperature within one day they are practically not hydrolyzed; less stable is bishydroperoxycycloheptane (C 7): in a day its one fifth part is hydrolyzed. Bishydroperoxydes with the cycles of C8 and C12 for the same time hydrolyzed to 80 and 90% respectively. Of the two linear bishydroperoxydes, 2,2-dihydroperoxydecane, with sterically unhindered center, is more resistant to hydrolysis than 6,6-dihydroperoxyundecane. Pleiades Publishing, Ltd., 2010.
- Terent'ev,Krivykh,Krylov,Ogibin, Yu. N.,Nikishin
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experimental part
p. 1667 - 1671
(2011/02/18)
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- Copper/ascorbic acid dyad as a catalytic system for selective aerobic oxidation of amines
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A new, environmentally benign system based on an ascorbic acid (vitamin C)/copper dyad is presented, which facilitates the oxidation of amines to carbonyl compounds. The oxidation utilizes aerobic oxygen as the ultimate electron scavenger, which accepts electrons in a cascade-like fashion via a Cu+/Cu2+ and ascorbic/dehydroascorbic acid couple. Dehydroascorbic acid, the oxidation agent, finally oxidizes amine substrates in a selective fashion after forming a Schiff base intermediate. The selectivity as well as generality of the method is demonstrated on various substrates.
- Srogl, Jiri,Voltrova, Svatava
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experimental part
p. 843 - 845
(2009/07/11)
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- An efficient protocol for the oxidative hydrolysis of ketone SAMP hydrazones employing SeO2 and H2O2 under buffered (pH 7) conditions
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An effective oxidative protocol for the liberation of ketones from SAMP hydrazones employing peroxyselenous acid under aqueous buffered conditions (pH 7) has been developed. The procedure proceeds without epimerization of adjacent stereocenters or dehydration, in representative SAMP alkylation and aldol reaction adducts, respectively.
- Smith III, Amos B.,Liu, Zhuqing,Simov, Vladimir
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experimental part
p. 3131 - 3134
(2010/03/24)
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- Beckmann-rearrangement of cyclododecanone oxime to ω-laurolactam in the gas phase
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The classical route for the industrial production of ω-laurolactam is the homogeneously catalyzed Beckmann-rearrangement of cyclododecanone oxime in the liquid state using fuming sulfuric acid catalyst. Contrary to that, a completely different way is shown in the present work. In addition to the use of a solid acid catalyst, the vapor phase was chosen. From a process technical point of view it is a superior route compared with the classical one. Following intensive investigations of the vapor phase behavior of substrate, product and the main by-products, a catalyst screening of the most promising materials was performed. In addition, a modification of the most active catalysts was carried out to get more information about reaction sites and to optimize the catalyst activity. Using an acid treated [Al,B]-BEA zeolite at a temperature of approx. 320 °C and reduced pressures, complete conversion combined with excellent selectivity of 98% were obtained. The accumulation of reactants in the fixed bed was less than 5 wt%. Furthermore, investigations of deactivation and regeneration behavior of the catalyst were done. It could be demonstrated that the catalytic material could be regenerated under oxidative atmosphere as well as under non-oxidative conditions through thermal desorption of the deactivating compounds without any measurable loss of catalytic performance.
- Eickelberg,Hoelderich
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experimental part
p. 42 - 55
(2009/06/17)
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- METHODS OF MAKING CYCLODODECATRIENE AND METHODS OF MAKING LAUROLACTONE
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The present disclosure provides processes for the preparation of dodecanedioic acid (DDDA).
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Page/Page column 5
(2009/10/01)
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- METHOD FOR THE PRODUCTION OF CYCLIC KETONES
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The present invention relates to a process for preparing a cyclic ketone having from 7 to 16 carbon atoms, which comprises at least the steps (a) oxidation of a composition (I) comprising at least one cyclic olefin which has from 7 to 16 carbon atoms and at least one C—C double bond by means of dinitrogen monoxide to give a composition (A),(b) treatment of the composition (A) with at least one base to give a composition (B).
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Page/Page column 9
(2009/12/04)
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- METHOD FOR THE PRODUCTION OF CYCLIC KETONES
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The present invention relates to a process for preparing a cyclic ketone having from 7 to 16 carbon atoms, which comprises at least the steps (a) oxidation of a composition (I) comprising at least one cyclic alkene which has from 7 to 16 carbon atoms and at least one C—C double bond by means of dinitrogen monoxide to give a composition (A), (b) treatment of the composition (A) with at least one base to give a composition (B), (c) hydrogenation of the composition (B) in the presence of at least one catalyst to give a composition (C), (d) purification of the composition (C), comprising at least the steps (di) thermal treatment of the composition (C) with at least one acid or at least one catalyst comprising at least one transition metal, (dii) further purification by a method selected from the group consisting of distillation, extraction and crystallization.
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Page/Page column 11
(2010/01/31)
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- Method for the Hydrogenation of Mass Fluxes Containing Aldehyde
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The present application relates to a process for reacting a composition I comprising at least one aldehyde with hydrogen in the presence of a catalyst in at least one main reactor and at least one postreactor, wherein at least 50% of the fresh hydrogen fed to the reaction system is fed into at least one postreactor. In a preferred embodiment, composition I comprises at least one further organic compound.
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Page/Page column 6
(2008/12/08)
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- Beckmann rearrangement of ketoximes to lactams by triphosphazene catalyst
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(Chemical Equation Presented) Triphosphazene, 1,3,5-triazo-2,4,6- triphosphorine-2,2,4,4,6,6-chloride (TAPC), was found to be an efficient catalyst for the Beckmann rearrangement of cyclohexanone oxime and cyclododecanone oxime to ε-caprolactam and laurolactam, which are raw materials of nylon-6 and nylon-12, respectively.
- Hashimoto, Masaharu,Obora, Yasushi,Sakaguchi, Satoshi,Ishii, Yasutaka
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p. 2894 - 2897
(2008/09/20)
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- Method for Improving the Color Number
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The present invention relates to a process for purifying a composition (I) at least comprising cyclododecanone. The process according to the invention for purifying a composition (I) at least comprising cyclododecanone comprises at least step (i) (i) irradiation of the composition (I).
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Page/Page column 6
(2009/01/20)
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- A new insight into the oxidation of cyclododecane with hydrogen peroxide in the presence of iron-substituted polyoxotungstates
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The catalytic homogeneous oxidation of cyclododecane with hydrogen peroxide in the presence of tetrabutylammonium salts of iron-substituted Keggin-type polyoxotungstates of general formula (TBA)4HzXW 11Fe(H2O)O39-nH2O (where X = P, Si, B, and z = 0-2) is described. In the reaction conditions reported, the corresponding alcohol, ketone, and hydroperoxide are obtained as the main reaction products. The catalytic activity of the anions with phosphorous, silicon, and boron is compared in different reaction conditions. These catalytic oxidation reactions seem to be radical processes, since they are totally inhibited in the presence of I2, a well-known radical scavenger. Thieme Stuttgart.
- Santos, Isabel C. M. S.,Sim?es, Mário M. Q.,Balula, M. Salete S.,Neves, M. Gra?a P. M. S.,Cavaleiro, José A. S.,Cavaleiro, Ana M. V.
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experimental part
p. 1623 - 1626
(2009/05/07)
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- Novel mesoporous silicoaluminophosphates as highly active and selective materials in the Beckmann rearrangement of cyclohexanone and cyclododecanone oximes
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Novel mesoporous silicoaluminophosphate molecular sieves with an MCM-41 type structure were synthesized and characterized using various techniques, including XRD, N2 adsorption, DRIFT, TEM, and 27Al, 29Si, and 31P MAS NMR. The surface acidity of the materials was determined by using pyridine and 2,6-dimethylpyridine as probe molecules. The catalytic activity of the mesoporous silicoaluminophosphates in the Beckmann rearrangement of cyclohexanone and cyclododecanone oximes was investigated and compared under gas- and liquid-phase (conventional vs microwave-assisted heating) conditions. The mesoporous silicoaluminophosphate materials are extremely active and selective in both reactions, giving yields comparable to those obtained on aluminosilicates and zeolites in the case of the vapor-phase Beckmann rearrangement of cyclohexanone oxime and the microwave-assisted Beckmann rearrangement of cyclododecanone oxime, respectively. The materials were also highly reusable after reactivation in vapor-phase reactions, with an increase in selectivity to the oxime, although a decrease in the durability (expressed as lifetime at quantitative conversion of the oxime) was also found.
- Conesa,Mokaya,Yang,Luque,Campelo,Romero
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- Oxidative cleavage of oximes with silica-gel-supported chromic acid in nonaqueous media
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A simple procedure for a clean and high-yielding oxidative deoximation of benzaldoximes and ketoximes using a silica-gel-supported chromic acid reagent has been developed. This solid-supported reagent allows us to carry out this reaction in nonaqueous dichloromethane reaction media. Copyright Taylor & Francis Group, LLC.
- Ali, Mohammed Hashmat,Greene, Stacie,Wiggin, Candace J.,Khan, Saira
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p. 1761 - 1767
(2007/10/03)
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- Selective oxidation of alkanes with molecular oxygen and acetaldehyde in compressed (supercritical) carbon dioxide as reaction medium
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The oxidation of cycloalkanes or alkylarenes with molecular oxygen and acetaldehyde as sacrificial co-reductant occurs efficiently in compressed (supercritical) carbon dioxide (scCO2) under mild multiphase conditions. No catalyst is required and high-pressure ATR-FTIR online measurements show that a radical reaction pathway is heterogeneously initiated by the stainless steel of the reactor walls. For secondary carbon atoms, high ketone to alcohol ratios are observed (3.5-7.9), most probably due to fast consecutive oxidation of alcoholic intermediates. Since C - C scission reactions are detected only to a very small extent, tertiary carbon atoms are transformed into the corresponding alcohols with high selectivity. Detailed analysis of the product distributions and other mechanistic evidence suggest that acetaldehyde acts not only as the sacrificial oxygen acceptor, but also as an efficient H-atom donor for peroxo and oxo radicals and as a crucial reductant for hydroperoxo intermediates. In comparison to other inert gases such as compressed N, or Ar, the use of carbon dioxide was shown to increase the yields of alkane oxygenates under identical reaction conditions.
- Theyssen, Nils,Hou, Zhenshan,Leitner, Walter
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p. 3401 - 3409
(2008/09/19)
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