- Direct and Selective Synthesis of Adipic and Other Dicarboxylic Acids by Palladium-Catalyzed Carbonylation of Allylic Alcohols
-
A general and direct synthesis of dicarboxylic acids including industrially important adipic acid by palladium-catalyzed dicarbonylation of allylic alcohol is reported. Specifically, the combination of PdCl2 and a bisphosphine ligand (HeMaRaphos) promotes two different carbonylation reactions with high activity and excellent selectivity.
- Beller, Matthias,Ge, Yao,Huang, Weiheng,Jackstell, Ralf,Liu, Jiawang,Neumann, Helfried,Yang, Ji
-
supporting information
p. 20394 - 20398
(2020/09/21)
-
- PROCESS FOR THE CO-PRODUCTION OF LONG CHAIN AMINO ACIDS AND DIBASIC ACIDS
-
There is disclosed a process for the co-production of long chain ω-amino acid and long chain dibasic acid, comprising: (1) reacting long chain ketoacid derivative with hydroxylamine or subjecting ketoacid derivative to an ammoximation to yield oxime derivative; (2) subjecting oxime derivative to Beckmann rearrangement to yield a mixture of mixed amide derivatives; (3) hydrolyzing the mixed amide derivatives to produce long chain ω-amino acid and long chain dibasic acid.
- -
-
Paragraph 0058-0061
(2019/02/01)
-
- Bio-based α,ω-Functionalized Hydrocarbons from Multi-step Reaction Sequences with Bio- and Metallo-catalysts Based on the Fatty Acid Decarboxylase OleTJE
-
OleT from Jeotgalicoccus sp. ATCC 8456 catalyzes the decarboxylation of ω-functionalized fatty acids to the corresponding alkenols, which can themselves serve as starting material for the synthesis of polymers and fine chemicals. To show the versatility of possible reactions, a series of in vitro reaction cascades was developed where an alkenol produced by the decarboxylation of ω-hydroxy fatty acids can be further converted into alkenylamines and diols. By coupling OleT with an alcohol dehydrogenase or alcohol oxidase as well as an amino-transaminase, an oxidative decarboxylation followed by the oxidation of the terminal alcohol and a subsequent reductive transamination could be carried out. By using different cofactors or electron sources, the reactions could be performed sequentially or simultaneously. The combination of enzymatic decarboxylation with a ruthenium catalyst in a chemo-enzymatic cascade provides a novel way to synthesize long-chain diols.
- Bojarra, Samiro,Reichert, Dennis,Grote, Marius,Baraibar, álvaro Gómez,Dennig, Alexander,Nidetzky, Bernd,Mügge, Carolin,Kourist, Robert
-
p. 1192 - 1201
(2018/02/13)
-
- Process for producing long chain amino acids and dibasic acids
-
There is disclosed a process for the production of long chain amino acid and long chain dibasic acid, comprising: (1) reacting long chain keto fatty acid with hydroxylamine or subjecting keto fatty acid to an ammoximation reaction to yield an oxime fatty acid; (2) subjecting the oxime fatty acid to the Beckmann rearrangement to yield a mixture of two amide fatty acids; (3) hydrolyzing the mixed amide fatty acids to produce long chain amino acid, long chain dibasic acid, short chain alkylamine, and alkanoic acid.
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-
Page/Page column 9
(2018/09/21)
-
- Fatty Acid Chain Shortening by a Fungal Peroxygenase
-
A recently discovered peroxygenase from the fungus Marasmius rotula (MroUPO) is able to catalyze the progressive one-carbon shortening of medium and long-chain mono- and dicarboxylic acids by itself alone, in the presence of H2O2. The mechanism, analyzed using H218O2, starts with an α-oxidation catalyzed by MroUPO generating an α-hydroxy acid, which is further oxidized by the enzyme to a reactive α-keto intermediate whose decarboxylation yields the one-carbon shorter fatty acid. Compared with the previously characterized peroxygenase of Agrocybe aegerita, a wider heme access channel, enabling fatty acid positioning with the carboxylic end near the heme cofactor (as seen in one of the crystal structures available) could be at the origin of the unique ability of MroUPO shortening carboxylic acid chains.
- Olmedo, Andrés,Río, José C. del,Kiebist, Jan,Ullrich, René,Hofrichter, Martin,Scheibner, Katrin,Martínez, Angel T.,Gutiérrez, Ana
-
supporting information
p. 16985 - 16989
(2017/11/27)
-
- Method for synthesizing muscone by utilizing beta-monomethyl methylglutarate
-
The invention discloses a method for synthesizing muscone by utilizing beta-monomethyl methylglutarate. According to the method, beta-monomethyl methylglutarate and alpha,omega-dodecanedioic acid monomethyl ester respectively prepared through a heteropoly acid catalytic transesterification method are used as raw materials, and Kolbe electrolysis, acyloin condensation and reduction reaction are performed to prepare the muscone. The method of the present invention has advantages of high raw material utilization rate, mold condition, easy control and environmental protection, and is suitable for industrial production .
- -
-
Paragraph 0023; 0024
(2017/12/05)
-
- Single-step access to long-chain α,ω-dicarboxylic acids by isomerizing hydroxycarbonylation of unsaturated fatty acids
-
Dicarboxylic acids are compounds of high value, but to date long-chain α,ω-dicarboxylic acids have been difficult to access in a direct way. Unsaturated fatty acids are ideal starting materials with their molecular structure of long methylene sequences and a carboxylate functionality, in addition to a double bond that offers itself for functionaliza-tion. Within this paper, we established a direct access to α,ω-dicarboxylic acids by combining isomerization and selective terminal carbonylation of the internal double bond with water as a nucleophile on unsaturated fatty acids. We identified the key elements of this reaction: a homogeneous reaction mixture ensuring sufficient contact between all reactants and a catalyst system allowing for activation of the Pd precursor under aqueous conditions. Experiments under pressure reactor conditions with [(dtbpx)Pd(OTf)2] as catalyst precursor revealed the importance of nucleophile and reactant concentrations and the addition of the diprotonated diphosphine ligand (dtbpxH2)(OTf)2 to achieve turnover numbers >120. A variety of unsaturated fatty acids, including a triglyceride, were converted to valuable long-chain dicarboxylic acids with high turnover numbers and selectivities for the linear product of >90%. We unraveled the activation pathway of the PdII precursor, which proceeds via a reductive elimination step forming a Pd0 species and oxidative addition of the diprotonated diphosphine ligand, resulting in the formation of the catalytically active Pd hydride species. Theoretical calculations identified the hydrolysis as the rate-determining step. A low nucleophile concentration in the reaction mixture in combination with this high energetic barrier limits the potential of this reaction. In conclusion, water can be utilized as a nucleophile in isomerizing functionalization reactions and gives access to long-chain dicarboxylic acids from a variety of unsaturated substrates. The activity of the catalytic system of hydroxycarbonylation ranks as one of the highest achieved for isomerizing functionalizations in combination with a high selectivity for the linear product.
- Goldbach, Verena,Falivene, Laura,Caporaso, Lucia,Cavallo, Luigi,Mecking, Stefan
-
p. 8229 - 8238
(2017/09/26)
-
- ENHANCED DIACID PRODUCTION WITH GENETICALLY MODIFIED MICRO-ORGANISMS
-
The present invention relates to a field of diacids, and more precisely to a method of producing diacids. The invention further relates to recombinant microorganisms comprising omega-oxidation and increased diacid production, and uses and methods related thereto.
- -
-
Page/Page column 28
(2016/12/12)
-
- Preparation of 1,12-twelve carbon b acid method
-
The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of 1, 12-lauryl binary acid. Under light irradiation light irradiation, cyclohexanone and a aqueous hydrogen peroxide solution carry out a photochemical reaction under the condition of zero organic solvents and zero catalysts so as to obtain the 1, 12-lauryl binary acid, an irradiation light source is ultraviolet light, visible light or the mixing light of the ultraviolet light and the visible light of 100-800nm. The preparation method of the 1, 12-lauryl binary acid has the advantages that the process is simple, organic solvents are not used, no metal ions are remained, the production efficiency is high, less three wastes are generated, and the cost is low.
- -
-
Paragraph 0032; 0033
(2017/03/08)
-
- PURIFICATION OF POLYCARBOXYLIC ACIDS
-
A process for purifying a polycarboxylic acid from a mixture is provided. Optionally, the mixture is an aqueous solution and optionally the process comprises an acidification step and/or the use of one or more organic solvents. Also provided in part are compositions of polycarboxylic acids.
- -
-
Paragraph 0056-0060
(2015/12/30)
-
- Cytotoxic linear acetylenes from a marine sponge Pleroma sp.
-
Bioassay-guided fractionation of the extract of the rare deep-sea marine sponge Pleroma sp. afforded seven new linear acetylenes, yakushynols A-F (1-6) and neopetroformyne E (7). The structures of 1-7 were determined by a combination of the analysis of spectroscopic data and chemical derivatization. Compounds 1-6 are the first examples of the sponge-derived acetylenes of the size of duryne with oxidation at the sixth carbon from the terminus. Compounds 1-5 and 7 exhibited moderate cytotoxic activity. A biosynthetic route of neopetroformyne A was inferred from the structural transition among sponge-derived linear acetylenes.
- Takanashi, Emi,Takada, Kentaro,Hashimoto, Masahiro,Itoh, Yoshiyuki,Ise, Yuji,Ohtsuka, Susumu,Okada, Shigeru,Matsunaga, Shigeki
-
p. 9564 - 9570
(2015/12/01)
-
- Six New Polyacetylenic Alcohols from the Marine Sponges Petrosia sp. and Halichondria sp.
-
Six new polyacetylenic alcohols, termed strongylotriols A and B; pellynols J, K, and L; and isopellynol A, together with three known polyacetylenic alcohols, pellynols A, B, and C were isolated from the marine sponges Petrosia sp., and Halichondria sp. collected in Okinawa, Japan. Their planer structures were determined based on 2D-NMR and mass spectrometric analysis of the degraded products by RuCl3 oxidation. The absolute stereochemistry of isolates was examined by their Mosher's esters. The strongylotriols were found to be optically pure compounds, whereas the pellynols are diastereomeric mixtures at the C-6 position. Proliferation experiments using the HeLa and K562 cell lines suggested that the essential structural units for activity are the "hexa-2,4-diyn-1,6-diol" and "pent-1-en-4-yn-3-ol" on the termini.
- Gabriel, Adeyemi Francis,Li, Zhen,Kusuda, Ryouhei,Tanaka, Chiaki,Miyamoto, Tomofumi
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p. 469 - 475
(2015/09/07)
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- ACYCLIC ALKENES VIA OZONOLYSIS OF MULTI-UNSATURATED CYCLOALKENES
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A method of making a compound of formula (IIa) by selective ozonolysis of a compound of formula (I) is provided, wherein A is a C6-C10 alkene chain with at least one double bond, R1 is a C1-C10 alkyl, and R3 is an oxygen-containing functional group.
- -
-
-
- TRANSFORMATION OF PEROXYACETAL INTERMEDIATE
-
A method for transforming a compound of formula IIa: to a compound of formula III: is provided, wherein A is a C6-C10 alkene chain with at least one double bond, R1 is a C1-C10 alkyl, and R3 is an oxygen-containing functional group.
- -
-
Paragraph 00259
(2015/06/03)
-
- Oxidative cleavage of olefins by in situ-generated catalytic 3,4,5,6-tetramethyl-2-iodoxybenzoic acid/oxone
-
Oxidative cleavage of a variety of olefins to the corresponding ketones/carboxylic acids is shown to occur in a facile manner with 3,4,5,6-tetramethyl-2-iodobenzoic acid (TetMe-IA)/oxone. The simple methodology involves mere stirring of the olefin and catalytic amount (10 mol %) of TetMe-IA and oxone in acetonitrile-water mixture (1:1, v/v) at rt. The reaction mechanism involves initial dihydroxylation of the olefin with oxone, oxidative cleavage by the in situ-generated 3,4,5,6-tetramethyl-2-iodoxybenzoic acid (TetMe-IBX), and oxidation of the aldehyde functionality to the corresponding acid with oxone. Differences in the reactivities of electron-rich and electron-poor double bonds have been exploited to demonstrate chemoselective oxidative cleavage in substrates containing two double bonds.
- Moorthy, Jarugu Narasimha,Parida, Keshaba Nanda
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p. 11431 - 11439
(2015/02/05)
-
- Microbial synthesis of medium-chain α,ω-dicarboxylic acids and ω-aminocarboxylic acids from renewable long-chain fatty acids
-
Biotransformation of long-chain fatty acids into medium-chain α,ω-dicarboxylic acids or ω-aminocarboxylic acids could be achieved with biocatalysts. This study presents the production of α,ω-dicarboxylic acids (e.g., C9, C11, C 12, C13) and ω-aminocarboxylic acids (e.g., C 11, C12, C13) directly from fatty acids (e.g., oleic acid, ricinoleic acid, lesquerolic acid) using recombinant Escherichia coli-based biocatalysts. ω-Hydroxycarboxylic acids, which were produced from oxidative cleavage of fatty acids via enzymatic reactions involving a fatty acid double bond hydratase, an alcohol dehydrogenase, a Baeyer-Villiger monooxygenase and an esterase, were then oxidized to α,ω- dicarboxylic acids by alcohol dehydrogenase (ADH, AlkJ) from Pseudomonas putida GPo1 or converted into ω-aminocarboxylic acids by a serial combination of ADH from P. putida GPo1 and an ω-transaminase of Silicibacter pomeroyi. The double bonds present in the fatty acids such as ricinoleic acid and lesquerolic acid were reduced by E. coli-native enzymes during the biotransformations. This study demonstrates that the industrially relevant building blocks (C9 to C13 saturated α,ω- dicarboxylic acids and ω-aminocarboxylic acids) can be produced from renewable fatty acids using biocatalysis.
- Song, Ji-Won,Lee, Jung-Hoo,Bornscheuer, Uwe T.,Park, Jin-Byung
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p. 1782 - 1788
(2014/06/09)
-
- Direct terminal alkylamino-functionalization via multistep biocatalysis in one recombinant whole-cell catalyst
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Direct and regiospecific amino-functionalization of non-activated carbon could be achieved using one recombinant microbial catalyst. The presented proof of concept shows that heterologous pathway engineering allowed the construction of a whole-cell biocatalyst catalyzing the terminal amino-functionalization of fatty acid methyl esters (e.g., dodecanoic acid methyl ester) and alkanes (e.g., octane). By coupling oxygenase and transaminase catalysis in vivo, both substrates are converted with absolute regiospecificity to the terminal amine via two sequential oxidation reactions followed by an amination step. Such demanding chemical three-step reactions achieved with a single catalyst demonstrate the tremendous potential of whole-cell biocatalysts for the production of industrially relevant building blocks. Copyright
- Schrewe, Manfred,Ladkau, Nadine,Buehler, Bruno,Schmid, Andreas
-
supporting information
p. 1693 - 1697
(2013/07/19)
-
- PROCESS FOR PRODUCING DODECANE-1, 12-DIOL BY REDUCTION OF LAURYL LACTONE PRODUCED FROM THE OXIDATION OF CYCLODODECANONE
-
A process for synthesizing dodecane-1,12-diol, and by-products thereof, by the reduction of lauryl lactone produced from the oxidation of cyclododecanone.
- -
-
Paragraph 00126
(2013/08/15)
-
- Divergent process for C10, C11 and C12 ω-amino acid and α,ω-dicarboxylic acid monomers of polyamides from castor oil as a renewable resource
-
Polyamides have great potentials for diverse applications and the present production of their monomers mostly relies on resources from fossil fuel. Starting from undecylenic acid, a natural resource, we have developed both divergent and efficient processes for C10, C11 and C 12 ω-amino acid and α,ω-dicarboxylic acid monomers of the polyamides.
- Koh, Moo-Hyun,Kim, Hyeonjeong,Shin, Nara,Kim, Hyun Su,Yoo, Dongwon,Kim, Young Gyu
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p. 1873 - 1878
(2012/08/07)
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- Reductive carboxylation of alkyl halides with CO2by use of photoinduced SmI2/Sm reduction system
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Upon visible-light irradiation, reductive carboxylation of alkyl halides takes place by using a Sml2/Sm mixed system under atmospheric CO 2 to afford the corresponding carboxylic acids in good to excellent yields.
- Nomoto, Akihiro,Kojo, Yusuke,Shiino, Go,Tomisaka, Yuri,Mitani, Ikuko,Tatsumi, Masahiko,Ogawa, Akiya
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scheme or table
p. 6580 - 6583
(2011/02/24)
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- Redox-active catalyst based on poly(anilinesulfonic acid)supported gold nanoparticles for aerobic alcohol oxidation in water
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The hybrid consisting of gold nanoparticles and poly(2-methoxyaniline-5- sulfonic acid), which works as a redox mediator for transferring protons and electrons, catalyzed the oxidation reaction of various alcohols in water under molecular oxygen.
- Saio, Daisuke,Amaya, Toru,Hirao, Toshikazu
-
experimental part
p. 2177 - 2182
(2010/11/04)
-
- Oxidative cleavage of alkenes using an in situ generated iodonium ion with oxone as a terminal oxidant
-
A facile and operationally convenient catalytic procedure for oxidative cleavage of alkenes is described. In situ formed [hydroxy(4-carboxyphenyl) iodonium]ion, 2, from the oxidation of 4-iodobenzoic acid, 1, has been shown to facilitate the cleavage of a variety of alkenes in presence of Oxone as a co-oxidant. Optimization of the reaction conditions using 1-phenyl-1- cyclohexene, 3, and the competitive oxidative cleavage of different substrates using the optimized conditions has uncovered important mechanistic details of the reaction.
- Thottumkara, Prem P.,Vinod, Thottumkara K.
-
supporting information; experimental part
p. 5640 - 5643
(2011/02/27)
-
- 2-iodoxybenzenesulfonic acid as an extremely active catalyst for the selective oxidation of alcohols to aldehydes, ketones, carboxylic acids, and enones with oxone
-
Electron-donating group-substituted 2-iodoxybenzoic acids (IBXs) such as5-Me-IBX (1g), 5-MeO-IBX (1h), and 4,5-Me2-IBX were superior to IBX 1a as catalysts for the oxidation of alcohols with Oxone (a trad emark of DuPont) under nonaqueous conditions, although Oxone was almost insoluble in most organic solvents. The catalytic oxidation proceeded more rapidly and cleanly in nitromethane. Furthermore, 2-iodoxybenzenesulfonic acid (IBS, 6a) was much more active than modified IBXs. Thus, we established a highly efficient and selective method for the oxidation of primary and secondary alcohols to carbonyl compounds such as aldehydes, carboxylic acids, and ketones with Oxone in nonaqueous nitromethane, acetonitrile, or ethyl acetate in the presence of 0.05-5molpercentof 6a, which was generated in situ from 2-iodobenzenesulfonic acid (7a) or its sodium salt. Cycloalkanones could be further oxidized to α,β- cycloalkenones or lactones by controlling the amounts of Oxone under the same conditions as above. When Oxone was used under nonaqueous conditions, Oxone wastes could be removed by simple filtration. Based on theoretical calculations, we considered that the relatively ionic character of the intramolecular hypervalent iodine-OSO2 bond of IBS might lower the twisting barrier of the alkoxyperiodinane intermediate 16.
- Uyanik, Muhammet,Akakura, Matsujiro,Ishihara, Kazuaki
-
supporting information; experimental part
p. 251 - 262
(2009/06/28)
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- METHODS OF MAKING CYCLODODECATRIENE AND METHODS OF MAKING LAUROLACTONE
-
The present disclosure provides processes for the preparation of dodecanedioic acid (DDDA).
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Page/Page column 6
(2009/10/01)
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- PROCESS FOR PRODUCING ALIPHATIC DICARBOXYLIC ACID COMPOUND
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The present invention discloses a process for producing an aliphatic dicarboxylic acid compound, which comprises oxidizing, with a nitrite or a nitrate in the presence of trifluoroacetic acid, an alicyclic secondary alcohol compound or an alicyclic ketone compound, in each of which at least one methylene group is bonded to the carbon atom having hydroxyl group bonded thereto or the carbon atom as a member of carbonyl group, wherein the reaction is conducted in the presence of water of 5 mass % or less relative to 100 mass % of the total of the trifluoroacetic acid and the water.
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Page/Page column 6
(2008/06/13)
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- Chemical compositions of secondary organic aerosol from the ozonolysis of cyclohexene in the absence of seed particles
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The composition of the aerosol from the ozonolysis of cyclohexene in the absence of seed particles has been investigated by laboratory chamber experiments. The aerosol collected on filters was analyzed by a liquid chromatography/atmospheric pressure chemical ionization-mass spectrometry. Low-molecular weight products, i.e., dicarboxylic acids, oxocarboxylic acids, and hydroxydicarboxylic acids, as well as oligomers with molecular weights more than 200 were found in the aerosol. Copyright
- Sato, Kei
-
p. 1584 - 1585
(2007/10/03)
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- Efficient oxidation of cycloalkanols by sodium nitrite with molecular oxygen in trifluoroacetic acid
-
Oxidation of aliphatic cycloalkanols by sodium nitrite in trifluoroacetic acid gave α,ω-dicarboxylic acids in good yields. Adipic acid was obtained in a quantitative yield from cyclohexanol using 1 equiv of sodium nitrite under oxygen atmosphere but the oxidation required more than 3 equiv of sodium nitrite under nitrogen atmosphere. The oxidation method was applicable to the conversion of 1-alkanols to the corresponding carboxylic acids.
- Matsumura, Yoshihiro,Yamamoto, Yutaka,Moriyama, Noriaki,Furukubo, Shigeru,Iwasaki, Fumiaki,Onomura, Osamu
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p. 8221 - 8224
(2007/10/03)
-
- Aerobic oxidation of cycloalkanes, alcohols and ethylbenzene catalyzed by the novel carbon radical chain promoter NHS (N-hydroxysaccharin)
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Replacement of Ishii's N-hydroxyphthalimide (NHPI) with the novel carbon radical chain promoter N-hydroxysaccharin (NHS) affords, in combination with metal salts, notably Co, or other additives, selective catalytic autoxidation of hydrocarbons, alcohols and alkylbenzenes under mild conditions (25-100°C, O2 1 atm). The effects of solvent, temperature and the nature of the additives were investigated to give an optimised oxidation protocol for the various systems. The NHS/Co combination was more reactive than NHPI/Co in the autoxidation of cycloalkanes. In contrast, the opposite order of reactivity was observed in the autoxidation of ethylbenzene and alcohols. It is suggested, on the basis of bond dissociation energy (BDE) considerations, that this is a result of a change in the rate-limiting step with the more reactive ethylbenzene and alcohol substrates. In the autoxidation of the model cycloalkane, cyclododecane, the best results (90% selectivity to a 4:1 mixture of alcohol and ketone at 24% conversion) were obtained with NHS/Co(acac)3 in PhCF3 at 80°C. Competition experiments revealed that, in contrast to what is commonly believed, formation of the dicarboxylic acid by ring opening is not a result of further oxidation of the ketone product. It is suggested that ring opened products are a result of β-scission of the cycloalkoxy radical formed via (metal-catalysed) decomposition of the hydroperoxide. This is suppressed in the presence of NHS (or NHPI) which efficiently scavenge the alkoxy radicals.
- Baucherel, Xavier,Gonsalvi, Luca,Arends, Isabel W. C. E.,Ellwood, Simon,Sheldon, Roger A.
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p. 286 - 296
(2007/10/03)
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- PROCESS FOR PRODUCTION OF DICARBOXYLIC ACIDS
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A process of the present invention produces a corresponding dicarboxylic acid by oxidative cleavage of a cycloalkane with oxygen and performs a reaction in the presence of a catalyst including an imide compound and a metallic compound, the imide compound having a cyclic imide skeleton represented by following Formula (I): wherein X is an oxygen atom or an-OR group, and wherein R is a hydrogen atom or a hydroxyl-protecting group, under conditions of a reaction temperature of 80°C or higher and a concentration of the cycloalkane in a system of 21% by weight or more. The imide compound includes, for example, N-hydroxyphthalimide. The amount of the imide compound is, for example, from about 0.000001 to about 0.01 mole per mole of the cycloalkane. In the production of a corresponding dicarboxylic acid by catalytic oxidation of a cycloalkane with oxygen, the present invention can yield the dicarboxylic acid in a high space time yield even using a small amount of the catalyst.
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Page/Page column 14-15; 19
(2008/06/13)
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- A new catalytic system for the selective aerobic oxidation of large ring cycloalkanes to ketones
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The combination of cobalt with N-hydroxysaccharin proved to be an effective catalyst for the aerobic oxidation of large ring cycloalkanes to the corresponding ketones.
- Baucherel, Xavier,Arends, Isabel W. C. E.,Ellwood,Sheldon, Roger A.
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p. 426 - 428
(2013/09/06)
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- Oxidative cleavage of vic-diols to aldehydes with dioxygen catalyzed by Ru(PPh3)3Cl2 on active carbon
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Formula presented A variety of vic-diols were first successfully cleaved to the corresponding aldehydes with dioxygen catalyzed by Ru(PPh3)3Cl2 on active carbon in fair to good yields. For example, treatment of 1,2-octandiol and 1,2-cyclooctanediol with dioxygen in the presence of Ru(PPh3)3Cl2/C in PhCF3 at 60°C for 15 h produced heptanal and 1,8-octanedial in 77% and 76% yields, respectively.
- Takezawa, Eiichiro,Sakaguchi, Satoshi,Ishii, Yasutaka
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p. 713 - 715
(2008/02/11)
-
- A new, modulated, oxidative ring cleavage of α-nitrocycloalkanones by Oxone: Synthesis of α,ω-dicarboxylic acids and α,ω-dicarboxylic acid monomethyl esters
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By the appropriate choice of the reaction conditions Oxone produces the ring cleavage of α-nitrocycloalkanones affording good yields of α,ω-dicarboxylic acids and α,ω-dicarboxylic acid monomethyl esters, respectively, regardless the ring size and/or the presence of an alkyl group as substituent.
- Ballini, Roberto,Curini, Massimo,Epifano, Francesco,Marcotullio, Maria Carla,Rosati, Ornelio
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p. 1049 - 1050
(2007/10/03)
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- Direct conversion of cyclohexane into adipic acid with molecular oxygen catalyzed by N-hydroxyphthalimide combined with Mn(acac)2 and Co(OAc)2
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Direct conversion of cyclohexane into adipic acid was achieved by the use of the radical catalyst, N-hydroxyphthalimide (NHPI), in the presence of a small amount of a transition metal. For instance, cyclohexane could be converted into adipic acid in 73% selectivity at 73% conversion under atmospheric oxygen (1 atm) in the presence of NHPI (10 mol %) and Mn(acac)2 (1 mol %) at 100 °C for 20 h. ESR measurements show that the formation of phthalimide N-oxyl generated from NHPI with O2 was assisted by Co(II) species. Thus, the oxidation of cyclohexane to adipic acid was found to be enhanced by the addition of a small amount of Co(OAc)2 to the NHPI/Mn(acac)2 system. The NHPI-catalyzed oxidation of cyclohexane provides an attractive direct method which has long been desired in the chemical industry for the manufacturing of adipic acid. The present oxidation seems to be the first practical environmentally friendly process, in which nitric acid is not used as the oxidant, for the production of adipic acid from cyclohexane.
- Iwahama, Takahiro,Syojyo, Kouichi,Sakaguchi, Satoshi,Ishii, Yasutaka
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p. 255 - 260
(2013/09/08)
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- Preparation of ω-hydroxy acids by reduction of α,ω-methylene diesters with NaBH4
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By reaction of the dicesium salts of long chain dicarboxylic acids (C atoms > 9) with methylene iodide the corresponding methylene diesters were prepared. These acylals, by reduction with NaBH4 in THF, give the corresponding ω-hydroxy acids.
- Benitez, Pilar,Delgado, Ana,Farrera, Joan-Anton,Ribo, Josep M.
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p. 1697 - 1702
(2007/10/03)
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- Process for the preparation of mono- or dicarboxylic acids from aldehydes, from their full acetals or hemiacetals or from mixtures thereof
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Process for the preparation of aliphatic or aromatic mono- or dicarboxylic acids of 4 to 22 carbon atoms by oxidation of the corresponding aldehydes having the same number of carbon atoms in a carboxylic acid from the group consisting of formic acid, acetic acid, and propionic acid or in a carboxylic acid/water mixture at a temperature of 50°-130° C. and at 1 to 25 bar and in the presence of an oxidizing agent.
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-
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- Alkane oxidation with molecular oxygen using a new efficient catalytic system: N-hydroxyphthalimide (NHPI) combined with Co(acac)n (n = 2 or 3)
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A novel class of catalysts for alkane oxidation with molecular oxygen was examined. N-Hydroxyphthalimide (NHPI) combined with Co(acac)n (n = 2 or 3) was found to be an efficient catalytic system for the aerobic oxidation of cycloalkanes and alkylbenzenes under mild conditions. Cycloalkanes were successfully oxidized with molecular oxygen in the presence of a catalytic amount of NHPI and Co(acac)2 in acetic acid at 100°C to give the corresponding cycloalkanones and dicarboxylic acids. Alkylbenzenes were also oxidized with dioxygen using this catalytic system. For example, toluene was converted into benzoic acid in excellent yield under these conditions. Ethyl- and butylbenzenes were selectively oxidized at their α-positions to form the corresponding ketones, acetophenone, and 1-phenyl-1-butanone, respectively, in good yields. A key intermediate in this oxidation is believed to be the phthalimide N-oxyl radical generated from NHPI and molecular oxygen using a Co(II) species. The isotope effect (kH/kD) in the oxidation of ethylbenzene and ethylbenzene-d10 with dioxygen using NHPI/Co(acac)2 was 3.8.
- Ishii, Yasutaka,Iwahama, Takahiro,Sakaguchi, Satoshi,Nakayama, Kouichi,Nishiyama, Yutaka
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p. 4520 - 4526
(2007/10/03)
-
- cis/trans-Ozonides of Cycloolefins
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Ozonolyses in pentane of the unsubstituted cycloolefins having eleven-, twelve-, fourteen- and sixteen-membered rings (1b-e) and of cyclohexadecen-8-one (12) gave the corresponding cis- (2b-e; cis-15a) and trans-ozonides (3b-e; trans-15a), whereas cyclodecene (1a) gave only the corresponding cis-ozonide (2a).Ozonolyses on polyethylene of the dimethyl-substituted cycloolefins bearing fourteen- and sixteen-membered rings (7b,c) also afforded cis- and trans-isomeric ozonides (8, 9), whereas from the twelve-membered ring (7a) only the corresponding cis-ozonide (8a) was formed. - Keywords: Ozonides; Cycloolefins
- Griesbaum, Karl,Ball, Volker,Beck, Johannes,McCullough, Kevin
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p. 1993 - 2000
(2007/10/03)
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- Oxidation of Ethers by NO3(radical) Generated from NO3- with Anodic Oxidation
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A radical NO3 generated by anodic oxidation of NO3- was found to be an effective species to the oxidation of ethers to the corresponding carboxylic acids and ketones, and this reaction was successfully applied to the synthesis of dihydrojasmone.
- Shono, Tatsuya,Yamamoto, Yoshinari,Takigawa, Katsuya,Maekawa, Hirofumi,Ishifune, Manabu,Kashimura, Shigenori
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p. 1045 - 1048
(2007/10/02)
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- Process for the preparation of alpha, omega-alkanedioic acids
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Process for the preparation of alpha, omega-alkanedicarboxylic acids of the general formula I STR1 in which A is an alkylene radical having 4-14 C atoms by reacting a cycloalkene of the general formula II STR2 in which A has the abovementioned meaning with ozone in the presence of an inert solvent, catalytically hydrogenating the peroxide solution formed, followed by oxidation of the dialdehyde formed to the diacid of the formula I in the presence of an inert aprotic solvent.
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- NEW METHOD FOR THE PRODUCTION OF 1,4-DIOXACYCLOHEXADECANE-5,16-DIONE FROM CYCLODECANONE
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A new method is proposed for the synthesis of 1,4-dioxacyclohexadecane-5,16-dione by the oxidation of 13,16-dioxabicyclohexadec-1(12)-ene, obtained from 2-hydroxycyclododecanone and ethylene glycol.The action of an aqueous or alcohol solution of potassium hydroxide on 2-acetoxy- or 2-hydroxycyclododecanone leads to oxidative cleavage of the C-C bond with the formation of 1,10-decanedicarboxylic acid.
- Zakharkin, L. I.,Guseva, V. V.
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p. 115 - 118
(2007/10/02)
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- Cationic amide/ester compositions as demulsifiers
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Novel cationic amide compositions having the structure STR1 where R1 represents an alkylene group of the formula Cn H2n, and alkenyl group of the formula Cn Hn, or a phenyl group, or mixtures thereof, where n equals 0 to 10; R2 represents Cm H2m, where m equals 1 to 4; R3 independently represents methyl, ethyl or propyl; and the combination of R4 and X- represents the remnant from a quaternizing agent have been discovered and have been found useful as demulsifiers in breaking petroleum emulsions as might be produced during fireflooding petroleum recovery procedures. In one embodiment, the cationic amide/ester compositions are made by reacting (1) a dicarboxylic acid of the formula: STR2 where R1 represents Cn H2n, where n equals 0 to 10, or an ester or an acid halide thereof; (2) and aminoalkylamine selected from the group consisting of dimethylaminopropylamine, dimethylaminoethylamine, diethylaminopropylamine, diethylaminoethylamine and mixtures thereof; (3) a quaternizing agent is selected from the group consisting of epichlorohydrin, dimethyl sulfate, alkyl halides and benzyl chloride; and (4) from about 0 to about 40 wt. % of at least one oxyalkylated surface active agent having HLB between about 7 and about 16.
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- Synthesis of α-haloadipic acids from 1,2-cyclohexanedione
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A preparative method for the synthesis of α-haloadipic acids 4a-c by oxidative cleavage of 1,2-cyclohexanedione (1) in copper(II) halide/hydrogen peroxide or copper(II) halide (catalyst)/alkali metal halide/hydrogen peroxide system is reported.
- Starostin,Mazurchik,Ignatenko,Nikishin
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p. 917 - 918
(2007/10/02)
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- Process for the dyeing of leather with anionic dyes and polyaminoamide resin as dyeing auxiliary
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To improve the affinity of anionic dyestuffs in the dyeing of leather materials, polycondensation products consisting of at least one amine of the formula STR1 in which the radicals have the meanings mentioned in the description with one dicarboxylic acid and, if desired, ω-aminocarboxylic acid or its lactam are highly suitable.
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- Process for the preparation of dodecanedioic acid
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A process for the production of dodecanedioic acid by oxidation of cyclododecene using a two phase system in which ruthenium tetroxide serves as the oxidizing agent in the organic phase, and ruthenium tetroxide is regenerated in the second phase, an aqueous phase containing cerium ions in the plus 4 state. The cerium plus 4 ions may be regenerated by electrolytic oxidation in a separate step.
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- Polymer containing a polyisobutylene-derived backbone
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Polymers, such as polysiobutylene or ethylene-propylene copolymers, are functionalized by reaction with an activated imine to yield novel polymers.
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- Method of functionalizing polymers
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Polymers, such as polyisobutylene or ethylene-propylene copolymers, are functionalized by reaction with an activated imine to yield novel polymers.
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- The Conversion of Aliphatic Primary Alcohols to the Corresponding Carboxylic Acids Using Calcium Hypochlorite
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The reaction of aliphatic primary alcohols with calcium hypochlorite in the presence of hydrochloric acid and excess tert-butanol produces the corresponding carboxylic acids in good yields.
- Kabalka, George W.,Chatla, Narayana,Wadgaonkar, Prakash P.,Deshpande, Sunil M.
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p. 1617 - 1623
(2007/10/02)
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