- SYSTEMS AND METHODS FOR SYNTHESIS OF PHENOLICS AND KETONES
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Embodiments herein relate to apparatus and systems for phenolic and ketone synthesis and methods regarding the same. In an embodiment, a method of producing phenolics and ketones is included. The method can specifically include forming a reaction mixture comprising nanocrystalline cellulose (NCC) and water. The method can also include contacting the reaction mixture with a metal oxide catalyst at a temperature of 350 degrees Celsius or higher and a pressure of at least about 3200 psi to form a reaction product mixture. The reaction product mixture can include at least about 20 wt. % phenolics and at least about 10 wt. % ketones as a percentage of the total mass of nanocrystalline cellulose (NCC). Other embodiments are also included herein.
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Paragraph 0080-0088
(2018/11/21)
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- DEHYDROGENATION OF CYCLOHEXANONE TO PRODUCE PHENOL
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In a process for the dehydrogenation of cyclohexanone to produce phenol, a feed comprising cyclohexanone is contacted with a dehydrogenation catalyst under dehydrogenation conditions comprising a temperature of less than 4000C and a pressure of less than 690 kPa, gauge, such 0.1 to 50 wt% of the cyclohexanone in said feed is converted to phenol and the dehydrogenation product contains less than 100 ppm by weight of alkylbenzenes.
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Page/Page column 22-23; 25
(2011/09/14)
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- Oxidative addition of allylic substrates to coordinatively unsaturated ruthenium compounds, [Ru(η5-C5Me5)(η-amidinate)]: Preparation, structure elucidation, and catalysis of novel ruthenium (IV)-η3-allyl complexes
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Oxidative addition reactions of allylic halides, acetates, and carbonates with [Ru(η5-C5Me5)(η-amidinate)] [amidinate: iPrNC(Me)=NiPr (1a), 1BuNC(Ph)=N1Bu (1b)], which shows signs of coordinative unsaturation, gave novel cationic π-allyl ruthenium(IV) species. The compounds [Ru(η3-allyl)(η5-C5Mes)(η 2-amidinate)]+X- were isolated by anion exchange of the products (X = PF6, BF4, BPh4), and were characterized by spectroscopic analysis. The crystallography of two of the [Ru(η3-allyl)(η5-C5Mes)(η 2-amidinate)] +X- revealed a four-legged piano stool structure in which two nitrogen atoms in the amidinate ligand and two carbon atoms in the η3-allyl ligands occupy the positions of four legs; the orientation of the η3-allyl ligand was endo. Although cyclic voltammograms of the precursor, [Ru(η5-C5Me5)(η-amidinate)], indicated possible oxidative addition of organic halides other than allylic halides to [Ru(η5-C5Me5)(η-amidinate)], only allylic halides gave the corresponding Ru(IV) products. The importance of prior coordination of the carbon-carbon double bond of allylic substrates was evidenced by NMR observation of the intermediate in the reaction of 1a or 1b with allyl acetate. Addition of nucleophiles such as PhLi, dimethyl methylsodiomalonate, and piperidine to the [Ru(η3-allyl)(η5-C5Me 5)(η2-amidinate)]+X- gave rise to allylation of these nucleophiles and regeneration of [Ru(η5-C5Me5)(η-amidinate)]. The reactions of allyl methyl carbonate with nucleophiles were also achieved by catalysis of either [Ru(η5C5Me5)(η-amidinate)] or [Ru(η3-allyl)(η5-C5Me 5)(η2-amidinate)]+X-.
- Kondo, Hideo,Kageyama, Akira,Yamaguchi, Yoshitaka,Haga, Masa-Aki,Kirchner, Karl,Nagashima, Hideo
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p. 1927 - 1937
(2007/10/03)
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- Rates and Equilibria of the Michael-Type Addition of Benzenethiol to 2-Cyclopenten-1-ones
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The triethylamine-catalyzed addition reactions of benzenethiol to 2-cyclopenten-1-one and its 2-and 3-methyl derivatives have been found to be appreciably reversible in chloroform solution. Rates and equilibria have been carefully measured at 25°C in order to assess the negative influence on addition exerted by methyl groups substituted on the carbon-carbon double bond. 2-Methyl-2-cyclopenten-1-one has been found to react with benzenethiol under kinetic control to give the cis adduct as the sole detectable product in a highly stereoselective anti addition process. However, on prolonged reaction times the system slowly evolved toward a new state of equilibrium in which the more stable trans adduct, derived from a syn addition mode, was the predominant isomer.
- Van Castelli, Valeria Axel,Bernardi, Fernando,Cort, Antonella Dalla,Mandolini, Luigi,Rossi, Ivan,Schiaffino, Luca
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p. 8122 - 8126
(2007/10/03)
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- Polymer pyrolysis and oxidation studies in a continuous feed and flow reactor: Cellulose and polystyrene
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A dual-zone, continuous feed tubular reactor is developed to assess the potential for formation of products from incomplete combustion in thermal oxidation of common polymers. Solid polymer (cellulose or polystyrene) is fed continuously into a volatilization oven where it fragments and vaporizes. The gas-phase polymer fragments flow directly into a second, main flow reactor to undergo further reaction. Temperatures in the main flow reactor are varied independently to observe conditions needed to convert the initial polymer fragments to CO2 and H2O. Combustion products are monitored at main reactor temperatures from 400 to 850 °C and at 2.0-s total residence time with four on-line GC/FIDs; polymer reaction products and intermediates are further identified by GC/MS analysis. Analysis of polymer decomposition fragments at 400 °C encompasses complex oxygenated and aromatic hydrocarbon species, which range from high-molecular-weight intermediates of ca. 300 amu, through intermediate mass ranges down to C1 and C2 hydrocarbons, CO, and CO2. Approximately 41 of these species are positively identified for cellulose and 52 for polystyrene. Products from thermal oxidation of cellulose and polystyrene are shown to achieve complete combustion to CO2 and H2O at a main reactor temperature of 850 °C under fuel-lean equivalence ratio and 2.0-s reaction time. A dual-zone, continuous feed tubular reactor is developed to assess the potential for formation of products from incomplete combustion in thermal oxidation of common polymers. Solid polymer (cellulose or polystyrene) is fed continuously into a volatilization oven where it fragments and vaporizes. The gas-phase polymer fragments flow directly into a second, main flow reactor to undergo further reaction. Temperatures in the main flow reactor are varied independently to observe conditions needed to convert the initial polymer fragments to CO2 and H2O. Combustion products are monitored at main reactor temperatures from 400 to 850°C and at 2.0-s total residence time with four on-line GC/FIDs; polymer reaction products and intermediates are further identified by GC/MS analysis. Analysis of polymer decomposition fragments at 400°C encompasses complex oxygenated and aromatic hydrocarbon species, which range from high-molecular-weight intermediates of ca. 300 amu, through intermediate mass ranges down to C1 and C2 hydrocarbons, CO, and CO2. Approximately 41 of these species are positively identified for cellulose and 52 for polystyrene. Products from thermal oxidation of cellulose and polystyrene are shown to achieve complete combustion to CO2 and H2O at a main reactor temperature of 850°C under fuel-lean equivalence ratio and 2.0-s reaction time.
- Park, Byung-Ik,Bozzelli, Joseph W.,Booty, Michael R.,Bernhard, Mary J.,Mesuere, Karel,Pettigrew, Charles A.,Shi, Ji-Chun,Simonich, Staci L.
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p. 2584 - 2592
(2007/10/03)
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- Hydrocarbonylating Cyclization of Dienes, 8. - Cyclization of 1,4-Dienes with Functional Groups in 3-Position
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1,4-Dienes 1a-i with functional groups at C-3 were synthesized and treated under the conditions of metal-cytalyzed hydrocarbonylating cyclization.Under the usual conditions no cyclization products could be isolated.Modifications of the reaction conditions did not lead to the expected cyclopentanones of type 2 or 3 either.Instead, the original functional groups are slit off.Depending on the reaction conditions, either the non-functionalized 2-cyclopentenones 5, the cyclopentanones 6, or the 2-cyclopentenones 7 with a functional group introduced from the solvent into the 2-methyl group are obtained.These unexpected products of type 7 at least formally correspond to allylic rearrangement products of the expected but not observed type-3 exo-methylenecyclopentanones.The mechanism of the formation of these products is discussed.
- Eilbracht, Peter,Huettmann, Gerd-Erich,Deussen, Rainer
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p. 1063 - 1070
(2007/10/02)
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- Synthesis of 2-Alkyl-2-cyclopenten-1-ones. A Versatile Kinetic Alkylation-Ozonolysis Procedure for the Preparation of γ-Ketoaldehydes
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A range of 2-alkyl-2-cyclopenten-1-ones including the prostaglandin precursor 2-(6-methoxycarbonylhexyl)-2-cyclopenten-1-one and the jasmonoid precursor 2--2-cyclopenten-1-one, have been prepared by a short synthetic route which begins with 6-methyl-5-hepten-2-one and generates the key 1,4-ketoaldehyde intermediates by a kinetic alkylation-ozonolysis procedure.
- Geraghty, Niall W. A.,Morris, Noreen M.
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p. 603 - 607
(2007/10/02)
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- New Methods for the Syntheses of α,β-Unsaturated Ketones, Aldehydes, and Nitriles by the Palladium-Catalyzed Reactions of Allyl β-Oxo Esters, Allyl 1-Alkenyl Carbonates, and Allyl α-Cyano Esters
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Allyl β-oxo esters, allyl 1-alkenyl carbonates, and allyl α-cyano esters are converted into α,β-unsaturated ketones, aldehydes, and nitriles by palladium-catalyzed intramolecular decarboxylation-dehydrogenation.Palladium-phosphine complexes such as Pd(OAc)2-PPh3, Pd(OAc)2-dppe, or Pd2(dba)3*CHCl3-PPh3, are effective catalysts.Yields depend on solvents and on the mole ratio of palladium to phosphine.The optimum Pd/P ratio for each substrate was determined.Use of nitriles as solvents is essential for the dehydrogenation.
- Minami, Ichiro,Nisar, Mohammad,Yuhara, Masami,Shimizu, Isao,Tsuji, Jiro
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p. 992 - 998
(2007/10/02)
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- Process for the preparation of alkylated cyclopentenones
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Cyclopentenones of formula STR1 wherein each of symbols R1 and R2, when taken separately, represents an alkyl radical of C1 to C6, or a hydrogen atom, or, when taken together, they represent a polymethylene, or one of them designates a hydrogen atom and the other an alkyl radical of C1 to C6, are prepared starting from compounds having formula STR2 wherein R stands for a C1 to C6 alkyl radical or a phenyl group, via a catalytic reaction promoted by a metallo-organic compound of formula wherein Me represents palladium or platinum, R3 represents a C1 to C3 alkyl radical or a phenyl group and X defines a halogen atom.
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- COPPER (I) CATALYSIS OF OLEFIN PHOTOREACTIONS -9. PHOTOBICYCLIZATION OF alpha -, beta -, AND gamma -ALKENYLALLYL ALCOHOLS.
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Cyclobutylcarbinyl alcohols of the bicyclo left bracket 3. 2. 0 right bracket heptane ring system are produced by UV irradiation of alpha -, beta -, and gamma -alkenylallyl alcohols in the presence of copper (I) trifluoromethanesulfonate (CuOTf). endo-2-Hydroxy epimers of bicyclo left bracket 3. 2. 0 right bracket heptan-2-ols are generated stereoselectively. This result as well as the effect of CuOTf on the **1H NMR spectrum of 4,4-dimethyl-1,6-heptadien-3-ol suggests that coordination of two C equals C bonds and the hydroxyl group with a single copper (I) is important. The derived bicyclo left bracket 3. 2. 0 right bracket heptan 2-ones fragment cleanly at 580 degree C to afford cyclopent-2-en-1-ones. Geometric isomerization competes with photobicyclization of (E)- and (Z)-octa-2,7-dien-1-ols.
- Salomon,Coughlin,Ghosh,Zagorski
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p. 998 - 1007
(2007/10/14)
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