WO2013062645A1 - Alkane oxidation - Google Patents
Alkane oxidation Download PDFInfo
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- WO2013062645A1 WO2013062645A1 PCT/US2012/047121 US2012047121W WO2013062645A1 WO 2013062645 A1 WO2013062645 A1 WO 2013062645A1 US 2012047121 W US2012047121 W US 2012047121W WO 2013062645 A1 WO2013062645 A1 WO 2013062645A1
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- WIPO (PCT)
- Prior art keywords
- alkane
- group
- manganese complex
- carboxylate group
- groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
- B01J31/1625—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups
- B01J31/1633—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups covalent linkages via silicon containing groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
- B01J31/182—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine comprising aliphatic or saturated rings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/30—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with halogen containing compounds, e.g. hypohalogenation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0202—Polynuclearity
- B01J2531/0208—Bimetallic complexes, i.e. comprising one or more units of two metals, with metal-metal bonds but no all-metal (M)n rings, e.g. Cr2(OAc)4
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0202—Polynuclearity
- B01J2531/0211—Metal clusters, i.e. complexes comprising 3 to about 1000 metal atoms with metal-metal bonds to provide one or more all-metal (M)n rings, e.g. Rh4(CO)12
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
- B01J2531/0219—Bimetallic complexes, i.e. comprising one or more units of two metals, with metal-metal bonds but no all-metal (M)n rings, e.g. Cr2(OAc)4
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0258—Flexible ligands, e.g. mainly sp3-carbon framework as exemplified by the "tedicyp" ligand, i.e. cis-cis-cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
- B01J2531/72—Manganese
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Definitions
- This disclosure relates to an alkane oxidation catalyst and methods of forming an alkane oxidation product.
- Alkane oxidation products are used in the production of plastics, fuels, nylons, pesticides, textiles, disinfectants, reagents, detergents, solvents, and others.
- alkane oxidation products include, but are not limited to, alcohols, aldehydes, ketones, and peroxides.
- This disclosure provides an alkane oxidation catalyst including a support modified with a carboxylate group, where the carboxylate group is functionalized with a manganese complex.
- the support may be a carbon support or an oxide support.
- the carbon support include, but are not limited to, activated carbon, which intrinsically contains a carboxylate group.
- oxide support examples include, but are not limited to, silicon dioxide (Si0 2 ), aluminum oxide (AI2O3), titanium silicon dioxide (Ti-Si0 2 ), aluminum silicate (Al 2 0 3 -Si0 2 ), titanium dioxide (Ti0 2 ), and cerium dioxide (Ce0 2) .
- the oxide support may be modified with the carboxylate group by depositing a silane group as an ester via heating the oxide support in refluxing pyridine to provide an ester-modified oxide support.
- the ester-modified oxide support may then be converted to carboxylic acid (CA) by heating the oxide support in refluxing aqueous solutions of mineral acid (e.g., hydrochloric acid (HQ)) to provide the support modified with the carboxylate group
- SA carboxylic acid
- HQ hydrochloric acid
- Silane groups include, but are not limited to, 2-(carboxymethoxy)-ethyltrimethoxysilane and ethyl 4- (triethoxysilyl)benzoate.
- oxide support "-C” to denote surface carboxylates synthesized from 2- (carbomethoxy)ethyltrimethoxysilane (e.g., the support modified with the carboxylate group may be represented as Si0 2 -C) and identified as oxide support "-B” to denote surface carboxylates synthesized from ethyl 4-(triethoxysilyl)benzoate (e.g., the support modified with the carboxylate group may be represented as Si0 2 -B).
- Remaining hydroxyl (OH) groups can be capped with a variety of silanes, such as propyltriethoxysilane (propyl), n-octyltrimethoxysilane (octyl), mixtures of perfluorododecyl- 1 H, 1 H,2H,2H-triethoxysilane / perfluoro-tetradecyl- 1 H, 1 H,2H,2H- triethoxysilane (perfluro), or hexamethyldisilazane / trimethylchlorosilane (trimethyl) (e.g., the support modified with the carboxylate group may be represented as Si0 2 -C- propyl, Si0 2 -C-octyl, Si0 2 -C-perfIuoro, or Si0 2 -C-trimethyl).
- silanes such as propyltriethoxysilane (propyl), n-oc
- the oxide support may be modified with the carboxylate group by depositing ditopic molecules, including, but not limited to, terephthalic acid (TA) and 3,4-dihydroxyhydrocinnamic acid (DHHCA), which coordinate with oxide supports and provide a carboxylate functionalization with the manganese complex.
- ditopic molecules including, but not limited to, terephthalic acid (TA) and 3,4-dihydroxyhydrocinnamic acid (DHHCA), which coordinate with oxide supports and provide a carboxylate functionalization with the manganese complex.
- a density of the carboxylate groups on the support may be in a range of from 0.01 to 1 carboxylate groups per square nanometer (groups/nm ) of oxide support "-C” or oxide support "-B” and in a range of from 1 to 6 groups/nm 2 for oxide supports modified by depositing ditopic molecules. This can be measured by absorption spectroscopy, thermogravimetric analysis, and/or nuclear magnetic resonance spectroscopy.
- Examples of the manganese complex include, but are not limited to,
- Each R is independently an alkyl group having 1 to 3 carbons. Examples of the alkyl groups include, but are not limited to, a methyl group, an ethyl group, and a propyl group.
- Each Z is independently hexafluorophosphate (PF 6 ⁇ ), perchlorate (C1CV), or bromine (Br " ).
- the carboxylate group can be functionalized with the manganese complex by bonding a manganese atom of the manganese complex to an oxygen atom of the carboxylate group.
- the manganese complex and the carboxylate groups on a surface of the support have a molar ratio in a range of from 1.0 : 0.3 to 1 : 20 manganese complex groups to carboxylate groups.
- the alkane oxidation catalyst can be formed by combining the support modified with the carboxylate group that is functionalized with the manganese complex at a temperature in a range of from -10 degrees Celsius (°C) to 50 °C in the presence of hydrogen peroxide.
- the alkane oxidation catalyst can be formed in the presence of a solvent.
- the solvent include, but are not limited to, acetonitrile, water, methanol, acetic acid, and acetone.
- the support is employed in a range of from 1 to 20 milligrams per milliliter of solvent (mg mL).
- the manganese complex is employed in a range of from 0.1 to 1.0 milimole per liter of solvent (mJW).
- Hydrogen peroxide is employed in a range of initial concentrations of from 0.1 to 0.5 moles per liter of solvent (M).
- This disclosure provides a method for oxidizing an alkane.
- the method includes oxidizing the alkane by contacting the alkane with the alkane oxidation catalyst in the presence of hydrogen peroxide to provide an alkane oxidation product.
- the alkane oxidation product include, but are not limited to alcohols, ketones, aldehydes, and alkylhydroperoxides.
- the hydrogen peroxide and the alkane have a molar ratio in a range of from 3 : 1 to 1 : 20 where the hydrogen peroxide includes the initial hydrogen peroxide and/or subsequent hydrogen peroxide.
- the method can include employing a solvent. Examples of the solvent are discussed herein.
- the method conditions include oxidizing the alkane at a temperature in a range of from -10 °C to 50 °C.
- the method includes contacting a support modified with a carboxylate group with a manganese complex and hydrogen peroxide to functionalize the carboxylate group with the manganese complex to form an alkane oxidation catalyst.
- the alkane includes linear alkanes and cyclic alkanes. Examples of linear alkanes include, but are not limited to, linear alkanes with 2 or more carbons (e.g., ethane, propane, butane, pentane, hexane, heptane, and octane).
- ethane may be oxidized to form an oxidation product, such as, acetaldehyde, ethanol, methanol, or formaldehyde.
- cyclic alkanes include, but are not limited to, cyclic alkanes with 6 or more carbons (e.g., cyclohexane, cycloheptane, cyclooctane).
- cyclohexane may be oxidized to form an oxidation product such as, cyclohexanol, cyclohexanone, or cyclohexylhydroperoxide.
- Gelest propyltriethoxysilane
- n-octyltrimethoxysilane Gelest
- mixtures of perfluorododecyl-lH,lH,2H,2H-triethoxysilane and perfluoro-tetradecyl- lH,lH,2H,2H-triethoxysilane Gelest
- mixtures of 1 ,1 ,1 ,3,3,3-hexamethyldisilazane and trimethylchlorosilane and pyridine 2-(carboxymethoxy)ethyltrimethoxysilane (Gelest); ethyl 4-(triethoxysilyl)benzoate (Gelest).
- Si0 2 -C, Si0 2 -B - Add Si0 2 (1 -2 grams (g)) and pyridine (50 ml) to a container and stir the contents of the container under nitrogen (N 2 ).
- 2- (carboxymethoxy)ethyltrimethoxysilane or ethyl 4-(triethoxysilyl)benzoate to the contents of the container (1.0 mmol per gram Si0 2 )), then heat the contents of the container at reflux for 24 hours. Filter solids from the contents of the container, wash solids with pyridine and ether, dry solids under vacuum, and extract solids by soxhlet extraction with benzene for 24 hours.
- Si0 2 -C and a silane 2.0 mmol silane per g Si0 2 -C
- n-octyltrimethoxysilane (octyl) commercial mixtures of perfluorododecyl- 1 H, 1 H,2H,2H-triethoxysilane / perfluoro-tetradecyl- 1 H, 1 H,2H,2H-triethoxysilane (perfluro)
- concentrations of these species are determined as a function of time using gas chromatography and are shown in Table 1.
- the turnover number is the maximum number of substrate (e.g., alkane) molecules that can be converted into product molecules after a given amount of time by a catalyst and is given by the equation: or alkane oxidation catalyst
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/353,453 US9024076B2 (en) | 2011-10-24 | 2012-07-18 | Alkane Oxidation |
CN201280059281.7A CN103958058B (en) | 2011-10-24 | 2012-07-18 | oxidation of alkanes |
EP12744146.7A EP2771118A1 (en) | 2011-10-24 | 2012-07-18 | Alkane oxidation |
BR112014009359A BR112014009359A2 (en) | 2011-10-24 | 2012-07-18 | alkane oxidation catalyst and method for oxidizing an alkane |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201161550595P | 2011-10-24 | 2011-10-24 | |
US61/550,595 | 2011-10-24 |
Publications (1)
Publication Number | Publication Date |
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WO2013062645A1 true WO2013062645A1 (en) | 2013-05-02 |
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ID=46639671
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/US2012/047121 WO2013062645A1 (en) | 2011-10-24 | 2012-07-18 | Alkane oxidation |
Country Status (5)
Country | Link |
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US (1) | US9024076B2 (en) |
EP (1) | EP2771118A1 (en) |
CN (1) | CN103958058B (en) |
BR (1) | BR112014009359A2 (en) |
WO (1) | WO2013062645A1 (en) |
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RU2707291C2 (en) | 2014-12-22 | 2019-11-26 | Родиа Операсьон | Catalysts for oxidising cycloalkanes and method of producing alcohols and ketones |
CN110831916A (en) * | 2017-05-25 | 2020-02-21 | 斯克利普斯研究所 | Direct oxidation of olefins to oxygenates |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5153161A (en) * | 1991-11-26 | 1992-10-06 | Lever Brothers Company, Division Of Conopco, Inc. | Synthesis of manganese oxidation catalyst |
US5329024A (en) | 1993-03-30 | 1994-07-12 | National Starch And Chemical Investment Holding Corporation | Epoxidation of olefins via certain manganese complexes |
EP0970951A1 (en) | 1998-07-09 | 2000-01-12 | K.U. Leuven Research & Development | A manganese oxidation catalyst, a method for its preparation and use thereof for catalytic epoxidation, catalytic cis-dihydroxylation and combined expoxidation-cis-dihydroxylation of olefins |
US20030054949A1 (en) | 2001-05-23 | 2003-03-20 | Chang Eddie L. | Immobilized metalchelate complexes for catalysis and decontamination of pesticides and chemical warfare nerve-agents |
US6646102B2 (en) | 2001-07-05 | 2003-11-11 | Dow Global Technologies Inc. | Process for manufacturing an alpha-dihydroxy derivative and epoxy resins prepared therefrom |
ES2333311T3 (en) | 2002-01-15 | 2010-02-19 | Lonza Ag | MANGANESE COMPLEX SALES (IV) AND ITS USE AS OXIDATION CATALYSTS. |
WO2007090461A1 (en) * | 2006-02-06 | 2007-08-16 | Ciba Holding Inc. | Use of metal complex compounds as oxidation catalysts |
-
2012
- 2012-07-18 EP EP12744146.7A patent/EP2771118A1/en not_active Withdrawn
- 2012-07-18 CN CN201280059281.7A patent/CN103958058B/en not_active Expired - Fee Related
- 2012-07-18 WO PCT/US2012/047121 patent/WO2013062645A1/en active Application Filing
- 2012-07-18 US US14/353,453 patent/US9024076B2/en active Active
- 2012-07-18 BR BR112014009359A patent/BR112014009359A2/en not_active IP Right Cessation
Non-Patent Citations (4)
Title |
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GEORGIY B. SHUL'PIN ET AL: "Oxidations by the system 'hydrogen peroxide-[Mn2L2O3][PF6]2 (L=1,4,7-trimethyl-1,4,7-triazacyclononane)-carboxylic acid'. Part 10: Co-catalytic effect of different carboxylic acids in the oxidation of cyclohexane, cyclohexanol, and acetone", TETRAHEDRON, vol. 64, no. 9, 1 February 2008 (2008-02-01), pages 2143 - 2152, XP055043041, ISSN: 0040-4020, DOI: 10.1016/j.tet.2007.12.033 * |
MAC LEOD T C O ET AL: "Mild oxidation of alkanes and toluene by tert-butylhydroperoxide catalyzed by an homogeneous and immobilized Mn(salen) complex", APPLIED CATALYSIS A: GENERAL, ELSEVIER SCIENCE, AMSTERDAM, NL, vol. 372, no. 2, 15 January 2010 (2010-01-15), pages 191 - 198, XP026798941, ISSN: 0926-860X, [retrieved on 20091030] * |
NICHOLAS J. SCHOENFELDT ET AL: "A heterogeneous, selective oxidation catalyst based on Mn triazacyclononane grafted under reaction conditions", CHEMICAL COMMUNICATIONS, vol. 46, no. 10, 1 January 2010 (2010-01-01), pages 1640, XP055043039, ISSN: 1359-7345, DOI: 10.1039/b920391e * |
NICHOLAS J. SCHOENFELDT ET AL: "Solid Cocatalysts for Activating Manganese Triazacyclononane Oxidation Catalysts", ACS CATALYSIS, vol. 1, no. 12, 20 October 2011 (2011-10-20), pages 1691 - 1701, XP055043033, ISSN: 2155-5435, DOI: 10.1021/cs200353x * |
Also Published As
Publication number | Publication date |
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US20140296578A1 (en) | 2014-10-02 |
CN103958058A (en) | 2014-07-30 |
BR112014009359A2 (en) | 2017-04-18 |
US9024076B2 (en) | 2015-05-05 |
CN103958058B (en) | 2016-11-23 |
EP2771118A1 (en) | 2014-09-03 |
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