- Hydroperoxidation of tertiary alkylaromatics catalyzed by N-hydroxyphthalimide and aldehydes under mild conditions
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A metal-free catalytic system consisting of an aldehyde and N-hydroxyphthalimide (NHPI) for the selective oxidation of tertiary alkylaromatics with molecular oxygen has been developed. Cumene was oxidized efficiently to the corresponding hydroperoxide under mild conditions. The molecule-induced homolysis between peracids generated in situ and NHPI ensured the formation of the phthalimide N-oxyl (PINO) radical even at room temperature. Investigations on aldehyde, solvent and temperature effects allowed us to achieve good conversions with high selectivity in hydroperoxide. The optimized procedure was successfully extended to phenylcyclohexane, a valuable alternative for the production of phenol. The mechanism is discussed in detail.
- Melone, Lucio,Gambarotti, Cristian,Prosperini, Simona,Pastori, Nadia,Recupero, Francesco,Punta, Carlo
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Read Online
- Copper-catalyzed radical ring-opening halogenation with HX
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An efficient copper-catalyzed radical ring-opening halogenation with HX (aq) is described. This protocol features redox-neutral conditions, green halogen sources, and a broad substrate scope, providing practical access to distally chlorinated, brominated and iodinated alkyl ketones and alkyl nitriles with moderate to good yields. This journal is
- Bai, Ming,Duan, Xin-Hua,Guo, Li-Na,Liu, Shuai,Sun, Qing-Xin,Xu, Peng-Fei
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supporting information
p. 8652 - 8655
(2021/09/04)
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- Benzylic Hydroperoxidation via Visible-Light-Induced Csp3-H Activation
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A highly efficient benzylic hydroperoxidation has been realized through a visible-light-induced Csp3-H activation. We believe that this reaction undergoes a direct HAT mechanism catalyzed by eosin Y. This approach features the use of a metal-free catalyst (eosin Y), an energy-economical light source (blue LED), and a sustainable oxidant (molecular oxygen). Primary, secondary, and tertiary hydroperoxides as well as silyl, benzyl, and acyl peroxides were successfully prepared with good yields and excellent functional group compatibility.
- Inoa, Joan,Patel, Mansi,Dominici, Grecia,Eldabagh, Reem,Patel, Anjali,Lee, John,Xing, Yalan
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p. 6181 - 6187
(2020/05/22)
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- Iron-Catalyzed Decarboxylative Olefination of Unstrained Carbon-Carbon Bonds Relying on Alkoxyl Radical Induced Cascade
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An iron-catalyzed decarboxylative olefination of unstrained carbon-carbon bonds via alkoxyl radical induced C-C bond cleavage is presented. This protocol features mild conditions (room temperature, redox-neutral), good substrate scope and functional group
- Gao, Pin,Wu, Hao,Yang, Jun-Cheng,Guo, Li-Na
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p. 7104 - 7108
(2019/09/30)
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- Conjugated copper(II) porphyrin polymer and N-hydroxyphthalimide as effective catalysts for selective oxidation of cyclohexylbenzene
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A nanomaterial catalyst of azo-bridged Cu(II) porphyrin polymer (CuII-APP) was synthesized and characterized by scanning electron microscopy, transmission electron microscopy and N2adsorption measurement. CuII-APP had a nanoporous structure, with the particle size of about 30?nm. Owing to the special structure, CuII-APP acted as an efficient heterogeneous catalyst for selective oxidation of cyclohexylbenzene into cyclohexylbenzene-1-hydroperoxide. When N-hydroxyphthalimide was used as co-catalyst, this binary catalyst system showed an obvious synergic effect. After being recovered and reused, CuII-APP and NHPI still had high catalytic activities.
- Tan, Zhiwei,Zhu, Junhui,Yang, Weijun
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- System and Process for Making Phenol and/or Cyclohexanone
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A system for producing high-purity phenol and/or cyclohexanone from cyclohexylbenzene oxidation includes a cyclohexylbenzene feed hydrogenation reactor, a bubble column oxidation reactor, a cyclohexylbenzene hydroperoxide concentrator, a cleavage reactor, and a separation and purification sub-system. The components and the integrated system are designed such that high-purity phenol and/or cyclohexanone can be produced at high energy efficiency.
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Paragraph 0048; 0049
(2015/12/24)
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- Method for Producing Phenol and/or Cyclohexanone
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In a process for producing phenol and cyclohexanone a feed comprising cyclohexylbenzene hydroperoxide and water in an amount from 1 to 15,000 ppm, based upon total weight of feed, is contacted with a cleavage catalyst comprising an aluminosilicate of the FAU type under cleavage conditions effective to convert at least a portion of the cyclohexylbenzene hydroperoxide into phenol and cyclohexanone.
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Paragraph 0078
(2014/10/16)
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- PROCESS FOR PRODUCING PHENOL
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In a process for producing phenol, a feed comprising cyclohexylbenzene hydroperoxide is contacted with a cleavage catalyst comprising an acidic ionic liquid under cleavage conditions effective to cleave at least a portion of said cyclohexylbenzene hydroperoxide and produce a cleavage product stream comprising phenol and cyclohexanone.
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Paragraph 0068
(2013/04/10)
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- PROCESS FOR PRODUCING PHENOL
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In a process for producing phenol, a feed comprising cyclohexylbenzene hydroperoxide is contacted with a cleavage catalyst comprising a fluorinated acidic resin under cleavage conditions effective to convert at least a portion of the cyclohexylbenzene hydroperoxide into phenol and cyclohexanone.
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Paragraph 0067
(2013/04/10)
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- PROCESS FOR PRODUCING PHENOL
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In a process for producing phenol, a mixture of cyclohexylbenzene with from 10 to 90 wt% of a solvent is contacted with oxygen in the presence of a catalyst and under conditions effective to oxidize at least a portion of the cyclohexylbenzene to cyclohexy
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Page/Page column 0075; 0077
(2013/07/31)
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- PHENOL AND CYCLOHEXANONE MIXTURES
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Disclosed herein is a process for producing phenol. The process includes oxidizing at least a portion of a feed comprising cyclohexylbenzene to produce an oxidation composition comprising cyclohexyl-1 -phenyl- 1 -hydroperoxide. The oxidation composition may then be cleaved in the presence of an acid catalyst to produce a cleavage reaction mixture comprising the acid catalyst, phenol and cyclohexanone. At least a portion of the cleavage reaction mixture may be neutralized with a basic material to form a treated cleavage reaction mixture. In various embodiments, the cleavage reaction mixture contains 1 wt% to 30 wt% phenol, 1 wt% to 30 wt% cyclohexanone and a complexation product.
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Page/Page column 30-31
(2012/04/04)
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- PROCESS FOR PRODUCING PHENOL
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In a process for producing phenol, cyclohexylbenzene is contacted with an oxygen- containing compound in the presence of a first catalyst under oxidation conditions effective to produce an oxidation product comprising cyclohexylbenzene hydroperoxide. At least part of the oxidation product and a polar solvent are then supplied to a cleavage reaction zone, where the said oxidation product and the polar solvent are contacted in the presence of a second catalyst under cleavage conditions including a temperature in excess of 50°C effective to convert at least a portion of the cyclohexylbenzene hydroperoxide into phenol and cyclohexanone.
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Page/Page column 16
(2012/06/01)
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- COMPOSITION COMPRISING CYCLOHEXYLBENZENE AND 1 - PHENYL - 1 -METHYLCYCLOPENTANE AND USE THEREOF IN OXIDATION PROCESSES
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Disclosed herein is an oxidation having: (i) greater than 0.2 wt% by weight of 1- phenyl- 1-methylcyclopentane; and (ii) greater than 50 wt% by weight of a second alkylaromatic compound. The composition may be oxidized to convert a portion of the 1- pheny
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Page/Page column 15
(2012/06/30)
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- PRODUCTION OF CYCLOHEXYLBENZENE HYDROPEROXIDE
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In a process for producing cyclohexylbenzene hydroperoxide, cyclohexylbenzene is contacted with oxygen to produce a reaction product comprising cyclohexylbenzene hydroperoxide and unreacted cyclohexylbenzene. The reaction product is then maintained under
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Page/Page column 20
(2012/10/18)
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- PROCESS FOR THE PREPARATION OF PHENOL AND CYCLOHEXANONE
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Process for the preparation of phenol and cyclohexanone which comprises : a. the synthesis of cyclohexylbenzene by the hydro- alkylation of benzene by contact with hydrogen or the alkylation of benzene with cyclohexene using Y zeolites; b. the selective aerobic oxidation of cyclohexylbenzene to the corresponding hydroperoxide catalyzed by N- hydroxy-derivatives in the presence of polar solvents; and c. the scission of the hydroperoxide of cyclohexylbenzene to phenol and cyclohexanone by homogeneous or heterogeneous acid catalysts; characterized in that the synthesis of cyclohexylbenzene takes place in the presence of a catalytic system comprising a Y zeolite and an inorganic ligand wherein the Y zeolite has a crystalline structure with openings consisting of (12) tetrahedra and the inorganic ligand is γ-alumina, and wherein said catalytic composition is characterized by a pore volume, obtained by adding the mesoporosity and macroporosity fractions, greater than or equal to 0.7 cm /g, wherein at least 30% of said volume consists of pores with a diameter greater than 100 nanometers.
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Page/Page column 15
(2011/02/24)
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- PROCESS FOR THE PRODUCTION OF ALKYLBENZENE HYDROPEROXIDES UNDER MILD CONDITIONS AND IN THE PRESENCE OF NEW CATALYTIC SYSTEMS
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Process for the preparation of hydroperoxides of alkylbenzenes characterized by the fact that the alkylbenzene reacts with oxygen in the presence of a catalytic system which includes an N-hydroxyimide or an N-hydroxysulfamide and a polar solvent.
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Page/Page column 3
(2011/10/19)
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- PROCESS FOR PRODUCING PHENOL
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Disclosed is a process for producing phenol or a substituted phenol and a co-product comprising the steps of (i) contacting a first stream comprising an alkylaromatic compound with a second stream comprising an oxygen-containing gas in the presence of a first catalyst comprising a cyclic imide under conditions to convert at least a portion of said alkylaromatic compound to an alkylaromatic hydroperoxide, (ii) producing an effluent stream comprising said cyclic imide, said alkylaromatic hydroperoxide, and said alkylaromatic compound wherein said effluent stream has an alkylaromatic hydroperoxide concentration of from 10 to 40 wt%; and (iii) contacting in a second reactor at least a portion of said effluent stream with a second catalyst to convert said alkylaromatic hydroperoxide to a product stream comprising phenol and said co-product.
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Page/Page column 21
(2010/09/17)
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- OXIDATION OF HYDROCARBONS
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In a process for oxidizing a hydrocarbon to the corresponding hydroperoxide, alcohol, ketone, carboxylic acid or dicarboxylic acid, a reaction medium comprising a hydrocarbon is contacted with an oxygen-containing gas in the presence of a catalyst comprising a cyclic imide of the general formula (I): wherein each of R1 and R2 is independently selected from hydrocarbyl and substituted hydrocarbyl radicals having 1 to 20 carbon atoms, or from the groups SO3H, NH2, OH and NO2, or from the atoms H, F, Cl, Br and I provided that R1 and R2 can be linked to one another via a covalent bond; each of Q1 and Q2 is independently selected from C, CH, N, and CR3; each of X and Z is independently selected from C, S, CH2, N, P and an element of Group 4 of the Periodic Table; Y is O or OH; k is O, 1, or 2; 1 is 0, 1, or 2; m is 1 to 3; and R3 can be any of the entities listed for R1. The contacting is conducted under conditions such as to maintain the concentration of both water and organic acids in the reaction medium below 50 ppm.
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Page/Page column 21; 25
(2009/06/27)
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- Oxidation of hydrocarbons
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In a process for oxidizing a hydrocarbon to the corresponding hydroperoxide, alcohol, ketone, carboxylic acid or dicarboxylic acid, a reaction medium comprising a hydrocarbon is contacted with an oxygen-containing gas in the presence of a catalyst compris
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Page/Page column 12; 21-22
(2009/09/26)
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- PROCESS FOR THE PRODUCTION OF ALKYLBENZENE HYDROPEROXIDES UNDER MILD CONDITIONS AND IN THE PRESENCE OF NEW CATALYTIC SYSTEMS
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Process for the preparation of hydroperoxides of alkylbenzenes characterized by the fact that the alkylbenzene reacts with oxygen in the presence of a catalytic system which includes an N-hydroxyimide or an N-hydroxysulfamide and a polar solvent.
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Page/Page column 11-12
(2009/10/22)
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- CATALYTIC PROCESS FOR THE PREPARATION OF HYDROPEROXIDES OF ALKYLBENZENES BY AEROBIC OXIDATION UNDER MILD CONDITIONS
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Process for the preparation of hydroperoxides of alkylbenzenes characterized by the fact that the alkyibenzene reacts with oxygen in the presence of a catalytic system consisting of an N-hydroxyimide associated with a peroxide activator having a peracid or dioxyrane structure, possibly generated in situ.
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Page/Page column 12
(2009/10/22)
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- Heterogeneous arylalkyl oxidation promoter
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A promoter can have utility in selective heterogeneous oxidation of arylalkyl hydrocarbons such as, for example, cyclohexyl benzene and/or sec-butyl benzene to form hydroperoxides. The promoter can include the product of contacting a solid support comprising a metal oxide surface and an iron compound. The solid support can include, for example, titanium dioxide and/or an iron oxide such as magnetite and can have magnetic susceptibility. A method for the oxidation of arylalkyl hydrocarbons to form hydroperoxides can include contacting 16 an arylalkyl hydrocarbon with oxygen in the presence of the promoter under catalytic oxidation conditions to form arylalkyl hydroperoxide, which can then be converted to phenol via cleavage 26. The method can include recovery 22 of the promoter from the arylalkyl hydroperoxide and can further include recycling the recovered promoter to the contacting 16. Where the solid support has magnetic susceptibility, the recovery 22 can include magnetic separation of the promoter.
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Page/Page column 6-7
(2009/01/24)
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- PROCESS FOR OXIDIZING ALKYLAROMATIC COMPOUNDS
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In a process for producing hydroperoxides, an alkylaromatic compound of general formula (I): in which R1 and R2 each independently represents hydrogen or an alkyl group having from 1 to 4 carbon atoms, provided that R1 and R2 may be joined to form a cyclic group having from 4 to 10 carbon atoms, said cyclic group being optionally substituted, and R3 represents hydrogen, one or more alkyl groups having from 1 to 4 carbon atoms or a cyclohexyl group, is contacted with oxygen in the presence of a catalyst comprising a polyoxometalate to produce a hydroperoxide of general formula (II): in which R1, R2 and R3 have the same meaning as in formula (I) and wherein the polyoxometalate comprises a polyoxotungstate substituted with at least one further transition metal. The hydroperoxide of formula (II) may then be converted to a phenol and an aldehyde or a ketone of the general formula R1COCH2R2 (III), in which R1 and R2 have the same meaning as in formula (I). In the case where the ketone is cyclohexanone, this may then be dehydrogenated to produce further phenol.
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Page/Page column 26-27
(2008/12/08)
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- Selective catalytic oxidation of cyclohexylbenzene to cyclohexylbenzene-1-hydroperoxide: A coproduct-free route to phenol
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A method is described for the highly selective oxidation of cyclohexylbenzene to cyclohexylbenzene-1-hydroperoxide. In the presence of 0.5mol% N-hydroxyphthalimide (NHPI) and 2mol% of the hydroperoxide product, without solvent, a selectivity of ca. 98% to the desired product was obtained at 32% conversion. The use of NHPI increases the selectivity for initial H-abstraction from the 1-position, vs the other positions in the cyclohexyl ring, suppresses byproduct formation via transannular hydrogen abstraction and increases the overall rate of reaction.
- Arends, Isabel W.C.E,Sasidharan, Manickam,Kühnle, Adolf,Duda, Mark,Jost, Carsten,Sheldon, Roger A
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p. 9055 - 9061
(2007/10/03)
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