DOCSLIB.ORG

Ce(IV) Oxidation of Cyclopentanone, Cyclohexanone, Cycloheptanone, Cyc1ooctanone, Acetone, Butanone, Acetoacetic Ester & Benzoylacetone

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Ce(IV) Oxidation of Cyclopentanone, Cyclohexanone, Cycloheptanone, Cyc1ooctanone, Acetone, Butanone, Acetoacetic Ester & Benzoylacetone Indian Joumal of Chemistry Vol. IotA. Autust 1976. pp. 519·58:J Ce(IV) Oxidation of Cyclopentanone, Cyclohexanone, Cycloheptanone, Cyc1ooctanone, Acetone, Butanone, Acetoacetic Ester & Benzoylacetone G. P. PANIGRAHI & PRAFULLA K. MISRO Department of Chemistry. Berhampur University. Berhampur 7 Received 28 July 1975; accepted 5 NOIJembeY 1975 Kinetics of oxidation of a series of cycloalkanones such as cyclopentanone, cyclohexanone, cyc1oheptanone and cyc1ooctanone and of aliphatic ketones like acetone, butanone, acetoacetic ester and benzoylacetone by Ce(IV) in HCIO, medium are reported. The order of reactivity among the cyclic ketones is cyclohexanone > cyclooctanone > cycloheptanone '" cyc1openta- none, and among the aliphatic ketones is benzoylacetone > acetoacetic ester> butanone > acetone. The oxidation of cyc1ohexanone and the aliphatic ketones involve. a free-radical mechanism. INETICS of oxidation of cyclohexanone by of the reaction is two at a constant (H+]. The first Ce(IV) has been studied earlier by Littler! and second order rate constants for the cyclic K who postulated that the keto-form is directly ketones are given in Table 1. attacked after if forms a complex with Ce(IV). Under the experimental conditions the reaction Shorter and ooworkerss-s and Santappa+ have shown mixture in the case of cyclohexanone developed a the formation of Ce(IV)-ketone complex while pink colour which is probably due to the formation studying the kinetics of oxidation of certain aliphatic of a complex of 2-hydroxycyclohexanone, an inter- ketones. However, no attempt has been made so mediate compound formed in the oxidation process. far to correlate structure and reactivity of these Hence, it can be safely presumed that the reactions substrates. Hence, it was thought worthwhile to are clean one-step processes and the kinetics are not investigate the oxidation of a series of cyclic ketones such as cyclopentanone, cyclohexanone, cyclo- heptanone, cyclooctanone as well as of acetone, TABLE 1 - RATE CONSTANTS FOR THE OXIDATION OF butanone, acetoacetic ester and benzoylacetone in CYCLIC KETONES aq. acetic acid containing 0·05, 0·1 and 0'15M HCIO, to establish correlation if any, between structure {[Ce(IV)) = 5·0 x 10-IM; [HClO,l = 0·05M; solvent. and reactivity of the ketones and to throw light on HOAc-water (40: 60, v/v); temp., 35°C} the mechanism of the reaction. l [Substrate] 10 kl 10'k. M (min-1) (litre mole=J. Materials and Methods (min+)" Ceric ammon,ium nitrate and perchloric acid used CVCLOHEXANONE were of T. Baker (analysed) grade. Acetic acid (analar BDH) was used as the solvent. The 0·075 23·0 30·7 ketones were of either AR or GR grade. For each 0·1005 33·9 33·9 0·2002 66·1 33·0 run about 0'02M Ce(IV) solution containing the 0·2512 81·9 32·8 required amount of HCIOt was prepared and standardized by adding a known excess of the CVCLOPENTANONE standard ferrous ammonium sulphate solution followed 0·06425 3·78 5·88 by back-titration of the unused Fe (II) against 0·0753 4·35 5·77 standard dichromate using Nvphenylanthranilic acid 0·1001 5·6 5·63 as the indicator. The substrate solution was prepared in aq. acetic acid. Ce(IV) an,d the substrate CVCLOHEPTANONE solutions (50 ml each) were equilibrated for 2 hr at 0·06505 3·50 5·40 the required temperature and mixed. Aliquots 0·07505 4·20 5·6 (5 ml) of the reaction mixture were taken out at 0·1001 5·62 5·60 different intervals and treated with 10 ml of standard CVCLOOCTANONE ferrous ammonium sulphate. The unused Fe (II) was determined as described above. 0·01534 2·40 15·90 0·024895 3·34 13·50 Results and Discussion 0·03833 5·14 13040 The oxidation reactions are first order each in *k. = kl/[Substrate]. substrate and the oxidant, and hence the total order 579 INDIAN J. CHEM., VOL. 14A, AUGUST 1976 complicated by any subsequent steps which. might occur due to oxidation 01 the 2-hydroxy ketone. TABLE 2 - SECOND ORDER RATE CONSTANTS (II a) FOR However, in the presence of excess Ce{IV), the pink OXIDATION OF ALIPHATIC KETONES colour of the reaction mixture is not observed. This [Solvent, hOAc-w •.tor (40: 60 v/v); ternp., 35°J is~derstandab~e as the .2-hydroxy compound im- medla~ely after Its fo~mahon IS oxidized further by [hCICJ4J the oxidant. the presence of excess ketone M Hence.In Acetone Acetoacetic Benzoyl- the oxidation product is 2-hydroxy ketone. ester acetone 2-Hydroxy ketone has also been obtained as the product in the oxidation 01 cyclohexanone by Mn{III) 0-025 0-0164 0-0424 3-13-1- 112-~6 0-050 0-01~2 o-os.i 3-674 124'YO pyrophosphate- . 0·100 4·366 152-70 Effect of varying [substrate) - Plots of 1/k1 versus 0-150 0·022 0-0725 1J(ketone] are Iinear and pass through the origin indicating that no complex is formed initially be~we~n cyclic ketones and Ce{IV), unlike in the TABLE 3 - SECOND ORDER OXIDATION H_ATES OF CYCLIC KETONES oxidation ot acetone by Ce{IV). Effect of structure on the reactivjty of cyclic ketones [Solvent, hCJAc-w ..tor (40: 60, v/v); temp. 35"J - An examination of Table 1 reveals that the order [h.CIO.] of reactivity among the cyclic ketones is cycle- k. (litre mole'? mirr") for M hexanone > cyclooctanone > cyclopentanone ,...... Cyclu- Cyclo- Cyclo- Cyclo- cycloheptanone, The higher reactivity of cycle- hexanuno peut.vnone hept.mone oct.mone hexanone requires explanation. It is quite possible 0-05 0-341 0-0576 0-0553 0-143 that the terminal hydrogen of the nearly strainless 0·10 U-441 0-1OS 0-U9~S 0-205 puckered residue (CHII). in cyclohexene fulfils 0-15 1-303 0-15~ 0·1700 0-377 the stereochemical irequrrements for hyperconjuga- tion with the cyclic C=C better than does the ~erminal hydrogen of the nearly flat residue, (CHII)a in cyclopentene, likely to be formed in a rapid step depends on two The order observed shows that even membered factors: (a) the inductive effect of the electronegative carbethoxy or benzoyl group which loosens the cyclic ketones (C and C ) react much faster than the II 8 adjacent proton thereby reducing the relative ther- odd membered ketones (CII and C7). It is interest- ing to recall the similar differences between the modynamic stability of the keto-form, and (b) the spectra of the even and odd membered ketones. conjugation effect of the unsaturated carbethoxy For even membered ketones, the spectrum changes or benzoyl group demanding a suitably situated suddenly at the melting point, while in the rest of double bond and thus increasing the relative the temperature range only slight changes are ob- thermodynamic stability of the enol-form. The served. For odd membered ring ketones the spectrum greater reactivity of the benzoyl group over the also changes, not at the melting point but at carbethoxy group is mainly due to factor (b). Hence a transition point which lies lower than the melting the stability and the percentage of enol-form are point. The change in spectrum may be attributed the highest in the case of benzoylacetone with the to the possible disappearance of one or more result that it has a maximum reactivity. In simple conformations at a given temperature. It is aliphatic ketones, an increase in the number of alkyl generally presumed that the most favoured confor- groups increases the rate as alkyl groups are known mation of cycloheptanone is the twist chair formf to increase the equilibrium enol contents. This which is responsible for the lowest rate of oxidation. indicates a dominating hyperconjugative effect of Similarly the lower reactivity of cyclopentanone alkyl groups. can be attributed to the existence of cyclopentanone P-G* plot for aliphatic series - Employing the in the half chair form (stable conformation) which Taft substituent constants (G*) as given below, an has greater symmetry", However, the reactivity attempt has been made to correlate structure and of the medium-sized rings are known to alternate reacti vit y : as is evidenced from the process involving Spa~Sp2 Substituent G* (Taft) conversions, such as solvolysis of cycloalkyl chlorides, -CH COO- 0·50 acetolysis of cycloalkyl tosylates and reactions of 2 cycloalkyl bromides with lithium or potassium -CHaCOC6HIi 0·60 -CHa 0·00 iodides", Strictly speaking the observed reactivity of a series of medium-sized cyclic derivatives depends Using the second order rate constants (ka) for mainly on their conformations. acetone, acetoacetic ester and benzoylacetone, a Reactivity of aliphatic ketones - The second order linear plot was obtained between log k2 and G* rate constants (k2) for Ce(IV) oxidation of aliphatic which gave a P value of +1·2. The data for ketones, namely acetone, butanone, benzoylacetone butanone could not be used as there was no Taft and acetoacetic ester in aq. acetic acid (40% v/v) substituent constant which could take into account are given in Table 2. The order of reactivity is the conjugative ability of the alkyl group. benzoylacetone > acetoacetic ester> butanone > Effect of varying acidity - The rate of oxidation acetone. In the aliphatic ketones studied, it can of cyclic ketones increases with increasing [HCIOJ be presumed that the stability of enols which are as seen from Table 3. The plots of log kg versus 580 PANIGRAHI & MISRO: Ce(I\') OXIDATION OF CYCLOALKANONES & ALIPHATIC KETONES [H+1are fairly linear but the plots of log k'/, versus Ho are better with unit slope. In the case of aliphatic ketones the increase in rate with increasing FAST acidity is marginal in 40% HOAc as seen from Table + CeiJYI ¢= COMPLEX 2.
Load more

Recommended publications
  • New Synthesis Routes for Production of Ε-Caprolactam by Beckmann
    New synthesis routes for production of ε-caprolactam by Beckmann rearrangement of cyclohexanone oxime and ammoximation of cyclohexanone over different metal incorporated molecular sieves and oxide catalysts Von der Fakultät für Mathematik, Informatik und Naturwissenschaften der RWTH Aachen University zur Erlangung des akademischen Grades eines Doktors der Naturwissenschaften genehmigte Dissertation vorgelegt von Anilkumar Mettu aus Guntur/Indien Berichter: Universitätprofessor Dr. Wolfgang F. Hölderich Universitätprofessor Dr. Carsten Bolm Tag der mündlichen Prüfung: 29.01.2009 Diese Dissertation ist auf den Internetseiten der Hochschulbibliothek online verfügbar. Dedicated to my Parents This work reported here has been carried out at the Institute for Chemical Technolgy and Heterogeneous Catalysis der Fakultät für Mathematik, Informatik und Naturwissenschaften in the University of Technology, RWTH Aachen under supervision of Prof. Dr. Wolfgang F. Hölderich between June 2005 and August 2008. ACKNOWLEDGEMENTS I would like to express my deepest sence of gratitude to my supervisor Prof. Dr. rer. nat. W. F. Hölderich for giving me the opportunity to do my doctoral study in his group. His guidance and teaching classes have allowed me to grow and learn my subject during my Ph.d. He has provided many opportunities for me to increase my abilities as a researcher and responsibilities as a team member. I am grateful for the financial support of this work from Sumitomo Chemicals Co., Ltd, Niihama, Japan (Part One) and Uhde Inventa-Fischer GmBH, Berlin (Part Two). Our collaborators at Sumitomo Chemicals Co., Ltd (Dr. C. Stoecker) and Uhde Inventa- Fischer GmBH (Dr. R. Schaller and Dr. A. Pawelski) provided thoughtful guidance and suggestions for each project.
    [Show full text]
  • Selective Hydrogenation of Phenol to Cyclohexanol Over Ni/CNT in the Absence of External Hydrogen
    energies Article Selective Hydrogenation of Phenol to Cyclohexanol over Ni/CNT in the Absence of External Hydrogen Changzhou Chen 1,2, Peng Liu 1,2, Minghao Zhou 1,2,3,*, Brajendra K. Sharma 3,* and Jianchun Jiang 1,2,* 1 Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry, Key Laboratory of Biomass Energy and Material, Jiangsu Province, National Engineering Laboratory for Biomass Chemical Utilization, Key and Open Laboratory on Forest Chemical Engineering, SFA, Nanjing 210042, China; [email protected] (C.C.); [email protected] (P.L.) 2 Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Nanjing Forestry University, Nanjing 210037, China 3 Illinois Sustainable Technology Center, Prairie Research Institute, one Hazelwood Dr., Champaign, University of Illinois at Urbana-Champaign, Champaign, IL 61820, USA * Correspondence: [email protected] (M.Z.); [email protected] (B.K.S.); [email protected] (J.J.) Received: 7 January 2020; Accepted: 11 February 2020; Published: 14 February 2020 Abstract: Transfer hydrogenation is a novel and efficient method to realize the hydrogenation in different chemical reactions and exploring a simple heterogeneous catalyst with high activity is crucial. Ni/CNT was synthesized through a traditional impregnation method, and the detailed physicochemical properties were performed by means of XRD, TEM, XPS, BET, and ICP analysis. Through the screening of loading amounts, solvents, reaction temperature, and reaction time, 20% Ni/CNT achieves an almost complete conversion of phenol after 60 min at 220 ◦C in the absence of external hydrogen. Furthermore, the catalytic system is carried out on a variety of phenol derivatives for the generation of corresponding cyclohexanols with good to excellent results.
    [Show full text]
  • Photooxidation of Cyclohexane by Visible and Near-UV Light Catalyzed by Tetraethylammonium Tetrachloroferrate
    catalysts Article Photooxidation of Cyclohexane by Visible and Near-UV Light Catalyzed by Tetraethylammonium Tetrachloroferrate Kira M. Fahy , Adam C. Liu, Kelsie R. Barnard, Valerie R. Bright, Robert J. Enright and Patrick E. Hoggard * Department of Chemistry and Biochemistry, Santa Clara University, Santa Clara, CA 95053, USA; [email protected] (K.M.F.); [email protected] (A.C.L.); [email protected] (K.R.B.); [email protected] (V.R.B.); [email protected] (R.J.E.) * Correspondence: [email protected]; Tel.: +1-408-554-7810 Received: 2 August 2018; Accepted: 18 September 2018; Published: 19 September 2018 Abstract: Tetraethylammonium tetrachloroferrate catalyzes the photooxidation of cyclohexane heterogeneously, exhibiting significant photocatalysis even in the visible portion of the spectrum. The photoproducts, cyclohexanol and cyclohexanone, initially develop at constant rates, implying that the ketone and the alcohol are both primary products. The yield is improved by the inclusion of 1% acetic acid in the cyclohexane. With small amounts of catalyst, the reaction rate increases with the amount of catalyst employed, but then passes through a maximum and decreases, due to increased reflection of the incident light. The reaction rate also passes through a maximum as the percentage of dioxygen above the sample is increased. This behavior is due to quenching by oxygen, which at the same time is a reactant. Under one set of reaction conditions, the photonic efficiency at 365 nm was 0.018 mol/Einstein. Compared to TiO2 as a catalyst, Et4N[FeCl4] generates lower yields at wavelengths below about 380 nm, but higher yields at longer wavelengths. Selectivity for cyclohexanol is considerably greater with Et4N[FeCl4], and oxidation does not proceed past cyclohexanone.
    [Show full text]
  • Phenol Hydrogenation Over Pd/Zro2 Using Ethanol As Hydrogen Source
    4th International Conference on Sensors, Measurement and Intelligent Materials (ICSMIM 2015) Phenol hydrogenation over Pd/ZrO2 using ethanol as hydrogen source Yunjie Shi1, a, Bin Wang1,b, Junjun Shen1,c and Rongrong Miao1,d* 1Faculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming 650500, China [email protected], [email protected], [email protected], d*[email protected] Keywords: Ethanol, Phenol, Hydrogenation, Pd/ZrO2 Abstract. Phenol hydrogenation over the Pd/ZrO2 catalyst has been carried out using ethanol as hydrogen source. The reaction temperature, catalyst and ethanol quantity are found to be influencing factors for effective phenol conversion. In all cases, low quantity (5%~10%) of ethanol and high temperature is efficient for a high phenol conversion. The results show that low quantity (5%~10%) of ethanol is efficient for high cyclohexanone selectivity at low temperature (573K). However, the selectivity of cyclohexanone, cyclohexanol and cyclohexane are insensitive to the ethanol quantity at high temperature (653K). It seems that ethanol plays an important dual role: as hydrogen source and as additive to control the phenol conversion and products selectivity. Introduction Cyclohexanone is the key raw material for the preparation of nylon 6 and adipic acid for nylon 66 [1,2]. The industrial production of cyclohexanone commonly involves the selective catalytic hydrogenation of phenol. On the other hand, phenol is an established environmental toxin and phenol-based waste originates form a variety of industrial sources including oil refineries, petrochemical units, polymeric resin manufacturing and plastic units [7]. Therefore, catalytic hydrogenation of phenol for cyclohexanone is an important chemical process, and has been widely studied [3-10].
    [Show full text]
  • Synthetic Turf Scientific Advisory Panel Meeting Materials
    California Environmental Protection Agency Office of Environmental Health Hazard Assessment Synthetic Turf Study Synthetic Turf Scientific Advisory Panel Meeting May 31, 2019 MEETING MATERIALS THIS PAGE LEFT BLANK INTENTIONALLY Office of Environmental Health Hazard Assessment California Environmental Protection Agency Agenda Synthetic Turf Scientific Advisory Panel Meeting May 31, 2019, 9:30 a.m. – 4:00 p.m. 1001 I Street, CalEPA Headquarters Building, Sacramento Byron Sher Auditorium The agenda for this meeting is given below. The order of items on the agenda is provided for general reference only. The order in which items are taken up by the Panel is subject to change. 1. Welcome and Opening Remarks 2. Synthetic Turf and Playground Studies Overview 4. Synthetic Turf Field Exposure Model Exposure Equations Exposure Parameters 3. Non-Targeted Chemical Analysis Volatile Organics on Synthetic Turf Fields Non-Polar Organics Constituents in Crumb Rubber Polar Organic Constituents in Crumb Rubber 5. Public Comments: For members of the public attending in-person: Comments will be limited to three minutes per commenter. For members of the public attending via the internet: Comments may be sent via email to [email protected]. Email comments will be read aloud, up to three minutes each, by staff of OEHHA during the public comment period, as time allows. 6. Further Panel Discussion and Closing Remarks 7. Wrap Up and Adjournment Agenda Synthetic Turf Advisory Panel Meeting May 31, 2019 THIS PAGE LEFT BLANK INTENTIONALLY Office of Environmental Health Hazard Assessment California Environmental Protection Agency DRAFT for Discussion at May 2019 SAP Meeting. Table of Contents Synthetic Turf and Playground Studies Overview May 2019 Update .....
    [Show full text]
  • Cyclohexanone
    CYCLOHEXANONE ALPHA CHEMICALS PTY LTD Chemwatch Hazard Alert Code: 2 Chemwatch: 1915 Issue Date: 05/09/2018 Version No: 6.1.7.7 Print Date: 21/06/2021 Safety Data Sheet according to WHS Regulations (Hazardous Chemicals) Amendment 2020 and ADG requirements S.GHS.AUS.EN SECTION 1 Identification of the substance / mixture and of the company / undertaking Product Identifier Product name CYCLOHEXANONE Chemical Name cyclohexanone C6-H10-O; Anon; anone; Hytrol o; ketohexamethylene; Nadone; pimelic pimelin ketone; pimelic ketone; cyclohexyl ketone; Hexanon; Sextone; Synonyms pennyroyal oil; Cat. No. 14033; Airex 930; Screen Opener Aerosol; OCD Thinner; Product Code: 8.22269 Proper shipping name CYCLOHEXANONE Chemical formula C6H10O Other means of identification Not Available CAS number 108-94-1 Relevant identified uses of the substance or mixture and uses advised against As a solvent for cellulose acetate, nitrocellulose, natural resins, vinyl resins, rubber, waxes, fats, shellac, and manufacture of ketone resins. In the production of adipic acid and caprolactam; production of polymers and resins. Reagent chemical. Used in wood stains; paint varnish and spot Relevant identified uses remover; degreasing of metals, polishes; textile dyeing and processing and in lubricating oil additives. Occurs naturally in the herb Pennyroyal and is responsible for the toxic effects in the misuse of Pennyroyal Oil in folk medicine, herbal teas. Details of the supplier of the safety data sheet Registered company name ALPHA CHEMICALS PTY LTD Address 4 ALLEN PLACE WETHERILL PARK NSW 2099 Australia Telephone 61 (0)2 9982 4622 Fax Not Available Website ~ Email [email protected] Emergency telephone number Association / Organisation ALPHA CHEMICALS PTY LTD Emergency telephone 61 (0)418 237 771 numbers Other emergency telephone Not Available numbers SECTION 2 Hazards identification Classification of the substance or mixture HAZARDOUS CHEMICAL.
    [Show full text]
  • Green Production Technology of Cyclohexanone
    N°456 / OC TOPIC(s) : Industrial chemistry / Alternative technologies Green Production Technology of Cyclohexanone AUTHORS Dongqiang MA / RESEARCH INSTITUTE OF PETROLEUM PROCESSING (RIPP),, SINOPEC, BEIJING 100083,, BEIJING Langyou WEN / SINOPEC, SINOPEC, BEIJING 100083, P. R., BEIJING Keyong YANG / SINOPEC, BEIJING 100083, P. R., BEIJING Baoning ZONG / SINOPEC, SINOPEC, BEIJING 100083, P. R. CHINA, BEIJING PURPOSE OF THE ABSTRACT 1 Introduction Cyclohexanone is an important organic chemical raw material and is the main intermediate for the manufacture of ?-caprolactam and adipic acid. It is also widely used as a solvent. Industrially, the production processes of cyclohexanone mainly include cyclohexane oxidation, phenol hydrogenation and cyclohexene hydration. Among the above processes, the application of the cyclohexane oxidation is most common. 2 Production technology of cyclohexanone The cyclohexane oxidation process uses an oxidizing agent (generally air) to oxidize cyclohexane to cyclohexyl hydroperoxide, and cyclohexyl hydroperoxide decomposes to a mixture of cyclohexanol and cyclohexanone (KA oil), and cyclohexanone obtained by dehydrogenation of cyclohexanol. The disadvantages of this process are: (1) the conversion of cyclohexane is low, only 3 to 5%, the yield of cyclohexanone is less than 80%; (2) a large amount of refractory waste alkali liquor is produced in the production process, so it is environment unfriendly; (3) intrinsic safety issues with oxidation processes. The phenol hydrogenation process is a relatively clean cyclohexanone production route, and the yield of cyclohexanone can reach 90% to 95%, which has the advantages of short process flow and high product purity. However, this process requires the vaporization of phenol and methanol, so the energy consumption is high; and the industrial application of the process is limited due to the shortage of phenol raw materials.
    [Show full text]
  • Interagency Committee on Chemical Management
    DECEMBER 14, 2018 INTERAGENCY COMMITTEE ON CHEMICAL MANAGEMENT EXECUTIVE ORDER NO. 13-17 REPORT TO THE GOVERNOR WALKE, PETER Table of Contents Executive Summary ...................................................................................................................... 2 I. Introduction .......................................................................................................................... 3 II. Recommended Statutory Amendments or Regulatory Changes to Existing Recordkeeping and Reporting Requirements that are Required to Facilitate Assessment of Risks to Human Health and the Environment Posed by Chemical Use in the State ............................................................................................................................ 5 III. Summary of Chemical Use in the State Based on Reported Chemical Inventories....... 8 IV. Summary of Identified Risks to Human Health and the Environment from Reported Chemical Inventories ........................................................................................................... 9 V. Summary of any change under Federal Statute or Rule affecting the Regulation of Chemicals in the State ....................................................................................................... 12 VI. Recommended Legislative or Regulatory Action to Reduce Risks to Human Health and the Environment from Regulated and Unregulated Chemicals of Emerging Concern ..............................................................................................................................
    [Show full text]
  • Adipic Acid Route: Oxidation of Cyclohexene Vs. Cyclohexane
    catalysts Article Adipic Acid Route: Oxidation of Cyclohexene vs. Cyclohexane Ana P. C. Ribeiro 1 , Elisa Spada 2, Roberta Bertani 2 and Luísa M. D. R. S. Martins 1,* 1 Centro de Química Estrutural and Departamento de Engenharia Química, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal; [email protected] 2 Department of Industrial Engineering, University of Padova, 35122 Padova, Italy; [email protected] (E.S.); [email protected] (R.B.) * Correspondence: [email protected]; Tel.: +351-218-419-389 Received: 20 November 2020; Accepted: 8 December 2020; Published: 10 December 2020 Abstract: A cleaner alternative to the current inefficient oxidation of cyclohexane to adipic acid is presented. Direct oxidation of neat cyclohexene by aq. hydrogen peroxide to adipic acid is selectively achieved in good yield (46%), in the presence of the recyclable C-homoscorpionate iron(II) complex 3 [FeCl2{κ -HC(pz)3}] (pz = pyrazol-1-yl) and microwave irradiation, by a nitrous oxide-free protocol. Keywords: cyclohexene; adipic acid; oxidation; nitrous oxide; C-scorpionate; iron; microwave; ionic liquid; recyclable 1. Introduction Adipic acid (AA) is a highly relevant commodity produced at a large scale (over 3.5 mio metric tons/year and growing by ca. 5%/year) [1,2] worldwide, as it constitutes a building block for several industrial processes. It is mostly used for the synthesis of Nylon-6,6 polyamide; therefore, the rising demand for engineered plastics requires increased production of AA. Currently, adipic acid is mainly obtained by an inefficient and environmentally harmful two-step process [1,3] involving catalytic cyclohexane oxidation to cyclohexanol and cyclohexanone mixture followed by its oxidation with nitric acid.
    [Show full text]
  • Liquid-Phase Hydrogenation of Phenol to Cyclohexanone Over Supported Palladium Catalysts
    CORE Metadata, citation and similar papers at core.ac.uk Provided by Universitas Diponegoro: Undip E-Journal System (UEJS) Portal Available online at BCREC Website: http://bcrec.undip.ac.id Bulletin of Chemical Reaction Engineering & Catalysis, 11 (3), 2016, 354-362 Research Article Liquid-phase Hydrogenation of Phenol to Cyclohexanone over Supported Palladium Catalysts Lihui Fan*, Luyang Zhang, Yanming Shen*, Dongbin Liu, Nasarul Wahab, Md Mahmud Hasan Department of Chemical Engineering, Shenyang University of Chemical Technology, China 110142 Received: 7th March 2016; Revised: 13rd May 2016; Accepted: 7th June 2016 Abstract The ZSM-5, -Al2O3, SiO2 and MgO supported Pd-catalysts were prepared for the phenol hydrogenation to cyclohexanone in liquid-phase. The natures of these catalysts were characterized by XRD, N2 adsorption-desorption analysis, H2-TPR, CO2-TPD and NH3-TPD. The catalytic performance of the supported Pd-catalyst for phenol hydrogenation to cyclohexanone is closely related to nature of the support and the size of Pd nanoparticles. The Pd/MgO catalyst which possesses higher basicity shows higher cyclohexanone selectivity, but lower phenol conversion owing to the lower specific surface area. The Pd/SiO2 catalyst prepared by precipitation gives higher cyclohexanone selectivity and phenol conversion, due to the moderate amount of Lewis acidic sites, and the smaller size and higher dispersion of Pd nanoparticles on the surface. Under the reaction temperature of 135 oC and H2 pressure of 1 MPa, after reacting for 3.5 h, the phenol conversion of 71.62% and the cyclohexanone selectivity of 90.77% can be obtained over 0.5 wt% Pd/SiO2 catalyst.
    [Show full text]
  • AP42 6.2 Adipic Acid Production Background Report
    BACKGROUND REPORT AP-42 SECTION 6.2 ADIPIC ACID PRODUCTION Prepared for U.S. Environmental Protection Agency OAQPS/TSD/EIB Research Triangle Park, NC 27711 July 1994 Pacific Environmental Services, Inc. P.O. Box 12077 Research Triangle Park, NC 27709 919/941-0333 AP-42 BACKGROUND REPORT TECHNICAL SUPPORT DIVISION U.S. ENVIRONMENTAL PROTECTION AGENCY Office of Air Quality Planning and Standards Research Triangle Park, NC 27711 ii This report has been reviewed by the Technical Support Division of the Office of Air Quality Planning and Standards, U.S. EPA. Mention of trade names or commercial products is not intended to constitute endorsement or recommendation for use. Copies of this report are available through the Library Services Office (MD-35), U.S. Environmental Protection Agency, Research Triangle Park, NC 27711. iii CONTENTS 1.0 INTRODUCTION ......................................................... 1 2.0 INDUSTRY DESCRIPTION ................................................ 2 2.1 GENERAL .................................................... 2 2.2 PROCESS DESCRIPTION ....................................... 2 2.3 EMISSIONS AND CONTROLS ................................... 3 2.4 REVIEW OF REFERENCES FOR CHAPTER 2 ...................... 5 2.5 REFERENCES FOR CHAPTER 2 .................................. 8 3.0 GENERAL EMISSION DATA REVIEW AND ANALYSIS PROCEDURES .......... 9 3.1 LITERATURE SEARCH AND SCREENING ........................ 9 3.2 EMISSION DATA QUALITY RATING SYSTEM .................... 10 3.3 EMISSION FACTOR QUALITY RATING SYSTEM
    [Show full text]
  • Photochemical Reactions of Cyclohexanone: Mechanisms and Dynamics Published As Part of the Journal of Physical Chemistry a Virtual Special Issue “Mark S
    Article pubs.acs.org/JPCA Photochemical Reactions of Cyclohexanone: Mechanisms and Dynamics Published as part of The Journal of Physical Chemistry A virtual special issue “Mark S. Gordon Festschrift”. † ‡ † ‡ Dorit Shemesh, Sergey A. Nizkorodov, and R. Benny Gerber*, , † Institute of Chemistry and The Fritz Haber Research Center, The Hebrew University, Jerusalem 91904, Israel ‡ Department of Chemistry, University of California, Irvine, California 92697, United States *S Supporting Information ABSTRACT: Photochemistry of carbonyl compounds is of major importance in atmospheric and organic chemistry. The photochemistry of cyclohexanone is studied here using on-the- fly molecular dynamics simulations on a semiempirical multi- reference configuration interaction potential-energy surface to predict the distribution of photoproducts and time scales for their formation. Rich photochemistry is predicted to occur on a picosecond time scale following the photoexcitation of cyclo- hexanone to the first singlet excited state. The main findings include: (1) Reaction channels found experimentally are confirmed by the theoretical simulations, and a new reaction channel is predicted. (2) The majority (87%) of the reactive trajectories start with a ring opening via C−Cα bond cleavage, supporting observations of previous studies. (3) Mechanistic details, time scales, and yields are predicted for all reaction channels. These benchmark results shed light on the photochemistry of isolated carbonyl compounds in the atmosphere and can be extended in the future to photochemistry of more complex atmospherically relevant carbonyl compounds in both gaseous and condensed-phase environments. I. INTRODUCTION representative examples are given), acetaldehyde,8 propanal,9 10 11 The photochemistry of carbonyl compounds is an important butanal and its derivatives, heptanal, and other small − 12 topic in organic and atmospheric chemistry.1 3 Atmospheric aldehydes.
    [Show full text]