124-04-9Relevant articles and documents
Catalytic Oxidative Cleveage of Vicinal Diols and Related Oxidations by Ruthenium Pyrochlore Oxides: New Catalysts for Low-Temperature Oxidations with Molecular Oxygen
Felthouse, Timothy R
, p. 7566 - 7568 (1987)
-
Optimization of adiponitrile hydrolysis in subcritical water using an orthogonal array design
Duan, Peigao,Wang, Yuanyuan,Yang, Yan,Dai, Liyi
, p. 241 - 258 (2009)
A study of the hydrolysis of adiponitrile (ADN) was performed in subcritical water to research the dependence on experimental conditions. An L25(56) orthogonal array design (OAD) with six factors at five levels using statistical analysis was employed to optimize the experimental conditions for each product in which the interactions between the variables were temporarily neglected. The six factors were adiponitrile concentration (ADN c, wt%), temperature (T), time (t h), percentage of additives (reactant/additive, wt/wt%), additives (A), and pressure (p, MPa). The effects of these parameters were investigated using the analysis of variance (ANOVA) to determine the relationship between experimental conditions and yield levels of different products. The results showed that (ADN c) and T had a significant influence on the yields of adipamide, adipamic acid, and adipic acid at p0.05. Time was the statistically significant factor for the yield of 5-cyanovalermic acid at p0.05 and (ADN c) was the significant factor for the yield of 5-cyanovaleramide at p0.1. Finally, five supplementary experiments were conducted under optimized conditions predicted by the Taguchi method; the results showed that the yield obtained of each product was no lower than that of the highest in the 25 experiments. Carbon balance was calculated to demonstrate the validity of the experimental technique and the reliability of the results. Based on the experimental results, a possible reaction mechanism was proposed.
Mercer et al.
, p. 1967 (1975)
Garin,D.L.
, p. 5254 - 5255 (1970)
Synthesis of AgWCNx Nanocomposites for the One-Step Conversion of Cyclohexene to Adipic Acid and Its Mechanistic Studies
Goyal, Reena,Sameer, Siddharth,Sarkar, Bipul,Bag, Arijit,Singhal, Nikita,Bordoloi, Ankur
, p. 16555 - 16565 (2017)
A novel catalyst composed of silver nanoparticles grafted on WCNx has been prepared by using a facile pH-adjusted method. The material reported in this study presents a non-mineral acid route for the synthesis of the industrially significant monomer adipic acid through the selective oxidation of cyclohexene. Ag has been stabilized in the hydrophobic matrix during the formation of the mesoporous silica material by using aniline as stabilizing agent. A cyclohexene conversion of 92.2 % with 96.2 % selectivity for adipic acid was observed with the AgWCNx-2 catalyst, therefore, the AgWCNx catalyst was found to be efficient for the direct conversion to adipic acid with respect to their monometallic counterparts. The energy profile diagrams for each reaction path by using the AgWCNx catalyst were studied along with their monometallic counterparts by using the Gaussian 09 package. The reported material can avoid the use of harmful phase-transfer catalysts (PTC) and/or chlorinated additives, which are two among other benefits of the reported work.
-
Doering,Haines
, p. 482,485 (1954)
-
Liquid-phase catalytic oxidation of C6-C7 cycloolefins into carboxylic acids in a pseudohomogeneous system
Alimardanov, Kh. M.,Sadygov,Garibov,Abbasov,Abdullaeva, M. Ya.,Dzhafarova
, p. 236 - 242 (2011)
Liquid-phase oxidation of cyclohexene, methylcyclohexene isomers, and norbornene with a 30% solution of hydrogen peroxide in a pseudohomogeneous system involving highly dispersed compounds of Group-VIb and -VIIIb metals supported by nanosize carbon particles was studied.
Oxidation of cyclohexene into adipic acid in aqueous dispersions of mesoporous oxides with built-in catalytical sites
Bohstroem, Zebastian,Rico-Lattes, Isabelle,Holmberg, Krister
, p. 1861 - 1869 (2010)
Reactant incompatibility is a common problem in organic chemistry. This study investigates the use of concentrated aqueous dispersions of mesoporous oxides to overcome incompatibility. Oxidation of cyclohexene into adipic acid using aqueous hydrogen peroxide as oxidant has been performed in a range of ordered and disordered mesoporous materials. The different mesoporous oxides have been characterised with diffraction techniques (XRD and SAXS), electron microscopy (TEM and SEM) and nitrogen adsorption isotherms (BET and BJH methods). The catalyst used in the reaction was either soluble sodium tungstate added to a reaction system based on mesoporous silica, alumina or a silica/alumina mixture; or a catalytic oxide, tungsten oxide or titania, present in the framework of the mesoporous material. Tungsten oxide, either used as the sole oxide material or as a mixed oxide with silica turned out to be very efficient and gave almost quantitative yield of adipic acid. A major advantage with having the catalyst chemically incorporated in the walls of the porous material is that it can be easily reused. The results from recycling experiments show that the catalytic activity is retained.
The irradiation chemistry of dilute aqueous solutions of cyclohexanone.
SERAT,MEAD
, p. 370 - 382 (1959)
-
-
Bloomfield,Jeffrey
, p. 120,123 (1944)
-
Alkene hydrogenation activity of enoate reductases for an environmentally benign biosynthesis of adipic acid
Joo, Jeong Chan,Khusnutdinova, Anna N.,Flick, Robert,Kim, Taeho,Bornscheuer, Uwe T.,Yakunin, Alexander F.,Mahadevan, Radhakrishnan
, p. 1406 - 1413 (2017)
Adipic acid, a precursor for Nylon-6,6 polymer, is one of the most important commodity chemicals, which is currently produced from petroleum. The biosynthesis of adipic acid from glucose still remains challenging due to the absence of biocatalysts required for the hydrogenation of unsaturated six-carbon dicarboxylic acids to adipic acid. Here, we demonstrate the first enzymatic hydrogenation of 2-hexenedioic acid and muconic acid to adipic acid using enoate reductases (ERs). ERs can hydrogenate 2-hexenedioic acid and muconic acid producing adipic acid with a high conversion rate and yield in vivo and in vitro. Purified ERs exhibit a broad substrate spectrum including aromatic and aliphatic 2-enoates and a significant oxygen tolerance. The discovery of the hydrogenation activity of ERs contributes to an understanding of the catalytic mechanism of these poorly characterized enzymes and enables the environmentally benign biosynthesis of adipic acid and other chemicals from renewable resources.
-
Noller,Kaneko
, p. 2442 (1935)
-
Direct oxidation of cyclohexene with inert polymeric membrane reactor
Buonomenna, Maria G.,Golemme, Giovanni,De Santo, Maria P.,Drioli, Enrico
, p. 252 - 258 (2010)
In this work, the use of PVDF flat membranes as contactors for direct solvent-free biphasic oxidation of cyclohexene to adipic acid has been reported. The oxidation has been carried out using 30% H2O2 and ammonium molybdate ((NH4)6Mo7O 24)inthe presence of succinic acid. The effect of different membranes as interfaces between the organic phase, containing cyclo- hexene, and the aqueous phase, with the oxidant and catalyst, has been studied and related to conversion and selectivity.
-
Hoot,Kobe
, p. 782 (1955)
-
Highly regioselective electrochemical synthesis of dioic acids from dienes and carbon dioxide
Li, Chuan-Hua,Yuan, Gao-Qing,Ji, Xiao-Chen,Wang, Xiu-Jun,Ye, Jian-Shan,Jiang, Huan-Feng
, p. 1529 - 1534 (2011)
A simple and efficient electrochemical method has been developed for highly regioselective synthesis of unsaturated 1,6-dioic acids from 1,3-dienes and CO2. The electrosynthesis was successfully carried out by using a nickel cathode and an aluminum anode in an undivided cell containing n-Bu 4NBr-DMF electrolyte with a constant current under 3 MPa pressure of CO2, and the sole 1,4-addition products were obtained in good to excellent yields. The plausible mechanism for electrodicarboxylation reaction of 1,3-butadiene with CO2 was discussed briefly. In addition, further research shows that 3-hexene-1,6-dioic acid could be easily converted into adipic acid via the electroreduction in the diluted H2SO4 solution.
Natural phosphate modified by vanadium: A new catalyst for oxidation of cycloalkanones and α-ketols with oxygen molecular
Dakkach, Mohamed,Atlamsani, Ahmed,Sebti, Sa?d
, p. 482 - 492 (2012)
In this work, we have studied the catalytic oxidative cleavage of C-C bonds of cycloalkanones and α-ketols, in the presence of natural phosphate (NP) type fluorapatite, Ca10(PO4)6F2, and dioxygen. The aim was to find a heterogeneous system clean and efficient alternative to the industrial oxidation of cyclohexanone to adipic acid with nitric acid. The modification of the NP by vanadium leads to the preparation of a new catalyst V/PN. The latter was characterized by: XRD, FTIR, SEM and BET. It appears that vanadium is well dispersed on the surface of the NP. Using 2-methylcyclohexanone as model substrate, we optimized the conditions of reaction in order to make the system 'V/PN/O2' more performance. The comparative study between the two catalytic systems 'PN/O2' and 'V/PN/O2' shows that the latter is more active. Finally, the system 'V/PN/O2' has been recycled but low leaching of vanadium was observed in the first use of the catalyst.
Intensification of cyclohexanone purification stage from impurities in caprolactam production using phase transfer catalysis
Martynenko,Glazko,Levanova,Portnova, Yu. V.
, p. 899 - 903 (2014)
Impurities in the oxidate, which was produced in the oxidation of cyclohexane in an industrial environment, were analyzed and identified. It is found that the amount of esters and ethers is 30% of the impurities produced, among which a cyclohexyl ethers amount is more than 50%. The process of purifying the oxidate from the impurities by hydrolysis in the presence of phase transfer catalysts and without them was studied. It has been shown that the use of trioctylmethyl ammonium chloride (Aliquat-336) in the the stage of saponification of esters enabled a removal of 90-96% of esters with reducing of reaction time in a 1.5-fold, in contrast to non-catalytic process.
Dawson-type polyoxometalates as green catalysts for adipic acid synthesis
Moudjahed,Dermeche,Benadji,Mazari,Rabia
, p. 72 - 77 (2016)
Dawson-type POMs series of formula α- and β-K6P2W18O62 isomers, α1- and α2-K6P2Mo5W13O62 isomers, α-K6P2Mo6W12O62 isomer and α1-K7P2Mo5VW12O62 isomer, have been used as catalysts for the liquid phase oxidation of cyclohexanol, cyclohexanone and cyclohexanol/cyclohexanone mixture to form adipic acid in presence of hydrogen peroxide without solvent, without phase-transfer agents and without adding acid. 31P NMR spectroscopy of different POMs after cyclohexanol oxidation showed the formation of new active species that can be attributed to "peroxo-POMox" form. An adipic acid yield of 69% was obtained from the oxidation of a mixture of cyclohexanol (50%) and cyclohexanone (50%) with α-K6P2Mo6W12O62 isomer.
Selective hydroxylation of cyclohexene over Fe-bipyridine complexes encapsulated into Y-type zeolite under environment-friendly conditions
Yamaguchi, Syuhei,Fukura, Tomohiro,Takiguchi, Keiko,Fujita, Chiharu,Nishibori, Maiko,Teraoka, Yasutake,Yahiro, Hidenori
, p. 261 - 267 (2015)
Fe-bipyridine complexes encapsulated into Na-Y ([Fe(bpy)3]2+@Y) were prepared and their catalytic activities for oxidation of cyclohexene with hydrogen peroxide in CH3CN and H2O solvents were investigated. The prepared [Fe(bpy)3]2+@Y was characterized by several methods and it was found that slightly distorted or compressed [Fe(bpy)3]2+ ions were formed within supercages of Y-type zeolite. [Fe(bpy)3]2+@Y catalyst exhibited both higher activity and higher selectivity to 2-cyclohexen-1-ol in water solvent than another Fe catalysts. In addition, the selective hydroxylation of cyclohexene to 2-cyclohexen-1-ol with molecular oxygen was successfully achieved for [Fe(bpy)3]2+@Y catalyst.
-
Durland,Adkins
, p. 429,431 (1939)
-
-
Bailey
, p. 993 (1958)
-
-
Dupont,Dulou
, p. 92 (1936)
-
Oxidative cleavage of cycloalkenes using hydrogen peroxide and a tungsten-based catalyst: Towards a complete mechanistic investigation
Cousin, Tony,Chatel, Gregory,Andrioletti, Bruno,Draye, Micheline
, p. 235 - 242 (2021)
The identification of the intermediates and by-products produced during the oxidative cleavage of cycloalkenes in the presence of H2O2 and a tungsten-based catalyst for the production of dicarboxylic acids has been carried out under various experimental conditions. On the basis of this mechanistic investigation and previous studies from the literature, a complete reaction scheme for the formation of the reaction products and by-products is proposed. In this hypothetical mechanism, the production of a hydroperoxyalcohol intermediate accounts for the two pathways proposed by Noyori and Venturello for the formation of the targeted dicarboxylic acid. In addition, Baeyer-Villiger oxidation of the mono-aldehyde intermediate allows explaining the formation of short chain diacids observed as by-products during the reaction. Hence, the proposed mechanism constitutes a real tool for scientists looking for a better understanding and those heading to set up environmentally friendly conditions for the oxidative cleavage of cycloalkenes.
Electron-transfer Oxidation of Organic compounds. Part 5. Oxidation of cyclohexanone by the Tris-2,2'-bipyridylruthenium(III) Cation
Audsley, Adrian J.,Quick, Geoffrey R.,Littler, John S.
, p. 557 - 560 (1980)
Evidence is presented, from kinetic and product studies, that the rate-determining step in the oxidation of cyclohexanone by the trisbipyridylruthenium(III) cation is a non-bonded electron-transfer process from the enol form of the substrate.This gives rise to a free radical and a ruthenium(II) species.The subsequent fate of the radical has been investigated.
Weber,Shepherd
, p. 4907 (1972)
An efficient method for the catalytic aerobic oxidation of cycloalkanes using 3,4,5,6-Tetrafluoro-N-Hydroxyphthalimide (F4-NHPI)
Guha, Samar K.,Ishii, Yasutaka
, p. 327 - 335 (2021/12/13)
N-Hydroxyphthalimide (NHPI) is known to be an effective catalyst for the oxidation of hydrocarbons. The catalytic activity of NHPI derivatives is generally increased by introducing an electron-withdrawing group on the benzene ring. In a previous report, two NHPI derivatives containing fluorinated alkyl chain were prepared and their catalytic activity was investigated in the oxidation of cycloalkanes. It was found that the fluorinated NHPI derivatives showed better yields for the oxidation reaction. As a continuation of our work with fluorinated NHPI derivatives, our next aim was to investigate the catalytic activity of the NHPI derivatives by introducing fluorine atoms in the benzene ring of NHPI. In the present research, 3,4,5,6-Tetrafluoro-N-Hydroxyphthalimide (F4-NHPI) is prepared and its catalytic activity has been investigated in the oxidation of two different cycloalkanes for the first time. It has been found that F4-NHPI showed higher catalytic efficiency compared with that of the parent NHPI catalyst in the present reactions. The presence of a fluorinated solvent and an additive was also found to accelerate the oxidation.
Efficient oxidation of cycloalkanes with simultaneously increased conversion and selectivity using O2 catalyzed by metalloporphyrins and boosted by Zn(AcO)2: A practical strategy to inhibit the formation of aliphatic diacids
Shen, Hai-Min,Wang, Xiong,Ning, Lei,Guo, A-Bing,Deng, Jin-Hui,She, Yuan-Bin
, (2020/11/20)
The direct sources of aliphatic acids in cycloalkanes oxidation were investigated, and a strategy to suppress the formation of aliphatic acids was adopted through enhancing the catalytic transformation of oxidation intermediates cycloalkyl hydroperoxides to cycloalkanols by Zn(II) and delaying the emergence of cycloalkanones. Benefitted from the delayed formation of cycloalkanones and suppressed non-selective thermal decomposition of cycloalkyl hydroperoxides, the conversion of cycloalkanes and selectivity towards cycloalkanols and cycloalkanones were increased simultaneously with satisfying tolerance to both of metalloporphyrins and substrates. For cyclohexane, the selectivity towards KA-oil was increased from 80.1% to 96.9% meanwhile the conversion was increased from 3.83 % to 6.53 %, a very competitive conversion level with higher selectivity compared with current industrial process. This protocol is not only a valuable strategy to overcome the problems of low conversion and low selectivity lying in front of current cyclohexane oxidation in industry, but also an important reference to other alkanes oxidation.
Novel WO3/SO42--ZrO2–TiO2 double bridge coordination catalyst hfor oxidation of cyclohexene
Liu, Xiangxue,Wang, Ke,Liu, Baoquan,Guo, Zhenmei,Zhang, Chao,Lv, Zhiguo
, (2021/05/19)
A solid super acid WO3/SO42--ZrO2–TiO2 catalyst was prepared with adjustable acidity via double bridge connection strategy for oxidation of cyclohexene (CHE) to adipic acid (AA). XRD, SEM and N2 adsorption-desorption isotherm indicated that WO3 was successfully decorated and was highly dispersed on SO42--ZrO2–TiO2 surface. An obvious stretching vibration peak (1125-1055 ?cm?1) in FT-IR illustrated that connection effect between SO42? and ZrO2–TiO2 was double bridge connection. NH3-TPD profile appeared a strong acid center peak (516 ?°C), while this center of solid super acid catalyst could reduce decomposition rate of H2O2 directly, and increase reaction time between CHE and H2O2 meanwhile. The marked catalytic performance was attributed to the synergistic effect between WO3 and SO42--ZrO2–TiO2. DFT calculation was employed to further analyze reaction process and system energy.