Aqueous Solutions of Mo‐V‐Phosphoric Heteropoly Acids as Bifunctional Catalysts For Preparation of 9,10‐Anthraquinone and its Hydrogenated Derivatives

Жижина, Е. Г.; Odyakov, V. F.

doi:10.1002/cctc.201200039

Cited by 22 publications

(6 citation statements)

References 22 publications

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“…As we have already mentioned [4,5], when we performed the one-pot process under P = 0.1 MPa and at T = 80˚C -90˚C without organic solvents or in the presence of solvents poorly mixing with water, we obtained the mixtures of 4 products (traces NQ + THA + DHA + AQ), AQ content never being higher than 50%. To solve problem of maximizing the AQ yield and purity in the onepot synthesis, we tried to optimize its conditions.…”

Section: Resultsmentioning

confidence: 67%

“…Earlier [4,5] we suggested to use the aqueous solutions of Mo-V-P heteropoly acids (HPA), which are simultaneously acid catalysts and oxidizers, to produce AQ via 1,4-naphthoquinone reaction with 1,3-butadiene. Using of HPA solutions as bifunctional catalysts allows to carry out the AQ synthesis as a one-pot process (See Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

“…In the previous studies [4,5] butadiene reaction with NQ in the HPA solution is shown to yield the product mixtures containing AQ and its partially hydrogenated derivatives THA and 1,4-dihydroAQ (DHA). With this regard, in the present work we tried to optimize the onepot process to obtain practically pure AQ.…”

Section: Introductionmentioning

confidence: 99%

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One-Pot Process of Anthraquinone Synthesis in the Presence of Mo-V-P Heteropoly Acid Solutions as a Bifunctional Catalysts

Gogin¹,

Жижина²

2013

MRC

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Acid-catalytic 1,3-butadiene condensation with para-quinones followed by the obtained product oxidation may be performed in one stage as one-pot process, if assisted by the aqueous solutions of Mo-V-P heteropoly acids with a composition of H a P z Mo y V x O b. 1,4-naphthoquinone condensation with 1,3-butadiene in the HPA solutions with no organic solvents yields 9,10-anthraquinone (AQ) mixed with tetrahydro-AQ (THA) and dihydro-AQ (DHA). However, AQ yield and its purity may be considerably improved by using water-mixable organic solvents, e.g., acetone, 1,4-dioxane, as well as high vanadium content HPA such as H 15 P 4 Mo 18 V 7 O 89 and H 17 P 3 Mo 16 V 10 O 89. Process optimization provides 70% yield of reaction product containing no less than 90% AQ.

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Section: Resultsmentioning

confidence: 67%

Section: Introductionmentioning

confidence: 99%

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One-Pot Process of Anthraquinone Synthesis in the Presence of Mo-V-P Heteropoly Acid Solutions as a Bifunctional Catalysts

Gogin¹,

Жижина²

2013

MRC

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“…The aqueous solutions of Мо‐V‐phosphoric heteropolyacids (HPA) and their acid salts are widely used as homogeneous catalysts for oxidation or oxidative dehydrogenation of different organic substrates by molecular oxygen :

\begin{matrix} true \\ right Su + \frac{1}{2} O_{2} \overset{HPA - italicx}{} SuO \end{matrix}

…”

Section: Introductionmentioning

confidence: 99%

“…At that, the HPA accepts m electrons reducing to an H m HPA. At stage (3), the H m HPA solution is oxidized by O 2 with the regeneration of the HPA solution :

\begin{matrix} true \\ right \frac{m}{2} Su + \frac{m}{2} H_{2} normalO + HPA \to \frac{m}{2} SuO + H_{m} HPA \end{matrix}

\begin{matrix} true \\ right H_{m} HPA + \frac{m}{4} O_{2} \to HPA + \frac{m}{2} H_{2} normalO \end{matrix}

…”

Section: Introductionmentioning

confidence: 99%

Regeneration of the Oxidation Catalysts Based on the Aqueous Solutions of Non‐Keggin Mo‐V‐P Heteropoly Acids by Molecular Oxygen

Жижина

Odyakov

2014

Int J of Chemical Kinetics

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Kinetic peculiarities of regeneration of the aqueous solutions of non‐Keggin‐type Mo‐V‐P heteropoly acids HaPzMoyVx′Ob (HPA‐x′) and their acidic salts by O2 are studied. The HPA‐x′ solutions have heightened thermal stability that permits to consider them as highly efficient catalysts for different oxidation processes. In the HPA‐x′ and their salts solutions, these peculiarities prove to be similar. The studied reaction is of the first order with respect to O2 and V(IV), if [V(IV)] is higher than 0.8 M. As [V(IV)] decreases during the reaction, its order with respect to V(IV) increases to the third. The apparent activation energy of the reaction at temperatures 150–170°С is 37.5 kJ mol−1. The obtained kinetic equation was used to calculate a new effective air reactor for the regeneration of the homogeneous HPA‐x′ catalyst in a pilot process of methylethylketone synthesis.

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Mo‐V‐Phosphoric Heteropoly Acids and Their Salts: Aqueous Solution Preparation – Challenges and Perspectives

et al. 2015

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Vanadium‐containing heteropoly acids (HPAs) are effective acidic and oxidizing catalysts in various reactions. The existing wide application of such catalysts requires their safe, waste‐free, and easy preparation on a large scale. Unfortunately, the so‐called ether method, first suggested more than 100 years ago, is still mainly used for the purpose, producing a lot of harmful waste material. Nowadays environmental safety requirements necessitate revision of such preparation processes and searching for alternative methods of synthesis. At present, there exist a range of new methods for preparing HPAs, with a so‐called peroxide method seeming to be the most generally applicable one. For this reason, the aim of this review is to discuss some recent progress in obtaining aqueous solutions of Keggin and Wells–Dawson Mo‐V‐P HPAs and their salts. These solutions can be used as individual homogeneous oxidation catalysts, bifunctional catalysts for one‐pot acidic and oxidizing transformations, or precursors for preparing their heterogeneous analogues.

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Aqueous Solutions of Mo‐V‐Phosphoric Heteropoly Acids as Bifunctional Catalysts For Preparation of 9,10‐Anthraquinone and its Hydrogenated Derivatives

Cited by 22 publications

References 22 publications

One-Pot Process of Anthraquinone Synthesis in the Presence of Mo-V-P Heteropoly Acid Solutions as a Bifunctional Catalysts

One-Pot Process of Anthraquinone Synthesis in the Presence of Mo-V-P Heteropoly Acid Solutions as a Bifunctional Catalysts

Regeneration of the Oxidation Catalysts Based on the Aqueous Solutions of Non‐Keggin Mo‐V‐P Heteropoly Acids by Molecular Oxygen

Mo‐V‐Phosphoric Heteropoly Acids and Their Salts: Aqueous Solution Preparation – Challenges and Perspectives

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