Heterogeneous catalytic reduction of substituted 5-acyl-1,3-dioxanes

Objectives. To study the hydrogenation of substituted 5-acyl-1,3-dioxanes in the presence of metal-containing catalysts (Pt/Re, Pd/C, Ni/kieselguhr, and Ni/Mo).

Methods. In order to determine the qualitative and quantitative composition of the reaction masses, the following analysis methods were used: gas-liquid chromatography (using the Kristall 2000 hardware complex); mass-spectroscopy (using Chromatec-Kristall 5000M device with NIST 2012); nuclear magnetic resonance (NMR) spectrometry (using Bruker AM-500 device with operating frequencies of 500 and 125 MHz).

Results. Hydrogenation of substituted 5-acyl-1,3-dioxanes obtained by condensation of carbonyl compounds with paraformaldehyde and sulfuric acid was used to synthesize heterocyclic alcohols in the presence of metal-containing catalysts with a conversion of the initial ketones of 60–90% and a formation selectivity of target products of 70–90%. Substances were analyzed and confirmed by gas-liquid chromatography, mass spectrometry and NMR spectroscopy.

Conclusions. The best catalyst for the reduction of substituted 5-acyl-1,3-dioxanes is Pd/C. By using this catalyst, it is possible to achieve a high selectivity for the formation of the corresponding heterocyclic alcohols at a conversion rate of the initial ketones of 60–90%.

1. Gafarov N.A., Kushnarenko V.M., Bugai D.E. Ingibitory korrozii: v 2 t. T. 2. Diagnostika i zashchita ot korrozii pod napryazheniem neftegazopromyslovogo oborudovaniya (Corrosion Inhibitors: in 2 v. V. 2. Diagnostics and Protection against Corrosion under Stress of Oil and Gas Equipment). Moscow: Khimiya; 2002. 367 p. (in Russ.).

2. Yakovenko E.A., Baimurzina Yu.L., Raskil’dina G.Z., Zlotskii S.S. Synthesis and herbicidal and antioxidant activity of a series of hetero- and carbocyclic derivatives of monochloroacetic acid. Russ. J. Appl. Chem. 2020;93(5):712–720. https://doi.org/10.1134/S1070427220050122

3. Kuz’mina, U.S., Raskil’dina, G.Z., Ishmetova, D.V., et al. Cytotoxic activity against SH-SY5Y neuroblastoma cells of heterocyclic compounds containing gemdichlorocyclopropane and/or 1,3-dioxacycloalkane fragments. Pharm. Chem. J. 2022;55(12):1293–1298. https://doi.org/10.1007/s11094-022-02574-6 [Original Russian Text: Kuz’mina, U.S., Raskil’dina, G.Z., Ishmetova, D.V., et al. Cytotoxic activity against SH-SY5Y neuroblastoma cells of heterocyclic compounds containing gem-dichlorocyclopropane and/or 1,3-dioxacycloalkane fragments. Khimiko-Farmatsevticheskii Zhurnal. 2022;55(12):27–32 (in Russ.). https://doi.org/10.30906/0023-1134-2021-55-12-27-32 ]

4. Maximov A.L., Nekhaev A.I., Ramazanov D.N. Ethers and acetals, promising petrochemicals from renewable sources. Pet. Chem. 2015;55(1):1–21. https://doi.org/10.1134/S0965544115010107 [Original Russian Text: Maximov A.L., Nekhaev A.I., Ramazanov D.N. Ethers and acetals, promising petrochemicals from renewable sources. Neftekhimiya. 2015;55(1):3–24 (in Russ.). https://doi.org/10.7868/S0028242115010104 ]

5. Samoilov V., Goncharova A., Zarezin D., Kniazeva M., Ladesov A., Maximov A. Bio-based solvents and gasoline components from renewable 2,3-butanediol and 1,2-propanediol: synthesis and characterization. Molecules. 2020; 25(7):1723. https://doi.org/10.3390/molecules25071723

6. Zlotskij S.S., Lesnikova E.T., Rachmankulov D.L., Timpe H.-J. Synthese von 5-Hydroxyalkyl- und 5-Alkenyl1,3-dioxanen. Z. Chem. 1990;30(8):281–282. https://doi.org/10.1002/zfch.19900300804

7. Borisova Y.G., Musin A.I., Yakupov N.V., Daminev R.R., Zlotskii S.S. Pd/C-catalyzed hydrogenation of substituted 5-acyl-1,3-dioxanes. Russ. J. Gen. Chem. 2021;91(9):1619–1622. https://doi.org/10.1134/S1070363221090036

8. Golosman E.Z., Efremov V.N. Industrial catalysts for the carbon oxides hydrogenation. Kataliz v promyshlennosti = Сatalysis in Industry. 2012;(5):36–55 (in Russ.).

9. Oosthuizen R.S., Nyamori V.O. Carbon nanotubes as supports for palladium and bimetallic catalysts for use in hydrogenation reactions. Platinum Metals Rev. 2011;55(3):154–169. https://doi.org/10.1595/147106711X577274

10. Khazipova A.N., Grigor’eva N.G., Korzhova L.F., Kutepov B.I. Hydrogenation of α-methylstyrene linear dimers in the presence of Pd- and Ni-containing catalysts. Russ. J. Appl. Chem. 2009;82(6):1065–1069. https://doi.org/10.1134/S1070427209060251

11. Mironenko R.M., Lavrenov A.V. An essay on the history of catalytic hydrogenation of organic compounds. From P. Sabatier and V.N. Ipatieff to the present days. Kataliz v promyshlennosti = Сatalysis in Industry. 2021;21(4):259–273 (in Russ.). https://doi.org/10.18412/1816-0387-2021-4-259-273

12. Karimov O.Kh. Purification of isoprene from acetylene impurities on the nickel catalyst. Promyshlennoe proizvodstvo i ispol’zovanie elastomerov = Industrial Production and Use Elastomers. 2019;(1):3–5 (in Russ.). https://doi.org/10.24411/2071-8268-2019-10101

13. Belyi A.S., Smolikov M.D., Kir’yanov D.I., Udras I.E. Modern views on the state of platinum in supported catalysts for production of motor fuels. Russ. J. Gen. Chem. 2007;77(12):2243–2254. https://doi.org/10.1134/S1070363207120298 [Original Russian Text: Belyi A.S., Smolikov M.D., Kir’yanov D.I., Udras I.E. Modern views on the state of platinum in supported catalysts for production of motor fuels. Rossiiskii Khimicheskii Zhurnal. 2007;51(4):38–47 (in Russ).]

14. Millan-Agorio M., Ramires T., Bermudes J.M., Puron G., Pinilla J.L. Crude oil refining catalyst and method of producing same: Pat. Application number PCT/RU20 15/000546. Publ. 02.02.2017.

15. Kaluža L. Activity of transition metal sulfides supported on Al2 O3 , TiO2 and ZrO2 in the parallel hydrodesulfurization of 1-benzothiophene and hydrogenation of 1-methyl-cyclohex- -1-ene. React. Kinet. Mech. Cat. 2015;114(2):781–794. https://doi.org/10.1007/s11144-014-0809-9

16. Touchy A.S., Hakim Siddiki S.M., Kon K., Shimizu K. Heterogeneous Pt catalysts for reductive amination of levulinic acid to pyrrolidones. ACS Catalysis. 2014;4(9):3045–3050. https://doi.org/10.1021/CS500757K

17. Sharova E.S., Faleev S.A., Ivanchina E.D., Gingazova M.S., Poluboyartsev D.S., Kravtsov A.V. Dynamics of properties of Pt-reforming catalysts in industrial operation. Kataliz v promyshlennosti = Сatalysis in Industry. 2013;(3):48–53 (in Russ).

18. Mao Z., Gu H., Lin X. Recent advances of Pd/C-catalyzed reactions. Catalysts. 2021;11(9):1078. https://doi.org/10.3390/catal11091078

19. Du R., Zhu C., Zhang P., Fan R. Selective hydrogenation of aromatic aminoketones by Pd/C сatalysis. Synthetic Communications. 2008;38(17):2889–2897. https://doi.org/10.1080/00397910801993719