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Pd-catalyzed transfer hydrogenolysis of benzylic alcohol in acidic 2-propanol

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Abstract

The hydrogenolysis of 1-phenylethanol over supported palladium catalyst (Pd/SiO2, Pd/C, Pd/Al2O3, Pd/MgO, or Pd/hydroxyapatite) in 2-propanol under reflux conditions (82 °C) was investigated. The effects of nine diffrent acid additives (formic acid, acetic acid, lactic acid, pyruvic acid, oxalic acid, malonic acid, succinic acid, malic acid, or p-toluenesulfonic acid) were also examined. Ethylbenzene and acetophenone were both produced in the presence of the acid additives; however, only acetophenone was produced in the absence of acid additive. Selectivity for ethylbenzene tended to increase with increasing acid strength of the additive, although there were some exceptions. The highest ethylbenzene selectivity (73.6%) was achieved over Pd/C catalyst in the presence of formic acid, and moderate selectivity (43–46%) was achieved over all of the Pd catalysts in the presence of oxalic acid. Deuterium-labeling experiments revealed a reaction pathway involving a hydrogen-transfer process, in which 2-propanol, formic acid, and 1-phenylethanol function as hydrogen donors.

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References

  1. Johnstone RAW, Wilby AH, Entwistle ID (1985) Heterogeneous catalytic transfer hydrogenation and its relation to other methods for reduction of organic compounds. Chem Rev 85:129–170

    Article  CAS  Google Scholar 

  2. Alonso F, Riente P, Yus M (2011) Nickel nanoparticles in hydrogen transfer reactions. Accounts Chem Res 44:379–391

    Article  CAS  Google Scholar 

  3. Gilkey MJ, Xu B (2016) Heterogeneous catalytic transfer hydrogenation as an effective pathway in biomass upgrading. ACS Catal 6:1420–1436

    Article  CAS  Google Scholar 

  4. Jin X, Yin B, Xia Q, Fang T, Shen J, Kuang L, Yang C (2019) Catalytic transfer hydrogenation of biomass-derived substrates to value-added chemicals on dual-function catalysts: Opportunities and challenges. Chemsuschem 12:71–92

    Article  CAS  Google Scholar 

  5. Shafaghat H, Lee IG, Jae J, Jung SC, Park YK (2019) Pd/C catalyzed transfer hydrogenation of pyrolysis oil using 2-propanol as hydrogen source. Chem Eng J 377:119986

    Article  CAS  Google Scholar 

  6. Shafaghat H, Tsang YF, Jeon JK, Kim JM, Kim Y, Kim S, Park YK (2020) In-situ hydrogenation of bio-oil/bio-oil phenolic compounds with secondary alcohols over a synthesized mesoporous Ni/CeO2 catalyst. Chem Eng J 382:122912

    Article  CAS  Google Scholar 

  7. Kim M, Ha JM, Lee KY, Jae J (2016) Catalytic transfer hydrogenation/hydrogenolysis of guaiacol to cyclohexane over bimetallic RuRe/C catalysts. Catal Comm 86:113–118

    Article  CAS  Google Scholar 

  8. Nagpure AS, Gogoi P, Lucas N, Chilukuri SV (2020) Novel Ru nanoparticle catalysts for the catalytic transfer hydrogenation of biomass-derived furanic compounds. Sustain Energ Fuels 4:3654–3677

    Article  CAS  Google Scholar 

  9. Musolino MG, Scarpino LA, Mauriello F, Pietropaolo R (2009) Selective transfer hydrogenolysis of glycerol promoted by palladium catalysts in absence of hydrogen. Green Chem 11:1511–1513

    Article  CAS  Google Scholar 

  10. Nie R, Peng X, Zhang H, Yu X, Lu X, Zhou D, Xia Q (2017) Transfer hydrogenation of bio-fuel with formic acid over biomass-derived N-doped carbon supported acid-resistant Pd catalyst. Catal Sci Technol 7:627–634

    Article  CAS  Google Scholar 

  11. Du J, Zhang J, Sun Y, Jia W, Si Z, Gao H, Tang X, Zeng X, Lei T, Liu S, Lin L (2018) Catalytic transfer hydrogenation of biomass-derived furfural to furfuryl alcohol over in-situ prepared nano Cu-Pd/C catalyst using formic acid as hydrogen source. J Catal 368:69–78

    Article  CAS  Google Scholar 

  12. Zeng Y, Wang Z, Lin W, Song W, Christensen JM, Jensen AD (2016) Hydrodeoxygenation of phenol over Pd catalysts by in-situ generated hydrogen from aqueous reforming of formic acid. Catal Comm 82:46–49

    Article  CAS  Google Scholar 

  13. Zakzeski J, Bruijnincx PCA, Jongerius AL, Weckhuysen BM (2010) The catalytic valorization of lignin for the production of renewable chemicals. Chem Rev 110:3552–3599

    Article  CAS  Google Scholar 

  14. Sawadjoon S, Lundstedt A, Samec JSM (2013) Pd-catalyzed transfer hydrogenolysis of primary, secondary, and tertiary benzylic alcohols by formic acid: a mechanistic study. ACS Catal 3:635–642

    Article  CAS  Google Scholar 

  15. Afewerki S, Palo-Nieto C, Cordova A (2020) Efficient heterogeneous palladium-catalyzed transfer hydrogenolysis of benzylic alcohols by formic acid. Synthesis 52:2330–2336

    Article  CAS  Google Scholar 

  16. Liu X, Lu G, Guo Y, Guo Y, Wang Y, Wang X (2006) Catalytic transfer hydrogenolysis of 2-phenyl-2-propanol over palladium supported on activated carbon. J Mol Catal A 252:176–180

    Article  CAS  Google Scholar 

  17. Feng J, Yang C, Zhang D, Wang J, Fu H, Chen H, Li X (2009) Catalytic transfer hydrogenolysis of α-methylbenzyl alcohol using palladium catalysts and formic acid. Appl Catal A 354:38–43

    Article  CAS  Google Scholar 

  18. Mao H, Liao X, Shi B (2011) Highly active and selective catalytic transfer hydrogenolysis of α-methylbenzyl alcohol catalyzed by supported Pd catalyst. Catal Comm 12:1177–1182

    Article  CAS  Google Scholar 

  19. Gross BH, Mebane RC, Armstrong DL (2001) Transfer hydrogenolysis of aromatic alcohols using Raney catalysts and 2-propanol. Appl Catal A 219:281–289

    Article  CAS  Google Scholar 

  20. Ukisu Y, Miyadera T (1997) Hydrogen­transfer hydrodehalogenation of aromatic halides with alcohols in the presence of noble metal catalysts. J Mol Catal A 125:135–142

    Article  CAS  Google Scholar 

  21. Ukisu Y (2015) Preparation of silica-supported Pd nanoparticle catalysts by an alcohol reduction method and evaluation of their catalytic properties in the dechlorination of an aromatic chloride. React Kinet Mech Catal 114:385–394

    Article  CAS  Google Scholar 

  22. Ukisu Y (2019) Hydrogen-transfer hydrodehalogenation of aromatic halides with a silica-supported palladium catalyst in alkaline 2-propanol: comparison between brominated and chlorinated anisoles. React Kinet Mech Catal 128:41–52

    Article  CAS  Google Scholar 

  23. Mori K, Hara T, Mizugaki T, Ebitani K, Kaneda K (2004) Hydroxyapatite-supported palladium nanoclusters: a highly active heterogeneous catalyst for selective oxidation of alcohols by use of molecular oxygen. J Am Chem Soc 126:10657–10666

    Article  CAS  Google Scholar 

  24. Thakar N, Polder NF, Djanashvili K, van Bekkum H, Kapteijin F, Moulijn JA (2007) Deuteration study to elucidate hydrogenolysis of benzylic alcohols over supported palladium catalysts. J Catal 246:344–350

    Article  CAS  Google Scholar 

  25. Saito Y, Yamashita M, Ito E, Meng N (1994) Hydrogen production from 2-propanol as a key reaction for a chemical heat pump with reaction couple of 2-propanol dehydrogenation/acetone hydrogenation. Int J Hydrogen Energy 19:223–226

    Article  CAS  Google Scholar 

  26. Ukisu Y, Miyadera T (2004) Dehydrogenation of 2-propanol with suspended noble metal catalysts: activity enhancement by the addition of sodium hydroxide. React Kinetic Catal Lett 81:305–311

    Article  CAS  Google Scholar 

  27. Ukisu Y, Miyadera T (2003) Hydrogen-transfer hydrodechlorination of polychlorinated dibenzo-p-dioxins and dibenzofurans catalyzed by supported palladium catalysts. Appl Catal B 40:141–149

    Article  CAS  Google Scholar 

  28. Stanislaus A, Cooper BH (1994) Aromatic Hydrogenation Catalysis: a review. Catal Rev 36:75–123

    Article  CAS  Google Scholar 

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Acknowledgements

The author gratefully acknowledges financial support from the National Institute of Advanced Industrial Science and Technology, Japan.

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  1. National Institute of Advanced Industrial Science and Technology (AIST), AIST Tsukuba West, 16-1 Onogawa, Tsukuba, Ibaraki, 305-8569, Japan

    Yuji Ukisu

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Correspondence to Yuji Ukisu.

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Ukisu, Y. Pd-catalyzed transfer hydrogenolysis of benzylic alcohol in acidic 2-propanol. Reac Kinet Mech Cat 134, 273–283 (2021). https://doi.org/10.1007/s11144-021-02063-z

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