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Highly Selective Vapor and Liquid Phase Transfer Hydrogenation of Diaryl and Polycyclic Ketones with Secondary Alcohols in the Presence of Magnesium Oxide As Catalyst

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Highly Selective Vapor and Liquid Phase Transfer Hydrogenation of Diaryl and Polycyclic Ketones with Secondary Alcohols in the Presence of Magnesium Oxide As Catalyst catalysts Article Highly Selective Vapor and Liquid Phase Transfer Hydrogenation of Diaryl and Polycyclic Ketones with Secondary Alcohols in the Presence of Magnesium Oxide as Catalyst Marek Gli ´nski*, Anna Markowska, Laura Wro ´nska , Anna Jerzak and Magdalena Tarkowska Faculty of Chemistry, Warsaw University of Technology, 00-664 Warsaw, Poland; [email protected] (A.M.); [email protected] (L.W.); [email protected] (A.J.); [email protected] (M.T.) * Correspondence: [email protected] Abstract: MgO has been shown to catalyze an almost quantitative hydrogen transfer from 2-octanol as the hydrogen donor to benzophenone to form benzhydrol, a useful intermediate product in the pharmaceutical industry. The hydrogen transfer from a series of alcohols to the carbonyl group of benzophenone, its ten derivatives, four polycyclic ketones, and 2-naphthyl phenyl ketone was carried out in liquid (LP) or vapor phase (VP). The dependence of reactivity on the structure of the hydrogen donor, reaction temperature, donor-acceptor ratio, amount of catalyst, and the type and position of substituents has been established. For both reaction modes, optimal conditions for selective synthesis Citation: Gli´nski,M.; Markowska, of the alcohols were determined and side reactions were investigated. The results indicate that the A.; Wro´nska,L.; Jerzak, A.; Tarkowska, M. Highly Selective reactivity of the ketone is suppressed by the presence of a methyl substituent in the ortho position to Vapor and Liquid Phase Transfer a much greater extent in LP mode. A scale-up was demonstrated in the liquid phase mode. Hydrogenation of Diaryl and Polycyclic Ketones with Secondary Keywords: magnesium oxide; transfer hydrogenation; benzophenones; 2-octanol; selective reduction Alcohols in the Presence of Magnesium Oxide as Catalyst. Catalysts 2021, 11, 574. https://doi.org/10.3390/ 1. Introduction catal11050574 Much attention in research is focused on transfer hydrogenation reactions on dif- ferent catalysts [1–4]. Although multiple studies using complex catalytic systems which Academic Editor: Valeria La Parola include magnesium compounds have been recently reported [5,6] pure MgO is known for its basicity and is therefore able to serve as a catalyst for multiple reactions without any Received: 15 April 2021 additives [7]. It is a cheap, nontoxic solid, which is easily separated from the post reaction Accepted: 27 April 2021 Published: 29 April 2021 mixture and can be reused. MgO has also been shown to catalyze transfer hydrogenation reactions of various carbonyl compounds into alcohols [8–13]. Similarly, other oxides, such Publisher’s Note: MDPI stays neutral as ZrO2 [14–16] and Al2O3 [17], zeolites [18,19], as well as other systems [20–26] have been with regard to jurisdictional claims in found to be active catalysts in hydrogen transfer. Reviews of the catalysts studied in such published maps and institutional affil- reactions are available in the literature [27,28]. Ethanol is often used as the hydrogen donor iations. because it is cheap and easily available, although other alcohols are good alternatives. In the current paper, only secondary alcohols were studied and the scale-up is performed with 2-octanol, whose industrial synthesis requires the use of a sole raw material; namely, Castor Oil, a product of plant origin. These heterogeneous catalysts are environmentally friendly and can be applied in one-pot organic synthesis reactions which do not require Copyright: © 2021 by the authors. Licensee MDPI, Basel, Switzerland. the use of toxic and corrosive solvents, gaseous hydrogen under pressure, or expensive, This article is an open access article moisture-sensitive and often hazardous hydride reagents. Moreover, they do not pro- distributed under the terms and duce inorganic salts as waste and reactions can be carried out in the vapor phase mode conditions of the Creative Commons under flowing conditions which is recommended by the rules of Green Chemistry [29]. Attribution (CC BY) license (https:// An additional benefit of implementing this method, is that the obtained product is pure creativecommons.org/licenses/by/ and the solid catalyst is easily separated from the post-reaction mixture. High selectiv- 4.0/). ity of the reaction and ease of purification of a compound is especially important in the Catalysts 2021, 11, 574. https://doi.org/10.3390/catal11050574 https://www.mdpi.com/journal/catalysts Catalysts 2021, 11, 574 2 of 16 pharmaceutical industry, in which benzhydrol is commonly used in the production of, e.g., antihistamines. Reduction of carbonyl compounds has been one of the most fundamental processes in organic chemistry [30,31]. It is usually carried out in the presence of catalysts containing transition metals deposited onto a support, and pressurized gaseous dihydrogen is used as a reducing agent. A second common method of reducing a carbonyl group is the use of metal hydrides; mainly sodium borohydride. This compound, due to its mild reactivity, reduces carbonyl compounds in a water-alcohol solution instead of anhydrous ether solutions, which is a very convenient and an important simplification of the method of reduction. However, both these methods have disadvantages such as the risks associated with the use of gaseous hydrogen under pressure, expensive, moisture-sensitive and hazardous hydride reagents, inorganic salts as waste, and often the need for toxic and corrosive solvents. The Meerwein–Ponndorf–Verley (MPV) reduction of aldehydes and ketones, a third method, is a classic example of a homogeneous route of hydrogen transfer reaction, which has been implemented to obtain various alcohols synthesized under mild conditions. A big advantage of the method is its selectivity, which enables a chemoselective reduction of α,β-unsaturated carbonyl compounds into unsaturated alcohols [32]. However, a major drawback of the method is the requirement to work in an anhydrous environment and the necessity to use a stoichiometric amount of aluminium alkoxides. In contrast to the previously described methods a heterogeneous route of MPV reduc- tion is freed from the abovementioned disadvantages and truly offers a green procedure for the synthesis of various alcohols. Catalytic transfer hydrogenation has been used in the reduction of many types of aldehydes and ketones: saturated [20,33,34], cyclic [21,35,36] and aralkyl [18,37,38], as well as α,β-unsaturated [8–10,39–42]. Although various carbonyl compounds have been reduced by this method, no systematic study of the reduction of diaryl ketones has been performed. Only benzophenone has been described in literature as the hy- drogen acceptor. Ramana and Pillai have studied the reduction of the ketone in gas phase over alumina doped with Na+ cations [43]. At 573 K and with the 2-propanol to benzophenone molar ratio (D/A) of 10, a 70% yield of benzhydrol has been observed. Vapour-phase transfer hydrogenation (TH) of benzophenone with 2-propanol (D/A = 3) has also been studied by Jyothi et al. [44]. At 473 K, in the presence of 6MgO·Al2O3 catalyst, 31% yield of benzhydrol has been noted. Hydrous zirconia, ZrO2·nH2O has shown a very high activity in TH of benzophenone with 2-propanol [45]. In its presence a quantitative yield of benzhydrol has been attained after 10 h of refluxing. On the other hand, very low activity of 2MgO·Al2O3 catalyst in the mentioned reaction with 2-propanol has been observed by Ruiz et al. After 24 h and at D/A = 30, a 4% yield of product has been found [20]. In the present work a thorough investigation of the reactivity of sixteen aromatic carbonyl compounds in the hydrogen transfer reduction by alcohols over magnesium oxide as the catalyst either in liquid or in vapor phase has been performed. The studied compounds were benzophenone and its ten derivatives, as well as four polycyclic ketones containing a benzene moiety, and 2-naphthyl phenyl methanone. The reduction of halogen containing derivatives of benzophenone and also 4-nitrobenzophenone was tested in order to determine if dehalogenation/denitrogenation reaction, which, very often accompanying the reduction of these compounds with a gaseous hydrogen in the presence of metallic catalysts, takes place under these reaction conditions. A broad spectrum of secondary alcohols as hydrogen donors from 2-propanol to 2-octanol was used due to the expected moderate reactivity of diaryl ketones in the liquid phase mode of TH reaction. 2. Results and Discussion 2.1. The Catalyst 2 −1 The specific surface area of the catalyst precursor, i.e., Mg(OH)2, is 30.4 m ·g and the pore volume is 0.17 cm3·g−1. Structural examination by powder X-ray diffraction has shown that the precursor comprises a single phase: as synthesized, the magnesium Catalysts 2021, 11, 574 3 of 17 2.1. The Catalyst Catalysts 2021, 11, 574 3 of 16 The specific surface area of the catalyst precursor, i.e., Mg(OH)2, is 30.4 m2·g−1 and the pore volume is 0.17 cm3·g−1. Structural examination by powder X-ray diffraction has shown that the precursor comprises a single phase: as synthesized, the magnesium hy- hydroxidedroxide crystalizes crystalizes in thein the trigonal trigonal system, system, in in the the P3m1P3m1 space group group as as exhibited exhibited by by brucite. brucite.The The TG-DTA TG-DTA analysis analysis revealed revealed that that Tmax T formax thefor decomposition the decomposition of Mg(OH) of Mg(OH)2 is 692.22 is K and 692.2 Kthe and weight the weight loss (320–873 loss (320–873 K) 30.61% K) 30.61% (exp), (exp),30.89% 30.89% (calc).(calc). The specificThe specific surface surface area area and and pore pore volume volume determined determined for for the the calcined calcined catalyst, MgO, MgO,were 129.2 129.2 m m22·g·g−1− and1 and 0.40 0.40 cm cm3·g−31·,g respectively.−1, respectively.
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