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    • 专利摘要:
    Procedure for obtaining aryl ketones. The invention describes a new general process of oxidation or aerobic rupture of compounds having a tertiary carbon directly attached to an aryl group, and polymers based on said structural monomer unit, to provide the corresponding aryl ketone using exclusively molecular oxygen as an oxidizing agent. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2724600A1
    申请号:ES201830218
    申请日:2018-03-06
    公开日:2019-09-12
    发明作者:Gabikaetxebarria Garazi Urgoitia；Faces Raul Sanmartin；Corral María Teresa Herrero；Perez Esther Dominguez
    申请人:Euskal Herriko Unibertsitatea；
    IPC主号:
    专利说明:

    [0001]
    [0002]
    [0003]
    [0004] Field of the Invention
    [0005] The present invention relates to the field of chemical synthesis and the preparation of raw materials, so it is framed in the sectors of the chemical industry and the plastics processing industry. In particular, the invention relates to a general process of oxidation or aerobic breakdown of compounds having a tertiary carbon directly attached to an aryl group, and polymers based on said structural monomer unit to provide the corresponding aryl ketone using exclusively molecular oxygen as an agent. oxidizing
    [0006]
    [0007] Background of the invention
    [0008] The oxidation of tertiary alkylbenzenes to aromatic or mixed ketones (alkyl aryl ketones) is a transformation that requires the oxidative breakage of CC bonds [Brazdil, JF Top. Catal. 2006, 38, 289-294; Shilov, AE; Shul'pin, GB in Activation and catalytic reactions of saturated hydrocarbons in the presence of metal complexes, Kluwer Academic, Dordrecht, Holland, 2002]. Said transformation is usually carried out with strong oxidants, usually hydroperoxide (H2O2, 'BuOO'Bu) [Rebelo, SLH; Simoes, MMQ; Neves, MGPMS; Cavaleiro, JAS J. Mol. Catal. A: Chem. 2003 . 201, 9-22; Estrada, AC; Simoes, MMQ; Adáo, P .; Pessoa, JC; Henriques, RT; Kuznetsov, ML; Avecilla, F .; Maurya, MR; Kumar, U .; Correia, I. Inorg. Chem. 2009 , 48, 3542-3561 ;; Zhu, M .; Wei, X .; Li, B .; Yuan, Y. Tetrahedron Lett. 2007 , 48, 9108-9111; Gao, Y .; Hu, G .; Zhong, J .; Shi, Z .; Zhu, Y .; Su, DS; Wang, J .; Bao, X .; Ma, D. Angew. Chem. Int. Ed. 2013 , 52, 2109-2113] although the use of iodosobenzene has also been described [Lee, NH; Byun, JC; Oh, T.-H. Bull. Korean Chem. Soc. 2005, 26, 454-456] and ozone [Neumann, R .; Khenkin, AM Chem. Commun.
    [0009] 1998 , 1967-1968]. The target ketones are obtained with moderate and variable yields and selectivities in all cases, and usually the only alkylbenzene derivative subjected to such reaction is cumene.
    [0010]
    [0011] Due to its abundance, low cost, environmental benignity and absence of toxic by-products, molecular oxygen is considered as an ideal, clean and economical oxidant. However, the oxidation methods of tertiary alkylbenzene derivatives using molecular oxygen provide in many cases significant amounts of the corresponding hydroperoxides and alcohols, with the degree of selectivity towards ketone formation being low. This occurs both in the presence of metallic catalysts of Ni, Cu, Ir, Co, Fe, etc., [Mu, C .; Huang, K .; Cheng, T .; Wang, H .; Yu, H .; Peng, F. Chem. Eng. J. 2016 , 306, 806-815; Xu, S .; Huang, C .; Zhang, J .; Chen, B. Korean J. Chem. Eng. 2009 , 26, 1568 1573; Yan, Y .; Chen, Y .; Yan, M .; Li, X .; Zeng, W. Cat. Commun. 2013, 35, 64-67; Yi, X.-Y .; Wang, G.-C. Ip, H.-F .; Wong, W.-Y .; Chen, L .; Sung, HH -Y .; Williams, ID; Leung W.-H. Eur. J. Inorg. Chem. 2014 , 6097-6103; Orlinska, B .; Zawadiak, J .; Gilner, D. Appl. Catal. As of 2005 , 287, 68-74] as in his absence [Melone, L .; Gambarotti, C .; Prosperini, S .; Pastori, N .; Recovery, F .; Punta, C. Adv. Synth.Catal. 2011 , 353, 147-154; Liao, S .; Peng, F .; Yu, H .; Wang, H. Appl. Catal. A: General 2014 , 47, 1-8; Chi, Y .; Zhu, M .; Li, Y .; Yu, H .; Wang H .; Peng, F. Catal. Sci. Technol. 2016 , 6, 2396-2402]. It should also be noted that in several cases medium or high pressures (> 4 atm) are necessary for the reaction to occur [Ison, A .; Xu, C .; Weakley, GK; Richardson, DE J. Mol. Chem. A: Chem. 2008 , 293, 1-7]. Only a few isolated examples have been described where an acceptable conversion and selectivity towards the ketone is combined, but in those cases several reaction steps and / or an amount of catalyst greater than 1 mol% have been required. In addition, in these cases there are important restrictions in terms of the structure of the substrates to be oxidatively degraded, limited only to cumene or tertiary 1,1-diarylalkanes [Nakamura, R.; Obora, Y .; Ishii, Y. Chem. Commun. 2008, 3417-3419; Farhadi, s .; Zaringhadama, P .; Sahamieh, RZ Tetrahedron Letters 2006, 47, 1965-1968; Mühldorf, B .; Wolf, R. Chem. Commun. 2015, 51, 8425-8428; Cancino, P .; Vega, A .; Santiago-Portillo, A .; Navalon, S .; Alvaro, M .; Aguirre, P .; Spodine, E .; Garcia, H. Catal. Sci. Technol 2016, 6, 3727-3736; Wittenberg, R .; Pradera, MA; Navio, JA Langmuir 1997, 13, 2373-2379]
    [0012]
    [0013] In some of the state-of-the-art procedures in the field of oxidation or oxidative breakdown of tertiary alkylbenzenes mediated by molecular oxygen, visible light has been used as a photocatalyst or photoactivator of the process [Geer, MF; Walla, MD; Solntsev, KM; Strassert, CA; Shimizu, LS J. Org. Chem. 2013, 78, 5568-5578; Melone, L.; Franchi, P .; Lucarini, M .; Punta, C. Adv. Synth.Catal. 2013, 355, 3210-3220; Lykakis; IN; Orfanopoulos, M. Tetrahedron Lett. 2004, 45, 7645-7649; Ni, L .; Ni, J .; Lv, Y .; Yang, P .; Cao, Y. Chem. Commun. 2009, 2171-2173]. In just one case, said light activation has led to the formation of the corresponding ketone, 10 mol% of a scandium catalyst and riboflavin tetraacetate being required, and the method limited to triphenylmethane and diphenylacetic acid being found as substrates [Mühldorf, B .; Wolf, R. Chem. Commun.2015, 51, 8425-8428].
    [0014]
    [0015] On the other hand, and as is well known in the state of the art, the enormous accumulation of residues of polymeric origin (packaging plastics and construction-assembly material, automotive and electrical components, among others) is a worldwide concern. In relation to this problem, there are reuse or recycling strategies for certain plastics, for example, polyethylene terephthalate (PET), and high density polyethylene (HDPE) [Najafi, SK Waste Manag. 2013, 33, 1898-1905; Zacarias, A .; Pereira, I .; Cerqueira, M. Polym. Degrad Stab. 2012, 97, 1158-1163; Sulyman, M .; Haponiuk, J .; Formela, K. Int. J. Environ. Sci. Technol. 2016, 7, 100-108]. However, for other types of plastics, such as polystyrene, commonly used in containers, utensils, insulation and construction systems, and therefore manufactured on a scale of several million tons per year (polystyrene is the fourth most consumed plastic in the world, behind polyethylene, polypropylene and PVC, and constitutes 8-9% of the world production of plastics), there are no simple reuse methods. In addition, similar to even commonly recycled plastics such as PET, the mechanical recycling cycles supported by polystyrene are very low (3 at most) [Wunsch, JR "Polystyrene: Synthesis, Production and Applications". iSmithers Rapra Publishing, 2000. ISBN 978-1-85957-191-0]. In this sense, another field of research that has received great attention in recent years, due not only to the aforementioned waste problems but also to the excessive dependence on petroleum derivatives, is the use of plastics as a source of new raw materials [ Fortman, DJ, Brutman, JP, Cramer, CJ, Hillmyer, MA, Dichtel, WR J. Am. Chem. Soc . 2015, 137, 14019-14022; García, JM Chem. 2016, 1, 813-815; Helms, BA; Russell, TP Chem2016, 1, 816-818] .However, in the case of polystyrene, despite the research carried out in search of procedures to achieve chemical degradation, the results achieved so far, whether with respect to depolymerization or with regard to other effective transformations that include oxidative degradations, are insufficient in terms of performance and / or selectivity [García, JM Chem. 2016, 1, 813-815; Marczewski, M .; Kaminska, E .; Marczewska, H .; Godek, M .; Rokicki, G .; J. Sokotowski, J. Appl. Catal., B2013, 129, 236-246; Woo, OS; Ayala, N .; Broadbelt, LJ Catal. Today2000, 55, 161-171; Tae, J.-W .; Jang, B.-S .; Kim, K.-H .; Park, D.-W.React.Kinet.Catal.Lett. 2005, 84, 167-174; Yuzawa, T .; Watanabe, C .; Nemoto, N .; Ohtani, H. Polym.Degrad. Stab. 2013, 98, 671-676]. When achieving such degradation, irradiation with gamma rays, ultraviolet light, and visible radiation has also been tested, with similar results [Zan, L., Wang, S .; Fa, W .; Hu, Y .; Tian, L .; Deng, K. Polymer2006, 47, 8155-8162; Crouzet, C .; Marchal, J. Makromol. Chem. 1976, 177, 2819-2832; Balakrishnan, RK; Guria, C. Polym. Degrad Stab 2007, 92, 1583-1591; Nakatani, H .; Miyazaki, K. J. Appl. Polym.Sci. 2013 , 3490-3496; Rabek, JF "Polymer photodegradation", Chapman & Hall, Cambridge, 1995].
    [0016] Thus, the selective transformation of tertiary alkylbenzenes into the corresponding mixed ketones, and in particular, the effective oxidative degradation of polystyrene, a polymer whose structural unit is sec-butylbenzene (tertiary alkylbenzene), in acetophenone is posed as a challenge of great interest, given the global scale at which said polymer is manufactured, its low recyclability, the serious problem of accumulation of waste thereof and the relevance of acetophenone, which can be reused as a raw material. In addition, if these transformations are carried out using molecular oxygen as the only reagent and also at atmospheric pressure, the industrial application of this methodology, both at the productive level and in the plastics recycling-reuse industry is evident.
    [0017] In view of the above, and despite the progress achieved so far, there is still a need to provide an alternative process for the selective transformation of compounds that generally have a tertiary carbon directly attached to an aryl group, such as tertiary alkylbenzenes, in the corresponding aryl ketones. Similarly, there is also a need to provide an alternative process for the effective oxidative degradation of polystyrene, a polymer whose structural unit is sec-butylbenzene (tertiary alkylbenzene), or derivatives thereof, which overcomes at least the disadvantages of the methodologies mentioned above.
    [0018]
    [0019] Compendium of the invention
    [0020]
    [0021] In a first aspect the invention relates to a process, which overcomes at least part of the aforementioned problems, to obtain an aryl ketone comprising treating with oxygen a compound of formula (I)
    [0022]
    [0023]
    [0024]
    [0025]
    [0026] which has at least one tertiary carbon -CH- attached directly to an aryl group (A), and also attached to two carbon atoms (C1) and (C2), of which the first carbon atom (C1) forms part of an aliphatic or aryl group, and the second carbon atom (C2) is part of a group selected from aliphatic, aryl, carbonyl and carboxyl,
    [0027] in the presence of visible light, a vanadium compound, an alkaline salt of an organic acid, and a triazole-derived compound of formula (II)
    [0028]
    [0029]
    [0030]
    [0031] where
    [0032] R and R ’are the same or different from each other, selected from hydrogen, alkyl and aryl; and R ’’ is selected from hydrogen, alkyl, or alkoxycarbonyl (-O-C (O) -R ’’), where R ’’ is alkyl, in a solvent,
    [0033] to obtain said aryl ketone of formula (III)
    [0034]
    [0035]
    [0036] wherein the tertiary carbon has been transformed into a carbonyl group (C = O), and is directly attached to said aryl group (A), and also attached to the first carbon atom (C1) that is part of an aliphatic group or aryl
    [0037]
    [0038] The process of the invention allows to obtain aryl ketones in an advantageous way from an economic, procedural and environmental point of view, and also allows its scaling to a multi-gram scale, so it can be carried out on an industrial scale.
    [0039] Another advantage of the process of the invention is that it not only solves the problem of the absence of effective, general and efficient methods for the oxidative breakdown of derivatives comprising a tertiary carbon directly attached to an aryl group, for example tertiary alkylbenzene derivatives, It also provides a solution to the problem of the lack of protocols for chemical recycling or useful transformation of polystyrene and / or its derivatives, which is closely related to the accumulation of residues of this polymer manufactured in huge quantities worldwide .
    [0040] In addition, the process of the invention provides acetophenone (the simplest alkyl aryl ketone that constitutes a raw material of great interest in the chemical industry) from polystyrene, in addition to some other compounds of interest from tertiary alkylbenzene derivatives, and in general of the starting compounds.
    [0041]
    [0042] Detailed description of the invention
    [0043] The present invention thus relates in a first aspect to a process for obtaining an aryl ketone comprising treating with oxygen a compound of formula (I)
    [0044]
    [0045]
    [0046]
    [0047]
    [0048] which has at least one tertiary carbon -CH- attached directly to an aryl group (A), and also attached to two carbon atoms (C1) and (C2), of which the first carbon atom (C1) forms part of an aliphatic or aryl group, and the second carbon atom (C2) is part of a group selected from aliphatic, aryl, carbonyl and carboxyl,
    [0049] in the presence of visible light, a vanadium compound, an alkaline salt of an organic acid, and a triazole-derived compound of formula (II)
    [0050]
    [0051]
    [0052]
    [0053] R and R ’are the same or different from each other, selected from hydrogen, alkyl and aryl; and R ’’ is selected from hydrogen, alkyl, or alkoxycarbonyl (-O-C (O) -R ’’), where R ’’ is alkyl, in a solvent,
    [0054] to obtain said aryl ketone of formula (III)
    [0055] c and °
    [0056]
    [0057]
    [0058]
    [0059] wherein the tertiary carbon has been transformed into a carbonyl group (C = O), and is directly attached to said aryl group A, and also attached to the first carbon atom (C1) that is part of an aliphatic or aryl group.
    [0060]
    [0061] In the context of the present invention the term "aliphatic" should be broadly understood as an organic group of a non-aromatic nature, composed of carbon and hydrogen, and optionally one or more heteroatoms preferably selected from the group of O, P and 5, cyclic, acyclic or mixed cyclic-acyclic, saturated or unsaturated. The aliphatic group has a variable number of carbon atoms, which varies over a wide range. Thus, in some particular embodiments the aliphatic group corresponds to a methyl radical, and in other embodiments it corresponds to a polymeric polystyrene moiety.
    [0062]
    [0063] In the context of the present invention, the aliphatic term includes, for example, non-limitingly an alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, and a polystyrene or a polystyrene derivative group, as defined in detail below. .
    [0064]
    [0065] Arilo
    [0066] In the context of the present invention the term "aryl" should be understood as a mono-, bi- or tricyclic monovalent aromatic or partially aromatic hydrocarbon ring having 6, 7, 8, 9, 10, 11, 12, 13 or 14 atoms carbon, particularly a ring having 6 carbon atoms, for example a phenyl group, or a ring having 9 carbon atoms, for example an indanyl or indenyl group, or a ring having 10 carbon atoms, for example a tetralinyl, dihydronaphthyl, or naphthyl group, or a ring having 13 carbon atoms, for example a fluorenyl group, or a ring having 14 carbon atoms, for example an anthranyl group, or a phenanthryl group. In the aryl group one or more hydrogens may be substituted by groups that are the same or different from each other selected from hydroxyl sulfonyl, cyano, alkyl, alkenyl, alkynyl, alkoxy, alkylthioxyl, aryloxy, arylthioxyl, heteroaryl, preferably by groups selected from C1-C6 alkyl , hydroxyl, sulfonyl, cyano, C1-C6 alkoxy, and more preferably by C1-C6 alkyl and C1-C6 alkoxy. According to some examples of the invention the aryl is phenyl. According to other examples the aryl is phenyl substituted with a C1-C6 alkyl group. According to other examples of the invention the aryl is naphthyl. According to other examples, the aryl is naphthyl substituted with a C1-C6 alkyl group or with a C1-C6 alkoxy group.
    [0067]
    [0068] I rent
    [0069] The term "alkyl" should be understood as a linear or branched, saturated monovalent hydrocarbon group having more than one carbon atom.
    [0070] In a particular embodiment the alkyl group has 1 to 14 carbon atoms, preferably 1 to 10, more preferably 1 to 6, for example 2, 3, 4 or 5 carbon atoms, such as a methyl, ethyl group, propyl, butyl, pentyl, hexyl, iso-propyl, iso-butyl, sec-butyl, tert-butyl, iso-pentyl. Particularly, said group has 1, 2, 3 or 4 carbon atoms, for example a methyl, ethyl, propyl, butyl, iso-propyl, iso-butyl, sec-butyl, tert-butyl group, more particularly 1, 2 or 3 carbon atoms, for example a methyl, ethyl, n-propyl or iso-propyl group.
    [0071] In the alkyl group one or more hydrogens may be substituted by groups equal or different from each other selected from hydroxyl, sulfonyl, cyano, alkoxy, alkylthioxyl, aryloxy, arylthioxy, cycloalkyl, cycloalkenyl, aryl, heteroaryl, and heterocyclyl, preferably by groups selected from hydroxyl, sulfonyl, cyano, C1-C6 alkoxy.
    [0072] Polystyrene residue
    [0073] In some particular embodiments of the invention, the tertiary -CH-group is part of a polystyrene polymer of the following formula (IV)
    [0074]
    [0075]
    [0076]
    [0077]
    [0078] or of a polystyrene derivative.
    [0079]
    [0080] In the context of the invention, "polystyrene derivative" means a polystyrene of the formula (III) in which one or more hydrogens of the aryl group or of the methylene group -CH 2 - may be substituted by the same or different groups between another selected from hydroxy, sulfonyl, cyano, alkoxy, alquiltioxilo, aryloxy, ariltioxilo, cycloalkyl, cycloalkenyl, aryl, heteroaryl, and heterocyclyl, preferably groups selected from hydroxy, sulfonyl, cyano, C 1 -C 6 -alkyl alkoxy and C 1 - C 6, and most preferably alkyl and C1 - C6 alkoxy C1 - C6. in formula (IV) n is an integer equal to or greater than 1, no particular upper limit, as this depends on the length of the polystyrene chain or derivative thereof.
    [0081]
    [0082] According to the particular embodiments in which the compound that is subjected to the process of the invention is a polystyrene or a polystyrene derivative, the first carbon atom (C 1 ) is part of an aliphatic group, which corresponds to a first moiety. Polystyrene polymer and the second carbon atom (C 2 ) forms part of another aliphatic group, which corresponds to a second polymeric polystyrene moiety, and where the first and second moieties may be the same or different from each other, and in number of monomer units
    [0083]
    [0084] The structure of polystyrene or polystyrene derivative is represented below, where -CH-tertiary groups are marked with an asterisk.
    [0085]
    [0086] - .....- [CH 2 -CH * (A)] n - C1H2-CH * (A) -C2H2 - [CH * (A) -CH 2 ] m -
    [0087] The polymeric moiety thus according to the present invention refers to the structural parts of polystyrene or derivative thereof, to the right and left of the -CH-tertiary, of which (C 1 ) and (C 2 ) form part respectively.
    [0088]
    [0089] In some examples, n and m are an integer, and can be the same or different from each other. In some cases when the tertiary carbon is from a polymer end monomer, n or m is zero. For example, n and / or m may be between 1 and 100, for example be 1, 10, 25, 50, 100, or particularly be between 100 and 2,000, for example, 200, 500, 1,000, 2,000.
    [0090]
    [0091] In a particular embodiment the compound that is subjected to the process of the invention may be a styrene copolymer comprising units of formula (IV) in its structure.
    [0092]
    [0093] Throughout this specification, and unless expressly stated otherwise, the term polystyrene refers to polystyrene and polystyrene derivatives.
    [0094] Alkenyl
    [0095] The term "alkenyl" should be understood as a linear or branched monovalent hydrocarbon group of 1 to 14 carbon atoms, which contains one or more double bonds, and which preferably has 2 to 10 carbon atoms, for example 2, 3, 4, 5 or 6 carbon atoms, particularly 2 or 3 carbon atoms, it being understood that in the case in which said alkenyl group contains more than one double bond, then said double bonds may be isolated or conjugated to each other. alkenyl is, for example, an ethenyl, n-propenyl, i-propenyl, n-butenyl, n-pentenyl, vinyl, or allyl group.
    [0096] In the alkenyl group one or more hydrogens may be substituted by groups that are the same or different from each other selected from hydroxyl, sulfonyl, cyano, alkyl, alkoxy, alkylthioxyl, aryloxy, arylthioxyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, and heterocyclyl groups, preferably by groups selected from hydroxyl, sulfonyl, cyano, C1-C6 alkyl, C1-C6 alkoxy and more preferably by C1-C6 alkyl and C1-C6 alkoxy.
    [0097]
    [0098] Alkynyl
    [0099] The term "alkynyl" should be understood as a linear or branched monovalent hydrocarbon group of 1 to 14 carbon atoms, which contains one or more triple bonds, and which preferably has 2 to 10 carbon atoms, for example 2, 3, 4, 5 or 6 carbon atoms, particularly 2 or 3 carbon atoms, it being understood that in the case in which said alkynyl group contains more than one triple bond, then said triple bonds may be isolated or conjugated to each other. alkynyl is, for example, ethynyl, propynyl (for example, 1-propynyl, 2-propynyl), butynyl (for example, 1-butynyl, 2-butynyl, 3-butynyl), pentinyl (for example, 1-pentinyl, 2 -pentinyl, 3-pentinyl, 4-pentinyl,) hexinyl (for example, 1-hexinyl, 2-hexinyl, 3-hexinyl, 4-hexinyl, 5-hexinyl), methylpropyl, 3-methyl-1-butynyl, 4- methyl-2-heptinyl and 4-ethyl-2-octinyl In the alkynyl group one or more hydrogens may be substituted by the same or different groups from each other selected from hydroxyl, sulfonyl, cyano, alkyl, alkoxy, alkylthioxyl, aryloxy, arylthioxy, cycloalkyl, cycloalkenyl, aryl, heteroaryl, and heterocyclyl, preferably by groups selected from hydroxyl, sulfonyl, cyano, C1-C6 alkyl, C1 alkoxy -C6, and more preferably by C1-C6 alkyl and C1-C6 alkoxy.
    [0100]
    [0101] In the context of the present invention, an alkenyl group or an alkynyl group may have one or more triple or double bonds, in turn respectively.
    [0102]
    [0103] Cycloalkyl
    [0104] The term "cycloalkyl" should be understood as a monovalent saturated mono or bicyclic ring containing 3, 4, 5, 6, 7 or 8 carbon atoms. Said cycloalkyl group is, for example, a monocyclic hydrocarbon ring, for example cyclopropyl, cyclobutyl , cyclopentyl, or cyclohexyl or a bicyclic hydrocarbon ring.In the cycloalkyl group one or more hydrogens may be substituted by groups equal to or different from each other selected from hydroxyl, sulfonyl, cyano, alkyl, alkenyl, alkynyl, alkoxy, alkylthioxyl, aryloxy, arylthioxyl , aryl, heteroaryl, and heterocyclyl, preferably by groups selected from C1-C6 alkyl, hydroxyl, sulfonyl, cyano, C1-C6 alkoxy, and more preferably by C1-C6 alkyl and C1-C6 alkoxy.
    [0105]
    [0106] Cycloalkenyl
    [0107] The term "cycloalkenyl" should be understood as a monovalent mono or bicyclic ring containing 3, 4, 5, 6, 7 or 8 carbon atoms, and at least one or two unsaturations, conjugated or not. Said cycloalkenyl ring is, for example. , cyclopropenyl, cyclobutenyl, cyclopentenyl or cyclohexenyl, where the bond between said ring and the carbon of the -CH-tertiary group can be with any carbon atom of said ring, both saturated and unsaturated. In the cycloalkenyl group one or more hydrogens can be substituted by groups equal or different from each other selected from hydroxyl, sulfonyl, cyano, alkyl, alkenyl, alkynyl, alkoxy, alkylthioxyl, aryloxy, arylthioxy, aryl, heteroaryl, and heterocyclyl, preferably by groups selected from C1-C6 alkyl, hydroxyl, sulfonyl, cyano, C1-C6 alkoxy, and more preferably by C1-C6 alkyl and C1-C6 alkoxy.
    [0108]
    [0109] Heterocyclyl
    [0110] "Heterocyclyl" refers to a stable ring of 3 to 15 members, non-aromatic, consisting of carbon atoms and with one or more heteroatoms, for example 1, 2, 3, 4, or 5 selected from the group consisting in oxygen and sulfur, preferably a 4 to 8 member ring with one or more heteroatoms, for example 1, 2 or 3, more preferably a 5 or 6 member ring with 1, 2 or 3 heteroatoms, and optionally one or more unsaturations , for example 1,2 or 3. For the purposes of this invention, the heterocycle may be a monocyclic, bicyclic or tricyclic ring system, which may include condensed ring systems; and the carbon or sulfur atoms in the heterocyclyl radical may be optionally oxidized; and the heterocyclyl radical may be saturated or partially unsaturated. Examples of such heterocycles include, but are not limited to, oxetane, tiethane, tetrahydrofuran, tetrahydrothiophene, oxirane, oxepane. In the heterocyclyl group one or more hydrogens may be substituted by groups that are the same or different from each other selected from hydroxyl, sulfonyl, cyano, alkyl, alkenyl, alkynyl, alkoxy, alkylthioxyl, aryloxy, arylthioxyl, aryl, heteroaryl, preferably by groups selected from alkyl C1-C6, hydroxyl, sulfonyl, cyano, C1-C6 alkoxy and more preferably by C1-C6 alkyl and C1-C6 alkoxy.
    [0111]
    [0112] Alkoxy
    [0113] The term "alkoxy" should be understood as a linear or branched saturated monovalent hydrocarbon group of the formula -O- (alkyl), in which the term "alkyl" has the values defined above. Said alkoxy group is preferably C1-C6 alkoxy, for example a methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, tert-butoxy, sec-butoxy, pentoxy, iso-pentoxy, or n group -hexoxy.
    [0114]
    [0115] Alkylthioxyl
    [0116] The term "alkylthioxyl" should be understood as a linear or branched saturated monovalent hydrocarbon group of the formula -S- (alkyl), in which the term "alkyl" has the values defined above. Said alkylthioxyl group is preferably -S- (C1-C6 alkyl) for example a methylthio, ethylthio, or n-propylthio group.
    [0117]
    [0118] Aryloxy
    [0119] The term "aryloxy" should be understood as a monovalent hydrocarbon group of the formula -O- (aryl), in which the term "aryl" has the values defined above. Said aryloxy group is preferably an aryloxy of 6 carbon atoms, for example a phenoxy group.
    [0120]
    [0121] Arylthioxyl
    [0122] The term "alkoxy" should be understood as a monovalent hydrocarbon group of the formula -S- (aryl), in which the term "aryl" has the values defined above. Said arylthioxyl group is preferably an arylthioxyl of 6 carbon atoms, for example a -S-phenyl group.
    [0123]
    [0124] Heteroaryl
    [0125] The term "heteroaryl" should be understood as a monocyclic or polycyclic heterocyclic group comprising 1, 2, 3 aromatic nuclei, said nuclei being linked with, and / or covalently linked with each other, at least one of such nuclei containing 1, 2 , 3 or 4 heteroatoms independently selected from the group consisting of O and S. Said heteroaryl is preferably a monocyclic or bicyclic group, for example furan, benzofuran and thiophene.
    [0126]
    [0127] Sulfonyl
    [0128] The term "sulfonyl" should be understood as a group of the formula -SO2R where R can be alkyl, where the term "alkyl" has the values defined above, preferably R is hydrogen or C1-C6 alkyl.
    [0129]
    [0130] Carbonyl
    [0131] The term "carbonyl" should be understood as a group of formula -C (O) H or a group of formula -C (O) R where R can be an alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, aryl or heteroaryl group as defined above, said carbonyl is in a particular embodiment a group -C (O) H.
    [0132]
    [0133] Carboxyl
    [0134] The term "carboxy" should be understood as a group of the formula -COOH, or a salt derived therefrom, such as sodium carboxylate (-COONa), potassium carboxylate or lithium carboxylate. The term "carboxy" should also be understood as the ester derived from the formula -COOR where R may be an alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, aryl or heteroaryl group, as defined above, preferably an aryl or alkyl group. Said carboxyl is in a particular embodiment a group of formula -COOH.
    [0135]
    [0136] The present invention is directed according to some particular embodiments to the process described above in which the compound being treated has at least one tertiary carbon -CH- directly attached to an aryl group (A), where the aryl group is selected from the group formed by phenyl and naphthyl, optionally substituted with one or more groups, preferably with one to 3 groups, selected from C1-C6 alkyl and C1-C6 alkoxy, preferably from C1-C4 alkyl and C1-C3 alkoxy, and more preferably from isobutyl and methoxy
    [0137] The invention is also directed, for example, to treating a compound in which the first carbon atom (C1) is part of a group selected from alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, heterocycloalkyl and aryl, preferably selected from alkyl and aryl, more preferably selected from C1-C6 alkyl and phenyl, and even more preferably from C1-C3 alkyl, for example methyl, and phenyl.
    [0138]
    [0139] The invention is also directed, for example, to treating a compound in which the second carbon atom (C2) is part of a group selected from alkyl, aryl, carbonyl and carboxyl, preferably selected from C1-C6 alkyl, for example methyl and ethyl, phenyl, -COOH and -C (O) H.
    [0140]
    [0141] Any of the combinations of the possible definitions of the aryl groups (A) and of the groups of which the carbon atoms (C1) and (C2) form part must be considered to be within the scope of the present invention.
    [0142]
    [0143] The present invention also addresses the process defined above in which the compound to be treated is a polystyrene, or a polystyrene derivative.
    [0144]
    [0145] In a particular embodiment the starting compound is polystyrene of the following formula (IV):
    [0146]
    [0147]
    [0148]
    [0149]
    [0150] where n is not particularly limited, although typically it can be between
    [0151]
    [0152]
    [0153] 10 and 10,000. In some embodiments, n is a number between 50 and 5,000, for example between 100 and 3,500, or for example between 500 and 2,500.
    [0154]
    [0155] Polystyrene is present in a multitude of products, for example, as waste from building materials, insulators, packaging, etc; it can be pure, syndiotactic or atactic; It can be expanded or extruded.
    [0156]
    [0157] In particular embodiments, polystyrene is selected from the following:
    [0158]
    [0159] [1] Polystyrene MW 35000
    [0160] [2] Polystyrene MW 1951
    [0161] [3] Polystyrene MW 269900
    [0162] [4] Polystyrene MW 211300
    [0163] [5] Polystyrene MW 353100
    [0164] [6] Polystyrene MW 430600
    [0165] [7] Polystyrene MW 5200
    [0166] [8] Polystyrene MW 65000
    [0167]
    [0168] When polystyrene is subjected to the process of the present invention, acetophenone is advantageously obtained, which is an essential raw material in the chemical industry, which is commonly used in the preparation, for example, of copolymeric resins (for example, bisphenol-type epoxy resins). F) common in all types of paints and coatings, inks and adhesives. In addition, acetophenone is used as an excipient and additive in certain drugs, as an ingredient in fragrances and perfumes, and as a precursor to the synthesis of various drugs and products of interest. The most commonly used methods for obtaining it as a raw material are derived from petroleum derivatives for large-scale production, and are Friedel-Crafts acylation of benzene with acetyl chloride or acetic anhydride, styrene Wacker oxidation and cumene self-oxidation .
    [0169]
    [0170] Therefore, the process of the invention allows, on the one hand, the elimination of a polymeric residue, such as polystyrene, while it is revalued, generating a raw material of great interest and application such as acetophenone.
    [0171]
    [0172] Vanadium compound
    [0173] Non-limiting examples of vanadium compound that can be used in the process of the invention to treat any of the compounds defined above are salts of vanadium (III), vanadium (IV) or vanadium (V), such as for example and not limiting vanadium (III) chloride, vanadyl acetylacetonate or vanadium oxide (V). Preferably the vanadium compound is vanadyl acetylacetonate.
    [0174]
    [0175] With respect to the amount of vanadium used, amounts between 0.01% and 0.0001% mole relative to the moles of the starting compound (except only in the case of polystyrene as described below) are suitable, although in a particular embodiment an amount of between 0.005% and 0.0005% molar is used, for example 0.001% molar with respect to the starting compound.
    [0176]
    [0177] The amount of vanadium compound when the starting compound is polystyrene or a derivative is typically between 1% and 5% by weight, particularly between 2 and 4% by weight, more particularly between 2.5% and 3.5% by weight. weight for example 3.1% or 3.3% by weight with respect to the amount of polystyrene or polystyrene derivative.
    [0178]
    [0179] Any of the compounds described above can be treated with any of the vanadium compounds defined above and in any of the amounts of vanadium defined above in any possible combination.
    [0180] Alkaline organic acid salt:
    [0181] Non-limiting examples of organic acids, whose alkaline salts can be used in the process of the invention are, for example, non-limiting, methanoic acid, propanoic acid, butanoic acid, or diacids / triacids such as citric, oxalic, malonic, and butanedioic acid . The alkali metal is for example sodium, potassium or lithium. In a preferred embodiment said alkaline salt is an alkali salt acetate, for example sodium acetate.
    [0182]
    [0183] With respect to the amount of said organic acid alkaline salt used, in a particular embodiment an amount of 5% molar to 20% molar is used, more particularly between 8% molar and 15% molar, for example 10% molar with respect to moles of the starting compound.
    [0184] Any of the compounds described above can be treated according to the process of the invention with any of the vanadium compounds defined above and in any of the vanadium amounts defined above; and any such combination may in turn be combined with any of the possible alkali metal organic salts defined above in any of the possible amounts defined above in any of its possible combinations.
    [0185]
    [0186] Triazole derivative.
    [0187] The reaction occurs in the presence of a triazole derivative of the formula (II) represented below. This derivative can be obtained according to the procedure described in Urgoitia, G .; SanMartin, R; Blacksmith, MT; Dominguez, E. Chem. Commun. 2015 , 51, 4799.
    [0188] Without wishing to be bound by any concrete theory, the inventors of the present invention believe that it may be possible for said triazole derivative to act as a ligand, possibly coordinating the vanadium species present in the reaction, and participating in the formation of reaction intermediates. .
    [0189] The triazole derivative has the following formula where
    [0190]
    [0191]
    [0192]
    [0193] R and R ’are the same or different from each other, selected from hydrogen, alkyl and aryl, where alkyl and aryl are as defined above;
    [0194] R ’’ is selected from hydrogen, alkyl, or alkoxycarbonyl (-O-C (O) -R ’’), where R ’’ is alkyl, and where the term alkyl is as defined above.
    [0195]
    [0196] In a particular embodiment R and R 'the same or different from each other, are selected from hydrogen, C1-C6 alkyl, preferably methyl, ethyl or propyl, and more preferably hydrogen, methyl, and aryl, preferably a ring of 6 carbon atoms, and more preferably they are hydrogen.
    [0197] In another particular embodiment R ’is C1-C6 alkyl, preferably methyl, ethyl or propyl, and more preferably methyl.
    [0198] In a preferred embodiment, the triazole-derived compound is methyl 3,5-bis - ((1 H-1,2,4-triazol-1-yl) methyl) benzoate.
    [0199]
    [0200] With respect to the amount of triazole derivative used, amounts from 0.01% to 0.0001 mol% relative to the moles of the starting compound (except only in the case of polystyrene as described below) are suitable for the reaction to have Instead, although in a particular embodiment, between 0.05% and 0.0005% molar is used, for example 0.001% molar.
    [0201]
    [0202] When the starting compound is polystyrene or a polystyrene derivative it is used in an amount typically between 1% and 5% by weight, particularly between 2 and 4% by weight, more particularly between 2.5% and 3.5% in weight, for example 3.1% or 3.3% by weight of triazole derivative with respect to the amount of polystyrene or polystyrene derivative.
    [0203]
    [0204] Any of the compounds described above can be treated according to the process of the invention with any of the vanadium compounds in any of the amounts of vanadium as defined above and with any of the alkaline salts of organic acids in any of the possible amounts as defined above, and any of the resulting possible combinations, may in turn be combined with any of the possible triazole derivatives defined above in any of the possible quantities defined above in any of their possible combinations.
    [0205] Visible light
    [0206] The visible light used in the process of the invention has a wavelength between 400 nm and 800 nm, for example between 400 nm and 600 nm, or for example between 400 and 500 nm. Preferably the wavelength between 400 nm and 450 nm, more preferably between 400 nm and 430 nm, and more preferably between 400 nm and 420 nm. According to some examples of the procedure, the visible light is selected from red, orange, yellow, green, cyan, light blue, turquoise, blue and violet, and preferably live violet light (400-420 nm) is used.
    [0207]
    [0208] Any of the compounds described above can be treated in accordance with the process of the invention with any of the vanadium compounds in any of the amounts of vanadium as defined above, with any of the alkaline salts of organic acids in any of the possible amounts as defined above, and with any of the possible triazole derivatives defined above in any of the possible amounts defined above, and any such possible resulting combinations, may in turn be combined with the use of any type of visible light defined above.
    [0209]
    [0210] Molecular oxygen:
    [0211] The treatment with molecular oxygen (dioxygen) is carried out a total pressure around atmospheric pressure that typically can be between 81 and 141.85 kPa (0.8 and 1.4 atm), preferably between 101.32 and 121 , 59 kPa (1 and 1.2 atm), more preferably at 101.32 kPa (1 atm).
    [0212]
    [0213] Any of the compounds described above can be treated in accordance with the process of the invention with any of the vanadium compounds in any of the amounts of vanadium as defined above, with any of the alkaline salts of organic acids in any of the possible amounts as defined above, with any of the possible triazole derivatives defined above in any of the possible amounts defined above, with any type of visible light defined above and any of said possible combinations may in turn be combined with the use of any pressure as defined above.
    [0214]
    [0215] Solvent
    [0216] The type of solvent is preferably of the ether type or a polyol solvent.
    [0217] In some particular embodiments of the process of the invention the solvent is selected from toluene, water, ethylene glycol, propylene glycol, glycerol, polyethylene glycol 400 (PEG-400), polyethylene glycol 1500 (PEG-1500) and mixtures thereof, more particularly it is used a
    [0218]
    [0219]
    [0220] ethylene glycol solvent, water, PEG 400, PEG 1500, glycerol and mixtures thereof. In a more preferred embodiment, a solvent selected from PEG 400, PEG 1500, glycerol and mixtures thereof, even more preferably PEG 400, is used.
    [0221] When the starting compound is polystyrene, the solvent is preferably a polyol, for example a polyethylene glycol, such as PEG 400.
    [0222] The amount of solvent can be determined in each particular case depending on the starting compound.
    [0223] When the starting compound is polystyrene or a polystyrene derivative, the amount of solvent typically used is between 50% and 80% v / m polystyrene, for example between 60% and 70%, or for example being 66% v / m , preferably PEG 400 being the solvent.
    [0224] Any of the compounds described above can be treated in accordance with the process of the invention with any of the vanadium compounds in any of the amounts of vanadium as defined above, with any of the alkaline salts of organic acids in any of the possible amounts as defined above, with any of the possible triazole derivatives defined above in any of the possible amounts defined above, with any type of visible light defined above, and at any pressure of those defined above, and for any of all possible resulting combinations any of the solvents described above can be used.
    [0225]
    [0226] Reaction times vary depending on the starting compound, but typically are around 24 hours. The temperature at which the reaction is carried out depends in each case on the starting compound itself, although in general the temperature is between 100 ° C and 150 ° C, for example between 105 ° C and 140 ° C. In some particular embodiments the temperature is between 110 ° C and 130 ° C, for example 115 and 125 ° C, or for example 120 ° C.
    [0227]
    [0228] The starting compounds are commercially available, or can be obtained by conventional synthesis methods.
    [0229]
    [0230] Some illustrative starting compounds and the compounds that are obtained respectively from them are the following:
    [0231]
    [0232] [1] sec-Butylbenzene Acetophenone
    [0233] [2] 2-Phenylpropanal Acetophenone
    [0234] [3] Acetophenone Cumene
    [0235] [4] Benzophenone diphenylacetic
    [0236] [5] Naproxen sodium 2-Acetyl-6-methoxynaphthalene
    [0237] [6] Ibuprofen 4‘-Isobutylacetophenone.
    [0238] [7] Triphenylmethane Benzophenone
    [0239] [8] Acetophenone hydratopic acid
    [0240]
    [0241] When the starting compound is polystyrene, acetophenone is obtained with yields typically equal to or greater than 50%, preferably equal to or greater than 60%, more preferably equal to or greater than 70%, even more preferably equal to or greater than 80%, still more preferably equal to or greater than 90%. In some examples, acetophenone is obtained with yields equal to or greater than 95%, or 97% or 99%.
    [0242]
    [0243] In some embodiments, vanadium (III) chloride, vanadyl acetylacetonate or vanadium oxide (V), preferably vanadyl acetylacetonate, are used in an amount of between 0.005% and 0.0005% molar, for example 0.001% molar relative to the starting compound , the starting compound being as defined above, except polystyrenes and polystyrene derivatives. These vanadium compounds in these amounts are used in combination for example with at least one triazole derivative of formula (II)
    [0244]
    [0245]
    [0246]
    [0247] where R and R 'the same or different from each other, are selected from hydrogen, C1-C3 alkyl, and phenyl, and R' 'is C1-C3 alkyl and preferably is 3,5-bis - ((1H-1,2, 4-Triazol-1-yl) methyl) methyl benzoate, in amounts between 0.005% and 0.0005% molar, for example 0.001% molar.
    [0248] In some of these embodiments, sodium acetate is used in amounts of between 8% molar and 15% molar, for example 10% molar relative to the moles of the starting compound, and in other of these embodiments in addition to using sodium acetate in these amounts preferably live violet light (400-420 nm), oxygen at pressure between 101.32 and 121.59 kPa (1 and 1.2 atm), and a solvent, preferably ethylene glycol, water, PEG 400, PEG 1500, are used, glycerol and mixtures thereof, more preferably PEG 400.
    [0249]
    [0250] In cases where polystyrene or polystyrene derivatives are treated, vanadium (III) chloride, vanadyl acetylacetonate or vanadium oxide (V), preferably vanadyl acetylacetonate, are used in an amount between 2.5% and 3, 5% by weight for example 3.1% or 3.3% by weight with respect to the amount of polystyrene or polystyrene derivative. These vanadium compounds in these amounts are used in combination for example with at least one triazole derivative of formula (II)
    [0251]
    [0252]
    [0253]
    [0254] where R and R 'the same or different from each other, are selected from hydrogen, C1-C3 alkyl, and phenyl, and R' 'is C1-C3 alkyl and preferably is 3,5-bis - ((1H-1,2, Methyl 4-triazol-1-yl) methyl) benzoate, in amounts between 2.5% and 3.5% by weight, for example 3.1% or 3.3% by weight of triazole derivative with respect to the amount of polystyrene or polystyrene derivative. In some of these embodiments, sodium acetate is used in amounts of 8% to 15% molar, for example 10% molar relative to the moles of polystyrene or polystyrene derivative, and in other of these embodiments in addition to using sodium acetate in these amounts preferably live violet light (400-420 nm), oxygen at pressure between 101.32 and 121.59 kPa (1 and 1.2 atm), and a solvent, preferably ethylene glycol, water, PEG 400, PEG 1500, are used, glycerol and mixtures thereof, more preferably PEG 400.
    [0255]
    [0256] The process of the invention is an economical and also advantageous procedure in terms of laboratory safety, since it is carried out at atmospheric pressure, or pressures close to atmospheric pressure. It is also done using a very cheap and abundant oxidant. In some particular embodiments it is also carried out in the presence of a cheap, sustainable and benign solvent from an environmental point.
    [0257]
    [0258] Thus, the process of the present invention in general has clear advantages over procedures known in the state of the art. These advantages derive
    [0259]
    [0260]
    [0261] not only of the high yield and selectivity towards the ketone obtained mostly as a reaction product, but also of the use of small amounts of a compound
    [0262] of vanadium (IV), such as vanadyl acetylacetonate and a triazole type ligand, and the fact that the process is carried out only with molecular oxygen at pressures around 1 atm.
    [0263]
    [0264] Compounds both starting and those obtained in the process herein
    [0265] invention may contain one or more asymmetric centers, depending on the location and
    [0266] the nature of the different substituents desired. There may be asymmetric carbon atoms in the (R) or (S) configuration, and provided that said asymmetric center is not part
    [0267] of the CH unit attached to the aryl (A), the configuration of said center will be maintained in the final product. In certain cases, there may also be asymmetry present due to the
    [0268] restricted rotation around a given link, for example, the central link that
    [0269] binds the two substituted aromatic rings of the specified compounds. Substituents
    [0270] in a ring they can also be present in the cis or trans form. All these configurations (including enantiomers and diastereomers) must be included
    [0271] within the scope of the present invention.
    [0272]
    [0273] Examples are presented below to illustrate the process of the invention that does not
    [0274] they should not be considered in any case as limiting the scope of the same.
    [0275]
    [0276] Examples
    [0277]
    [0278] Example 1
    [0279]
    [0280] 1.1. Obtaining acetophenone VO (acac) 2 and 3,5-bis ((1H-1,2,4-triazol-1-yl) methyl) benzoate
    [0281] of methyl
    [0282]
    [0283]
    [0284]
    [0285]
    [0286] In a round bottom flask, sec-butylbenzene (155 pL, 1 mmol), sodium acetate was mixed
    [0287] (8 mg, 0.1 mmol), vanadyl acetylacetonate (20pL of a 5 x 10-4 M solution in PEG
    [0288] 400, 0.00001 mmol) and 3,5-bis - ((1H-1,2,4-triazol-1-yl) methyl) methyl benzoate (20pL of a 5 x 10-4 M solution in PEG 400, 0.00001 mmol ) in PEG 400 (1 mL) at room temperature
    [0289] under oxygen atmosphere (1 atm). The mixture was heated at 120 ° C for 24 hours under light
    [0290] live violet (400-420 nm), maintaining vigorous agitation at all times. It was allowed to temper, and the crude was purified by flash chromatography (AcOEt / Hexane 1: 9) to provide
    [0291] Acetophenone as a colorless liquid (106 mg, 89%). NMR-1H (CDCh, 5h, ppm) 2.61 (s,
    [0292] 3H, CH3), 7.42-7.63 (m, 3H, Harom), 7.96 (t, J = 8, 2H, Harom); 13C-NMR (CDCh, 5th, ppm) 26.5
    [0293] (CH3), 128.2 (C arom-H), 128.5 (C arom-H), 133.0 (C arom-H), 137.1 (Cq-arom), 198.1 (CO) 121.1 (MH +); EMAR calculated for C8H7O 120.1510; found for 120.1512.
    [0294]
    [0295] 1.2. Obtaining acetophenone using VCl 3 and methyl 3,5-bis ((1 H-1,2,4-triazol-1-yl) methyl) benzoate
    [0296]
    [0297] In a round bottom flask, sec-butylbenzene (155 pL, 1 mmol), sodium acetate was mixed
    [0298] (8 mg, 0.1 mmol), vanadium (III) chloride (20pL of a 5 x 10-3 M solution in DMA, 0.0001
    [0299] mmol) and methyl 3,5-bis - ((1H-1,2,4-triazol-1-yl) methyl) benzoate (20pL of a 5x10 solution
    [0300] 3 M in DMA, 0.0001 mmol) in PEG 400 (1 mL) at room temperature under an atmosphere of
    [0301]
    [0302]
    [0303] oxygen (1 atm). The mixture was heated at 120 ° C for 24 hours under violet light (400-420 nm), maintaining vigorous stirring at all times. After the preparation and purification steps described in example 1.1, acetophen was obtained as a colorless liquid (66 mg, 55%).
    [0304]
    [0305] 1.3. Obtaining acetophenone using V 2 OR 5 and methyl 3,5-bis ((1 H-1,2,4-triazol-1-yl) methyl) benzoate
    [0306]
    [0307] In a round bottom flask, sec-butylbenzene (155 pL, 1 mmol), sodium acetate (8 mg, 0.1 mmol), vanadium oxide (V) (20pL of a 5 x 10-3 M solution in DMA, 0.0001) was mixed mmol) and methyl 3,5-bis - ((1H-1,2,4-triazol-1-yl) methyl) benzoate (20pL of a 5 x 10 3M solution in DMA, 0.0001 mmol) in PEG 400 ( 1 mL) at room temperature under oxygen atmosphere (1 atm). The mixture was heated at 120 ° C for 24 hours under violet light (400-420 nm), maintaining vigorous stirring at all times. After the preparation and purification steps described in Example 1.1, acetophen was obtained as a colorless liquid (48 mg, 40%).
    [0308]
    [0309] 1.4. Obtaining acetophenone using VO (acac) 2 and methyl 3,5-bis ((1H-1,2,4-triazol-1-yl) methyl) benzoate in ethylene glycol
    [0310]
    [0311] In a round bottom flask, sec-butylbenzene (155 pL, 1 mmol), sodium acetate (8 mg, 0.1 mmol), vanadyl acetylacetonate (20pL of a 5 x 10-3 M solution in DMA, 0.0001 mmol) were mixed and 3,5-bis - ((1 H-1,2,4-triazol-1-yl) methyl) methyl benzoate (20pL of a 5 x 10-3 M solution in DMA, 0.0001 mmol) in ethylene glycol (1 mL) at room temperature under oxygen atmosphere (1 atm). The mixture was heated at 120 ° C for 24 hours under violet light (400-420 nm), maintaining vigorous stirring at all times. After the preparation and purification steps described in Example 1.1, acetophen was obtained as a colorless liquid (51 mg, 43%).
    [0312]
    [0313] 1.5. Obtaining acetophenone using VO (acac) 2 and methyl 3,5-bis ((1H-1,2,4-triazol-1-yl) methyl) benzoate in glycerol
    [0314]
    [0315] In a round bottom flask, sec-butylbenzene (155 pL, 1 mmol), sodium acetate (8 mg, 0.1 mmol), vanadyl acetylacetonate (20pL of a 5 x 10-3 M solution in DMA, 0.0001 mmol) were mixed and 3,5-bis - ((1 H-1,2,4-triazol-1-yl) methyl) methyl benzoate (20pL of a 5 x 10-3 M solution in DMA, 0.0001 mmol) in glycerol (1 mL) at room temperature under oxygen atmosphere (1 atm). The mixture was heated at 120 ° C for 24 hours under violet light (400-420 nm), maintaining vigorous stirring at all times. After the preparation and purification steps described in example 1.1, acetophen was obtained as a colorless liquid (61 mg, 51%).
    [0316]
    [0317] 1.6. Obtaining acetophenone using VO (acac) 2 and methyl 3,5-bis ((1H-1,2,4-triazol-1-yl) methyl) benzoate in toluene
    [0318]
    [0319] In a round bottom flask, sec-butylbenzene (155 pL, 1 mmol), sodium acetate (8 mg, 0.1 mmol), vanadyl acetylacetonate (20pL of a 5 x 10-3 M solution in DMA, 0.0001 mmol) were mixed and 3,5-bis - ((1 H-1,2,4-triazol-1-yl) methyl) methyl benzoate (20pL of a 5 x 10-3 M solution in DMA, 0.0001 mmol) in toluene (1 mL) at room temperature under oxygen atmosphere (1 atm). The mixture was heated at 120 ° C for 24 hours under violet light (400-420 nm), maintaining vigorous stirring at all times. After the preparation and purification steps described in Example 1.1, acetophen was obtained as a colorless liquid (10 mg, 9%).
    [0320]
    [0321]
    [0322] 1.7. Obtaining acetophenone using VO (acac) 2 and methyl 3,5-bis ((1H-1,2,4-triazol-1-yl) methyl) benzoate in mixture of PEG 400: water
    [0323]
    [0324] In a round bottom flask, sec-butylbenzene (155 pL, 1 mmol), sodium acetate (8 mg, 0.1 mmol), vanadyl acetylacetonate (20pL of a 5 x 10-3 M solution in DMA, 0.0001 mmol) were mixed and 3,5-bis - ((1 H-1,2,4-triazol-1-yl) methyl) methyl benzoate (20pL of a 5 x 10-3 M solution in DMA, 0.0001 mmol) in PEG 400: water ( 1 mL, 1: 1) at room temperature under oxygen atmosphere (1 atm). The mixture was heated at 120 ° C for 24 hours under violet light (400-420 nm), maintaining vigorous stirring at all times. After the preparation and purification steps described in Example 1.1, acetophen was obtained as a colorless liquid (31 mg, 26%).
    [0325]
    [0326] Example 2. Preparation of acetophenone from 2-phenylpropanal using VO (acac) 2 and methyl 3,5-bis ((1 H-1,2,4-triazol-1-yl) methyl) benzoate
    [0327]
    [0328] In a round bottom flask, 2-phenylpropanal (133 pL, 1 mmol), sodium acetate (8 mg, 0.1 mmol), vanadyl acetylacetonate (20pL of a 5 x 10-4 M solution in PEG-400, 0.00001 mmol were mixed ) and 3,5-bis ((1H-1,2,4-triazol-1-yl) methyl) methyl benzoate (20pL of a 5 x 10-4M solution in PEG-400, 0.00001 mmol) in PEG 400 (1 mL) at room temperature under oxygen atmosphere (1 atm). The mixture was heated at 120 ° C for 24 hours under violet light (400-420 nm), maintaining vigorous stirring at all times. After the preparation and purification steps described in Example 1.1, acetophen was obtained as a colorless liquid (97 mg, 81%)
    [0329]
    [0330] Example 3. Preparation of acetophenone from cumene using VO (acac) 2 and methyl 3,5-bis ((1 H-1,2,4-triazol-1-yl) methyl) benzoate
    [0331]
    [0332] In a round bottom flask, cumene (139 pL, 1 mmol), sodium acetate (8 mg, 0.1 mmol), vanadyl acetylacetonate (20pL of a 5 x 10-4 M solution in PEG-400, 0.00001 mmol) were mixed and 3,5-bis ((1H-1,2,4-triazol-1-yl) methyl) methyl benzoate (20pL of a 5 x 10-4M solution in PEG-400, 0.00001 mmol) in PEG 400 (1 mL) at room temperature under oxygen atmosphere (1 atm). The mixture was heated at 120 ° C for 48 hours under violet light (400-420 nm), maintaining vigorous stirring at all times. After the preparation and purification steps described in example 1.1, acetophen was obtained as a colorless liquid (91 mg, 76%)
    [0333]
    [0334] Example 4. Preparation of benzophenone using VO (acac) 2 and methyl 3,5-bis ((1 H-1,2,4-triazol-1-yl) methyl) benzoate
    [0335]
    [0336]
    [0337]
    [0338]
    [0339] Diphenylacetic acid (212 mg, 1 mmol), sodium acetate (8 mg, 0.1 mmol), vanadyl acetylacetonate (20pL of a 5 x 10-4 M solution in PEG-400, 0.00001 mmol) were mixed in a round bottom flask and methyl 3,5-bis ((1 H-1,2,4-triazol-1-yl) methyl) benzoate (20pL of a 5 x 10-4 M solution in PEG-400, 0.00001 mmol) in. The mixture was heated to 120 ° C
    [0340]
    [0341]
    [0342] for 24 hours under violet light (400-420 nm), maintaining vigorous agitation at all times. After the preparation and purification steps described in Example 1.1, benzophenone was obtained as a white solid (164 mg, 90%). 1H-NMR (CDCh, 5 h , ppm): 7.42-7.52 (m, 4H, Harom), 7.54-7.62 (m, 2H, Harom), 7.79-7.82 (m, 4H, Harom); 13C-NMR (CDCh, 5th, ppm): 128.2 (Carom), 129.9 (Carom), 132.3 (Carom), 132.5 (Cq-arom), 196.6 (CO); MS (m / z): 183.2 (MH +); HRMS calculated for C13H10O 182.2220; found for 182.2218.
    [0343]
    [0344] Example 5. Preparation of 2-acetyl-6-methoxynaphthalene using VO (acac) 2 and methyl 3,5-bis ((1 H-1,2,4-triazol-1-yl) methyl) benzoate
    [0345]
    [0346]
    [0347]
    [0348]
    [0349] In a round bottom flask, sodium naproxen (212 mg, 1 mmol), sodium acetate (8 mg, 0.1 mmol), vanadyl acetylacetonate (20pL of a 5 x 10-4 M solution in PEG-400, 0.00001 mmol) were mixed and methyl 3,5-bis ((1H-1,2,4-triazol-1-yl) methyl) benzoate (20pL of a 5 x 10-4M solution in PEG-400, 0.00001 mmol) in PEG 400 ( 1 mL) at room temperature under oxygen atmosphere (1 atm). The mixture was heated at 120 ° C for 24 hours under violet light (400-420 nm), maintaining vigorous stirring at all times. After the preparation and purification steps described in Example 1.1, 2-acetyl-6-methoxynaphthalene was obtained as a beige powder (84 mg, 42%). 1H-NMR (CDCh, 5h, ppm): 2.71 (s, 3H, CH3); 3.96 (s, 3H, OCH3), 7.12-7.24 (m, 2H, Harom), 7.78 (d, 1H, J -9.7, Harom); 7.86 (d, 1H, J -9.1, Harom), 8.01 (d, 1H, J -10.4, Harom); 8.40 (s, 1H, Harom); 13C-NMR (CDCl3, 5c, ppm): 26.6 (CH3), 55.4 (OCH3), 105.7 (C arom), 119.7 (C arom), 124.7 (C arom), 127.1 (C arom), 17.8 (C arom) , 130.1 (Carom), 131.1 (Carom), 132.6 (Cq-arom), 137.3 (Cq-arom), 159.7 (Cq-arom), 197.9 (CO); MS (m / z): 201.2 (MH +); EMAR calculated for C13H12O2200.2370; found for 200.2369.
    [0350]
    [0351] Example 6. Preparation of 4-isobutylacetophenone using VO (acac) 2 and methyl 3,5-bis ((1 H-1,2,4-triazol-1-yl) methyl) benzoate
    [0352]
    [0353]
    [0354]
    [0355]
    [0356] In a round bottom flask, ibuprofen (206 mg, 1 mmol), sodium acetate (8 mg, 0.1 mmol), vanadyl acetylacetonate (20pL of a 5 x 10-4 M solution in PEG-400, 0.00001 mmol) were mixed and 3,5-bis ((1H-1,2,4-triazol-1-yl) methyl) methyl benzoate (20pL of a 5 x 10-4M solution in PEG-400, 0.00001 mmol) in PEG 400 (1 mL) at room temperature under oxygen atmosphere (1 atm). The mixture was heated at 120 ° C for 48 hours under violet light (400-420 nm), maintaining vigorous stirring at all times. After the preparation and purification steps described in Example 1.1, 4'-isobutylacetophenone was obtained as a colorless liquid (143 mg, 81%). 1H-NMR (CDCh, 5h, ppm): 0.91 (d, 6H, J -6.7, OH3); 1.81-1.97 (m, 1H, CH), 2.53 (d, 2H, J -7.2, OH2); 2.58 (s, 3H, OH3); 7.23 (d, 2H, J -8.1, Harom); 7.88 (d, 2H, J -8.2, Harom); 13C-NMR (CDCl3, 5th, ppm): 22.3 (OH3), 26.5 (OH3), 3.01 (CH),
    [0357]
    [0358]
    [0359] 45.4 (CH 2 ), 128.3 (C arom ), 129.3 (C arom ), 135.1 (C q-arom ), 147.6 (C q-arom ), 197.8 (CO); MS (m / z): 177.2 (MH + ); HRMS calculated for C 12 H 16 O 176.2590; found for 176,2591.
    [0360]
    [0361] Example 7. Preparation of benzophenone from triphenylmethane using VO (acac) 2 and methyl 3,5-bis ((1 H-1,2,4-triazol-1-yl) methyl) benzoate
    [0362]
    [0363] In a round bottom flask triphenylmethane (244 mg, 1 mmol), sodium acetate (8 mg, 0.1 mmol), vanadyl acetylacetonate (20pL of a 5 x 10-4 M solution in PEG-400, 0.00001 mmol) were mixed and 3,5-bis ((1H-1,2,4-triazol-1-yl) methyl) methyl benzoate (20pL of a 5 x 10-4M solution in PEG-400, 0.00001 mmol) in PEG 400 (1 mL) at room temperature under oxygen atmosphere (1 atm). The mixture was heated at 120 ° C for 48 hours under violet light (400-420 nm), maintaining vigorous stirring at all times. After the preparation and purification steps described in Example 1.1, benzophenone was obtained as a white solid (138 mg, 76%).
    [0364]
    [0365] Example 8. Preparation of acetophenone from hydratopic acid using VO (acac) 2 and methyl 3,5-bis ((1 H-1,2,4-triazol-1-yl) methyl) benzoate
    [0366]
    [0367] In a round bottom flask, hydratopic acid (136 pL, 1 mmol), sodium acetate (8 mg, 0.1 mmol), vanadyl acetylacetonate (20pL of a 5 x 10-4 M solution in PEG-400, 0.00001 mmol) were mixed and methyl 3,5-bis ((1H-1,2,4-triazol-1-yl) methyl) benzoate (20pL of a 5 x 10-4M solution in PEG-400, 0.00001 mmol) in PEG 400 ( 1 mL) at room temperature under oxygen atmosphere (1 atm). The mixture was heated at 120 ° C for 24 hours under violet light (400-420 nm), maintaining vigorous stirring at all times. After the preparation and purification steps described in Example 1.1, acetophenone was obtained as a colorless liquid (102 mg, 85%).
    [0368]
    [0369] Example 9. Preparation of acetophenone from MW 35000 polystyrene using VO (acac) 2 and methyl 3,5-bis ((1 H-1,2,4-triazol-1-yl) methyl) benzoate
    [0370]
    [0371] MW 35000 polystyrene (150 mg, 4.28 x 10-3 mmol), sodium acetate (40pL of a 1.07 x 10-5 M solution in PEG-400, 4.28 x 10 were mixed in a round bottom flask -4 mmol), vanadyl acetylacetonate (5 mg, 1.88 x 10-2 mmol) and 3,5-bis ((1 H-1,2,4-triazol-1-yl) methyl) methyl benzoate (7 mg, 2.34 x 10-2 mmol) in PEG 400 (100 pL) at room temperature under oxygen atmosphere (1 atm). The mixture was heated at 120 ° C for 24 hours under violet light (400-420 nm), maintaining vigorous stirring at all times. After the preparation and purification steps described in Example 1.1, acetophenone was obtained as a colorless liquid (113 mg, 85%).
    [0372]
    [0373] Example 10. Preparation of acetophenone from MW 35000 polystyrene using VO (acac) 2 and methyl 3,5-bis ((1 H-1,2,4-triazol-1-yl) methyl) benzoate
    [0374] MW 35000 polystyrene (20 g, 0.57 mmol), sodium acetate (4 mg, 0.05 mmol), vanadyl acetylacetonate (5 mg, 1.88 x 10-2 mmol) and 3.5- were mixed in a round bottom flask bis ((1H-1,2,4-triazol-1-yl) methyl) methyl benzoate (7 mg, 2.34 x 10-2 mmol) in PEG 400 (13 mL) at room temperature under oxygen atmosphere (1 atm ). The mixture was heated at 120 ° C for 48 hours under violet light (400-420 nm), maintaining vigorous stirring at all times. After the preparation and purification steps described in Example 1.1, acetophenone was obtained as a colorless liquid (11.75 g, 66%).
    [0375]
    [0376]
    [0377] Example 11. Preparation of acetophenone from polystyrene MW 1951 using VO (acac) 2 and methyl 3,5-bis ((1 H-1,2,4-triazol-1-yl) methyl) benzoate
    [0378]
    [0379] In a round bottom flask were mixed MW 1951 atactic polystyrene (150 mg, 7.68 x 10-2 mmol), sodium acetate (40pL of a 1.07 x 10-5 M solution in PEG-400, 4.28 x 10-4 mmol), vanadyl acetylacetonate (5 mg, 1.88 x 10-2 mmol) and methyl 3,5-bis ((1H-1,2,4-triazol-1-yl) methyl) benzoate ( 7 mg, 2.34 x 10-2 mmol) in PEG 400 (100 pL) at room temperature under oxygen atmosphere (1 atm). The mixture was heated at 120 ° C for 24 hours under violet light (400-420 nm), maintaining vigorous stirring at all times. After the preparation and purification steps described in Example 1.1, acetophenone was obtained as a colorless liquid (77 mg, 58%).
    [0380]
    [0381] Example 12. Preparation of acetophenone from polystyrene MW 269900 using VO (acac) 2 and methyl 3,5-bis ((1 H-1,2,4-triazol-1-yl) methyl) benzoate
    [0382]
    [0383] In a round bottom flask were mixed atactic polystyrene MW 269900 (150 mg, 5.55 x 10-4 mmol), sodium acetate (40pL of a 1.07 x 10-5 M solution in PEG-400, 4.28 x 10-4 mmol), vanadyl acetylacetonate (5 mg, 1.88 x 10-2 mmol) and methyl 3,5-bis ((1H-1,2,4-triazol-1-yl) methyl) benzoate ( 7 mg, 2.34 x 10-2 mmol) in PEG 400 (100 pL) at room temperature under oxygen atmosphere (1 atm). The mixture was heated at 120 ° C for 48 hours under violet light (400-420 nm), maintaining vigorous stirring at all times. After the preparation and purification steps described in Example 1.1, acetophenone was obtained as a colorless liquid (94 mg, 70%).
    [0384]
    [0385] Example 13. Preparation of acetophenone from polystyrene MW 211300 using VO (acac) 2 and methyl 3,5-bis ((1 H-1,2,4-triazol-1-yl) methyl) benzoate
    [0386]
    [0387] In a round bottom flask were mixed MW 211300 atactic polystyrene (150 mg, 7.09 x 10-4 mmol), sodium acetate (40pL of a 1.07 x 10-5 M solution in PEG-400, 4.28 x 10-4 mmol), vanadyl acetylacetonate (5 mg, 1.88 x 10-2 mmol) and methyl 3,5-bis ((1H-1,2,4-triazol-1-yl) methyl) benzoate ( 7 mg, 2.34 x 10-2 mmol) in PEG 400 (100 pL) at room temperature under oxygen atmosphere (1 atm). The mixture was heated at 120 ° C for 48 hours under violet light (400-420 nm), maintaining vigorous stirring at all times. After the preparation and purification steps described in Example 1.1, acetophenone was obtained as a colorless liquid (94 mg, 70%).
    [0388]
    [0389] Example 14. Preparation of acetophenone from polystyrene MW 353100 using VO (acac) 2 and methyl 3,5-bis ((1 H-1,2,4-triazol-1-yl) methyl) benzoate
    [0390]
    [0391] In a round bottom flask were mixed MW 353100 atactic polystyrene (150 mg, 4.24 x 10-4 mmol), sodium acetate (40pL of a 1.07 x 10-5 M solution in PEG-400, 4.28 x 10-4 mmol), vanadyl acetylacetonate (5 mg, 1.88 x 10-2 mmol) and methyl 3,5-bis ((1H-1,2,4-triazol-1-yl) methyl) benzoate ( 7 mg, 2.34 x 10-2 mmol) in PEG 400 (100 pL) at room temperature under oxygen atmosphere (1 atm). The mixture was heated at 120 ° C for 48 hours under violet light (400-420 nm), maintaining vigorous stirring at all times. After the preparation and purification steps described in Example 1.1, acetophenone was obtained as a colorless liquid (114 mg, 85%).
    [0392]
    [0393] Example 15. Preparation of acetophenone from polystyrene MW 430600 using VO (acac) 2 and methyl 3,5-bis ((1 H-1,2,4-triazol-1-yl) methyl) benzoate
    [0394]
    [0395] In a round bottom flask were mixed atactic polystyrene MW 430600 (150 mg, 3.48 x 10-4 mmol), sodium acetate (40pL of a 1.07 x 10-5 M solution in PEG-400, 4.28 x 10-4 mmol), vanadyl (IV) acetylacetonate (5 mg, 1.88 x 10-2 mmol) and 3,5-bis ((1H-1,2,4-triazol-1-yl) methyl) benzoate of methyl (7 mg, 2.34 x 10-2 mmol) in PEG 400 (100 pL) at room temperature under oxygen atmosphere (1 atm). The mixture was heated at 120 ° C for 48 hours under violet light (400-420 nm), maintaining vigorous stirring at all times. After the preparation and purification steps described in Example 1.1, acetophenone was obtained as a colorless liquid (109 mg, 82%).
    [0396]
    [0397] Example 16. Preparation of acetophenone from MW 5200 polystyrene using VO (acac) 2 and methyl 3,5-bis ((1 H-1,2,4-triazol-1-yl) methyl) benzoate
    [0398]
    [0399] In a round bottom flask were mixed MW 5200 atactic polystyrene (150 mg, 3.00 x 10-2 mmol), sodium acetate (40pL of a 1.07 x 10-5 M solution in PEG-400, 4.28 x 10-4 mmol), vanadyl acetylacetonate (5 mg, 1.88 x 10-2 mmol) and methyl 3,5-bis ((1H-1,2,4-triazol-1-yl) methyl) benzoate ( 7 mg, 2.34 x 10-2 mmol) in PEG 400 (100 pL) at room temperature under oxygen atmosphere (1 atm). The mixture was heated at 120 ° C for 48 hours under violet light (400-420 nm), maintaining vigorous stirring at all times. After the preparation and purification steps described in Example 1.1, acetophenone was obtained as a colorless liquid (92 mg, 66%).
    [0400]
    [0401] Example 17. Preparation of acetophenone from MW 65000 polystyrene using VO (acac) 2 and methyl 3,5-bis ((1 H-1,2,4-triazol-1-yl) methyl) benzoate
    [0402]
    [0403] In a round bottom flask were mixed MW 65000 atactic polystyrene (150 mg, 2.30 x 10-3 mmol), sodium acetate (40pL of a 1.07 x 10-5 M solution in PEG-400, 4.28 x 10-4 mmol), vanadyl acetylacetonate (5 mg, 1.88 x 10-2 mmol) and methyl 3,5-bis ((1H-1,2,4-triazol-1-yl) methyl) benzoate ( 7 mg, 2.34 x 10-2 mmol) in PEG 400 (100 pL) at room temperature under oxygen atmosphere (1 atm). The mixture was heated at 120 ° C for 48 hours under violet light (400-420 nm), maintaining vigorous stirring at all times. After the preparation and purification steps described in Example 1.1, acetophenone was obtained as a colorless liquid (77 mg, 58%).
    权利要求:
    Claims (18)
    [1]
    1. A process for obtaining an aryl ketone comprising treating with oxygen a compound of formula (I)

    [2]
    2. A process according to claim 1, wherein the compound being treated has at least one tertiary carbon -CH- attached directly to an aryl group (A), wherein the aryl group is selected from the group consisting of phenyl and naphthyl, optionally substituted with one or more groups, preferably with one to 3 groups, selected from C1-C6 alkyl and C1-C6 alkoxy, preferably C1-C4 alkyl and C1-C3 alkoxy, more preferably isobutyl and methoxy.
    [3]
    3. The method according to claim 1 or 2, wherein the compound being treated has a first carbon atom (C1) which is part of a group selected from alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, heterocycloalkyl and aryl, preferably selected from alkyl and aryl, more preferably selected from C1-C6 alkyl and phenyl, and even more preferably from C1-C3 alkyl and phenyl.
    2
    [4]
    4. A process according to any one of claims 1 to 3, wherein the compound being treated has a second carbon atom (C2) which is part of a group selected from alkyl, aryl, carbonyl and carboxyl, preferably selected from C1 alkyl -C6, phenyl, -COOH and -C (O) H.
    [5]
    5. The method according to any one of claims 1 to 4, wherein the compound that is treated is polystyrene of formula (IV)

    [6]
    6. The method according to any one of the preceding claims, wherein the vanadium compound is selected from the group of salts of vanadium (III), vanadium (IV) and vanadium (V).
    [7]
    7. The method according to claim 6, wherein the salt is selected from vanadium chloride (III), vanadyl acetylacetonate and vanadium oxide (V).
    [8]
    8. The method according to any one of claims 1 to 4 and 6-7, wherein the amount of vanadium used is between 0.01% and 0.0001 mol% relative to the moles of the starting compound.
    [9]
    9. Method according to any one of claims 1, 5, 6-7, wherein the amount of vanadium used is between 1% and 5% by weight with respect to the amount of polystyrene or polystyrene derivative.
    [10]
    10. Process according to any one of the preceding claims, wherein the alkaline salt of organic acid is sodium acetate.
    [11]
    Method according to any one of the preceding claims, in which the alkaline salt is used in an amount of 5% molar to 20% molar with respect to the moles of the starting compound.
    [12]
    12. The method according to any one of the preceding claims, wherein the triazole derivative is methyl 3,5-bis - ((1 H-1,2,4-triazol-1-yl) methyl) benzoate.
    [13]
    13. A method according to any one of claims 1 to 4, 6-7, 8, 10-12, wherein the amount of triazole derivative used is between 0.01% and 0.0001 mol% relative to the moles of the starting compound .
    [14]
    14. A method according to any one of claims 1, 5, 6-7, 9, 10-12, wherein the amount of triazole derivative used is between 1% and 5% by weight with respect to the amount of polystyrene or derived from polystyrene.
    [15]
    15. The method according to any one of the preceding claims, wherein the visible light that is used is selected from red, orange, yellow, green, cyan, light blue, turquoise, blue and violet, and preferably the live violet light is used ( 400-420 nm).
    [16]
    16. P roce im ient according to one of the preceding iv indications, in which the treatment with molecular oxygen is carried out at a total pressure between 81 and 141, 85 kPa (0.8 and 1.4 atm).
    [17]
    17. P rocedim iento according to one of the preceding iv indications, in which the isolate used is read from among others, water, ethylene glycol, propylene glycol, glycerol, polyethylene glycol 400 (PEG -400), polyethylene g licol 1500 (PEG -1500) and its mixtures.
    [18]
    18. A procedure according to Re iv Indication 17, in which the isolate is read from PEG 400, PEG 1500, g liquerol and mixtures thereof.
    2
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