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    • 专利摘要:
    The present invention relates to a hybrid material comprising an MOF of copper and nickel with oxamate ligands {IMAGEN-01} containing sub-nanometric metal clusters, preferably less than 7 atoms, confined in the channels of the MOF, to its method of obtaining and its use as a catalyst in the formation of higher value-added compounds, for example cycloheptatrienes. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2683051A1
    申请号:ES201730226
    申请日:2017-02-22
    公开日:2018-09-24
    发明作者:Emilio José PARDO MARÍN；Antonio LEYVA PÉREZ；Jesús FERRANDO SORIA；Avelino Corma Canós
    申请人:Consejo Superior de Investigaciones Cientificas CSIC；Universidad Politecnica de Valencia；Universitat de Valencia；
    IPC主号:
    专利说明:

    Subnanometric metal clusters confined in metal-organic networks as catalysts for the synthesis of cycloheptatrienes and derivatives Field of the Invention
    The present invention describes sub-nanometric metal clusters confined in the channels of a structured metal-organic material or MOF (acronym for "Metal-Organic Framework"), its method of obtaining and its use as a catalyst in the formation of cycloheptatriennes and derivatives of industrial interest. State of the art
    Recently, sub-nanometric clusters of different metals have aroused the interest of the scientific community and the chemical industry by showing extreme catalytic activity and very good selectivity for different organic reactions (Argo, AM, Odzak, JF, Lai, FS & Gates, BC, Nature 415, 623–626 (2002); Oliver-Meseguer, J., Cabrero-Antonino, JR, Dominguez, I., Leyva-Perez, A. & Corma, A., Science. 338, 1452– 1455 (2012); Boronat, M., Leyva-Pérez, A. & Corma, A., Acc. Chem. Res. 47, 834-844 (2014)). Despite the efforts made, there is a need for synthesis methods that allow us to obtain clusters with a well-known structure, shape and nuclearity (Corma, A. et al., Nat. Chem. 5, 775-781 (2013); Tyo, EC & Vajda, S., Nat. Nanotechnol. 10, 577-588 (2015); Liu, L., Díaz, U., Arenal, R., Agostini, G., Concepción, P. & Corma, A ., Nature Mater. Doi: 10.1038 / nmat4757 (2016)).
    In this sense, MOFs (Furukawa, H., Cordova, KE, O'Keeffe, M. & Yaghi, OM, Science 341, 974 (2013)) have appeared in recent years as very versatile materials to encapsulate catalytic metals within of your channels In addition, these regular and well-defined channels are theoretically perfect chemical environments for obtaining information about the nature of the metallic catalytic species by monocrystalline X-ray crystallography. 1-2 nm nanoparticles have been successfully confined in the channels of certain MOFs ((a) Guo, Z. et al. ACS Catal. 4, 1340-1348 (2014). (B) Liu, H. et al. Angew . Chem., Int. Ed. 55, 5019–5023 (2016). (C) Yang, Q., Xu, Q., Yu, S.-H. & Jiang, H.-L. Angew. Chem., Int. Ed. 55, 3685–3689 (2016). (D) Liu, L. et al. Nanoscale 8, 1407–1412 (2016). (E) Li, X. et al. ACS Catal. 6, 3461– 3468 (2016). (F) Coupry, DE et al. Chem. Commun. 52, 5175-5178 (2016))), but sub-nanometric metal particles in their channels have not been obtained and unambiguously characterized as MOFs with metals confined in their channels obtained to date have not been robust enough
    and crystalline as to allow the determination of its crystalline structure by diffraction of
    X-rays.
    On the other hand, metallic carbenoids are intermediate catalytic species in different processes in organic synthesis, many of them industrial (Maas, G., Angew. Chem., Int. Ed. 48, 8186-8195 (2009)). Normally, these carbenoid intermediates are obtained exclusively with catalysts of noble metal complexes such as rhodium (Anciaux,
    A. J. et al. J. Org. Chem. 46, 873–876 (1981)) and gold (Seidel, G. & Fürstner, A. Angew. Chem., Int. Ed. 53, 4807–4811 (2014)). It is difficult to find carbenoid catalysts based on cheaper and less toxic metals (Solé, D., Mariani, F., Bennasar, M.-L. & Fernández, I., Angew. Chem., Int. Ed. 55, 6467– 6470 (2016)), despite the progress that would mean both academically and industrially. If, in addition, the metal is supported on a solid and has a well-defined structure without ligands, as mentioned above, the catalyst would be even more interesting industrially (Maestre, L. et al. Chem. Sci. 6, 1510– 1515 (2015)). Other transformations catalyzed by non-noble metals without ligands, fundamental in organic synthesis, such as hydrogenations and carbon-carbon couplings, among others (Wu, X.-F., Anbarasan, P., Neumann, H. & Beller, M., Angew. Chem., Int. Ed. 49, 9047-9050 (2010)) could be carried out in situ after the carbenoid-mediated reaction. In this way, we would have a multifunctional solid catalyst to perform cascade processes with reactions of high interest. And this is another objective achieved in the present invention, since MOFs with sub-nanometer metal clusters confined in their channels obtained in accordance with the present invention have been shown to have a catalytic activity and selectivity towards certain reactions of interest far superior to that of similar compounds known to date.
    Cycloheptatrienes and derivatives of the general formula: (where X is C, N, S or O, and R represents any organic substituent or atoms other than carbon) are difficult to prepare due to the high steric hindrance of the 7-member cycles, where Atoms cannot be spatially compacted as in 5 or 6 member cycles and where they do not have the freedom of movement as in larger cycles or linear chains. However, they have potential industrial applications as functionalized C7 compounds, both in themselves as fragrances or drugs, or as precursors of polymers or other molecules of industrial interest. Unfortunately, the methods of preparation to date are basically two: one more direct by dearomatization of aromatic rings and another (s) indirect through synthetic sequences in several steps (McKervey, MA, Tuladhar, SM & Twohig, MF, J Chem. Soc., Chem. Commun. 129-130 (1984)). In principle, only the dearomatization of aromatic rings can have industrial application, but to date the only catalysts that can perform the transformation efficiently are rhodium compounds in solution (a) Anciaux, A. J. et al. J. Org. Chem. 46, 873-876 (1981), very expensive, toxic, and not recoverable.
    The difficulty of obtaining new catalysts with a well-defined structure has recently been highlighted in publications such as Xinle li et at, “Controlling catalytic properties of Pd nanoclusters through their chemical environment at the atomic level using isoreticular metal-organic frameworks”, ACS Catal. 2016, 3461-3468. In this work, which describes nanoclusters (that is, clusters of a size larger than the subanometric) of Pd supported in MOFs, the technical difficulties currently existing to control the catalytic properties of this type of compounds are revealed hybrids and therefore the difficulty in obtaining effective, stable and reusable catalysts.
    Patent document ES 2277531 B2 describes methods of obtaining atomic quantum clusters. However, the method used is by kinetic control, and in addition the clusters are not synthesized in MOF channels.
    In the publication of Barea et al in J. Am. Chem. So. 2005, 127, 18026-18030, the preparation of stabilized Co nano particles in the nanopores of crystalline molecular matrices such as zeolites is described. Also, in Juan-Alcañiz et al, the Journal of Catalysis, 307 (2013) 295-304 describes the inclusion in MOFs of new metallic functionalities through the use of oxamate as a chelating agent. In any case, the catalysts obtained according to the invention exceed in more than one order of magnitude in catalytic activity those described in these publications.
    In patent document CN105664944 A, Cu subnanometric catalysts supported on MOF structures are also described; however, throughout that document there is simply talk of "MOFs" in general, and it does not seem plausible that the invention described therein can be applicable to all known MOFs. Nor does it refer to the size of the clusters obtained, and in addition the preparation procedure is also different, as well as the uses of the catalysts obtained (the removal of organic pollutants in water).
    Finally, in the publication of T. Grancha, J. Ferrando-Soria, H.-C. Zhou, J. Gascon, B. Seoane, J. Pasán, O. Fabelo, M. Julve and E. Pardo, in Angew. Chem., Int. Ed. 2015, 54, 6521-6525 MOFs of similar structure to those used in the present invention are described. However, such MOFs are not described in combination with metal clusters confined in their channels, nor are the procedures for preparing MOFs with metal clusters confined in their channels, since all of this has been developed in the present invention and therefore after said publication. In addition, the possibility of obtaining MOFs with metal clusters confined in their channels from these compounds that are stable, reusable and useful in the synthesis of cycloheptatrienes and their derivatives in a single step was not obvious, since the catalytic activity of the hybrid material The result depends on various non-independent parameters related to size, shape, interaction between materials and quantum effects, whose effect is currently very difficult to predict. And in addition, until now it had not been possible to achieve this type of hybrid materials with a stability against reducing agents sufficient to allow confinement in their cluster channels of a small number of metal atoms.
    The present invention describes the possibility of preparing subnanometric metal clusters confined in the matrix of topologically and electronically well-defined MOFs because they have proved to be robust and crystalline enough to be characterized by X-rays and to resist the action of the reducing agents necessary to generate and confine atomic clusters in the channels of said compounds. Likewise, we describe the use of these metal clusters as sub-nanometer catalysts supported in MOFs for a reaction such as the inter- and intra-molecular Buchner ring expansion (McKervey, MA, Tuladhar, SM & Twohig, MF, J. Chem. Soc., Chem. Commun. 129–130 (1984)), in addition to consecutive reactions to them such as hydrogenations and carbon-carbon couplings, catalyzed in situ by the same sub-nanometric metal cluster supported in MOFs, in the which have shown an activity and selectivity far superior to that of similar compounds. With this methodology, the preparation of cycloheptatriene molecules and derivatives is described, in a single step and in a wide range and variety, using the sub-nanometric metal clusters confined in the MOF structure. In addition, the solid catalyst can be repeatedly recovered and reused, maintaining its activity and catalytic selectivity. Description of the invention
    In general, the present invention relates to a hybrid material comprising a copper and nickel MOF with oxamate ligands Ni2II {NiII 4 [CuII 2 (Me3mpba) 2] 3} · 54H2O (NiII @ MOF) containing subnanometric metal clusters , preferably of less than 7 atoms, confined in the MOF channels, to its method of obtaining and its use as a catalyst in the formation of compounds of greater added value, for example cycloheptatriennes.
    Thus, in a first aspect, the present invention is directed to a hybrid material characterized in that it comprises a structured metal-organic material (MOF) of copper and nickel with oxamate ligands of the formula Ni2II {NiII 4 [CuII 2 (Me3mpba) 2] 3 } · 54H2O (NiII @ MOF) containing porous channels, and subnanometric metal clusters of less than 7 atoms confined in said channels.
    In this regard, "inmates" means herein that the clusters are substantially within the pore of the MOF and not simply perched on any of its outer surfaces. On the other hand, by “supported” it is intended to indicate that the MOF acts as a support for the clusters and, therefore, the clusters are attached to any of the pore walls of the MOF. Therefore, the clusters described herein can be said to be at the same time "confined" in the pores of the MOF and "supported" in the MOF.
    The MOFs used in the present invention have been shown to have the following advantageous properties:
    - They are robust enough to withstand the addition of a reducer without decomposing and thus, in the reduction process only clusters with a reduced number of metal atoms confined in the pores are obtained, instead of nanoparticles with many metal atoms; Y
    - They are crystalline and resistant enough to allow determination by X-rays of the structure of these clusters and thus be able to characterize them unambiguously.
    The metals of which the aforementioned metal clusters are composed, are preferably selected from palladium, iron, nickel, copper, cobalt, gold, platinum, rhodium, silver and combinations thereof, and more preferably between palladium, iron, gold, Platinum and combinations thereof. Said metal is preferably present in a percentage by weight with respect to the MOF between 0.01 and 15%, and more preferably between 1 and 5%.
    In a second aspect, the present invention also relates to the method of obtaining the hybrid material comprising at least the following steps:
    - adsorption of at least one metal in the porous channels a metal-organic material
    structured (MOF) copper and nickel with oxamate ligands of formula
    Ni2II {NiII 4 [CuII 2 (Me3mpba) 2] 3} · 54H2O (NiII @ MOF); and -reduction of the adsorbed metal in the porous channels of the MOF by at least one
    reducing agent,
    thus forming subnanometric metal clusters of less than 7 atoms confined in the MOF channels.
    Finally, in a third aspect, the present invention also relates to the use of these hybrid materials as catalysts in catalytic transformation reactions of aromatic compounds. Surprisingly, these catalysts have proven to be stable, reusable and possess a high catalytic activity in various catalytic transformation reactions of aromatic compounds, such as the synthesis of cycloheptatriennes and their derivatives in a single step.
    The metal adsorbed in the first stage of the preparation process is preferably selected from palladium, iron, nickel, copper, cobalt, gold, platinum, rhodium or silver and combinations thereof, and more preferably from palladium, iron, gold, platinum and combinations thereof. In addition, said metal can be in the MOF channels in the form of any water soluble salt, such as halide, acetate and nitrate, among others (Figure 1).
    According to this procedure, the metal is deposited in the MOF channels in the form of a soluble salt and in amounts preferably between 0.01 and 15%, and more preferably between 1 and 5%, as a percentage by weight of metal over the weight of the MOF , or between 0.01 and 20% by weight, more preferably between 1 and 10%, as a percentage by weight of the soluble metal salt over the weight of the MOF.
    According to a particular embodiment of the present invention, a reducing agent preferably selected from sodium borohydride, hydrazine, hydrogen gas, and combinations thereof, and more preferably is sodium borohydride, is used in the method of preparation that we are describing. Said reducing agent can be used, for example, at room temperature, in water, methanol or combinations thereof, as can be seen in Figure 2. In addition, the reduction step can be carried out following the step of adsorption of the metal in the channels of the MOF, or it can be carried out at a later time, for example as a stage prior to the catalysis reaction when the hybrid material is to be used as a catalyst.
    The amount of reducing agent used is preferably between 1 and 20 equivalents, and more preferably between 1 and 5 equivalents.
    According to a particular embodiment of the present invention, in the process of obtaining the hybrid material described above, sodium borohydride is preferably used as a reducing agent at a concentration between 1 and 5 equivalents.
    In addition, the present invention also relates to the use of the hybrid material obtained according to the method of production described above as a catalyst in different reactions.
    According to a general embodiment of the present invention, the use as catalyst of the metal clusters supported in the MOF occurs after contacting the solid catalyst with an aromatic compound, preferably selected from benzene, toluene, xylenes, anisoles, halobenzenes, and combinations thereof. Some concrete examples that are not intended to be limiting include monocyclic (benzene and its derivatives, furan and its derivatives, pyrrole, pyridine and its derivatives, and thiophene and its derivatives) and polycyclic (anthracene and its derivatives, indole and its derivatives), in amounts preferably less than 10% mol of catalytic metal with respect to the aromatic compound.
    According to a preferred embodiment, the material described in the present invention is used in processes for obtaining products with the general formula:
    where links with dashed lines represent single or double bonds; X can be C, N, O and S; n can vary between 0 and 1; R1 is an alkyl selected from methyl, ethyl, tert-butyl and benzyl; R2 and R3 are substituents such as alkyls, ethers, halogens, esters, aromatic rings and fused rings, or combinations thereof.
    The contact of the hybrid material as a catalyst with the aromatic compound can be carried out in a discontinuous reaction system or in a continuous CSTR or fixed bed reactor.
    In the processes in which the material of the present invention is used as a catalyst, at least one diazo compound can be added to the reaction mixture, an addition that can be carried out in its pure form or dissolved in the aromatic compound a react, in volumes preferably from 1: 1 to 1: 200, and more preferably from 1: 100, and at a suitable addition rate so as not to exceed a 0.02 M concentration at any time. The reaction can be carried out either discontinuously or continuously, in amounts of 10,000 to 10 equivalents of diazo compound with respect to the catalytic metal, preferably 1000 to 100 equivalents.
    Said catalytic reaction can be carried out at a set reaction temperature between 25 ° C and 150 ° C, preferably between 70 ° C and 120 ° C. In addition, the reaction time is between 0.5 to 48 h, preferably between 1 and 24 h, which refers to batch reactions.
    According to a particular embodiment of the present invention, after the reaction other reagents can be used to perform a cascade reaction, either H2 gas, or organic reagents for carbon-carbon coupling.
    According to a particular embodiment of the present invention, the batch reaction can be carried out in a suspension of the solid MOF catalyst, which contains the catalytic metal, dispersed in the aromatic compound, and the diazo compound is controlled in addition.
    According to another particular embodiment of the present invention, the reaction can be carried out in a continuous fixed bed reactor, where the aromatic compound continuously passes through the catalyst at the reaction temperature and where the diazo compound is added in a controlled manner.
    According to a particular embodiment, once the carbenoid-mediated reaction is over, a second reaction can be carried out under H2 atmosphere and under the same experimental conditions as the formation of cycloheptatriene, to give rise to the corresponding saturated cycloheptans.
    According to another particular embodiment, once the carbenoid-mediated reaction is over, a second reaction with aromatic halides can be carried out, under the same experimental conditions as the formation of cycloheptatriene, to give rise to the corresponding substituted cycloheptatriene (Reaction of Heck)
    It is important to note that the hybrid material of the present invention used as a solid catalyst can be repeatedly recovered and reused, substantially maintaining its activity and catalytic selectivity.
    Throughout the description and the claims the word "comprises" is not intended to exclude the presence of other technical characteristics, additives, components or steps. For those skilled in the art, other objects, advantages and features of the invention will be derived partly from the description and partly from the practice of the invention.
    Figures Brief description of the figures
    Figure 1: Structure of the MOF, where the positions of the NiII cations to exchange with the incorporated metals are observed. The oxamato-metal basic ligand unit is enlarged for better viewing.
    Figure 2: Structure of the MOF after the reduction of the exchanged cations, and formation of the clusters.
    Examples
    Non-limiting examples of the present invention are detailed below:
    Example 1: PdII synthesis procedure adsorbed in the MOF.
    [PdII (NH3) 4] [PdII 2 (NH3) 7] 0.5 {NiII 4 [CuII 2 (Me3mpba) 2] 3} · 52H2O was prepared as a powder after contacting 20 g (5.8 mmol) of the corresponding MOF NiII (T. Grancha, J. Ferrando-Soria, H.-C. Zhou, J. Gascon, B. Seoane, J. Pasán, O. Fabelo, M. Julve, E. Pardo, Angew. Chem., Int Ed. 2015, 54, 6521-6525) with 1 L of a solution in water of [Pd (NH3) 4] Cl2 (14 mmol). At the end of the exchange, the sample was filtered and washed with the same solution at room temperature. Green prisms suitable for monocrystalline X-ray diffraction are obtained after contacting 5 mg (0.0015 mmol) of the corresponding NiII MOF with 5 mL of a water solution of [Pd (NH3) 4] Cl2 (0.004 mmol). Anal .: calc (%) for Cu6Ni4Pd2C78H186.5N19.5O88 (3634.8): C, 25.71; H, 5.20; N, 7.69. Found: C, 25.78; H, 5.13; N, 7.65. IR (KBr): v = 3014, 2951 and 2913 cm – 1 (C-H), 1607 cm – 1 (C = O).
    Example 2: Synthesis procedure of Pd clusters confined in the MOF.
    Pd2 @ Na3 {NiII 4 [CuII 2 (Me3mpba) 2] 3} · 56H2O was prepared as a powder using the compound of example 1 (10 g) suspended in a mixture H2O / CH3OH (1: 2), at which an excess of NaBH4 divided into several fractions is added, and added progressively for 24 h. After this time, the sample was filtered and washed with the same solution at room temperature. Anal .: calc (%) for Cu6Ni4Pd2Na3C78H172N12O92 (3648.1): C, 25.68; H, 4.75; N, 4.61. Found: C, 25.68; H, 4.63; N, 4.65. IR (KBr): v = 3013, 2964 and 2914 cm – 1 (C-H), 1603 cm – 1 (C = O).
    Example 3: Preparation procedure for ethyl cyclohepta-2,4,6-trienocarboxylate (3 double bonds, X = C, n = 1, R1 = ethyl, R2 = R3 = hydrogen) in batch by catalysis with confined Pd clusters in the MOF.
    Pd4 @ MOF (10 mg, 0.5 mol%) is added in a 50 mL round bottom flask with double mouth, equipped with a magnetic stirrer and reflux. Benzene (30 mL) is added and the mixture is placed in a preheated oil bath at 80 ° C. Under magnetic stirring, a solution of ethyl diazoacetate (0.75 mmol) in benzene (10 mL) is added for 5 h by syringe pump, and after this time the mixture is allowed to react an additional 3 h. After cooling, the solid is recovered by filtration or decantation, washed with dichloromethane, and reused. The organic phase recovered by filtration and washing is concentrated in a rotary evaporator and dried in a vacuum pump to give the final product as a yellowish oil (91%). IR (u, cm –1): 2981, 1737. 1H NMR (O, ppm; J, Hz): 6.58 (2xCH, 2H, t, J = 3.0), 6.19 (2xCH, 2H, d, J = 8.9) , 5.36 (2xCH, 2H, dd, J = 8.9, 5.6), 4.19 (CH2, 2H, q, J = 7.0), 2.46 (CH, 1H, t, J = 5.6),
    1.24 (CH3, 3H, t, J = 7.1). 13C NMR (O, ppm): 173.1 (C), 130.9 (2xCH), 125.6 (2xCH), 117.2 (2xCH), 61.0 (CH2), 44.1 (CH), 14.2 (CH3).
    Example 4: Preparation procedure for ethyl cyclohepta-2,4,6-trienocarboxylate (3 double bonds, X = C, n = 1, R1 = ethyl, R2 = R3 = hydrogen) in continuous by catalysis with confined Pd clusters in the MOF.
    A paper cartridge with Pd4 @ MOF catalyst (100 mg) was placed in a 25 mL Soxhlet apparatus connected at the top with a condenser. Benzene (100 mL) is added in a 250 mL round bottom flask with two mouths equipped with a magnetic stirrer and connected to the Soxhlet apparatus at the bottom. This flask was placed in a preheated oil bath at 80 ° C. In this way, benzene recirculates all the time through the catalyst. Then, ethyl diazoacetate (10 mmol) is added with a syringe pump, under reflux, continuously for 24 hours. In this way, a solution of ~ 1 gram of cycloheptatriene in 100 mL of benzene (~ 0.1 M, 90% yield) is obtained. The solid catalyst was recovered and washed with dichloromethane to be reused again.
    Example 5: Preparation procedure for ethyl methylcyclohepta-2,4,6-trienocarboxylate (3 double bonds, X = C, n = 1, R1 = ethyl, R2 = methyl, R3 = hydrogen) in batch by catalysis with clusters of Pd confined in the MOF.
    Pd4 @ MOF (10 mg, 0.5 mol%) is added in a 50 mL round bottom flask with double mouth, equipped with a magnetic stirrer and reflux. Toluene (30 mL) is added and the mixture is placed in a preheated oil bath at 80 ° C. Under magnetic stirring, a solution of ethyl diazoacetate (0.75 mmol) in benzene (10 mL) is added for 5 h by syringe pump, and after this time the mixture is allowed to react an additional 3 h. After cooling, the solid is recovered by filtration or decantation, washed with dichloromethane, and reused. The organic phase recovered by filtration and washing is concentrated in a rotary evaporator and dried in a vacuum pump to give the final product as a yellowish oil (57%, 2-methyl / 3-methyl / 4-methyl <5:42:53). IR (u, cm –1): 2927, 1743. 1H NMR (O, ppm; J, Hz; underlined diagnostic signals): 2-methyl: 6.48-5.55 (5xCH, 5H), 4.20 (CH2, 2H, q, J = 7.0), 2.75 (CH, 1H, d, J = 6.7), 2.19 (CH3, 3H, s), 1.26 (CH3, 3H, t, J = 7.0); 3-methyl: 6.39-5.98 (3xCH, 3H), 4.95-4.65 (2xCH, 2H), 4.14 (CH2, 2H, q, J = 7.0), 2.15 (CH, 1H, t, J = 5.0), 1.86 ( CH3, 3H, s), 1.21 (CH3, 3H, t, J = 7.0); 4-methyl: 6.39-5.98 (2xCH, 2H), 5.35 (3xCH, 3H, mult), 4.15 (CH2, 2H, q, J = 7.0), 2.47 (CH, 1H, t, J = 5.3), 1.98 ( CH3, 3H, s), 1.22 (CH3, 3H, t, J = 7.0). 13C NMR (O, ppm; if not indicated, values are common for all three isomers): 173.9-169.7 (C),
    139.8 (2xC 2-methyl), 131.2-113.8 (CH), 68.1-60.7 (CH2), 48.9-39.7 (CH), 24.0-20.7 (CH3), 14.2-14.0 (CH3).
    Example 6: Preparation process for ethyl dimethylcyclohepta-2,4,6-trienocarboxylate (3 double bonds, X = C, n = 1, R1 = ethyl, R2 = methyl, R3 = methyl) in batch by catalysis with clusters of Pd confined in the MOF.
    Pd4 @ MOF (10 mg, 0.5 mol%) is added in a 50 mL round bottom flask with double mouth, equipped with a magnetic stirrer and reflux. P-xylene (30 mL) is added and the mixture is placed in a preheated oil bath at 80 ° C. Under magnetic stirring, a solution of ethyl diazoacetate (0.75 mmol) in benzene (10 mL) is added over 5 h
    by syringe pump, and after this time the mixture is allowed to react an additional 3 h.
    After cooling, the solid is recovered by filtration or decantation, washed with dichloromethane, and reused. The organic phase recovered by filtration and washing is concentrated on a rotary evaporator and dried in a vacuum pump to give the final product as a yellowish oil (64%, 1,4-dimethyl / 2,5-dimethyl / 3,6-dimethyl <5:26:69). IR (u, cm –1): 2983, 2931, 1741. 1H NMR (O, ppm; J, Hz; underlined diagnostic signals): 2,5-dimethyl: 6.14-5.59 (2xCH, 2H), 4.71-4.18 ( 2xCH, 2H), 4.24 (CH2, 2H, q, J = 7.0), 2.79 (CH, 1H, d, J = 7.0), 1.96 (CH3, 3H, s), 1.87 (CH3, 3H, s), 1.20 (CH3, 3H, t, J = 7.0); 3,6-dimethyl: 7.17-7.02 (2xCH, 2H), 5.99-5.92 (2xCH, 2H),
    4.20 (CH2, 2H, q, J = 7.0), 2.24 (CH, 1H, t, J = 10.0), 1.88 (2xCH3, 6H, s), 1.21 (CH3, 3H, t, J = 7.0). 13C NMR (O, ppm; values are common for all three isomers): 178.7-171.0 (C),
    132.8 (2xC), 128.7-119.2 (CH), 63.6-60.6 (CH2), 51.5-47.2 (CH), 23.8-20.4 (CH3), 14.2-13.8 (CH3).
    Example 7: Preparation procedure for ethyl methoxycyclohepta-2,4,6-trienecarboxylate (3 double bonds, X = C, n = 1, R1 = ethyl, R2 = methoxy, R3 = hydrogen) in batch by catalysis with clusters of Pd confined in the MOF.
    Pd4 @ MOF (10 mg, 0.5 mol%) is added in a 50 mL round bottom flask with double mouth, equipped with a magnetic stirrer and reflux. Anisole (30 mL) is added and the mixture is placed in a preheated oil bath at 80 ° C. Under magnetic stirring, a solution of ethyl diazoacetate (0.75 mmol) in benzene (10 mL) is added for 5 h by syringe pump, and after this time the mixture is allowed to react an additional 3 h. After cooling, the solid is recovered by filtration or decantation, washed with dichloromethane, and reused. The organic phase recovered by filtration and washing is concentrated in a rotary evaporator and dried in a vacuum pump to give the final product as a yellowish oil (92%, 2-methoxy / 3-methoxy / 4-methoxy 27: <5:68). IR (u, cm –1): 2984, 1738. 1H NMR (O, ppm; J, Hz; underlined diagnostic signals): 2-methoxy: 6.42-6.16 (3xCH, 3H), 5.48-5.40 (2xCH, 2H) ,
    4.11 (CH2, 2H, q, J = 7.0), 3.56 (CH3, 3H, s), 3.23 (CH, 1H, d, J = 7.3), 1.18 (CH3, 3H, t, J = 7.1); 4-methoxy: 6.13 (CH, 1H, ddd, J = 8.0, 6.7, 1.1), 6.00 (CH, 1H, dt, J = 9.9, 3.3), 5.79 (CH, 1H, dd, J = 6.6, 1.7) , 5.54 (CH, 1H, quintd, J = 5.6, 1.7), 5.19 (CH, 1H, ddd, J = 8.8, 5.2, 0.7),
    4.18 (CH2, 2H, q, J = 7.0), 3.58 (CH3, 3H, s), 2.62 (CH, 1H, t, J = 5.0), 1.23 (CH3, 3H, t, J = 7.1). 13C NMR (O, ppm): 2-methoxy: 170.1 (C), 149.1 (C), 128.0 (CH), 126.9 (CH), 124.5 (CH),
    117.8 (CH), 97.3 (CH), 60.9 (CH2), 56.6 (CH3), 48.9 (CH), 14.3 (CH3); 4-methoxy: 172.9 (C),
    160.0 (C), 124.8 (CH), 122.1 (CH), 119.9 (CH), 117.1 (CH), 104.8 (CH), 61.0 (CH2), 54.7 (CH3), 44.0 (CH), 14.2 (CH3).
    Example 8: Preparation procedure for tert-butyl cyclohepta-2,4,6-trienocarboxylate (3 double bonds, X = C, n = 1, R1 = tert-butyl, R2 = R3 = hydrogen) in batch by catalysis with Pd clusters confined in the MOF.
    Pd4 @ MOF (10 mg, 0.5 mol%) is added in a 50 mL round bottom flask with double mouth, equipped with a magnetic stirrer and reflux. Benzene (30 mL) is added and the mixture is placed in a preheated oil bath at 80 ° C. Under magnetic stirring, a solution of tert-butyl diazoacetate (0.75 mmol) in benzene (10 mL) is added for 5 h by syringe pump, and after this time the mixture is allowed to react an additional 3 h. After cooling, the solid is recovered by filtration or decantation, washed with dichloromethane, and reused. The organic phase recovered by filtration and washing is concentrated in a rotary evaporator and dried in a vacuum pump to give the final product as a yellowish oil (32%). IR (u, cm –1): 2926, 1732. 1H NMR (O, ppm; J, Hz): 6.56 (2xCH, 2H, t, J = 4.0), 6.16 (2xCH, 2H, d, J = 8.9) , 5.34 (2xCH, 2H, dd, J = 8.9, 5.6), 2.38 (CH, 1H, t, J = 5.6), 1.48 (3xCH3, 9H, s). 13C NMR (O, ppm): 172.2 (C), 134.5 (2xCH), 128.3 (2xCH), 118.4 (2xCH), 45.1 (CH), 27.9 (3xCH3).
    Example 9: Preparation procedure of benzyl cyclohepta-2,4,6-trienocarboxylate (3 double bonds, X = C, n = 1, R1 = benzyl, R2 = R3 = hydrogen) in batch by catalysis with confined Pd clusters in the MOF.
    Pd4 @ MOF (10 mg, 0.5 mol%) is added in a 50 mL round bottom flask with double mouth, equipped with a magnetic stirrer and reflux. Benzene (30 mL) is added and the mixture is placed in a preheated oil bath at 80 ° C. Under magnetic stirring, a solution of benzyl diazoacetate (0.75 mmol) in benzene (10 mL) is added for 5 h by syringe pump, and after this time the mixture is allowed to react an additional 3 h. After cooling, the solid is recovered by filtration or decantation, washed with dichloromethane, and reused. The organic phase recovered by filtration and washing is concentrated in a rotary evaporator and dried in a vacuum pump to give the final product as a yellowish oil (73%). IR (u, cm –1): 2985, 1738. 1H NMR (O, ppm; J, Hz): 7.43-7.34 (5xCH, 5H), 6.69 (2xCH, 2H, t, J = 3.1), 6.30 (2xCH , 2H, d, J = 8.8), 5.50 (2xCH, 2H, dd, J = 8.8, 5.6),
    5.29 (CH2, 2H, s), 2.67 (CH, 1H, t, J = 5.6). 13C NMR (O, ppm): 172.9 (C), 135.9 (C), 130.9 (2xCH), 128.5 (2xCH), 128.4 (CH), 128.2 (2xCH), 125.7 (2xCH), 116.7 (2xCH), 66.8 ( CH2),
    44.0 (CH).
    Example 10: Procedure for preparing ethyl cycloheptacarboxylate (no double bond, X = C, n = 1, R1 = ethyl, R2 = R3 = hydrogen) in batch by catalysis with Pd clusters confined in the MOF.
    Pd4 @ MOF (10 mg, 0.5 mol%) is added in a 50 mL round bottom flask with double mouth, equipped with a magnetic stirrer and reflux. Benzene (30 mL) is added and the mixture is placed in a preheated oil bath at 80 ° C. Under magnetic stirring, a solution of ethyl diazoacetate (0.75 mmol) in benzene (10 mL) is added for 5 h by syringe pump, and after this time the mixture is allowed to react an additional 3 h. After cooling, the liquid is concentrated and a hydrogen atmosphere is placed. The flask is placed back in the preheated bath at 80 ° C and reacted until all double bonds are hydrogenated. The solid is recovered by filtration or decantation and washed with dichloromethane. The organic phase recovered by filtration and washing is concentrated in a rotary evaporator and dried in a vacuum pump to give the final product.
    Example 11: Preparation procedure for ethyl phenylcyclohepta-2,4,6-trienecarboxylate (3 double bonds, X = C, n = 1, R1 = ethyl, R2 = benzene, R3 = hydrogen) in batch by catalysis with clusters of Pd confined in the MOF.
    Pd4 @ MOF (10 mg, 0.5 mol%) is added in a 50 mL round bottom flask with double mouth, equipped with a magnetic stirrer and reflux. Benzene (30 mL) is added and the mixture is placed in a preheated oil bath at 80 ° C. Under magnetic stirring, a solution of ethyl diazoacetate (0.75 mmol) in benzene (10 mL) is added for 5 h by syringe pump, and after this time the mixture is allowed to react an additional 3 h. After cooling, the liquid is concentrated and iodobenzene (1 mmol), potassium acetate (2 mmol) and N-methyl pyrrolidone (5 mL) are added. The reaction mixture is placed back in the pre-heated bath, at 130 ° C this time, and reacted until all double bonds are hydrogenated. The solids are recovered by filtration. The organic phase recovered by filtration and washing is washed with water, dried and concentrated on a rotary evaporator to give the final product.
    Example 12: Preparation of sub-nanometer clusters of Fe, Pt, Ag and Au.
    Following a procedure identical to that described for Pd (examples 1 and 2), hybrid materials and the corresponding sub-nanometer clusters of Fe, Pt, Ag and Au have been synthesized, in addition to their bimetallic mixtures. The procedure consisted of: 1. insertion of the corresponding salt: (NH4) 2Fe (SO4) 2 · 6H2O, [Pt (NH3) 4] Cl2, AgNO3 and AuCl3 (as described in example 1). 2. Reduction using any of the reducers described above (as described in example 2). All these species have shown catalytic activity in the synthesis of cycloheptatrienes and derivatives (examples 311).
    Similarly, the inventors are of the conviction that the invention described herein may be equally applicable to other metals, such as Ni, Cu, Co or Rh, to say some illustrative examples.
    权利要求:
    Claims (24)
    [1]
    one. Hybrid material characterized in that it comprises a structured metal-organic material (MOF) of copper and nickel with oxamate ligands of the formula Ni2II {NiII 4 [CuII 2 (Me3mpba) 2] 3} · 54H2O (NiII @ MOF) containing porous channels, and subnanometric metal clusters of less than 7 atoms confined in said channels.
    [2]
    2. Hybrid material according to claim 1, characterized in that the metal of the subnanometric metal clusters is selected from the group consisting of palladium, iron, nickel, copper, cobalt, gold, platinum, rhodium or silver and combinations thereof.
    [3]
    3. Hybrid material according to claim 2, characterized in that the metal of the subnanometric metal clusters is selected from the group consisting of palladium, iron, gold, platinum and combinations thereof.
    [4]
    Four. Hybrid material according to claim 3, characterized in that the metal of the subnanometric metal clusters is palladium.
    [5]
    5. Hybrid material according to any one of the preceding claims 1 to 4, characterized in that the metal of the sub-nanometric metal clusters is in a percentage by weight with respect to the MOF of between 0.01 and 15%.
    [6]
    6. Hybrid material according to claim 5, characterized in that the metal of the sub-nanometric metal clusters is in a percentage by weight with respect to the MOF of between 1 and 5%.
    [7]
    7. Method of obtaining a hybrid material according to any one of claims 1 to 6 above characterized in that it comprises the steps of:
    - adsorption of at least one metal in the porous channels a structured metal-organic material (MOF) of copper and nickel with oxamate ligands of the formula Ni2II {NiII 4 [CuII 2 (Me3mpba) 2] 3} · 54H2O (NiII @ MOF); Y
    - reduction of adsorbed metal in the porous channels of the MOF by at least one reducing agent,
    thus forming subnanometric metal clusters of less than 7 atoms confined in the MOF channels.
    [8]
    8. Method of obtaining a hybrid material according to claim 7, characterized in that the at least one metal adsorbed in the porous channels of the MOF is selected from the
    group consisting of palladium, iron, nickel, copper, cobalt, gold, platinum, rhodium or silver and
    combinations thereof.
    [9]
    9. Process for obtaining a hybrid material according to claim 8, characterized in that the at least one metal adsorbed in the porous channels of the MOF is selected from the group consisting of palladium, iron, gold, platinum, and combinations thereof.
    [10]
    10. Method of obtaining a hybrid material according to claim 9, characterized in that the metal adsorbed in the MOF channels is palladium.
    [11]
    eleven. Process for obtaining a hybrid material according to any of claims 7 to 10, characterized in that the metal adsorbed in the MOF channels is added to the MOF in the form of any water soluble salt of the metal.
    [12]
    12. Process for obtaining a hybrid material according to claim 11, characterized in that the water soluble salt of the metal is a metal halide, acetate or nitrate.
    [13]
    13. Process for obtaining a hybrid material according to claims 11 or 12, characterized in that the water soluble salt of the metal is added to the MOF in a weight percentage of salt with respect to the MOF of between 0.01 and 20%.
    [14]
    14. Process for obtaining a hybrid material according to claim 13, characterized in that the water soluble salt of the metal is added to the MOF in a weight percentage of salt with respect to the MOF of between 1 and 10%.
    [15]
    fifteen. Process for obtaining a hybrid material according to any one of claims 7 to 14, characterized in that the reducing agent is selected from the group consisting of sodium borohydride, hydrazine, hydrogen gas, and combinations thereof.
    [16]
    16. Process for obtaining a hybrid material according to claim 15, characterized in that the reducing agent is sodium borohydride.
    [17]
    17. Process for obtaining a hybrid material according to any of claims 7 to 16, characterized in that the reducing agent is added in the reduction stage at a concentration of between 1 and 20 equivalents.
    [18]
    18. Process for obtaining a hybrid material according to claim 17, characterized in that the reducing agent is added in the reduction stage at a concentration of between 1 and 5 equivalents.
    [19]
    19. Process for obtaining a hybrid material according to any one of claims 7 to 18, characterized in that the metal reduction stage is carried out following the metal adsorption stage in the MOF channels.
    [20]
    twenty. Procedure for obtaining a hybrid material according to any one of the
    5 claims 7 to 18 characterized in that the metal reduction stage is carried out after the metal adsorption stage and as a previous stage before the use of the hybrid material as a catalyst.
    [21]
    21. Use of a hybrid material according to any one of claims 1 to 6 as a catalyst.
    22. Use of a hybrid material according to claim 21 as a catalyst in catalytic transformation reactions of an aromatic compound.
    [23]
    23. Use of a hybrid material according to claims 21 or 22 wherein the catalytic transformation reaction of an aromatic compound is carried out continuously.
    [24]
    24. Use of a hybrid material according to claims 21 or 22 wherein the catalytic transformation reaction of an aromatic compound is carried out batchwise.
    [25]
    25. Use of a hybrid material according to any one of claims 22 to 24, characterized in that the aromatic compound that is transformed is selected from benzene and its derivatives, toluene and its derivatives, xylenes, anisoles, halobenzenes, and combinations thereof.
    Use of a hybrid material according to claim 25 in obtaining by catalysis of products with the general formula:
    where links with dashed lines represent single or double bonds; X can be C, N, O and S; n can vary between 0 and 1; R1 is an alkyl selected from methyl, ethyl, R2 R3
    tert-butyl and benzyl; and are substituents selected from alkyls, ethers, halogens, esters, aromatic rings and fused rings, or combinations thereof.
    Figure 1
    Figure 2
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    WO2018154166A1|2018-08-30|
    ES2683051B1|2019-06-26|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE102005037893A1|2005-08-10|2007-02-15|Süd-Chemie AG|Process for the preparation of highly active metal / metal oxide catalysts|CN109158127B|2018-07-02|2020-07-31|浙江大学|Palladium-loaded ferrocenyl ultrathin metal organic framework nanosheet and preparation method thereof|
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