WO2011048247A1 - Method for obtaining hybrid catalysts composed of transition-metal complexes encapsulated in porous silica, titania or zirconia nanoparticles - Google Patents

Method for obtaining hybrid catalysts composed of transition-metal complexes encapsulated in porous silica, titania or zirconia nanoparticles Download PDF

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WO2011048247A1
WO2011048247A1 PCT/ES2010/070663 ES2010070663W WO2011048247A1 WO 2011048247 A1 WO2011048247 A1 WO 2011048247A1 ES 2010070663 W ES2010070663 W ES 2010070663W WO 2011048247 A1 WO2011048247 A1 WO 2011048247A1
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titania
nanoparticles
silica
organometallic complex
transition
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PCT/ES2010/070663
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Spanish (es)
French (fr)
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Alberto COELHO COTÓN
Eddy SOTELO PÉREZ
Francisco GUITIÁN RIVERA
Alvaro GIL GONZÁLEZ
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Universidade De Santiago De Compostela
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
    • B01J2231/4211—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
    • B01J2231/4255—Stille-type, i.e. RY + R'3SnR'', in which R is alkenyl, aryl, R' is alkyl and R'' is alkenyl or aryl
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
    • B01J2231/4261—Heck-type, i.e. RY + C=C, in which R is aryl
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
    • B01J2231/4266—Sonogashira-type, i.e. RY + HC-CR' triple bonds, in which R=aryl, alkenyl, alkyl and R'=H, alkyl or aryl
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/824—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/828—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel

Definitions

  • the present invention relates to the development of hybrid catalyst systems.
  • These 5 systems comprise nanoparticles of silica, titania or zirconia in which transition metal catalytic complexes are encapsulated by direct interaction with a non-functionalized inorganic matrix.
  • These new materials facilitate the implementation of environmentally friendly processes (Green chemistry). It also refers to preparation procedures.
  • Transitions catalyzed by transition metals and especially those that employ catalytic systems containing Palladium, occupy a prominent place among the synthetic methodologies of modern Organic Chemistry. These transformations allow efficient access to highly complex structures, using experimental conditions5 that are soft and respectful of the environment. Much of the progress made in this area is a consequence of the development of the catalytic systems available today, homogeneous or heterogeneous, which have different advantages and disadvantages.
  • the catalyst In homogeneous catalysis, the catalyst is dispersed in the reaction medium, which usually results in greater efficiency of the catalytic process and high selectivity.
  • heterogeneous catalysis is preferred on an industrial scale, mainly because of the possibility of recovering and reusing the catalyst.
  • hybrid catalytic systems guarantees an efficient catalysis by offering the homogeneous catalyst an environment of a heterogeneous nature that supports it and which, depending on the structure of the latter, chemically stabilizes it. Additionally, 0 this type of materials allows a treatment similar to heterogeneous catalysts, facilitating the processes of purification, recovery and reuse of the catalyst.
  • a representative example of this type of materials has been recently described (ChemFiles Aldrich, 2004, Vol. 4, No. 7 and references cited there), using a highly crosslinked polyurea matrix as support.
  • titania or zirconia In order to evaluate the novelty and inventive activity of the new materials described in the present invention, the most significant structural characteristics of the catalytic systems, which make up the current state of the subject, especially those formed by silica nanoparticles, are listed below. titania or zirconia:
  • the established catalytic materials are formed by a functionalized polymer matrix, that is, in addition to the inorganic polymer structure that supports them, these materials incorporate a spacer or linker grouping.
  • This linker is incorporated into the matrix during the polymerization step, usually combining a non-functionalized teratraalkoxide [typically Si (OEt) 4 ] and a functionalized tetraalkoxide [eg Si (OEt) 3 R].
  • a non-functionalized teratraalkoxide typically Si (OEt) 4
  • a functionalized tetraalkoxide eg Si (OEt) 3 R
  • the spacer group (or linker) is formed by carbon chains (typically: alkyl, alkylaryl, aminoalkyl, aminoacidic, etc.) that covalently bind to the polymer matrix. These groupings usually contain a functional group whose function is to allow the fixation of the metallic species to the functionalized solid support (by chelation or ionic interaction).
  • this invention describes new materials with catalytic activity that provide novelties related to the structure of the polymer matrix of the nanoparticle, as well as the way in which the catalytic species are fixed to it. Additionally, the procedure claimed in this application constitutes a simple, economical, robust and efficient synthesis method.
  • the present invention provides a hybrid catalytic system, formed by a non-functionalized polymer matrix that incorporates an organometallic complex, whose preparation process involves a single robust, efficient and economical synthetic step.
  • the new materials developed have two key elements that distinguish them from other catalytic systems: the polymer matrix does not contain spacer groups and / or Linkers (not functionalized), the way in which the catalytic species are fixed to the solid support (when they are trapped in the matrix during the polymerization / encapsulation process).
  • the matrix can be nanoparticles of different materials (Si0 2, Ti0 2 Zr0 or 2). Porosity and nanometric dimensions provide a large specific surface area, which increases the distribution of the catalyst in the nanoparticles as a whole and therefore the catalytic efficiency of the system. These systems are stable and reusable, they also have the advantage that they prevent the contamination of the reaction products by the catalyst, which makes them suitable for use among others, in the pharmaceutical industry, in addition to being used in environmentally friendly synthesis methodologies.
  • the invention is directed to a chemically stable hybrid catalytic system comprising non-functionalized silica, titania or zirconia nanoparticles (and therefore do not contain spacers and / or functional groups) that support an organometallic complex of a transition metal
  • a chemically stable hybrid catalytic system comprising non-functionalized silica, titania or zirconia nanoparticles (and therefore do not contain spacers and / or functional groups) that support an organometallic complex of a transition metal
  • Another novel aspect of the invention relates to the way in which the organometallic species are fixed (encapsulated) to the polymer matrix, by direct interaction with the solid support during the formation of the nanoparticles.
  • the invention is directed to a process for the preparation of said system, which comprises the addition of an organometallic complex on a reaction mixture composed of a non-functionalized silicon tetra-alkyloxide, titanium or zirconium in a solution, while hydrolysis / condensation occurs according to a sol-gel process.
  • the invention is directed to the use of said system in organic synthesis reactions, in the pharmaceutical, chemical or agrochemical industry, and in environmentally friendly chemical processes characteristic of Green Chemistry.
  • Figure 1 Image obtained by electron microscopy (SEM) of a sample of non-functionalized Si0 2 nanoparticles in which Pd (PPh 3 ) 4 is encapsulated.
  • hybrid catalyst system means a system in which a homogeneous component with catalytic properties is fixed to a non-functionalized polymer matrix.
  • the homogeneous component is an organometallic complex of a transition metal and the polymeric matrix consists of silica, titania or zirconia nanoparticles. Fixing the homogeneous component to the polymer matrix produces a heterogenization effect, which prevents the complex Organometallic diffusion to the reaction medium, although its catalytic efficiency does not diminish. Said fixation is carried out by capturing the homogeneous component in the matrix without mediation of functional groups or Linkers during the stage of particle formation.
  • This type of fixation avoids the use of functionalized supports, provides stability to the new material and additionally guarantees levels of crosslinking of the polymer (encapsulation) that prevent the release of the organometallic complex to the reaction medium and the consequent contamination of the reaction products with traces of metals Simultaneously, the porous nature of the solid support facilitates the migration of the reactants into the nanoparticles, where they are transformed into products to later return to the solvent.
  • polymer matrix nonfunctionalized means a solid support of a polymeric nature which does not contain spacer chains and / or functional groups (for example Si0 2, Ti0 2 Zr0 or 2).
  • nanoparticles refers to stable structures with homogeneous, reproducible and modulable characteristics, in size and shape, which constitute a cross-linking matrix, whose average size is less than 1 micrometer, that is, between 1 and 999 nm, preferably between 50 and 600 nm.
  • average size means the average diameter of the nanoparticle population, which comprises the matrix structure.
  • the average size of these systems is measured by image analysis using SEM (scanning electron microscopy).
  • organometallic complex means a homogeneous catalyst of an organometallic nature that contains in its structure a transition metal.
  • the transition metal of the organometallic complex is selected from Palladium, Platinum, Cobalt, Nickel.
  • the organometallic complex is preferably selected from (PdC; -. ( ⁇ ⁇ ) Pd (PPh 3) 4, ⁇ 5 ⁇ (i ⁇ PPh K Pt (PPh 3), i, ⁇ ⁇ .. PPh>) ⁇ ( ' ! ⁇ . [Ni (acac) 2 ] 3 .
  • the organometallic complex is in a proportion between 0.05 and 5% by weight.
  • the process of preparing the catalyst systems of the present invention comprises a single step of adding an organometallic complex onto a reaction mixture.
  • Said reaction mixture is composed of a silicon, titanium or zirconium tetraalkylalkoxide in a solution in which a hydrolysis / condensation process is taking place according to a sol-gel process.
  • the sol-gel process is widely known in the state of the art (J. Colloid Interface Sci., 26, p62, 1968. Langmuir 14, p5396, 1998. J. Amer. Chem. Soc. 128, p 968, 2006. Colloids Surf. 1997, p7, 2002. Biomaterials, 25, p723, 2004).
  • the sol-gel process involves the hydrolysis and condensation of metalorganic precursors that results in a gel consisting of a network of interconnected metal-oxygen-metal bonds in three dimensions. For example, if the precursor were tetraethoxysilane [Si (OEt) 4 ], a gel with Si-O-Si bonds would be obtained.
  • the reaction mixture in which hydrolysis / condensation is occurring comprises ammonia, water and an alkyl alcohol.
  • these procedures have been modified, by including a stage in the synthesis of the nanoparticles, which consists in adding the homogeneous catalyst to the reaction mixture in which the synthesis is taking place, seeking that the inclusion of the catalyst in the Silica nanoparticle, titania or zirconia, can be performed in the same synthesis operation of said nanoparticle, which simplifies and economizes its obtaining.
  • the synthesis of silica nanoparticles is carried out by hydrolysis / condensation of Si tetraethylalkoxide, by reaction with NH 4 OH and H 2 0 in Ethanol.
  • the reaction is started by adding Si tetra-ethyl alkoxide to the mixture.
  • the final concentration in the mixture of each of the reagents determines the size of the nanoparticles.
  • the concentration of the reagents in the reaction mixture was: NH 4 OH 1 M, H 2 0 1.3 M and 0.17 M for the tetraethylalkoxide of Si .
  • the reaction medium After approximately 15 minutes of adding the alkoxide, the reaction medium begins to become cloudy, with a whitish color that increases its intensity with the passage of weather. At that time the organometallic compound (homogeneous catalyst), Pd (PPh 3 ) 4 is added to the mixture.
  • the reaction medium is kept under continuous stirring at an approximate temperature of 22 ° C for approximately 12 hours. Once this time has elapsed, the reaction product is separated and washed. The mixture is centrifuged, the supernatant is removed and the nanoparticles are redispersed in ethanol. This process is repeated three times. Next, three more redispersed washings of the nanoparticles in water are performed.
  • the final sample is allowed to dry at room temperature and the final product, Si0 2 -Pd (PPh 3 ) 4, is obtained as a fine powder.
  • the final product Si0 2 -Pd (PPh 3 ) 4
  • concentrations of NH 4 OH and H 2 average particle sizes of 133 nm were obtained.
  • concentrations 105 and 220 nm particles were also obtained.
  • Figure 1 shows the non-functionalized S1O 2 nanoparticles in which Pd (PPh 3 ) 4 is encapsulated.
  • the image obtained by electron microscopy (SEM), shows particles with an average size of 133 nm.
  • SEM electron microscopy
  • Figure 2 the presence of Palladium in the particles of the sample of the Figure is confirmed by an elementary chemical analysis by X-ray dispersive energy (EDS).
  • the ability of the metal that is encapsulated in the nanoparticles to pass into the reaction medium has also been evaluated.
  • the three-phase method was used, using another reagent supported on a silica matrix as an auxiliary: mercaptopropi ⁇ -si ⁇ ice ((Si () 2 ) -CH 2 -CH 2 -CH 2 -SH) (Paris, M., Valette, D., Fagnou,., J.
  • the experiments carried out involve the initial incubation of mercaptopropyl silica with the catalyst (2% mol, Pd (PPh 3 ) 4 for the reaction of Suzuki and Pd (PPh 3 ) 2 Cl 2 for Sonogashira, Heck and Stille) for 1 hour and subsequently adding the remaining reactants to the reaction vial. After 24 hours have elapsed under the same experimental conditions described for the type experiment, the absence of coupling products is checked, by comparison with a previously obtained authentic sample (TLC and HPLC), and that the starting products remain unchanged.
  • the catalyst 20% mol, Pd (PPh 3 ) 4 for the reaction of Suzuki and Pd (PPh 3 ) 2 Cl 2 for Sonogashira, Heck and Stille
  • the hybrid catalysts were prepared [Si0 2 -
  • the hybrid catalyst is recovered by filtration, washed 3 times (10 mL) with the solvent used therein and subsequently with water (10 mL) and dried under vacuum.
  • This same catalyst has been used in at least 5 experiments without appreciating a significant decrease in its catalytic capacity, evaluated according to the percentages of yield of the products obtained in each transformation. As an example it follows yields obtained during reaction of 4-bromobenzonitrile with phenylboronic acid using recycled catalyst: 2nd experiment: 74%, 3rd experiment: 75%, 4th experiment: 70%, 4 or experiment: 70 %.
  • the catalyst is recovered by filtration, washed 3 times (10 mL) with the solvent used therein and subsequently with water (10 mL) and dried under vacuum.
  • This same catalyst has been used in at least 5 experiments without appreciating a significant decrease in its catalytic capacity, evaluated according to the percentages of yield of the products obtained in each transformation.
  • the yields obtained during the reaction of iodobenzene with phenylacetylene are indicated below using the recycled catalyst: 2nd experiment: 80%, 3rd experiment: 79%, 4th experiment: 78%, 4th experiment: 80%>.
  • the catalyst is recovered by filtration, washed 3 times (10 mL) with the solvent used therein and subsequently with water (10 mL) and dried under vacuum.
  • This same catalyst has been used in at least 5 experiments without appreciating a significant decrease in its catalytic capacity, evaluated according to the percentages of yield of the products obtained in each transformation. As an example it follows yields obtained during reaction of 4-bromobenzonitrile with propargyl alcohol using the recycled catalyst 2 or experiment: 73%, 3rd experiment: 75%, 4th experiment: 73%, 4th experiment: 75 %.
  • the catalyst is recovered by filtration, washed 3 times (10 mL) with the solvent used therein and subsequently with water (10 mL) and dried under vacuum.
  • This same catalyst has been used in at least 5 experiments without appreciating a significant decrease in its catalytic capacity, evaluated according to the percentages of yield of the products obtained in each transformation. For example it follows yields obtained during reaction of 4-iodobenzonitrilo with acrylate using the recycled catalyst: 2 or experiment: 95%, 3rd experiment: 95%, 4th experiment: 92%, 4th experiment: 93%

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Abstract

The present invention describes a chemically stable hybrid catalytic system that comprises non-functionalized silica, titania or zirconia nanoparticles and a transition-metal organometallic complex. In the novel materials described, the catalytic species are encapsulated in the polymeric matrix by means of direct interaction therewith, without the need to incorporate linkers or functional groups. Also described is a method for obtaining said catalytic system in a single step by means of the sol-gel method, using reactions comprising hydrolysis and condensation of alkoxides of Si, Ti or Zr in a medium to which the transition-metal organometallic complexes are added whilst hydrolysis/condensation of the alkoxide takes place. Said catalytic systems are used in the synthesis of organic compounds and in the chemical and pharmaceutical industries.

Description

PROCEDIMIENTO DE OBTENCIÓN DE CATALIZADORES HÍBRIDOS COMPUESTOS POR COMPLEJOS DE METALES DE TRANSICIÓN ENCAPSULADOS EN NANOP ARTICULAS POROSAS DE SÍLICE, TITANIA O CIRCONIA  PROCEDURE FOR OBTAINING HYBRID CATALYSTS COMPOSED BY COMPLEXES OF TRANSITION METALS ENCAPSULATED IN NANOP POROUS ARTICLES OF SILICON, TITANIA OR CIRCONIA
Sector de la técnica Technical sector
La presente invención se refiere al desarrollo de sistemas catalíticos híbridos. Estos 5 sistemas comprenden nanopartículas de sílice, titania o circonia en las que se encapsulan complejos catalíticos de metales de transición por interacción directa con una matriz inorgánica no funcionalizada. Estos nuevos materiales facilitan la implementación de procesos respetuosos con el medio ambiente (Química verde). También se refiere a procedimientos de preparación. The present invention relates to the development of hybrid catalyst systems. These 5 systems comprise nanoparticles of silica, titania or zirconia in which transition metal catalytic complexes are encapsulated by direct interaction with a non-functionalized inorganic matrix. These new materials facilitate the implementation of environmentally friendly processes (Green chemistry). It also refers to preparation procedures.
0 Antecedentes de la invención 0 Background of the invention
Las reacciones catalizadas por metales de transición, y en especial aquellas que emplean sistemas catalíticos que contienen Paladio, ocupan un lugar prominente entre las metodologías sintéticas de la Química Orgánica moderna. Estas transformaciones permiten acceder de forma eficiente a estructuras de gran complejidad, empleando condiciones5 experimentales suaves y respetuosas con el medio ambiente. Gran parte de los avances alcanzados en este tema son consecuencia del desarrollo de los sistemas catalíticos hoy disponibles, homogéneos o heterogéneos, que presentan diferentes ventajas e inconvenientes. En la catálisis homogénea el catalizador está disperso en el medio de reacción, lo que habitualmente se traduce en una mayor eficiencia del proceso catalítico y0 una alta selectividad. Pese a estas ventajas, la catálisis heterogénea es la preferida a escala industrial, principalmente por la posibilidad de recuperar y reutilizar el catalizador. Sin embargo, y a pesar del enorme potencial de este tipo de transformaciones, su aplicación en áreas como las industrias farmacéutica y agroquímica permanece limitada por la incapacidad de satisfacer, de forma eficiente, los rigurosos controles establecidos por las5 agencias reguladoras en relación con las cantidades de metales presentes en medicamentos y productos fitosanitarios.  Transitions catalyzed by transition metals, and especially those that employ catalytic systems containing Palladium, occupy a prominent place among the synthetic methodologies of modern Organic Chemistry. These transformations allow efficient access to highly complex structures, using experimental conditions5 that are soft and respectful of the environment. Much of the progress made in this area is a consequence of the development of the catalytic systems available today, homogeneous or heterogeneous, which have different advantages and disadvantages. In homogeneous catalysis, the catalyst is dispersed in the reaction medium, which usually results in greater efficiency of the catalytic process and high selectivity. Despite these advantages, heterogeneous catalysis is preferred on an industrial scale, mainly because of the possibility of recovering and reusing the catalyst. However, despite the enormous potential of this type of transformation, its application in areas such as the pharmaceutical and agrochemical industries remains limited due to the inability to satisfy, in an efficient way, the rigorous controls established by the 5 regulatory agencies in relation to the amounts of metals present in medicines and phytosanitary products.
El desarrollo de sistemas catalíticos híbridos, garantiza una catálisis eficiente al ofrecer al catalizador homogéneo un entorno de naturaleza heterogénea que le sirve de soporte y que, dependiendo de la estructura de este último, lo estabiliza químicamente. Adicionalmente,0 este tipo de materiales permite un tratamiento similar a los catalizadores heterogéneos, facilitando los procesos de purificación, recuperación y reutilización del catalizador. Un ejemplo representativo de este tipo de materiales ha sido descrita recientemente (ChemFiles Aldrich, 2004, Vol. 4, No. 7 y referencias citadas allí), empleando una matriz de poliurea altamente entrecruzada como soporte. The development of hybrid catalytic systems guarantees an efficient catalysis by offering the homogeneous catalyst an environment of a heterogeneous nature that supports it and which, depending on the structure of the latter, chemically stabilizes it. Additionally, 0 this type of materials allows a treatment similar to heterogeneous catalysts, facilitating the processes of purification, recovery and reuse of the catalyst. A representative example of this type of materials has been recently described (ChemFiles Aldrich, 2004, Vol. 4, No. 7 and references cited there), using a highly crosslinked polyurea matrix as support.
Una de las estrategias más exitosas en este tema es la heterogenización de catalizadores homogéneos por fijación a materiales poliméricos de naturaleza orgánica (p. e. poliestireno) o inorgánica (p. e. sílice, zeolitas). Actualmente diferentes productores comercializan catalizadores que incorporan metales de transición (ej. Pd, Pt, Ru ó Rh) soportados sobre poliestireno o silicagel para ser empleados en diferentes reacciones de acoplamiento.  One of the most successful strategies in this area is the heterogenization of homogeneous catalysts by fixing to polymeric materials of an organic nature (eg polystyrene) or inorganic (eg silica, zeolites). Currently, different producers sell catalysts that incorporate transition metals (eg Pd, Pt, Ru or Rh) supported on polystyrene or silica gel to be used in different coupling reactions.
Con el objetivo de evaluar la novedad y actividad inventiva de los nuevos materiales descritos en la presente invención se relacionan a continuación las características estructurales más significativas de los sistemas catalíticos, que conforman el estado actual del tema, en especial aquellos formados por nanopartículas de sílice, titania o circonia: In order to evaluate the novelty and inventive activity of the new materials described in the present invention, the most significant structural characteristics of the catalytic systems, which make up the current state of the subject, especially those formed by silica nanoparticles, are listed below. titania or zirconia:
1) En general, los materiales catalíticos establecidos, están formados por una matriz polimérica funcionalizada, o sea, además de la estructura polimérica inorgánica que les sirve de soporte estos materiales incorporan un agrupamiento espaciador o linker.  1) In general, the established catalytic materials are formed by a functionalized polymer matrix, that is, in addition to the inorganic polymer structure that supports them, these materials incorporate a spacer or linker grouping.
2) Este linker se incorpora en la matriz durante la etapa de polimerización, habitualmente combinando un teratraalcóxido no funcionalizado [típicamente Si(OEt)4] y un tetraalcóxido funcionalizado [por ejemplo Si(OEt)3R]. 2) This linker is incorporated into the matrix during the polymerization step, usually combining a non-functionalized teratraalkoxide [typically Si (OEt) 4 ] and a functionalized tetraalkoxide [eg Si (OEt) 3 R].
3) El grupo espaciador (o linker) está formado por cadenas carbonadas (típicamente: alquílicas, alquilarílicas, aminoalquílicas, aminoácidicas, etc.) que se unen de forma covalente a la matriz polimérica. Estos agrupamientos habitualmente contienen un grupo funcional cuya función es permitir la fijación de las especies metálicas al soporte sólido funcionalizado (por quelación o interacción iónica). 3) The spacer group (or linker) is formed by carbon chains (typically: alkyl, alkylaryl, aminoalkyl, aminoacidic, etc.) that covalently bind to the polymer matrix. These groupings usually contain a functional group whose function is to allow the fixation of the metallic species to the functionalized solid support (by chelation or ionic interaction).
4) Otra característica destacable de los materiales descritos hasta el momento deriva de la forma en que las especies metálicas se fijan al soporte sólido, que se realiza por a través de los grupos funcionales que incorpora el linker. 4) Another remarkable feature of the materials described so far derives from the way in which the metallic species are fixed to the solid support, which is carried out through the functional groups that the linker incorporates.
Ejemplos representativos de este tipo de materiales se describen en los siguientes documentos: US2007184970, EP1559477A1, US2009/0163656A1, ChemComm, 1996, 1497-1498, (http://www.sigrnaaldrich.com/chemistry/ chemistryproducts. html? TablePage= 16278454). Representative examples of this type of materials are described in the following documents: US2007184970, EP1559477A1, US2009 / 0163656A1, ChemComm, 1996, 1497-1498, (http://www.sigrnaaldrich.com/chemistry/ chemistryproducts. Html? TablePage = 16278454).
Sin embargo, a pesar de sus ventajas, la utilización de estos nuevos sistemas catalíticos se ve limitada por su precio, así como por la relativamente baja carga neta del catalizador que puede incorporar la matriz polimérica, que a su vez depende en gran medida de los grupos funcionales que se encuentran unidos al soporte sólido. Adicionalmente, su preparación requiere procedimientos experimentales que conllevan varias etapas de síntesis y purificación y, su naturaleza funcionalizada, requiere la obtención de tetraalcóxidos f ncionalizados específicos (que aportarán los Linkers donde serán fijados las especies metálicas) cuya síntesis en muchas ocasiones no es trivial.  However, despite their advantages, the use of these new catalytic systems is limited by their price, as well as by the relatively low net charge of the catalyst that the polymer matrix can incorporate, which in turn depends largely on the functional groups that are attached to the solid support. Additionally, its preparation requires experimental procedures that involve several stages of synthesis and purification and, its functionalized nature, requires obtaining specific functionalized tetraalkoxides (which will be provided by the Linkers where the metallic species will be fixed) whose synthesis is often not trivial.
A la vista del estado de la técnica, y de los inconvenientes que presentan los sistemas híbridos basados en matrices poliméricas funcionalizadas que se emplean en la actualidad, esta invención describe nuevos materiales con actividad catalítica que aportan novedades relacionadas con la estructura de la matriz polimérica de la nanopartícula, así como en la forma en que las especies catalíticas se fijan a la misma. Adicionalmente, el procedimiento reivindicado en esta solicitud constituye un método de síntesis sencillo, económico, robusto y eficiente.  In view of the state of the art, and the drawbacks of hybrid systems based on functionalized polymer matrices that are currently used, this invention describes new materials with catalytic activity that provide novelties related to the structure of the polymer matrix of the nanoparticle, as well as the way in which the catalytic species are fixed to it. Additionally, the procedure claimed in this application constitutes a simple, economical, robust and efficient synthesis method.
Breve descripción de la invención  Brief Description of the Invention
La presente invención proporciona un sistema catalítico híbrido, formado por una matriz polimérica no funcionalizada que incorpora un complejo organometálico, cuyo procedimiento de preparación conlleva un único paso sintético robusto, eficiente y económico. Los nuevos materiales desarrollados poseen dos elementos claves que los distinguen de otros sistemas catalíticos: la matriz polimérica no contiene grupos espaciadores y/o Linkers (no funcionalizada), la forma en que las especies catalíticas son fijadas al soporte sólido (al quedar atrapadas en la matriz durante el proceso de polimerización/encapsulación).  The present invention provides a hybrid catalytic system, formed by a non-functionalized polymer matrix that incorporates an organometallic complex, whose preparation process involves a single robust, efficient and economical synthetic step. The new materials developed have two key elements that distinguish them from other catalytic systems: the polymer matrix does not contain spacer groups and / or Linkers (not functionalized), the way in which the catalytic species are fixed to the solid support (when they are trapped in the matrix during the polymerization / encapsulation process).
Una ventaja adicional que proporciona la presente invención es que la matriz puede ser de nanopartículas de distintos materiales (Si02, Ti02 o Zr02). La porosidad y las dimensiones nanométricas, proporcionan una gran superficie específica, lo que aumenta la distribución del catalizador en el conjunto de las nanopartículas y por tanto la eficiencia catalítica del sistema. Estos sistemas son estables y reutilizables, además tienen la ventaja de que impiden la contaminación de los productos de reacción por el catalizador, lo que los hace adecuados para su empleo entre otras, en la industria farmacéutica, además de que pueden ser utilizados en metodologías de síntesis respetuosas con el medio ambiente. An additional advantage provided by the present invention is that the matrix can be nanoparticles of different materials (Si0 2, Ti0 2 Zr0 or 2). Porosity and nanometric dimensions provide a large specific surface area, which increases the distribution of the catalyst in the nanoparticles as a whole and therefore the catalytic efficiency of the system. These systems are stable and reusable, they also have the advantage that they prevent the contamination of the reaction products by the catalyst, which makes them suitable for use among others, in the pharmaceutical industry, in addition to being used in environmentally friendly synthesis methodologies.
Así, en un aspecto la invención se dirige a un sistema catalítico híbrido químicamente estable que comprende nanopartículas de sílice, titania o circonia no funcionalizadas (y por tanto no contienen espaciadores y/o grupos funcionales) que sirven de soporte a un complejo organometálico de un metal de transición. Otro aspecto novedoso de la invención se refiere a la forma en que las especies organometálicas son fijadas (encapsuladas) a la matriz polimérica, por interacción directa con el soporte sólido durante la formación de las nanopartículas.  Thus, in one aspect the invention is directed to a chemically stable hybrid catalytic system comprising non-functionalized silica, titania or zirconia nanoparticles (and therefore do not contain spacers and / or functional groups) that support an organometallic complex of a transition metal Another novel aspect of the invention relates to the way in which the organometallic species are fixed (encapsulated) to the polymer matrix, by direct interaction with the solid support during the formation of the nanoparticles.
En otro aspecto, la invención se dirige a un procedimiento para la preparación de dicho sistema, que comprende la adición de un complejo organometálico sobre una mezcla de reacción compuesta por un tetra-alquilalcóxido de silicio no funcionalizado, titanio o zirconio en una disolución, mientras se produce una hidrólisis/condensación según un proceso sol-gel.  In another aspect, the invention is directed to a process for the preparation of said system, which comprises the addition of an organometallic complex on a reaction mixture composed of a non-functionalized silicon tetra-alkyloxide, titanium or zirconium in a solution, while hydrolysis / condensation occurs according to a sol-gel process.
En otro aspecto, la invención se dirige al uso de dicho sistema en reacciones de síntesis orgánica, en la industria farmacéutica, química o agroquímica, y en procesos químicos respetuosos con el medio ambiente característicos de la Química Verde.  In another aspect, the invention is directed to the use of said system in organic synthesis reactions, in the pharmaceutical, chemical or agrochemical industry, and in environmentally friendly chemical processes characteristic of Green Chemistry.
Breve descripción de las figuras:  Brief description of the figures:
Figura 1. Imagen obtenida mediante microscopía electrónica (SEM) de una muestra de nanopartículas de Si02 no funcionalizadas en las que se encuentra encapsulado Pd(PPh3)4.Figure 1. Image obtained by electron microscopy (SEM) of a sample of non-functionalized Si0 2 nanoparticles in which Pd (PPh 3 ) 4 is encapsulated.
Figura 2. Análisis químico elemental mediante energía dispersiva de Rayos X (EDS) de la muestra de la Figura 1. La presencia de Au se debe al proceso de metalizado superficial de la muestra para su análisis. Figure 2. Elemental chemical analysis by X-ray dispersive energy (EDS) of the sample of Figure 1. The presence of Au is due to the surface metallizing process of the sample for analysis.
Descripción detallada de la invención Detailed description of the invention
En la presente invención, por el término sistema catalítico híbrido se entiende un sistema en donde un componente homogéneo con propiedades catalíticas está fijado a una matriz polimérica no funcionalizada. En concreto, el componente homogéneo es un complejo organometálico de un metal de transición y la matriz polimérica está constituida por nanopartículas de sílice, titania o circonia. La fijación del componente homogéneo a la matriz polimérica produce un efecto de heterogenización, que impide al complejo organometálico su difusión al medio de reacción, aunque su eficacia catalítica no disminuye. Dicha fijación se realiza por captura del componente homogéneo en el seno matricial sin mediación de grupos funcionales o Linkers durante la etapa de formación de las partículas. Este tipo de fijación evita la utilización de soportes funcionalizados, aporta estabilidad al nuevo material y adicionalmente garantiza niveles de entrecruzamiento del polímero (encapsulación) que evitan la liberación del complejo organometálico al medio de reacción y la consiguiente contaminación de los productos de reacción con trazas de metales. Simultáneamente la naturaleza porosa del soporte sólido facilita la migración de los reaccionantes al interior de las nanopartículas, donde se transforman en productos para posteriormente retornar al disolvente. In the present invention, the term "hybrid catalyst system" means a system in which a homogeneous component with catalytic properties is fixed to a non-functionalized polymer matrix. Specifically, the homogeneous component is an organometallic complex of a transition metal and the polymeric matrix consists of silica, titania or zirconia nanoparticles. Fixing the homogeneous component to the polymer matrix produces a heterogenization effect, which prevents the complex Organometallic diffusion to the reaction medium, although its catalytic efficiency does not diminish. Said fixation is carried out by capturing the homogeneous component in the matrix without mediation of functional groups or Linkers during the stage of particle formation. This type of fixation avoids the use of functionalized supports, provides stability to the new material and additionally guarantees levels of crosslinking of the polymer (encapsulation) that prevent the release of the organometallic complex to the reaction medium and the consequent contamination of the reaction products with traces of metals Simultaneously, the porous nature of the solid support facilitates the migration of the reactants into the nanoparticles, where they are transformed into products to later return to the solvent.
Por el término "matriz polimérica no funcionalizada" se entiende un soporte sólido de naturaleza polimérica que no contiene cadenas espaciadoras y/o grupos funcionales (por ejemplo Si02, Ti02 o Zr02). By "polymer matrix nonfunctionalized" means a solid support of a polymeric nature which does not contain spacer chains and / or functional groups (for example Si0 2, Ti0 2 Zr0 or 2).
Por el término "nanopartículas" se hace referencia a estructuras estables y de características homogéneas, reproducibles y modulables, en tamaño y forma, que constituyen una matriz de entrecruzamiento, cuyo tamaño medio es inferior a 1 micrómetro, es decir, de entre 1 y 999 nm, preferiblemente de entre 50 y 600 nm. The term "nanoparticles" refers to stable structures with homogeneous, reproducible and modulable characteristics, in size and shape, which constitute a cross-linking matrix, whose average size is less than 1 micrometer, that is, between 1 and 999 nm, preferably between 50 and 600 nm.
Por el término "tamaño promedio" se entiende el diámetro promedio de la población de nanopartículas, que comprende la estructura matricial. El tamaño promedio de estos sistemas se mide mediante análisis de imagen mediante SEM (Microscopía electrónica de barrido). The term "average size" means the average diameter of the nanoparticle population, which comprises the matrix structure. The average size of these systems is measured by image analysis using SEM (scanning electron microscopy).
Por el término complejo organometálico se entiende un catalizador homogéneo de naturaleza organometálica que contiene en su estructura un metal de transición. En un aspecto particular, el metal de transición del complejo organometálico se selecciona entre Paladio, Platino, Cobalto, Níquel. En un aspecto más particular, el complejo organometálico se selecciona preferentemente entre ( PdC ;.-( ΡΡΙι <) . Pd(PPh3)4, Ι5·( i í PPh . K Pt(PPh3),i, \ ¡{ PPh > ) ·( '! ·. [Ni(acac)2]3. The term "organometallic complex" means a homogeneous catalyst of an organometallic nature that contains in its structure a transition metal. In a particular aspect, the transition metal of the organometallic complex is selected from Palladium, Platinum, Cobalt, Nickel. In a more particular aspect, the organometallic complex is preferably selected from (PdC; -. (ΡΡΙι <) Pd (PPh 3) 4, Ι 5 · (i í PPh K Pt (PPh 3), i, \ {.. PPh>) · ( ' ! ·. [Ni (acac) 2 ] 3 .
En un aspecto particular, el complejo organometálico se encuentra en una proporción entre el 0,05 y el 5% en peso. El procedimiento de preparación de los sistemas catalíticos de la presente invención comprende una única etapa de adición de un complejo organometálico sobre una mezcla de reacción. Dicha mezcla de reacción está compuesta por un tetra-alquilalcóxido de silicio, titanio o zirconio en una disolución en la que se está produciendo un proceso de hidrólisis/condensación según un proceso sol-gel. In a particular aspect, the organometallic complex is in a proportion between 0.05 and 5% by weight. The process of preparing the catalyst systems of the present invention comprises a single step of adding an organometallic complex onto a reaction mixture. Said reaction mixture is composed of a silicon, titanium or zirconium tetraalkylalkoxide in a solution in which a hydrolysis / condensation process is taking place according to a sol-gel process.
El proceso sol-gel es ampliamente conocido en el estado de la técnica (J. Colloid Interface Sci., 26, p62, 1968. Langmuir 14, p5396, 1998. J. Amer. Chem. Soc. 128, p 968, 2006. Colloids Surf.197, p7, 2002. Biomaterials, 25, p723, 2004). El proceso sol-gel implica la hidrólisis y condensación de precursores metalorgánicos que da lugar a un gel que consiste en una red de enlaces metal-oxígeno-metal interconectada en tres dimensiones. Por ejemplo, si el precursor fuese tetraetoxisilano [Si(OEt)4] se obtendría un gel con enlaces Si-O-Si. The sol-gel process is widely known in the state of the art (J. Colloid Interface Sci., 26, p62, 1968. Langmuir 14, p5396, 1998. J. Amer. Chem. Soc. 128, p 968, 2006. Colloids Surf. 1997, p7, 2002. Biomaterials, 25, p723, 2004). The sol-gel process involves the hydrolysis and condensation of metalorganic precursors that results in a gel consisting of a network of interconnected metal-oxygen-metal bonds in three dimensions. For example, if the precursor were tetraethoxysilane [Si (OEt) 4 ], a gel with Si-O-Si bonds would be obtained.
En un aspecto particular de la invención, la mezcla de reacción en la que se está produciendo la hidrólisis/condensación comprende amoníaco, agua y un alcohol alquílico. En la presente invención se han modificado estos procedimientos, al incluir una etapa en la síntesis de las nanopartículas, que consiste en adicionar el catalizador homogéneo a la mezcla de reacción en la que se está produciendo la síntesis, buscando que la inclusión del catalizador en la nanopartícula de sílice, titania o circonia, pueda realizarse en la misma operación de síntesis de dicha nanopartícula, lo que simplifica y economiza su obtención. A continuación, para una mayor comprensión de las características y ventajas de la presente invención, se hará referencia a una serie de ejemplos que de forma explicativa completan la descripción anterior, sin suponer en modo alguno que ésta se vea limitada a los mismos.  In a particular aspect of the invention, the reaction mixture in which hydrolysis / condensation is occurring comprises ammonia, water and an alkyl alcohol. In the present invention these procedures have been modified, by including a stage in the synthesis of the nanoparticles, which consists in adding the homogeneous catalyst to the reaction mixture in which the synthesis is taking place, seeking that the inclusion of the catalyst in the Silica nanoparticle, titania or zirconia, can be performed in the same synthesis operation of said nanoparticle, which simplifies and economizes its obtaining. Next, for a better understanding of the characteristics and advantages of the present invention, reference will be made to a series of examples that in an explanatory way complete the above description, without assuming in any way that it is limited thereto.
Ejemplo 1  Example 1
La síntesis de nanopartículas de sílice se realiza mediante la hidrólisis/condensación del tetra-etilalcóxido de Si, por reacción con NH4OH y H20 en Etanol. La reacción se inicia al añadir a la mezcla tetra-etilalcóxido de Si. La concentración final en la mezcla de cada uno de los reactivos determina el tamaño de las nanopartículas. Para obtener partículas de un tamaño promedio entorno a 150 nm, la concentración de los reactivos en la mezcla de reacción fue de: NH4OH 1 M, H20 1,3 M y 0,17 M para el tetra-etilalcoxido de Si. A los 15 minutos aproximadamente de añadir el alcóxido, el medio de reacción comienza a ponerse turbio, con una coloración blanquecina que aumenta su intensidad con el paso del tiempo. En ese momento se añade a la mezcla el compuesto organometálico (catalizador homogéneo), Pd(PPh 3)4. El medio de reacción se mantiene en agitación continua a una temperatura aproximada de 22 °C durante aproximadamente 12 horas. Una vez transcurrido ese tiempo se procede a la separación y lavado del producto de reacción. Se centrifuga la mezcla, se retira el sobrenadante y se redispersan las nanopartículas en etanol. Este proceso se repite tres veces. A continuación se realizan tres lavados más redíspersa do las nanopartículas en agua. La muestra final se deja secar a temperatura ambiente y se obtiene el producto final, Si02-Pd(PPh3 )4, como un polvo fino. Con las concentraciones indicadas de NH4OH y H20, se obtuvieron tamaños promedio de partícula de 133 nm. Variando estás concentraciones se obtuvieron también partículas de 105 y 220 nm. The synthesis of silica nanoparticles is carried out by hydrolysis / condensation of Si tetraethylalkoxide, by reaction with NH 4 OH and H 2 0 in Ethanol. The reaction is started by adding Si tetra-ethyl alkoxide to the mixture. The final concentration in the mixture of each of the reagents determines the size of the nanoparticles. To obtain particles of an average size around 150 nm, the concentration of the reagents in the reaction mixture was: NH 4 OH 1 M, H 2 0 1.3 M and 0.17 M for the tetraethylalkoxide of Si . After approximately 15 minutes of adding the alkoxide, the reaction medium begins to become cloudy, with a whitish color that increases its intensity with the passage of weather. At that time the organometallic compound (homogeneous catalyst), Pd (PPh 3 ) 4 is added to the mixture. The reaction medium is kept under continuous stirring at an approximate temperature of 22 ° C for approximately 12 hours. Once this time has elapsed, the reaction product is separated and washed. The mixture is centrifuged, the supernatant is removed and the nanoparticles are redispersed in ethanol. This process is repeated three times. Next, three more redispersed washings of the nanoparticles in water are performed. The final sample is allowed to dry at room temperature and the final product, Si0 2 -Pd (PPh 3 ) 4, is obtained as a fine powder. With the indicated concentrations of NH 4 OH and H 2 0, average particle sizes of 133 nm were obtained. By varying these concentrations, 105 and 220 nm particles were also obtained.
En la Figura 1 se muestran las nanopartículas de S1O2 no funcionalizadas en las que se encuentra encapsulado Pd(PPh3)4. La imagen, obtenida mediante microscopía electrónica (SEM), muestra partículas con un tamaño medio de 133 nm. En la Figura 2, se confirma la presencia de Paladio en las partículas de la muestra de la Figura mediante un análisis químico elemental mediante energía dispersiva de Rayos X (EDS). Figure 1 shows the non-functionalized S1O 2 nanoparticles in which Pd (PPh 3 ) 4 is encapsulated. The image, obtained by electron microscopy (SEM), shows particles with an average size of 133 nm. In Figure 2, the presence of Palladium in the particles of the sample of the Figure is confirmed by an elementary chemical analysis by X-ray dispersive energy (EDS).
Ejemplo 2  Example 2
Siguiendo exactamente el mismo procedimiento del Ejemplo 1, pero añadiendo en este caso como catalizador homogéneo Pd(PPh3)2Cl2 en lugar de Pd(PPh3)4, se obtuvieron nanopartículas de Si02 no funcionalizadas en las que se encuentra encapsulado Pd(PPh3)2Cl2. Following exactly the same procedure as in Example 1, but adding in this case as a homogeneous catalyst Pd (PPh 3 ) 2 Cl 2 instead of Pd (PPh 3 ) 4 , non-functionalized Si0 2 nanoparticles were obtained in which Pd is encapsulated (PPh 3 ) 2 Cl 2 .
Ejemplo 3.  Example 3
Como parte de la caracterización físico-química de las nanopartículas preparadas se ha evaluado también la capacidad del metal que se encuentra encapsulado en las nanopartículas para pasar al medio de reacción. Para ello se empleó el método de las tres fases, utiliza do como auxiliar otro reactivo soportado sobre u a matriz de sílice: la mercaptopropií-siíice ((Si()2)-CH2-CH2-CH2-SH) (Parisién, M., Valette, D., Fagnou, ., J.As part of the physicochemical characterization of the prepared nanoparticles, the ability of the metal that is encapsulated in the nanoparticles to pass into the reaction medium has also been evaluated. For this, the three-phase method was used, using another reagent supported on a silica matrix as an auxiliary: mercaptopropií-siíice ((Si () 2 ) -CH 2 -CH 2 -CH 2 -SH) (Paris, M., Valette, D., Fagnou,., J.
Org. Chem., 2005, 70, 7578; Davics, l. W., Matty, L., Hughes, D. L,, Reider, P. 1, J.Am.Org. Chem., 2005, 70, 7578; Davics, l. W., Matty, L., Hughes, D. L ,, Reider, P. 1, J.Am.
Chem, Soc, 2001, 123, 10139; Rebeck, J., Gavina, F., J. Am. Chem. Soc, 1974, 96, 71 12). Está bien documentado que el grupo tiol de este reactivo es capaz de reaccionar con las especies de paladio que se encuentran en solución, ''secuestrándolo" y fijando elChem, Soc, 2001, 123, 10139; Rebeck, J., Gavina, F., J. Am. Chem. Soc, 1974, 96, 71 12). It is well documented that the thiol group of this reagent is capable of reacting with palladium species found in solution, '' sequestering it 'and fixing the
Paladio a la sílice. Inieialmente, y con el objetivo de validar la efectividad de la mercaptopropil-silica, se han estudiado diferentes reacciones (Suzuki, Sonogashira, Heck y Stille) empleando el correspondiente catalizador homogéneo [Pd(PPh3)4, Pd(PPh3)2Cl2] . Todos los experimentos se han realizado en DMF, empleando 150 mg de mercptopropil siiica y manteniendo el iodobenceno corno electrófílo orgánico (0,5 mmol) y utilizando ácido femlhorónieo (0.6 mmol), femlaeetileno (0.55 mmol) acrílato de metilo (0.6 mmol), o tributiifeniiestannano (0,6 mmol) como contraparte para las reacciones de Suzuki, Sonogashira, Heck y Stille. Los experimentos realizado conllevan la incubación inicial de la mercaptopropil sílica con el catalizador (2% mol, Pd(PPh3)4 para la reacción de Suzuki y Pd(PPh3)2Cl2 para Sonogashira, Heck y Stille) durante 1 hora y adicionando posteriormente el resto de reaccionantes al vial de reacción. Una vez transcurridas 24 horas bajo las mismas condiciones experimentales que se describe para el experimento tipo se comprueba la ausencia de productos de acoplamiento, por comparación con una muestra autentica previamente obtenida (TLC y HPLC), y que los productos de partida permanecen inalterados. Palladium on silica. Initially, and with the aim of validating the effectiveness of mercaptopropyl-silica, different reactions have been studied (Suzuki, Sonogashira, Heck and Stille) using the corresponding homogeneous catalyst [Pd (PPh 3 ) 4 , Pd (PPh 3 ) 2 Cl 2 ]. All experiments have been carried out in DMF, using 150 mg of sialic mercptopropyl and maintaining organic electrophilic iodobenzene (0.5 mmol) and using phemlhoronium acid (0.6 mmol), femlaethylene (0.55 mmol) methyl acrylic (0.6 mmol), or tributiifeniiestannan (0.6 mmol) as a counterpart for the reactions of Suzuki, Sonogashira, Heck and Stille. The experiments carried out involve the initial incubation of mercaptopropyl silica with the catalyst (2% mol, Pd (PPh 3 ) 4 for the reaction of Suzuki and Pd (PPh 3 ) 2 Cl 2 for Sonogashira, Heck and Stille) for 1 hour and subsequently adding the remaining reactants to the reaction vial. After 24 hours have elapsed under the same experimental conditions described for the type experiment, the absence of coupling products is checked, by comparison with a previously obtained authentic sample (TLC and HPLC), and that the starting products remain unchanged.
Figure imgf000009_0001
De forma análoga se ha procedido con los catalizadores híbridos preparados [Si02-
Figure imgf000009_0001
Similarly, the hybrid catalysts were prepared [Si0 2 -
Pd(PPh3)2Cl2 y Si02-Pd(PPh3)4 ] en las cuatro reacciones modelo empleadas a lo largo del trabajo (Suzuki, Sonogashira, Heck y Stille) para el iodobenceno, comprobándose que en presencia de la mercaptopropil-silica todas ellas conducen a los esperados productos de acoplamiento cruzado. Pd (PPh 3 ) 2 Cl 2 and Si0 2 -Pd (PPh 3 ) 4 ] in the four model reactions used throughout the work (Suzuki, Sonogashira, Heck and Stille) for iodobenzene, checking that in The presence of mercaptopropyl-silica all lead to the expected cross-coupling products.
Estos resultados confirman, de forma inequívoca, que estos complejos organometálicos de paladio se encuentran encapsulados en las nanopartículas y no tienen capacidad de migrar al medio de reacción.  These results confirm, unequivocally, that these organometallic palladium complexes are encapsulated in the nanoparticles and have no ability to migrate to the reaction medium.
Figure imgf000010_0001
Figure imgf000010_0001
Ejemplo 4. Reacciones de acoplamiento empleando nanopartículas de sílice Example 4. Coupling reactions using silica nanoparticles
Catalizadores híbridos formados por nanopartículas de sílice preparadas según el procedimiento descrito: [Si02-Pd(PPh3)4 y Si02-Pd(PPh3)2Cl2], se han empleado como catalizadores en las reacciones de Suzuki, Heck, Sonogashira y Stille. Hybrid catalysts formed by silica nanoparticles prepared according to the procedure described: [Si0 2 -Pd (PPh 3 ) 4 and Si0 2 -Pd (PPh 3 ) 2 Cl 2 ], have been used as catalysts in the reactions of Suzuki, Heck, Sonogashira and Stille.
Ejemplo 4.1  Example 4.1
Procedimiento General para la Reacción de Suzuki: A una mezcla equimolecular (0.1 mmol) de bromobenceno y ácido 4-tolilborónico en dimetoxietano (5 mL) se adiciona Na2C03 (0.3 mmol), H20 (3 mL) y 60 mg del catalizador híbrido (Si02-Pd(PPh3)4). La mezcla se calienta a 90°C durante 4 horas, se deja enfriar a temperatura ambiente, se filtra y el filtrado se evapora a sequedad y purifica por cromatografía de columna para obtener un sólido blanco cuyas características analíticas y espectroscópicas se corresponden con el 4-metilbifenilo.
Figure imgf000011_0001
General Procedure for Suzuki Reaction: To a equimolecular mixture (0.1 mmol) of bromobenzene and 4-tolylboronic acid in dimethoxyethane (5 mL) Na 2 C0 3 (0.3 mmol), H 2 0 (3 mL) and 60 mg are added of the hybrid catalyst (Si0 2 -Pd (PPh 3 ) 4 ). The mixture is heated at 90 ° C for 4 hours, allowed to cool to room temperature, filtered and the filtrate is evaporated to dryness and purified by column chromatography to obtain a white solid whose analytical and spectroscopic characteristics correspond to 4- methylbiphenyl
Figure imgf000011_0001
Figure imgf000011_0002
Figure imgf000011_0002
Una vez finalizada la reacción se recupera el catalizador híbrido por filtración, se lava 3 veces (10 mL) con el disolvente empleado en la misma y posteriormente con agua (10 mL) y se seca a vacío. Este mismo catalizador se ha empleado en al menos 5 experimentos sin que se aprecie una importante disminución en su capacidad catalítica, evaluada en función de los porcentajes de rendimiento de los productos obtenidos en cada transformación. A modo de ejemplo se indica a continuación los rendimientos obtenidos durante la reacción del 4-bromobenzonitrilo con el ácido fenilborónico empleando el catalizador reciclado: 2º experimento: 74%, 3º experimento: 75%, 4º experimento: 70%, 4o experimento: 70%. Once the reaction is finished, the hybrid catalyst is recovered by filtration, washed 3 times (10 mL) with the solvent used therein and subsequently with water (10 mL) and dried under vacuum. This same catalyst has been used in at least 5 experiments without appreciating a significant decrease in its catalytic capacity, evaluated according to the percentages of yield of the products obtained in each transformation. As an example it follows yields obtained during reaction of 4-bromobenzonitrile with phenylboronic acid using recycled catalyst: 2nd experiment: 74%, 3rd experiment: 75%, 4th experiment: 70%, 4 or experiment: 70 %.
Ejemplo 4.2 Example 4.2
Procedimiento General para la Reacción de Stille: A una mezcla equimolecular (0.1 mmol) de bromobenceno y tribuil-vinil estannano en dimetilformamida (7 mL) se adicionan 60 mg del catalizador soportado en nanopartículas de sílice (Si02-Pd(PPh3)2Cl2). La mezcla se calienta a 90 °C durante 6 horas, se deja enfriar a temperatura ambiente, se filtra y el filtrado se evapora a sequedad y purifica por cromatografía de columna para obtener un sólido blanco cuyas características analíticas y espectroscópicas se corresponden con el estireno.
Figure imgf000012_0001
General Procedure for the Stille Reaction: 60 mg of the catalyst supported on silica nanoparticles (Si0 2 -Pd (PPh 3 ) 2 are added to an equimolecular mixture (0.1 mmol) of bromobenzene and tributyl vinyl stannan in dimethylformamide (7 mL) Cl 2 ). The mixture is heated at 90 ° C for 6 hours, allowed to cool to room temperature, filtered and the filtrate is evaporated to dryness and purified by column chromatography to obtain a white solid whose analytical and spectroscopic characteristics correspond to styrene.
Figure imgf000012_0001
Una vez finalizada la reacción se recupera el catalizador por filtración, se lava 3 veces (10 mL) con el disolvente empleado en la misma y posteriormente con agua (10 mL) y se seca a vacío. Este mismo catalizador se ha empleado en al menos 5 experimentos sin que se aprecie una importante disminución en su capacidad catalítica, evaluada en función de los porcentajes de rendimiento de los productos obtenidos en cada transformación. A modo de ejemplo se indica a continuación los rendimientos obtenidos durante la reacción del iodobenceno con el fenilacetileno empleando el catalizador reciclado: 2º experimento: 80 %, 3º experimento: 79%, 4º experimento: 78%, 4º experimento: 80%>. Once the reaction is finished, the catalyst is recovered by filtration, washed 3 times (10 mL) with the solvent used therein and subsequently with water (10 mL) and dried under vacuum. This same catalyst has been used in at least 5 experiments without appreciating a significant decrease in its catalytic capacity, evaluated according to the percentages of yield of the products obtained in each transformation. By way of example, the yields obtained during the reaction of iodobenzene with phenylacetylene are indicated below using the recycled catalyst: 2nd experiment: 80%, 3rd experiment: 79%, 4th experiment: 78%, 4th experiment: 80%>.
Ejemplo 4.3 Example 4.3
Procedimiento General para la Reacción de Sonogashira: A una mezcla equimolecular (0.1 mmol) de bromobenceno y etinilbenceno en dimetilformamida (7 mL) se adiciona trietilamina (0.2 mmol) y 60 mg del catalizador soportado en nanopartículas de sílice (Si02-Pd(PPh3)2Cl2). La mezcla se calienta a 55 °C durante 6 horas, se deja enfriar a temperatura ambiente, se filtra y el filtrado se evapora a sequedad y purifica por cromatografía de columna para obtener un sólido blanco cuyas características analíticas y espectroscópicas se corresponden con el 1,2-difeniletileno.
Figure imgf000013_0001
General Procedure for the Reaction of Sonogashira: Triethylamine (0.2 mmol) and 60 mg of the catalyst supported on silica nanoparticles (Si0 2 -Pd (PPh3) are added to an equimolecular mixture (0.1 mmol) of bromobenzene and ethynylbenzene in dimethylformamide (7 mL) ) 2 Cl 2 ). The mixture is heated at 55 ° C for 6 hours, allowed to cool to room temperature, filtered and the filtrate is evaporated to dryness and purified by column chromatography to obtain a white solid whose analytical and spectroscopic characteristics correspond to 1, 2-diphenylethylene.
Figure imgf000013_0001
Figure imgf000013_0002
Figure imgf000013_0002
Una vez finalizada la reacción se recupera el catalizador por filtración, se lava 3 veces (10 mL) con el disolvente empleado en la misma y posteriormente con agua (10 mL) y se seca a vacío. Este mismo catalizador se ha empleado en al menos 5 experimentos sin que se aprecie una importante disminución en su capacidad catalítica, evaluada en función de los porcentajes de rendimiento de los productos obtenidos en cada transformación. A modo de ejemplo se indica a continuación los rendimientos obtenidos durante la reacción del 4-bromobenzonitrilo con el alcohol propargílico empleando el catalizador reciclado: 2o experimento: 73%, 3º experimento: 75%, 4º experimento: 73%, 4º experimento: 75%. Ejemplo 4.4 Once the reaction is finished, the catalyst is recovered by filtration, washed 3 times (10 mL) with the solvent used therein and subsequently with water (10 mL) and dried under vacuum. This same catalyst has been used in at least 5 experiments without appreciating a significant decrease in its catalytic capacity, evaluated according to the percentages of yield of the products obtained in each transformation. As an example it follows yields obtained during reaction of 4-bromobenzonitrile with propargyl alcohol using the recycled catalyst 2 or experiment: 73%, 3rd experiment: 75%, 4th experiment: 73%, 4th experiment: 75 %. Example 4.4
Procedimiento General para la Reacción de Heck: A una mezcla equimolecular (0.1 mmol) de bromobenceno y acrilato de etilo en dimetilformamida (7 mL) se adiciona trietilamina (0.2 mmol) y 60 mg del catalizador soportado en nanopartículas de sílice (Si02-Pd(PPh3)2Cl2). La mezcla se calienta a 100 °C durante 6 horas, se deja enfriar a temperatura ambiente, se filtra y el filtrado se evapora a sequedad y purifica por cromatografía de columna para obtener un sólido blanco cuyas características analíticas y espectroscópicas se corresponden con el 3-fenilacrilato de etilo.
Figure imgf000014_0001
General Procedure for the Heck Reaction: Triethylamine (0.2 mmol) and 60 mg of the catalyst supported on silica nanoparticles (Si0 2 -Pd) are added to an equimolecular mixture (0.1 mmol) of bromobenzene and ethyl acrylate in dimethylformamide (7 mL) (PPh 3 ) 2 Cl 2 ). The mixture is heated at 100 ° C for 6 hours, allowed to cool to room temperature, filtered and the filtrate is evaporated to dryness and purified by column chromatography to obtain a white solid whose analytical and spectroscopic characteristics correspond to 3- ethyl phenylacrylate.
Figure imgf000014_0001
TEA TORCH
Figure imgf000014_0002
Figure imgf000014_0002
Una vez finalizada la reacción se recupera el catalizador por filtración, se lava 3 veces (10 mL) con el disolvente empleado en la misma y posteriormente con agua (10 mL) y se seca a vacío. Este mismo catalizador se ha empleado en al menos 5 experimentos sin que se aprecie una importante disminución en su capacidad catalítica, evaluada en función de los porcentajes de rendimiento de los productos obtenidos en cada transformación. A modo de ejemplo se indica a continuación los rendimientos obtenidos durante la reacción del 4-iodobenzonitrilo con el acrilato de metilo empleando el catalizador reciclado: 2o experimento: 95%, 3º experimento: 95%, 4º experimento: 92%, 4º experimento: 93%. Once the reaction is finished, the catalyst is recovered by filtration, washed 3 times (10 mL) with the solvent used therein and subsequently with water (10 mL) and dried under vacuum. This same catalyst has been used in at least 5 experiments without appreciating a significant decrease in its catalytic capacity, evaluated according to the percentages of yield of the products obtained in each transformation. For example it follows yields obtained during reaction of 4-iodobenzonitrilo with acrylate using the recycled catalyst: 2 or experiment: 95%, 3rd experiment: 95%, 4th experiment: 92%, 4th experiment: 93%

Claims

REIVINDICACIONES
1.- Sistema catalítico híbrido químicamente estable formado por un complejo organometálico de un metal de transición encapsulado en nanopartículas de una matriz polimérica inorgánica no f ncionalizada, por interacción directa con la matriz.  1.- Chemically stable hybrid catalyst system formed by an organometallic complex of a transition metal encapsulated in nanoparticles of a non-functionalized inorganic polymer matrix, by direct interaction with the matrix.
2 - Sistema, según la reivindicación 1, donde el diámetro medio de las nanopartículas de sílice, titania o circonia está comprendido entre 1 y 999 nm, preferiblemente entre 50 y 600 nm. 2 - System according to claim 1, wherein the average diameter of the silica, titania or zirconia nanoparticles is between 1 and 999 nm, preferably between 50 and 600 nm.
3.- Sistema, según la reivindicación 1 y 2, donde el metal de transición se selecciona entre Paladio, Platino, Cobalto, o Níquel.  3. System according to claim 1 and 2, wherein the transition metal is selected from Palladium, Platinum, Cobalt, or Nickel.
4.- Sistema, según la reivindicación 1, 2 y 3, donde la matriz polimérica inorgánica es de sílice, titania o circonia. 4. System according to claim 1, 2 and 3, wherein the inorganic polymer matrix is silica, titania or zirconia.
5. - Sistema, según la reivindicación 3, donde el complejo organometálico se encuentra en una proporción entre el 0,05 y el 5% en peso.  5. - System according to claim 3, wherein the organometallic complex is in a proportion between 0.05 and 5% by weight.
6. - Procedimiento para la preparación de un sistema como se define en cualquiera de las reivindicaciones 1 a 5, que comprende la encapsulación, por interacción directa con la matriz de sílice, titania o circonia, de un complejo organometálico de un metal de transición mediante la adición de éste durante la hidrólisis/condensación en una mezcla de reacción que contiene un tetra-alquilalcóxido no funcionalizado de silicio, titanio o zirconio, según un proceso sol-gel.  6. - Procedure for the preparation of a system as defined in any one of claims 1 to 5, comprising the encapsulation, by direct interaction with the silica matrix, titania or zirconia, of an organometallic complex of a transition metal by the addition thereof during hydrolysis / condensation in a reaction mixture containing a non-functionalized silicon, titanium or zirconium tetra-alkylalkoxide, according to a sol-gel process.
7.- Procedimiento, según la reivindicación 6, donde el complejo organometálico tiene como metal de transición Paladio, Platino, Cobalto, o Níquel. 7. Method according to claim 6, wherein the organometallic complex has as transition metal Palladium, Platinum, Cobalt, or Nickel.
8. - Procedimiento según las reivindicaciones 6 y 7, donde la mezcla de reacción disolución comprende amoníaco, agua y un alcohol alquílico.  8. - Method according to claims 6 and 7, wherein the reaction mixture solution comprises ammonia, water and an alkyl alcohol.
9. - Uso del sistema definido en las reivindicaciones 1 a 5, en reacciones de síntesis orgánica, en la industria farmacéutica, química o agroquímica, y en procesos químicos respetuosos con el medio ambiente característicos de la Química Verde.  9. - Use of the system defined in claims 1 to 5, in organic synthesis reactions, in the pharmaceutical, chemical or agrochemical industry, and in environmentally friendly chemical processes characteristic of Green Chemistry.
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POLSHETTIWAR, V. ET AL.: "Silica-supported palladium: Sustainable catalysts for cross-coupling reactions", COORDINATION CHEMISTRY REVIEWS, vol. 253, 13 June 2009 (2009-06-13), pages 2599 - 2626, XP026640913, DOI: doi:10.1016/j.ccr.2009.06.001 *
TALHAMI, A. ET AL.: "Sol-gthe intrapped dichlorobis(triphenylphosphine)palladiumas an efficient recyclable catalyst for the cross-couplingof aryl halides with indium- and rtheated alkylating reagents.", APPLIED CATALYSIS A: GENERAL, vol. 312, 2006, pages 115 - 119 *

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