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    • 专利摘要:
    GTM-3 enantio-enriched chiral microporous material Preparation procedure and uses. The present invention relates to a new chiral zeolitic material of composition a SiO2 : b GeO2 : c X2 O3 : d YO2, with ITV structure, prepared with a specific chiral organic structure directing agent, the (1S, 2S) -N-ethyl-N-methyl-pseudoephedrinium or its enantiomer, (1R, 2R) -N-ethyl-N-methyl-pseudoephedrine, which implies that the material is enriched in one of the enantiomorphic crystalline forms, to the procedure by which said material is obtained, as well as to its application in adsorption and catalysis processes. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2871374A1
    申请号:ES202030360
    申请日:2020-04-28
    公开日:2021-10-28
    发明作者:Sainz Luis Gomez-Hortigüela；Pariente Joaquin Perez；Hernandez David Nieto；MAESTRO Mª BEATRIZ BERNARDO；La Serna Valdes Ramon De；Vaque Raquel Sainz
    申请人:Consejo Superior de Investigaciones Cientificas CSIC；
    IPC主号:
    专利说明:

    [0005] The present invention refers to a new chiral zeolitic material with composition a SÍO 2 : b Ge02: c X 2 O 3 : d YO 2 , with ITV structure, prepared with a specific chiral organic structure directing agent, el (1S, 2S ) -N-ethyl-N-methyl-pseudoephedrine or its enantiomer, the (1R, 2R) -N-ethyl-N-methyl-pseudoephedrine, which implies that the material is enriched in one of the enantiomorphic crystalline forms, to the procedure by which said material is obtained, as well as its application in adsorption and catalysis processes. The present invention is situated in the sector of zeolitic materials with catalytic and adsorbent properties, and in the sector of the chemical and pharmaceutical industry.
    [0007] BACKGROUND OF THE INVENTION
    [0009] Zeolites are crystalline microporous aluminosilicates with a defined three-dimensional structure made up of SIO 4 and AIO 4 tetrahedra. The three-dimensional arrangement of these tetrahedral units in different geometric arrangements gives rise to the formation of very diverse microporous structures (more than 240), generating pore systems and cavities of molecular dimensions. This ordered porosity gives them the property of acting as molecular sieves, allowing the differentiation of chemical species based on their geometric properties, that is, their shape and size. The incorporation of Al + 3 or other trivalent elements in the inorganic zeolitic network generates a negative charge in the network that is compensated by the presence of cations in the pores and / or cavities. These cations can be replaced by protons, thus generating Bronsted acid centers. Not only Al but many other elements can be incorporated into the zeolitic network to replace Si (any element that is incorporated into the tetrahedral network of a zeolite is commonly called T), generating materials with different catalytic properties, which can be used both in acid, basic, redox catalysis reactions, or even bifunctional if other functionalities are added.
    [0010] Chirality is the property of an object not to be superimposable with its mirror image. The biopolymers that make up living beings are chiral, with only one of the specular forms (called enantiomers) forming part of said biopolymers. Thus, due to this asymmetric functioning of life, the metabolism of living beings distinguishes between the enantiomers of a chiral compound: in many cases, the biochemical properties of one enantiomer and another are different and even, in certain cases, one of the enantiomers have beneficial properties in the body, while the other can be harmful, as was the case with the drug thalidomide in the last century.
    [0012] The enantiomers of a chiral compound have exactly the same physicochemical properties, and this makes their separation extremely difficult. Thus, the main current challenge in the synthesis of chiral compounds consists in preparing them enantioselectively. In this sense, the manifestation of the chirality of an organic compound only takes place in the presence of a chiral environment, that is, when interacting with another chiral element. Therefore, one of the greatest current challenges of the chemical and pharmaceutical industry consists in the development of solid materials that are capable of discriminating between the enantiomers of chiral compounds, through adsorption or asymmetric catalysis processes. Obtaining said enantioselective solids would have a transcendental impact on the fine chemical industries (pharmaceuticals, cosmetics, etc.) as it would allow obtaining chiral compounds enriched in the enantiomer of interest. In fact, today there is a trend in the pharmaceutical industry towards the so-called chiral switch, consisting of a transition from the commercialization of chiral drugs in racemic form, as was traditionally done, to doing it in enantiomerically pure form, with the consequent improvement in sustainability and the reduction of adverse effects on the body.
    [0014] In this context, a particularly interesting type of zeolitic materials are those with a chiral structure, where the structure crystallizes in a chiral space group, generating a long-range helical arrangement of the TO 4 units. In particular, there are a number of zeolitic structures with inherently chiral topologies, including zeolite beta polymorph A (BEA) (zeolitic structural types are named with a three-letter code), chiral zinc phosphate (CZP), OSB berilosilicate -1 (OSO), the mineral goosecreekite (GOO), the aluminophosphate Cobalt CoAPO-CJ40 (JRY), Linde Type J aluminosilicate (LTJ), and ITQ-37 (ITV) or SU-32 (STW) germanosilicates, the latter also prepared in the form of pure silica (HPM-1). The existence of these materials demonstrates the viability of this type of chiral zeolitic structures. However, except in a particular case that will be mentioned below, all these materials obtained by direct synthesis are made up of a 50% mixture of enantiomorphic crystals of both laterality (as in the case of the STW or ITV structure), or either by intergrowths of polymorphs that are in turn mixtures of enantiomorphic domains at 50% (as in the case of polymorph A in zeolite beta). This clearly demonstrates the enormous difficulty of obtaining these chiral zeolites in enantio-enriched form, despite the great effort applied by various research groups over the years. Of course, the existence of crystals made up of 50% for each enantiomorphic form makes it impossible to use these materials in enantioselective discrimination processes. In a particular case, it was possible to enrich a material with a CZP structure through the use of chiral nucleotides in a post-synthesis secondary crystallization process [Zhang et al., Angew Chem Int Ed 48 (2009) 6049-6051]; However, this material is not stable to the generation of porosity, and therefore cannot be applied in asymmetric processes.
    [0016] The synthesis of zeolitic materials generally requires the addition of organic compounds to the synthesis gels that direct the crystallization process towards a certain structure, where the shape and size of the organic agent determines the porosity of the resulting material, thus transferring its geometric properties to the zeolite through a template effect. These organic compounds are commonly referred to as structure directing agents (ADEs). In this context, very recently it has been possible to prepare a chiral zeolitic material with STW structure enriched in one of the enantiomorphic crystals by using a specific chiral organic agent in the synthesis [Brand et al., PNAS 114 (2017) 5101 5106] By means of a suitable selection of the molecular structure of the organic agent based on imidazolium rings, the preparation of which was tremendously complicated, it was possible to transfer its asymmetric geometric properties to the chiral zeolitic material STW that crystallized around. In fact, it was demonstrated that this enantio-enriched chiral material is capable of carrying out adsorption and catalysis processes in an enantioselective manner, which demonstrates the applicability of this type of materials in asymmetric processes. However, such applicability is in this case limited to small molecules given the pore size of this zeolite, which has 10T channels.
    [0018] One of the zeolites of greatest interest discovered in recent years is the ITQ-37 zeolite (WO 2007/099190 A1), of ITV structural code, which crystallizes in a chiral space group [Sun et al., Nature 458 (2009) 1154 -1157], The great interest of this structure lies in the combination of its pore size delimited by 30T rings, with large openings of 4.3 x 19.3 Á, together with the chiral nature of its structure, forming a gyroidal system of channels with asymmetric openings. Thus, depending on the laterality of the zeolitic structure, the material can potentially crystallize in the cubic space group P4i32 or P4332, giving rise to the two enantiomorphic crystals. This structure was obtained in the form of a germanosilicate, in the presence of high Ge contents, and using a highly complex achiral organic agent (C22N2H40). However, the fact of using an achiral organic agent (since, despite having four stereogenic centers, it is a meso form) necessarily implies that the ITQ-37 polycrystalline material is composed of a 50% mixture of enantiomorphic crystals. of both laterality (racemic conglomerate). Consequently, ITQ-37 zeolite will not be able to carry out enantioselective discrimination processes.
    [0020] Subsequent studies have shown that the same structure (ITV) can be obtained in the presence of other organic agents [Qian et al., Microporous Mesoporous Mater. 164 (2012) 88-92; Chen et al., CrystEngComm. 18 (2016) 2735 2741; Zhang et al., Chem. Commun. 55 (2019) 2753-2756], although all of them are polycyclic compounds of great size and complexity, which shows the great difficulty in obtaining organic agents that direct the formation of a structure with such a complex porous system. In any case, in none of the materials with ITV structure obtained to date has the enrichment of the structure in one of the enantiomorphic crystals been demonstrated. In this context, an essential challenge would be to try to obtain this zeolitic structure enriched in one of the enantiomorphic crystals (P4i32 or P4332), which could potentially develop enantioselective discrimination processes.
    [0021] DESCRIPTION OF THE INVENTION
    [0023] The present invention provides a new chiral zeolitic material by using the organic cation (1S, 2S) -N-ethyl-N-methyl-pseudoephedrion or its enantiomer (1R, 2R) -N-ethyl-N-methyl-pseudoephedrine as the agent. structure director (Figure 1, ADE5), in the presence of a source of Si and a source of Ge, a source of fluoride anions and water, which leads to the crystallization of this new crystalline microporous material called GTM-3 with ITV structure, as long as the crystallization process is carried to moderate temperatures (below 1300C). This observation is highly unexpected given the great difference between the molecular structure of this organic compound (Figure 1, ADE5), of reduced size and with a single ring, and that of the organic agents that have given rise to this zeolite up to now ( Figure 2, ADE1-ADE4), all of them polycyclic and large.
    [0025] A novelty of the GTM-3 material obtained by the process described in the present invention consists in the use of a new organic compound as a directing agent of the ITV structure, easily prepared from a readily available chiral natural product, the alkaloid ( 1S, 2S) -pseudoephedrine or its enantiomer (1R, 2R) -pseudoephedrine, by alkylation reactions (see example 1 and Figure 3). The particular interest of this organic agent is that it is extremely specific for directing the crystallization of the ITV structure, as evidenced by the fact that other organic molecules derived from the same alkaloid precursors, with very similar structures (Figure 1), such as the (1S, 2S) -N, N-dimethylpseudoephedrine (where the ethyl group is replaced by a methyl, ADE7), the (1S, 2S) -N-methyl-N-propyl-pseudoephedrine (where the ethyl group is replaced by a propyl, ADE8), or (1R, 2S) -N-methyl-N-ethyl-ephedrine (where only the absolute configuration of C1, ADE6 is reversed) do not direct the formation of this structure, giving rise to amorphous materials. The fact that such subtle changes in the molecular structure of the organic agent of the present invention prevent the formation of the ITV structure demonstrates a great specificity of the organic agent towards this structure, a relationship that is very unusual in zeolitic materials science. Likewise, the difference in the porosity of the material obtained GTM-3, with a system of three-dimensional pores of up to 19.3 Á (approaching the range of the mesopore), is also very unexpected, and therefore novel, compared to the microporous structures obtained. above with other derivatives of (1R, 2S) -ephedrine and (1S, 2S) pseudoephedrine, where non-chiral structures were invariably obtained and with pore systems smaller than 7.3 A. In turn, it is surprising that despite the large pore size in the GTM-3 material, the organic agent used does not develop -u- type interactions between its aromatic rings to form large supramolecular entities, contrary to what happened in non-chiral materials obtained with other ephedrine derivatives. The main novelty of this invention is that the use of (1S, 2S) -N-methyl-N-ethyl-pseudoephedrine, or its enantiomer (1R, 2R) -N-methyl-N-ethyl-pseudoephedrine, allows to obtain this GTM-3 zeolitic structure enriched in one or the other of the enantiomorphic crystals of the ITV structure (P4i32 or P4332), which, together with its high porosity, allows large molecules to be processed enantioselectively. Said material with an enantio-enriched ITV structure can be used as an adsorbent or asymmetric catalyst to selectively prepare the enantiomers of interest of chiral organic compounds, with the formidable repercussion that this has in fine chemical industries, particularly in the pharmaceutical industry. .
    [0027] The great effectiveness as a directing agent of structure of this organic compound allows the preparation of the GTM-3 material at unusually low temperatures, even below 100 ° C (it has even been obtained up to 60 ° C). This observation is also very unexpected since the synthesis of zeolitic materials with a high T (IV) / T (III) ratio (T (IV) being a tetravalent element such as silicon or germanium, and T (III) a trivalent element such as aluminum, gallium or boron), or in the absence of T (III) elements, as is the case with the present invention, it generally requires crystallization temperatures above 1300C, usually in the range 150-175 ° C. On the other hand, the great effectiveness of the organic agent used in the present invention makes it possible to obtain the GTM-3 material in the presence of small amounts of Ge in the gel, with Si / Ge ratios from 1 to for example 8 (see examples 3 to 15 ), usually with a Si / Ge ratio between 3 and 5, although these values of temperature and Ge content do not limit the scope of the present invention. These Ge content values are significantly lower than those obtained in the ITQ-37 zeolite described above (which was obtained with Si / Ge ratios around 1), which in turn implies an advantage in the GTM-3 material. that the presence of high amounts of Ge implies a low stability against hydrolysis, and therefore a limited applicability of the resulting material.
    [0028] Therefore, the present invention refers, in a first aspect, to a new chiral microporous material called GTM-3, hereinafter material of the invention, characterized by:
    [0029] • have a chemical composition in its anhydrous calcined form a SiÜ 2 : b GeO2: c X 2 Ü 3 : d YÜ 2 , where X is one or more trivalent elements, Y is one or more tetravalent elements other than Si or Ge, the relation b / a can take any value greater than 0, c / ( a + b) can take any value between 0 and 0.2, both inclusive, and d / ( a + b) can take any value between 0 and 0, 2, both included;
    [0030] • have an ITV structure;
    [0031] • and be enantio-enriched in one or another of the enantiomorphic crystalline forms of the ITV structure.
    [0032] It is enantio-enriched as P4i32 or P4332 depending on being prepared using as an organic structure directing agent the cation (1S, 2S) -N-ethyl-N-methylpseudoephedrine or the cation (1R, 2R) -N-ethyl-N- methyl-pseudoephedrine, respectively.
    [0034] By "chiral microporous material called GTM-3" of the present invention is meant a material essentially enantio-enriched in one or other of the enantiomorphic crystalline forms, P4i32 or P4332, described in the present invention. In the present invention, by "essentially enantio-enriched" it is understood that the material contains a greater proportion of one of the enantiomorphic crystal forms P4i32 or P4332. And in the present invention, by "organic structure directing agent or ADE" is understood to be a determined organic compound whose use leads to the crystallization of a determined zeolitic structural topology; in particular the cation (1S, 2S) -N-ethyl-N-methyl-pseudoephedrinium or its enantiomer the (1R, 2R) -N-ethyl-N-methyl-pseudoephedrinium leads to the specific crystallization of the ITV structure, enriched in one or another enantiomorphic crystal form P4i32 or P4332, described above. This structure directing agent can be in the form of hydroxide, halide, preferably iodide, or their mixtures.
    [0036] The technical advantages of the GTM-3 material described in the present invention are:
    [0037] • possess low amounts of Ge, which will significantly improve the hydrothermal stability of the calcined material;
    [0038] • presence of elements other than Si or Ge, such as Al, B, Ti or Sn, conferring catalytic properties to the resulting material;
    [0039] • the specific use of these chiral organic agents enables the preferential enantioselective crystallization of one of the enantiomorphic crystals (P4i32 or P4332), which in turn enables the use of the material as an adsorbent or asymmetric catalyst in processes of enantioselective discrimination, of transcendental importance in the fine chemical and pharmaceutical industry.
    [0041] In the present invention, "ITV structure" is understood as the corresponding zeolite structure as described in the database of the International Zeolite Association (IZA) [http://europe.iza-structure.org/IZA-SC/framework .php STC = ITV; Sun et al., Nature 458 (2009) 1154-1157], with three-dimensional pores delimited by 30T rings, and presenting an X-ray diffraction pattern as shown in Figure 4.
    [0043] In a preferred embodiment of the material of the present invention, the ITV structure in its uncalcined form is defined by having a characteristic X-ray diffraction pattern, recorded with a Philips X'PERT diffractometer using Ka radiation from copper with a filter of Ni, and comprising the following values of angles 20 (0) and distance d (Á):
    [0048] In the present invention, "distance d" is understood as the lattice or interplanar spacing or distance that complies with Bragg's law and is measured in Angstrom (Á). In zeolitic materials, such as those of the present invention, for two structures to be the same, the essential thing is that the diffraction maxima (referred to the position of the angle in degrees, that is, the value of 20) must be the same between the two structures, since they correspond to the lattice spacing (distance d (Á)) associated with the hkl planes corresponding to the structure that is defined, but not the relative intensities, since these also depend on other factors such as crystal size, presence of heteroatoms or material occluded in the pores of the material, crystallinity of the material, etc.
    [0050] In another more preferred embodiment for the values of angles 20 (0) and distance d (Á) described above, respectively, it comprises the following values of relative intensities (l / l or) 100:
    [0055] and where the relative intensities are represented by "e" = 40-100, "f" = 60-100, "m" = 40-60, "b" = 0-60 and "d" = 0-40.
    [0057] In the present invention, "relative intensity o (l / lo) -100" is understood as the ratio obtained by dividing the intensity obtained for an angle 20 in the X-ray diffraction diagram by the highest intensity obtained in said diagram and the result multiplied by 100, this operation is carried out for all the intensities and independently in all the diagrams obtained, in such a way that each intensity of each diagram is in a range from O to 100.
    [0059] In another preferred embodiment of the material of the invention, X is one or more trivalent elements selected from the group Al, B, ln, Ga, Fe, Cr, Ti, V and combinations thereof. These elements induce acidic properties in materials.
    [0061] In another preferred embodiment of the material of the invention characterized in that Y is one or more tetravalent elements selected from the group Sn, Ti, V and combinations thereof. These elements induce redox properties in materials.
    [0062] In another preferred embodiment of the material of the invention the relationships c / ( a + b) and d / ( a + b) can take values between 0 and 0.2, both inclusive.
    [0064] In another preferred embodiment of the material of the invention characterized in that c / ( a + b) and d / ( a + b) are 0.
    [0066] In another preferred embodiment of the material of the invention characterized in that X is Al, B or a mixture of both.
    [0068] In another preferred embodiment of the material of the invention, the organic agent (1S, 2S) -N-ethyl-N-methyl-pseudoephedrine or (1R, 2R) -N-ethyl-N-methyl-pseudoephedrine, remains occluded in the pores of the final material, maintaining its chemical integrity. It is demonstrated in Example 16.
    [0070] In another preferred embodiment of the material of the invention, the pores of the material are empty by eliminating the organic material trapped in said pores (and channels).
    [0072] A second aspect of the invention refers to the catalyst characterized in that it comprises the crystalline microporous material GTM-3 described above where the pores of the material are empty, and it is combined with one or more hydrogenating-dehydrogenating components.
    [0074] In the present invention we understand by "hydrogenating dehydrogenating components" elements that can induce hydrogen transfer reactions, such as, for example, Pd, Pt, Co or Ni.
    [0076] A third aspect of the invention refers to the process for preparing the GTM-3 crystalline microporous material of the present invention, characterized in that it comprises the following steps:
    [0077] a) Prepare a synthesis gel by mixing at least a source of Si, a source of Ge, a source of water, a source of the cation (1R, 2R) -N-ethyl-N-methylpseudoephedrine or a source of the cation ( 1S, 2S) -N-ethyl-N-methyl-pseudoephedrine, and a source of fluoride;
    [0078] b) subjecting the synthesis gel obtained in step (a) to a temperature between 580C and 1300C for a time between 6 hours and 1 month until the crystalline microporous material is formed;
    [0079] c) recovering the GTM-3 crystalline microporous material obtained in step (b); and optionally further comprises an additional step (d) subsequent to the recovery step (c), of eliminating the occluded organic matter from the material recovered in step (c), which can be carried out by means of heat treatment or by extraction, preferably it is carried out by calcination heat treatment at a temperature between 250 ° C and 600 ° C for a time of between 1 h and 48 h. Preferably, the GTM-3 material is calcined in a quartz reactor at 500 ° C for 4 hours in air flow.
    [0081] An advantage of the process is to use an easily prepared chiral organic compound as structure directing agent, and from chiral precursors derived from natural products available in the two enantiomeric forms, (15.25) and (1R, 2R). The source of the corresponding organic cation (1S, 2S) -N-ethyl-N-methyl-pseudoephedrine or its enantiomer (1R, 2R) -N-ethyl-N-methyl-pseudoephedrine, is in the form of hydroxide or ROH, where R refers to the organic cation, and they are (15.25) -N-ethyl-N-methyl-pseudoephedrine hydroxide or (1R, 2R) -N-ethyl-N-methylpseudoephedrine hydroxide, respectively. Optionally, instead of (1S, 2S) -N-ethyl-N-methyl-pseudoephedrine hydroxide or (1R, 2R) -N-ethyl-N-methyl-pseudoephedrine hydroxide, it refers to a halide, as per example fluoride, chloride, bromide, iodide or analogous anions of the organic cation.
    [0083] In a more preferred embodiment of the process the source of fluoride (ZF) in step (a) is hydrofluoric acid or ammonium fluoride. In an even more preferred embodiment, the source of fluoride is HF (hydrofluoric acid). The fluoride source acts as a mineralizing agent.
    [0085] The source of silicon is selected from tetraethylorthosilicate, SIO 2 Aerosil, SIO 2 colloidal, or any other source of Si known to any person skilled in the art. In a preferred embodiment, the source of Si is tetraethylorthosilicate.
    [0087] In another preferred embodiment of the process, the synthesis gel preparation of step (a) comprises a source of Ge. Preferably the source of Ge is carbon dioxide. Ge.
    [0089] In another preferred embodiment, the preparation of the synthesis gel of step (a) further comprises adding variable amounts of other trivalent elements (X), which can be selected from Al, B, ln, Ga, Fe, Cr, Ti, V and combinations thereof, and / or tetravalents (Y) other than Si or Ge, which can be selected from Sn, Ti, V and combinations thereof, to induce acidic and redox properties in the material of the invention .
    [0091] In another preferred embodiment of the process after step (a) and before step (b) a corresponding amount of crystals of GTM-3 material obtained previously is added that will act as seeds, and stirred until homogeneous; the use of seeds favors the crystallization of the material of the invention, increasing its crystallinity and reducing the crystallization time. They can be added to the synthesis mixture, in a proportion of up to 25% (in percentage by weight based on the total of oxides). In a more preferred embodiment, 10% (in percentage by weight relative to total oxides) of GTM-3 crystals previously obtained as seeds is added.
    [0093] In another preferred embodiment of the process, it also comprises in step (a) stirring the synthesis mixture obtained until homogeneous.
    [0095] In another preferred embodiment of the process, the preparation of the synthesis gel of step (a) comprises the following sub-steps:
    [0096] i. add to an aqueous solution of a salt of the cation (1S, 2S) -N-ethyl-N-methylpseudoephedrinium or its enantiomer (1R, 2R) -N-ethyl-N-methyl-pseudoephedrine, at least one source of Ge in the gel;
    [0097] ii. adding to the mixture obtained in step (i) variable amounts of at least one source of silicon, preferably with high Si / Ge ratios, equal to or greater than 3; and
    [0098] iii. add to the mixture obtained in step (ii) a source of fluoride as a mineralizing agent.
    [0100] In a more preferred embodiment of the process, step ii) of the synthesis gel preparation further comprises adding variable amounts of other elements trivalents (X), which can be selected from Al, B, ln, Ga, Fe, Cr, Ti, V and combinations thereof, and / or tetravalents (Y) other than Si or Ge, which can be selected from Sn, Ti, V and combinations thereof, to induce acid and redox properties in the material.
    [0102] In another more preferred embodiment, in step i) of the synthesis gel preparation, the source of the R cation is an aqueous solution of the hydroxide of (1S, 2S) -N-ethyl-N-methylpseudoephedrine or of (1R, 2R ) -N-ethyl-N-methyl-pseudoephedrine at a given concentration. In another more preferred embodiment of the synthesis gel preparation, the aqueous solution of the organic agent has a concentration of around 25-35% in percentage by weight. In a still more preferred embodiment, the source of R is an aqueous solution of the hydroxide of (1S, 2S) -N-ethyl-N-methyl-pseudoephedrine or (1R, 2R) -N-ethyl-N-methyl-pseudoephedrine a a concentration of around 30% by weight.
    [0104] In another more preferred embodiment after stage i) and before stage iii) of the synthesis gel preparation, the synthesis mixture is stirred until homogeneity and the desired composition are reached, if the silicon source of sub-stage (ii) selected is tetraethylorthosilicate, the loss of ethanol due to the decomposition of the tetraethylorthosilicate is monitored.
    [0106] In a preferred embodiment of the procedure, the synthesis gel of step (a) is A Si02: B Ge02: C X203: D Y02: E ROH: F ZF: G H20, where ROH and ZF have been described above, and where the Values A, B, C, D, E, F and G refer to the relative molar composition of each of the components of the synthesis gel, and where the B / A ratio has a value greater than 0 and less than or equal to 2, the ratio E / ( A + B) has values between 0.1 and 1, inclusive, the ratio G / ( A + B) has values between 0.5 and 10, both inclusive, and the ratio F / ( A + B) has values between 0.1 and 1, both included, where X is one or more trivalent elements previously described, Y is one or more tetravalent elements other than Si or Ge, previously described and where C / ( A + B ) and D / ( A + B) have values between 0 and 0.2, both inclusive. In a still more preferred embodiment, the ratio G / ( A + B) has a value between 3 and 7, both inclusive. In yet another more preferred embodiment, the ratio F / ( A + B) has a value of 0.25. In yet another more preferred embodiment, the E / ( A + B) ratio has a value of 0.25.
    [0107] In another preferred embodiment of the process, the synthesis gel of step (a) is A SÍO 2 : B Ge 02 : C X 2 O 3 : E ROH: F ZF: G H 2 0, where ROH, ZF and X have been described above, the values A, B, C, E, F and G refer to the relative molar composition of each of the components of the synthesis gel, and where the B / A ratio has values between 0.1 and 1, both included, the ratio E / ( A + B) has values between 0.1 and 0.5, both included, the ratio F / ( A + B) has values between 0.1 and 0.5, both included, the The G / ( A + B) ratio has values between 0.5 and 10, inclusive, X is Al or B, and the C / ( A + B) ratio has values between 0 and 0.2, inclusive. In another more preferred embodiment, X is B or Al, and the C / ( A + B) ratio has a value between 0.005 and 0.03, inclusive. In yet another still more preferred embodiment, X is B or Al, and the C / ( A + B) ratio has a value of 0.007.
    [0109] In another preferred embodiment of the process, the synthesis gel of step (a) is A Si0 2 : B Ge0 2 : D Y0 2 : E ROH: F ZF: G H 2 0, where ROH, ZF and Y have been previously described , the values A, B, D, E, F and G refer to the relative molar composition of each of the components of the synthesis gel, and where the B / A ratio has values between 0.1 and 1, both included , the ratio E / ( A + B) has values between 0.1 and 0.5, both inclusive, the ratio F / ( A + B) has values between 0.1 and 0.5, both inclusive, the ratio G / ( A + B) has values between 0.5 and 10 inclusive, Y is Ti or Sn, and the relationship D / ( A + B) has values between 0 and 0.2 inclusive. In another more preferred embodiment, Y is Sn or Ti, and the D / ( A + B) ratio has a value between 0.005 and 0.03, inclusive. In yet another more preferred embodiment, Y is Sn or Ti, and the D / ( A + B) ratio has a value of 0.007.
    [0111] In another more preferred embodiment of the process, the synthesis gel of step (a) is A SÍO 2 : B GeÜ 2 : E ROH: F ZF: G H 2 O, where ROH and ZF have been described previously, the values A, B, E, F and G refer to the relative molar composition of each of the components of the synthesis gel, and where the B / A ratio has values between 0.1 and 1, both included, the E / ( A + B) has values between 0.1 and 0.5, both inclusive, the ratio F / ( A + B) has values between 0.1 and 0.5, both inclusive, and the ratio G / ( A + B) it has values between 0.5 and 10, both inclusive. In yet another more preferred embodiment, the B / A ratio has values between 0.33 and 0.125, both inclusive. In yet another more preferred embodiment, the E / ( A + B) ratio has a value of 0.25.
    [0113] In another embodiment of step (b) of the process of the present invention, it is thermally the mixture obtained in stage (a) or sub-stage (iii) at a temperature between 58 ° C and 130 ° C for a time of between 6 h and 1 month, preferably at a temperature equal to or less than 1100 ° C, and equal to or greater than 600 ° C for a time of between 1 and 15 days, more preferably at a temperature equal to or less than 1000C and equal to or greater than 60 ° C for a time of between 4 and 15 days, and still more preferred at a temperature of 1000C for a time of 6 days.
    [0115] In another more preferred embodiment, after stage (a) or sub-stage (iii) of the preparation of the synthesis gel and before stage (b), the synthesis mixture obtained in stage (a) or (iii) is transferred into a suitable container, more preferably if the crystallization temperature is higher than 800C it is transferred to an autoclave with or without stirring or if the crystallization temperature is equal to or lower than 80 0C, it is transferred to other containers such as pyrex jars, with or without agitation.
    [0117] In another more preferred embodiment, the time to which the synthesis mixture of step (b) is subjected to heat treatment is equal to or greater than 6 hours. In another even more preferred embodiment the time is greater than 18 hours and less than 30 days. In another still more preferred embodiment the time is 6 days.
    [0119] In another embodiment of the process for obtaining the material of the present invention, the recovery step (c) is carried out by filtration or centrifugation. Preferably by filtration, more preferably the obtained solids are filtered, washed with abundant ethanol and water and dried in air.
    [0121] In another preferred embodiment of the process for obtaining the material of the present invention, obtaining ROH is carried out by obtaining the quaternary ammonium cation (1S, 2S) -N-ethyl-N-methyl-pseudoephedrine or (1R, 2R) -N-ethyl-N-methyl-pseudoephedrine by alkylation reactions from (1S, 2S) -pseudoephedrine or (1R, 2R) -pseudoephedrine, and its subsequent conversion to the hydroxide form.
    [0123] In another preferred embodiment of the process in step (a) the Si source is tetraethylorthosilicate, and the Ge source is Ge dioxide. In a more preferred embodiment of the process in step (a) the aqueous solution of the organic agent hydroxide of (1S, 2S) -N-ethyl-N-methyl-pseudoephedrine or hydroxide of (1R, 2R) -N-ethyl-Nmethyl-pseudoephedrine, is in a concentration between 25% and 30% by weight. In an even more preferred embodiment the source of fluorine is hydrofluoric acid at 48% by weight and the gel composition is 0.25 ROH: 0.833 SIO 2 : 0.167 Ge02: 0.25 HF: 6.5 H20. In an even more preferred embodiment the heat treatment is 1000C for 6 days; the solids obtained after said heat treatment are filtered, washed with ethanol and water, and dried in air.
    [0125] In another preferred embodiment of the process in step (a) the Si source is tetraethylorthosilicate, the Ge source is Ge dioxide, and the Al source is Al isopropoxide. In a more preferred embodiment of the process in step (a ) the aqueous solution of the organic agent hydroxide of (1S, 2S) -N-ethyl-N-methyl-pseudoephedrine or hydroxide of (1R, 2R) -N-ethyl-N-methyl-pseudoephedrine, is in a concentration between the 25% and 30% by weight. In an even more preferred embodiment the source of fluorine is hydrofluoric acid at 48% by weight and the gel composition is 0.25 ROH: 0.833 SIO 2 : 0.167 Ge02: 0.007 AI 2 O 3 : 0.25 HF: 6.5 H 2 O. In an even more preferred embodiment the heat treatment is 1000C for 14 days; the solids obtained after said heat treatment are filtered, washed with ethanol and water, and dried in air.
    [0127] In another preferred embodiment of the process in step (a) the Si source is tetraethylorthosilicate, and the Ge source is Ge dioxide. In a more preferred embodiment of the process in step (a) the aqueous solution of the organic agent hydroxide of (1S, 2S) -N-ethyl-N-methyl-pseudoephedrine or hydroxide of (1R, 2R) -N-ethyl-N -methyl-pseudoephedrine, is in a concentration of between 25% and 30% by weight. In an even more preferred embodiment the source of fluorine is hydrofluoric acid at 48% by weight and the composition of the gel is 0.25 ROH: 0.833 SIO 2 : 0.167 Ge02: 0.25 HF: 6.5 H 2 O. In a Even more preferred embodiment, the corresponding amount of seeds of GTM-3 (previously prepared) is added to the mixture obtained, stirred until homogeneous and the synthesis mixture obtained is subjected to a heat treatment of 1000C for 3 days; the solids obtained after said heat treatment are filtered, washed with ethanol and water, and dried in air.
    [0129] A fourth aspect of the invention refers to the use of the GTM-3 material in adsorption processes for organic compounds. In a preferred embodiment it is the use as an enantioselective adsorbent for chiral organic compounds.
    [0130] A fifth aspect of the invention refers to the use of the GTM-3 material as a catalyst in reactions with organic compounds. In a preferred embodiment it is the use as an asymmetric catalyst in reactions with chiral organic compounds.
    [0132] The use of a very specific enantiopure chiral compound, (1S, 2S) -N-ethyl-N-methylpseudoephedrine or its enantiomer (1R, 2R) -N-ethyl-N-methyl-pseudoephedrine, as structure directing agent, leads to that the GTM-3 material thus obtained is enriched in one or another of its enantiomorphic crystalline forms (with space group P4i32 or P4332) depending on whether one or the other enantiomer of the organic agent is used, as demonstrated by a series of enantioselective crystallization experiments in presence of crystal seeding (see examples 14 and 15). Thus, the enrichment of GTM-3 in one of the enantiomorphic crystalline forms implies that it can be used in adsorption or asymmetric catalysis processes to discriminate between enantiomers of chiral compounds.
    [0134] The technical advantages of the use of the GTM-3 material described in the present invention is that the specific use of these chiral organic agents allows the crystallization of the GTM-3 material enriched in one or another enantiomorphic crystalline form through the use of the chiral precursor of configuration ( 1S, 2S) or (1R, 2R), respectively.
    [0136] Another aspect of the present invention refers to the use of the material of the invention in enantioselective discrimination processes, both adsorption and asymmetric catalysis.
    [0138] Throughout the description and claims the word "comprise" and its variants are not intended to exclude other technical characteristics, additives, components or steps. For those skilled in the art, other objects, advantages and characteristics of the invention will emerge in part from the description and in part from the practice of the invention. The following examples and figures are provided by way of illustration, and are not intended to be limiting of the present invention.
    [0140] BRIEF DESCRIPTION OF THE FIGURES
    [0142] Figure 1. Molecular structure of the organic agent that has given rise to the ITV structure in the present invention (in its two enantiomeric forms ADE5-SS and ADE5 RR), and of other very similar organic compounds that do not give rise to the ITV structure (ADE6-8), which demonstrates the high specificity of ADE5 to the ITV structure.
    [0144] Figure 2. Molecular structure of the organic agents that have given rise to the ITV structure so far, reported in the bibliography.
    [0146] Figure 3. Detail of the synthesis scheme of the directing agent of chiral structure; shown for the (1S, 2S) enantiomer, being exactly the same for the (1R, 2R) enantiomer.
    [0148] Figure 4. Characteristic X-ray diffraction pattern of the GTM-3 material, prepared with a Si / Ge ratio in the gel of 5 and at 1000C.
    [0150] Figure 5. Solid state 27AI nuclear magnetic resonance in the magic angle of the AI-GTM-3 (SS) material, obtained as indicated in example 10.
    [0152] Figure 6 . X-ray diffraction patterns from enantioselective crystallization experiments. Above: using GTM-3 seeding (SS), using the same enantiomer (SS) for the synthesis gel (gray, case A in example 14) or the opposite (RR) (black, case B in example 14). Bottom: using GTM-3 seeding (RR), using the opposite enantiomer (SS) for the synthesis gel (gray, case C in example 15) or the same (RR) (black, case D in example 15).
    [0154] Figure 7. Solid state 13C nuclear magnetic resonance in the magic angle of the GTM-3 (SS) material obtained according to example 3 (black line), and of a solution in D 2 O of the cation (1S, 2S) -N -ethyl-N-methyl-pseudoephedrine (gray line), as explained in Example 16.
    [0156] Figure 8. X-ray diffraction patterns of the GTM-3 material (prepared with a Si / Ge ratio in the 5a 1000C gel according to example 3) recorded in-situ during the calcination process (as explained in example 17) : bottom: original GTM-3 (SS) (black line); medium: GTM-3 (SS) at 5500C (gray line); top: GTM-3 (SS) calcined at 5500C and subsequently cooled to room temperature (light gray line).
    [0158] Figure 9. X-ray diffraction pattern of the GTM-3 material, prepared with a Si / Ge ratio in the gel from 5 to 1000C as indicated in example 3, after calcination at 5000C for 4 hours in air, as explained in example 18.
    [0160] Figure 10. N2 adsorption / desorption isotherm of the calcined GTM-3 (SS) material, as explained in Example 18.
    [0162] EXAMPLES
    [0164] Next, several examples are described that illustrate the details of the preparation of chiral organic agents, of various GTM-3 materials object of the present invention in different compositions, as well as the evidence of the enrichment of GTM-3 in one or the other. enantiomorphic crystalline form as a function of using one or the other enantiomer of the organic agent. These examples do not, however, limit the present invention. Hereinafter, the GTM-3 material obtained in the presence of the enantiomer (1S, 2S) -N-ethyl-N-methyl-pseudoephedrinium will be called GTM-3 (SS), and that obtained in the presence of the enantiomer (1R, 2R) - N-ethyl-N-methyl-pseudoephedrine will be referred to as GTM-3 (RR).
    [0166] Example 1: Synthesis of the structure directing agent: (1S, 2S) -N-ethyl-N-methyl-pseudoephedrine hydroxide.
    [0168] The synthesis of the directing agent of structure starts from the alkaloid (1S, 2S) -pseudoephedrine or (1R, 2R) -pseudoephedrine; the choice of the starting enantiomer of the precursor determines the final absolute configuration of the structure directing agent. The synthesis consists of three stages, a first addition of a methyl group, a second addition of an ethyl group (Figure 3), and a final ion exchange of the iodide to the corresponding hydroxide.
    [0170] In a typical synthesis of (1S, 2S) -N-ethyl-N-methyl-pseudoephedrine hydroxide, 15.10 g of formaldehyde (37% pp in aqueous solution) and 23.00 g of formic acid (95% pp). The flask is cooled in an ice bath, and then 25.00 g of (1S, 2S) -pseudoephedrine are added very slowly. Reflux the mixture overnight. Then 18.20 g of hydrochloric acid (37% pp) are added, keeping the flask with the mixture in an ice bath. Then, successive extractions of the product are carried out washing with diethyl ether. The aqueous phase is then collected, to which an aqueous solution of sodium hydroxide (25% pp) is added until reaching a pH of 12, giving rise to the formation of an oily product. Finally, in a separating funnel, the product is extracted with diethyl ether, collecting the organic phase. Subsequently, traces of water are removed from the organic phase with potassium carbonate (K2CO3), and the solvent is removed on a rotary evaporator. An oil is thus obtained containing (1S, 2S) -N-methyl-pseudoephedrine, with a yield of around 80%.
    [0172] In the second stage of the reaction, 20.00 g of (1S, 2S) -N-methylpseudoephedrine are dissolved in 400 mL of acetonitrile, and 34.85 g of iodoethane is added little by little while keeping the mixture stirring and cooling. with an ice bath. The mixture is allowed to warm to room temperature and is thus kept under stirring for 5 days. The solvent is then evaporated on a rotary evaporator, forming a precipitate which is washed with diethyl ether. The product, (1S, 2S) -N-ethyl-N-methyl-pseudoephedrine iodide, is obtained with yields of around 90%.
    [0174] The last stage of the synthesis consists of the anionic exchange of iodide for hydroxide, using an anionic resin (Amberlite IRN-78). 34.30 g of (1S, 2S) -N-ethyl-N-methyl-pseudoephedrine iodide are dissolved in 400 ml of water under stirring and at a temperature of 500 ° C. 102 g of anionic resin are then added and the mixture is stirred for 7 days at room temperature. Once the exchange is complete, the resulting aqueous solution is concentrated by evaporating part of the water in the rotary evaporator at 400C until the desired concentration (between 25 and 30% by weight) is reached.
    [0176] Example 2: Synthesis of the structure directing agent: (1R, 2R) -N-ethyl-N-methyl-pseudoephedrine hydroxide.
    [0178] The synthesis of the hydroxide of (1R, 2R) -N-ethyl-N-methyl-pseudoephedrine is carried out in exactly the same way as in Example 1, but starting in this case from the enantiomer (1R, 2R) -pseudoephedrine.
    [0180] In a typical synthesis of (1R, 2R) -N-ethyl-N-methyl-pseudoephedrine hydroxide, 15.10 g of formaldehyde (37% pp in aqueous solution) and 23.00 g of formaldehyde are mixed in a flask under magnetic stirring. of formic acid (95% pp). The flask is cooled in a ice bath, and then 25.00 g of (1R, 2R) -pseudoephedrine are added very slowly. Reflux the mixture overnight. Then 18.20 g of hydrochloric acid (37% pp) are added, keeping the flask with the mixture in an ice bath. Subsequently, successive extractions of the product are carried out, washing with diethyl ether. The aqueous phase is then collected, to which an aqueous solution of sodium hydroxide (25% pp) is added until reaching a pH of 12, giving rise to the formation of an oily product. Finally, in a separating funnel, the product is extracted with diethyl ether, collecting the organic phase. Subsequently, traces of water are removed from the organic phase with potassium carbonate (K2CO3), and the solvent is removed on a rotary evaporator. An oil is thus obtained containing (1R, 2R) -N-methyl-pseudoephedrine, with a yield of around 80%.
    [0182] In the second stage of the reaction, 20.00 g of (1R, 2R) -N-methylpseudoephedrine are dissolved in 400 mL of acetonitrile, and 34.85 g of iodoethane is added little by little while keeping the mixture stirring and cooling. with an ice bath. The mixture is allowed to warm to room temperature and is thus kept under stirring for 5 days. The solvent is then evaporated on a rotary evaporator, forming a precipitate which is washed with diethyl ether. The product, (1R, 2R) -N-ethyl-N-methyl-pseudoephedrine iodide, is obtained with yields of around 90%.
    [0184] The last stage of the synthesis consists of the anionic exchange of iodide for hydroxide, using an anionic resin (Amberlite IRN-78). 34.30 g of (1R, 2R) -N-ethyl-N-methyl-pseudoephedrine iodide are dissolved in 400 ml of water with stirring and at a temperature of 500 ° C. 102 g of anionic resin are then added and the mixture is stirred for 7 days at room temperature. Once the exchange is complete, the resulting aqueous solution is concentrated by evaporating part of the water in the rotary evaporator at 400C until the desired concentration (between 25 and 30% by weight) is reached.
    [0186] Examples 3 through 13 below include various preparations of the GTM-3 material using various synthetic conditions.
    [0188] Example 3: Preparation of the GTM-3 material with a Si / Ge ratio in the gel of 5 from (1S, 2S) -N-ethyl-N-methyl-pseudoephedrine.
    [0189] This example shows a typical GTM-3 preparation, with a Si / Ge ratio in the gel of 5, and using the enantiomer (1S, 2S) -N-ethyl-N-methyl-pseudoephedrine as the organic agent.
    [0191] 0.57 g of Ge02 are dissolved in 6.36 g of aqueous hydroxide solution of (1S, 2S) -N-ethyl-N-methyl-pseudoephedrine with a concentration of 28.8% (pp). Then 5.76 g of tetraethylorthosilicate are added, leaving the mixture to stir to remove the ethanol. Finally 0.34 g of hydrofluoric acid (48% pp) are added, and it is stirred until homogeneous with the aid of a spatula. The prepared gel has a composition of: 0.25 ROH: 0.833 Si02: 0.167 Ge02: 0.25 HF: 6.5 H20, where ROH is (1S, 2S) -N-ethyl-N-methyl-pseudoephedrine hydroxide.
    [0193] The gel is transferred to Teflon sleeves, which are inserted into steel autoclaves and heated at 1000C for 6 days in a static regime. The solid obtained is filtered, washed with ethanol and water and dried. The solid obtained, GTM-3 (SS), presents the characteristic X-ray diffraction pattern of the ITV structure, showing the main diffraction maxima listed below:
    [0198] This material has an average Si / Ge ratio of 2.8, measured by SEM-EDX (Scanning Electron Microscopy with Energy Dispersive X-ray analyzer), giving a Ge content significantly lower than that of ITQ-37 zeolite. In turn, it has a C / N ratio of 12.8 (with 13 being the theoretical value of the organic cation), and an organic content of 19.3% (measured by Elemental Analysis CHN). The complete incorporation of the organic cation in the GTM-3 material is verified by Nuclear Magnetic Resonance in example 16, and the resistance of the GTM-3 material to the elimination of the organic in examples 17 and 18.
    [0199] Example 4: Preparation of the GTM-3 material with a Si / Ge ratio in the gel of 5 from (1R, 2R) -N-ethyl-N-methyl-pseudoephedrine.
    [0201] In this example, the enantiomer (1R, 2R) -N-ethyl-N-methyl-pseudoephedrine is used as an organic agent, under the same synthesis conditions as in example 3.
    [0203] 0.57 g of Ge02 are dissolved in 6.25 g of aqueous hydroxide solution of (1R, 2R) -N-ethyl-N-methyl-pseudoephedrine of concentration 29.3% (pp). Then 5.76 g of tetraethylorthosilicate are added, leaving the mixture to stir to remove the ethanol. Finally 0.34 g of hydrofluoric acid (48% pp) are added, and it is stirred until homogeneous with the aid of a spatula. The prepared gel has a composition of: 0.25 ROH: 0.833 Si02: 0.167 Ge02: 0.25 HF: 6.5 H20, where ROH is (1R, 2R) -N-ethyl-N-methyl-pseudoephedrine hydroxide.
    [0205] The gel is transferred to Teflon sleeves, which are inserted into steel autoclaves and heated at 1000C for 6 days in a static regime. The solid obtained is filtered, washed with ethanol and water and dried. The solid obtained, GTM-3 (RR), presents the characteristic X-ray diffraction pattern of the ITV structure, showing the main diffraction maxima listed below:
    [0210] Example 5: Preparation of the GTM-3 material with a Si / Ge ratio in the gel of 5 from (1S, 2S) -N-ethyl-N-methyl-pseudoephedrine, with a water content in the gel of 3.
    [0212] In this example the water content in the gel molar composition is reduced from 6.5 (as in Examples 3 and 4) to 3.
    [0214] 0.67 g of Ge02 are dissolved in 7.56 g of aqueous hydroxide solution of (1S, 2S) -N-ethyl-N-methyl-pseudoephedrine with a concentration of 28.8% (pp). Next, 6.84 g of tetraethylorthosilicate are added, allowing the mixture to stir for the time necessary to remove the ethanol and water required to reach the desired composition. Finally, 0.40 g of hydrofluoric acid (48% pp) are added, and it is stirred until homogeneous with the aid of a spatula. The prepared gel has a composition of: 0.25 ROH: 0.833 SÍO 2 : 0.167 Ge02: 0.25 HF: 3.0 H20, where ROH is (1S, 2S) -N-ethyl-N-methylpseudoephedrine hydroxide.
    [0216] The gel is transferred to Teflon sleeves, which are inserted into steel autoclaves and heated at 1000C for 14 days in a static regime. The solid obtained is filtered, washed with ethanol and water and dried. The solid obtained, GTM-3 (SS), presents the characteristic X-ray diffraction pattern of the ITV structure, showing the main diffraction maxima listed below:
    [0220] Example 6 : Preparation of the GTM-3 material with a Si / Ge ratio in the gel of 5 from (1S, 2S) -N-ethyl-N-methyl-pseudoephedrine, using SÍO 2 Aerosil as source of Si.
    [0222] In this example SÍO 2 Aerosil is used as the source of Si (instead of tetraethylorthosilicate as in the previous examples).
    [0224] 0.82 g of GeC > 2 are dissolved in 9.21 g of aqueous hydroxide solution of (1S, 2S) -N-ethyl-N-methyl-pseudoephedrine with a concentration of 28.8% (pp). Then 2.36 g of SIO 2 Aerosil and 0.12 g of water (milliQ) are added, allowing the mixture to stir until homogeneous. Finally, 0.49 g of hydrofluoric acid (48% pp) are added, and it is stirred until homogeneous with the aid of a spatula. The prepared gel has a composition of: 0.25 ROH: 0.833 Si02: 0.167 Ge02: 0.25 HF: 6.5 H20, where ROH is (1S, 2S) -N-ethyl-N-methyl-pseudoephedrine hydroxide.
    [0226] The gel is transferred to Teflon covers, which are inserted into steel autoclaves and heated at 1000C for 7 days in a static regime. The solid obtained is filtered, washed with ethanol and water and dried. The solid obtained, GTM-3 (SS), presents the pattern of characteristic X-ray diffraction of the ITV structure, showing the main diffraction maxima listed below:
    [0230] Example 7: Preparation of the GTM-3 material with a Si / Ge ratio in the gel of 5 from (1S, 2S) -N-ethyl-N-methyl-pseudoephedrine, using NH 4 F as a source of fluoride.
    [0232] In this example ammonium fluoride is used as the source of fluoride (instead of hydrofluoric acid as in the previous examples).
    [0234] 0.47 g of GeC > 2 are dissolved in 5.33 g of aqueous hydroxide solution of (1S, 2S) -N-ethyl-N-methyl-pseudoephedrine with a concentration of 28.8% (pp). Then 4.83 g of tetraethylorthosilicate and 0.11 g of water (milliQ) are added, allowing the mixture to stir for the time necessary to remove the ethanol. Finally 0.26 g of ammonium fluoride are added and the mixture is stirred until homogeneous with the aid of a spatula. The prepared gel has a composition of: 0.25 ROH: 0.833 SÍO 2 : 0.167 Ge 0 2 : 0.25 NH 4 F: 6.5 H 2 O, where ROH is (1S, 2S) -N-ethyl hydroxide -N-methyl-pseudoephedrine.
    [0236] The gel is transferred to Teflon covers, which are inserted into steel autoclaves and heated at 1000C for 7 days in a static regime. The solid obtained is filtered, washed with ethanol and water and dried. The solid obtained, GTM-3 (SS), presents the characteristic X-ray diffraction pattern of the ITV structure, showing the main diffraction maxima listed below:
    [0241] Example 8: Preparation of the GTM-3 material with a Si / Ge ratio in the gel of 5 from (1S, 2S) -N-ethyl-N-methyl-pseudoephedrine, at a temperature of 60 ° C.
    [0243] In this example the temperature of the hydrothermal crystallization treatment is reduced to 60 ° C (instead of 1000 ° C as in previous examples), thus allowing the use of pyrex cans instead of autoclaves.
    [0245] 0.57 g of Ge02 are dissolved in 6.36 g of aqueous hydroxide solution of (1S, 2S) -N-ethyl-N-methyl-pseudoephedrine with a concentration of 28.8% (pp). Then add 5.76 g of tetraethylorthosilicate, allowing the mixture to stir to remove the ethanol. Finally 0.34 g of hydrofluoric acid (48% pp) are added, and it is stirred until homogeneous with the aid of a spatula. The prepared gel has a composition of: 0.25 ROH: 0.833 Si02: 0.167 Ge02: 0.25 HF: 6.5 H20, where ROH is (1S, 2S) -N-ethyl-N-methyl-pseudoephedrine hydroxide.
    [0247] The gel is transferred to pyrex jars, which are heated at 60 ° C for 14 days in a static regime. The solid obtained is filtered, washed with ethanol and water and dried. The solid obtained, GTM-3 (SS), presents the characteristic X-ray diffraction pattern of the ITV structure, showing the main diffraction maxima listed below:
    [0252] Example 9: Preparation of GTM-3 material with a Si / Ge ratio in the gel of 3 from (1S, 2S) -N-ethyl-N-methyl-pseudoephedrine.
    [0254] In this example the Ge content is increased to a Si / Ge ratio in the gel of 3 (instead of 5 as in the previous examples).
    [0256] 0.74 g of GeÜ 2 are dissolved in 5.38 g of aqueous hydroxide solution of (1S, 2S) -N-ethyl-N-methyl-pseudoephedrine with a concentration of 29.7% (pp). Then 4.52 g of tetraethylorthosilicate are added, leaving the mixture to stir to remove the ethanol. Finally, 0.30 g of hydrofluoric acid (48% pp) are added, and it is stirred until homogeneous with the aid of a spatula. The prepared gel has a composition of: 0.25 ROH: 0.75 SÍO 2 : 0.25 Ge02: 0.25 HF: 6.5 H20, where ROH is (1S, 2S) -N-ethyl-N hydroxide -methylpseudoephedrine.
    [0258] The gel is transferred to Teflon sleeves, which are inserted into steel autoclaves and heated at 1000C for 6 days in a static regime. The solid obtained is filtered, washed with ethanol and water and dried. The solid obtained, GTM-3 (SS), presents the characteristic X-ray diffraction pattern of the ITV structure, showing the main diffraction maxima listed below:
    [0263] Example 10: Preparation of the material AI-GTM-3 with a Si / Ge ratio in the gel of 3, and a T / AI ratio of 70, from (1S, 2S) -N-ethyl-N-methyl-pseudoephedrine , and with sowings.
    [0265] This example demonstrates the possibility of obtaining the material object of the invention in the presence of aluminum in the synthesis gel, in this particular case, not limiting the scope of the invention, Al is introduced into the gel in a T / AI ratio in the gel equal to 70. In addition, seeds of previously prepared GTM-3 material are also introduced into the gel to promote crystallization, although its presence is not essential to form the material in the presence of Al.
    [0267] 0.60 g of Ge02 are dissolved in 4.21 g of aqueous hydroxide solution of (1S, 2S) -N-ethyl-N-methyl-pseudoephedrine with a concentration of 30.8% (pp). Subsequently, 3.67 g of tetraethylorthosilicate and 0.07 g of Al isopropoxide are added, leaving the mixture to stir to remove the ethanol, isopropanol, and water required to achieve the desired composition. 1.15 g of hydrofluoric acid (10% pp) are then added. Finally, 0.16 g of GTM-3 material prepared previously (according to example 9) are added, and it is stirred until homogeneous. The prepared gel has a composition of: 0.25 ROH: 0.75 Si02: 0.25 Ge02: 0.007 Al203: 0.25 HF: 3.68 H20, where ROH is (1S, 2S) -N-ethyl hydroxide -N-methyl-pseudoephedrine, and with 10% (by weight with respect to the sum of Si02 and Ge02) of seed of solid GTM-3 (SS) prepared previously.
    [0269] The gel is transferred to Teflon sleeves, which are inserted into steel autoclaves and heated at 1000C for 9 days in a static regime. The solid obtained is filtered, washed with ethanol and water and dried. The solid obtained, AI-GTM-3 (SS), presents the characteristic X-ray diffraction pattern of the ITV structure, showing the main diffraction maxima listed below:
    [0274] The incorporation of Al in the material AI-GTM-3 (SS) is demonstrated by solid state NMR of 27AI (Figure 5), where the presence of a single signal at 50 ppm shows the incorporation of Al in tetrahedral positions of the structure ITV.
    [0276] Example 11: Preparation of material B-GTM-3 with a Si / Ge ratio in the gel of 5, and a T / B ratio of 70, from (1S, 2S) -N-ethyl-N-methyl-pseudoephedrine .
    [0278] This example demonstrates the possibility of obtaining the material object of the invention in the presence of boron in the synthesis gel, in this particular case, not limiting the scope of the invention, B is introduced into the gel in a T / B ratio in the gel equal to 70.
    [0280] 0.35 g of GeC > 2 are dissolved in 3.68 g of aqueous hydroxide solution of (1S, 2S) -N-ethyl-N-methyl-pseudoephedrine of concentration 30.6% (pp). Subsequently, 3.54 g of tetraethylorthosilicate, 0.018 g of boric acid and 0.20 g of water (milliQ) are added, leaving the mixture to stir to remove the ethanol. Finally 0.21 g of hydrofluoric acid (48% pp) are added, and it is stirred until homogeneous with the aid of a spatula. The prepared gel has a composition of: 0.25 ROH: 0.833 SÍO 2 : 0.167 GeÜ 2 : 0.007 B 2 O 3 : 0.25 HF: 6.5 H 2 O, where ROH is hydroxide of (1S, 2S) - N-ethyl-N-methyl-pseudoephedrine.
    [0281] The gel is transferred to Teflon sleeves, which are inserted into steel autoclaves and heated at 1000C for 14 days in a static regime. The solid obtained is filtered, washed with ethanol and water and dried. The solid obtained, B-GTM-3 (SS), presents the characteristic X-ray diffraction pattern of the ITV structure, showing the main diffraction maxima listed below:
    [0286] Example 12: Preparation of the Sn-GTM-3 material with a Si / Ge ratio in the gel of 5, and a T / Sn ratio of 140, from (1S, 2S) -N-ethyl-N-methyl-pseudoephedrine .
    [0287] This example demonstrates the possibility of obtaining the material object of the invention in the presence of tin in the synthesis gel, in this particular case, not limiting the scope of the invention, Sn is introduced into the gel in a T / Sn ratio in the gel equal to 140.
    [0289] 0.35 g of GeC > 2 are dissolved in 4.03 g of aqueous hydroxide solution of (1S, 2S) -N-ethyl-N-methyl-pseudoephedrine of concentration 27.9% (pp). Subsequently, 3.53 g of tetraethylorthosilicate and 0.038 g of tin tetrachloride are added, leaving the mixture to stir to remove the ethanol. Finally 0.21 g of hydrofluoric acid (48% pp) are added, and it is stirred until homogeneous with the aid of a spatula. The prepared gel has a composition of: 0.25 ROH: 0.833 SÍO 2 : 0.167 Ge02: 0.007 SnÜ 2 : 0.25 HF: 6.5 H 2 O, where ROH is (1S, 2S) -N-ethyl hydroxide -N-methyl-pseudoephedrine.
    [0291] The gel is transferred to Teflon sleeves, which are inserted into steel autoclaves and heated at 1000C for 6 days in a static regime. The solid obtained is filtered, washed with ethanol and water and dried. The solid obtained, Sn-GTM-3 (SS), presents the characteristic X-ray diffraction pattern of the ITV structure, showing the main diffraction maxima listed below:
    [0296] Example 13: Preparation of the Ti-GTM-3 material with a Si / Ge ratio in the gel of 5, and a T / Ti ratio of 140, from (1S, 2S) -N-ethyl-N-methyl-pseudoephedrine .
    [0298] This example demonstrates the possibility of obtaining the material object of the invention in the presence of titanium in the synthesis gel, in this particular case, not limiting the scope of the invention, Ti is introduced into the gel in a T / Ti ratio in the gel equal to 140.
    [0300] 0.35 g of GeC > 2 are dissolved in 4.02 g of aqueous hydroxide solution of (1S, 2S) -N-ethyl-N-methyl-pseudoephedrine of concentration 27.9% (pp). Subsequently, 3.53 g of tetraethylorthosilicate and 0.04 g of titanium (IV) isopropoxide are added, leaving the mixture to stir to remove the ethanol. Finally 0.21 g of hydrofluoric acid (48% pp) are added, and it is stirred until homogeneous with the aid of a spatula. The prepared gel has a composition of: 0.25 ROH: 0.833 SÍO 2 : 0.167 GeC > 2 : 0.007 TIO 2 : 0.25 HF: 6.5 H 2 O, where ROH is (1S, 2S) -N hydroxide -ethyl-N-methyl-pseudoephedrine.
    [0302] The gel is transferred to Teflon sleeves, which are inserted into steel autoclaves and heated at 1000C for 42 days in a static regime. The solid obtained is filtered, washed with ethanol and water and dried. The solid obtained, Ti-GTM-3 (SS), presents the characteristic X-ray diffraction pattern of the ITV structure, showing the main diffraction maxima listed below:
    [0306] The following examples 14 and 15 suppose conclusive evidence that the GTM-3 material is enriched in one or another enantiomorphic crystalline form depending on whether one or another enantiomer of the organic agent is used, (1S, 2S) -N-ethyl-N-methyl -pseudoephedrine or (1S, 2S) -N-ethyl-N-methyl-pseudoephedrine. Said evidence is given by the fact that, if the same enantiomer of the organic agent is used to prepare the seed and for the synthesis gel, crystallization is notably faster than in the case of preparing the seed and the synthesis gel with different enantiomers. This verifies that the GTM-3 crystals from the seed are able to recognize the different enantiomers of the synthesis gel.
    [0308] Example 14: Enantioselective crystallization of the GTM-3 material with a Si / Ge ratio in the gel of 8 from (1S, 2S) -N-ethyl-N-methyl-pseudoephedrine or (1R, 2R) -N-ethyl- N-methyl-pseudoephedrine, with GTM-3 (SS) seeds.
    [0310] A) 0.26 g of Ge02 are dissolved in 4.07 g of aqueous hydroxide solution of (1S, 2S) -N-ethyl-N-methyl-pseudoephedrine of concentration 30.6% (pp). Then 4.18 g of tetraethylorthosilicate and 0.27 g of water (milliQ) are added, leaving the mixture to stir to remove the ethanol. Then 0.23 g of hydrofluoric acid (48% pp) are added and the mixture is stirred. Finally, 0.073 g of seeds of GTM-3 (SS) material prepared above (with the enantiomer (1S, 2S) -N-ethyl-N-methyl-pseudoephedrine, according to example 3) are added and stirred until homogeneous. The prepared gel has a composition of: 0.25 ROH: 0.89 Si02: 0.11 Ge02: 0.25 HF: 6.5 H20, where ROH is (1S, 2S) -N-ethyl-N- hydroxide methyl-pseudoephedrine, and with 5% (by weight with respect to the sum of Si02 and Ge02) of solid seed GTM-3 (SS) prepared with the same enantiomer as that used in the gel.
    [0312] B) On the other hand, the same experiment is carried out using the same seeds of GTM-3 (SS), but in this case adding the other enantiomer, (1R, 2R) -N-ethyl-N-methyl pseudoephedrine, on the gel. 0.26 g of GeC > 2 are dissolved in 4.26 g of aqueous hydroxide solution of (1R, 2R) -N-ethyl-N-methyl-pseudoephedrine of concentration 29.3% (pp). Then 4.18 g of tetraethylorthosilicate and 0.08 g of water (milliQ) are added, allowing the mixture to stir to remove the ethanol. Then 0.23 g of hydrofluoric acid (48% pp) are added and the mixture is stirred. Finally, 0.073 g of seeds of GTM-3 (SS) material prepared above (with the enantiomer (1S, 2S) -N-ethyl-N-methylpseudoephedrine, according to example 3) are added and stirred until homogeneous. The prepared gel has a composition of: 0.25 ROH: 0.89 SÍO 2 : 0.11 GeÜ 2 : 0.25 HF: 6.5 H 2 O, where ROH is (1R, 2R) -N- hydroxide ethyl-N-methyl-pseudoephedrine, and with 5% (by weight with respect to the sum of SIO 2 and GeÜ 2 ) of solid seed GTM-3 (SS) prepared with the enantiomer opposite to that used in the gel.
    [0314] The gels are transferred to Teflon sleeves, which are inserted into steel autoclaves and heated at 1000C for 3 days under static conditions. The solids obtained are filtered, washed with ethanol and water and dried. In the case of using the same enantiomer in the synthesis gel (1S, 2S) as in the preparation of the seed (1S, 2S) (case A), the solid obtained, GTM-3 (SS), presents the pattern of X-ray diffraction characteristic of GTM-3, crystallizing remarkably faster due to seeding prepared with the same enantiomer. On the contrary, in the case of using the opposite enantiomer in the synthesis gel (1R, 2R) than in the preparation of the seed (1S, 2S) (case B), the crystallization of the GTM-3 material is much slower (see Figure 6-above).
    [0316] Example 15: Enantioselective crystallization of the GTM-3 material with a Si / Ge ratio in the gel of 8 from (1S, 2S) -N-ethyl-N-methyl-pseudoephedrine or (1R, 2R) -N-ethyl- N-methyl-pseudoephedrine, with GTM-3 (RR) seeds.
    [0318] Next, the enantioselective crystallization experiments of the GTM-3 material from Example 14 are repeated, but in this case using seeds of GTM-3 prepared previously with the enantiomer (1R, 2R) -N-ethyl-N-methyl-pseudoephedrine.
    [0320] C) 0.26 g of GeÜ 2 are dissolved in 3.60 g of aqueous hydroxide solution of (1S, 2S) -N-ethyl-N-methyl-pseudoephedrine of concentration 34.6% (pp). Then 4.18 g of tetraethylorthosilicate and 0.74 g of water (milliQ) are added, leaving the mixture to stir to remove the ethanol. Then 0.23 g of hydrofluoric acid (48% pp) are added and the mixture is stirred. Finally, 0.073 g of seeds of prepared GTM-3 (RR) material are added. above (with the opposite enantiomer, (1R, 2R) -N-ethyl-N-methyl-pseudoephedrine, according to example 4), and stir until homogeneous. The prepared gel has a composition of: 0.25 ROH: 0.89 SÍO 2 : 0.11 GeC > 2 : 0.25 HF: 6.5 H 2 O, where ROH is (1S, 2S) -N hydroxide -ethyl-N-methyl-pseudoephedrine, and with 5% (by weight with respect to the sum of SIO 2 and Ge02) of solid seed GTM-3 (RR) prepared with the opposite enantiomer to that used in the gel.
    [0322] D) On the other hand, the same experiment is carried out using the same seeds of GTM-3 (RR), but in this case adding the same enantiomer (1R, 2R) -N-ethyl-N-methylpseudoephedrine in the gel. 0.26 g of GeÜ 2 are dissolved in 4.25 g of aqueous hydroxide solution of (1R, 2R) -N-ethyl-N-methyl-pseudoephedrine with a concentration of 29.3% (pp). Then 4.18 g of tetraethylorthosilicate and 0.09 g of water (milliQ) are added, allowing the mixture to stir to remove the ethanol. Then 0.23 g of hydrofluoric acid (48% pp) are added and the mixture is stirred. Finally, 0.073 g of seeds of GTM-3 (RR) material prepared above (with the enantiomer (1R, 2R) -N-ethyl-N-methylpseudoephedrine, according to example 4) are added and stirred until homogeneous. The prepared gel has a composition of: 0.25 ROH: 0.89 SÍO 2 : 0.11 Ge02: 0.25 HF: 6.5 H 2 O, where ROH is (1R, 2R) -N-ethyl hydroxide -N-methyl-pseudoephedrine, and with 5% (by weight with respect to the sum of SIO 2 and Ge02) of solid seed GTM-3 (RR) prepared with the same enantiomer as used in the gel.
    [0324] The gels are transferred to Teflon sleeves, which are inserted into steel autoclaves and heated at 1000C for 3 days under static conditions. The solids obtained are filtered, washed with ethanol and water and dried. In the case of using the same enantiomer in the synthesis gel (1R, 2R) as in the preparation of the seed (1R, 2R) (case D), the solid obtained, GTM-3 (RR), presents the pattern of Characteristic X-ray diffraction, crystallizing remarkably faster due to seeding prepared with the same enantiomer. On the contrary, in the case of using the opposite enantiomer in the synthesis gel (1S, 2S) than in the preparation of the seed (1R, 2R) (case C), the crystallization of the GTM-3 material is much slower (see Figure 6-below).
    [0326] The same experiments of examples 14 and 15 were repeated increasing the seeding to 10% (by weight with respect to the sum of SIO 2 and GeÜ 2 ), giving similar enantioselective crystallization results. Thus, this clearly shows that the materials GTM-3 (SS) and GTM-3 (RR) are at least enriched in one or the other. of enantiomorphic crystal forms.
    [0328] Example 16: Characterization of the GTM-3 (SS) material prepared according to example 3, with a Si / Ge ratio of 5, by Solid State Nuclear Magnetic Resonance at the Magic Angle.
    [0330] The GTM-3 (SS) material prepared as described in example 3 was characterized by Solid State Nuclear Magnetic Resonance at the Magic Angle of 13C to confirm the integrity of the chiral organic species (1S, 2S) -N-ethyl- N-methylpseudoephedrine. In the GTM-3 (SS) material, bands are observed at 8.5, 13.9, 50.3, 64.7, 70.1, 74.8, 130.2 and 141.7 ppm (Figure 7-line black), very similar to the bands observed for a dissolution in D 2 O of the cation (1S, 2S) -N-ethyl-N-methylpseudoephedrine (Figure 7-gray line), which shows its complete incorporation inside of the GTM-3 material.
    [0332] Example 17: X-ray diffraction experiment at controlled temperature of the GTM-3 (SS) material prepared according to example 3, with a Si / Ge ratio of 5: thermal stability of the material.
    [0334] An X-ray diffraction experiment is carried out at increasing temperature of the GTM-3 material obtained according to the procedure described in example 3 (black line-bottom), to monitor the calcination process in air in situ (Figure 8). It is observed that at 5500C the structure is maintained (the diffraction maxima are maintained in the same positions, only varying the relative intensities due to the elimination of the organic) (gray-medium line). Once the GTM-3 material has been calcined and cooled to room temperature (light gray line-top), the structure of the material is also maintained.
    [0336] Example 18: Calcination in air and characterization of the GTM-3 (SS) material prepared according to example 9, with a Si / Ge ratio of 3: stability and resistance to organic removal.
    [0338] The GTM-3 (SS) material prepared with a Si / Ge 3 ratio was calcined at 5000C in air for 4 hours. The X-ray diffraction of this calcined material (Figure 9) again demonstrates the resistance of the structure to the elimination of organic. Likewise, the adsorption / desorption isotherm of N2 (Figure 10) demonstrates the high porosity of the material, with a micropore volume of 0.31 cm3 / g and an external area (BET) of 866 m2 / g.
    权利要求:
    Claims (18)
    [1]
    1.- A GTM-3 crystalline microporous material, characterized by:
    • have a chemical composition in its anhydrous calcined form a SiÜ 2 : b GeÜ 2 : c X 2 Ü 3 : d YÜ 2 , where X is one or more trivalent elements, Y is one or more tetravalent elements other than Si or Ge, the b / a relationship can take any value greater than 0, c / ( a + b) can take any value between 0 and 0.2, inclusive, and d / ( a + b) can take any value between 0 and 0 , 2, both included;
    • have structuralTV;
    • and be enantio-enriched in one or another of the enantiomorphic crystalline forms of the ITV structure.
    [2]
    2.- The material according to claim 1, wherein the ITV structure in its uncalcined form is defined by having a characteristic X-ray diffraction pattern thereof, recorded with a Philips X'PERT diffractometer using Ka radiation from copper with a Ni filter, and comprising the following values of angles 20 (0) and distance d (Á):

    [3]
    3.- Material according to claim 2, where for the values of angles 20 (0) and distance d (Á) it comprises values of relative intensities (l / l or) 100 of:

    [4]
    4. - The material according to any of claims 1 to 3, where X is at least one trivalent element selected from the group consisting of Al, B, ln, Ga, Fe, Cr, Ti, V and combinations thereof.
    [5]
    5. - Material according to claim 4, where X is Al, B or any of their combinations.
    [6]
    6. The material according to any of claims 1 to 5, wherein Y is at least one tetravalent element selected from the group consisting of Sn, Ti, V and combinations thereof.
    [7]
    7. The material according to any of claims 1 to 6, where c / ( a + b) and d / ( a + b) are 0.
    [8]
    8. - The material according to any of claims 1 to 7, wherein the pores of the material are empty by elimination of organic material.
    [9]
    9. - Catalyst characterized in that it comprises the GTM-3 crystalline microporous material according to claim 8, together with at least one hydrogenating dehydrogenating component.
    [10]
    10. - Procedure for preparing the crystalline microporous material GTM-3 according to claims 1 to 8, characterized in that it comprises the following steps:
    a) Prepare a synthesis gel mixing at least a source of Si, a source of Ge, a source of water and a source of the cation (1R, 2R) -N-ethyl-Nmethyl-pseudoephedrine or a source of the cation (1S, 2S) -N-ethyl-N-methylpseudoephedrine, and a source of fluoride;
    b) subjecting the synthesis gel obtained in step (a) to a temperature between 580C and 1300C for a time between 6 hours and 1 month until the crystalline microporous material is formed, and
    c) recovering the GTM-3 crystalline microporous material obtained in step (b); and optionally further comprises an additional step (d) subsequent to the recovery step (c), of eliminating the occluded organic matter from the material recovered in step (c), which can be carried out by means of heat treatment or by extraction, preferably it is carried out by calcination heat treatment at a temperature between 2500C and 6000C for a time between 1 h and 48 h.
    [11]
    11. - Process for preparing the material according to claim 10, characterized in that the source of the organic cation of step (a) is in the form of hydroxide or halide.
    [12]
    12. - Process for preparing the material according to any of claims 10 or 11, characterized in that the source of silicon in step (a) is selected from tetraethylorthosilicate, SÍO 2 Aerosil, and SÍO 2 colloidal, preferably the source of Si it is tetraethylorthosilicate.
    [13]
    13. - Process for preparing the material according to any of claims 10 to 12, wherein the source of Ge in step (a) is Ge dioxide.
    [14]
    14. - Process for preparing the material according to any of claims 10 to 13, characterized in that the preparation of the synthesis gel of step (a) further comprises adding variable amounts of other trivalent elements (X), which can be selected from between Al, B, ln, Ga, Fe, Cr, Ti, V and combinations thereof, and / or tetravalents (Y) other than Si or Ge, which can be selected from Sn, Ti, V and combinations of the same.
    [15]
    15. - Process for preparing the material according to claims 10 to 14, wherein the source of fluoride in step (a) is hydrofluoric acid or ammonium fluoride.
    [16]
    16. Process for preparing the material according to claims 10 to 15, where after stage (a) and before stage (b) crystals of previously obtained GTM-3 material are added that will act as seeds.
    [17]
    17.- Use of the crystalline microporous material GTM-3 according to claim 8 as an adsorbent for organic compounds
    [18]
    18. Use of the crystalline microporous material GTM-3 according to claim 8 as a catalyst in reactions with organic compounds.
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2007099190A1|2006-02-28|2007-09-07|Consejo Superior De Investigaciones Científicas|A microporous crystalline material, zeolite itq-37, preparation method and use|
    JPS5843394B2|1975-03-10|1983-09-27|Kojin Kk|
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