POLINORBORNENOS OF VINYL ADDITION WITH GROUPS TRISPIRAZOLILBORATO (Machine-translation by Google Tra

专利摘要:
Vinyl addition polynucleotides with trispyrazolylborate groups. The present invention provides novel functionalized polymers of formula (I), wherein ligands of the trispyrazolylborate type are anchored to the structure of polyvinylborne vinyl. In this way, the new polymeric compound can coordinate metals with catalytic activity and, after the reaction, the polymer can be separated by filtration of the desired product and reused again. Additionally, the present invention also provides a process for obtaining the functionalized polymers of formula (I). (Machine-translation by Google Translate, not legally binding)
公开号:ES2678671A1
申请号:ES201730176
申请日:2017-02-14
公开日:2018-08-16
发明作者:Ana Carmen ALBÉNIZ JIMÉNEZ；Jesús Ángel MOLINA DE LA TORRE
申请人:Universidad de Valladolid；
IPC主号:

专利说明:

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DESCRIPTION
VINYL ADDITION POLYNORBORNINS WITH TRISPIRAZOLILBORATO GROUPS Technical sector
The present invention is within the field of polymerization functionalization. In particular, it constitutes an advance in the synthesis of polymers with ligands capable of coordinating metals that give rise to materials with properties of interest to the industry or, if the metals have catalytic activity, which can be used as catalyst support. In particular, the polymers described herein contain in their structure tridentate trispyrazolylborate type ligands. These ligands make it possible to carry out catalysis reactions successfully and, their introduction into the structure of the vinyl addition polynorbornene described herein results in polymers that can be used to obtain recoverable and recyclable catalysts.
State of the art
The so-called scorpionate ligands are an important class of polydentate ligands that coordinate metals very effectively, generally occupying three adjacent coordination positions. Among them, trispyrazolylborate-type ligands (RBpz3-, R = H, generally; pz = pyrazole or substituted pyrazole) have been widely used and metal complexes with this ligand have been used as models of the active centers of certain metalloenzymes [M . Sallmann, C. Limberg, Acc. Chem. Res. 2015, 48, 2734-2743] or have given rise to magnetic properties of interest to the industry [P. Hamon, J. -Y. Thépot, M. Le Floch, M. -E. Boulon, O. Cador, S. Golhen, L. Ouahab, L. Fadel, J. -Y. Saillard, J.-R. Hamon, Angew. Chem. Int. Ed. 2008, 47, 8687-8691]. However, the most prominent application of trispyrazolylborate type ligands is the synthesis of complexes of the general formula RBpz3MLn that are catalysts of a large number of reactions of interest to the industry [a) MM Díaz-Requejo, A. Caballero, TR Belderraín , MC Nicasio, S. Trofimenko, PJ Pérez, J. Am. Chem. Soc. 2002, 124, 978983. b) NA Foley, JP Lee, Z. KE, TB Gunnoe, TR Cundari, Acc. Chem. Res. 2009 , 42, 585-597]. These include those that involve the functionalization of sand or alkanes [a) M. M. Díaz-Requejo, P. J. Pérez, Chem. Rev. 2008, 108, 3379-3394; b) A. Caballero, E. Despagnet-Ayoub, M. M. Díaz-Requejo, A. Díaz-Rodríguez, M. E. González-
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Núñez, R. Mello, B. K. Muñoz, W.-S. Ojo, G. Asensio, M. Etienne, P. J. Pérez, Science, 2011, 332, 835-838; c) A. Caballero, P. J. Pérez, J. Organomet. Chem. 2015, 793, 108-113; d) A. Olmos, B. Noverges, A. Caballero, G. Asensio, P. J. Pérez, patent application No. WO2015 / 181415 A1; e) B. A. McKeown, J. P. Lee, J. Mei, T. R. Cundan, T. B. Gunnoe, Eur. J. Inorg. Chem. 2016, 2296-2311]. The direct conversion of a C-H bond of an arene or an alkane into a C-X bond, with a desired functional group X, is very chemically demanding. However, it is very convenient, since it involves the direct use of the available raw materials without the need to transform them into other intermediate reagents and carry out several reaction steps, as in many of the conventional procedures used.
The activity and selectivity of the catalysts containing trispyrazolylborate type ligands, RBpz3-, can be modulated simply by varying the nature of the R group and, above all, the substituents in the pyrazole fragment that lead to trispyrazolylborates with different electronic and size characteristics. The possibility of having a wide family of ligands that allow a fine adjustment of the characteristics of the metal complexes is an important advantage of these derivatives.
At present, one of the main challenges of synthetic chemistry is to achieve sustainable processes for the construction of molecules. For this, it is essential, among other aspects, to obtain more active and selective catalysts, as well as to avoid the generation of waste after the reactions. One of the strategies to achieve this objective is the use of catalysts supported on a solid, so that they can be easily separated from the desired products and, additionally, can be reused. When recycling the catalyst, this process avoids discarding it after each reaction and allows, in fact, to increase its activity since the total number of catalytic cycles that it provides during its useful life can become very high.
There are some precedents, which are specified below, of the synthesis of trispyrazolylborate bound to polymers. In particular, the literature collects several examples of polystyrene to which a trispyrazolylborate group is attached by an intermediate aryl group, that is, Pol-C6H4-BPz3- [a) Y. Qin, C. Cui, F. Jakle, Macromolecules 2008, 41, 2972-2974. b) Y. Qin, P. O. Shipman, F. Jakle, Macromol. Rapid Commun 2012, 33, 562-567; c) P. J. Desrochers, A. J. Pearce, T. R. Rogers, J. S. Rodman, Eur. J. Inorg. Chem. 2016, 24652473]. An example of an analogue to trispyrazolylborate has also been published.
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polymer where boron is bound to a polystyrene, with ramifications of polyethylene glycol, through one of the heterocyclic substituents: one of the pyrazole groups has been replaced by a benzotriazole to get Pol-benzotriazolBHpz2- [P. J. Desrochers, B. M. Besel, A. L. Corken, J. R. Evanov, A. L. Hamilton, D. L. Nutt, R. M. Tarkka, Inorg. Chem. 2011, 50, 1931-1941].
In all cases, only the derivative Pol-Bpz3- is synthesized, where pz is pyrazole. This is an important limitation for the subsequent application of the functionalized polymer, since the nature of the substituents in the pyrazole fragment is not modified and, consequently, it is not possible to adjust the activity and selectivity of the catalysts containing trispyrazolylborate type ligands, RBpz3-.
The present invention provides new functionalized polymers of formula (I), where trispyrazolylborate type ligands are anchored to the structure of vinyl polynorbornenes. These polymers are capable of withstanding both mild and more demanding reaction conditions. In this way, the new polymeric compound can coordinate metals with catalytic activity and, after the reaction, the polymer can be filtered off the desired product and reused.
The vinyl addition polynorbornene has a completely aliphatic polycyclic skeleton, which has demonstrated remarkable stability as a support in other catalytic processes in which it has been used. Thus, stanyl vinyl addition polynorbornenes are recyclable reagents in Stille coupling reactions catalyzed by palladium [a) AC Albéniz, JC Casares, P. Espinet, B. Martín-Ruiz, MM Villavieja, R. Benavente, patent application No. ES2237309 A1, 2003. b) N. Carrera, E. Gutiérrez, R. Benavente, MM Villavieja, AC Albéniz, P. Espinet, Chem. Eur. J. 2008, 14, 10141-10148; c) AC Albéniz, S. Martínez- Arranz, P. Espinet, patent application No. WO2012160228 A1 / ES20110030827, 2011. d) S. Martínez-Arranz, N. Carrera, AC Albéniz, P. Espinet, A. Vidal- Moya, Adv. Synth Catal., 2012, 354, 3551-3560]. Vinyl addition polynorbornenes have also been used as a support for carbine or proline type organocatalysts with excellent recyclability [a) J. A. Molina de la Torre, A. C. Albéniz, ChemCatChem, 2014, 6, 3547-3552; b) I. K. Sagamanova, S. Sayalero, S. Martínez-Arranz, A. C. Albéniz, M. A. Pericás, Catal. Sci. Technol., 2015, 5, 754-764]. Likewise, vinyl polynorbornenes functionalized with carbeno ligands have been used to anchor palladium complexes, as well as the use of these polymers
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functionalized as catalysts in Suzuki or Negishi C-C bond formation reactions [J. A. Molina de la Torre, A. C. Albéniz, ChemCatChem, 2016, 8, 2241-2248].
All of the above applications are based on the functionalization of vinyl addition polynorbornenes containing alkyl bromine or alkylazide groups. However, these derivatives are not suitable precursors for the introduction of -Bpz3 groups. Therefore, the present invention starts with vinyl (II) polynorbornenes containing "pendant" alkenyl groups along the polymer chain. Thus, the method described herein allows to obtain, from these polymers of formula (II) , polymers with groups - Bpz3 anchored to a completely aliphatic polymer, both in its skeleton and in the chains that bind the -Bpz3 to said skeleton.
An important advantage of the polymer of formula (I) described in this patent application is that it can be obtained by simple synthesis, and the pyrazole groups present in the Pol-Bpz3 ligand can be any pyrazole, with or without substituents. This versatility is a great advantage for later application. Another additional advantage of the polymer of formula (I) is that the union between the -Bpz3 group and the vinyl polynorbornene takes place by means of an alkyl chain, more flexible than the previously used aryl anchors.
Description of the invention
The present invention provides a compound belonging to a new family of vinyl addition polynorbornenes with trispyrazolylborate groups. In particular, the present invention relates to a vinyl polynorbornene of formula (I)
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where
image 1
(I)
R1, R2 and R3 are the same or different monovalent groups; R4 is hydrogen or hydrocarbyl;
M is a monovalent metal; m takes values between 25 and 200; n takes integer values between 0 and 18; and the ratio x / y takes values between 30 and 0.
10 For each specific polymer, m is a variable value depending on the molecular weight distribution of the different initial polymers (Mw, Mn and the relationship between these values or polydispersity). Preferably, m takes values between 50 and 200 for the copolymers, that is, when x / y is different from 0 and, in particular, when the ratio x / y has a value between 1 and 4. In other preferred embodiments, m takes a value between 25 and 50 for the homopolymer (that is, when x / y = 0).
The polymeric compound of formula (I) is characterized in that the ratio of monomers x / y comprises values between 30 and 0, preferably the ratio x / y has a value between 1 and 4. The variation of this ratio x / y allows to have polymers with trispyrazolylborate groups more or less distant from each other in the polymer chain. Thus, in the polymer of formula (I) it is possible to favor the interaction of a single group -Bpz3 or two with a transition metal with different coordination possibilities and even different oxidation numbers, which can be important depending on the application to be given to the vinyl polyborbornene of formula (I).
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These compounds of formula (I) are very slightly soluble in organic solvents, the less soluble the higher the x / y ratio.
The vinyl polynorbornene of formula (I) is characterized in that R1, R2 and R3 are monovalent groups, the same or different. In particular embodiments of the present invention, R1, R2 and R3 can be independently selected from the group consisting of hydrogen, hydrocarbyl, halogen and pseudohalogen.
In this patent application it should be understood that the term "hydrogen" also comprises any of its isotopes. In particular, R1, R2 and / or R3 may be deuterium.
Additionally, R1, R2 and / or R3 can be a halogen such as fluorine, chlorine, bromine or iodine. Preferably, one or more of the substituents R1, R2 and R3 are bromine.
According to the general common knowledge in this sector of the art, hydrocarbyl is understood as, for example, an aryl, alkyl, alkenyl, alkynyl or heteroaryl group. Preferably, the hydrocarbyl that may be present in the polymeric compound of formula (I) may be an aryl, alkyl or heteroaryl group.
In the present patent application, aryl is understood as an aromatic ring formed by carbon atoms, where the ring may contain one or more hydrocarbon substituents or contain heteroatoms, in particular non-depressable groups such as keto, ether, ester, cyano, nitro , sulfonate, amido or thioether. Preferably, R1, R2 and / or R3 are a C5-C14 aryl, such as, for example, 2,4,6-trimethylphenyl.
Additionally, alkyl means an aliphatic chain that can be linear, branched or cyclic, and may or may not contain heteroatoms, in particular, non-depressable groups such as keto, ether, ester, cyano, nitro, sulfonate, amido or thioether. Preferably, R1, R2 and / or R3 are a C1-C8 alkyl such as, for example, methyl.
In this document it is understood that an alkenyl is an aliphatic chain that contains at least one carbon-carbon double bond and can be linear, branched or cyclic. Preferably, one or more of the substituents R1, R2 and R3 are a C2-C8 alkenyl. Plus
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preferably, one or more of the substituents R1, R2 and R3 are selected from a vinyl group and a C3-C8 allyl group.
According to common general knowledge in this sector of the art, it is understood that an alkynyl is an aliphatic chain that contains at least one carbon-carbon triple bond and can be linear, branched or cyclic. Preferably, one or more of the substituents R1, R2 and R3 are a C2-C8 alkynyl.
By "heteroaryl" is meant an aromatic ring, preferably C5-C6, where the ring contains a heteroatom that may be preferably N, S or O.
Likewise, pseudohalogen means any monovalent group assimilable to halogen, for example, -CN or -NO2.
In preferred embodiments of the present invention, the substituents R1, R2 and R3 can be independently selected from the group consisting of hydrogen, methyl, 2,4,6-trimethylphenyl and bromine.
In the compound of formula (I) described herein, R4 may be hydrogen or hydrocarbyl. Preferably, R4 is a hydrocarbyl group. More preferably, R4 is an alkyl. In particular, a C1-C8 aliphatic chain that can be linear, branched or cyclic. Particularly preferred alkyl groups are methyl or ethyl. Thus, the vinyl polynorbornene of formula (I) comprises a totally aliphatic scaffolding, so that the polymer functionalization is concentrated in the group -Bpz3.
In the compound of formula (I) described herein, n is an integer value between 0 and 18. Preferably, n may have an integer value between 0 and 4.
In the vinyl polynorbornene of formula (I) of the present invention, M is a monovalent metal. In particular, M can be selected from the group consisting of alkali metal, transition metal of group 11 (Cu, Ag or Au) and thallium. Preferably, M can be selected from the group consisting of Li, Cu and Ag.
The vinyl polynorbornene comprised in the compound of formula (I) of the present invention can be obtained by vinyl addition polymerization of norbornene
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(bicyclo [2.2.1] hept-2-eno, NB) or its derivatives, and is characterized in that it maintains in its skeleton the bicyclic units of the NB and, therefore, its main chains are completely aliphatic, as the resonance spectra show 13C nuclear magnetic solution or solid state (CP-MAS). Groups containing trispyrazolylborate of the type - (CHR4) nBpz3-, where pz is a fragment of formula CR1-CR2-CR3-NN) are attached to the main polymer backbone, and where R1, R2 and R3 are the same or different monovalent groups , preferably hydrogen, hydrocarbyl, halogen or pseudohalogen, R4 is hydrogen or hydrocarbyl, and n comprises integer values between 0 and 18. The presence of the -Bpz3 groups in the vinyl polynorbornene of formula (I) is evidenced in the nuclear magnetic resonance records of 11B.
Additionally, this patent application describes a synthesis process of the polymers of formula (I) of the present invention, characterized in that the process comprises:
a) hydroboration of a vinyl polynorbornene of formula (II) to obtain a polymeric compound of formula (III); Y
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b) reaction of the polymeric compound of formula (III) obtained in the previous step with a pyrazole derivative (IV), followed by a basic compound comprising the monovalent metal M to obtain the vinyl polynorbornene of formula (I);
image3
where
R1, R2, R3, R4, M, m, n and the ratio x / y maintain the meaning indicated in this document with respect to the vinyl polynorbornene of formula (I).
The procedure described in this document allows almost any pyrazole (IV) to be used. Taking into account the wide variety of substituted pyrazoles available, this synthesis procedure offers great versatility, since it allows to obtain 10 vinyl polynorbornenes of formula (I) with a wide range of trispyrazolylborate groups.
In particular, the hydroboration step a) takes place by reacting vinyl polynorbornenes of formula (II) with a hydroboration agent such as, for example, BHBr2.SMe2, in an organic solvent such as dichloromethane under reflux.
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Unlike the procedures known in the state of the art, the process described in the present patent application allows the trispyrazolylborate group to be anchored to a polymer through an alkyl group (- CHR4) nCH2-CH2-, more flexible than aryl anchors hitherto used. In addition, this procedure allows the versatile synthesis of 20 trispyrazolylborates with different substituents (R1, R2, R3) supported in the polymer, which does not limit the obtaining of a wide family of polymeric trispyrazolylborates.
According to a preferred embodiment, the polymers of formula (II) can be synthesized by copolymerization of norbornene and an alkenylnorbornene (V), where R4 is
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hydrogen or hydrocarbyl, and n takes integer values between 0 and 18, by using a Ni (N) or Pd (II) catalyst.
image4
The ratio x / y in the polymer (II) can be modified by varying the relative proportions of norbornene and alkenylnorbornene (V) in the initial mixture that is subjected to copolymerization.
Hydroboration is carried out on said polymer (II), preferably with BHBr2SMe2 in dichloromethane as solvent, at reflux. To this polymer derived from hydroboration (III) is added pyrazole or a pyrazole derivative of the general formula (IV) ¿R1-CR2-CR3-NN), where R1, R2 and R3 have the same meaning as in the compound of formula (I). Subsequently, a basic compound comprising the metal M, preferably LDA (lithium di-isopropylamide), is added, which leads to the polynorbornene with trispyrazolylborate groups of formula (I).
The procedure described in this document can be carried out without the need to isolate the intermediates obtained at the different stages of the process, or by isolating only one of these intermediates.
The nature of the metal M containing the polymer can be varied either by modifying the base used in step b) of the process, or by including a subsequent step c), where the reaction of the polymer (I) obtained in step b) takes place. , preferably M is Li, with a salt of another monovalent metal (M '), preferably a salt of Cu or Ag.
According to a particularly preferred embodiment, the process described in this patent application comprises a step c), wherein the polymer of formula (I) where M is equal to Li reacts with a copper salt (I), preferably CuI in acetonitrile, or silver (I), preferably AgBF4 in tetrahydrofuran, giving rise to polymers (I), where M is Cu or Ag, respectively.
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The solubility of vinyl addition polynorbornenes with trispyrazolylborate groups is very low in a large number of conventional organic solvents. This is an advantage to obtain catalysts supported in polymeric ligands, since it allows their easy separation of reaction mixtures by simple filtration and recycling.
Examples
The present invention is illustrated by the following examples that should not be considered limiting thereof. The notation used for structural characterization data is shown in the figure.
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Example 1. Synthesis of VA-PNB-NB- (CH2) 2B (3,5-diMepz) 3Li (3,5-diMepz = 3,5-dimethylpyrazole) with x / y = 1.25.
The vinyl polynorbornene of the formula VA-PNB-NBCH = CH2 is dissolved, corresponding to the compound of formula (II) where n is zero, x / y = 1.25, Mw = 45663 Daltons, Mw / Mn = 2.36, m = 80-190 (5 g, 21.02 mmol of -CH = CH2) in CH2Cl2 (350 mL) under nitrogen. The dibromoborane dimethyl sulfide adduct (21 mL of a 1.0 M solution in CH2Cl2, 21 mmol) is added dropwise onto this solution and the mixture is refluxed for 5 hours. It is then cooled to a temperature between 20-25 ° C and 3,5-dimethylpyrazole (8.083 g, 81.08 mmol) is added. After stirring for 16 hours at a temperature between 20-25 ° C, the mixture is cooled to -78 ° C and a freshly prepared solution of
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lithium diisopropylamide (63.06 mmol) in a mixture of THF and hexane. The solution of lithium diisopropylamide is previously obtained by mixing LinBu (39.4 mL of a 1.6 M solution in hexane, 63.04 mmol) and NHPr2 (9 mL, 63.03 mmol) in THF (50 mL ) at -78 ° C. The reaction mixture containing the polymer is stirred for 16 hours while slowly reaching a temperature between 20-25 ° C. After this time, it evaporates to dryness and the residue is washed repeatedly with acetonitrile (6 x 50 mL). The resulting solid is filtered under nitrogen, washed with acetonitrile (6 x 30 mL) and dried in vacuo. The polymer is obtained as an orange solid (10.62 g, yield: 93%). 13C CP-MAS NMR (100.61 MHz): 157-145 (a, C1, C3), 117-110 (a, C2), 72-25 (a, Ca, Cp, polyNB), 2515 (a, Me3 , Me1). 11B MORE NMR (128.38 MHz): 0.9 (a). IR (net, cm-1): 1541, 1415, 1344, 1165, 1034, 781.
Example 2. Synthesis of VA-PNB-NB- (CH2) 2B (3,5-diMepz) 3Li (3,5-diMepz = 3,5-dimethylpyrazole) with x / y = 27.4.
This polymer is prepared in the same manner described in Example 1, but starting from a vinyl polynorbornene of formula VA-PNB-NBCH = CH2 with a ratio x / y = 27.4. Said polymer is synthesized by copolymerization of norbornene and 5-vinyl-2-norbornene with an initial ratio between them 10: 1.
Example 3. Synthesis of VA-PNB-NB- (CH2) 2B (3,5-diMe, 4-Brpz) 3Li (3,5-diMe, 4-Brpz = 3,5-dimethyl, 4-bromopyrazole) with x / y = 1.25.
The same vinyl polynorbornene of formula VA-PNB-NBCH = CH2 used in Example 1 (x / y = 1.25.5 g, 21.02 mmol of -CH = CH2) is dissolved in CH2Cl2 (350 mL) under nitrogen . The dibromoborane dimethyl sulfide adduct (21 mL of a 1.0 M solution in CH2Cl2, 21 mmol) is added dropwise onto this solution and the mixture is refluxed for 5 hours. It is then cooled to a temperature between 20-25 ° C and 3,5-dimethyl-4-bromopyrazole (18.4 g, 105.1 mmol) is added. After stirring for 48 hours at reflux, the yellowish mixture is cooled to -78 ° C and a freshly prepared solution of lithium diisopropylamide (63.06 mmol) in a mixture of THF and hexane is added dropwise thereto. The solution of lithium diisopropylamide is previously obtained by mixing LinBu (39.4 mL of a 1.6 M solution in hexane, 63.04 mmol) and NHiPr2 (9 mL, 63.03 mmol) in THF (50 mL ) at -78 ° C. The reaction mixture containing the polymer is stirred for 16 hours while slowly reaching a temperature between 20-25 ° C. After this
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time is evaporated to dryness and the residue is washed repeatedly with acetonitrile (6 x 50 mL). The resulting solid is filtered under nitrogen, washed with acetonitrile (6 x 30 mL) and dried in vacuo. The polymer is obtained as a light brown solid (15.69 g, yield: 96%). 13C CP-MAS NMR (100.61 MHz): 158-145 (a, C1, C3), 106-98 (a, C2), 70-25 (a, Ca, Cp, polyNB), 25-15 (a , Me3, Me1). 11B MAS NMR (128.38 MHz): 2.1 (a). IR (net, cm-1): 1526, 1416, 1339, 1160, 1082, 1036, 836, 760, 508.
Example 4. Synthesis of VA-PNB-NB- (CH2) 2B (3-Mespz) 3Li (3-Mespz = 3- (2,4,6-trimethylphenyl) pyrazole) with x / y = 1.15.
The vinyl polynorbornene of formula VA-PNB-NBCH = CH2 corresponding to the compound of formula (II) where n is zero, x / y = 1.15, Mw = 40727 Daltons, Mw / Mn = 4, m = 40- 180 (0.3 g, 1.31 mmol of -CH = CH2) in CH2Cl2 (30 mL) under nitrogen. The dibromoborane dimethyl sulfide adduct (1.3 mL of a 1.0 M solution in CH2Cl2, 1.3 mmol) is added dropwise onto this solution and the mixture is refluxed for 5 hours. It is then cooled to a temperature between 20-25 ° C and 3- (2,4,6-trimethylphenyl) pyrazole (0.976 g, 5.24 mmol) is added. After stirring for 40 hours at reflux, the mixture is cooled to -78 ° C and a freshly prepared solution of lithium diisopropylamide (3.93 mmol) in a mixture of THF and hexane is added dropwise thereto. The solution of lithium diisopropylamide is previously obtained by mixing LinBu (2.46 mL of a 1.6 M solution in hexane, 3.93 mmol) and NHiPr2 (0.56 mL, 3.93 mmol) in THF ( 7 mL) at -78 ° C. The reaction mixture containing the polymer is stirred for 30 min at -78 ° C and 90 min at a temperature between 20-25 ° C. After this time, it evaporates to dryness and the residue is treated with acetonitrile (20 mL). The resulting solid is filtered under nitrogen, washed with acetonitrile (5 x 10 mL) and dried in vacuo. The polymer is obtained as a yellowish solid (0.7025 g, yield: 67%). 13C CP-MAS NMR (100.61 MHz): 154-148 (a, C1), 145-136 (a, C3, Short, Cpara), 136-132 (a, C¡pso), 132-124 (a , Cmeta), 112-100 (a, C2), 65-25 (a, Ca, Cp, polyNB), 25-17 (a, Ar-Me). 11B MORE NMR (128.38 MHz): 3 (br). IR (net, cm-1): 1449s, 1100s, 849s, 770s, 441m.
Example 5. Synthesis of VA-PNB-NB- (CH2) 4B (3,5-diMepz) 3Li (3,5-diMepz = 3,5-dimethylpyrazole) with x / y = 2.12.
This polymer is prepared by the procedure described in Example 1 but using as a starting polymer the derivative VA-PNB-NBCH2CH2CH = CH2, corresponding to the compound
of formula (II) where n is equal to 2 and R4 is hydrogen, x / y = 2.12, (2.87 mmol of -CH = CH2 / g polymer) and Mw = 34261 Daltons, Mw / Mn = 1, 77, m = 55-98, synthesized by copolymerization of norbornene and 5- (4-but-1-enyl) -2-norbornene and using as catalyst [Ni (C6F5) 2 (SbPh3) 2] with an initial relationship between them 50: 50: 1. Yield: 95%. 13C CP-5 MAS NMR (100.61 MHz): 160-150 (a, C1, C3), 118-110 (a, C2), 70-25 (a, Ca, Cp, CH2-CH2, polyNB), 25-15 (a, Me3, Me1). 11B MAS NMR (128.38 MHz): 3 (a). IR (net, cm-1): 1539s, 1416s, 1344s, 1166m, 1034s, 774s, 646m, 452m.
Example 6. Synthesis of VA-PNB-NB- (CH2) 2B (3,5-diMepz) 3Cu (NCMe) (3,5-diMepz = 3,510 dimethylpyrazole).
On a suspension of VA-PNB-NB (CH2) 2B (pzMe2) 3Li prepared according to Example 1 (10.2401 g, 18.9 mmol) in acetonitrile (40 mL) under nitrogen atmosphere a solution of Cul ( 3.6 g, 18.9 mmol) in acetonitrile (120 mL). The mixture is stirred for 15 hours at a temperature between 20-25 ° C. The solid is filtered under nitrogen, washed with deoxygenated acetonitrile (6 x 50 mL) and dried in vacuo. 11.7324 g are obtained, yield: 97%. ICP-MS Cu: 90,485 mg Cu / g polymer. 13C CP-MAS NMR (100.61 MHz): 155-145 (a, C1, C3), 117 (br, NCMe), 114-100 (a, C2), 65-19 (a, Ca, Cp, polyNB ), 19-9 (a, Me3, Me1), 2 (NCMe). 11B MAS NMR (128.38 MHz): -1.5 (a).
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权利要求:
Claims (9)
[1]
1.- A vinyl polynorbornene of formula (I),
image 1
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image2
(I)
where
R1, R2 and R3 are the same or different monovalent groups; R4 is hydrogen or hydrocarbyl;
M is a monovalent metal; m takes values between 25 and 200; n takes integer values between 0 and 18; and the ratio x / y takes values between 30 and 0.
[2]
2. - The vinyl polynorbornene according to claim 1, wherein R4 is hydrocarbyl.
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[3]
3. - A vinyl polynorbornene with trispyrazolylborate groups according to claim 2, wherein R4 is alkyl.
[4]
4. The vinyl polynorbornene according to any of claims 1 to 3, wherein R1, R2 and R3 are independently selected from the group consisting of hydrogen, hydrocarbyl,
halogen and pseudohalogen.
[5]
5. The vinyl polynorbornene according to claim 4, wherein the hydrocarbyl is selected from the group consisting of alkyl, aryl and heteroaryl.
6- The vinyl polyborbornene according to any of claims 1 to 5, wherein M is selected from the group consisting of alkali metal, transition metal of group 11 and thallium.
5 7- Procedure for obtaining a vinyl polynorbornene (I) as defined in a
any one of claims 1 to 6, characterized in that the process comprises: a) hydroboration of a vinyl polynorbornene of formula (II) to obtain a polymeric compound of formula (III); Y
image3
10
b) reaction of the polymeric compound of formula (III) obtained in the previous step with a pyrazole derivative (IV) followed by a basic compound comprising the monovalent metal M to obtain the vinyl polynorbornene of formula (I);
image4
BBr2
image5
5
10
fifteen
twenty
25
30
where
R1, R2 and R3 are the same or different monovalent groups;
R4 is hydrogen or hydrocarbyl;
M is a monovalent metal; m takes values between 25 and 200; n takes integer values between 0 and 18; and the ratio x / y takes values between 30 and 0.
[8]
8. - The process for obtaining a vinyl polynorbornene of formula (I) according to claim 7, wherein the intermediate obtained in step a) is not isolated.
[9]
9. - The process for obtaining a vinyl polynorbornene of formula (I) according to any of claims 7 or 8, wherein the vinyl polynorbornene of formula (II) is obtained by copolymerization of norbornene and an alkenylnorbornene (V) in the presence of a Ni (II) or Pd (II) catalyst,
R4 is hydrogen or hydrocarbyl, and n takes integer values between 0 and 18.
[10]
10. - The process for obtaining a vinyl polynorbornene of formula (I) according to any of claims 7 to 9, wherein the process comprises the reaction of a vinyl polynorbornene of formula (I) wherein M is a monovalent metal, with a salt of a second monovalent metal M ', where M' is a monovalent metal other than M, to obtain a second polymer of formula (I), where the monovalent metal is M '.
[11]
11. The process for obtaining a vinyl polynorbornene of formula (I) according to claim 10, wherein the process comprises the reaction of a vinyl polynorbornene of formula (I) wherein M is lithium, with a salt of a second monovalent metal M ' , where M 'is selected from the group consisting of Cu and Ag.
image6
where

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同族专利:

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公开号 | 公开日

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ES2678671B1|2019-07-09|

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WO2018150061A1|2018-08-23|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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EP2314369A1|2009-10-23|2011-04-27|Hamilton Sundstrand Corporation|Film-based system and method for carbon dioxide separation|

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ES201730176A|ES2678671B1|2017-02-14|2017-02-14|POLINORBORNENOS OF VINYL ADDITION WITH GROUPS TRISPIRAZOLILBORATO|ES201730176A| ES2678671B1|2017-02-14|2017-02-14|POLINORBORNENOS OF VINYL ADDITION WITH GROUPS TRISPIRAZOLILBORATO|

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PCT/ES2017/070839| WO2018150061A1|2017-02-14|2017-12-21|Vinylic addition polynorbornenes with trispyrazolylborate groups|