Process for preparing high-purity norbornene silylether

Abstract

A process for preparing high-purity norbornene alkyl silyl ethers is disclosed and claimed. Specifically, a process for preparing high-purity norbornene methyl silyl ethers on an industrial scale is disclosed and claimed. The high-purity monomer prepared according to the process of the present invention is useful for various applications, and such applications include, but are not limited to, the preparation of high-quality and high-purity polynorbornene that can be used in various electronic applications.

Description

Technology Field

[0001] Cross-citation of related applications

[0002] This application claims the benefit of U.S. Provisional Application No. 63 / 452,364 filed on March 15, 2023, and incorporates the entire disclosure thereof by reference into this specification.

[0003] Embodiments of the present invention relate to an industrial-scale process for preparing various norbornene silyl ethers. More specifically, the invention relates to a process for preparing high-purity norbornene alkyl silyl ethers useful as monomers in various industrial applications, which are included as starting materials in the manufacture of electronic and optoelectronic polymer materials. Background Technology

[0004] Functionalized norbornene monomers are widely used in the formulation of polymers with various applications, particularly in the electronics industry. In particular, polynorbornene is utilized in various electronic materials due to its unique film-forming properties that possess various electronic material characteristics. Among other applications, these include use as dielectrics, photoresists, and protective layers. However, since very high-purity materials are required for these applications, it is especially important that the various functionalized norbornene monomers are free from impurities that could hinder the formation of high molecular weight polymers.

[0005] U.S. Patent Publication No. 9,382,271 discloses a process for preparing various norbornenealkylsilylether monomers. However, the process disclosed in the same patent requires stoichiometric amounts of bases such as tert-butoxide potassium, and thus generates a large amount of waste. For this reason, such a process is not industrially desirable and entails enormous costs for waste disposal.

[0006] From the above, it is necessary to develop an environmentally friendly and industrially feasible process for preparing high-purity norbornenealkylsilylether monomers.

[0007] Other purposes and uses of the present invention are described in the following detailed description. The problem to be solved

[0008] A process for preparing a high-purity norbornene alkyl silyl ether of Formula (I) is further described below. Specifically, a process for preparing an industrial-scale high-purity norbornene methyl silyl ether is disclosed. Surprisingly, a catalytic amount of tris(pentafluorophenyl)borane promotes the reaction between the norbornene alkanol of Formula (II) and the silane of Formula (III) as described herein. The high-purity norbornene alkyl silyl ether monomer of Formula (I) prepared according to the process of the present invention is useful for various applications, and such applications include, but are not limited to, the preparation of high-quality and high-purity polynorbornene available for use in various electronic applications. Specific details for implementing the invention

[0009] The articles "a," "an," and "the" used in this specification are deemed to include multiple objects unless explicitly and unambiguously limited to one object.

[0010] Numbers, numerical values, and / or formulas representing amounts of components, reaction conditions, etc., described in this specification and the claims attached to this specification reflect various indeterminate factors of measurements taken to obtain such numbers, numerical values, and / or formulas, so unless otherwise noted, they are all deemed to include the term "approximately."

[0011] Where a numerical range is disclosed in this specification, such range is continuous and includes both the minimum and maximum values ​​of the range, as well as each value between the minimum and maximum values. Also, where a range indicates an integer, it includes each integer between the minimum and maximum values ​​of the range. Furthermore, where multiple ranges are provided to describe a feature or characteristic, such ranges may be combined. That is, unless specifically stated otherwise, all ranges disclosed in this specification should be understood to include any and all sub-ranges included therein. For example, the specified range "1 to 10" should be considered to include any and all sub-ranges between the minimum value 1 and the maximum value 10. Exemplary sub-ranges of the range 1 to 10 include, for example, 1 to 6.1, 3.5 to 7.8, and 5.5 to 10, but are not limited thereto.

[0012] The expression "alkyl" as used in this specification refers to a straight-chain or branched-chain saturated hydrocarbon substituent having a specific number of carbon atoms. Specific alkyl groups include methyl, ethyl, n-propyl, isopropyl, tert-butyl, etc. Derivative expressions such as "alkoxy," "thioalkyl," "alkoxyalkyl," "hydroxyalkyl," "alkyl carbonyl," "alkoxycarbonylalkyl," "alkoxycarbonyl," "diphenylalkyl," "phenylalkyl," "phenylcarboxyalkyl," and "phenoxyalkyl" should be interpreted accordingly.

[0013] The expression "cycloalkyl" as used in this specification includes all known cyclic groups. Representative examples of "cycloalkyl" include, for instance, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, but are not limited thereto. Derivative expressions such as "cycloalkoxy," "cycloalkylalkyl," "cycloalkylaryl," and "cycloalkylcarbonyl" should be interpreted accordingly.

[0014] The expression “perhaloalkyl” as used herein refers to an alkyl group as defined above, wherein all hydrogen atoms of said alkyl group are substituted with halogen atoms selected from fluorine, chlorine, bromine, or iodine. Examples of illustrative examples include, for instance, trifluoromethyl, trichloromethyl, tribromomethyl, triiodomethyl, pentafluoroethyl, pentachloroethyl, pentabromoethyl, pentaiodoethyl, and straight-chain or branched heptafluoropropyl, heptachloropropyl, heptabromopropyl, nonafluorobutyl, nonachlorobutyl, undecafluoropentyl, undecachloropentyl, tridecafluorohexyl, tridecachlorohexyl, etc. Derivative expression “perhaloalkoxy” should be interpreted accordingly. In addition, some of the alkyl groups described in this specification, for example, “alkyl,” etc., may be partially fluorinated, that is, only some of the hydrogen atoms of the said alkyl group are substituted with fluorine atoms, and should be interpreted accordingly.

[0015] The expression "acyl" as used in this specification has the same meaning as "alkane oil" and may be structurally represented as "R-CO-", wherein R is an "alkyl" as defined in this specification having a specific number of carbon atoms. Additionally, "alkyl carbonyl" has the same meaning as "acyl" as defined in this specification. Specifically, "(C1-C4)acyl" means formyl, acetyl, or ethanol oil, propane oil, n-butane oil, etc. Derivative expressions such as "acyloxy" and "acyloxyalkyl" should be interpreted accordingly.

[0016] The term "aryl" as used herein refers to a substituted or unsubstituted phenyl or naphthyl. Specific examples of substituted phenyl or naphthyl include, for instance, o-, p-, m-tolyl, 1,2-, 1,3-, 1,4-xylyl, 1-methylnaphthyl, 2-methylnaphthyl, etc. "Substituted phenyl" or "substituted naphthyl" includes any one of the possible substituents further defined herein or those known in the art.

[0017] The expression "arylalkyl" used in this specification means that an aryl defined in this specification is further bonded to an alkyl defined in this specification. Representative examples include, for instance, benzyl, phenylethyl, 2-phenylpropyl, 1-naphthylmethyl, 2-naphthylmethyl, etc.

[0018] The expression “alkenyl” as used in this specification refers to a non-cyclic linear or branched hydrocarbon chain having a specific number of carbon atoms and containing at least one carbon-carbon double bond, and includes ethenyl, and linear or branched propenyl, butenyl, pentenyl, hexenyl, etc. The derived expressions “arylalkenyl” and quinary or sixary “heteroarylalkenyl” should be interpreted accordingly. Examples of such derived expressions include furan-2-ethenyl, phenylethenyl, 4-methoxyphenylethenyl, etc.

[0019] The term "heteroaryl" as used in this specification includes all known heteroatoms containing aromatic radicals. Representative pentatonic heteroaryl radicals include furanyl, thienyl or thiophenyl, pyrroleyl, isopyroleyl, pyrazolyl, imidazoleyl, oxazoleyl, thiazoleyl, isothiazoleyl, etc. Representative hexaatonic heteroaryl radicals include radicals such as pyridineyl, pyridazineyl, pyrimidineyl, pyrazineyl, and triazineyl. Representative examples of bicyclic heteroaryl radicals include, for instance, radicals such as benzofuranyl, benzothiophenyl, indoleyl, quinolinyl, isoquinolinyl, cinnolyl, benzimidazolyl, indazoleyl, pyridofuranyl, and pyridothienyl.

[0020] The term "heterocyclic" as used in this specification includes all known heteroatoms containing cyclic radicals. Representative 5-membered heterocyclic radicals include tetrahydrofuranyl, tetrahydrothiophenyl, pyrrolidinyl, 2-thiazolinyl, tetrahydrothiazolyl, tetrahydrooxazoleyl, etc. Representative 6-membered heterocyclic radicals include piperidineyl, piperazineyl, morpholineyl, thiomopolinyl, etc. Other various heterocyclic radicals are not limited and include, for example, aziridineyl, azepanyl, diazepanyl, diazabicyclo[2.2.1]hept-2-yl, triazocandyl, etc.

[0021] "Halogen" or "halo" means chloro, fluoro, bromo, and iodo.

[0022] In a broad sense, the term “substitution” is intended to include all acceptable substituents of an organic compound. In any one of the specific embodiments disclosed herein, the term “substitution” means being substituted with one or more substituents independently selected from the group consisting of (C1-C6)alkyl, (C2-C6)alkenyl, (C1-C6)perfluoroalkyl, phenyl, hydroxy, -CO2H, ester, amide, (C1-C6)alkoxy, (C1-C6)thioalkyl, and (C1-C6)perfluoroalkoxy. However, any of other suitable substituents known to those skilled in the art may also be used in these embodiments.

[0023] Any atom that does not satisfy the valence in the text, description of the drawings, examples, and tables of the specification is presumed to have an appropriate number of hydrogen atoms that satisfy such valence.

[0024] For this reason, according to the embodiment of the present invention, a process for preparing a compound of formula (I) is provided.

[0025] (I)

[0026] In this regard,

[0027] n is an integer between 1 and 10 inclusive, where one or more CH2s are (C1-C 10 )alkyl or (C1-C 10 It may be substituted with a perfluoroalkyl group, and

[0028] m is an integer between 0 and 2 inclusive, and

[0029] R1, R2, and R3 may be the same or different and independently of each other hydrogen, halogen, methyl, ethyl, straight-chain or branched-chain (C3-C 12 )alkyl, (C3-C 12 )cycloalkyl, (C6-C 12 )bicycloalkyl, (C7-C 14)tricycloalkyl, (C6-C 10 )aryl, (C6-C 10 )aryl(C1-C3)alkyl, (C5-C 10 )heteroaryl, (C5-C 10 )heteroaryl(C1-C3)alkyl, (C1-C 12 )alkoxy, (C3-C 12 )cycloalkoxy, (C6-C 12 )bicycloalkoxy, (C7-C 14 )Tricycloalkoxy, (C6-C 10 )aryloxy(C1-C3)alkyl, (C5-C 10 )heteroaryloxy(C1-C3)alkyl, (C6-C 10 )aryloxy, (C5-C 10 Selected from the group consisting of )heteroaryloxy, and, (C1-C6)acyloxy, and

[0030] R4, R5, and R6 may be the same or different and independently of each other methyl, ethyl, straight-chain or branched-chain (C3-C 12 )alkyl, and, substituted or unsubstituted (C6-C 14 Selected from the group consisting of aryls,

[0031] The process in question is,

[0032] The step of introducing a solution of tris(pentafluorophenyl)borane into a suitable reactor under an inert atmosphere, and

[0033] In the above solution, the compound of formula (II)

[0034] (II)

[0035] and silane of formula (III)

[0036] R4R5R6SiH (III)

[0037] A step of adding simultaneously at a temperature of approximately 40℃ to approximately 90℃ over a period of approximately 10 minutes to approximately 120 minutes, and

[0038] A step of reacting the reaction mixture for an additional at least about 15 minutes, and

[0039] The step of cooling the reaction mixture to room temperature and treating it with an aqueous solution of a base selected from the group consisting of lithium carbonate, lithium bicarbonate, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonium hydroxide, tetramethylammonium hydroxide, and pyridine;

[0040] The step includes distilling the reaction mixture under reduced pressure at a temperature of about 130°C to about 170°C to obtain the compound of formula (I).

[0041] Surprisingly, it was found that by quantitatively adding a mixture containing substantially equimolar amounts of the compound of formula (II) and the compound of formula (III) to a solution containing a catalytic amount of tris(pentafluorophenyl)borane, the compound of formula (I) can be obtained in quantitative yield and high purity as summarized in Scheme I.

[0042] Scheme I

[0043]

[0044] In addition, various other Lewis acid catalysts having the same properties as tris(pentafluorophenyl)borane may also be used as catalysts in the process of the present invention. In this specification, "Lewis acid" refers to any substance that introduces an electron pair to form a covalent bond. That is, it is an electron pair acceptor. Examples of such Lewis acids include, but are not limited to, tris(2,4,6-trifluorophenyl)borane, tris(2,6-difluorophenyl)borane, tris(4-fluorophenyl)borane, and tris(4-trifluoromethylphenyl)borane.

[0045] In general, to cause the desired reaction as shown in Scheme I, it is advantageous to use a Lewis acid that is soluble in a solvent that is commercially compatible or compatible with the compounds of Formulas (II) and (III). Accordingly, the Lewis acid of Formula (IV) is a suitable Lewis acid applicable to the process of the present invention.

[0046] M(R7) x X y (IV)

[0047] Here, M is selected from the group consisting of boron, aluminum, gallium, indium, and thallium, and R7 may independently be identical or different from each other, and are substituted monovalent (C6-C 14 )represents an aryl, wherein the aryl is substituted with at least one electron-withdrawing group selected from the group consisting of -CF3, -NO2, -CN, and halogens, X is a halogen, x is an integer from 1 to 3, and y is an integer from 0 to 3, provided that x+y=3. In some embodiments, R7 is substituted with at least two halogens. In some other embodiments, a Lewis acid suitable for the process of the present invention is represented by formula (V).

[0048] B(R8) x X y (V)

[0049] Here, each R8 may independently be identical or different from one another, and is a substituted monovalent (C6-C 14 )represents an aryl, wherein the aryl is substituted with at least one electron-withdrawing group selected from the group consisting of -CF3, -NO2, -CN and halogens, x is a halogen, x is an integer from 1 to 3, and y is an integer from 0 to 3, provided that x+y=3. In some embodiments, R7 is substituted with at least two halogens.

[0050] Advantageously, it has been found that tris(pentafluorophenyl)borane provides good catalytic activity in the preparation of the compound of Formula (I). As described above, since the amount of tris(pentafluorophenyl)borane used is a catalytic amount, there is minimal inconvenience in purifying the final product. The amount of tris(pentafluorophenyl)borane that can be used generally depends on the type of compound of Formula (I) being prepared. Generally, the amount of tris(pentafluorophenyl)borane used is 0.1 mol% or less relative to the amount of the compound of Formula (II) used. That is, the molar ratio of Formula (II) to tris(pentafluorophenyl)borane is generally 2000:≤2. In several other embodiments, the molar ratio of the compound of Formula (II) to tris(pentafluorophenyl)borane is generally about 2000:1. That is, the mole percentage of tris(pentafluorophenyl)borane is about 0.05 mole% with respect to the mole of the compound of Formula (II) used. Accordingly, in some embodiments, tris(pentafluorophenyl)borane lower than 0.1 mole%, such as 0.05 mole%, 0.001 mole%, or less, may be used to obtain a compound of Formula (I) of higher purity. Likewise, in some other embodiments, tris(pentafluorophenyl)borane higher than 0.2 mole% may be used depending on the type of compound of Formula (I) being prepared. All such variations in the catalyst amount of tris(pentafluorophenyl)borane used are included within the scope of the process of the present invention.

[0051] By implementing the process conditions according to the present invention, it has become possible to prepare a compound of formula (I) of high purity. As used herein, "high purity" means a product in which no other impurities are present. Accordingly, in some embodiments, the compound of formula (I) prepared according to the present invention has a purity of at least 99%. In some other embodiments, the compound of formula (I) has a purity of at least 99.5%. In yet another embodiment, the compound of formula (I) has a purity of at least 99.8%.

[0052] By suitably using various silanes of Formula (III), various norbornenalkanols of Formula (II) can be used to form the corresponding silyl ether of Formula (I). In some embodiments, the compound of Formula (II) used has n as 1, R1, R2, and R3 as hydrogen, R4 as methyl, and R5 and R6 as phenyl.

[0053] Generally, the process of the present invention is carried out under an inert atmosphere. Any known inert atmosphere may be used herein. In some embodiments, the inert atmosphere used is nitrogen. Other inert atmospheres that may be used include helium or argon.

[0054] Surprisingly, it was found that when an equimolar mixture of the compound of Formula (II) and the compound of Formula (III) is added to a solution of tris(pentafluorophenyl)borane at a suitably low temperature, the compound of Formula (I) is formed. Tris(pentafluorophenyl)borane can be dissolved in any inert solvent. Suitable solvents include hydrocarbon solvents such as hexane, heptane, petroleum ether, benzene, toluene, and xylene, halohydrocarbon solvents such as dichloromethane, 1,1-dichloroethane, chloroform, and carbon tetrachloride, and mixtures of any combination thereof. In some embodiments, the solvent used is toluene.

[0055] As described above, generally, the compound of formula (II) and the compound of formula (III) used are in equal molar ratios. However, various other molar ratios that can result in a high yield of the compound of formula (I) may also be used, as is fully understood by those skilled in the art. Accordingly, in some embodiments, the compound of formula (III) is used in a slightly excess. For example, it is thought that using the compound of formula (III) in excess by 5 to 10 mol% results in a higher yield of the compound of formula (I).

[0056] As shown in Scheme I, according to the process of the present invention, a roughly equimolar mixture of the compound of Formula (II) and the compound of Formula (III) is slowly added to a stirred solution of tris(pentafluorophenyl)borane under an inert atmosphere to form the compound of Formula (I) while simultaneously generating hydrogen. The reaction can suitably be carried out at a temperature appropriately raised above room temperature. For example, such a reaction can be carried out in a suitable reactor system in a temperature range of about 40°C to about 90°C. In some embodiments, the reaction can be carried out in a temperature range of about 50°C to about 80°C, in some other embodiments in a temperature range of about 60°C to about 70°C, and in some other embodiments at a temperature of about 65°C. In some other embodiments, the reaction can be carried out at a temperature higher than about 90°C.

[0057] Generally, since the reaction between the compound of Formula (II) and the compound of Formula (III) is exothermic in the presence of tris(pentafluorophenyl)borane, the addition of the reactants is carried out in a predetermined order. The mixture is generally added slowly over a period of at least one hour. In some embodiments, the addition of the mixture is carried out over a period of about 10 minutes to 120 minutes. In some other embodiments, it is possible to carry out the addition of the mixture for more than 120 minutes, which is obvious to those skilled in the art. After the addition of the mixture, it is generally advantageous to carry out the reaction for an additional period of about 10 minutes or 20 minutes or more. Suitable reactor systems include, but are not limited to, vented glass reactors, suitable glass vessels and / or reactors, and glass-lined metal ones.

[0058] After the reaction is complete, it is very important to remove all residual catalyst tris(pentafluorophenyl)borane from the reaction mixture. Advantageously, it has been found that it is possible to remove substantially all residual tris(pentafluorophenyl)borane by treating the reaction mixture with a suitable base. Suitable bases include, but are not limited to, alkali metal bases such as hydroxides, alkoxides, carbonates, or bicarbonates of lithium, sodium, potassium, or cesium, and alkaline earth metal bases such as hydroxides, alkoxides, carbonates, or bicarbonates of calcium or magnesium. Suitable inorganic or organic bases include, but are not limited to, ammonia, trialkylamines, imidazoles, pyridine, etc. Specific alkali groups include lithium hydroxide, lithium methoxide, lithium ethoxide, lithium tert-butoxide, lithium carbonate, lithium bicarbonate, sodium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium methoxide, potassium ethoxide, potassium tert-butoxide, potassium carbonate, potassium bicarbonate, cesium hydroxide, cesium methoxide, cesium ethoxide, cesium tert-butoxide, cesium carbonate, cesium bicarbonate, calcium hydroxide, calcium methoxide, calcium ethoxide, calcium tert-butoxide, calcium carbonate, calcium bicarbonate, magnesium hydroxide, magnesium methoxide, magnesium ethoxide, magnesium tert-butoxide, magnesium carbonate, magnesium bicarbonate, ammonia, trimethylamine, triethylamine, imidazole, and any combination of mixtures thereof. It is possible. In some embodiments, the base used to remove tris(pentafluorophenyl)borane is sodium carbonate in aqueous form.

[0059] Generally, the progress of the reaction can be monitored by taking a sample from the reactor and analyzing it using an appropriate method such as thin-layer chromatography (TLC), gas chromatography (GC), liquid chromatography (LC) or high-performance liquid chromatography (HPLC), or a combination of GC / mass spectrometry (MS), LC / MS, or other known techniques.

[0060] The various norbornenalkanols of Formula (II) described herein are known and can be easily prepared by known methods. For example, U.S. Patent Publication No. 9,382,271 describes a process for preparing high-purity norbornenalkanols, and the relevant parts thereof are incorporated herein by reference.

[0061] After treatment with an aqueous sodium carbonate solution, the reaction mixture is isolated and distilled. It has been found that it is advantageous to remove volatile organic substances, such as solvents (e.g., toluene) present in the resulting product mixture, at a relatively low temperature and under reduced pressure conditions. Accordingly, in several embodiments, distillation is performed on the resulting product mixture at a temperature of about 130°C to 160°C and a pressure of 100 to 200 Torr. Subsequently, vacuum distillation is performed on the product at a temperature of about 160°C to 170°C and 1 to 2 Torr to obtain a compound of formula (I) of very high purity as described in this specification.

[0062] Surprisingly, by carrying out the process of the present invention, a compound of Formula (I) that substantially does not contain boron remaining from the catalyst used can also be obtained. Accordingly, in some embodiments, the amount of boron present in the compound of Formula (I) is less than 5 ppm, less than 4 ppm, less than 3 ppm, less than 2 ppm, and less than 1 ppm. In some other embodiments, the amount of boron present in the compound of Formula (I) is about 1 ppm to 2 ppm. It is very important that the compound of Formula (I) is not only of high purity but also does not contain boron. This is because the said compound is used as a monomer in the preparation of high-quality polymers, and this point is illustrated in the following specific examples.

[0063] In another embodiment of the present invention, a process for preparing a compound of formula (I) described herein is further provided, which,

[0064] A step of introducing a solution of tris(pentafluorophenyl)borane into toluene in a suitable reactor under a nitrogen atmosphere, and

[0065] A step of adding to the above solution in stoichiometric amounts a compound of Formula (II) described herein and a silane of Formula (III) described herein at a temperature of about 60°C to about 70°C over about 120 minutes, and

[0066] A step of completely reacting the reaction mixture for an additional 15 to 30 minutes, and

[0067] The step of cooling the reaction mixture to room temperature and treating it with sodium carbonate, and

[0068] A step of removing toluene by vacuum distillation at a temperature of approximately 130°C and 100–200 Torr, and

[0069] The method includes the step of obtaining a compound of formula (I) having a purity of at least 99% and a residual boron of less than about 5 ppm by distilling under reduced pressure at a temperature of about 160°C to 170°C and less than 1 Torr.

[0070] In another embodiment of the present invention, a process for preparing (bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(methyl)diphenylsilane of formula (IB) is also provided.

[0071] (IB)

[0072] The process in question is,

[0073] A step of introducing a solution of tris(pentafluorophenyl)borane into toluene in a suitable reactor under a nitrogen atmosphere, and

[0074] A step of adding equimolar amounts of norbornene methanol (IIIB) and methyl diphenylsilane (IIIB) to the above solution over a period of about 100 minutes to about 120 minutes, and

[0075] (IIB)

[0076] (C6H5)2(CH3)SiH (IIIB)

[0077] A step of reacting the reaction mixture for an additional approximately 20 minutes, and

[0078] The step of cooling the reaction mixture to room temperature and treating it with sodium carbonate, and

[0079] A step of removing toluene by evaporation, and

[0080] The method comprises the step of obtaining (bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(methyl)diphenylsilane of formula (IB) by distilling under reduced pressure, with a purity of at least 99% and a residual boron of less than about 2 ppm. In another embodiment of the process of the present invention, the (bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(methyl)diphenylsilane has a purity of at least 99.8% and a residual boron of less than about 1 ppm.

[0081] The present invention is further explained by the following examples, which are provided for illustrative purposes and do not limit the scope of the invention.

[0082] (General) Examples

[0083] The following abbreviations are used to describe several compounds, apparatuses, and / or methods employed in this specification to explain specific embodiments of the invention.

[0084] NBMeOH: Norbornene methanol; DPMS: Diphenylmethylsilane; FAB: Tris(pentafluorophenyl)borane; Pd-12O6: Acetonitrile)bis(triisopropylphosphine)palladium(acetate)tetrakis(pentafluorophenyl)borate; DANFABA: Dimethylanilium tetrakis(pentafluorophenyl)borate; EA: Ethyl acetate; GC-FID: Gas chromatography-flame ionization detector; GPC: Gel permeation chromatography; M W : Weight-average molecular weight; PDI: Dispersion index

[0085] Example 1

[0086] NBMeOSiPh2Me: (bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(methyl)diphenylsilane

[0087] A solution of toluene (2930 mL) containing FAB (0.98 g) was placed in a stirred reactor of appropriate size. Subsequently, the reactor was sealed, filled with nitrogen, and a pressure test was performed. The reactor was operated in vent mode by flowing a high flow rate of nitrogen through the vent system. The reactor was heated to 65°C. After reaching the temperature, a mixture of NBMeOH (584 g) and DPMS (971 g) was quantitatively added to the reactor (over 100 minutes) to produce hydrogen and the compound of the present invention. Once the quantitative addition was complete, the reaction mixture was maintained at this temperature for 20 minutes and then cooled to room temperature (approx. 25°C). A solution of sodium carbonate (4100 g, 2.5 wt%) was added to the cooled reaction mixture and stirred for 30 minutes. After allowing the layer to settle for about 30 to 45 minutes, the lower aqueous layer was decanted and discarded. The process was repeated twice with ion-exchanged water (4100g). Afterwards, volatile organic substances (mainly toluene) were removed under reduced pressure (about 100 Torr and 160°C).

[0088] Subsequently, the obtained compound of the present invention was purified by vacuum distillation using a short-pass wipe film evaporator. Minor impurities (about 5 wt%) were removed by a first distillation pass at 130°C and about 1 Torr. The compound of the present invention was obtained by a second distillation pass at 164°C and about 1 Torr (about 85% recovery). The purity of the compound of the present invention was >99%, as determined by GC FID and yield. Residual boron (derived from FAB) was about 1 ppm.

[0089] By polymerizing the compound of the present invention, a high-quality polymer was obtained as shown below.

[0090] Copolymerization of the compound of the present invention of Example 1

[0091] Toluene (15 mL), hexylnorbornene (0.8 g), the compound of the present invention of Example 1 (1.5 g), and 1-hexene (0.2 g) were added to a 40 mL vial and heated to 80 °C. Then, a catalyst solution of Pd-12O6 (0.00044 g) and DANFABA (0.00029 g) in 0.1 mL of anhydrous EA was added to the reaction mixture to initiate polymerization. After 35 minutes, 0.2 g of hexylnorbornene dissolved in 0.4 mL of toluene was further added. After 3.5 hours, the conversion rate of the obtained polymer was 82%. The molecular weight of the polymer was determined by GPC, and M W : 156,000 and PDI: 3.1.

[0092] Comparative Example 1

[0093] NBMeOSiPh2Me: (bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(methyl)diphenylsilane

[0094] A toluene (2900 mL) solution of FAB (0.98 g) was placed in a stirred reactor of appropriate size. Then, the reactor was sealed, filled with nitrogen, and a pressure test was performed. Afterward, the reactor was operated in vent mode by flowing a high flow rate of nitrogen through the vent system. Then, the reactor was heated to 65°C. A mixture of NBMeOH (584 g) and DPMS (971 g) was quantitatively added to the reactor (over 100 minutes) to produce hydrogen and the compound of the present invention. Once the quantitative addition was completed, the mixture was maintained at a reaction temperature of 65°C and reacted for an additional period of 20 minutes. Then, to inactivate the FAB, pyridine (26 g) was added by sealed transfer, the contents were cooled, and discharged by sealed transfer. Afterward, volatile organic matter (mainly toluene) was removed by stripping under reduced pressure (about 100 Torr and 160°C).

[0095] Subsequently, the obtained crude compound of the present invention was purified by vacuum distillation using a short-pass wipe film evaporator. Minor residual impurities (about 5 wt%) were further removed by a first distillation pass at 130°C and about 1 Torr. The compound of the present invention was obtained by a second distillation pass at 164°C and about 1 Torr (about 85% recovery). The purity of the compound of the present invention was >99%, as determined by GC FID. Residual boron (derived from FAB) was about 12 ppm.

[0096] The following example shows that the compound of the present invention prepared in Comparative Example 1 produces a copolymer of inferior quality with a low conversion rate.

[0097] Copolymerization of the compound of the present invention of Comparative Example 1

[0098] Toluene (15 mL), hexylnorbornene (0.8 g), NBMeOSiPh2Me of Comparative Example 1 (1.5 g), and 1-hexene (0.2 g) were added to a 40 mL vial and heated to 80 °C. Subsequently, a catalyst solution of Pd-12O6 (0.00044 g) and DANFABA (0.00029 g) in 0.1 mL of anhydrous EA was added to the reaction mixture, and polymerization was initiated. After 35 minutes, 0.2 g of hexylnorbornene dissolved in 0.4 mL of toluene was further added. After 3.5 hours, the conversion rate of the obtained polymer was 36%. The molecular weight of the polymer was determined by GPC, and M W : 245,000 and PDI: 2.1.

[0099] Comparative Example 2

[0100] NBMeOSiPh2Me: (bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(methyl)diphenylsilane

[0101] Comparative Example 2 shows that if the reactants are added in an order other than the order described in the process of the present invention, the conversion rate decreases and the purity of the compound of the present invention decreases.

[0102] Norbornene methanol NBMeOH (10 g) and toluene (100 mL) were added to a suitable 4-neck round-bottom flask equipped with a thermometer insert, a stirrer, an N2 inlet with a septum, a gas outlet, an oil bubbler, and a reflux condenser. Subsequently, FAB (0.82 g) as a 10 wt% solution in toluene (9 mL) was added under high flow rate N2. To this stirred mixture, a toluene (80 mL) solution of diphenylmethylsilane (15.9 g) was slowly added dropwise, and gas generation and exothermic reaction were controlled (while maintaining the temperature below 50°C). After the addition was completed (about 1 hour), the reaction mixture was stirred for 18 hours.

[0103] Afterwards, the reaction mixture was filtered through a silica gel plug (diameter 10 cm × height 2.5 cm). The silica gel plug was washed with toluene (100 mL × 2), and the residual washing solvent from the silica gel cake was checked by TLC to confirm that the target product had already eluted from the plug. The obtained solution was concentrated to a small amount, and 8.9 g (yield 34%) of the target substance was isolated as a colorless liquid without further purification.

[0104] Although the present invention has been described with reference to the above embodiments, the present invention is not limited to the embodiments and encompasses the general scope described above in this specification. Various modifications and embodiments may be made without departing from the spirit and scope thereof.

Claims

Claim 1 As a process for preparing the compound of formula (I), (I) In Equation (I), n is an integer between 1 and 10 inclusive, where one or more CH2s (C1-C 10 )alkyl or (C1-C 10 )may be substituted with perfluoroalkyl, m is an integer from 0 to 2, R1, R2, and R3 may be the same or different, and independently hydrogen, halogen, methyl, ethyl, straight-chain or branched-chain (C3-C 12 )alkyl, (C3-C 12 )cycloalkyl, (C6-C 12 )bicycloalkyl, (C7-C 14 )tricycloalkyl, (C6-C 10 )aryl, (C6-C 10 )aryl(C1-C3)alkyl, (C5-C 10 )heteroaryl, (C5-C 10 )heteroaryl(C1-C3)alkyl, (C1-C 12 )alkoxy, (C3-C 12 )cycloalkoxy, (C6-C 12 )bicycloalkoxy, (C7-C 14 )Tricycloalkoxy, (C6-C 10 )aryloxy(C1-C3)alkyl, (C5-C 10 )heteroaryloxy(C1-C3)alkyl, (C6-C 10 )aryloxy, (C5-C 10 Selected from the group consisting of )heteroaryloxy and, (C1-C6)acyloxy, R4, R5, and R6 may be the same or different and independently methyl, ethyl, straight-chain or branched-chain (C3-C 12 )alkyl, and, substituted or unsubstituted (C6-C 14 Selected from the group consisting of aryls, the process comprises the steps of introducing a solution of tris(pentafluorophenyl)borane into a suitable reactor under an inert atmosphere, and adding to the solution a mixture of the compound of formula (II) and the silane of formula (III) over a period of 10 to 120 minutes at a temperature of 25°C to 80°C. (II) R4R5R6SiH (III) A reaction mixture, comprising the steps of reacting the reaction mixture for an additional 15 to 120 minutes, cooling the reaction mixture to 25°C and treating it with a suitable base selected from the group consisting of lithium carbonate, lithium bicarbonate, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonium hydroxide, tetramethylammonium hydroxide, and pyridine, and distilling the reaction mixture under vacuum at a temperature of 130°C to 170°C to obtain the compound of formula (I). Claim 2 A process according to claim 1, wherein the compound of formula (I) has a purity of at least 99%. Claim 3 A process according to claim 1, wherein the compound of formula (I) has a purity of at least 99.5%. Claim 4 A process according to claim 1, wherein the compound of formula (I) has a purity of at least 99.8%. Claim 5 A process according to claim 1, wherein n is 1, R1, R2, and R3 are each hydrogen, R4 is methyl, and R5 and R6 are each phenyl. Claim 6 A process according to claim 1, wherein tris(pentafluorophenyl)borane is present in a catalytic amount. Claim 7 A process according to claim 1, wherein the amount of tris(pentafluorophenyl)borane used is less than 0.2 mol% with respect to the mole of the compound of formula (II) used. Claim 8 A process according to claim 1, wherein the amount of tris(pentafluorophenyl)borane used is 0.1 mol% to 0.2 mol% with respect to the moles of the compound of formula (II) used. Claim 9 A process according to claim 1, wherein the inert atmosphere is nitrogen. Claim 10 A process according to claim 1, wherein tris(pentafluorophenyl)borane is dissolved in toluene. Claim 11 As a process for preparing the compound of formula (I), (I) In Equation (I), n is an integer between 1 and 10 inclusive, where one or more CH2s (C1-C 10 )alkyl or (C1-C 10 )may be substituted with perfluoroalkyl, m is an integer from 0 to 2, R1, R2, and R3 may be the same or different, and independently hydrogen, halogen, methyl, ethyl, straight-chain or branched-chain (C3-C 12 )alkyl, (C3-C 12 )cycloalkyl, (C6-C 12 )bicycloalkyl, (C7-C 14 )tricycloalkyl, (C6-C 10 )aryl, (C6-C 10 )aryl(C1-C3)alkyl, (C5-C 10 )heteroaryl, (C5-C 10 )heteroaryl(C1-C3)alkyl, (C1-C 12 )alkoxy, (C3-C 12 )cycloalkoxy, (C6-C 12 )bicycloalkoxy, (C7-C 14 )Tricycloalkoxy, (C6-C 10 )aryloxy(C1-C3)alkyl, (C5-C 10 )heteroaryloxy(C1-C3)alkyl, (C6-C 10 )aryloxy, (C5-C 10 Selected from the group consisting of )heteroaryloxy and, (C1-C6)acyloxy, R4, R5, and R6 may be the same or different and independently methyl, ethyl, straight-chain or branched-chain (C3-C 12 )alkyl, and, substituted or unsubstituted (C6-C 14 Selected from the group consisting of aryls, the process comprises the steps of introducing a solution of tris(pentafluorophenyl)borane into toluene in a suitable reactor under a nitrogen atmosphere, and adding to the solution a mixture of the compound of formula (II) and the silane of formula (III) at a temperature of 60°C to 70°C over 120 minutes. (II) R4R5R6SiH (III) A process comprising the steps of further reacting the above reaction mixture completely over a period of 15 to 30 minutes, cooling the above reaction mixture to 25°C and treating it with sodium carbonate, removing toluene by vacuum distillation at a temperature of 130°C and 100 to 200 Torr, and vacuum distilling at a temperature of 160°C to 170°C and less than 1 Torr to obtain a compound of formula (I) having at least 99% purity and less than 5 ppm of residual boron. Claim 12 A process according to claim 11, wherein the compound of formula (I) has a purity of at least 99.5% and a residual boron of less than 2 ppm. Claim 13 A process according to claim 11, wherein n is 1, R1, R2, and R3 are each hydrogen, R4 is methyl, and R5 and R6 are each phenyl. Claim 14 A process according to claim 11, wherein tris(pentafluorophenyl)borane is present in a catalytic amount. Claim 15 A process according to claim 11, wherein the amount of tris(pentafluorophenyl)borane used is less than 0.2 mol% with respect to the mole of the compound of formula (II) used. Claim 16 A process according to claim 11, wherein the amount of tris(pentafluorophenyl)borane used is 0.1 mol% to 0.2 mol% with respect to the moles of the compound of formula (II) used. Claim 17 A process for preparing (bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(methyl)diphenylsilane with a purity of at least 99.8% in claim 11. Claim 18 As a process for preparing (bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(methyl)diphenylsilane of formula (IB), (IB) A step of introducing a solution of tris(pentafluorophenyl)borane into toluene in a suitable reactor under a nitrogen atmosphere, and a step of adding equimolar amounts of norbornene methanol (IIB) and methyl diphenylsilane (IIIB) to the solution over a period of 100 to 120 minutes, and A process comprising the steps of reacting a (IIB)(C6H5)2(CH3)SiH (IIIB) reaction mixture for an additional 20 minutes, cooling the reaction mixture to 25°C and treating it with sodium carbonate, removing toluene by evaporation, and distilling under vacuum to obtain (bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(methyl)diphenylsilane of formula (IB) with a purity of at least 99% and a residual boron of less than 2 ppm. Claim 19 In claim 18, the (bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(methyl)diphenylsilane is a process having a purity of at least 99.8% and a residual boron of less than 1 ppm. Claim 20 delete

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