suzuki coupling reactions of diphenyl and triphenyl compounds

Abstract

This invention relates to a novel method for synthesizing compounds, the method comprising at least the following steps; (I x In the presence of an organoboron compound containing one or more groups selected from vinyl, alkyl vinyl, and vinyl alcohol groups having 3 to 5 carbon atoms, the following chemical formula (I) a1 The precursor compound, represented by ) undergoes a Suzuki coupling reaction. The synthesized compound can serve as an advanced or high-performance material for inkjet adaptive planarization compositions. It can be used in nanotechnology processes to fabricate semiconductor / display devices, such as liquid crystal, quantum dot, or OLED displays fabricated on substrates and controlled by semiconductors. a1 )

Description

Technical Field

[0001] This invention relates to a method for synthesizing a chemical compound, and to compounds obtained by or that can be obtained by the method. Background Technology

[0002] In the semiconductor industry, miniaturization has been a continuous trend in order to improve the performance of microchips. However, achieving 7-nanometer and smaller node technologies significantly increases complexity and requires some new process and material solutions.

[0003] Multilayer patterning plays a crucial role in the transfer of fine photolithographic patterns to substrates, and its importance will continue to grow as the industry enters the next stage of advanced node development.

[0004] In these multilayer processes, spin-coated carbon (SOC) underlayers with high etch resistance and good gap-filling properties are crucial. As critical dimensions reach tens of nanometers, surface morphology becomes a major performance challenge. Currently, there is no reliable method for achieving such thin-layer planarization using conventional chemical mechanical polishing (CMP) processes. Therefore, developing new strategies capable of achieving high levels of planarization is a focus of industry attention.

[0005] Inkjet adaptive planarization (IAP) is a method derived from nanoimprint lithography (NIL) for planarizing substrate surfaces. To this end, droplets of a photocurable composition are printed onto the substrate surface, with the droplet pattern customizable to existing morphologies. A superstrate is then brought into direct contact with the printed liquid to form a flat liquid layer. This layer is typically cured under UV light, and removing the superstrate yields a flat surface suitable for subsequent processing steps.

[0006] These cured layers combine high etch resistance, high mechanical strength, and good thermal stability, meeting the requirements for hard mask materials in multilayer processes for next-generation microchip development.

[0007] State-of-the-art photocurable compositions typically contain high levels of acrylate monomers as classic nanoimprint lithography (NIL) resists.

[0008] US2020 / 0339828A1 (Canon) claims, for example, the use of a photocurable composition comprising a polymerizable material and a photoinitiator, wherein at least 90% by weight of the polymerizable material comprises an acrylate monomer containing an aromatic group; and the photocurable composition has a total carbon content of at least 70% after curing.

[0009] US2021 / 0070906A1 (Canon) covers the use of a curable composition comprising a polymerizable material and an initiator, wherein the polymerizable material comprises a first monomer and a second monomer, the second monomer comprising a cyclic structure selected from maleimide rings, pyranone rings, or 2-furanone rings, and wherein the second monomer is soluble in the first monomer, and the viscosity of the curable composition is less than 10 cP. Furthermore, the formulation may also contain another monomer comprising substituted or unsubstituted divinylbenzene.

[0010] US2021 / 0198400A1 (Canon) relates to a light-curable composition comprising 1,3-benzoxazine and an acrylate monomer.

[0011] US2022 / 0185914A1 (Canon) describes a photocurable composition comprising, based on the total weight of the photocurable composition, about 15% to 85% by weight of a polymerizable material (divinylbenzene; in the examples) and 15% to 85% by weight of at least one polyfunctional acrylate monomer (examples, claims).

[0012] Patent documents

[0013] US 2020 / 0339828A1

[0014] US 2021 / 0070906A1

[0015] US 2021 / 0198400A1

[0016] US 2022 / 0185914A1

[0017] Non-patent literature

[0018] No literature Summary of the Invention

[0019] However, the inventors have recently discovered that one or more important issues still need improvement, as described below: providing a new synthetic method for the compound, preferably a novel compound capable of achieving a carbon-rich planar substrate; providing a novel compound with low viscosity and relatively low vapor pressure, preferably suitable for inkjet printing; providing a novel compound with improved crosslinking properties, preferably capable of forming a highly crosslinked thermosetting material after UV-induced free radical polymerization; and / or providing a novel compound that achieves improved thermal stability after curing, preferably cured at about 350°C or higher; achieving lower shrinkage after curing by providing a novel compound synthesized using a new synthetic method; and / or achieving improved etch resistance of the cured layer by providing a novel compound synthesized using a new synthetic method; achieving improved planarization properties of the cured layer by providing a novel compound synthesized using a new synthetic method, i.e., achieving planarization properties on different pattern morphologies of the substrate; achieving a cost-effective and / or environmentally friendly new synthetic method; and providing a new synthetic method with fewer process steps.

[0020] The inventors aimed to solve one or more of the problems mentioned above.

[0021] Then, the inventors unexpectedly discovered that the features defined in the claims can solve one or more of the above-mentioned technical problems.

[0022] Specifically, a new method for synthesizing compounds has been discovered, which includes at least the following steps:

[0023] (I x In the presence of an organoboron compound containing one or more groups selected from vinyl, alkyl vinyl, and vinyl alcohol groups having 3 to 5 carbon atoms, the following chemical formula (I) a1 The precursor compound represented by (I) undergoes a Suzuki-coupling reaction to form a compound of formula (I). a1 Compounds derived from the precursor compound,

[0024] -(I a1 )

[0025] in

[0026] 1≤x≤5, 0≤y≤4, 0≤z≤5;

[0027] n is 1 or 0, m is 1 or 0, 1≤n+m≤2, preferably n+m=1, more preferably n=0, m=1;

[0028] When m is 1 and n is 0, 3≤x+z≤10; when m is 0 and n is 1, 3≤x+y≤9; when m and n are both 1, 3≤x+z+y≤14.

[0029] R va1 R va2 and R va3 The atom is a hydrogen atom, preferably selected from F, Cl, Br, I, and more preferably Br;

[0030] R a1 R a2 and R a3 Each time it appears, it is selected independently or interdependently from H, D or alkyl groups having 1 to 5 carbon atoms;

[0031] L is selected, in the same or different manner, from the group consisting of direct bonds, alkylene groups having 1 to 15 carbon atoms, and alkenyl groups having 2 to 15 carbon atoms each time it appears.

[0032] Wherein, one or more non-adjacent CH2 groups of the alkylene or alkenylene group may be replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS, or CONH, and wherein one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2.

[0033] In another embodiment, the invention also relates to the use of the compounds of the invention in forming a layer, preferably in forming an underlayer spin-coated carbon.

[0034] In another embodiment, the invention also relates to compounds obtained by or that can be obtained by the method of the invention.

[0035] Technical effects of the invention

[0036] This invention provides one or more of the following technical effects: providing a novel compound synthesis method, preferably providing a novel compound capable of achieving a carbon-rich planar substrate; providing a novel compound with low viscosity and relatively low vapor pressure, preferably suitable for inkjet printing; providing a novel compound with improved crosslinking properties, preferably capable of forming a highly crosslinked thermosetting material after UV-induced free radical polymerization; and / or providing a novel compound that achieves improved thermal stability after curing, preferably cured at about 350°C or higher; achieving lower shrinkage after curing by providing a novel compound synthesized using a novel synthesis method; and / or achieving improved etch resistance of the cured layer by providing a novel compound synthesized using a novel synthesis method; achieving improved planarization performance of the cured layer by providing a novel compound synthesized using a novel synthesis method, i.e., achieving planarization performance on different pattern morphologies of the substrate; achieving a cost-effective and / or environmentally friendly new synthesis method; and providing a new synthesis method with fewer process steps.

[0037] Terminology Definition

[0038] The terms used in this article have the following meanings:

[0039] The articles “a,” “one,” and “the” include multiple references unless otherwise explicitly and unambiguously limited to one reference.

[0040] Since all figures, values ​​and / or expressions relating to the amount of ingredients, reaction conditions, etc., as used herein and in the appended claims are subject to various measurement uncertainties encountered in obtaining such values, they shall in all cases be understood to be modified by the term “about”, unless otherwise stated.

[0041] The numerical ranges disclosed herein are continuous and include the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe a feature or property, these ranges may be combined. In other words, unless otherwise stated, all ranges disclosed herein should be understood to include any and all subranges contained therein.

[0042] For example, it is stated that the range "1 to 10" should be considered as including any and all subranges between the minimum value of 1 and the maximum value of 10. Indicative subranges of the range 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8, and 5.5 to 10, etc. Detailed Implementation

[0043] According to the present invention, the method for synthesizing the compound includes at least the following steps;

[0044] (I x In the presence of an organoboron compound containing one or more groups selected from vinyl, alkyl vinyl, and vinyl alcohol groups having 3 to 5 carbon atoms, the following chemical formula (I) a1 The precursor compound represented by (I) undergoes a Suzuki coupling reaction to form a compound of formula (I) a1 Compounds derived from the precursor compound,

[0045] -(I a1 )

[0046] in

[0047] 1≤x≤5, 0≤y≤4, 0≤z≤5;

[0048] n is 1 or 0, m is 1 or 0, 1≤n+m≤2, preferably n+m=1, more preferably n=0, m=1;

[0049] When m is 1 and n is 0, 3≤x+z≤10; when m is 0 and n is 1, 3≤x+y≤9; when m and n are both 1, 3≤x+z+y≤14.

[0050] R va1 R va2 and R va3 The atom is a hydrogen atom, preferably selected from F, Cl, Br, I, and more preferably Br;

[0051] R a1 R a2 and R a3 Each time it appears, it is selected independently or interdependently from H, D or alkyl groups having 1 to 5 carbon atoms;

[0052] L is selected, in the same or different manner, from the group consisting of direct bonds, alkylene groups having 1 to 15 carbon atoms, and alkenyl groups having 2 to 15 carbon atoms each time it appears.

[0053] Wherein, one or more non-adjacent CH2 groups of the alkylene or alkenylene group may be replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS, or CONH, and wherein one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2.

[0054] According to the present invention, the precursor compound (I) a1 The derived compound is represented by chemical formula (I):

[0055] (I)

[0056] in

[0057] 1≤x≤5, 0≤y≤4, 0≤z≤5;

[0058] n is 1 or 0, m is 1 or 0, 1≤n+m≤2, preferably n+m=1, more preferably n=0, m=1;

[0059] When m is 1 and n is 0, 3≤x+z≤10; when m is 0 and n is 1, 3≤x+y≤9; when m and n are both 1, 3≤x+z+y≤14.

[0060] R vb1 R vb2 and R vb3 Each time it appears, it is selected independently or interdependently from vinyl, alkyl vinyl or vinylol groups having 3 to 5 carbon atoms, preferably vinyl;

[0061] R b1 R b2 and Rb3 Each time it appears, it is selected independently or interdependently from H, D or alkyl groups having 1 to 5 carbon atoms;

[0062] L is selected, in the same or different manner, from the group consisting of direct bonds, alkylene groups having 1 to 15 carbon atoms, and alkenyl groups having 2 to 15 carbon atoms each time it appears.

[0063] Wherein, one or more non-adjacent CH2 groups of the alkylene or alkenylene group may be replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS or CONH, and wherein one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2, wherein formula (I) does not include 3,4',5-trivinyl-1,1'-biphenyl (1,1'-Biphenyl, 3,4',5-triethenyl).

[0064] In a preferred embodiment of the present invention, R vb1 R vb2 and R vb3 It is vinyl.

[0065] It is believed that the crosslinking density can be increased when the monomer compound contains one or more carbon rings and at least three vinyl groups. This may further improve the thermal stability and chemical resistance of the cured film.

[0066] It is believed that compounds with high carbon content (preferably 80% or higher) are beneficial for forming carbon-rich, flat underlayers, and their low viscosity and relatively low vapor pressure make them ideal for inkjet printing processes, particularly the inkjet adaptive planarization (IAP) process according to the invention. Furthermore, it is believed that the first monomer compound of the invention can form a highly crosslinked thermosetting material after UV-induced free radical polymerization. The high crosslinking density contributes to its improved chemical and thermal stability, which is key to its use as a hard mask.

[0067] Preferably, chemical formula (I) and / or (I) a1 The L in the alkylene group is a direct bond, a straight-chain alkylene group having 1 to 5 carbon atoms, or a straight-chain alkenyl group having 2 to 5 carbon atoms. Preferably, L is a straight-chain alkylene group having 1 to 5 carbon atoms or a straight-chain alkenyl group having 2 to 5 carbon atoms. One or more non-adjacent CH2 groups of the alkylene group or alkenyl group may be replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS, or CONH. One or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2. More preferably, L is a straight-chain alkylene group having 1 to 5 carbon atoms.

[0068] Preferably, chemical formulas (I) and (I) a1 n is 0 and m is 1.

[0069] In a preferred embodiment of the present invention, the chemical formula (I) a1 The precursor compound is represented by the chemical formula (Ia2).

[0070] -(Ia2)

[0071] R va1 R va2 and R va3 The atom is a hydrogen atom, preferably selected from F, Cl, Br, I, and more preferably Br;

[0072] R a1 R a2 and R a3 Each time it appears, it is selected independently or interdependently from H, D, or alkyl groups having 1 to 5 carbon atoms, preferably R. a1 R a2 and R a3 All are H;

[0073] L is a straight-chain alkylene group with 1 to 5 carbon atoms, or a straight-chain alkenyl group with 2 to 5 carbon atoms.

[0074] Wherein, one or more non-adjacent CH2 groups of the alkylene or alkenylene group may be replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS or CONH, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2.

[0075] Table A below lists preferred examples of this compound.

[0076] Table A:

[0077]

[0078]

[0079] More preferably, the precursor compounds mentioned in Table A' below can be used.

[0080] Table A':

[0081]

[0082]

[0083] Such precursor compounds of the present invention can be synthesized by known methods or the methods described in the working examples.

[0084] In a preferred embodiment of the present invention, the compound of formula (I) is composed of the following chemical formula (I) 2 One of the following represents the value of x; where 1≤x≤5, 0≤z≤5, and 3≤x+z≤10.

[0085] (I 2 )

[0086] Where 1≤x≤5, 0≤z≤5, and 3≤x+z≤10;

[0087] L is a straight-chain alkylene group with 1 to 5 carbon atoms, or a straight-chain alkenyl group with 2 to 5 carbon atoms.

[0088] Wherein, one or more non-adjacent CH2 groups of the alkylene or alkenylene group may be replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS or CONH, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2.

[0089] Table B below lists preferred examples of this compound.

[0090] Table B:

[0091]

[0092]

[0093] In a preferred embodiment of the present invention, L is a direct bond, 2≤x≤5, 2≤z≤5, and 4≤x+z≤10.

[0094] The following are examples of the preferred implementation schemes described above.

[0095] The compound was selected from , , or .

[0096] In another preferred embodiment of the invention, L is a straight-chain alkylene group having 1 to 5 carbon atoms or a straight-chain alkenyl group having 2 to 5 carbon atoms, wherein one or more non-adjacent CH2 groups of the alkylene group or alkenyl group may be replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS, or CONH, and wherein one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2.

[0097] More preferably, the compounds in the other preferred embodiment described above are selected from the table below.

[0098]

[0099] According to the present invention, compounds obtained by or capable of being obtained by the method of the present invention can be used to manufacture a cured layer, preferably a photocurable layer formed from the compounds of the present invention. In a preferred embodiment, the photocurable layer can be used as an interlayer insulating film for semiconductor devices, or as a spin-on carbon substrate (SOC) for manufacturing semiconductor devices. Examples include LSI, system LSI, DRAM, SDRAM, RDRAM, or D-RDRAM.

[0100] In a preferred embodiment of the present invention, step (I) x The organoboron compound of the above-mentioned type contains at least one vinyl group, preferably, the organoboron compound is composed of a chemical formula (I... o )express;

[0101] R o1 -B(R o2 )3·A -(I o )

[0102] in

[0103] R o1 It is a vinyl group, an alkyl vinyl group having 3 to 5 carbon atoms or a vinyl alcohol group, preferably a vinyl group;

[0104] R o2 The atom is a hydrogen atom, preferably selected independently from F, Cl, Br, and I each time it appears, and more preferably from F;

[0105] A is a monovalent cation, preferably selected from H. + Li + Na + K + 、Rb + Cs + 、Fr + Li is preferred. + Na + K + 、Rb + K is preferred. + .

[0106] Preferred use is falling into chemical formula (I) o (The range of known compounds, such as potassium vinyltrifluoroborate)

[0107] In a preferred embodiment of the present invention, step (I) x The Suzuki coupling reaction is carried out in the presence of a palladium catalyst, preferably selected from one or more members of the group consisting of: (I) pThe palladium catalysts represented by ) are Pd2(dba)3-n(dba), Pd2(dba)3, Pd(OAc)2, Pd(PPh3)4, and [1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene](3-chloropyridyl)palladium(II) dichloride (PEPPSI). TM -IPr: CAS 905459-27-0).

[0108] Pd(R p1 )2·(X p )2 -(I p )

[0109] in

[0110] R p1 The atom is a hydrogen atom, preferably selected independently from F, Cl, Br, and I each time it appears, and more preferably Cl;

[0111] X p The catalyst is Amphos (di-tert-butyl(4-dimethylaminophenyl)phosphine) or dtbpf (di-tert-butylphosphinoferrocene). Preferably, the palladium catalyst is selected from Pd(R p1 )2·(X p )2 -(I p Where X p It is Amphos (di-tert-butyl(4-dimethylaminophenyl)phosphine), Pd2(dba)3-n(dba) or Pd2(dba)3.

[0112] Preferably, step (I) x The experiment is carried out at a temperature ranging from 10°C to 90°C, preferably from 20°C to 80°C, and more preferably from 35°C to 65°C.

[0113] In a preferred embodiment of the present invention, step (I) x The Suzuki coupling reaction is carried out in the presence of a solvent or a mixture of solvents. Preferably, the solvent or solvent mixture is selected from one or more polar aprotic solvents, and more preferably, it is selected from one or more members of the group consisting of: dichloromethane (boiling point: 39.6°C), acetone (boiling point: 56.05°C), tetrahydrofuran (boiling point: 66°C), ethyl acetate (boiling point: 77.11°C), acetonitrile (boiling point: 81.3~82.1°C), pyridine (boiling point: 115°C), dimethylformamide (boiling point: 153°C), dimethyl sulfoxide (boiling point: 189°C), hexamethylphosphoramide (boiling point: 235.5°C), dimethylpropenylurea (boiling point: 246.5°C), and sulfolane (boiling point: 286°C).

[0114] In a preferred embodiment of the present invention, step (I)x The Suzuki coupling reaction is carried out in the presence of a basic material. More preferably, the basic material is selected from NaOH, TiOH, Ti2Co3, TiOEt, NaOMe, or any combination thereof. These materials perform best in THF or H2O solvent systems. Alternatively, the basic material is selected from K2CO3, K3PO4, or any combination thereof. These materials perform best in DMF. Even more preferably, the basic material is selected from NaOH, TiOH, Ti2Co3, TiOEt, NaOMe, or any combination thereof. Even more preferably, the basic material is selected from NaOH, TiOH, Ti2Co3, TiOEt, NaOMe, or any combination thereof, and the solvent contains at least THF, H2O, or both THF and H2O. Particularly preferred is that the basic material selected from NaOH, TiOH, Ti2Co3, TiOEt, NaOMe, or any combination thereof is used in THF or H2O solvent.

[0115] For more detailed information on Suzuki's associations, see, for example, Ishiyama, T.; Miyaura, N.; Suzuki, A. Synlett, 1991, 687; Miyaura, N; Suzuki, A. Chem. Rev., 1995, 95, 2457; Beller, M; Fischer, H.; Herrmann, WA; Ofele, K.; Brossmer, C. Angew.Chem. Int. Ed. 1995, 34, 1848; Suzuki, A. Proc. Jpn. Acad., Ser. B. 2004, 80, 8, 359.

[0116] - Step (I) w Deoxygenation reaction

[0117] In a preferred embodiment of the present invention, the method further includes the following steps (I) w Preferably, the method is in step (I) x The preceding step (I) includes the aforementioned step. w ):

[0118] (I w By applying an acid catalyst and a reducing agent, the chemical formula (I) is... c1 The precursor compound represented by (I) undergoes a deoxygenation reaction of its alcohol group to synthesize the product of formula (I). a1 ) precursor compounds.

[0119] (I c1This is a provisional version; it will be replaced with an optimized version later.

[0120] in

[0121] 1≤x≤5, 0≤y≤4, 0≤z≤5;

[0122] n is 1 or 0, m is 1 or 0, 1≤n+m≤2, preferably n+m=1, more preferably n=0, m=1;

[0123] When m is 1 and n is 0, 3≤x+z≤10; when m is 0 and n is 1, 3≤x+y≤9; when m and n are both 1, 3≤x+z+y≤14.

[0124] R va1 R va2 and R va3 The atom is a hydrogen atom, preferably selected from F, Cl, Br, I, and more preferably Br;

[0125] R a1 R a2 and R a3 Each time it appears, it is selected independently or interdependently from H, D or alkyl groups having 1 to 5 carbon atoms;

[0126] L is selected, in the same or different manner, from alkylene groups having 1 to 15 carbon atoms and alkenyl groups having 2 to 15 carbon atoms in each occurrence.

[0127] In this embodiment, at least one non-adjacent CH2 group of the alkylene or alkenylene group is replaced by COH.

[0128] Preferably, formula (I) c1 The precursor compounds can be selected from Table C below.

[0129] Table C:

[0130]

[0131] In a preferred embodiment, the acid catalyst is trifluoromethanesulfonic acid (TFMSA), trifluoroacetic acid (TFA), boron trifluoride-diethyl ether complex (BF3OEt2), and indium(III) chloride (InCl3); the reducing agent is triethylsilane (Et3SiH), dimethylchlorosilane (Me2SiHCl), and sodium borohydride (NaBH4). Preferably, in step (I) wThe following combinations were used: trifluoromethanesulfonic acid (TFMSA) as an acid catalyst and triethylsilane (Et3SiH) as a reducing agent; trifluoroacetic acid (TFA) and triethylsilane (Et3SiH); dimethylchlorosilane (Me2SiHCl) and indium(III) chloride (InCl3); and trifluoroacetic acid (TFA) and sodium borohydride (NaBH4).

[0132] In the preferred embodiment, step (I) w The experiment is conducted at temperatures ranging from -20°C to 20°C, preferably from -10°C to 10°C.

[0133] In the preferred embodiment, step (I) w The reaction is carried out in the presence of a solvent or a mixture of solvents. Preferably, the solvent or solvent mixture is selected from haloalkanes, more preferably from one or more members of the group consisting of fluoroalkanes, chlorinated alkanes, bromoalkanes and iodoalkanes, more preferably from chloromethane, dichloromethane (DCM), chloroform, chloroethane, dichloroethane, chloroethane, bromomethane, dibromomethane, bromoethane, dibromoethane and any combination thereof; preferably from dichloromethane (DCM), chloroform or mixtures thereof. For more detailed information on the deoxygenation reaction, see, for example, Journal of Medicinal Chemistry. 2003, 46, 453-456, Chemistry - A European Journal, Supporting Information, “Methylene Bridging Effect on the Structures, Lewis Acidities and Optical Properties of Semi-planar Triarylboranes.”

[0134] Combinations of Et3SiH / BF3OEt2, Et3SiH / TFA, InCl3 / Me2SiHCl, and / or NaBH4 / TFA in DCM can be used.

[0135] - Step (I) z )

[0136] In a preferred embodiment of the present invention, the method further includes the following steps (I) z Preferred step (I) w )after:

[0137] (I z In the presence of n-butyllithium, formula (I) z1The precursor A and formula (I) represent the precursor A and formula (I). z1 The precursor B reaction is represented by ().

[0138] Precursor A -(I z1 Precursor B -(I z2 )

[0139] in

[0140] X z1 From 1 to 6; X z2 The range is from 0 to 5;

[0141] R vz1 and R vz2 The atom is a hydrogen atom, preferably selected from F, Cl, Br, I, and more preferably Br;

[0142] R az1 and R az2 Each time they appear, they are selected independently or interdependently from H, D, or alkyl groups having 1 to 5 carbon atoms.

[0143] Preferred use is falling into chemical formula (I) z1 ) and (I z2 The range of publicly available compounds, such as 1,3-dibromobenzene (Merck, CAS: 108-36-1) and 3-bromobenzaldehyde (Merck, CAS: 3132-99-8).

[0144] In a preferred embodiment of the present invention, the reaction step (I) z The process is carried out in the presence of a solvent or a mixture of solvents, preferably, the solvent being selected from diethyl ether, tetrahydrofuran (THF), tetramethylethylenediamine (TMEDA), or any combination thereof.

[0145] Reaction quenching, solvent removal, and drying can be carried out using known methods, such as quenching with isopropanol, followed by washing with deionized water and removing the solvent under vacuum at 40°C; or quenching with salt treatment (salt water), followed by extraction of the aqueous phase with DCM and drying with Na2SO4.

[0146] The present invention is further illustrated by the following embodiments, which should not be construed as limiting. Those skilled in the art will recognize that various modifications, additions, and alterations can be made to the invention without departing from the spirit and scope of the invention as defined in the appended claims.

[0147] Example

[0148] Part A: Synthesis of Compounds

[0149] Reference Example 1: Preparation of bis(3-vinylphenyl)methane

[0150]

[0151] Step 1: Synthesis of bis(3-bromophenyl)methanol

[0152]

[0153] 1,3-Dibromobenzene (Merck, CAS: 108-36-1, 33.7 g, 143 mmol) was dissolved in anhydrous diethyl ether (Merck, 585 mL). The solution was cooled to -78 °C, and a solution of n-butyllithium (1.6 M in hexane, 98 mL, 156 mmol) was added dropwise. Then, 3-bromobenzaldehyde (Merck, CAS: 3132-99-8, 24 g, 130 mmol) was added, and the reaction mixture was brought to room temperature with stirring. The reaction was carefully quenched with 100 mL of brine, and the aqueous phase was separated and extracted three times with DCM. The combined organic phases were dried over Na2SO4, filtered, and the solvent was removed under vacuum to give 51.6 g (116%) of a brown oily substance, which was ready for use without further purification.

[0154] Step 2: Synthesis of bis(3-bromophenyl)methanol

[0155]

[0156] Bis(3-bromophenyl)methanol (51.6 g, 140 mmol) was dissolved in 400 mL of DCM, treated with triethylsilane (Merck, CAS: 617-86-7, 88 mL, 550 mmol), and cooled to 0 °C. Trifluoromethanesulfonic acid (Merck, CAS: 1493-13-6, 48 mL, 550 mmol) was added dropwise, and the mixture was stirred at room temperature for 3 hours. Ice was carefully added, and the aqueous phase was separated three times with DCM. The combined organic phases were dried over Na2SO4, filtered, and the solvent was removed under vacuum to give 110 g of a yellow oil. Crystallization in ethanol gave the product (35 g, 78%).

[0157] 1 H NMR (500 MHz, chloroform-d): δ = 7.38 (dt, J = 7.9, 1.4 Hz, 2H), 7.35(d, J = 1.9 Hz, 2H), 7.19 (t, J = 7.7 Hz, 2H), 7.12 (d, J = 7.7 Hz, 2H), 3.93 (s, 2H) ppm.

[0158] Step 3: Synthesis of bis(3-vinylphenyl)methane

[0159]

[0160] Bis(3-bromophenyl)methanol (29 g, 90 mmol) was dissolved in anhydrous THF (1.4 L), treated with potassium vinyltrifluoroborate (Merck, CAS: 13682-77-4, 196 mmol, 26 g), and stirred at room temperature under nitrogen protection until dissolved. NaOH solution (250 mL, 10 wt%) and Pd(amphos)Cl2 (Merck, CAS: 887919-35-9, 2.5 g, 3.6 mmol) were added, and the reaction mixture was stirred at 50 °C for 12 h. The mixture was cooled to room temperature, treated with water, and extracted three times with ethyl acetate. The combined organic phases were dried over Na2SO4, filtered, and the solvent was removed under vacuum. The crude product was purified by silica gel column chromatography using heptane as solvent, finally yielding 12.3 g (62.5%) of a colorless liquid.

[0161] 1 H NMR (500 MHz, chloroform-d): δ = 7.35 – 7.26 (m, 6H), 7.13 (dt, J = 6.7, 2.0 Hz, 2H), 6.74 (dd, J = 17.6, 10.9 Hz, 2H), 5.77 (d, J = 17.5 Hz, 2H), 5.27 (d, J = 10.9 Hz, 2H), 4.02 (s, 2H) ppm.

[0162] Reference Example 2: Preparation of 3,3'-divinyl-1,1'-biphenyl

[0163]

[0164] Reference Example 2 was synthesized using 3,3'-dibromo-1,1'-biphenyl (CAS: 16400-51-4) under the same conditions as step 3 of Reference Example 1.

[0165] 1 H NMR (500 MHz, chloroform-d) δ = 7.68 (q, J = 1.5 Hz, 2H), 7.55 (dt, J =6.2, 2.2 Hz, 2H), 7.51 – 7.44 (m, 4H), 6.85 (dd, J = 17.6, 10.9 Hz, 2H), 5.89 (dd, J = 17.6, 0.9 Hz, 2H), 5.36 (dd, J = 10.9, 0.9 Hz, 2H) ppm.

[0166] Reference Example 3: Preparation of 1,2,4,5-Tetravinylbenzene

[0167]

[0168] Reference Example 3 was synthesized using 1,2,4,5-tetrabromobenzene (Merck, CAS: 636-28-2) under the same conditions as step 3 of Reference Example 1.

[0169] 1 ¹H NMR (500 MHz, dichloromethane-d²) δ = 7.54 (s, 2H), 6.98 (dd, J = 17.4, 11.0 Hz, 4H), 5.66 (dd, J = 17.4, 1.3 Hz, 4H), 5.32 (dd, J = 11.0, 1.3 Hz, 4H) ppm.

[0170] Synthetic Example 1: Preparation of 1,3-divinyl-5-(3-vinylbenzyl)benzene

[0171]

[0172] In summary, the same synthesis conditions as in Reference Example 1 were used. In step 1, 1,3,5-tribromobenzene (Merck, CAS: 626-39-1) was used instead of 1,3-dibromobenzene.

[0173] 18.5 g (78%) of colorless liquid was obtained in the Suzuki step.

[0174] 1 ¹H NMR (500 MHz, chloroform-d) δ = 7.35 (d, J = 1.8 Hz, 1H), 7.34 – 7.26 (m, 3H), 7.18 (d, J = 1.5 Hz, 2H), 7.13 (dt, J = 6.9, 1.9 Hz, 1H), 6.73 (ddd, J = 17.6, 10.8, 3.7 Hz, 3H), 5.78 (ddd, J = 17.6, 4.4, 0.9 Hz, 3H), 5.28 (ddd, J = 10.9, 5.6, 1.0 Hz, 3H), 4.01 (s, 2H) ppm.

[0175] Synthetic Example 2: Preparation of 1,3-divinyl-5-(2-vinylbenzyl)benzene

[0176]

[0177] In summary, the same synthesis conditions as in Reference Example 1 were used. In step 1, 1,3,5-tribromobenzene (Merck, CAS: 626-39-1) was used instead of 1,3-dibromobenzene, and 2-bromobenzaldehyde (Merck, CAS: 6630-33-7) was used instead of 3-bromobenzaldehyde.

[0178] 4.4 g (90%) of colorless liquid was obtained in the Suzuki step.

[0179] 1 H NMR (500 MHz, chloroform-d) δ = 7.57 (dd, J = 7.1, 2.1 Hz, 1H), 7.35 –7.19 (m, 3H), 7.16 (dd, J = 7.0, 2.0 Hz, 1H), 7.10 (d, J = 1.5 Hz, 2H), 6.99(dd, J = 17.3, 11.0 Hz, 1H), 6.70 (dd, J = 17.6, 10.8 Hz, 2H), 5.76 (d, J =1.0 Hz, 1H), 5.72 (d, J = 1.0 Hz, 1H), 5.68 (dd, J = 17.3, 1.4 Hz, 1H), 5.30(dd, J = 11.0, 1.4 Hz, 1H), 5.26 (dd, J = 10.8, 0.9 Hz, 2H), 4.09 (s, 2H)ppm.

[0180] Synthetic Example 3: Preparation of 1,3-divinyl-5-(4-vinylbenzyl)benzene

[0181]

[0182] In summary, the same synthesis conditions as in Reference Example 1 were used. In step 1, 1,3,5-tribromobenzene (Merck, CAS: 626-39-1) was used instead of 1,3-dibromobenzene, and 4-bromobenzaldehyde (Merck, CAS: 1122-91-4) was used instead of 3-bromobenzaldehyde.

[0183] 17.5 g (97%) of colorless liquid was obtained in the Suzuki step.

[0184] 1¹H NMR (500 MHz, chloroform-d) δ = 7.42 – 7.38 (m, 2H), 7.36 (s, 1H), 7.24– 7.17 (m, 4H), 6.75 (d, J = 17.6, 10.9, 8.1 Hz, 3H), 5.81 (s, 1H), 5.82 –5.73 (m, 2H), 5.31 (s, 1H), 5.30 – 5.24 (m, 2H), 4.01 (s, 2H) ppm.

[0185] Synthetic Example 4: Preparation of bis(3,5-divinylphenyl)methane

[0186]

[0187] In summary, the same synthesis conditions as in Reference Example 1 were used. In step 1, 1,3,5-tribromobenzene (Merck, CAS: 626-39-1) was used instead of 1,3-dibromobenzene, and 3,5-dibromobenzaldehyde (Merck, CAS: 56990-02-4) was used instead of 3-bromobenzaldehyde.

[0188] 4.5 g (63%) of colorless solid was obtained in the Suzuki step.

[0189] 1 H NMR (500 MHz, chloroform-d) δ = 7.34 (d, J = 1.7 Hz, 2H), 7.17 (d, J =1.6 Hz, 4H), 6.71 (dd, J = 17.6, 10.8 Hz, 4H), 5.77 (dd, J = 17.7, 0.9 Hz,4H), 5.27 (dd, J = 10.8, 0.9 Hz, 4H), 3.99 (s, 2H) ppm.

[0190] Synthetic Example 5: Preparation of 3,3',5,5'-Tetravinyl-1,1'-Biphenyl

[0191]

[0192] Example 5 was synthesized using 3,3',5,5'-tetrabromobiphenyl (CAS: 16400-50-3) under the same conditions as step 3 of Reference Example 1.

[0193] 1H NMR (500 MHz, THF-d8) δ = 7.65 (d, J = 1.5 Hz, 4H), 7.55 (t, J =1.7 Hz, 2H), 6.85 (dd, J = 17.6, 10.9 Hz, 4H), 5.93 (dd, J = 17.6, 0.9 Hz,4H), 5.31 (dd, J = 10.8, 0.9 Hz, 4H) ppm.

[0194] Synthetic Example 7: Preparation of 3,3',5-trivinyl-1,1'-biphenyl

[0195]

[0196] Step 1: Synthesis of 3,3',5-tribromo-1,1'-biphenyl

[0197]

[0198] 3-Bromo-1-iodobenzene (Merck, CAS: 591-18-4, 20 g, 70.7 mmol) and 3,5-dibromophenylboronic acid (Merck, CAS: 117695-55-3, 19.8 g, 70.7 mmol) were dissolved together in toluene (325 mL) and water (300 mL). K₂CO₃ (48.9 g, 353 mmol) and tetrakis(triphenylphosphine)palladium (Merck, 0.41 g, 0.35 mmol) were added, and the mixture was refluxed and stirred overnight under nitrogen protection. The mixture was cooled to room temperature and the phases were separated. The aqueous phase was extracted three times with ethyl acetate, the organic phases were combined and dried over Na₂SO₄, filtered, and evaporated to dryness. The crude product was purified by silica gel column chromatography using heptane as eluent to give 18.5 μL (67%) of colorless solid.

[0199] Step 2: Synthesis of 3,3',5-trivinyl-1,1'-biphenyl

[0200] Example 7 was synthesized using 3,3',5-tribromo-1,1'-biphenyl (step 1) under the same conditions as step 3 of Example 1.

[0201] 1¹H NMR (500 MHz, chloroform-d) δ = 7.68 (d, J = 1.9 Hz, 1H), 7.60 – 7.50 (m, 3H), 7.52 – 7.43 (m, 3H), 6.85 (ddd, J = 17.6, 10.9, 4.3 Hz, 3H), 5.94 – 5.85 (m, 3H), 5.37 (dd, J = 11.0, 4.6 Hz, 3H) ppm.

[0202] Synthetic Example 8: Preparation of 1,3-divinyl-5-(3-vinylphenoxy)benzene

[0203]

[0204] Step 1: Synthesis of 1,3-dibromo-5-(3-bromophenoxy)benzene

[0205]

[0206] 3-Bromophenol (Merck, CAS: 591-20-8, 6.8 g, 39.4 mmol) was dissolved together with 1,3-dibromo-5-fluorobenzene (Merck, CAS: 1435-51-4, 10 g, 39.4 mmol) and K₂CO₃ (5.4 g, 39.4 mmol) in DMF (91.5 mL) and treated overnight at 160 °C under nitrogen protection. The reaction mixture was cooled to room temperature and treated with water to produce an oil. The aqueous phase was extracted twice with MTBE, and the combined organic phases were dried over Na₂SO₄, filtered, and evaporated to dryness. Finally, the crude product was purified by silica gel column chromatography (heptane / ethyl acetate, 9:1) to give 13 g (81%) of colorless solid.

[0207] 1 H NMR (500 MHz, chloroform-d) δ = 7.45 (t, J = 1.6 Hz, 1H), 7.35 (ddd, J =7.9, 1.8, 1.0 Hz, 1H), 7.27 (t, J = 8.1 Hz, 1H), 7.21 (t, J = 2.1 Hz, 1H), 7.10 (d, J = 1.6 Hz, 2H), 6.98 (ddd, J = 8.2, 2.4, 1.0 Hz, 1H) ppm.

[0208] Step 2: Synthesis of 1,3-divinyl-5-(3-vinylphenoxy)benzene

[0209] Example 8 was synthesized using 1,3-dibromo-5-(3-bromophenoxy)benzene (step 1) under the same conditions as step 3 of Example 1.

[0210] 1 H NMR (500 MHz, chloroform-d) δ = 7.33 (t, J = 7.9 Hz, 1H), 7.25 – 7.17(m, 2H), 7.13 (t, J = 2.1 Hz, 1H), 7.02 (d, J = 1.4 Hz, 2H), 6.95 (dd, J =8.1, 2.4 Hz, 1H), 6.71 (ddd, J = 17.6, 10.8, 6.7 Hz, 3H), 5.77 (d, J = 17.6Hz, 3H), 5.31 (dd, J = 10.8, 3.1 Hz, 3H) ppm.

[0211] Synthetic Example 9: Preparation of 1,3-divinyl-5-(4-vinylphenoxy)benzene

[0212]

[0213] Step 1: Synthesis of 1,3-dibromo-5-(4-bromophenoxy)benzene

[0214] The synthesis was performed according to step 1 of Example 8, wherein 4-bromophenol (Merck, CAS: 106-41-2) was used instead of 3-bromophenol. 11 g (69%) of colorless solid was obtained.

[0215] 1 H NMR (500 MHz, THF-d8) δ = 7.55 – 7.50 (m, 2H), 7.48 (t, J = 1.7 Hz,1H), 7.16 (d, J = 1.7 Hz, 2H), 7.03 – 6.95 (m, 2H) ppm.

[0216] Step 2: Synthesis of 1,3-divinyl-5-(4-vinylphenoxy)benzene

[0217] Example 9 was synthesized using 1,3-dibromo-5-(4-bromophenoxy)benzene (step 1) under the same conditions as step 3 of Example 1.

[0218] 1 H NMR (500 MHz, THF- d8) δ = 7.42 – 7.36 (m, 2H), 7.25 (t, J = 1.6 Hz,1H), 7.02 (d, J = 1.6 Hz, 2H), 6.99 – 6.93 (m, 2H), 6.68 (ddd, J = 17.6,10.9, 3.0 Hz, 3H), 5.76 (dd, J = 17.6, 1.0 Hz, 2H), 5.67 (dd, J = 17.6, 1.0Hz, 1H), 5.22 (dd, J = 11.0, 1.0 Hz, 2H), 5.14 (dd, J = 11.0, 1.0 Hz, 1H)ppm.

[0219] Part B: Preparation of photocurable compositions for evaluating synthetic compounds

[0220] - As a reference embodiment 1 a 2 b And as Example 1 a 2 a 3 a 8 c and 9 c Preparation of photocurable compositions

[0221] Table 1 shows an overview of different compositions based on a single vinylbenzene component and in non-limiting amounts of a) 3 wt% Irgacure OXE02 (BocSciences, CAS: 478556-66-0) and 3 wt% Irgacure 651 (Merck, CAS: 24650-42-8); or b) 3 wt% Irgacure OXE02 and 3 wt% Irgacure 819 (Merck, CAS: 162881-26-7); or c) 6 wt% Irgacure OXE02. The curing energy was 5.5 J / cm at a wavelength of 365 nm. 2 .

[0222] For example, Reference Example 1 in Table 1 a This indicates that the compound in Reference Example 1 was used with a) 3% by weight of Irgacure OXE02 (BocSciences, CAS: 478556-66-0) and 3% by weight of Irgacure 651.

[0223] Example 1 aThis indicates that the compound in Synthesis Example 1 was used with a) 3 wt% Irgacure OXE02 (BocSciences, CAS: 478556-66-0) and 3 wt% Irgacure 651.

[0224] Similarly, Example 2 a This indicates that the compound in Synthesis Example 2 was used with a) 3% by weight of Irgacure OXE02 (BocSciences, CAS: 478556-66-0) and 3% by weight of Irgacure 651.

[0225] viscosity

[0226] The viscosity of the light-curable composition was measured using an Anton Paar MCR 92 rheometer (Anton Paar, Graz, Austria) with a conical plate geometry. Viscosity was measured at 23°C using a rotating conical plate geometry (d=25mm) for 500 s. -1 The shear rate was measured.

[0227] Thermal stability of the photocured layer

[0228] The photocurable film was prepared by coating a 60µm thick photocurable composition layer in a sandwich device consisting of two glass plates, and then curing it at room temperature with UV light of wavelength 365nm at different curing energies (5.5J / cm²). 2 or 10J / cm 2 The film is prepared by curing with UV light. After UV curing, the film is baked at 250°C for 2 minutes on a hot plate and then measured by TGA (TADiscovery or TA TGA Q50).

[0229] - Preparation of the photocurable compositions as reference examples 4 and 5

[0230] As described in Table 2, reference photocurable compositions 4 and 5 containing at least one polyvinylbenzene compound were prepared. The proportions of the polyethylene compound used in these compositions varied. Reference Example 4 contained a small amount of a polyfunctional acrylate monomer (SR295, CAS: 4986-89-4). All compositions also contained 5.6 to 5.7% by weight of Irgacure OXE02.

[0231] - Preparation of photocurable compositions as working examples (WE) 10 to 14

[0232] As shown in Table 2, light-curable compositions of WE10 to 14 were prepared. All compositions also contained 5.6 to 5.7% by weight of Irgacure OXE02.

[0233] Table 2 summarizes examples using different proportions of polyethylene compounds and 5.6% by weight of Irgacure OXE02. The light-curable compositions were tested at 10 J / cm². 2 Curing is performed, followed by a 2-minute post-exposure baking at 250°C on a hot plate.

[0234] Table 1:

[0235]

[0236] a 3% by weight Irgacure OXE02 and 3% by weight Irgacure 651

[0237] b 3% by weight Irgacure OXE02 and 3% by weight Irgacure 819

[0238] c 6% by weight Irgacure OXE02

[0239] Table 2:

[0240]

[0241] Part C: Synthesis of preferred specific polyhalogenated benzene examples:

[0242] Example C-1: 1,3-Dibromo-5-(3-bromobenzyl)benzene:

[0243]

[0244] Step 1: Synthesis of (3-bromophenyl)(3,5-dibromophenyl)methanol

[0245]

[0246] Synthesis option a)

[0247] 1,3,5-Tribromobenzene (5 g, 0.02 mol) was dissolved in tetrahydrofuran (0.617 mol). The solution was cooled to -15 °C, and isopropyl magnesium chloride solution (2 M in THF, 8.3 mL, 0.02 mol) was added dropwise. The reaction mixture was stirred at this temperature for 2 hours. Then, the reaction temperature was raised to 0 °C, and 3-bromobenzaldehyde (3.8 g, 0.017 mol) dissolved in THF (16.8 mL, 0.208 mol) was added. The reaction mixture was stirred at 0 °C for 1 hour, and then heated to room temperature. The reaction was carefully quenched with hydrochloric acid (40 mL, 0.04 mol). Dichloromethane was added, and the aqueous phase was separated. The organic phase was washed twice with deionized water, and the solvent was removed under vacuum at 40 °C. A light brown residue (6.6 g, 98.7% yield) was given.

[0248] Synthesis option b)

[0249] 1,3,5-Tribromobenzene (56.2 g, 0.178 mol) was dissolved in diethyl ether (4.86 mol). The suspension was cooled to -70 °C, and a solution of n-butyllithium (2.5 M in hexane, 46.2 mL, 0.195 mol) was added dropwise. The reaction mixture was stirred at this temperature for 1 hour. Then, 3-bromobenzaldehyde (30 g, 0.16 mol) was added dropwise. The reaction mixture was brought to room temperature. The reaction was carefully quenched with isopropanol (2.9 g, 0.049 mol). The organic layer was washed three times with deionized water. The solvent was then removed under vacuum at 40 °C. A light brown residue (74.4 g, 93.7% yield) was given.

[0250] Step 2: Synthesis of 1,3-dibromo-5-(3-bromobenzyl)benzene

[0251]

[0252] (3-Bromophenyl)(3,5-Dibromophenyl)methanol (2.84 g, 0.0067 mol) was dissolved in 20 mL of DCM. Triethylsilane (3.16 g, 0.027 mol) was added, and the mixture was cooled to 0 °C. Trifluoromethanesulfonic acid (4.0 g, 0.027 mol) was added dropwise, and the mixture was stirred at room temperature for 3 hours. The reaction was then quenched with deionized water (20 g, 1.1 mol). The organic layer was washed repeatedly with water and NaHCO3 solution (5%). The solvent was then removed under vacuum (40 °C) to give a brown solid (5.5 g). The crude product (HPLC purity 91.7%) was purified by crystallization in n-heptane. The product was obtained in 63.9% yield (1.8 g, purity 97%).

[0253] Alternatives to trifluoromethanesulfonic acid include, for example, trifluoroacetic acid and trimethylsilane trifluoromethanesulfonic acid.

[0254] Example 2 (C-2): 1,3-Dibromo-5-[(4-bromophenyl)methyl]benzene:

[0255]

[0256] In summary, the same synthesis conditions as in Example C-1 were used. In step 1, 4-bromobenzaldehyde (Merck, CAS: 1122-91-4) was used instead of 3-bromobenzaldehyde.

[0257] Example 3 (C-4): 1-Bromo-3-[(4-Bromophenyl)methyl]benzene:

[0258]

[0259] In summary, the same synthesis conditions as in Example C-1 were used. In step 1, 1,3-dibromobenzene (Merck, CAS: 108-36-1) was used instead of 1,3,5-tribromobenzene, and 4-bromobenzaldehyde (Merck, CAS: 1122-91-4) was used instead of 3-bromobenzaldehyde.

[0260] Example 4 (C-4): 1,4-Dibromo-2-(3,5-Dibromobenzyl)benzene

[0261]

[0262] In summary, the same synthesis conditions as in Example C-1 were used. In step 1, 2,5-dibromobenzaldehyde (Merck, CAS: 74553-29-04) was used instead of 3-bromobenzaldehyde.

[0263] Part D: Synthesis of preferred specific examples of polyvinylbenzene:

[0264] Example D-1: 1,3-Divinyl-5-[(3-vinylphenyl)methyl]benzene:

[0265]

[0266] Steps 1 and 2 follow the same procedure as the preferred polyhalogenated benzene example described in Part C.

[0267] Step 3: Synthesis of 1,3-divinyl-5-[3-vinylphenyl)methyl]benzene

[0268]

[0269] 1,3-Dibromo-5-[(3-bromophenyl)methyl]benzene (500 g, 1.2 mol, from Example C-1), potassium vinyltrifluoroborate (95%, 565 g, 4.0 mol), and bis-(di-tert-butyl-(4-dimethylaminophenyl)phosphine)-dichloropalladium(II) (1.3 g, 0.0032 mol) were dissolved in tetrahydrofuran (4.3 L). The mixture was heated to 50 °C. At this temperature, a sodium hydroxide solution (w-50%, 1.19 L, 14.6 mol) was added dropwise. The reaction mixture was stirred overnight at 50 °C. Then, 2.6 L of n-heptane (17.9 mol) and 14.9 L of water were added. The aqueous phase was separated. An aqueous solution of N-acetylcysteine ​​(99.2 g, 0.61 mol) (3.3 L, 183.3 mol) was added to the organic layer. The mixture was heated to 60 °C and stirred for 1 hour. The aqueous phase was then separated. The organic phase was filtered using an alumina sand filter. The solvent in the resulting filtrate was removed under vacuum (40°C) to give a liquid product (282.4 g, yield 94.2%).

[0270] GC-MS: Product yield 96.1%.

[0271] Example D-2: 1-[(3,5-divinylphenyl)methyl]-3,5-divinylbenzene:

[0272]

[0273] In summary, the same synthesis conditions as in Example D-1 were used. In step 1, 3,5-dibromobenzaldehyde (Merck, CAS: 56990-02-4) was used instead of 3-bromobenzaldehyde.

[0274] The Suzuki step yielded 4.5 g (63% yield) of colorless solid.

[0275] Example D-3: 1,3-Divinyl-5-(2-vinylbenzyl)benzene

[0276]

[0277] In summary, the same synthesis conditions as in Example D-1 were used. In step 1, 2-bromobenzaldehyde (Merck, CAS: 6630-33-7) was used instead of 3-bromobenzaldehyde.

[0278] The Suzuki step yielded 4.4 g (90% yield) of a colorless liquid.

[0279] Example D-4: 1,3-Divinyl-5-(4-vinylbenzyl)benzene

[0280]

[0281] In summary, the same synthesis conditions as in Example D-1 were used. In step 1, 4-bromobenzaldehyde (Merck, CAS: 1122-91-4) was used instead of 3-bromobenzaldehyde.

[0282] The Suzuki step yielded 17.5 g (97% yield) of a colorless liquid.

[0283] Example D-5: 1,4-Divinyl-2-(3,5-Divinyl)benzene

[0284]

[0285] In summary, the same synthesis conditions as in Example D-1 were used. In step 1, 2,5-dibromobenzaldehyde (Merck, CAS: 74553-29-04) was used instead of 3-bromobenzaldehyde.

Claims

1. A method for synthesizing a compound, comprising at least the following steps: (I x In the presence of an organoboron compound containing one or more groups selected from vinyl, alkyl vinyl, and vinyl alcohol groups having 3 to 5 carbon atoms, the following chemical formula (I) a1 The precursor compound represented by (I) undergoes a Suzuki coupling reaction to form a compound of formula (I) a1 Compounds derived from the precursor compound, -(I a1 ) in 1≤x≤5, 0≤y≤4, 0≤z≤5; n is 1 or 0, m is 1 or 0, 1≤n+m≤2, preferably n+m=1, more preferably n=0, m=1; When m is 1 and n is 0, 3≤x+z≤10; when m is 0 and n is 1, 3≤x+y≤9; when m and n are both 1, 3≤x+z+y≤14. R va1 R va2 and R va3 The atom is a hydrogen atom, preferably selected from F, Cl, Br, I, and more preferably Br; R a1 R a2 and R a3 Each time it appears, it is selected independently or interdependently from H, D or alkyl groups having 1 to 5 carbon atoms; L is selected, in the same or different manner, from the group consisting of direct bonds, alkylene groups having 1 to 15 carbon atoms, and alkenyl groups having 2 to 15 carbon atoms each time it appears. Wherein, one or more non-adjacent CH2 groups of the alkylene or alkenylene group may be replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS or CONH, and wherein one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2.

2. The method according to claim 1, wherein, From formula (I) a1 Compounds derived from precursor compounds of (I) are derived from chemical formula (I) b1 )express, -(I b1 ) in 1≤x≤5, 0≤y≤4, 0≤z≤5; n is 1 or 0, m is 1 or 0, 1≤n+m≤2, preferably n+m=1, more preferably n=0, m=1; When m is 1 and n is 0, 3≤x+z≤10; when m is 0 and n is 1, 3≤x+y≤9; when m and n are both 1, 3≤x+z+y≤14. R vb1 R vb2 and R vb3 Each time it appears, it is selected independently or interdependently from vinyl, alkyl vinyl or vinylol groups having 3 to 5 carbon atoms, preferably vinyl; R b1 R b2 and R b3 Each time it appears, it is selected independently or interdependently from H, D or alkyl groups having 1 to 5 carbon atoms; L is selected, in the same or different manner, from the group consisting of direct bonds, alkylene groups having 1 to 15 carbon atoms, and alkenyl groups having 2 to 15 carbon atoms each time it appears. Wherein, one or more non-adjacent CH2 groups of the alkylene or alkenylene group may be replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS or CONH, and wherein one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2, wherein formula (I) does not include 3,4',5-trivinyl-1,1'-biphenyl.

3. The method according to claim 1 or 2, wherein L is a direct bond, a straight-chain alkylene group having 1 to 5 carbon atoms, or a straight-chain alkenyl group having 2 to 5 carbon atoms, preferably, L is a straight-chain alkylene group having 1 to 5 carbon atoms or a straight-chain alkenyl group having 2 to 5 carbon atoms, wherein one or more non-adjacent CH2 groups of the alkylene group or alkenyl group may be replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS, or CONH, and wherein one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2, more preferably, L is a straight-chain alkylene group having 1 to 5 carbon atoms.

4. The method according to any one of claims 1 to 3, wherein n is 0 and m is 1.

5. The method according to any one of the preceding claims, wherein the organoboron compound contains at least one vinyl group, preferably, the organoboron compound is composed of chemical formula (I... o )express: R o1 -B(R o2 )3·A -(I o ) in R o1 It is a vinyl group, an alkyl vinyl group having 3 to 5 carbon atoms or a vinyl alcohol group, preferably a vinyl group; R o2 The atom is a hydrogen atom, preferably selected independently from F, Cl, Br, and I each time it appears, and more preferably from F; A is a monovalent cation, preferably selected from H. + Li + Na + K + 、Rb + Cs + 、Fr + Li is preferred. + Na + K + 、Rb + K is preferred. + .

6. The method according to any one of the preceding claims, wherein step (I) x The Suzuki coupling is carried out in the presence of a palladium catalyst, preferably selected from one or more members of the group consisting of: formula (I) p The palladium catalysts represented by ) are Pd2(dba)3-n(dba), Pd2(dba)3, Pd(OAc)2, Pd(PPh3)4 and [1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene](3-chloropyridinyl)palladium(II) dichloride; Pd(R p1 )2·(X p )2 -(I p ) in R p1 The atom is a hydrogen atom, preferably selected independently from F, Cl, Br, and I each time it appears, and more preferably Cl; X p The catalyst is Amphos (di-tert-butyl(4-dimethylaminophenyl)phosphine) or dtbpf (di-tert-butylphosphinoferrocene); preferably, the palladium catalyst is selected from Pd(R p1 )2·(X p )2 -(I p )where X p It is Amphos (di-tert-butyl(4-dimethylaminophenyl)phosphine), Pd2(dba)3-n(dba) or Pd2(dba)3.

7. The method according to any one of the preceding claims, wherein step (I) x The experiment is carried out at a temperature ranging from 10°C to 90°C, preferably from 20°C to 80°C, and more preferably from 35°C to 65°C.

8. The method according to any one of the preceding claims, wherein step (I) x The process is carried out in the presence of a solvent or a mixture of solvents; preferably, the solvent or solvent mixture is selected from one or more polar aprotic solvents, preferably selected from one or more members of the group consisting of: dichloromethane (boiling point: 39.6°C), acetone (boiling point: 56.05°C), tetrahydrofuran (boiling point: 66°C), ethyl acetate (boiling point: 77°C), acetonitrile (boiling point: 81.3~82.1°C), pyridine (boiling point: 115°C), dimethylformamide (boiling point: 153°C), dimethyl sulfoxide (boiling point: 189°C), hexamethylphosphoramide (boiling point: 235.5°C), dimethylpropenylurea (boiling point: 246.5°C), and sulfolane (boiling point: 286°C).

9. The method according to any one of the preceding claims further includes the following step (I) w ): (I w By applying an acid catalyst and a reducing agent, the chemical formula (I) is... c1 The precursor compound represented by (I) undergoes a deoxygenation reaction of its alcohol group to synthesize the product of formula (I). a1 Precursor compounds of ) (I c1 This is a provisional version; it will be replaced with an optimized version later. in 1≤x≤5, 0≤y≤4, 0≤z≤5; n is 1 or 0, m is 1 or 0, 1≤n+m≤2, preferably n+m=1, more preferably n=0, m=1; When m is 1 and n is 0, 3≤x+z≤10; when m is 0 and n is 1, 3≤x+y≤9; when m and n are both 1, 3≤x+z+y≤14. R va1 R va2 and R va3 The atom is a hydrogen atom, preferably selected from F, Cl, Br, I, and more preferably Br; R a1 R a2 and R a3 Each time it appears, it is selected independently or interdependently from H, D or alkyl groups having 1 to 5 carbon atoms; L is selected, in the same or different manner, from alkylene groups having 1 to 15 carbon atoms and alkenyl groups having 2 to 15 carbon atoms in each occurrence. in, At least one non-adjacent CH2 group of the alkylene or alkenylene group is replaced by COH.

10. The method according to claim 9, wherein the acid catalyst is trifluoromethanesulfonic acid (TFMSA), trifluoroacetic acid (TFA), boron trifluoride-diethyl ether complex (BF3OEt2), and indium(III) chloride (InCl3); and the reducing agent is triethylsilane (Et3SiH), dimethylchlorosilane (Me2SiHCl), and sodium borohydride (NaBH4); preferably, in step (I) of claim 9 w The combinations of trifluoromethanesulfonic acid (TFMSA) as an acid catalyst and triethylsilane (Et3SiH) as a reducing agent, the combination of trifluoroacetic acid (TFA) and triethylsilane (Et3SiH), the combination of dimethylchlorosilane (Me2SiHCl) and indium(III) chloride (InCl3), and the combination of trifluoroacetic acid (TFA) and sodium borohydride (NaBH4) are used.

11. The method according to claim 9 or 10, wherein step (I) w The experiment is conducted at temperatures ranging from -20°C to 20°C, preferably from -10°C to 10°C.

12. The method according to any one of claims 9 to 11, wherein step (I) w The process is carried out in the presence of a solvent or a mixture of solvents; preferably, the solvent or solvent mixture is selected from haloalkanes, more preferably from one or more members of the group consisting of fluoroalkanes, chlorinated alkanes, bromoalkanes and iodoalkanes, more preferably from chloromethane, dichloromethane (DCM), chloroform, chloroethane, dichloroethane, chloroethane, bromomethane, dibromomethane, bromoethane, dibromoethane and any combination thereof; preferably from dichloromethane (DCM), chloroform or mixtures thereof.

13. The method according to any one of the preceding claims further includes the following step (I) z Preferred step (I) w )after: (I z In the presence of n-butyllithium, formula (I) z1 The precursor A and formula (I) represent the precursor A and formula (I). z1 The precursor B reaction is represented by (). Precursor A -(I z1 Precursor B -(I z2 ) in X z1 From 1 to 6; X z2 The range is from 0 to 5; R vz1 and R vz2 The atom is a hydrogen atom, preferably selected from F, Cl, Br, I, and more preferably Br; R az1 and R az2 Each time they appear, they are selected independently or interdependently from H, D, or alkyl groups having 1 to 5 carbon atoms.

14. The method according to claim 13, wherein the reaction step (I) z The process is carried out in the presence of a solvent or a mixture of solvents, preferably selected from diethyl ether, tetrahydrofuran (THF), tetramethylethylenediamine (TMEDA), or any combination thereof.

15. A compound obtained by or capable of being obtained by any one of claims 1 to 14.

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