Mechano-redox reaction using piezoelectric material and manufacturing method using said reaction

Abstract

The present invention relates to a production method for a highly reactive intermediate. The production method includes: preparing an electron-accepting active compound (1); preparing a piezoelectric material (3); and applying mechanical strain to the piezoelectric material (3) while the electron-accepting active compound (1) and the piezoelectric material (3) are present, performing one-electron reduction of the compound (1), and generating a corresponding highly reactive intermediate. The present invention also relates to a redox reaction method using the production method and a redox reaction product production method.

Description

[Technical field]

[0001] The present invention relates to a mechanoredox reaction utilizing a piezoelectric material, and more particularly to a mechanoredox reaction and a method for producing a redox reaction product using the reaction method. [Background technology]

[0002] In recent years, photoredox reactions have been actively studied as organic synthesis reactions that utilize electrical oxidation-reduction. In this reaction, a catalyst is excited by light irradiation, and electron transfer from the catalyst to a substrate or from the substrate to the catalyst is utilized (see Non-Patent Documents 1 to 4). However, this reaction requires a large amount of solvent and efficient stirring, and the reaction setup can be complicated. Furthermore, since light irradiation does not easily reach the inside of the reaction vessel, the efficiency is not necessarily good. It cannot be applied to reactants that do not transmit light. [Prior art documents] [Non-patent literature]

[0003] [Non-Patent Document 1] Munetaka Akita and Takashi Koike, J. Synth. Org. Chem., Jpn, Vol. 74, No. 11, pages 1036-1046, 2016. [Non-Patent Document 2] DA Nagib; DW MacMillan "Trifluoromethylation of arenes and heteroarenes by means of photoredox catalysis" Nature, 2011, 480, 224-228, 10.1038 / nature10647. [Non-Patent Document 3] CK Prier; DA Rankic; DW MacMillan "Visible light photoredox catalysis with transition metal complexes: applications in organic synthesis" Chem Rev, 2013, 113, 5322-5363, 10.1021 / cr300503r. [Non-Patent Document 4] DM Schultz; TP Yoon "Solar synthesis: prospects in visible light photocatalysis" Science, 2014, 343, 1239176, 10.1126 / science.1239176. Summary of the Invention [Problem to be solved by the invention]

[0004] That is, photoredox reactions require efficient irradiation of the solution with light, but this is problematic in that it is difficult to scale up and industrialize the reaction, because it becomes increasingly difficult to irradiate the solution with light in a large reaction vessel, and oxygen must be strictly removed from the solution to avoid quenching by oxygen of the excited species (or intermediate) generated by the irradiation with light, etc. In principle, there is a problem that the reaction cannot be used for reactions of colored substances, suspension solutions, and polymers that do not transmit light.

[0005] Therefore, there is a need for a novel redox reaction that can reduce the amount of solvent used, preferably does not require a solvent, can react in the presence of air, does not require light irradiation, and is easier to scale up, and a novel method for producing a reaction product using the reaction. Such novel redox reactions are of great interest both academically and industrially.

[0006] The present disclosure aims to provide novel methods for generating (or producing) highly reactive intermediates, novel methods for redox reactions, and methods for producing redox reaction products using such redox reactions. [Means for solving the problem]

[0007] As a result of intensive research, the present inventors have found that by applying mechanical force by a ball mill in the presence of a piezoelectric material, a highly reactive intermediate can be generated and a redox reaction (also called a mechanoredox reaction) can proceed. Furthermore, they have found that such a redox reaction (or mechanoredox reaction) utilizing mechanical force can reduce the amount of solvent, can react in the presence of air, does not require light irradiation, and is easier to scale up, and have completed the present invention.

[0008] The present disclosure includes the following aspects. 1. Preparing an electron-accepting active compound (1); Providing a piezoelectric material (3); and In the presence of an electron-accepting active compound (1) and a piezoelectric material (3), a mechanical strain (or force) is applied to the piezoelectric material (3) to cause a one-electron reduction of the compound (1) to generate a corresponding highly reactive intermediate. 1. A method for generating (or producing) a highly reactive intermediate, comprising: 2. The electron-accepting active compound (1) is The following general formula (I-1): A 1 -Xn [A 1 is selected from an aryl group which may have a substituent and a heteroaryl group which may have a substituent, X is a leaving group, and n is an integer of 1 or more; The following formulas (I-2a) to (I-2c): [ka] [R 12 each independently represents a hydrogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an amino group, a fluorine group, a chlorine group, a cyano group, a nitro group, or the like; R12 R may be crosslinked to each other, may form a cyclic structure, and may further have other substituents. 12 may be further interrupted by, for example, an oxygen atom, a sulfur atom, a nitrogen atom, a carbonyl group, an ester bond, or the like. - X 12 indicates an anion.] a trifluoromethyl compound selected from trifluoromethyl-dibenzothiophene (I-2a) which may have a substituent represented by the formula: The following general formula (I-3): CBr 4 (I-3a) or CHI 3 (I-3b) and The following general formula (I-4): [ka] [R 14 ~R 17 may be the same or different and are each independently selected from hydrogen, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, and an optionally substituted heteroaryl group; R 14 and R 15 , R 14 and R 16 , R 15 and R 17 , R 16 and R 17 etc. may be bonded to each other to form a ring, R 18 may be hydrogen or a substituent. Activated fatty acid represented by 2. The method for generating (or producing) a highly reactive intermediate according to claim 1, wherein the highly reactive intermediate is selected from the group consisting of 3. The electron-accepting active compound (1) is In general formula (I-1) A 1The aryl group which may have a substituent includes a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a biphenyl group, a terphenyl group, a pyrenyl group, a perylenyl group, and a triphenylenyl group. A 1 The heteroaryl group which may have a substituent includes a sulfur-containing heteroaryl group, an oxygen-containing heteroaryl group, a nitrogen-containing heteroaryl group, and a heteroaryl group containing two or more kinds of heteroatoms. Leaving groups X include iodine, bromine, chlorine, and diazonium salts. The method for generating (or producing) the compound according to claim 2, wherein the compound is selected from aryl compounds having a leaving group represented by formula (I-1): 4. Piezoelectric materials (3) include barium titanate, strontium titanate, lithium niobate, tourmaline, quartz, topaz, sucrose, and Rochelle salt (KNaC 4 H 4 O 6 4H 2 O), ortho-gallium phosphate (GaPO 4 ), langasite (La 3 Ga 5 SiO 14 ), lead titanate (PbTiO 3 ), lead zirconate titanate, potassium niobate (KNbO 3 ), lithium tantalate (LiTaO 3 ), sodium tungstate (NaXWO 3 ), zinc oxide (ZnO, Zn 2 O 3 ), Ba 2 NaNb 5 O 5 , Pb 2 KNb 5 O 15 , lithium tetraborate (Li 2 B 4 O 7 ) Potassium sodium niobate ((K,Na)NbO 3 ), bismuth ferrite (BiFeO 3 ), sodium niobate (NaNbO 3 ), Bismuth titanate (Bi 4 Ti 3 O 12), Sodium bismuth titanate (Na 0.5 B i0.5 TiO 3 ), polyvinylidene fluoride, aluminum nitride (AlN), gallium phosphate (GaPO 4 4. The method for generating (or manufacturing) according to any one of 1 to 3 above, wherein the material includes at least one selected from the group consisting of gallium arsenide (GaAs), ... and gallium arsenide (GaAs). 5. The method for (generating or producing) the piezoelectric material (3) according to any one of 1 to 4 above, wherein the piezoelectric material (3) is present in an amount of 0.5 mol % or more and 1,500 mol % or less, based on the number of moles obtained by multiplying the number of moles of compound (1) by the valence (100%). 6. The method for generating (or producing) a highly reactive intermediate according to any one of 1 to 5 above, wherein the highly reactive intermediate comprises at least one selected from a radical, an anion radical, and an anion. 7. A redox reaction method comprising the method for generating (or producing) a highly reactive intermediate according to any one of 1 to 6 above, A redox reaction method comprising: a highly reactive intermediate undergoing a redox reaction to produce a redox reaction product. 8. Preparing an electron-accepting active compound (1); Providing a piezoelectric material (3); and In the presence of an electron-accepting active compound (1) and a piezoelectric material (3), mechanical strain is applied to the piezoelectric material (3) to reduce the compound (1) by one electron to generate a corresponding highly reactive intermediate, which then undergoes a redox reaction by itself to generate a redox reaction product; 8. The redox reaction method according to claim 7, comprising: 9. The redox reaction of the electron-accepting active compound (1) is The activated fatty acid represented by formula (I-4) as the electron-accepting active compound (1) undergoes a redox reaction by itself. 9. The redox reaction method according to claim 8, comprising: 10. Further providing at least one compound (2) selected from an aromatic compound (2-1), a diboronic acid ester (2-2), and an aliphatic alcohol (2-3), which may contain a heteroatom; applying mechanical strain to the piezoelectric material (3) in the presence of the electron-accepting active compound (1) and the piezoelectric material (3) as well as the compound (2), to reduce the compound (1) by one electron to generate a corresponding highly reactive intermediate, which reacts with the compound (2) to generate a redox reaction product; 8. The redox reaction method according to claim 7, comprising: 11. What is the redox reaction between electron-accepting compound (1) and compound (2)? A redox reaction between an aryl compound having a leaving group represented by formula (I-1) as an electron-accepting active compound (1) and an aromatic compound (2-1) or a diboronic acid ester (2-2) which may contain a heteroatom as a compound (2); A redox reaction between a trifluoromethyl compound represented by formulae (I-2a) to (I-2-c) as an electron-accepting active compound (1) and an aromatic compound (2-1) which may contain a heteroatom as a compound (2); and A redox reaction between a bromide or iodide represented by formula (I-3) as an electron-accepting active compound (1) and an aliphatic alcohol (2-3) as a compound (2); 11. The redox reaction method according to claim 10, wherein the redox reaction is selected from the following: 12. Compound (2) is The following general formula (II-1): A 2 -H [A 2 is selected from an aryl group which may have a substituent, and a heteroaryl group which may have a substituent; The following general formula (II-2): [ka] [R 1 ~R 4 are each independently selected from hydrogen, an alkyl group which may have a substituent, and an aryl group which may have a substituent; R 1 and R 2 may be mutually bonded, R 3 and R 4may be bonded to each other]; and The following general formula (II-3): [ka] [R 23 may be the same or different and are each independently selected from hydrogen, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, and an aryl group which may have a substituent; R 23 and R 23 may be bonded to each other], 12. The redox reaction method according to any one of the above items 7 and 10 to 11, which is selected from the following. 13. The aromatic group in the aromatic compound (2-1) which may contain a heteroatom may be selected from an aryl group which may have a substituent and a heteroaryl group which may have a substituent; The aryl group which may have a substituent includes a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a biphenyl group, a terphenyl group, a pyrenyl group, a perylenyl group, a triphenylenyl group, and a coronenyl group. The heteroaryl group which may have a substituent includes a sulfur-containing heteroaryl group, an oxygen-containing heteroaryl group, a nitrogen-containing heteroaryl group, and a heteroaryl group containing two or more kinds of heteroatoms. The diboronic acid esters (2-2) include diboronic acid alkyl esters, diboronic acid alkylene glycol esters, diboronic acid aryl esters, diboronic acid arylene glycol esters, and tetrahydroxydiborane. The aliphatic alcohols (2-3) include primary aliphatic alcohols and secondary aliphatic alcohols. 13. The redox reaction method according to any one of 7 and 10 to 12 above. 14. The redox reaction method according to any one of the above items 7 and 10 to 13, wherein the equivalent ratio of compound (1) to compound (2) (compound (1) / compound (2)) is 10 / 1 to 1 / 10. 15. A method for producing a redox reaction product, which uses the redox reaction method according to any one of 7 to 14 above. Effect of the Invention

[0009] The (mechano)redox reaction method and the method for generating (or producing) the reaction product according to the embodiment of the present invention can reduce the amount of solvent, can react in the presence of air, does not require light irradiation, and is easier to scale up. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] In one aspect of the present invention, Preparing an electron-accepting active compound (1); Providing a piezoelectric material (3); and In the presence of an electron-accepting active compound (1) and a piezoelectric material (3), a mechanical strain is applied to the piezoelectric material (3) to cause a one-electron reduction of the compound (1) to generate a corresponding highly reactive intermediate. The present invention provides a method for generating (or producing) a highly reactive intermediate, comprising:

[0011] A method for generating (or producing) a highly reactive intermediate according to an embodiment of the present invention includes providing an electron-accepting active compound (1). In an embodiment of the present invention, the electron-accepting active compound (1) is a compound that receives electrons generated from the piezoelectric material (3) to which physical stress (or strain) is applied, and generates a highly reactive intermediate. The electron-accepting active compound (1) is not particularly limited as long as it is a compound capable of generating a highly reactive intermediate (e.g., a radical, an anion radical, an anion, etc.), and is preferably capable of undergoing a redox reaction.

[0012] The electron-accepting active compound (1) is The following general formula (I-1): A 1 -Xn [A 1is selected from an aryl group which may have a substituent and a heteroaryl group which may have a substituent, X is a leaving group, and n is an integer of 1 or more; The following formulas (I-2a) to (I-2c): [ka] [R 12 each independently represents a hydrogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an amino group, a fluorine group, a chlorine group, a cyano group, a nitro group, or the like; R 12 R may be crosslinked to each other, may form a cyclic structure, and may further have other substituents. 12 may be further interrupted by, for example, an oxygen atom, a sulfur atom, a nitrogen atom, a carbonyl group, an ester bond, or the like. - X 12 indicates an anion.] a trifluoromethyl compound selected from trifluoromethyl-dibenzothiophene (I-2a) which may have a substituent represented by the formula: The following general formula (I-3): CBr 4 (I-3a) or CHI 3 (I-3b) and The following general formula (I-4): [ka] [R 14 ~R 17 may be the same or different and are each independently selected from hydrogen, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, and an optionally substituted heteroaryl group; R 14 and R 15 , R14 and R 16 , R 15 and R 17 , R 16 and R 17 etc. may be bonded to each other to form a ring, R 18 may be hydrogen or a substituent. It is preferably selected from:

[0013] The aryl compound having a leaving group represented by the above general formula (I-1) is not particularly limited as long as it is a compound that can receive electrons generated from the piezoelectric material (3) to which a physical stress (or strain) is applied, and generate a highly reactive intermediate (for example, an aryl radical which may have a substituent or a heteroaryl radical which may have a substituent, etc.).

[0014] In general formula (I-1), The leaving group X can include, for example, iodine, bromine, chlorine, a diazonium salt, and preferably includes a diazonium salt.

[0015] In general formula (I-1), A 1 The aryl group (or aromatic hydrocarbon group) which may have the substituent can include, for example, a phenyl group, a naphthyl group, an anthracenyl group (or anthracene group), a phenanthrenyl group (or phenanthrene group), a biphenyl group, a terphenyl group, a pyrenyl group (or pyrene group), a perylenyl group (or perylene group), and a triphenylenyl group (or triphenylene group). It is preferable that the alkyl group contains a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a biphenyl group, or a terphenyl group.

[0016] In general formula (I-1), A 1 Heteroaryl groups which may bear the following substituents are, for example: (or heteroaromatic groups) are, for example: Sulfur-containing heteroaryl groups such as thiophenyl group (thiophene group or thienyl group), benzothienyl group, dibenzothienyl group, etc.; Oxygen-containing heteroaryl groups such as furanyl (or furan) groups, benzofuranyl groups, dibenzofuranyl groups, phenyldibenzofuranyl groups, and dibenzofuranylphenyl groups; nitrogen-containing heteroaryl groups such as a pyrronyl group (or a pyrrole group), a benzopyronyl group, a dibenzopyronyl group, a pyridyl group (or a pyridine group), a pyrimidinyl group (or a pyrimidine group), a pyrazyl group (or a pyrazine group), a quinolyl group (or a quinoline group), an isoquinolyl group (or an isoquinoline group), a carbazolyl group (or a carbazole group), a 9-phenylcarbazolyl group, an acridinyl group (or an acridine group), a quinazolyl group (or a quinazoline group), a quinoxalyl group (or a quinoxaline group), a 1,6-naphthyridinyl group, a 1,8-naphthyridinyl group, and a porphyrin group (or a porphyrin ring); It can include heteroaryl groups that contain two or more heteroatoms (eg, nitrogen and sulfur), such as benzothiazolyl groups (or benzothiazole groups). It is preferable that the alkyl group contains a thiophenyl group, a furyl group, a pyronyl group, a benzthiophenyl group, a benzfuranyl group, a benzpyronyl group, a dibenzthiophenyl group, a dibenzfuranyl group, or a dibenzpyronyl group.

[0017] The substituents which the aryl group and heteroaryl group may have are not particularly limited as long as they can carry out the redox reaction targeted by the present invention. The substituents are, for example, an alkyl group having 1 to 24 carbon atoms, for example, 1 to 18, for example, 1 to 12, for example, 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, etc.); an alkoxy group having 1 to 24 carbon atoms, for example, 1 to 18, for example, 1 to 12, for example, 1 to 8 carbon atoms (for example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, etc.); a cycloalkyl group having 3 to 24 carbon atoms, for example, 3 to 18, for example, 3 to 12, for example, 3 to 8 carbon atoms (for example, a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, etc.); an alkenyl group having 1 to 24 carbon atoms, for example, 1 to 18, for example, 1 to 12, for example, 1 to 8 carbon atoms (for example, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, an octenyl group, etc.); an alkynyl group having 1 to 24 carbon atoms, for example, 1 to 18, for example, 1 to 12, for example, 1 to 8 carbon atoms (for example, an ethynyl group, a propynyl group, a butynyl group, a pentynyl group, a hexynyl group, an octynyl group, etc.); an aryl group having 5 to 24 carbon atoms, for example, 5 to 18, for example, 5 to 12, for example, 5 to 8 carbon atoms (for example, a phenyl group, a naphthyl group, a biphenyl group, etc.); an aryloxy group having 5 to 24, for example, 5 to 18, for example, 5 to 12, for example, 5 to 8 carbon atoms (for example, a phenoxy group, a naphthyloxy group, a biphenyloxy group, etc.); a heteroaryl group having 4 to 24 carbon atoms, for example, 1 to 18, for example, 1 to 12, for example, 1 to 8 carbon atoms (for example, a thiophenyl group, a furanyl group, a carbazole group, a benzothiophenyl group, a benzofuranyl group, an indolyl group, a pyrrolyl group, a pyridyl group, etc.); an acyl group having 1 to 24 carbon atoms, for example, 1 to 18, for example, 1 to 12, for example, 1 to 8 carbon atoms (for example, an acetyl group, a propionyl group, a butanoyl group, a pentanoyl group, a heptanoyl group, and a group in which a carbonyl group contained in the acyl group is substituted with an ester group or an amide group, etc.); an alkoxycarbonyl group having 1 to 24 carbon atoms, for example, 1 to 18, for example, 1 to 12, for example, 1 to 8 carbon atoms (for example, a methoxycarbonyl group, an ethoxycarbonylcarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a tert-butoxycarbonyl group, a pentoxycarbonyl group, etc.); an amino group having 1 to 24, for example, 1 to 18, for example, 1 to 12, for example, 1 to 8 carbon atoms (for example, a diphenylamino group, a dimethylamino group, etc.); Contains fluorine (including partially fluorinated and fully fluorinated), cyano, and nitro groups. The substituents may be crosslinked to each other, or the substituents may together form a cyclic structure (aromatic group). Furthermore, the above-mentioned substituents may further have the above-mentioned substituents.

[0018] A of an aryl compound having a leaving group represented by the general formula (I-1) 1 More specifically, for example, the following groups can be exemplified as: naphthyl groups, such as naphthyl groups, aryl (e.g., phenyl, etc.) naphthyl groups, etc.; Phenanthrenyl group; anthracenyl groups such as anthracenyl groups, aryl (e.g., phenyl, etc.) anthracenyl groups, diaryl (e.g., dinaphthyl, etc.) anthracenyl groups; pyrenyl groups such as pyrenyl groups, alkyl (e.g., t-butyl, etc.) pyrenyl groups; biphenyl groups, biphenyl groups having alkylene (e.g., propylene, isopropylene, etc.) bridges; Phenyl groups such as a phenyl group, an alkyl (e.g., methyl, t-butyl)phenyl group, a dialkyl (e.g., dimethyl)phenyl group, an alkoxy (e.g., methoxy)phenyl group, a dialkylamino (e.g., dimethylamino)phenyl group, a diaryl (e.g., diphenyl)aminophenyl group, a perfluoroalkyl (e.g., trifluoromethyl)phenyl group, an alkyl (e.g., ethyl)oxycarbonylphenyl group, an alkanoyl (e.g., acyl)phenyl group, a fluorophenyl group, a chlorophenyl group, a bromophenyl group, a nitrophenyl group, and a cyanophenyl group; Aryl (e.g., phenyl, etc.) substituted carbazolyl groups; anthracene-9.10-dione group, Aryl (eg, phenyl, etc.) substituted thienyl group, alkyloxycarbonyl (eg, methyloxycarbonyl, etc.) substituted thienyl group. As the aryl compound (aromatic compound) having a leaving group, a commercially available compound can be used.

[0019] In an embodiment of the present invention, The following formulas (I-2a) to (I-2c): [ka] [R 12 each independently represents a hydrogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an amino group, a fluorine group, a chlorine group, a cyano group, a nitro group, or the like; R 12 R may be crosslinked to each other, may form a cyclic structure, and may further have other substituents. 12 may be further interrupted by, for example, an oxygen atom, a sulfur atom, a nitrogen atom, a carbonyl group, an ester bond, or the like. - X 12 indicates an anion.] The trifluoromethyl compound selected from trifluoromethyl-dibenzothiophene (I-2a), which may have a substituent, trifluoromethyl-diphenyl mercaptan (I-2b), which may have a substituent, and trifluoromethanesulfonyl chloride (I-2c), which are represented by the following formula (I-2a), is not particularly limited as long as it is a compound that can receive electrons generated from the piezoelectric material (3) to which a physical stress (or strain) is applied, and generate a trifluoromethyl radical.

[0020] For each of formulas (I-2a) and (I-2b), R 12 R 12 may or may not be identical, R 12 The number of R is not particularly limited, and may be 2 or more. 12 In the case of formula (I-2b), R 12 may be present in an amount of 2 to 10, may be present in an amount of 2 to 8, or may be present in an amount of 2 to 6. As long as each of formulas (I-2a) and (I-2b) can generate a trifluoromethyl radical by receiving an electron generated from the piezoelectric material (3), R 12 is not particularly limited.

[0021] R 12can include, for example, hydrogen, an alkyl group, an alkoxy group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an amino group, fluorine, chlorine, a cyano group, and a nitro group. 12 may be present in two or more, R 12 may be cross-linked to each other, R 12 may form a cyclic structure, R 12 R may further have other substituents. 12 may be further interrupted by, for example, an oxygen atom, a sulfur atom, a nitrogen atom, a carbonyl group, an ester bond, or the like.

[0022] R 12 For example, an alkyl group having 1 to 24 carbon atoms, for example, 1 to 18, for example, 1 to 12, for example, 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, etc.); an alkoxy group having 1 to 24 carbon atoms, for example, 1 to 18, for example, 1 to 12, for example, 1 to 8 carbon atoms (for example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, etc.); a cycloalkyl group having 3 to 24 carbon atoms, for example, 3 to 18, for example, 3 to 12, for example, 3 to 8 carbon atoms (for example, a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, etc.); an alkenyl group having 1 to 24 carbon atoms, for example, 1 to 18, for example, 1 to 12, for example, 1 to 8 carbon atoms (for example, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, an octenyl group, etc.); an alkynyl group having 1 to 24 carbon atoms, for example, 1 to 18, for example, 1 to 12, for example, 1 to 8 carbon atoms (for example, an ethynyl group, a propynyl group, a butynyl group, a pentynyl group, a hexynyl group, an octynyl group, etc.); an aryl group having 5 to 24 carbon atoms, for example, 5 to 18, for example, 5 to 12, for example, 5 to 8 carbon atoms (for example, a phenyl group, a naphthyl group, a biphenyl group, etc.); an aryloxy group having 5 to 24, for example, 5 to 18, for example, 5 to 12, for example, 5 to 8 carbon atoms (for example, a phenoxy group, a naphthyloxy group, a biphenyloxy group, etc.); a heteroaryl group having 4 to 24 carbon atoms, for example, 1 to 18, for example, 1 to 12, for example, 1 to 8 carbon atoms (for example, a thiophenyl group, a furanyl group, a carbazole group, a benzothiophenyl group, a benzofuranyl group, an indolyl group, a pyrrolyl group, a pyridyl group, etc.); an acyl group having 1 to 24 carbon atoms, for example, 1 to 18, for example, 1 to 12, for example, 1 to 8 carbon atoms (for example, an acetyl group, a propionyl group, a butanoyl group, a pentanoyl group, a heptanoyl group, and a group in which a carbonyl group contained in the acyl group is substituted with an ester group or an amide group, etc.); an alkoxycarbonyl group having 1 to 24 carbon atoms, for example, 1 to 18, for example, 1 to 12, for example, 1 to 8 carbon atoms (for example, a methoxycarbonyl group, an ethoxycarbonylcarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a tert-butoxycarbonyl group, a pentoxycarbonyl group, etc.); an amino group having 1 to 24, for example, 1 to 18, for example, 1 to 12, for example, 1 to 8 carbon atoms (for example, a diphenylamino group, a dimethylamino group, etc.); Includes fluorine (including partial fluorine substitution and full fluorine substitution), chlorine (including partial chlorine substitution and full fluorine substitution), cyano group, and nitro group.

[0023] R 12 may be cross-linked to each other, R 12 The R groups may together form a cyclic structure (aromatic group). 12 is further described as R 12 R 12 may be further interrupted by, for example, an oxygen atom, a sulfur atom, a nitrogen atom, a carbonyl group, an ester bond, or the like.

[0024] As long as each of the formulas (I-2a) and (I-2b) can receive an electron generated from the piezoelectric material (3) and generate a trifluoromethyl radical, - X 12is not particularly limited.

[0025] - X 12 represents an anion and can include, for example, a trifluoromethanesulfonate group, a tetrafluoroborate group, and the like.

[0026] In an embodiment of the present invention, The following general formula (I-3): CBr 4 (I-3a) or CHI 3 (I-3b) can be used as the electron-accepting active compound (1). CBr 4 (I-3a) can be used to brominate the compound, 3 Iodination can be achieved using (I-3b).

[0027] In an embodiment of the present invention, The following general formula (I-4): [ka] [R 14 ~R 17 may be the same or different and are each independently selected from hydrogen, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, and an optionally substituted heteroaryl group; R 14 and R 15 , R 14 and R 16 , R 15 and R 17 , R 16 and R 17 etc. may be bonded to each other to form a ring, R 18 may be hydrogen or a substituent. can be used as the electron-accepting active compound (1). The activated fatty acid is not particularly limited as long as it can accept electrons generated from the piezoelectric material (3) and generate a highly reactive intermediate, and it is preferable that the activated fatty acid can release carbon dioxide and undergo a redox reaction by itself (without reacting with other compounds) to generate an olefin.

[0028] For the activated fatty acid represented by formula (I-4), R 14 ~R 17 may be the same or different from each other. As long as the compound of formula (I-4) can generate a highly reactive intermediate by receiving electrons generated from the piezoelectric material (3), R 14 ~R 17 is not particularly limited.

[0029] R 14 ~R 17 can be selected from, for example, hydrogen, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, and a heteroaryl group which may have a substituent.

[0030] Examples of the alkyl group which may have a substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, and an octyl group. Examples of the alkenyl group which may have a substituent include an ethenyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, and a pentenyl group. Examples of the alkynyl group which may have a substituent include an acetylenyl group, a propynyl group, a butynyl group, a pentynyl group, and a hexynyl group. Examples of the alkoxy group which may have a substituent include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a t-butoxy group, a pentoxy group, a hexoxy group, and an octoxy group. The aryl group which may have a substituent includes, for example, a phenyl group, a naphthyl group, a biphenyl group, and the like. Examples of the heteroaryl group which may have a substituent include a thiophenyl group, a furanyl group, a pyrrole group, and a carbazole group.

[0031] The substituents that may be present above may be selected from an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an ester group, a carbonyl group, an amino group, a cyano group, a nitro group, a fluorine group, a chlorine group, and the like. R 14 ~R 17 They may be cross-linked to each other or may form a ring. The substituent may further have a substituent. 14 ~R 17 The substituents which it may have may be interrupted by oxygen, nitrogen, sulfur atoms, carbonyl groups, ester groups, and the like.

[0032] In formula (I-4), R 18 is hydrogen or a substituent, R 18 The number of is not particularly limited. As long as the compound represented by formula (I-4) can generate a highly reactive intermediate by receiving electrons generated from the piezoelectric material (3), R 18 is not particularly limited.

[0033] R 18 can include, for example, hydrogen, an alkyl group, an alkoxy group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an amino group, fluorine, chlorine, a cyano group, and a nitro group. 18 may be present in two or more, R 18 may be cross-linked to each other, R 18 may form a cyclic structure, R 18 R may further have other substituents. 18 may be further interrupted by, for example, an oxygen atom, a sulfur atom, a nitrogen atom, a carbonyl group, an ester bond, or the like.

[0034] R 18 For example, an alkyl group having 1 to 24 carbon atoms, for example, 1 to 18, for example, 1 to 12, for example, 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, etc.); an alkoxy group having 1 to 24 carbon atoms, for example, 1 to 18, for example, 1 to 12, for example, 1 to 8 carbon atoms (for example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, etc.); a cycloalkyl group having 3 to 24 carbon atoms, for example, 3 to 18, for example, 3 to 12, for example, 3 to 8 carbon atoms (for example, a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, etc.); an alkenyl group having 1 to 24 carbon atoms, for example, 1 to 18, for example, 1 to 12, for example, 1 to 8 carbon atoms (for example, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, an octenyl group, etc.); an alkynyl group having 1 to 24 carbon atoms, for example, 1 to 18, for example, 1 to 12, for example, 1 to 8 carbon atoms (for example, an ethynyl group, a propynyl group, a butynyl group, a pentynyl group, a hexynyl group, an octynyl group, etc.); an aryl group having 5 to 24 carbon atoms, for example, 5 to 18, for example, 5 to 12, for example, 5 to 8 carbon atoms (for example, a phenyl group, a naphthyl group, a biphenyl group, etc.); an aryloxy group having 5 to 24, for example, 5 to 18, for example, 5 to 12, for example, 5 to 8 carbon atoms (for example, a phenoxy group, a naphthyloxy group, a biphenyloxy group, etc.); a heteroaryl group having 4 to 24 carbon atoms, for example, 1 to 18, for example, 1 to 12, for example, 1 to 8 carbon atoms (for example, a thiophenyl group, a furanyl group, a carbazole group, a benzothiophenyl group, a benzofuranyl group, an indolyl group, a pyrrolyl group, a pyridyl group, etc.); an acyl group having 1 to 24 carbon atoms, for example, 1 to 18, for example, 1 to 12, for example, 1 to 8 carbon atoms (for example, an acetyl group, a propionyl group, a butanoyl group, a pentanoyl group, a heptanoyl group, and a group in which a carbonyl group contained in the acyl group is substituted with an ester group or an amide group, etc.); an alkoxycarbonyl group having 1 to 24 carbon atoms, for example, 1 to 18, for example, 1 to 12, for example, 1 to 8 carbon atoms (for example, a methoxycarbonyl group, an ethoxycarbonylcarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a tert-butoxycarbonyl group, a pentoxycarbonyl group, etc.); an amino group having 1 to 24, for example, 1 to 18, for example, 1 to 12, for example, 1 to 8 carbon atoms (for example, a diphenylamino group, a dimethylamino group, etc.); Includes fluorine (including partial fluorine substitution and full fluorine substitution), chlorine (including partial chlorine substitution and full fluorine substitution), cyano group, and nitro group.

[0035] R 18 may be 2 or more, R 18 may be cross-linked to each other, R 18 The R groups may together form a cyclic structure (aromatic group). 18 is further described as R 18 R 18 may be further interrupted by, for example, an oxygen atom, a sulfur atom, a nitrogen atom, a carbonyl group, an ester bond, or the like.

[0036] A method for generating (or producing) a highly reactive intermediate according to an embodiment of the present invention comprises: Providing a piezoelectric material (3). In an embodiment of the present invention, the piezoelectric material (3) is a material capable of generating a voltage when mechanical strain is applied (piezoelectricity), and is not particularly limited as long as it is capable of generating a highly reactive intermediate.

[0037] The piezoelectric material (3) can be, for example, barium titanate, strontium titanate, lithium niobate, tourmaline, quartz, topaz, sucrose, Rochelle salt (KNaC 4 H 4 O 6 4H 2 O), ortho-gallium phosphate (GaPO 4 ), langasite (La 3 Ga 5 SiO 14 ), lead titanate (PbTiO3 ), lead zirconate titanate, potassium niobate (KNbO 3 ), lithium tantalate (LiTaO 3 ), sodium tungstate (NaXWO 3 ), zinc oxide (ZnO, Zn 2 O 3 ), Ba 2 NaNb 5 O 5 , Pb 2 KNb 5 O 15 , lithium tetraborate (Li 2 B 4 O 7 ) Potassium sodium niobate ((K,Na)NbO 3 ), bismuth ferrite (BiFeO 3 ), sodium niobate (NaNbO 3 ), Bismuth titanate (Bi 4 Ti 3 O 12 ), Sodium bismuth titanate (Na 0.5 Bi 0.5 TiO 3 ), polyvinylidene fluoride, aluminum nitride (AlN), gallium phosphate (GaPO 4 ), gallium arsenide (GaAs), and the like.

[0038] As the piezoelectric material (3), titanates such as barium titanate, strontium titanate, lead titanate, bismuth titanate, sodium bismuth titanate, and lead zirconate titanate, niobates such as lithium niobate, sodium niobate, potassium niobate, and sodium potassium niobate, and zinc oxide are preferable.

[0039] A method for generating (or producing) a highly reactive intermediate according to an embodiment of the present invention comprises: In the presence of an electron-accepting active compound (1) and a piezoelectric material (3), a mechanical strain is applied to the piezoelectric material (3) to cause a one-electron reduction of the compound (1) to generate a corresponding highly reactive intermediate. Includes.

[0040] In an embodiment of the present invention, the one-electron reduction of compound (1) to generate the corresponding highly reactive intermediate can be carried out in the presence of compound (1) and piezoelectric material (3) (preferably by shaking and applying mechanical strain). Compound (1) may be a solid at 40°C.

[0041] In the present disclosure, a solvent may or may not be used, and the use of the solvent can be appropriately selected. A solvent that is usually used in a (photocatalytic) redox reaction (e.g., aromatic solvents such as benzene, toluene, xylene, mesitylene, etc., ether solvents such as diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, dimethoxyethane, 1,4-dioxane, etc., alcohol solvents such as methanol, ethanol, t-butanol, etc., polar solvents such as acetonitrile, dimethylformamide, dimethylacetamide, etc.) can be appropriately used as necessary. The reaction can also be carried out without using a solvent substantially.

[0042] In an embodiment of the present invention, the solvent may be present in an amount of, for example, 0.01 to 3 microL / mg based on the total mass of the compound (1) and the piezoelectric material (3).

[0043] The generation of the highly reactive intermediate (mixing temperature) can usually be carried out at room temperature (for example, 5 to 40° C.), but can also be carried out with heating as appropriate. The mixing method may be any method capable of mixing, such as shaking, rubbing, pressing, dispersing, kneading, or crushing, and capable of imparting mechanical strain to the piezoelectric material (3). The mixing method (or the method of imparting mechanical strain) is not particularly limited as long as it allows the production of the highly reactive intermediate of the present disclosure to be carried out.

[0044] Such devices include, for example: Grinding machines such as ball mills, rod mills, jet mills, SAG mills, etc.; Rotary mills, grinding machines, etc. Horizontal cylinder, V-type, double cone type, square cube type, S-type and continuous V-type (horizontal axis rotation) vessel rotating type mixers; Horizontal cylindrical, V-shaped, double cone and ball mill type (with baffle blades) rotating vessel mixers; (rotary vibration) vessel-rotating mixers such as rocking and cross-rotary types; Fixed vessel (horizontal axis rotating) mixers such as ribbon, paddle, single rotor and bag mill types; Fixed vessel mixers (vertical axis rotation) such as ribbon type, screw type, planetary type, turbine type, high speed flow type, rotating disk type and Mahler type; Mixing equipment of the (vibrating) stationary vessel type, such as vibrating mill type and sieves; (Fluidization) fluid movement type mixers such as heterogeneous fluidized bed, swirling fluidized bed, riser type and Jot pump type; The reaction can be carried out using a (gravity) fluid motion type mixer such as a gravity type or static mixer, but as long as the reaction proceeds, the method and the device used are not particularly limited. For the mixer, for example, see Table 5 and Figure 9 of Sakashita "Powder Mixing Process Technology" Color Materials, 77(2), 75-85 (2004).

[0045] The mixing speed can also be selected appropriately. The mixing time can also be appropriately selected. In the embodiment of the present invention, the mixing time can be, for example, 15 minutes or more, 30 minutes or more, 45 minutes or more, 60 minutes or more, 2 hours or less, 3 hours or less, 5 hours or less, or 10 hours or less.

[0046] The amount of piezoelectric material (3) is not particularly limited as long as it is an amount that can generate a highly reactive intermediate, and may be, for example, 0.5 mol % or more and 1500 mol % or less, based on the number of moles obtained by multiplying the number of moles of compound (1) by the valence (100%). In an embodiment of the present invention, the highly reactive intermediate produced is usually used as it is in the (mechano)redox reaction described below.

[0047] In another aspect of the present invention, there is provided a (mechano)redox reaction method comprising the above-mentioned method for generating (or producing) a highly reactive intermediate, The highly reactive intermediate undergoes a (mechano)redox reaction to produce a (mechano)redox reaction product, thereby providing a (mechano)redox reaction method.

[0048] The highly reactive intermediate obtained by the above-mentioned preparation method can, for example, undergo a redox reaction by itself to give a redox reaction product, or can undergo a redox reaction with another compound to give a redox reaction product. Any redox reaction can be selected in consideration of the highly reactive intermediate and the electron-accepting active compound (1) that generates it.

[0049] In an embodiment of the present invention, Preparing an electron-accepting active compound (1); Providing a piezoelectric material (3); and In the presence of an electron-accepting active compound (1) and a piezoelectric material (3), mechanical strain is applied to the piezoelectric material (3) to reduce compound (1) by one electron, generating a corresponding highly reactive intermediate, which then undergoes a redox reaction by itself to generate a redox reaction product. The present invention provides a redox reaction method comprising the steps of:

[0050] The electron-accepting active compound (1), piezoelectric material (3), and reaction conditions (e.g., reaction time, reaction temperature, quantitative relationship, and apparatus) of the redox reaction method can be referred to those described in the above-mentioned highly reactive intermediate production method.

[0051] In an embodiment of the present invention, the redox reaction of the electron-accepting active compound (1) is The activated fatty acid represented by formula (I-4) as the electron-accepting active compound (1) undergoes a redox reaction by itself. may include. As the activated fatty acid represented by formula (I-4), reference can be made to the above-mentioned compounds.

[0052] For example, when the activated fatty acid represented by formula (I-4) undergoes a redox reaction with itself, it can be decarboxylated to give a compound having a double bond (e.g., an olefin), for example, as shown in the following formula. [ka] [(I-4), R 14 ~R 18 , (3) is as described above.]

[0053] In an embodiment of the present invention, the highly reactive intermediate can undergo a redox reaction with a compound (2) that can react with it (i.e., a reaction substrate) to generate a redox reaction product. For example, the compound (2) can be a reaction substrate that can react with the highly reactive intermediate selected from a radical, an anion radical, and an anion. Examples of such a compound (2) include an aromatic compound (2-1) that may contain a heteroatom, a diboronic acid ester (2-2), and an aliphatic alcohol (2-3), etc. Thus, in an embodiment of the present invention, a method for producing a piezoelectric material comprising the steps of: providing an electron-accepting active compound (1); providing a piezoelectric material (3); further providing a compound (2); and applying mechanical strain to the piezoelectric material (3) in the presence of the electron-accepting active compound (1) and the piezoelectric material (3) as well as the compound (2), thereby reducing the compound (1) by one electron to generate a corresponding highly reactive intermediate, which then reacts with the compound (2) to generate a redox reaction product; The present invention provides a redox reaction method comprising the steps of:

[0054] In an embodiment of the present invention, further providing at least one compound (2) selected from an aromatic compound (2-1), which may contain a heteroatom, a diboronic acid ester (2-2), and an aliphatic alcohol (2-3); In the presence of an electron-accepting active compound (1) and a piezoelectric material (3), as well as a compound (2), a mechanical strain is applied to the piezoelectric material (3) to cause a one-electron reduction of the compound (1) to generate a corresponding highly reactive intermediate, which reacts with the compound (2) to generate a redox reaction product; The present invention provides a redox reaction method comprising the steps of: In the redox reaction method between the electron-accepting active compound (1) and the compound (2), for example, a chemical bond selected from a CB bond, a CC bond, a C-Br bond, and a CI bond can be formed.

[0055] The redox reaction method according to an embodiment of the present invention comprises the steps of: An aromatic compound (2-1) which may contain a heteroatom, a diboronic acid ester (2-2) and an aliphatic alcohol (2-3) The method includes providing at least one compound (2) selected from the following: In the embodiment of the present invention, the aromatic compound (2-1), which may contain a heteroatom, the diboronic acid ester (2-2), and the aliphatic alcohol (2-3) are not particularly limited as long as they can carry out the redox reaction targeted by the present invention.

[0056] In an embodiment of the present invention, Compound (2) is, for example, The following general formula (II-1): A 2 -H [A 2 is selected from an aryl group which may have a substituent, and a heteroaryl group which may have a substituent; The following general formula (II-2): [ka] [R 1 ~R 4 are each independently selected from hydrogen, an alkyl group which may have a substituent, and an aryl group which may have a substituent; R 1 and R 2 may be mutually bonded, R 3 and R4 may be bonded to each other]; and The following general formula (II-3): [ka] [R 23 may be the same or different and are each independently selected from hydrogen, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, and an aryl group which may have a substituent; R 23 and R 23 may be bonded to each other], It is preferably selected from:

[0057] In an embodiment of the present invention, the aromatic compound (2-1) which may contain a heteroatom is not particularly limited as long as the redox reaction proceeds. More specifically, in the general formula (II-1), A 2 The aryl group (or aromatic hydrocarbon group) which may have the substituent can include, for example, a phenyl group, a naphthyl group, an anthracenyl group (or anthracene group), a phenanthrenyl group (or phenanthrene group), a biphenyl group, a terphenyl group, a pyrenyl group (or pyrene group), a perylenyl group (or perylene group), a triphenylenyl group (or triphenylene group), and a coronyl group (or coronene group). It is preferable that the alkyl group contains a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a biphenyl group, a terphenyl group, a pyrenyl group, a perylenyl group, a triphenylenyl group, or a coronyl group.

[0058] In general formula (II-1), A 2 Heteroaryl groups which may bear the following substituents are, for example: (or heteroaromatic groups) are, for example: Sulfur-containing heteroaryl groups such as thiophenyl group (thiophene group or thienyl group), benzothienyl group, dibenzothienyl group, etc.; Oxygen-containing heteroaryl groups such as furanyl (or furan) groups, benzofuranyl groups, dibenzofuranyl groups, phenyldibenzofuranyl groups, and dibenzofuranylphenyl groups; nitrogen-containing heteroaryl groups such as a pyrronyl group (or a pyrrole group), a benzopyronyl group, a dibenzopyronyl group, a pyridyl group (or a pyridine group), a pyrimidinyl group (or a pyrimidine group), a pyrazyl group (or a pyrazine group), a quinolyl group (or a quinoline group), an isoquinolyl group (or an isoquinoline group), a carbazolyl group (or a carbazole group), a 9-phenylcarbazolyl group, an acridinyl group (or an acridine group), a quinazolyl group (or a quinazoline group), a quinoxalyl group (or a quinoxaline group), a 1,6-naphthyridinyl group, a 1,8-naphthyridinyl group, and a porphyrin group (or a porphyrin ring); It can include heteroaryl groups that contain two or more heteroatoms (eg, nitrogen and sulfur), such as benzothiazolyl groups (or benzothiazole groups). It is preferable that the alkyl group contains a thiophenyl group, a furyl group, a pyronyl group, a benzthiophenyl group, a benzfuranyl group, a benzpyronyl group, a dibenzthiophenyl group, a dibenzfuranyl group, or a dibenzpyronyl group.

[0059] The substituents which the aryl group and heteroaryl group may have are not particularly limited as long as they can carry out the redox reaction targeted by the present invention. The substituents are, for example, an alkyl group having 1 to 24 carbon atoms, for example, 1 to 18, for example, 1 to 12, for example, 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, etc.); an alkoxy group having 1 to 24 carbon atoms, for example, 1 to 18, for example, 1 to 12, for example, 1 to 8 carbon atoms (for example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, etc.); a cycloalkyl group having 3 to 24 carbon atoms, for example, 3 to 18, for example, 3 to 12, for example, 3 to 8 carbon atoms (for example, a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, etc.); an alkenyl group having 1 to 24 carbon atoms, for example, 1 to 18, for example, 1 to 12, for example, 1 to 8 carbon atoms (for example, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, an octenyl group, etc.); an alkynyl group having 1 to 24 carbon atoms, for example, 1 to 18, for example, 1 to 12, for example, 1 to 8 carbon atoms (for example, an ethynyl group, a propynyl group, a butynyl group, a pentynyl group, a hexynyl group, an octynyl group, etc.); an aryl group having 5 to 24 carbon atoms, for example, 5 to 18, for example, 5 to 12, for example, 5 to 8 carbon atoms (for example, a phenyl group, a naphthyl group, a biphenyl group, etc.); an aryloxy group having 5 to 24, for example, 5 to 18, for example, 5 to 12, for example, 5 to 8 carbon atoms (for example, a phenoxy group, a naphthyloxy group, a biphenyloxy group, etc.); a heteroaryl group having 4 to 24 carbon atoms, for example, 1 to 18, for example, 1 to 12, for example, 1 to 8 carbon atoms (for example, a thiophenyl group, a furanyl group, a carbazole group, a benzothiophenyl group, a benzofuranyl group, an indolyl group, a pyrrolyl group, a pyridyl group, etc.); an acyl group having 1 to 24 carbon atoms, for example, 1 to 18, for example, 1 to 12, for example, 1 to 8 carbon atoms (for example, an acetyl group, a propionyl group, a butanoyl group, a pentanoyl group, a heptanoyl group, and a group in which a carbonyl group contained in the acyl group is substituted with an ester group or an amide group, etc.); an alkoxycarbonyl group having 1 to 24 carbon atoms, for example, 1 to 18, for example, 1 to 12, for example, 1 to 8 carbon atoms (for example, a methoxycarbonyl group, an ethoxycarbonylcarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a tert-butoxycarbonyl group, a pentoxycarbonyl group, etc.); an amino group having 1 to 24, for example, 1 to 18, for example, 1 to 12, for example, 1 to 8 carbon atoms (for example, a diphenylamino group, a dimethylamino group, etc.); Contains fluorine (including partially fluorinated and fully fluorinated), cyano, and nitro groups. The substituents may be crosslinked to each other, or the substituents may together form a cyclic structure (aromatic group). Furthermore, the above-mentioned substituents may further have the above-mentioned substituents.

[0060] A of an aryl compound represented by the general formula (II-1) which may have a substituent 2 More specifically, for example, the following groups can be exemplified as: naphthyl groups, such as naphthyl groups, aryl (e.g., phenyl, etc.) naphthyl groups, etc.; Phenanthrenyl group; anthracenyl groups such as anthracenyl groups, aryl (e.g., phenyl, etc.) anthracenyl groups, diaryl (e.g., dinaphthyl, etc.) anthracenyl groups; pyrenyl groups such as pyrenyl groups, alkyl (e.g., t-butyl, etc.) pyrenyl groups; Collonyl groups, alkyl (e.g., t-butyl, etc.) collonyl groups, and the like; biphenyl groups, biphenyl groups having alkylene (e.g., propylene, isopropylene, etc.) bridges; Phenyl groups such as a phenyl group, an alkyl (e.g., methyl, t-butyl)phenyl group, a dialkyl (e.g., dimethyl)phenyl group, an alkoxy (e.g., methoxy)phenyl group, a dialkylamino (e.g., dimethylamino)phenyl group, a diaryl (e.g., diphenyl)aminophenyl group, a perfluoroalkyl (e.g., trifluoromethyl)phenyl group, an alkyl (e.g., ethyl)oxycarbonylphenyl group, an alkanoyl (e.g., acyl)phenyl group, a fluorophenyl group, a chlorophenyl group, a bromophenyl group, a nitrophenyl group, and a cyanophenyl group; Aryl (e.g., phenyl, etc.) substituted carbazolyl groups; anthracene-9.10-dione group, thienyl groups, aryl (eg, phenyl, etc.)-substituted thienyl groups, alkyl-substituted thienyl groups, alkoxycarbonyl (eg, methoxycarbonyl, tert-butoxycarbonyl, etc.)-substituted thienyl groups, and other thienyl groups. furanyl groups, aryl (eg, phenyl, etc.)-substituted furanyl groups, alkyl-substituted furanyl groups, and alkoxycarbonyl (eg, methoxycarbonyl, tert-butoxycarbonyl, etc.)-substituted furanyl groups. pyronyl groups, aryl (e.g., phenyl, etc.)-substituted pyronyl groups, alkyl-substituted pyronyl groups, and alkoxycarbonyl (e.g., methoxycarbonyl, tert-butoxycarbonyl, etc.)-substituted pyronyl groups. benzpyronyl groups such as a benzpyronyl group, an aryl (for example, phenyl)-substituted benzpyronyl group, an alkyl-substituted benzpyronyl group, and an alkoxycarbonyl (for example, methoxycarbonyl, tert-butoxycarbonyl group)-substituted benzpyronyl group. As the aryl compound (aromatic compound) which may have a substituent, a commercially available compound can be used.

[0061] In an embodiment of the present invention, the diboronic acid ester (2-2) is not particularly limited as long as it has a BB bond and undergoes a redox reaction with the above-mentioned electron-accepting active compound (1) to give a product in which a BC bond is formed.

[0062] In an embodiment of the present invention, diboronic esters (2-2) include diboronic acid monoesters and diboronic acids, such as tetrahydroxydiborane. The diboronic acid esters (2-2) include diboronic acid alkyl esters, diboronic acid alkylene glycol esters, diboronic acid aryl esters, diboronic acid arylene glycol esters, and tetrahydroxydiborane.

[0063] In an embodiment of the present invention, the diboronic acid ester (including an ester and an acid) (2-2) is, more specifically, for example, General formula (II-2): [ka] [R 1 ~R 4are each independently selected from hydrogen, an alkyl group which may have a substituent, and an aryl group (or an aromatic hydrocarbon group) which may have a substituent; R 1 and R 2 may be mutually bonded, R 3 and R 4 may be mutually combined].

[0064] In formula (II-2), R 1 ~R 4 are each independently selected from hydrogen, an alkyl group which may have a substituent, and an aryl group which may have a substituent; R 1 and R 2 may be mutually bonded, R 3 and R 4 may be mutually bonded. 1 and R 2 may together form a ring structure, R 3 and R 4 may form a cyclic structure together. The cyclic structure may be an aromatic group, such as a 1,2-phenylene group.

[0065] Examples of the alkyl group that may have a substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, etc. Furthermore, two alkyl groups may be bonded together, and R 1 -R 2 and R 3 -R 4 Examples of the alkyl group include an ethylene group, a 1,1,2,2-tetramethylethylene group, a 2,2-dimethylpropylene group, and a hexylene group (or a 1,1,3-trimethylpropylene group). The aryl group which may have a substituent is selected from, for example, a phenyl group, a naphthyl group, a biphenyl group, and the like.

[0066] The substituents that the alkyl group and the aryl group may have can be selected from alkyl groups, aryl groups, alkoxy groups, aryloxy groups, etc. The substituents may be crosslinked to each other. The substituents may further have a substituent.

[0067] More specifically, diboronic acid esters include, for example, bis(pinacolato)diboron, bis(neopentyl glycolate)diboron, bis(hexylene glycolato)diboron, bis(catecholato)diboron, and the like. As the diboronic acid ester (2-2), a commercially available product can be used.

[0068] In the present disclosure, the aliphatic alcohol (2-3) means that a hydroxyl group is bonded to a carbon atom of an aliphatic group, and the aliphatic group may be linear or cyclic, and may or may not have a substituent. The aliphatic group may be interrupted by a heteroatom such as oxygen, nitrogen, or sulfur, or a functional group such as a carbolic group, an ester group, or an amide group, and is not particularly limited as long as the redox reaction targeted by the present invention can be carried out.

[0069] In an embodiment of the present invention, the aliphatic alcohol (2-3) is, more specifically, for example, The following general formula (II-3): [ka] [R 23 may be the same or different and are each independently selected from hydrogen, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, and an aryl group which may have a substituent; R 23 and R 23 may be mutually combined].

[0070] Examples of the alkyl group which may have a substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, and an octyl group. Examples of the alkenyl group which may have a substituent include an ethenyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, and a pentenyl group. Examples of the alkynyl group which may have a substituent include an acetylenyl group, a propynyl group, a butynyl group, a pentynyl group, and a hexynyl group. Furthermore, two R 23 They may be linked together to form a ring structure. The aryl group which may have a substituent may be selected from, for example, a phenyl group, a naphthyl group, a biphenyl group, and the like.

[0071] The aforementioned substituents may be selected from alkyl groups, aryl groups, alkoxy groups, aryloxy groups, ester groups, carbonyl groups, amino groups, nitro groups, cyano groups, fluorine, chlorine, etc. 23 They may be cross-linked to each other or may form a ring. The substituent may further have a substituent. 23 The alkyl group, alkenyl group, alkynyl group, etc. may be interrupted by an oxygen, nitrogen or sulfur atom, etc.

[0072] Examples of the aliphatic alcohol include primary aliphatic alcohols and secondary aliphatic alcohols.

[0073] In an embodiment of the present invention, the redox reaction of the electron-accepting active compound (1) and the compound (2) may include, for example, the following reaction: A redox reaction between an aryl compound having a leaving group represented by formula (I-1) as an electron-accepting active compound (1) and an aromatic compound (2-1) or a diboronic acid ester (2-2) which may contain a heteroatom as a compound (2); A redox reaction between a trifluoromethyl compound represented by formulae (I-2a) to (I-2c) as an electron-accepting active compound (1) and an aromatic compound (2-1) which may contain a heteroatom as a compound (2); and A redox reaction between a bromide or iodide represented by formula (I-3) as an electron-accepting active compound (1) and an aliphatic alcohol (2-3) as a compound (2).

[0074] For example, when an aryl compound having a leaving group represented by formula (I-1) is subjected to a redox reaction with an aromatic compound (2-1) which may contain a heteroatom, a compound can be obtained in which the aromatic ring of the aryl compound having a leaving group is directly bonded to the aromatic ring of the aromatic compound (2-1) which may contain a heteroatom. For example, it is shown by the following formula. [ka] [(I-1), A 1 ,X,n,(II-1),A 2 , (3) is as described above.]

[0075] For example, when an aryl compound having a leaving group represented by formula (I-1) is subjected to a redox reaction with a diboronic acid ester (2-2), a compound in which the aromatic ring of the aryl compound having a leaving group has a boronic acid ester as a substituent can be obtained. For example, it is shown by the following formula. [ka] [(I-1), A 1 ,X,n,(II-2),R 1 ~R 4 , (3) is as described above.]

[0076] For example, when a trifluoromethyl compound represented by formulae (I-2a) to (I-2c) is subjected to a redox reaction with an aromatic compound (2-1) which may contain a heteroatom, a compound in which the aromatic compound (2-1) which may contain a heteroatom is trifluoromethylated can be obtained. For example, it is shown by the following formula. [ka] [(I-2a)~(1-2c), (II-1), A 2 , (3) is as described above.]

[0077] For example, when a bromide or iodide represented by formula (I-3) is subjected to a redox reaction with an aliphatic alcohol (2-3), a compound in which the hydroxyl group of the aliphatic alcohol (2-3) is substituted with bromine or iodine can be obtained. [ka] [(I-3a)~(1-3b), (II-3), R 23 , (3) is as described above.]

[0078] The redox reaction method according to an embodiment of the present invention comprises the steps of: The method includes applying a mechanical strain to the piezoelectric material (3) in the presence of an electron-accepting active compound (1) and a piezoelectric material (3) as well as a compound (2), thereby reducing the compound (1) by one electron to generate a corresponding highly reactive intermediate, which then reacts with the compound (2) to generate a redox reaction product.

[0079] The electron-accepting active compound (1), the piezoelectric material (3), and the reaction conditions (e.g., reaction time, reaction temperature, quantitative relationship, and apparatus) of the redox reaction method can be referred to those described in the above-mentioned highly reactive intermediate production method.

[0080] In an embodiment of the present invention, the redox reaction between compound (1) and compound (2) can be carried out in the presence of a piezoelectric material (3) (preferably by shaking and applying mechanical strain). Either or both of compound (1) and compound (2) may be solid at 40°C.

[0081] In the present disclosure, a solvent may or may not be used, and the use of the solvent can be appropriately selected. A solvent that is generally used in a redox reaction using a photocatalyst (e.g., aromatic solvents such as benzene, toluene, xylene, mesitylene, etc., ether solvents such as diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, dimethoxyethane, 1,4-dioxane, etc., alcohol solvents such as methanol, ethanol, t-butanol, etc., polar solvents such as acetonitrile, dimethylformamide, dimethylacetamide, etc.) can be appropriately used as necessary. The reaction can also be carried out without actively using a solvent.

[0082] In an embodiment of the present invention, the solvent may be present in an amount of, for example, 0.01 to 3 microL / mg based on the total mass of compound (1), compound (2), and piezoelectric material (3).

[0083] The redox reaction (mixing temperature) can usually be carried out at room temperature (for example, 5 to 40° C.), but can be carried out with heating as appropriate. The mixing method may be any method capable of mixing, such as shaking, rubbing, pressing, dispersing, kneading, or crushing, and capable of imparting mechanical strain to the piezoelectric material (3). The mixing method (or the method of imparting mechanical strain) is not particularly limited as long as it can cause the redox reaction of the present disclosure to proceed.

[0084] As such a device, the device described above can be used. The mixing time can also be appropriately selected. In the embodiment of the present invention, the mixing time can be, for example, 15 minutes or more, 30 minutes or more, 45 minutes or more, 60 minutes or more, 2 hours or less, 3 hours or less, 5 hours or less, or 10 hours or less.

[0085] The equivalent ratio of compound (1) to compound (2) (compound (1) / compound (2)) is not particularly limited as long as it is an equivalent ratio that allows the redox reaction to proceed, and may be, for example, 10 / 1 to 1 / 10.

[0086] The amount of piezoelectric material (3) is not particularly limited as long as it is an amount that can cause the redox reaction to proceed. For example, the amount may be 0.5 mol % or more and 1500 mol % or less, based on the number of moles obtained by multiplying the number of moles of compound (1) by the valence (100%).

[0087] The obtained redox reaction product can be purified as appropriate. The purification method is not particularly limited as long as the redox reaction product can be purified. For example, conventional methods such as recrystallization and column chromatography can be used as the purification method.

[0088] In a further aspect, the present invention provides a method for producing a redox reaction product using a redox reaction method. The formulas and terms described in the redox reaction method can be directly applied to the method for producing the redox reaction product.

[0089] In the embodiment of the present invention, the piezoelectric material (3) can be used repeatedly, which can reduce the cost of raw materials. The reaction can proceed without a solvent or with a suitable solvent, so a suitable solvent can be used in a suitable amount.

[0090] In the embodiments of the present invention, the above-mentioned electron-accepting active compound (1), piezoelectric material (3), method for applying mechanical strain (or mixing method), aromatic compound (2-1) which may contain a heteroatom, at least one compound (2) selected from diboronic acid ester (2-2) and aliphatic alcohol (2-3), method for producing a highly reactive intermediate, explanations on a redox reaction method, etc. may be referred to insofar as they are applicable to each embodiment.

[0091] It is believed that the reaction method and production method according to the embodiment of the present invention exhibit excellent effects for these reasons, but the present invention is not limited by these reasons in any way. EXAMPLES

[0092] The present invention will be specifically and in detail explained below with reference to examples and comparative examples. However, these examples are merely one embodiment of the present invention, and the present invention is not limited to these examples in any way.

[0093] The compounds used in this example are specifically illustrated in the following examples. The compounds used in the present examples, such as the electron-accepting active compound (1), the aromatic compound (2-1) which may contain a heteroatom, the diborane ester (2-2), and the piezoelectric material (3), were commercially available products and used without purification unless otherwise specified.

[0094] The redox reaction was carried out at room temperature using a ball mill MM400 manufactured by Retsch (now Verder Scientific Co., Ltd.).

[0095] Example 1 4-Chlorophenyldiazonium tetrafluoroborate (1a) (67.9 mg, 0.3 mmol, 1.0 equiv), furan (2-1a) (306.3 mg, 4.5 mmol, 15.0 equiv), and barium titanate (3a) (349.8 mg, 1.5 mmol, 5.0 equiv) were added to a 1.5 mL stainless steel ball mill jar containing a 5 mm diameter stainless steel ball under air. The lid of the ball mill jar was closed, and the jar was attached to a ball mill (Retsch MM400 type) and shaken for 60 minutes (30 Hz). After the reaction was completed, the barium titanate and inorganic salts were removed by passing the reaction mixture through a short silica gel column chromatography with diethyl ether. After removing the diethyl ether with an evaporator, the product was purified by silica gel column chromatography to isolate the desired reaction product (38.9 mg, 0.219 mmol, 73% isolated yield). The results of Example 1 are also shown in Table 1.

[0096] Examples 2 to 7 and Comparative Example 1 The reactions of Examples 2 to 7 were carried out using the same method as that described in Example 1, except that the barium titanate (3a) in Example 1 was replaced with strontium titanate (3b), lithium niobate (3c) and zinc oxide (3d), the stirring speed was changed to 10 Hz or 20 Hz, the size of the ball mill jar was changed, and the ball size was changed, to obtain reaction products. Furthermore, the reaction of Comparative Example 1 was carried out using the same method as that described in Example 2, except that the barium titanate (3a) in Example 1 was not used. The results of Examples 2 to 7 and Comparative Example 1 are shown in Table 1.

[0097] [Table 1]

[0098] Examples 7 to 18 The reactions of Examples 8 to 18 were carried out using the same method as that described in Example 7, except that the 4-chlorophenyldiazonium tetrafluoroborate (1a) in Example 7 was replaced with various diazonium tetrafluoroborate (1b) to (1m), to obtain reaction products. For completeness, the results of Example 7 are also shown in Table 2.

[0099] [Table 2]

[0100] Examples 21 to 24 The reactions of Examples 21 to 24 were carried out in the same manner as in Example 7, except that the 4-chlorophenyldiazonium tetrafluoroborate (1a) in Example 7 was replaced with various diazonium tetrafluoroborate (1f) to (1n), and heteroaromatic compounds (2-1b) to (2-1c) were used in addition to furan (2-1a), to obtain reaction products. The results are shown in Table 3.

[0101] [Table 3]

[0102] Examples 27-28 The reactions of Examples 27 and 28 were carried out in the same manner as in Example 7, except that 4-chlorophenyldiazonium tetrafluoroborate (1a) in Example 7 was replaced with 4-nitrophenyldiazonium tetrafluoroborate (1f), furan (2-1a) was replaced with polycyclic aromatic compounds (2-1d) to (2-1e), and 0.12 μL of acetonitrile was used per mg of the total mass of all solid reactants used, to obtain reaction products. The results are shown in Table 4.

[0103] [Table 4]

[0104] Example 31 The reaction of Example 31 was carried out using the same method as that described in Example 7, except that 4-chlorophenyldiazonium tetrafluoroborate (1a) in Example 7 was replaced with 4-tert-butylphenyldiazonium tetrafluoroborate (1k), the BaTiO3 used after the reaction was recovered, the reaction was repeated using the recovered BaTiO3, and the reaction was repeated a total of five times with BaTiO3 recovered each time the reaction was carried out, to obtain a reaction product. The results are shown in Table 5.

[0105] [Table 5]

[0106] Example 41 In a 5 mL stainless steel ball mill jar containing a 7.5 mm diameter stainless steel ball, 4-chlorophenyldiazonium tetrafluoroborate (1a) (0.3 mmol, 1.0 equiv), bis-pinacolatodiboron (2-2a) (76.2 mg, 0.3 mmol, 1.0 equiv), barium titanate (3a) (349.8 mg, 1.5 mmol, 5.0 equiv), and acetonitrile (59 microL) (0.12 μL per mg of total mass of all solid reactants used) were added under air. The ball mill jar was closed with a lid and placed in a ball mill (Retsch MM400 type) and shaken and stirred for 180 minutes (30 Hz). After the reaction was completed, the barium titanate and inorganic salts were removed by passing the reaction mixture through a short silica gel column chromatography with diethyl ether. After removing the diethyl ether using an evaporator, the desired boronized reaction product was isolated by purification using silica gel column chromatography (4-2a, 61% isolated yield). The results of Example 41 are also shown in Table 6.

[0107] Examples 42 to 50 The reactions of Examples 42 to 50 were carried out using the same method as that described in Example 41, except that the 4-chlorophenyldiazonium tetrafluoroborate (1a) in Example 42 was replaced with various diazonium tetrafluoroborate (1b) to (1m), to obtain reaction products. The results of Examples 42 to 50 are shown in Table 6.

[0108] [Table 6]

[0109] Examples 51 to 58, Comparative Example 51 The reactions of Examples 51 to 58 were carried out using the same method as that described in Example 41, except that the acetonitrile and its amount, and the stirring time of Example 41 were changed to the liquid and its amount (0.20 μL per mg of the total weight of all solid reactants used), and the stirring time, as shown in Table 7. Furthermore, the reaction of Comparative Example 51 was carried out using the same method as that described in Example 51, except that the barium titanate (3a) of Example 51 was not used. In Comparative Example 51, substantially no reaction product was obtained. The results of Examples 51 to 58 and Comparative Example 51 are shown in Table 7.

[0110] [Table 7]

[0111] Example 59 The reaction was carried out in the same manner as described in Example 49, except that instead of using a ball mill at 30 Hz for 3 hours, the reaction was carried out by hammering 200 times to give the reaction product (4-2k) in 43% (NMR) yield.

[0112] Example 61 3-methyl-1H-indole (39.4 mg, 0.3 mmol, 1.0 equiv) (2-1f), 2,8-Difluoro-5-(trifluoromethyl)-5H-dibenzo[b,d]thiophen-5-ium trifluoromethanesulfonate (263.2 mg, 0.6 mmol, 2.0 equiv) (1-2a1), and barium titanate (349.8 mg, 1.5 mmol, 5.0 equiv) (3a) were added to a 1.5 mL stainless steel ball mill jar containing a 5 mm diameter stainless steel ball under air. The ball mill jar was closed with a lid, and the mixture was placed in a ball mill (Retsch MM400 type) and shaken for 60 minutes at 30 Hz. After the reaction was completed, the barium titanate and inorganic salts were removed by passing the reaction mixture through a short silica gel column chromatography with ethyl acetate. After removing the ethyl acetate with an evaporator, the target reaction product (4-3a) was isolated by purification with silica gel column chromatography (31.7 mg, 0.159 mmol, 53% isolated yield).

[0113] [Table 8]

[0114] Examples 62 to 68 In a 1.5 mL stainless steel ball mill jar containing a 5 mm diameter stainless steel ball, 3-methyl-1H-indole (0.6 mmol, 2.0 equiv) (2-1f), 2,8-Difluoro-5-(trifluoromethyl)-5H-dibenzo[b,d]thiophen-5-ium Trifluoromethanesulfonate (0.3 mmol, 1.0 equiv) (1-2a1) or 2,3,7,8-Tetrafluoro-5-(trifluoromethyl)-5H-dibenzo[b,d]thiophen-5-ium Trifluoromethanesulfonate (0.3 mmol, 1.0 equiv) (1-2a2), piezoelectric material (1.5 mmol, 5.0 equiv) (3), and liquid (0.20 μL per mg of total mass of all solid reactants used) were added under air. The lid of the ball mill jar was closed, and the mixture was placed in a ball mill (Retsch MM400 type) and shaken and stirred for 90 minutes (30 Hz). 19 The yield was determined by F-NMR analysis, and the results are shown in Table 9.

[0115] [Table 9]

[0116] Examples 69 to 72 The reactions of Examples 69 to 72 were carried out using the same method as described in Example 64 above, except that the size of the stainless steel ball mill jar, the size of the stainless steel balls, and the shaking time and shaking speed were changed. After the reaction was completed, the crude product was 19 The yield was determined by F-NMR analysis, and the results are shown in Table 10.

[0117] [Table 10]

[0118] Examples 73 to 84 The reactions of Examples 73 to 84 were carried out using the same method as described in Example 72 above, except that 3-methyl-1H-indole (2.0 equiv) (2-1f) was replaced with various aromatic compounds (2-1g) to (2-1q). After the reaction was completed, the reaction mixture was passed through short silica gel column chromatography with ethyl acetate or diethyl ether to remove barium titanate and inorganic salts. After removing the ethyl acetate or diethyl ether with an evaporator, the product was purified by silica gel column chromatography or gel permeation chromatography (GPC) to obtain the desired reaction product (4-3). On the other hand, after the reaction was completed, the crude product was 19 The NMR yield was determined by F-NMR analysis. The results are shown in Table 11. In Table 11, the yield indicates the isolated yield, and the NMR yield is shown in parentheses. The CF3 product (4-3m) of Example 84 is CF3-substituted melatonin.

[0119] [Table 11]

[0120] Examples 85 to 91 The reactions of Examples 85 to 91 were carried out using the same method as described in Examples 73 to 84 above, except that 3-methyl-1H-indole (2.0 equiv) (2-1f) was replaced with various aromatic compounds (2-1r) to (2-1x). The results are shown in Table 12. In Table 12, the yields indicate isolated yields, and the NMR yields are shown in parentheses. Examples 85 to 87 are examples of electron-rich aromatic compounds, and Examples 88 to 91 are examples of tryptophan-containing peptides.

[0121] [Table 12]

[0122] Example 92 The reaction was carried out in the same manner as in Example 64, except that 0.1 μL / mg of acetone was used and the reaction was carried out by 250 hammer strokes instead of 1.5 hours at 30 Hz using a ball mill, to give the reaction product (4-2a) in 13% (NMR) yield.

[0123] The redox reactions of Examples 1 to 92 include preparing an electron-accepting active compound (1); preparing at least one compound (2) selected from an aromatic compound (2-1) that may contain a heteroatom and a diboronic acid ester (2-2); and subjecting compound (1) to a redox reaction with compound (2) in the presence of a piezoelectric material (3). Thus, a chemical bond selected from CB and CC bonds can be formed, the amount of solvent can be reduced, the reaction can be carried out in the presence of air, light irradiation is not required, and scale-up is easier.

[0124] In Comparative Examples 1 and 51, the piezoelectric material (3) is not used, and therefore the redox reaction does not proceed. [Industrial Applicability]

[0125] In the reaction method according to the embodiment of the present invention, the amount of solvent can be reduced, the reaction can be carried out in the presence of air, light irradiation is not required, and scale-up is easier.

[0126] Related Applications This application claims priority under Article 4 of the Paris Convention from application number 2019-163323 filed in Japan on September 6, 2019. The contents of this application are incorporated herein by reference.

Claims

1. Providing an electron-accepting active compound (1); Providing a piezoelectric material (3); further providing at least one compound (2) selected from an aromatic compound (2-1), a diboronic acid ester (2-2), and an aliphatic alcohol (2-3), which may contain a heteroatom; and In the presence of an electron-accepting active compound (1), a piezoelectric material (3) and a compound (2), a mechanical strain is applied to the piezoelectric material (3), and the electron-accepting compound (1) undergoes one-electron reduction and undergoes a redox reaction with the compound (2) to generate a redox reaction product; A method for producing a redox reaction product, comprising: The electron-accepting active compound (1) is The following general formula (I-1): A 1 -Xn [A 1 is selected from an aryl group which may have a substituent and a heteroaryl group which may have a substituent, X is a leaving group including iodine, bromine, chlorine, and a diazonium salt, and n is an integer of 1 or more], and The following formulas (1-2a) to (I-2c): 【Chemistry 1】 [R 12 each independently includes hydrogen, an alkyl group, an alkoxy group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an amino group, fluorine, chlorine, a cyano group, a nitro group, or the like, and R 12 may be crosslinked with each other, may form a cyclic structure, or may further have other substituents. R 12 may be further interrupted by, for example, an oxygen atom, a sulfur atom, a nitrogen atom, a carbonyl group, an ester bond, or the like. -X 12 represents an anion.] a trifluoromethyl compound selected from trifluoromethyl-dibenzothiophene (I-2a) which may have a substituent represented by the following formula: is selected from Piezoelectric materials (3) include barium titanate, lithium niobate, tourmaline, quartz, topaz, sucrose, Rochelle salt (KNaC4H4O6・4H2O), At least one selected from ortho-gallium phosphate (GaPO4), langasite (La3Ga5SiO14), lead titanate (PbTiO3), lead zirconate titanate, potassium niobate (KNbO3), lithium tantalate (LiTaO3), sodium tungstate (NaXWO3), zinc oxide (ZnO, Zn2O3), Ba2NaNb5O5, Pb2KNb5O15, lithium tetraborate (Li2B4O7), sodium potassium niobate ((K,Na)NbO3), bismuth ferrite (BiFeO3), sodium niobate (NaNbO3), bismuth titanate (Bi4Ti3O12), sodium bismuth titanate (Na0.5Bi0.5TiO3), polyvinylidene fluoride, aluminum nitride (AlN), gallium phosphate (GaPO4), and gallium arsenide (GaAs), Manufacturing method.

2. The electron-accepting active compound (1) is In general formula (I-1) A １ The aryl group, which may have a substituent, includes a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a biphenyl group, a terphenyl group, a pyrenyl group, a perylenyl group, and a triphenylenyl group. A １ The heteroaryl group which may have a substituent includes a sulfur-containing heteroaryl group, an oxygen-containing heteroaryl group, a nitrogen-containing heteroaryl group, and a heteroaryl group containing two or more kinds of heteroatoms. Leaving groups X include iodine, bromine, chlorine, and diazonium salts; The method according to claim 1, wherein the aryl compound is selected from aryl compounds having a leaving group represented by formula (I-1):

3. The redox reaction between the electron-accepting compound (1) and compound (2) is A redox reaction between an aryl compound having a leaving group represented by formula (I-1) as an electron-accepting active compound (1) and an aromatic compound (2-1) or a diboronic acid ester (2-2) which may contain a heteroatom as a compound (2); and A redox reaction between a trifluoromethyl compound represented by the formulae (I-2a) to (I-2c) as an electron-accepting active compound (1) and an aromatic compound (2-1) which may contain a heteroatom as a compound (2). The method according to claim 1 or 2, wherein the compound is selected from the group consisting of

4. Compound (2) is The following general formula (II-1): A ２ -H [A ２ is selected from an aryl group which may have a substituent, and a heteroaryl group which may have a substituent]; The following general formula (II-2): 【Chemistry 2】 [R １ ~R ４ are each independently selected from hydrogen, an alkyl group which may have a substituent, and an aryl group which may have a substituent; R １ and R ２ may be mutually bonded, R ３ and R ４ may be bonded to each other]; and The following general formula (II-3): 【Chemistry 3】 [R ２３ may be the same or different and are each independently selected from hydrogen, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, and an optionally substituted aryl group; R ２３ and R ２３ may be bonded to each other], The redox reaction method according to any one of claims 1 to 3, wherein the redox reaction is selected from the group consisting of

5. The aromatic group in the aromatic compound (2-1) which may contain a heteroatom may be selected from an aryl group which may have a substituent and a heteroaryl group which may have a substituent; The aryl group which may have a substituent includes a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a biphenyl group, a terphenyl group, a pyrenyl group, a perylenyl group, a triphenylenyl group, and a coronenyl group. The heteroaryl group which may have a substituent includes a sulfur-containing heteroaryl group, an oxygen-containing heteroaryl group, a nitrogen-containing heteroaryl group, and a heteroaryl group containing two or more kinds of heteroatoms. The diboronic acid esters (2-2) include diboronic acid alkyl esters, diboronic acid alkylene glycol esters, diboronic acid aryl esters, diboronic acid arylene glycol esters, and tetrahydroxydiborane. The aliphatic alcohol (2-3) includes primary aliphatic alcohols and secondary aliphatic alcohols. The method according to any one of claims 1 to 4.

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