Boron compound, lewis base complex thereof, and methods for producing hydride, polymer, and adduct using these

Abstract

This boron compound is represented by formula (1). In formula (1), X1 and X2 are each independently selected from among electron-withdrawing groups, Y1 and Y2 are each independently selected from among hydrogen and electron-donating groups, with hydrogen not being selected for both simultaneously, R1 is selected from among C1-24 organic groups, the C1-24 organic group may have a substituent, and n is selected from among the integers from 0 to 2.

Description

Boron compounds, Lewis base complexes thereof, and methods for producing hydrides, polymers, and adducts using the same

[0001] The present invention relates to novel boron compounds, Lewis base complexes thereof, and methods for producing hydrides, polymers, and adducts using them.

[0002] Transition metal catalysts traditionally used in hydrogenation reactions are poisoned by carbon monoxide, making it difficult to use crude hydrogen gas as a hydrogen source for hydrogenation reactions. In recent years, catalysts that generate a state known as FLP (frustrated Lewis pair), which enables heterolytic cleavage of molecular hydrogen using only organic compounds without the use of metals, have made it possible to proceed with hydrogenation reactions without the use of transition metal catalysts. Non-Patent Documents 1 and 2 describe boron compounds having a phenyl group partially substituted with fluorine as catalysts for the hydrogenation of imines and quinoline derivatives substituted at the 2- and / or 8-positions. On the other hand, Non-Patent Document 2 also describes that quinoline itself without any substituents is difficult to hydrogenate using an FLP catalyst because FLP is unlikely to occur. Furthermore, catalytic hydrogenation of unsubstituted quinoline in the presence of high concentrations of carbon monoxide and / or carbon dioxide has not been investigated, regardless of whether it is a transition metal catalyst or an FLP catalyst.

[0003] Patent Document 1 discloses a method for hydrogenating unsaturated compounds using tris(pentafluorophenyl)borane as a catalyst. However, under conditions in which carbon monoxide or carbon dioxide coexist at high concentrations, the activity of existing FLP-type catalysts is significantly reduced, and the reaction cannot be completed. Therefore, there is a need for a catalyst that can suppress catalyst poisoning in the hydrogenation reaction and complete the reaction even under conditions in which high concentrations of carbon dioxide coexist.

[0004] Patent Document 2 discloses a hydrogenation reaction using (2,6-dichlorophenyl)bis(3,5-dichloro-2,6-difluorophenyl)borane (ASB) or tris(3,5-dichloro-2,6-difluorophenyl)borane (MHB) as a catalyst. It is reported that the use of the boron compound of Patent Document 2 suppresses catalyst poisoning in the hydrogenation reaction even in the presence of high concentrations of carbon monoxide and / or carbon dioxide, and can be used as a catalyst for smoothly promoting the hydrogenation reaction of 2-methylquinoline. However, the catalytic activity for unsubstituted quinoline has not been investigated.

[0005] JP 2017-206474 A Patent No. 7079696

[0006] Journal of Organometallic Chemistry, vol. 847, 2017, pp. 258-262Chemistry-A European Journal, vol. 18, 2012, pp. 574-585.

[0007] There are still insufficient types of boron compounds that can be used as catalysts or the like that can suppress catalyst poisoning in hydrogenation reactions and allow the reactions to proceed smoothly, preferably even under conditions where high concentrations of carbon monoxide and / or carbon dioxide coexist. It cannot be said that what boron compounds have desirable properties is fully understood. Boron compounds with desirable properties are of interest both academically and industrially.

[0008] An object of the present invention is to provide novel boron compounds and to provide novel catalysts and the like containing them.

[0009] After extensive research, the present inventors have noticed that the boron compounds disclosed in Patent Documents 1 and 2 share a common feature in that the meta position of the aryl group bonded to boron is substituted with an electron-withdrawing group. The present inventors have then found that novel boron compounds in which the meta position of the aryl group bonded to boron is substituted with an electron-donating group can exhibit excellent properties, which has led to the completion of the present invention.

[0010] This specification includes the following embodiments: 1. A boron compound represented by the following formula (1): [In the above formula (1), X １ and X ２ are each independently selected from electron-withdrawing groups; Y １ and Y ２ are each independently selected from hydrogen and an electron donating group, but are not both hydrogen; R １ is selected from organic groups having 1 to 24 carbon atoms, the organic groups having 1 to 24 carbon atoms may have a substituent, and n is selected from integers of 0 to 2. 2. A Lewis base complex of a boron compound represented by the following formula (2): [In the above formula (2), X １ and X ２ are each independently selected from electron-withdrawing groups; Y １ and Y ２ are each independently selected from hydrogen and an electron donating group, but are not both hydrogen; R １ is selected from organic groups having 1 to 24 carbon atoms, the organic group having 1 to 24 carbon atoms optionally having a substituent, n is selected from an integer of 0 to 2, and LB is selected from Lewis bases. 3. A chemical composition comprising the boron compound according to 1 above or the Lewis base complex according to 2 above. 4. A hydrogenation catalyst comprising the boron compound according to 1 above or the Lewis base complex according to 2 above. 5. A method for producing a hydride using the hydrogenation catalyst according to 4 above. 6. A method for producing a hydride, comprising using the hydrogenation catalyst according to 4 above in the presence of crude hydrogen gas. 7. A polymerization initiator comprising the boron compound according to 1 above or the Lewis base complex according to 2 above. 8. A method for producing a polymer, comprising using the polymerization initiator according to 7 above. 9. A Lewis acid catalyst comprising the boron compound according to 1 above. 10. A method for producing an adduct, comprising using the Lewis acid catalyst according to 9 above.

[0011] In the boron compound according to an embodiment of the present invention, the meta position of the aryl group bonded to boron is substituted with an electron-donating group. The novel boron compound and Lewis base complex of the present invention can be suitably used to produce hydrides, polymers, adducts, and the like.

[0012] Figure 1 shows the novel boron compounds. Figure 2 shows the Lewis base complexes of the novel boron compounds.

[0013] 1. Boron Compound The boron compound according to an embodiment of the present invention is represented by the following formula (1). [In the above formula (1), X １ and X ２ are each independently selected from electron-withdrawing groups; Y １ and Y ２ are each independently selected from hydrogen and an electron donating group, but are not both hydrogen; R １ is selected from organic groups having 1 to 24 carbon atoms, the organic groups having 1 to 24 carbon atoms may have a substituent, and n is selected from integers of 0 to 2.

[0014] In the boron compound according to the embodiment of the present invention, the (2-X １ , 3-Y １ , 5-Y ２ , 6-X ２ Regarding the phenyl group (hereinafter also referred to as "substituted phenyl group"), the following points are important: (1) In order to sterically protect the boron center and to give the substituted phenyl group electron-withdrawing properties, a substituent (X) at the ortho position is used. １ , X ２ (2) To appropriately control the electron affinity of the boron center and the stability of the Lewis base complex, a substituent (Y) at the meta position is introduced. １ , Y ２ ) by introducing an electron-donating group into one or both of the groups.

[0015] In the above formula (1), X １ and X ２ are each independently selected from electron-withdrawing groups. Examples of the electron-withdrawing group include a halogeno group, a nitro group, a cyano group, a fluoroalkyl group, and substituted sulfonyl groups such as a trifluoromethanesulfonyl group, an alkylsulfonyl group, and an arylsulfonyl group. A fluoroalkyl group, a trifluoromethanesulfonyl group, and a halogeno group are preferred, a halogeno group selected from a bromo group, a chloro group, and a fluoro group is more preferred, and a chloro group and a fluoro group are most preferred. １ and X ２may be the same or different. For example, X １ is a halogeno group, and X ２ may be a group other than a halogeno group (e.g., a substituted sulfonyl group). １ and X ２ When both are halogeno groups, X １ is a fluoro group, and X ２ may be a chloro group.

[0016] In the above formula (1), Y １ and Y ２ are each independently selected from hydrogen and an electron donating group, but are not both hydrogen. １ and X ２ may both be selected from electron-donating groups, or one may be hydrogen and the other may be selected from electron-donating groups, but not both may be hydrogen. In this specification, the electron-donating group refers to a group that has the property of donating electrons to the phenyl group when bonded to the phenyl group, and is not particularly limited as long as the boron compound targeted by the present invention can be obtained. Examples of electron-donating groups include alkyl, alkenyl, alkynyl, cycloalkyl, alkoxy, amino, alkylamido, dialkylamino, silyl, trialkylsilyl, triarylsilyl, and alkylarylsilyl. Preferred electron-donating groups are alkyl, alkenyl, alkynyl, cycloalkyl, alkoxy, amino, alkylamido, dialkylamino, and trialkylsilyl, with alkyl, alkenyl, alkoxy, and trialkylsilyl being more preferred.

[0017] The number of carbon atoms in the alkyl is preferably 1 to 24, more preferably 1 to 18, even more preferably 1 to 15, and even more preferably 1 to 12. The number of carbon atoms in the alkenyl is preferably 2 to 24, more preferably 2 to 18, even more preferably 2 to 15, and even more preferably 2 to 12. The number of carbon atoms in the alkynyl is preferably 2 to 24, more preferably 2 to 18, even more preferably 2 to 15, and even more preferably 2 to 12. The number of carbon atoms in the cycloalkyl is preferably 3 to 24, more preferably 3 to 18, even more preferably 3 to 15, and even more preferably 3 to 12. The number of carbon atoms in the alkoxy is preferably 1 to 24, more preferably 1 to 18, even more preferably 1 to 15, and even more preferably 1 to 12. The number of carbon atoms in the alkylamide is preferably 3 to 27, more preferably 3 to 21, even more preferably 3 to 18, and even more preferably 3 to 12. The number of carbon atoms in the dialkylamino is preferably 2 to 48, more preferably 2 to 36, even more preferably 2 to 30, and even more preferably 2 to 24. The number of carbon atoms in the trialkylsilyl is preferably 3 to 72, more preferably 3 to 54, even more preferably 3 to 45, and even more preferably 3 to 36.

[0018] Examples of the alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, n-hexyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, and n-eicosyl groups. Examples of the alkenyl include ethenyl, n-propenyl, isopropenyl, n-butenyl, isobutenyl, n-pentenyl, n-hexenyl, n-dodecenyl, n-tridecenyl, n-tetradecenyl, n-hexadecenyl, n-octadecenyl, and n-eicosenyl groups. Examples of the alkynyl include ethynyl, n-propynyl, n-butynyl, isobutynyl, n-pentynyl, n-hexynyl, n-dodecynyl, n-tridecynyl, n-tetradecynyl, n-hexadecynyl, n-octadecynyl, and n-eicosynyl. Examples of the cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, and adamantyl. Examples of the alkoxy include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, t-butoxy, pentoxy, and hexoxy. Examples of the alkylamide include a methylamide group, an ethylamide group, an n-propylamide group, an isopropylamide group, an n-butylamide group, an isobutylamide group, a t-butylamide group, an n-pentylamide group, an n-hexylamide group, an n-dodecylamide group, an n-tridecylamide group, an n-tetradecylamide group, an n-hexadecylamide group, an n-octadecylamide group, and an n-eicosylamide group.Examples of the dialkylamino include a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a di-n-butylamino group, a diisobutylamino group, a di-t-butylamino group, a di-n-pentylamino group, a di-n-hexylamino group, a di-n-dodecylamino group, a di-n-tridecylamino group, a di-n-tetradecylamino group, a di-n-hexadecylamino group, a di-n-octadecylamino group, and a di-n-eicosylamino group. Examples of the trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group, a tri-n-propylsilyl group, a triisopropylsilyl group, a tri-n-butylsilyl group, a triisobutylsilyl group, a tri-t-butylsilyl group, a tri-n-pentylsilyl group, a tri-n-hexylsilyl group, a tri-n-dodecylsilyl group, a tri-n-tridecylsilyl group, a tri-n-tetradecylsilyl group, a tri-n-hexadecylsilyl group, a tri-n-octadecylsilyl group, and a tri-n-eicosylsilyl group.

[0019] In the above formula (1), n ​​is an integer of 0 to 2. n is preferably 0 to 1. When n is 0, boron is bonded to three (2-X １ , 3-Y １ , 5-Y ２ , 6-X ２ ) phenyl group (substituted phenyl group) is bonded to the boron, and when n is 1, two substituted phenyl groups are bonded to the boron. When the number of substituted phenyl groups bonded to the boron is 2 or 3, the properties as a catalyst and the like are improved, and this is preferable. The boron compound may have one substituted phenyl group, two substituted phenyl groups, or three substituted phenyl groups. When the boron compound has two or more substituted phenyl groups, the substituted phenyl groups may be the same or different from each other.

[0020] In the above formula (1), R １The organic group having 1 to 24 carbon atoms represented by the formula (I) is not particularly limited as long as it can provide the boron compound intended by the present invention, and examples thereof include an alkyl group having 1 to 24 carbon atoms, a cycloalkyl group having 3 to 24 carbon atoms, an aryl group having 3 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, a linear or cyclic alkoxyalkyl group having 2 to 24 carbon atoms, an arylalkyl group having 7 to 24 carbon atoms, an arylalkoxy group having 7 to 24 carbon atoms, an alkylthio group having 1 to 24 carbon atoms, an arylthio group having 6 to 24 carbon atoms, and an arylalkylthio group having 7 to 24 carbon atoms.

[0021] When n is 0, the boron compound is R １ When n is 1, the boron compound does not have one R １ When n is 2, the boron compound has two R １ When n is 2, the boron compound has two R １ may be the same or different.

[0022] R in the above formula (1) １ Regarding the above, examples of the alkyl group having 1 to 24 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-hexadecyl group, an n-octadecyl group, an n-eicosyl group, etc. An alkyl group having 1 to 18 carbon atoms is preferred, and an alkyl group having 1 to 10 carbon atoms is more preferred.

[0023] Examples of cycloalkyl groups having 3 to 24 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, and adamantyl groups. Among these, cycloalkyl groups having 3 to 18 carbon atoms are preferred, and cycloalkyl groups having 3 to 12 carbon atoms are more preferred.

[0024] Examples of the aryl group having 3 to 24 carbon atoms include a phenyl group, a naphthyl group, an indenyl group, a biphenyl group, a phenanthrenyl group, an anthracenyl group, a 4-pyridyl group, and a tolyl group. An aryl group having 3 to 18 carbon atoms is preferred, and an aryl group having 3 to 15 carbon atoms is more preferred. １ is (2-X １ , 3-Y １ , 5-Y ２ , 6-X ２ ) does not contain a phenyl group (also called a "substituted phenyl group"), and R １ The substituted phenyl group in the above formula (1) is excluded.

[0025] Examples of alkoxy groups having 1 to 24 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, t-butoxy, pentoxy, and hexoxy groups. Alkoxy groups having 1 to 18 carbon atoms are preferred, alkoxy groups having 1 to 15 carbon atoms are more preferred, and alkoxy groups having 1 to 10 carbon atoms are even more preferred.

[0026] Examples of aryloxy groups having 6 to 24 carbon atoms include phenoxy, 1-naphthyloxy, p-ethylphenoxy, 3,5-diphenylphenoxy, 3,5-bis(3',4'-bis(trifluoromethyl)phenyl)phenoxy, 4-n-octylphenoxy, etc. Aryloxy groups having 6 to 18 carbon atoms are preferred, and aryloxy groups having 6 to 15 carbon atoms are more preferred.

[0027] Examples of the linear or cyclic alkoxyalkyl group having 2 to 24 carbon atoms include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxymethyl group, a methoxyethoxymethyl group, an ethoxyethoxyethyl group, etc. Among these, an alkoxyalkyl group having 2 to 18 carbon atoms is preferred, and an alkoxyalkyl group having 2 to 15 carbon atoms is more preferred.

[0028] Examples of the arylalkyl group having 7 to 24 carbon atoms include a benzyl group, a 2-phenylethyl group, a 1-methyl-1-phenylethyl group, etc. An arylalkyl group having 7 to 18 carbon atoms is preferred, and an arylalkyl group having 7 to 15 carbon atoms is more preferred.

[0029] Examples of arylalkoxy groups having 7 to 24 carbon atoms include benzyloxy groups, chlorobenzyloxy groups, α-methylbenzyloxy groups, α,α-dimethylbenzyloxy groups, phenylethyloxy groups, etc. Arylalkoxy groups having 7 to 18 carbon atoms are preferred, and arylalkoxy groups having 7 to 15 carbon atoms are more preferred.

[0030] Examples of alkylthio groups having 1 to 24 carbon atoms include methylthio, ethylthio, propylthio, n-butylthio, s-butylthio, t-butylthio, i-propylthio, etc. Alkylthio groups having 1 to 18 carbon atoms are preferred, and alkylthio groups having 1 to 15 carbon atoms are more preferred.

[0031] Examples of the arylthio group having 6 to 24 carbon atoms include a phenylthio group, a phenylmethanethio group, an o-, m-, or p-tolylthio group, and groups derived from thiosalicylic acid and esters thereof. An arylthio group having 6 to 18 carbon atoms is preferred, and an arylthio group having 6 to 15 carbon atoms is more preferred.

[0032] Examples of the arylalkylthio group having 7 to 24 carbon atoms include a methylthiophenyl group, an ethylthiophenyl group, a propylthiophenyl group, an n-butylthiophenyl group, an s-butylthiophenyl group, a t-butylthiophenyl group, an i-propylthiophenyl group, etc. An arylalkylthio group having 7 to 18 carbon atoms is preferred, and an arylalkylthio group having 7 to 15 carbon atoms is more preferred.

[0033] Examples of substituents that the organic group having 1 to 24 carbon atoms may have include electron-withdrawing groups such as halogen atoms, nitro groups, and cyano groups, hydroxyl groups, alkoxy groups, aryloxy groups, carboxyl groups and salts thereof, alkoxycarbonyl groups, acyloxy groups, aroyloxy groups, amino groups, aminocarbonyl groups, cyano groups, sulfone groups and salts thereof, alkylsulfonyl groups, alkylsulfanyl groups, alkylsulfinyl groups, alkylsulfenyl groups, arylsulfonyl groups, arylsulfanyl groups, arylsulfinyl groups, arylsulfenyl groups, linear or cyclic alkyl groups, linear or cyclic alkenyl groups, aryl groups, heteroaryl groups, linear or cyclic dialkylamino groups, linear or cyclic dialkylaminocarbonyl groups, and linear or cyclic alkoxyalkyl groups. These substituents may further have a substituent. Note that "optionally having a substituent" means that one or more hydrogen atoms of the organic group are substituted with a substituent. For example, a substituted alkyl group refers to an alkyl group having a structure in which one or more hydrogen atoms of the alkyl group are substituted with a substituent. The above R １ The organic group having 1 to 24 carbon atoms, which may have a substituent, represented by the formula (I), preferably has 2 or more carbon atoms, more preferably 4 or more carbon atoms, and even more preferably 6 or more carbon atoms, and preferably has 22 or less carbon atoms, and more preferably has 20 or less carbon atoms.

[0034] The above R １ The organic group having 1 to 24 carbon atoms represented by the formula (I) preferably has an electron-withdrawing substituent. This is because it is believed that this can further improve the Lewis acidity of the Lewis acid compound portion in the boron compound according to the embodiment of the present invention, thereby further enhancing the performance as a catalyst. As the electron-withdrawing group, a group consisting of a halogen atom is preferred among the above-mentioned nitro group, cyano group, and halogen atom. Examples of the group consisting of a halogen atom include a fluoro group, a chloro group, a bromo group, and an iodo group, and among these, a fluoro group and / or a chloro group is particularly preferred. The above-mentioned R １The organic group having 1 to 24 carbon atoms represented by the formula (I) is preferably an alkyl group or an aryl group, and more preferably an aryl group which may have a substituent.

[0035] The above R １ Specifically, the organic group having 1 to 24 carbon atoms represented by the formula (I) is preferably an aryl group or a heteroaryl group, and examples thereof include a 4-pyridyl group, a 2,5-difluoro-4-pyridyl group, a 2,6-difluoro-4-pyridyl group, a 2,3,6-trifluoro-4-pyridyl group, a 2,3,5,6-tetrafluoro-4-pyridyl group, a 2-fluorophenyl group, a 2,3-difluorophenyl group, a 2,4-difluorophenyl group, a 2,5-difluorophenyl group, a 2,6-difluorophenyl group, a 3,5-difluorophenyl group, a 2,3,6-trifluorophenyl group, a 2,4,6-trifluorophenyl group, a 2,4,6-trifluorophenyl group, a 2,5-difluorophenyl group, a 2,6-difluorophenyl group, a 3,5-difluorophenyl group, a 2,3,6-trifluorophenyl group, a 2,4,6-trifluorophenyl group, a 2,5-difluorophenyl group, a 2 ...5- a 2,3,5,6-tetrafluorophenyl group, a 2-chlorophenyl group, a 2,3-dichlorophenyl group, a 2,4-dichlorophenyl group, a 2,5-dichlorophenyl group, a 2,6-dichlorophenyl group, a 3,5-dichlorophenyl group, a 2,3,6-trichlorophenyl group, a 2,4,6-trichlorophenyl group, a 2,3,5,6-tetrachlorophenyl group, a 3,5-bis(trifluoromethyl)phenyl group, a 2,6-difluoro-4-chlorophenyl group, a 2,6-difluoro-4-trifluoromethylphenyl group, a 2,6-difluoro-3-chlorophenyl group, ,6-difluoro-3,5-dichlorophenyl group is more preferred, 2,6-difluorophenyl group, 2,6-dichlorophenyl group, 2,6-difluoro-3-chlorophenyl group, 2,6-difluoro-3,5-dichlorophenyl group is even more preferred, and 2,6-dichlorophenyl group, 2,6-difluoro-3,5-dichlorophenyl group is particularly preferred.

[0036] 2. Lewis Base Complex of Boron Compound The Lewis base complex of a boron compound according to an embodiment of the present invention is represented by the following formula (2). [In the above formula (2), X １ and X ２ are each independently selected from a halogeno group; １ and Y ２are each independently selected from hydrogen and an electron donating group, but are not both hydrogen; R １ is selected from organic groups having 1 to 24 carbon atoms, which may have a substituent; n is selected from integers of 0 to 2; and LB is selected from Lewis bases.

[0037] In this specification, the Lewis base is generally called a Lewis base, and is not particularly limited as long as it includes at least one atom selected from the group consisting of Groups 14, 15, and 16, which has at least one electron pair (lone electron pair) not used in a covalent bond, can donate the electron pair to boron to form a coordinate bond, and can form a boron compound-Lewis base complex as the object of the present invention. ２ O, CO, chain ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran (THF), triphenylphosphine (PPh ３ ), phosphines such as triethylphosphine oxide (Et ３ Examples of the Lewis base include phosphine oxides such as acetonitrile (P═O), nitriles such as acetonitrile, amines such as triethylamine, and heterocyclic compounds containing nitrogen or oxygen. Preferred Lewis bases are nitriles such as acetonitrile, linear and cyclic ethers, phosphines, amines, and heterocyclic compounds.

[0038] The above formula (2) represents a structure in which the boron compound of the above formula (1) and a Lewis base form a complex. １ and X ２ , Y １ and Y ２ , and n is X in the above formula (1). １ and X ２ , Y １ and Y ２ , and n respectively. １ and X ２ , Y １ and Y ２ , and the description (explanation) of n refer to X in the above formula (1). １ and X ２ , Y １ and Y２ , and n are the same as those described above. １ and X ２ , Y １ and Y ２ , as well as the description (explanation) of n.

[0039] 3. Chemical Composition The chemical composition according to an embodiment of the present invention comprises the boron compound and / or Lewis base complex of the boron compound according to the embodiment of the present invention. Examples of the chemical composition according to an embodiment of the present invention include a chemical composition before the reaction in the production of a hydride, a composition containing the hydride after the reaction, a monomer composition before the reaction in the production of a polymer, a composition containing the polymer (resin) after the reaction, a chemical composition before the reaction in the production of an adduct, and a composition containing the adduct after the reaction, as described below.

[0040] 4. Method for Producing a Hydride In a method for producing a hydride according to an embodiment of the present invention, the boron compound and / or Lewis base complex of the boron compound according to the embodiment of the present invention is used as a hydrogenation catalyst. The method for producing a hydride according to an embodiment of the present invention preferably includes a step of adding a hydrogen atom to at least one unsaturated bond of an unsaturated compound using hydrogen gas or crude hydrogen gas as a hydrogen source in the presence of the hydrogenation catalyst (also referred to as a "hydrogenation step"). Note that the "hydride" refers to a compound in which a hydrogen atom is added to at least one unsaturated bond of an unsaturated compound, and is sometimes referred to as a "hydrogenated compound." When the unsaturated compound contains two or more unsaturated bonds, a hydrogen atom may be added to only one unsaturated bond, or may be added to two or more unsaturated bonds. Therefore, the hydride in the method for producing a hydride according to an embodiment of the present invention may be either an unsaturated compound or a saturated compound.

[0041] The "crude hydrogen gas" is a mixed gas containing hydrogen produced from hydrocarbons such as natural gas, naphtha, heavy oil, coal, petroleum exhaust gas, and shale oil, alcohols such as methanol and ethanol, and organic waste such as biomass and industrial waste plastics, and also contains carbon monoxide and / or carbon dioxide. The crude hydrogen gas may be produced in a large chemical plant, or may be supplied from a small home reformer. The hydrogen content of the crude hydrogen gas is not particularly limited, as it can be selected as desired depending on the raw materials and equipment used. However, from the viewpoint of smoothly promoting the hydrogenation reaction, a preferred hydrogen content is 20 mol% or more and less than 99.9 mol%, more preferably 50 mol% or more and less than 99.9 mol%, and even more preferably 70 mol% or more and less than 99.9 mol%, relative to 100 mol% of the total of hydrogen, carbon monoxide, and carbon dioxide.

[0042] In the method for producing a hydrogenated product according to an embodiment of the present invention, the unsaturated compound used in the hydrogenation reaction is an imine, a nitrogen-containing heterocyclic compound, an aldehyde, a ketone, an alkene, an alkyne, an oligomer or polymer having an unsaturated bond, or the like, and one or more of these can be used. Examples of the nitrogen-containing unsaturated heterocyclic compound include pyridines, pyrazines, quinolines, acridines, 1,10-phenanthrolines, and indoles. The oligomer or polymer having an unsaturated bond may have one or more unsaturated bonds in the same molecule.

[0043] Examples of hydrogenated compounds obtainable by the method for producing a hydrogenated product according to an embodiment of the present invention include nitrogen-containing heterocyclic compounds such as amines, piperidines, piperazines, tetrahydroquinolines, tetrahydrophenanthrolines, and indolines; alcohols, alkanes, and alkenes.

[0044] A solvent can be used in the method for producing a hydrogenated product of the present invention. The solvent that can be used is preferably one that does not react with the boron compound and / or Lewis base complex of the boron compound of the present invention serving as a hydrogenation catalyst or inhibit the subsequent hydrogenation reaction of the unsaturated compound, and that can adequately dissolve the boron compound and / or Lewis base complex of the boron compound of the present invention and the unsaturated compound. Examples of suitable solvents include aromatic hydrocarbon solvents such as toluene; aliphatic hydrocarbon solvents such as n-hexane; ketone solvents such as acetone; alcohol solvents such as methanol; ether solvents such as tetrahydrofuran; ester solvents such as ethyl acetate; nitrile solvents such as acetonitrile; halogenated hydrocarbon solvents such as dichloromethane; amide solvents such as dimethylformamide; sulfoxide solvents such as dimethyl sulfoxide; lactone solvents such as γ-butyrolactone; and carbonate ester solvents such as ethylene carbonate. More preferred are aromatic hydrocarbon solvents such as toluene; aliphatic hydrocarbon solvents such as n-hexane; ether solvents such as tetrahydrofuran; and halogenated hydrocarbon solvents such as dichloromethane. Mixtures of two or more of the above solvents can also be used. In addition, when the boron compound and / or Lewis base complex of the boron compound, unsaturated compound, etc. according to the embodiment of the present invention are dissolved in a solvent in advance, the solvents for these solutions may be the same or different, or the process may be carried out without using a solvent.

[0045] In the method for producing a hydride according to an embodiment of the present invention, it is preferable to carry out hydrogenation by dissolving the boron compound and / or Lewis base complex of the boron compound, or the unsaturated compound according to an embodiment of the present invention in a solvent and mixing with a hydrogen source such as hydrogen gas or crude hydrogen gas. The hydrogenation reaction according to the present invention can also be carried out while adding a hydrogen source. Another feature of the embodiment of the present invention is that the hydrogenation reaction can be carried out under conditions of near atmospheric pressure or slight pressure. The pressure may be atmospheric pressure, but carrying out the hydrogenation reaction under pressurized conditions allows the hydrogenation reaction to be carried out more efficiently. When carrying out under pressurized conditions, if the pressure is too high, the energy required for pressurization becomes large and the reaction may become inefficient. Therefore, a pressure of 500 atmospheres or less is preferable, 100 atmospheres or less is more preferable, and 50 atmospheres or less is particularly preferable.

[0046] The method for producing a hydrogenated product according to an embodiment of the present invention includes the hydrogenation step as an essential feature, but may also include other steps, such as a purification step, a catalyst deactivation step, a dilution step, a concentration step, an extraction step, a step of recovering unreacted raw materials, a filtration step, and a catalyst recovery step.

[0047] For example, if the hydrogenated compound becomes insoluble or crystallizes and precipitates, a step of filtering out the precipitate may be provided. If the hydrogenated compound is solid, a step of washing with a poor solvent such as n-hexane may be provided. If the hydrogenated compound is solid, a drying step may be provided. The drying step may be carried out under reduced pressure. If the hydrogenated compound is liquid, a step of purifying it by distillation or the like may be provided.

[0048] When the catalyst is to be reused, it can be insolubilized or crystallized to precipitate, recovered by a filtration step, and reused in the next reaction.

[0049] 5. Polymer Production Method In a polymer production method according to an embodiment of the present invention, the boron compound and / or Lewis base complex of the boron compound according to the above-described embodiment of the present invention is used as an initiator. In a polymer production method according to an embodiment of the present invention, a compound having a cationically polymerizable group, such as an oxirane group (oxirane ring), an oxetane group (oxetane ring), an ethylene sulfide group, a dioxolane group, a trioxolane group, a vinyl ether group, or a styryl group, can be polymerized using the boron compound and / or Lewis base complex of the boron compound according to the above-described embodiment of the present invention as an initiator. Known conditions can be applied as polymerization conditions, and the reaction can also be accelerated by applying heat.

[0050] The polymer production method according to the embodiment of the present invention includes the polymerization step as an essential feature, but may also include other steps, such as a purification step, a catalyst deactivation step, a dilution step, a concentration step, an extraction step, a step of recovering unreacted raw materials, a filtration step, and a catalyst recovery step.

[0051] For example, when the polymerized compound is insolubilized or crystallized and precipitates, a step of filtering out the precipitate may be provided. When the polymerized compound is solid, a step of washing with a poor solvent such as n-hexane may be provided. When the polymerized compound is solid, a drying step may be provided. The drying step may be carried out under reduced pressure. When the polymerized compound is liquid, a step of purifying it by distillation or the like may be provided. In the case of a compound that forms a three-dimensional crosslinked structure upon polymerization, the polymerization reaction may be continued without removing the initiator, and the polymerized product may be obtained as is.

[0052] When the initiator is to be reused, it can be insolubilized or crystallized to precipitate, recovered by a filtration step, and reused in the next reaction.

[0053] 6. Method for Producing Adducts In a method for producing an adduct according to an embodiment of the present invention, the boron compound according to the embodiment of the present invention is used as a Lewis acid catalyst. The method for producing an adduct according to the present invention is not particularly limited, as long as it is a reaction promoted by Lewis acid activation of an oxygen functional group or a nitrogen functional group, and a reaction promotion effect is expected. For example, the addition reaction of a carbon nucleophile, such as an enol derivative, an allyl silicon compound, or an allyl boron compound, to a carbonyl compound such as an aldehyde or ketone; the addition reaction of a carbon nucleophile, such as an enol derivative, an allyl silicon compound, or an allyl boron compound, to an alkene or an α,β-unsaturated carbonyl compound, or a heteroatom nucleophile, such as an alcohol, a phenol, a carboxylic acid, an amide, an amine, a thiol, or a phosphine; the Diels-Alder reaction; and the like can be carried out in good yield by using the boron compound according to an embodiment of the present invention as a Lewis acid catalyst.

[0054] The method for producing an adduct of the present invention essentially includes the addition reaction step, but may also include other steps, such as a purification step, a catalyst deactivation step, a dilution step, a concentration step, an extraction step, a step of recovering unreacted raw materials, a filtration step, and a catalyst recovery step.

[0055] For example, when the adduct becomes insoluble or crystallizes and precipitates, a step of filtering out the precipitate may be provided. When the adduct is solid, a step of washing with a poor solvent such as n-hexane may be provided. When the adduct is solid, a drying step may be provided. The drying step may be carried out under reduced pressure. When the adduct is liquid, a step of purifying it by distillation or the like may be provided.

[0056] When the catalyst is to be reused, it can be insolubilized or crystallized to precipitate, recovered by a filtration step, and reused in the next reaction.

[0057] 7. Catalyst for Hydrogenation of Unsaturated Compounds Using Crude Hydrogen Gas as a Hydrogen Source In the hydrogenation reaction of unsaturated compounds using crude hydrogen gas as a hydrogen source, the boron compound and / or Lewis base complex of the boron compound of the present invention is used as the hydrogenation catalyst. The catalyst for hydrogenation of unsaturated compounds using crude hydrogen gas as a hydrogen source according to an embodiment of the present invention suppresses catalyst poisoning in the hydrogenation reaction, even in the presence of high concentrations of carbon monoxide and / or carbon dioxide, allowing the hydrogenation reaction to proceed smoothly and enabling the target product to be obtained in high yield. Here, the term "crude hydrogen gas" is as defined above.

[0058] The present invention will be specifically and in detail explained below with reference to Examples and Comparative Examples, but these Examples are merely one embodiment of the present invention, and the present invention is not limited by these Examples. In the description of the Examples, unless otherwise specified, parts by weight and % by weight are based on the parts not taking into account the solvent.

[0059] Example 1. Synthesis of tris(2,6-difluoro-3,5-bis(trimethylsilyl)phenyl)borane (1a) (i) Synthesis of (5-bromo-2,4-difluorophenyl)trimethylsilane 1,5-Dibromo-2,4-difluorobenzene (21.8 g, 80.0 mmol, 1.3 M THF solution) at 0° C. ｉPrMgCl (96.0 mL, 96.0 mmol, 1.0 M diethyl ether solution) was added dropwise, and the mixture was stirred at 30° C. for 3 hours. The reaction solution was added to a solution of trimethylsilyltrifluoromethanesulfonate (27.3 mL, 151.3 mmol) and AgOAc (1.3 g, 8.0 mmol) in THF (280 mL) at 0° C., and the mixture was stirred at 30° C. for 18 hours. NH ４ After adding Cl (20 mL), the solvent was evaporated under reduced pressure. The organic layer was extracted with hexane (100 mL x 3), washed with water (20 mL x 3) and saturated brine (20 mL x 3), and then washed with Na ２ SO ４ The mixture was dried using HCl and filtered. The solvent was removed by evaporation under reduced pressure to give (5-bromo-2,4-difluorophenyl)trimethylsilane as a cloudy yellow liquid (18.6 g, 70.2 mmol, 88%). The resulting liquid was dried over 4 Å molecular sieves and used in the next experiment without further purification.

[0060] 1 H NMR (400 MHz, CDCl3): δ 7.49 (dd, 4 J H,F = 8.4 Hz, 5.6 Hz, 1H, Ar-H), 6.82 (t, 3 J H,F = 8.4 Hz, 1H, Ar-H), 0.31 (d, J = 0.8 Hz, 18H, Si(CH3)3). 19 F NMR (376 MHz, CDCl3): δ -101.8 (m, 1F), -105.2 (q, J = 8.8 Hz, 1F).

[0061] (ii) Synthesis of (4,6-difluoro-1,3-phenylene)bis(trimethylsilane) (5-bromo-2,4-difluorophenyl)trimethylsilane (10.6 g, 40.0 mmol, 1.3 M THF solution) at 0° C. ｉPrMgCl (60.0 mL, 60.0 mmol, 1.0 M diethyl ether solution) was added dropwise, and the mixture was stirred at 30° C. for 1.5 hours. The reaction solution was added to a solution of trimethylsilyltrifluoromethanesulfonate (19.0 mL, 105.2 mmol) and AgOAc (0.7 g, 4.0 mmol) in THF (150 mL) at 0° C., and the mixture was stirred at 30° C. for 7 hours. NH ４ After adding Cl (10 mL), the solvent was evaporated under reduced pressure. The organic layer was extracted with hexane (100 mL × 3), washed with water (20 mL × 3) and saturated brine (20 mL × 3), and then washed with Na ２ SO ４ The residue was dried using a 4 Å molecular sieve and filtered. The solvent was removed under reduced pressure, and the residue was purified using silica gel column chromatography (developing solvent: hexane) to obtain (4,6-difluoro-1,3-phenylene)bis(trimethylsilane) as a colorless liquid (7.4 g, 28.8 mmol, 72%). The resulting liquid was dried using a 4 Å molecular sieve and used in the next experiment without further purification.

[0062] 1 H NMR (400 MHz, CDCl3): δ 7.38 (t, 4 J H,F = 7.2 Hz, 1H, Ar-H), 6.66 (t, 3 J H,F = 9.0 Hz, 1H, Ar-H), 0.31 (s, 18H, Si(CH3)3). 13 C{ 1 H} NMR (101 MHz, CDCl3): δ 169.2 (dd, 1 J C,F = 246.4 Hz, 3 J C,F = 12.1 Hz), 141.5 (t, 3 J C,F = 13.1 Hz), 121.4 (m), 102.6 (dt, J = 5.1 Hz, J = 28.8 Hz), -0.89. 19 F NMR (376 MHz, CDCl3): δ -99.8 (t, J H,F= 7.5 Hz, 2F). HRMS (EI + ): m / z Calcd for C 12 H 20 F2Si2 258.1072, found 258.1075.

[0063] (iii) Synthesis of (4,6-difluoro-5-iodo-1,3-phenylene)bis(trimethylsilane) nBuLi (26.7 mL, 32.0 mmol, 1.2 M hexane solution) was slowly added to diisopropylamine (4.5 mL, 32.0 mmol, 0.3 M THF solution) at −60° C. After stirring the reaction solution at −60° C. for 1 hour, (4,6-difluoro-1,3-phenylene)bis(trimethylsilane) (5.5 g, 21.3 mmol, 0.2 M THF solution) was added at −78° C. After stirring the reaction solution at −78° C. for 1 hour, I ２ (10.8 g, 42.6 mmol, 1.1 M THF solution) was added, and the mixture was stirred at room temperature for 14 hours. ２ S ２ O ３ After adding an aqueous solution (50 mL), the mixture was extracted with hexane (200 mL × 2) and diethyl ether (100 mL × 1), washed with saturated saline (50 mL × 3), and then added with Na ２ SO ４ The residue was dried using a hexane distillation column and filtered. The solvent was removed by distillation under reduced pressure, and the residue was purified by silica gel column chromatography (developing solvent: hexane). The solvent was removed by distillation under reduced pressure, and the resulting solid was washed with ethanol to obtain (4,6-difluoro-5-iodo-1,3-phenylene)bis(trimethylsilane) as colorless crystals (6.4 g, 16.6 mmol, 78%). The resulting crystals were purified by sublimation at 100°C under reduced pressure (approximately 0.2 mmHg) and then used in the subsequent reaction.

[0064] 1 H NMR (400 MHz, C6D6): δ 7.36 (t, 4 J H,F = 6.8 Hz, 1 H, Ar-H), 0.22 (s, 18H, Si(CH3)3). 13 C{ 1H} NMR (101 MHz, C6D6): δ 168.4 (dd, 1 J C,F = 244.4 Hz, 3 J C,F = 6.1 Hz), 141.5 (t, 3 J C,F = 26.3 Hz), 122.5 (d, J = 35.4 Hz), 72.1, -1.2. 19 F NMR (376 MHz, C6D6): δ -81.7 (d, 4 J H,F = 7.5 Hz, 2F). HRMS (EI + ): m / z Calcd for C 12 H 19 F2Si2I1 384.0038, found 384.0043.

[0065] (iv) Synthesis of tris(2,6-difluoro-3,5-bis(trimethylsilyl)phenyl)borane (1a) (4,6-difluoro-5-iodo-1,3-phenylene)bis(trimethylsilane) (3.2 g, 8.3 mmol, 0.2 M THF solution) at 0° C. ｉ PrMgCl (5.1 mL, 8.3 mmol, 2.0 M THF solution) was slowly added. The reaction solution was stirred at 0° C. for 1.5 hours, and then BF ３ ・OEt ２ (0.3 mL, 2.6 mmol) was quickly added at -10°C. After stirring overnight at room temperature, the solvent was evaporated under reduced pressure. The resulting solid was extracted with hexane and filtered through Celite. After the solvent was evaporated under reduced pressure, the solid was dissolved in warm hexane and allowed to stand at 15 to 20°C to obtain colorless crystals of tris(2,6-difluoro-3,5-bis(trimethylsilyl)phenyl)borane with a purity of 95-98% in a yield of 35% (717.8 mg, 0.92 mmol).

[0066] 1 H NMR (400 MHz, C6D6): δ 7.78 (t, 4 J H,F= 7.0 Hz, 3H, Ar-H), 0.26 (s, 54H, Si(CH3)3). 11 B NMR (128 MHz, C6D6): Not observed. 13 C{ 1 H} NMR (101 MHz, C6D6): δ 172.2 (dd, 1 J C,F = 248.5 Hz, 3 J C,F = 12.1 Hz), 146.6 (dt, J = 15.2 Hz, J = 3.0 Hz), 121.3 (m), 118.7 (t, J = 28.3 Hz), -1.0. 19 F NMR (376 MHz, C6D6): δ -86.7 (d, 4 J H,F = 7.5 Hz, 6F).

[0067] Example 2. Synthesis of tris(2,6-difluoro-3,5-diallylphenyl)borane (1b) (i) Synthesis of 1,5-diallyl-2,4-difluorobenzene 1,5-Dibromo-2,4-difluorobenzene (8.2 g, 30.0 mmol, 0.3 M THF solution) at 0° C. ｉ PrMgCl (22.5 mL, 45.0 mmol, 2.0 M THF solution) was added dropwise. After stirring the reaction solution at room temperature for 1.5 hours, allyl bromide (5.1 mL, 60.3 mmol) was added at 0° C. After stirring at room temperature for 20 hours, ｉ PrMgCl (22.5 mL, 45.0 mmol, 2.0 M THF solution) was added dropwise and stirred for 2 hours. Allyl bromide (3.6 mL, 42.6 mmol) was added at 0°C, and then stirred at room temperature for 19 hours. NH ４ After adding an aqueous solution of Cl (15 mL), the solvent was evaporated under reduced pressure. The organic layer was extracted with hexane (100 mL × 3), washed with water (20 mL × 3) and saturated saline (20 mL × 3), and then washed with Na ２ SO ４The residue was dried using HCl and filtered. The solvent was removed by distillation under reduced pressure to obtain 1,5-diallyl-2,4-difluorobenzene as a colorless liquid (5.6 g, 28.8 mmol, 96%). The obtained liquid was used in the next experiment without further purification. An isolated sample for NMR measurement was obtained by distillation under reduced pressure (approximately 0.2 mmHg) at 70°C.

[0068] 1 H NMR (400 MHz, CDCl3): δ 6.98 (t, 4 J H,F = 8.6 Hz, 1H, Ar-H), 6.75 (t, 3 J H,F = 9.6 Hz, 1H, Ar-H), 5.92 (m, 2H, CH2CH=CH2), 5.06 (m, 4H, CH2CH=CH2), 3.34 (d, J = 6.4 Hz, 4H, CH2CH=CH2). 13 C{ 1 H} NMR (101 MHz, C6D6): δ 159.7 (dd, 1 J C,F = 247.5 Hz, J = 12.1 Hz), 135.9, 132.1 (q, J = 5.7 Hz), 122.8 (m), 116.2 (m), 103.6 (m), 32.7. 19 F NMR (376 MHz, CDCl3): δ -121.1 (t, J = 9.4 Hz, 2F). HRMS (EI + ): m / z Calcd for C 12 H 12 F2 194.0907, found 194.0902.

[0069] (ii) Synthesis of 1,5-diallyl-2,4-difluoro-3-iodobenzene Diisopropylamine (6.1 mL, 43.5 mmol, 0.4 M in THF) ｎBuLi (27.2 mL, 43.5 mmol, 1.6 M hexane solution) was slowly added at −78° C. After stirring the reaction solution at −78° C. for 1 hour, 1,5-diallyl-2,4-difluorobenzene (5.6 g, 29.0 mmol, 0.2 M THF solution) was slowly added at −78° C. After stirring the reaction solution at −78° C. for 1 hour, I ２ (14.6 g, 58.0 mmol, 0.4 M THF solution) was added, and the mixture was stirred at room temperature for 12 hours. ２ S ２ O ３ After adding an aqueous solution (50 mL), the mixture was extracted with hexane (100 mL x 2) and diethyl ether (100 mL x 1), washed with saturated saline (50 mL x 3), and then added with Na ２ SO ４ The solvent was evaporated under reduced pressure, and then the volatiles were evaporated at 95°C under reduced pressure (approximately 0.2 mmHg), and further distilled at 170°C under reduced pressure (approximately 0.2 mmHg) to obtain 1,5-diallyl-2,4-difluoro-3-iodobenzene as a colorless liquid (7.1 g, 22.2 mmol, 77%).

[0070] 1 H NMR (400 MHz, C6D6): δ 6.59 (t, 4 J H,F = 8.2 Hz, 1H, Ar-H), 5.65 (m, 2H, CH2CH=CH2), 4.89 (m, 4H, CH2CH=CH2), 3.03 (d, J = 6.4 Hz, 4H, CH2CH=CH2). 13 C{ 1 H} NMR (101 MHz, C6D6): δ 159.3 (dd, 1 J C,F = 245.4 Hz, ３ J C,F = 5.1 Hz), 135.4, 131.9 (q, 3 J C,F = 5.4 Hz), 123.5 (m), 116.6 (m), 71.6 (t, J = 30.3 Hz), 33.1 (t, 3 J C,F = 4.0 Hz).19 F NMR (376 MHz, C6D6): δ -102.0 (d, 4 J H,F = 7.5 Hz, 2F). HRMS (EI + ): m / z Calcd for C 12 H 11 F2I 319.9874, found 319.9883.

[0071] (iii) Synthesis of tris(2,6-difluoro-3,5-diallylphenyl)borane (1b) 1,5-diallyl-2,4-difluoro-3-iodobenzene (2.0 g, 6.3 mmol, 0.2 M THF solution) at room temperature ｉ PrMgCl (3.2 mL, 6.3 mmol, 2.0 M THF solution) was added. The reaction solution was stirred at room temperature for 1 hour, and then BF ３ ・OEt ２ (0.3 mL, 2.0 mmol) was added and stirred at room temperature overnight. After evaporating the volatile components under reduced pressure, hexane was added and the mixture was filtered through Celite, and again, all of the volatile components were evaporated under reduced pressure. A sufficient amount of acetonitrile was added to the obtained crude product, and after stirring at room temperature, the solvent was evaporated under reduced pressure. Next, pentane was added and stirred vigorously, resulting in the precipitation of a white solid. The resulting white solid was collected by filtration. Furthermore, the pentane solution of the mother liquor was left at -30°C, resulting in the formation of white crystals. These solids and crystals were collected together, and the CH ３ The CN complex (2b) was obtained in a yield of 26% (320.8 mg, 0.5 mmol). ３ The CN complex was dissolved in toluene and dried under reduced pressure to obtain tris(2,6-difluoro-3,5-diallylphenyl)borane (1b) in a yield of 23% (265.1 mg, 0.4 mmol).

[0072] CH ３ NMR of CN complex 1 H NMR (400 MHz, CD3CN): δ 6.89 (t, 4 J H,F= 8.2 Hz, 3H, Ar-H), 5.92 (m, 6H, CH2CH=CH2), 4.98 (m, 12H, CH2CH=CH2), 3.24 (d, J = 6.0 Hz, 12H, CH2CH=CH2), 1.96 (s, CH3CN). 11 B NMR (128 MHz, CD3CN): -9.6. 13 C{ 1 H} NMR (101 MHz, CD3CN): δ 162.8 (dd, J = 1 J C,F = 243.4 Hz, 15.2 Hz), 137.7, 130.5 (m), 122.2 (m), 115.9, 33.7. Resonances of the C ipso with respect to the boron atom were not observed. 19 F NMR (376 MHz, CD3CN): δ -113.9 (d, 4 J H,F = 7.5 Hz, 6F). NMR of tris(2,6-difluoro-3,5-diallylphenyl)borane 1 H NMR (400 MHz, C6D6): δ 6.93 (t, 4 J H,F = 8.2 Hz, 3H, Ar-H), 5.75 (m, 6H, CH2CH=CH2), 4.94 (m, 12H, CH2CH=CH2), 3.13 (d, J = 6.4 Hz, 12H, CH2CH=CH2). 11 B NMR (128 MHz, C6D6): Not observed. 13 C{ 1 H} NMR (101 MHz, C6D6): δ 161.6 (dd, 1 J C,F = 249.5 Hz, J = 11.1 Hz), 136.3, 135.9, 122.7 (m), 116.3, 32.9. ipsowith respect to the boron atom were not observed. 19 F NMR (376 MHz, C6D6): δ -110.0 (d, 4 J H,F = 7.5 Hz, 6F).

[0073] Examples 3-4 and Comparative Examples 1-2. Hydrogenation of quinoline using hydrogen gas. A hydrogenation reaction of quinoline (Qin) was carried out in the presence of various boron compounds. The procedure is as follows. A 30 mL autoclave was charged with quinoline (2.0 mmol), boron compounds (1a), (1b), (1'c), and (1'd) (0.1 mmol; 5 mol%), tetradecane (internal standard), and toluene. After sealing, the autoclave was heated under reduced pressure. ２ The mixture was pressurized to 10 atm and stirred at 100°C for 8 hours. After cooling to room temperature, the mixture was degassed and the yield of hydrogenated quinoline (H4-Qin) was calculated using GC. The results are shown in the table below.

[0074] Examples 5-6. Hydrogenation of quinoline using a mixed gas containing hydrogen. In the presence of a boron compound or its acetonitrile complex, H ２ / CO / CO ２ A hydrogenation reaction of quinoline was carried out using a mixed gas of 1 / 1 / 1 (molar ratio).

[0075] Example 5: Quinoline (263.2 mg, 2.0 mmol), tris(2,6-difluoro-3,5-diallylphenyl)borane (1b) (59.8 mg, 0.1 mmol; 5 mol%), tetradecane (142.5 mg; internal standard), and toluene (1.3 mL) were placed in a 30 mL autoclave. After sealing, ２ / CO / CO ２ The mixture was pressurized (20 atm each) and stirred for 8 hours at 100° C. After cooling to room temperature and degassing, hydrogenated quinoline (H4-Qin) was obtained in a GC yield of >99%.

[0076] Example 6. In a 10 mL recovery flask, CH ３CN complex (2b) (63.2 mg, 0.1 mmol; 5 mol%) was weighed, and 2-3 mL of toluene was added. The volatile components were then distilled off under reduced pressure. To this was added toluene (1.3 mL) and tetradecane (141.5 mg; internal standard), and the mixture was transferred to a 30 mL autoclave. Quinoline (253.0 mg, 2.0 mmol) was then added, and the autoclave was sealed. ２ / CO / CO ２ The contents were pressurized (20 atm each) and stirred for 8 hours at 100° C. After cooling to room temperature and degassing, hydrogenated quinoline was obtained in a GC yield of 77%.

[0077] In an embodiment of the present invention, the boron compound has an aryl group bonded to boron substituted at the meta position with an electron-donating group. The novel boron compound and Lewis base complex of the present invention can be suitably used to produce hydrides, polymers, adducts, and the like. [Related Applications] This application claims priority under Article 4 of the Paris Convention or Article 41 of the Japanese Patent Act, based on Japanese Patent Application No. 2023-095773 filed on June 9, 2023, the contents of which are incorporated herein by reference.

Claims

1. A boron compound represented by the following formula (1): 【Chemistry 1】 [In the above formula (1), X １ and X ２ are each independently selected from electron-withdrawing groups; Y １ and Y ２ are each independently selected from electron donating groups; R １ is selected from organic groups having 1 to 24 carbon atoms, the organic groups having 1 to 24 carbon atoms may have a substituent, and n is selected from integers of 0 to 2.

2. A Lewis base complex of a boron compound represented by the following formula (2): 【Chemistry 2】 [In the above formula (2), X １ and X ２ are each independently selected from electron-withdrawing groups; Y １ and Y ２ are each independently selected from electron donating groups; R １ is selected from organic groups having 1 to 24 carbon atoms, which may have a substituent; n is selected from integers of 0 to 2; and LB is selected from Lewis bases.

3. A chemical composition comprising the boron compound of claim 1 or the Lewis base complex of claim 2.

4. A hydrogenation catalyst comprising the boron compound according to claim 1 or the Lewis base complex according to claim 2.

5. A method for producing a hydrogenated product, using the hydrogenation catalyst according to claim 4.

6. A method for producing a hydrogenated product, comprising using the hydrogenation catalyst according to claim 4 in the presence of crude hydrogen gas.

7. A polymerization initiator comprising the boron compound according to claim 1 or the Lewis base complex according to claim 2.

8. A method for producing a polymer, comprising using the polymerization initiator according to claim 7.

9. A Lewis acid catalyst comprising the boron compound of claim 1.

10. A method for producing an adduct, comprising using the Lewis acid catalyst according to claim 9.

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