Complex of alkali metal fluoride salt and disubstituted aluminum hydride, and method, for producing reductively substituted alkene from substituted alkyne, that uses said complex

Abstract

The present invention relates to: [1] a complex of an alkali metal fluoride salt and an aluminum compound represented by general formula (1), and a method for producing said complex; and [2] a method, for reductively producing a substituted alkene from a substituted alkyne, that uses said complex. (In general formula (1), R1 and R2 are each independently an alkyl group or an aromatic group.)

Description

A complex of an alkali metal fluoride salt and disubstituted aluminum hydride, and a method for producing a substituted alkene reductively from a substituted alkyne using the complex.

[0001] This invention relates to a complex of an alkali metal fluoride salt and a disubstituted aluminum hydride, and to a method for producing a substituted alkene reductively from a substituted alkyne using the complex.

[0002] Carbon-carbon double bonds in organic compounds can exist in both E and Z forms. For example, 9-octadecenoic acid, which contains a carbon-carbon double bond, exists in both elaidic acid (9(E)-9-octadecenoic acid) with an E-form carbon-carbon double bond and oleic acid (9(Z)-9-octadecenoic acid) with a Z-form carbon-carbon double bond. Elaidic acid activates cholesteryl ester transfer proteins, while oleic acid does not. As described above, differences in the structure of carbon-carbon double bonds in organic compounds can lead to differences in the physiological activity of these compounds. Therefore, when producing organic compounds containing carbon-carbon double bonds, it is necessary to selectively produce either the E or Z form.

[0003] Non-Patent Document 1 discloses a trans-selective reduction reaction of disubstituted alkynes to disubstituted alkenes using lithium diisobutylmethylaluminum hydride prepared from diisobutylaluminum and methyllithium. Non-Patent Document 2 discloses a trans-selective reduction reaction of substituted alkynes to substituted alkenes using a catalytic or excess amount of lithium aluminum hydride under a hydrogen atmosphere. Non-Patent Document 3 also discloses an E-selective reduction reaction of substituted alkynes to substituted alkenes using lithium aluminum hydride.

[0004] Journal of the American Chemical Society, Vol. 89, p. 5085-5086, 1967. Tetrahedron, Vol. 22, p. 1741-1746, 1966. Tetrahedron, Vol. 23, p. 4509-4515, 1967.

[0005] However, diisobutylaluminum and methyllithium used in Non-Patent Document 1, and lithium aluminum hydride used in Non-Patent Documents 2 and 3, are highly reactive and can react with water vapor in the air. Furthermore, the hydrogen used in Non-Patent Document 2 requires special equipment for use. For this reason, the method for producing E-selectively substituted alkenes from alkynes described in Non-Patent Documents 1 or 2 is not easily applicable industrially. The present invention relates to a complex of an alkali metal fluoride salt and disubstituted aluminum hydride that can be used industrially, and a method for producing a reductive substituted alkene from substituted alkynes using the same.

[0006] The present invention relates to the following [1] to [4]. [1] A complex of an alkali metal fluoride salt and an aluminum compound represented by the following general formula (1). (In general formula (1), R １ and R ２ (Each of these is an alkyl group or an aromatic group.) [2] A method for producing the complex according to [1], comprising mixing the alkali metal fluoride salt and the aluminum compound represented by the general formula (1) in an organic solvent. [3] A method for producing a substituted alkene reductively from a substituted alkyne using the complex according to [1]. [4] A method for introducing a substituent reductively into a substituted alkyne using the complex according to [1].

[0007] According to the present invention, it is possible to provide a complex of an alkali metal fluoride salt and an aluminum compound represented by general formula (1) that can be used industrially, and a method for producing a reductive substituted alkene from a substituted alkyne using the same.

[0008] [Complex of alkali metal fluoride salt and aluminum compound represented by general formula (1)] The complex of alkali metal fluoride salt and aluminum compound represented by general formula (1) of the present invention (hereinafter sometimes referred to as "the complex of the present invention") consists of an alkali metal fluoride salt and an aluminum compound represented by general formula (1). The complex of the present invention may have a solvent coordinated to it.

[0009] (Alkali metal fluoride salt) The alkali metal fluoride salt forms a so-called art complex with an aluminum compound represented by the general formula (1) having Lewis acidity. Examples of the alkali metal fluoride salt include lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, francium fluoride, etc. From the viewpoints of economy, the stability of the complex of the present invention, and the reactivity with a substituted alkyne, at least one selected from the group consisting of sodium fluoride, potassium fluoride, and cesium fluoride is preferable, and cesium fluoride is more preferable.

[0010] (Aluminum compound represented by the general formula (1)) The aluminum compound represented by the general formula (1) is a disubstituted aluminum hydride in which two hydrogen atoms of aluminum hydride are substituted with an alkyl group or an aromatic group.

[0011]

[0012] In the general formula (1), R １ and R ２ are each independently an alkyl group or an aromatic group. R １ and R ２ may be the same or different, and from the viewpoint of obtaining the aluminum compound represented by the general formula (1), it is preferably the same.

[0013] R １ and R ２ Examples of the alkyl group as include linear alkyl groups and branched alkyl groups, and in this specification, the branched alkyl group includes a cyclic alkyl group. R １ and R ２ are preferably linear alkyl groups and branched alkyl groups having 4 to 10 carbon atoms, more preferably branched alkyl groups having 4 to 10 carbon atoms, and still more preferably alkyl groups branched at the α-position or β-position having 4 to 10 carbon atoms.

[0014] Examples of alkyl groups branched at the α or β position with 4 to 10 carbon atoms include sec-butyl group, tert-butyl group, isobutyl group, 1-methylbutyl group, 1-ethylbutyl group, 1-methylpentyl group, 1-ethylpentyl group, 1-propylpentyl group, 1-butylpentyl group, 2-methylbutyl group, 2-ethylbutyl group, 2-methylpentyl group, 2-ethylpentyl group, 2-propylpentyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopentylmethyl group, cyclohexylmethyl group, and cycloheptylmethyl group.

[0015] R １ and R ２ Examples of aromatic groups include phenyl groups, 1-naphthyl groups, and 2-naphthyl groups. １ and R ２ The aromatic group may be substituted with an alkyl group having 1 to 3 carbon atoms.

[0016] R １ and R ２ From the viewpoint of the stability of the complex of the present invention and its reactivity with substituted alkynes, a group selected from isobutyl group, 2-methylbutyl group, 2-ethylbutyl group, 2-methylpentyl group, 2-ethylpentyl group, 2-propylpentyl group, cyclohexylmethyl group, and phenyl group is preferred, a group selected from isobutyl group, 2-methylbutyl group, and phenyl group is more preferred, and in addition to the above, from the viewpoint of economy, isobutyl group is even more preferred.

[0017] The complex of the present invention (cesium fluoride:diisobutylaluminum hydride = 1 mol:1 mol) when cesium fluoride is used as the alkali metal fluoride salt and diisobutylaluminum hydride is used as the aluminum compound represented by general formula (1) １ The H-NMR data is shown below. １ ¹H-NMR measurements were performed using AVANCE300 (Bruker), with deuterated benzene solvent used as the measurement solvent, and the protons of benzene in deuterated benzene were measured. １ The peak of H) was set to a baseline of 7.16 ppm. １ H-NMR (300MHz, C ６ D６ , δ ｐｐｍ ): 2.30-2.15 (m, 2H, CH x 2), 1.40-1.30 (d, 12H, CH ３ ×4), 0.86 (d, J=6.6Hz, 1H, Al-H), 0.13-0.01 (m, 4H, CH ２ (x2)

[0018] (Method for producing a complex of an alkali metal fluoride salt and an aluminum compound represented by general formula (1)) The complex of the present invention can be obtained by mixing and stirring an alkali metal fluoride salt and an aluminum compound represented by general formula (1) in an organic solvent.

[0019] The mixture of an alkali metal fluoride salt and an aluminum compound represented by general formula (1) may be prepared by adding a solution of the aluminum compound represented by general formula (1) and an organic solvent to the alkali metal fluoride salt, or by adding the aluminum compound represented by general formula (1) to a suspension of the alkali metal fluoride salt and an organic solvent, or by adding a solution of the aluminum compound represented by general formula (1) and an organic solvent to a solution of the aluminum compound represented by general formula (1) and an organic solvent.

[0020] When mixing an alkali metal fluoride salt with an aluminum compound represented by general formula (1), from the viewpoint of converting all of the aluminum compound represented by general formula (1) into a complex, it is preferable to use 0.5 mol or more, more preferably 0.7 mol or more, and even more preferably 1.0 mol or more of the alkali metal fluoride salt per mol of the aluminum compound represented by general formula (1). Furthermore, there is no particular upper limit on the amount of alkali metal fluoride salt, but from the viewpoint of economy, it is preferable to use 1.3 mol or less, more preferably 1.2 mol or less, and even more preferably 1.1 mol or less of the alkali metal fluoride salt per mol of the aluminum compound represented by general formula (1).

[0021] Organic solvents used for mixing alkali metal fluoride salts with aluminum compounds represented by general formula (1) include alkanes, aromatic compounds, and ether compounds. The organic solvent should be dried by a conventional method. Examples of alkanes used as organic solvents include hexane and cyclohexane. Examples of aromatic compounds used as organic solvents include benzene and toluene. Examples of ether compounds used as organic solvents include tert-butyl methyl ether, tert-butyl ethyl ether, cyclopentyl methyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, and 1,4-dioxane. Among these, alkanes are preferred as the organic solvent, and hexane is more preferred, as it facilitates the determination of complex formation, as will be described later.

[0022] The temperature at which the alkali metal fluoride salt and the aluminum compound represented by general formula (1) are mixed is preferably 0°C or higher, more preferably 10°C or higher, even more preferably 20°C or higher, and preferably 40°C or lower, more preferably 35°C or lower, and even more preferably 30°C or lower. The time for mixing the alkali metal fluoride salt and the aluminum compound represented by general formula (1) is preferably 10 minutes or more, more preferably 20 minutes or more, even more preferably 25 minutes or more, and preferably 3 hours or less, more preferably 2 hours or less, and even more preferably 1 hour or less.

[0023] The formation of a complex between an alkali metal fluoride salt and an aluminum compound represented by general formula (1) can be confirmed, for example, by measuring the NMR of the product. When an alkali metal fluoride salt and an aluminum compound represented by general formula (1) form a complex, the fluorine atom coordinated to the aluminum atom influences the NMR of the aluminum compound represented by general formula (1). １ and R ２ The peak of origin shifts. Also, the R of aluminum compounds represented by general formula (1) １ and R ２ The originating peak and the fluorine atom coordinated to the aluminum atom ( １９Coupling with F) may be observed. Furthermore, when complex formation is carried out in an alkane, if complex formation has not progressed, precipitation of the alkali metal fluoride salt will be observed immediately when stirring is stopped. However, if complex formation has progressed, the obtained complex will be colloidally dispersed in the alkane and will not precipitate, so the completion of complex formation can be confirmed by stopping the stirring of the reaction system. After the completion of complex formation between the alkali metal fluoride salt and the aluminum compound represented by general formula (1), the complex can be isolated by distilling off the organic solvent. Alternatively, after the completion of complex formation between the alkali metal fluoride salt and the aluminum compound represented by general formula (1), the suspension of the complex may be used directly in the next reaction. If the reaction solvent used in the next reaction is different from the organic solvent used during complex formation, the organic solvent used for complex formation may be distilled off, and then the solvent may be replaced with the reaction solvent used in the next reaction, and the complex of the alkali metal fluoride salt and the aluminum compound represented by general formula (1) may be dissolved or suspended before use. In other words, the complex of the present invention includes not only isolated complexes but also solutions or suspensions of the complex of the present invention. The present invention also includes a method for producing substituted alkenes, which comprises the steps of preparing a reaction solution by adding an alkali metal fluoride and an aluminum compound represented by general formula (1) to a reaction solvent and mixing and stirring, and further adding a substituted alkyne to the reaction solution and mixing and stirring.

[0024] Furthermore, the complex of the present invention can be stored for a long period of time by dissolving or suspending it in the above-mentioned organic solvent, which is an alkane and / or aromatic compound. In addition, the complex of the present invention can be stored in the ether compounds shown below as organic solvents for the reaction. For example, when the complex of the present invention is prepared as an ethylene glycol dimethyl ether solution, it can be stored for 6 months at -18°C and for more than 1 week at 4°C.

[0025] [Method for producing substituted alkenes reductively from substituted alkynes] The following describes a method for producing substituted alkenes reductively from substituted alkynes using the complex of the present invention (hereinafter also referred to as "the method for producing substituted alkenes of the present invention"). That is, the method for producing substituted alkenes of the present invention is a method for reducing substituted alkynes to substituted alkenes. The method for producing substituted alkenes of the present invention is carried out by mixing and stirring the complex of the present invention and the substituted alkyne in an organic solvent. Note that the hydrogen atoms introduced when reducing substituted alkynes to substituted alkenes are hydrogen atoms ( １ H), deuterium atom ( ２ H), and tritium atoms ( ３ Any two selected from H) may be used. Note that any two of the above may be of the same type. As the organic solvent used in the substituted alkene production method of the present invention, ether compounds are preferred. Examples of ether compounds include cyclopentyl methyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and 1,4-dioxane. Alternatively, the organic solvent may be a mixed solvent of the ether compound and the organic solvent used in the method for producing the complex of the present invention.

[0026] (Substitutive Alkynes) The substituted alkynes used in the substituted alkene production method of the present invention may be monosubstituted alkynes having a substituent on one of the carbon-carbon triple bonds, or disubstituted alkynes having substituents on both of the carbon-carbon triple bonds.

[0027] Examples of substituents for monosubstituted alkynes include aliphatic groups and aromatic groups, and aromatic groups are preferred from the viewpoint of reactivity with the complex of the present invention.

[0028] By reducing a disubstituted alkyne using the complex of the present invention, E-substituted alkenes can be selectively produced.

[0029] Substituents for disubstituted alkynes include aliphatic groups and aromatic groups. From the viewpoint of reactivity with the complex of the present invention, it is preferable that at least one substituent of the disubstituted alkyne is an aromatic group. Furthermore, from the viewpoint of selectively obtaining E-substituted alkenes, it is preferable that one substituent of the substituted alkyne is an aromatic group and the other substituent is an aliphatic group.

[0030] Aliphatic groups as substituents for substituted alkynes include alkyl groups and alkenyl groups. Alkyl and alkenyl groups may be linear or branched. In this specification, branched alkyl and alkenyl groups include cyclic alkyl and alkenyl groups. Carbon atoms in the aliphatic group and the hydrogen atoms substituted therefor may be substituted with nitrogen atoms, oxygen atoms, sulfur atoms, etc. However, it is preferable that there is no hydrogen atom on the nitrogen atom. Aromatic groups as substituents for substituted alkynes include aromatic hydrocarbon groups such as phenyl, naphthyl, and anthuryl groups; nitrogen-containing aromatic groups such as pyrrolyl, pyridinyl, pyridadinyl, pyrimidine, pyrazinyl, triazinyl, indolyl, and quinolyl groups; oxygen-containing aromatic groups such as furanyl and benzofuranyl groups; and sulfur-containing aromatic groups such as thiophenyl and benzothiophenyl groups. It is preferable that nitrogen-containing aromatic groups do not have a hydrogen atom on the nitrogen atom.

[0031] The aliphatic and aromatic groups acting as substituents on the substituted alkyne may have further substituents. Substituents for the aliphatic and aromatic groups can be any group that does not react with the complex of the present invention, such as halogen atoms like chlorine and bromine atoms, disubstituted amino groups, alkoxy groups, and thioalkyl groups.

[0032] The complex of the present invention may be mixed with a substituted alkyne by adding the substituted alkyne to a solution or suspension of the complex of the present invention and an organic solvent, or by adding the solution or suspension of the complex of the present invention and an organic solvent to the substituted alkyne. The substituted alkyne may also be used as a solution with an organic solvent. After producing the complex of the present invention, the solvent may be replaced as needed, and the substituted alkyne may be added, thereby allowing the production of the complex and the substituted alkene to be carried out in a one-pot system.

[0033] From the viewpoint of reaction efficiency, the molar ratio of the complex of the present invention to the substituted alkyne is preferably 1 mol or more, more preferably 1.5 mol or more, and even more preferably 1.8 mol or more, of the complex of the present invention per 1 mol of substituted alkyne, and from the viewpoint of economic efficiency, it is 4 mol or less, more preferably 3.5 mol or less, and even more preferably 3.2 mol or less.

[0034] The reaction temperature of the substituted alkene production method of the present invention is preferably 50°C or higher, more preferably 80°C or higher, even more preferably 90°C or higher, and even more preferably 100°C or higher, and preferably 150°C or lower, more preferably 140°C or lower, even more preferably 130°C or lower, and even more preferably 120°C or lower. The reaction time of the substituted alkene production method of the present invention is preferably 30 minutes or more, more preferably 1 hour or more, and even more preferably 1.5 hours or more, from the viewpoint of improving production efficiency, and preferably 4 hours or less, more preferably 3 hours or less, and even more preferably 2.5 hours or less, from the viewpoint of suppressing isomerization of the obtained substituted alkene.

[0035] The completion of the reaction in the substituted alkene production method of the present invention can be determined by confirming the presence of the substituted alkyne in the reaction system. The presence or absence of the substituted alkyne can be confirmed, for example, by thin-layer chromatography. Alternatively, the amount of the substituted alkyne can be checked every 1 to 2 hours using gas chromatography, liquid chromatography, etc., and the reaction may be considered complete when the decrease in the amount of substituted alkyne stops changing or the change in the decrease becomes small.

[0036] After the reaction is complete, the reaction system is cooled to room temperature, and the reaction is stopped by adding an aqueous solution of alkali metal hydroxide. After thorough stirring, the substituted alkene obtained is extracted using an extraction solvent with a separatory funnel, dried, concentrated, and the resulting residue is purified by chromatography or the like to obtain the purified substituted alkene. Examples of alkali metal hydroxides include sodium hydroxide and potassium hydroxide. Examples of extraction solvents include water-insoluble organic solvents such as hexane, ethyl acetate, and toluene. Drying can be performed using, for example, sodium sulfate or magnesium sulfate. Examples of chromatography include gel permeation chromatography, silica gel column chromatography, and reversed-phase column chromatography, and gel permeation chromatography is preferred because it allows for the separation of the E- and Z-isomers of the obtained alkene.

[0037] [Method for reductively introducing substituents to substituted alkynes] The following describes a method for reductively introducing substituents to substituted alkynes using the complex of the present invention (hereinafter also referred to as "the substituent introduction method of the present invention"). The compound obtained in the substituent introduction method of the present invention is a compound in which substituents have been introduced to the above-mentioned substituted alkene. A substituent means a group other than a hydrogen atom, and the substituent to be introduced is preferably a group selected from halogen atoms, alkyl groups, and aromatic groups.

[0038] In the introduction of substituents to substituted alkynes using the complex of the present invention, the substituents and hydrogen atoms are introduced into the substituted alkyne, thereby obtaining a substituted alkene reductively. The introduction of substituents and hydrogen atoms into the substituted alkyne is thought to proceed by anti-addition, which is carried out from opposite sides of the carbon-carbon triple bond of the substituted alkyne. In the introduction of substituents to monosubstituted alkynes using the complex of the present invention, substituents are selectively introduced based on Markovnikov's rule. That is, when substituents are introduced into a monosubstituted alkyne, further substituents are introduced to the carbon to which the substituent of the alkyne is bonded, thereby selectively obtaining an exo-disubstituted alkene. Furthermore, in the introduction of substituents to a disubstituted alkyne in which one substituent is an aromatic group using the complex of the present invention, further substituents are introduced to the carbon to which the aromatic group is bonded.

[0039] The substituent introduction method of the present invention is carried out by mixing and stirring the complex of the present invention and the substituted alkyne in an organic solvent, and then further mixing and stirring the substrate corresponding to the substituent to be introduced. The organic solvent used in the substituent introduction method of the present invention is the same as the organic solvent used in the substituted alkene production method of the present invention described above, and the preferred organic solvent is also the same.

[0040] (Substitutive Alkynes) Examples of substituted alkynes used in the substituent introduction method of the present invention include the same substituted alkynes as those used in the substituted alkene production method of the present invention described above, and preferred substituted alkynes are also the same.

[0041] The substituents on substituted alkynes include aliphatic groups and aromatic groups. From the viewpoint of reactivity and stereoselective acquisition of substituted alkenes, it is preferable that at least one substituent on the substituted alkyne is an aromatic group.

[0042] (Substrate) The substrate used in the substituent introduction method of the present invention can be selected depending on the substituent to be introduced. For example, when introducing a halogen atom as a substituent, a halogenating agent can be used as the substrate. For example, when introducing an alkyl group as a substituent, an alkylating agent can be used as the substrate. For example, when introducing an aromatic group as a substituent, an aromatic halide, an aromatic triflate, etc. can be used as the substrate.

[0043] Examples of halogenating agents include elemental bromine and elemental iodine, N-chlorosuccinimide, N-bromosuccinimide, and N-iodosuccinimide.

[0044] Examples of alkylating agents include alkyl iodides such as methyl iodide, ethyl iodide, propyl iodide, butyl iodide, pentyl iodide, hexyl iodide, octyl iodide, and decyl iodide, as well as alkyl triflates such as methyl triflate, ethyl triflate, propyl triflate, butyl triflate, pentyl triflate, hexyl triflate, octyl triflate, and decyl triflate. Examples of aromatic groups contained in aromatic halides and aromatic triflates include aromatic hydrocarbon groups such as phenyl, naphthyl, and anthuryl groups, nitrogen-containing aromatic groups such as pyrrolyl, pyridinyl, pyridadinyl, pyrimidine, pyrazinyl, triazinyl, indolyl, and quinolyl groups, oxygen-containing aromatic groups such as furanyl and benzofuranyl groups, and sulfur-containing aromatic groups such as thiophenyl and benzothiophenyl groups. The halogen atoms in the aromatic halide are preferably bromine and iodine atoms, with iodine atoms being more preferred. The alkyl group in the alkylating agent, and the aromatic groups in the aromatic halide and aromatic triflate, may have substituents. Examples of substituents on the alkyl group in the alkylating agent include disubstituted amino groups, alkoxy groups, and thioalkyl groups. Examples of substituents on the aromatic groups in the aromatic halide and aromatic triflate include alkyl groups, disubstituted amino groups, alkoxy groups, and thioalkyl groups.

[0045] When introducing aromatic groups using the substituent introduction method of the present invention, a transition metal catalyst may be used. As the transition metal catalyst, for example, known transition metal catalysts used in so-called cross-coupling reactions can be used.

[0046] The mixing and stirring of the complex of the present invention and the substituted alkyne in an organic solvent can be carried out in the same manner as in the above-described method for producing a substituted alkene reductively from a substituted alkyne. In the substituent introduction method of the present invention, the molar ratio of the complex of the present invention to the substituted alkyne is preferably 1 mol or more, more preferably 1.5 mol or more, and even more preferably 1.8 mol or more, of the complex of the present invention per 1 mol of substituted alkyne, from the viewpoint of reaction efficiency, and from the viewpoint of economy, it is 4 mol or less, more preferably 3.5 mol or less, and even more preferably 3.2 mol or less.

[0047] The completion of the reaction between the complex of the present invention and the substituted alkyne can be confirmed in the same manner as the completion of the reaction in the above-described method for producing substituted alkenes of the present invention. After confirming the completion of the reaction between the complex of the present invention and the substituted alkyne, the substrate may be further mixed. Mixing may be performed by adding the substrate to a solution of the reaction product of the complex of the present invention and the substituted alkyne, or by adding a solution of the reaction product of the complex of the present invention and the substituted alkyne. The substrate may be used as a solution with an organic solvent.

[0048] The molar ratio of the reaction product between the complex of the present invention and the substituted alkyne to the substrate is, from the viewpoint of reaction efficiency, preferably 1 mol or more, more preferably 1.5 mol or more, and even more preferably 2 mol or more, per 1 mol of the theoretical value of the reaction product between the complex of the present invention and the substituted alkyne, when the substrate is a halogenating agent, and from the viewpoint of economic efficiency, preferably 5 mol or less, more preferably 4 mol or less, and even more preferably 3.5 mol or less. The molar ratio of the reaction product between the complex of the present invention and the substituted alkyne to the substrate is, from the viewpoint of reaction efficiency, preferably 1 mol or more, more preferably 2 mol or more, and even more preferably 4 mol or more, per 1 mol of the theoretical value of the reaction product between the complex of the present invention and the substituted alkyne, when the substrate is an alkylating agent, and from the viewpoint of economic efficiency, preferably 15 mol or less, more preferably 13 mol or less, and even more preferably 11 mol or less, The molar ratio of the reaction product between the complex of the present invention and the substituted alkyne to the substrate is, from the viewpoint of reaction efficiency, preferably 1 mol or more of the substrate per 1 mol of the theoretical value of the reaction product between the complex of the present invention and the substituted alkyne, when the substrate is an aromatic halide or aromatic triflate, and from the viewpoint of economy, preferably 2 mol or less, more preferably 1.5 mol or less, and even more preferably 1.2 mol or less.

[0049] The reaction temperature when the reaction product of the complex of the present invention and the substituted alkyne reacts with the substrate varies depending on the substrate used. When the substrate is a halogenating agent, the temperature is preferably 0°C to 30°C. When the substrate is an alkylating agent, the temperature is preferably 80°C or higher, more preferably 90°C or higher, even more preferably 100°C or higher, and preferably 140°C or lower, more preferably 130°C or lower, and even more preferably 125°C or lower. When the substrate is an aromatic halide or aromatic triflate, the temperature is preferably 50°C or higher, more preferably 60°C or higher, even more preferably 65°C or higher, and preferably 90°C or lower, more preferably 80°C or lower, and even more preferably 75°C or lower.

[0050] In the substituent introduction method of the present invention, the completion of the reaction can be determined by confirming the reaction product of the complex of the present invention and the substituted alkyne in the reaction system. The presence or absence of the reaction product of the complex of the present invention and the substituted alkyne can be confirmed, for example, by thin-layer chromatography. The reaction product of the complex of the present invention and the substituted alkyne can be confirmed on thin-layer chromatography as a substituted alkene obtained by the above-mentioned method for producing substituted alkenes. Alternatively, the amount of the reaction product of the complex of the present invention and the substituted alkyne (i.e., the substituted alkyne) can be checked every 1 to 2 hours using gas chromatography, liquid chromatography, etc., and the reaction may be considered complete when the decrease in the amount of the reaction product of the complex of the present invention and the substituted alkyne stops changing or the change in the decrease becomes small.

[0051] After the reaction is complete, the reaction system can be cooled to room temperature, and the reaction can be stopped by adding a suitable known quencher to each substrate to halt the reaction. Methods for extracting and purifying compounds in which substituents have been introduced to substituted alkenes are the same as those used in the extraction and purification methods for substituted alkenes in the present invention described above.

[0052] In the following examples, various physical properties were measured by the following methods.

[0053] <Equipment used for compound identification and analysis> (Nuclear Magnetic Resonance Spectrometer (NMR)) ・AVANCE 500 (Bruker) ・AVANCE 500T (Bruker) ・AVANCE 400 (Bruker) ・AVANCE 300 (Bruker) Chemical shift correction is performed when deuterated chloroform solvent is used as the deuterated solvent. １ ¹H-NMR is used to analyze the protons of chloroform in deuterated chloroform. １ The peak of H) is set to the reference level of 7.26 ppm. １３ In C-NMR, the carbon of deuterated chloroform ( １３ When peak C is set to a reference of 77.0 ppm and deuterated benzene solvent is used as the deuterated solvent, １ 1H-NMR is used to analyze benzene protons ( １ The peak of H) is set to the reference level of 7.16 ppm. １３ In C-NMR, the carbon of heavy benzene ( １３The peak at C) was set to a reference level of 128.0 ppm. The NMR measurement of the complex of cesium fluoride and diisobutylaluminum hydride was performed by sealing the reference compound in the inner container of a double-walled tube and the complex dissolved in diethylene glycol dimethyl ether in the outer container. The reference compound was: １ In 1H-NMR, heavy water is used, and the hydrogen in heavy water ( １ Set the peak of H) to 4.81 ppm. １９ F-NMR shows didimethyl sulfoxide (DMSO-d ６ Using perfluorobenzene dissolved in ), the fluorine of perfluorobenzene ( １９ The peak of F) is set to the baseline of 164.9 ppm. ２７ Al-NMR shows heavy water (D ２ Using aluminum nitrate dissolved in O), the aluminum of aluminum nitrate ( ２７ The peak of Al was set as the baseline of 0.00 ppm.

[0054] <Example 1> A complex of an alkali metal fluoride salt and an aluminum compound represented by general formula (1) was prepared by the method shown below.

[0055] Example 1-1 (Preparation of a hexane suspension of a complex of cesium fluoride and diisobutylaluminum hydride) Cesium fluoride (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) (121.5 mg, 0.80 mmol) was weighed into a 10 mL reaction vessel and dried by stirring at 100°C for 1 hour under reduced pressure using a vacuum pump. After the reaction vessel was subjected to an argon atmosphere, it was cooled to room temperature and diisobutylaluminum hydride (reagent, 1 M hexane solution, manufactured by Tokyo Chemical Industry Co., Ltd.) (0.8 mL, 0.8 mmol) was added. By stirring at room temperature for 30 minutes, a white complex of cesium fluoride and diisobutylaluminum hydride was obtained as a hexane suspension. Immediately after adding diisobutylaluminum hydride, precipitation of cesium fluoride was observed when stirring was stopped, but after stirring for 30 minutes, no precipitation was observed even when stirring was stopped.

[0056] The hexane was removed from a hexane suspension of a complex of cesium fluoride and diisobutylaluminum hydride under reduced pressure, and the complex was dissolved in dehydrated debenzene with metallic sodium. NMR was then measured. Similarly, diisobutylaluminum hydride was dissolved in dehydrated debenzene with metallic sodium, and NMR was measured. The NMR data for the complex of cesium fluoride and diisobutylaluminum hydride are shown below. １ H-NMR (300MHz, C ６ D ６ , δ ｐｐｍ ): 2.30-2.15 (m, 2H, CH x 2), 1.40-1.30 (d, 12H, CH ３ ×4), 0.86 (d, J=6.6Hz, 1H, Al-H), 0.13-0.01 (m, 4H, CH ２ ×2) The NMR data for diisobutylaluminum hydride is shown below. １ H-NMR (300MHz, C ６ D ６ , δ ｐｐｍ ): 3.07 (br s, 1H, Al-H), 2.09-1.97 (m, 2H, CH x 2), 1.08 (d, J = 6.6Hz, 12H, CH ３ ×4), 0.47 (d, J=6.9Hz, 4H, CH ２ (x2)

[0057] Comparing the NMR data of the complex of cesium fluoride and diisobutylaluminum hydride with the NMR data of diisobutylaluminum hydride, it can be seen that the chemical shift of the methylene proton on the carbon bonded to the aluminum atom was shifted at a high field. This is thought to be because the formation of the complex between cesium fluoride and diisobutylaluminum hydride made the aluminum atom electron-rich, shielding the methylene proton on the carbon bonded to the aluminum atom, thus causing the chemical shift of the methylene proton to shift at a high field. In addition, the shape of the methylene proton peak changed from a double line (d) to a multiple line (m). This is thought to be due to the coupling of the methylene proton with the fluorine atom coordinated to the aluminum atom upon the formation of the complex between cesium fluoride and diisobutylaluminum hydride. Furthermore, it can be seen that the chemical shift of the proton bonded to the aluminum atom was shifted at a high field. In addition, the NMR data for the complex of cesium fluoride and diisobutylaluminum hydride showed a double-line peak shape for the hydrogen atom on the aluminum atom. This is thought to be because the formation of the complex between cesium fluoride and diisobutylaluminum hydride resulted in the coupling of the hydrogen atom on the aluminum atom with the fluorine atom coordinated to the aluminum atom.

[0058] A suspension of cesium fluoride in diethylene glycol dimethyl ether １９ When F-NMR was measured, cesium fluoride did not dissolve in diethylene glycol dimethyl ether, therefore fluorine ( １９ Although the peak F) was not observed, when a hexane solution of diisobutylaluminum hydride was added, fluorine was added to -153.1 ppm, -160.6 ppm, -168.4 ppm, -172.8 ppm, and -177.1 ppm. １９ A peak F) appeared. This is because cesium fluoride and diisobutylaluminum hydride form a complex, and fluorine ( ) originates from the cesium fluoride in the complex dissolved in diethylene glycol dimethyl ether. １９This is thought to be because peak F) was observed. Similarly, the diethylene glycol dimethyl ether suspension of diisobutylaluminum hydride ２７ Al-NMR measurements showed that diisobutylaluminum hydride does not dissolve in diethylene glycol dimethyl ether, therefore aluminum ( ２７ Although no peak for Al was observed, when cesium fluoride was added, aluminum ( ) was detected at 122.4 ppm and 137.4 ppm. ２７ A peak of Al appeared. This is due to the formation of a complex between cesium fluoride and diisobutylaluminum hydride, resulting in aluminum (Al) originating from the diisobutylaluminum hydride in the complex dissolved in diethylene glycol dimethyl ether. ２７ This is thought to be because a peak in Al was observed.

[0059] Example 1-2 (Preparation of a complex of sodium fluoride and diisobutylaluminum hydride) Sodium fluoride (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) (33.6 mg, 0.80 mmol) was weighed into a 10 mL reaction vessel. After the reaction vessel was subjected to an argon atmosphere, diisobutylaluminum hydride (reagent, 1 M hexane solution, manufactured by Tokyo Chemical Industry Co., Ltd.) (0.8 mL, 0.8 mmol) was added at room temperature. By stirring at room temperature for 30 minutes, a white complex of sodium fluoride and diisobutylaluminum hydride was obtained as a hexane suspension. Immediately after adding diisobutylaluminum hydride, precipitation of sodium fluoride was observed when stirring was stopped, but after stirring for 30 minutes, no precipitation was observed even when stirring was stopped.

[0060] Examples 1-3 (Preparation of a complex of potassium fluoride and diisobutylaluminum hydride) Potassium fluoride (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) (46.5 mg, 0.80 mmol) was weighed into a 10 mL reaction vessel. After the reaction vessel was subjected to an argon atmosphere, diisobutylaluminum hydride (reagent, 1 M hexane solution, manufactured by Tokyo Chemical Industry Co., Ltd.) (0.8 mL, 0.8 mmol) was added at room temperature. By stirring at room temperature for 30 minutes, a white complex of sodium fluoride and diisobutylaluminum hydride was obtained as a hexane suspension. Immediately after adding diisobutylaluminum hydride, precipitation of potassium fluoride was observed when stirring was stopped, but after stirring for 30 minutes, no precipitation was observed even when stirring was stopped.

[0061] <Manufacturing Examples> The manufacturing methods and NMR data for the substituted alkynes used as raw materials in Examples 2 to 5 below are shown.

[0062] Manufacturing Example 1: Manufacturing of 4-ethynylbiphenyl Based on the description in ACS Nano, 10(7), 7023-7030, 2016, 4-bromoviphenyl (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) and trimethylsilylacetylene (reagent, manufactured by Junsei Chemical Co., Ltd.) was used to manufacture 4-[2-(trimethylsilyl)ethynyl]-1,1'-biphenyl. Subsequently, based on the description in Angewandte Chemie, International Edition, 62, e202312633, 2023, 4-ethynylbiphenyl was manufactured from 4-[2-(trimethylsilyl)ethynyl]-1,1'-biphenyl. The NMR data for 4-ethynylbiphenyl is shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ ): 7.65-7.59 (m, 6H), 7.52-7.47 (m, 2H), 7.44-7.39 (m, 1H), 3.19 (s, 1H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 141.5, 140.2, 132.5, 128.8, 127.7, 127.0, 126.9, 120.9, 83.5, 77.8.

[0063] Manufacturing Example 2: Production of 1-phenyl-1-decine Based on the description in Angewandte Chemie, International Edition, 44, 6863-6866, 2005, 1-phenyl-1-decine was produced from iodobenzene (reagent, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 1-decine (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.). The NMR data for 1-phenyl-1-decine is shown below. １ H-NMR (300MHz, CDCl ３ , δ ｐｐｍ ): 7.41-7.37 (m, 2H), 7.29-7.26 (m, 3H), 2.40 (t, J=6.9Hz, 2H), 1.65-1. 55 (m, 2H), 1.47-1.40 (m, 2H), 1.40-1.22 (m, 8H), 0.89 (t, J=7.2Hz, 3H). １３ C-NMR (125MHz, CDCl ３ , δ ｐｐｍ ): 131.5, 128.2, 127.4, 124.1, 90.5, 80.5, 31.8, 29.2, 29.1, 28.9, 28.8, 22.7, 19.4, 14.1.

[0064] Manufacturing Example 3: Production of 1-phenyl-1-hexine Based on the description in Tetrahedron Letters, 54, 6874-6877, 2013, 1-phenyl-1-hexine was produced from iodobenzene (reagent, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 1-hexine (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.). The NMR data for 1-phenyl-1-hexine is shown below. １ H-NMR (500MHz, CDCl ３ , δ ｐｐｍ ): 7.40-7.37 (m, 2H), 7.30-7.25 (m, 3H), 2.42 (t, J = 7.0Hz, 2H), 1.62-1.57 (m, 2H), 1.54-1.46 (m, 2H), 0.95 (t, J = 7.0Hz, 3H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 131.5, 128.2, 127.4, 124.1, 90.4, 80.5, 30.9, 22.0, 19.1, 13.6.

[0065] Production Example 4 Production of 1-Phenyl-1-pentyne Referring to the description in Angewandte Chemie, International Edition, 44, 6863-6866, 2005, 1-phenyl-1-pentyne was produced from iodobenzene (reagent, manufactured by FUJIFILM Wako Pure Chemical Corporation) and 1-pentyne (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.). The NMR data of 1-phenyl-1-pentyne are shown below. １ H-NMR (400 MHz, CDCl ３ , δ ｐｐｍ ): 7.43 - 7.40 (m, 2H), 7.31 - 7.26 (m, 3H), 2.40 (t, J = 7.2 Hz, 2H), 1.69 - 1.60 (m, 2H), 1.07 (t, J = 7.2 Hz, 3H). １３ C-NMR (100 MHz, CDCl ３ , δ ｐｐｍ ): 131.5, 128.2, 127.4, 124.1, 90.2, 80.7, 22.2, 21.4, 13.5.

[0066] Production Example 5 Production of 1-Phenyl-1-octyne Referring to the description in Angewandte Chemie, International Edition, 44, 6863-6866, 2005, 1-phenyl-1-octyne was produced from iodobenzene (reagent, manufactured by FUJIFILM Wako Pure Chemical Corporation) and 1-octyne (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.). The NMR data of 1-phenyl-1-octyne are shown below. １ H-NMR (400 MHz, CDCl ３ , δ ｐｐｍ ): 7.40 - 7.37 (m, 2H), 7.29 - 7.26 (m, 3H), 2.40 (t, J = 7.2 Hz, 2H), 1.64 - 1.56 (m, 2H), 1.50 - 1.42 (m, 2H), 1.36 - 1.30 (m, 4H), 0.91 (t, J = 6.8 Hz, 3H). １３ C-NMR (100 MHz, CDCl ３ , δ ｐｐｍ ): 131.5, 128.2, 127.4, 124.1, 90.5, 80.5, 31.4, 28.7, 28.6, 22.6, 19.4, 14.0.

[0067] Manufacturing Example 6: Manufacturing of (phenylethynyl)cyclohexane Based on the description in Angewandte Chemie, International Edition, 44, 6863-6866, 2005, (phenylethynyl)cyclohexane was manufactured from iodobenzene (reagent, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and ethynylcyclohexane (reagent, manufactured by Sigma-Aldrich Japan LLC). The NMR data for (phenylethynyl)cyclohexane is shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ ): 7.42-7.38 (m, 2H), 7.30-7.24 (m, 3H), 2.62-2.56 (m, 1H), 1.93-1.86 (m, 2H), 1.81-1.73 (m, 2H), 1.60-1.50 (m, 3H), 1.41-1.31 (m, 3H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 131.6, 128.1, 127.4, 124.1, 94.4, 80.5, 32.7, 29.7, 25.9, 24.9.

[0068] Manufacturing Example 7: Manufacturing of 3,3-dimethyl-1-butyne-1-ylbenzene Trimethylsilylethynylbenzene was manufactured from iodobenzene (reagent, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and trimethylsilylacetylene (reagent, manufactured by Junsei Chemical Co., Ltd.), based on the description in Angewandte Chemie, International Edition, 44, 6863-6866, 2005. 3,3-dimethyl-1-butyne-1-ylbenzene was manufactured from 2-methyl-2-chloropropane (reagent, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and trimethylsilylethynylbenzene, based on the description in Org. Lett., 18, 3937-3939, 2016. NMR data for 3,3-dimethyl-1-butyne-1-ylbenzene are shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ ): 7.39-7.36 (m, 2H), 7.29-7.24 (m, 3H), 1.32 (s, 9H). １３ C-NMR (100MHz, CDCl３ , δ ｐｐｍ ): 131.5, 128.1, 127.4, 124.1, 98.5, 79.0, 31.1, 27.9.

[0069] Manufacturing Example 8: Preparation of 1-(4-methylphenyl)-1-hexine Based on the description in Chemical Communications, 60, 1719-1722, 2024, 1-(4-methylphenyl)-1-hexine was prepared from 4-iodotoluene (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) and 1-hexine (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.). The NMR data for 1-(4-methylphenyl)-1-hexine is shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ ): 7.28 (d, J = 8.0 Hz, 2H), 7.08 (d, J = 8.0 Hz, 2H), 2.40 (t, J = 6.8 Hz, 2H), 2 .33 (s, 3H), 1.62-1.55 (m, 2H), 1.51-1.45 (m, 2H), 0.95 (t, J=7.6Hz, 3H). １３ C-NMR (125MHz, CDCl ３ , δ ｐｐｍ ): 137.4, 131.4, 128.9, 121.0, 89.5, 80.5, 30.9, 22.0, 21.3, 19.1, 13.6.

[0070] Manufacturing Example 9: Preparation of 1-(4-trifluoromethylphenyl)-1-hexine Based on the description in Chemistry—An Asian Journal, 9, 3005-3010, 2014, 1-(4-trifluoromethylphenyl)-1-hexine was prepared from 4-bromobenzotrifluoride (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) and 1-hexine (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.). The NMR data for 1-(4-trifluoromethylphenyl)-1-hexine is shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ ): 7.53 (d, J = 8.4 Hz, 2H), 7.48 (d, J = 8.4 Hz, 2H), 2.43 (t, J = 6.8 Hz, 2H), 1.62-1.56 (m, 2H), 1.51-1.45 (m, 2H), 0.96 (t, J=7.2Hz, 3H).１３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 131.8, 129.2 (q, ２ J Ｃ－Ｆ =32.2Hz), 128.0, 125.1(q, ３ J Ｃ－Ｆ =4.0Hz), 124.0(q, １ J Ｃ－Ｆ =272.6Hz), 93.3, 79.5, 30.6, 22.0, 19.1, 13.6.

[0071] Manufacturing Example 10: Preparation of 1-(4-bromophenyl)-1-hexine Based on the description in Org. Lett., 5, 1451-1454, 2003, 1-(4-bromophenyl)-1-hexine was prepared from 1-bromo-4-iodobenzene (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) and 1-hexine (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.). The NMR data for 1-(4-bromophenyl)-1-hexine is shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ ): 7.40 (d, J = 8.4 Hz, 2H), 7.24 (d, J = 8.4 Hz, 2H), 2.39 (t, J = 6.8 Hz, 2H), 1.62-1.55 (m, 2H), 1.52-1.42 (m, 2H), 0.95 (t, J=7.6Hz, 3H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 133.0, 131.4, 123.1, 121.5, 91.7, 79.6, 30.7, 22.0, 19.1, 13.6.

[0072] Manufacturing Example 11: Preparation of 1-(3-bromophenyl)-1-hexine Based on the description in Angewandte Chemie, International Edition, 44, 6863-6866, 2005, 1-(3-bromophenyl)-1-hexine was prepared from 1-bromo-3-iodobenzene (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) and 1-hexine (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.). The NMR data for 1-(3-bromophenyl)-1-hexine is shown below. １ H-NMR (400MHz, CDCl３ , δ ｐｐｍ ): 7.54 (t, J = 1.6 Hz, 1H), 7.39 (d, J = 8.0 Hz, 1H), 7.31 (d, J = 8.0 Hz, 1H), 7.14 (dd, J = 8.0, 8.0 Hz, 1H), 2.40 (t, J = 6.8Hz, 2H), 1.62-1.55 (m, 2H), 1.52-1.42 (m, 2H), 0.95 (t, J = 7.2Hz, 3H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 134.3, 130.6, 130.1, 129.6, 126.1, 122.0, 92.0, 79.2, 30.7, 22.0, 19.0, 13.6.

[0073] Manufacturing Example 12: Production of 1-(4-chlorophenyl)-1-hexine Based on the description in Org. Lett., 5, 1451-1454, 2003, 1-(4-chlorophenyl)-1-hexine was produced from 1-chloro-4-iodobenzene (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) and 1-hexine (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.). The NMR data for 1-(4-chlorophenyl)-1-hexine is shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ ): 7.32-7.29 (m, 2H), 7.26-7.23 (m, 2H), 2.40 (t, J=7.2Hz, 2H), 1.62-1.54 (m, 2H), 1.52-1.42 (m, 2H), 0.95 (s, 3H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 133.3, 132.7, 128.4, 122.6, 91.5, 79.5, 30.7, 22.0, 19.1, 13.6.

[0074] Manufacturing Example 13: Preparation of 1-(2-chlorophenyl)-1-hexine Based on the description in Eur. J. Org. Chem., 68, 2888-2902, 2003, 1-(2-chlorophenyl)-1-hexine was prepared from 1-chloro-2-iodobenzene (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) and 1-hexine (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.). The NMR data for 1-(2-chlorophenyl)-1-hexine is shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ ): 7.44-7.41 (m, 1H), 7.38-7.35 (m, 1H), 7.21-7.14 (m, 2H), 2.48 (t, J = 6 .8Hz, 2H), 1.66-1.59 (m, 2H), 1.56-1.47 (m, 2H), 0.96 (t, J=7.2Hz, 3H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 135.7, 133.3, 129.1, 128.4, 126.3, 123.9, 96.1, 77.5, 30.7, 21.9, 19.3, 13.6.

[0075] Manufacturing Example 14: Preparation of 1-(3-chlorophenyl)-1-hexine Based on the description in Chemical Communications, 55, 10623-10626, 2019, 1-(3-chlorophenyl)-1-hexine was prepared from 1-chloro-3-iodobenzene (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) and 1-hexine (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.). The NMR data for 1-(3-chlorophenyl)-1-hexine is shown below. １ H-NMR (500MHz, CDCl ３ , δ ｐｐｍ ): 7.37 (s, 1H), 7.27-7.18 (m, 3H), 2.40 (t, J = 7.0Hz, 2H), 1.62-1.55 (m, 2H), 1.51-1.43 (m, 2H), 0.95 (t, J = 7.5Hz, 3H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ): 134.0, 131.5, 129.7, 129.4, 127.7, 125.9, 91.9, 79.3, 30.7, 22.0, 19.1, 13.6.

[0076] Manufacturing Example 15: Preparation of 1-(2-fluorophenyl)-1-hexine Based on the description in Angewandte Chemie, International Edition, 44, 6863-6866, 2005, 1-(2-fluorophenyl)-1-hexine was prepared from 1-fluoro-2-iodobenzene (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) and 1-hexine (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.). The NMR data for 1-(2-fluorophenyl)-1-hexine is shown below. １ H-NMR (500MHz, CDCl ３ , δ ｐｐｍ ): 7.39 (ddd, J=7.5, 7.5, 1.5Hz, 1H), 7.26-7.21 (m, 1H), 7.07-7.02 (m, 2H), 2.4 6 (t, J=7.0Hz, 2H), 1.64-1.58 (m, 2H), 1.53-1.45 (m, 2H), 0.95 (t, J=7.5Hz, 3H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ):162.8(d, １ J Ｃ－Ｆ =249.5Hz), 133.5, 129.0(d, ３ J Ｃ－Ｆ =8.0Hz), 123.7(d, ３ J Ｃ－Ｆ =4.0Hz), 115.3(d, ２ J Ｃ－Ｆ =22.1Hz), 112.6(d, ３ J Ｃ－Ｆ =16.1Hz), 95.9, 73.8, 30.7, 22.0, 19.3, 13.6.

[0077] Manufacturing Example 16: Manufacturing of 1-(3,5-dichlorophenyl)-1-hexine Based on the description in Angewandte Chemie, International Edition, 44, 6863-6866, 2005, 1-(3,5-dichlorophenyl)-1-hexine was manufactured from 1,3-dichloro-5-iodobenzene (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) and 1-hexine (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.). The NMR data for 1-(3,5-dichlorophenyl)-1-hexine is shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ ): 7.263 (s, 2H), 7.259 (s, 1H), 2.40 (t, J = 6.8Hz, 2H), 1.62-1.54 (m, 2H), 1.51-1.42 (m, 2H), 0.95 (t, J = 7.2Hz, 3H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 134.6, 129.8, 127.8, 127.0, 93.3, 78.3, 30.5, 22.0, 19.0, 13.6.

[0078] Manufacturing Example 17: Manufacturing of 1-(4-n-butoxyphenyl)-1-hexine Referring to the description in Chemical Communications, 2756-2758, 2009, 1-n-butoxy-4-iodobenzene was manufactured from 4-iodophenol (reagent, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 1-bromobutane (reagent, manufactured by Tokyo Chemical Industries, Ltd.). Subsequently, referring to the description in Angewandte Chemie, International Edition, 62, e202310436, 2023, 1-(4-n-butoxyphenyl)-1-hexine was manufactured from 1-n-butoxy-4-iodobenzene and 1-hexine (reagent, manufactured by Tokyo Chemical Industries, Ltd.). The NMR data for 1-(4-n-butoxyphenyl)-1-hexine is shown below. １ H-NMR (500MHz, CDCl ３ , δ ｐｐｍ): δ7.31 (dd, J=6.5, 2.0Hz, 2H), 6.79 (dd, J=6.5, 2.0Hz, 2H), 3.94 (t, J=6.5Hz, 2H), 2.39 (t, J=7.0Hz, 2H) ), 1.78-1.72 (m, 2H), 1.61-1.55 (m, 2H), 1.52-1.44 (m, 4H), 0.97 (t, J = 7.5Hz, 3H), 0.94 (t, J = 7.5Hz, 3H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 158.6, 132.8, 116.0, 114.4, 88.6, 80.3, 67.7, 31.3, 31.0, 22.0, 19.2, 19.1, 13.8, 13.6.

[0079] Manufacturing Example 18: Manufacturing of 1-(3-n-butoxyphenyl)-1-hexine Referring to the description in Chemical Communications, 2756-2758, 2009, 1-n-butoxy-3-iodobenzene was manufactured from 3-iodophenol (reagent, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 1-bromobutane (reagent, manufactured by Tokyo Chemical Industries, Ltd.). Subsequently, referring to the description in Angewandte Chemie, International Edition, 62, e202310436, 2023, 1-(3-n-butoxyphenyl)-1-hexine was manufactured from 1-n-butoxy-3-iodobenzene and 1-hexine (reagent, manufactured by Tokyo Chemical Industries, Ltd.). The NMR data for 1-(3-n-butoxyphenyl)-1-hexine is shown below. １ H-NMR (500MHz, CDCl ３ , δ ｐｐｍ ): δ7.16 (dd, J=8.0, 8.0Hz, 1H), 6.97 (d, J=7.5Hz, 1H), 6.92 (s, 1H), 6.81 (dd, J=8.0, 2.5Hz, 1H), 3.94 (t, J=6.5Hz, 2H), 2 .40 (t, J=7.0, 2H), 1.78-1.72 (m, 2H), 1.62-1.55 (m, 2H), 1.52-1.44 (m, 4H), 0.97 (t, J=7.5Hz, 3H), 0.95 (t, J=7.5Hz, 3H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ): 158.9, 129.1, 125.0, 123.9, 117.1, 114.6, 90.1, 80.5, 67.7, 31.3, 30.8, 22.0, 19.2, 19.1, 13.8, 13.6.

[0080] Manufacturing Example 19: Manufacturing of 2-(1-hexynyl)benzo[b]thiophene Based on the description in Organic & Biomolecular Chemistry, 21, 3844-3849, 2023, 2-(1-hexynyl)benzo[b]thiophene was manufactured from 2-iodobenzothiophene (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) and 1-hexyn (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.). The NMR data for 2-(1-hexynyl)benzo[b]thiophene is shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ ): 7.75-7.68 (m, 2H), 7.34-7.31 (m, 3H), 2.47, (t, J = 7.2Hz, 2H), 1.66-1.58 (m, 2H), 1.53-1.44 (m, 2H), 0.96 (t, J = 7.6Hz, 3H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 139.8, 139.2, 127.6, 125.0, 124.5, 124.3, 123.5, 121.9, 96.7, 74.1, 30.5, 22.0, 19.5, 13.6.

[0081] Manufacturing Example 20: Manufacturing of 2-(1-hexynyl)benzo[b]furan Referring to the description in Organic Letters, 23, 4888-4892, 2021, 2-iodobenzo[b]furan was manufactured from 2,3-benzofuran (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) and iodine (reagent, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). Subsequently, referring to the description in Chem. Sci., 13, 7873, 2021, 2-(1-hexynyl)benzo[b]furan was manufactured from 2-iodobenzo[b]furan and 1-hexine (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.). The NMR data for 2-(1-hexynyl)benzo[b]furan is shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ): 7.52 (d, J = 7.6 Hz, 1H), 7.42 (dd, J = 8.0, 0.8 Hz, 1H), 7.29 (ddd, J = 7.2, 7.2, 1.2 Hz, 1H), 7.21 (ddd, J = 7.2, 7.2 , 0.8Hz, 1H), 6.81 (s, 1H), 2.50 (t, J = 7.2Hz, 2H), 1.67-1.60 (m, 2H), 1.55-1.45 (m, 2H), 0.96 (t, J = 7.2Hz, 3H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 154.5, 139.3, 127.8, 125.0, 123.0, 120.9, 111.0, 110.0, 97.0, 71.2, 30.3, 22.0, 19.3, 13.6.

[0082] Manufacturing Example 21: Manufacturing of 4-(1-hexynyl)-1,1'-biphenyl Based on the description in Angewandte Chemie, International Edition, 55(15), 4808-4813, 2016, 4-(1-hexynyl)-1,1'-biphenyl was manufactured from 4-bromoviphenyl (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) and 1-hexyn (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.). The NMR data for 4-(1-hexynyl)-1,1'-biphenyl is shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ ): 7.58 (d, J = 8.4 Hz, 2H), 7.52 (d, J = 8.4 Hz, 2H), 7.47-7.41 (m, 4H), 7.36-7.32 (m, 1H) , 2.44 (t, J=6.8Hz, 2H), 1.65-1.57 (m, 2H), 1.55-1.45 (m, 2H), 0.97 (t, J=7.6Hz, 3H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 140.5, 140.2, 131.9, 128.8, 127.4, 126.9, 126.8, 123.1, 91.1, 80.4, 30.9, 22.0, 19.2, 13.6.

[0083] Manufacturing Example 22: Manufacturing of 1-(2-naphthyl)-1-hexine Based on the description in Angewandte Chemie, International Edition, 55, 4808-4813, 2016, 1-(2-naphthyl)-1-hexine was manufactured from 2-bromonaphthalene (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) and 1-hexine (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.). The NMR data for 1-(2-naphthyl)-1-hexine is shown below. １ H-NMR (500MHz, CDCl ３ , δ ｐｐｍ ): 7.90 (s, 1H), 7.80-7.73 (m, 3H), 7.48-7.43 (m, 3H), 2.47 (t, J = 7.2 Hz, 2H), 1.67-1.60 (m, 2H), 1.57-1.47 (m, 2H), 0.98 (t, J=7.2Hz, 3H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 133.1, 132.4, 131.0, 128.7, 127.8, 127.6, 127.5, 126.3, 126.2, 121.5, 90.8, 80.9, 30.9, 22.1, 19.2, 13.6.

[0084] Manufacturing Example 23: Manufacturing of 1-(1-naphthyl)-1-hexine Based on the description in Angewandte Chemie, International Edition, 62, e202310436, 2023, 1-(1-naphthyl)-1-hexine was manufactured from 1-iodonaphthalene (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) and 1-hexine (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.). The NMR data for 1-(1-naphthyl)-1-hexine is shown below. １ H-NMR (500MHz, CDCl ３ , δ ｐｐｍ ): 8.35 (d, J = 8.4Hz, 1H), 7.84 (d, J = 7.6Hz, 1H), 7.78 (d, J = 8.4Hz, 1H), 7.63 (d, J = 7.2Hz, 1H), 7.58-7.48 (m, 2H), 7.40 (dd, J=8.0, 7.2Hz, 1H), 2.59 (t, J=6.8Hz, 2H), 1.75-1.67 (m, 2H), 1.63-1.52 (m, 2H), 1.01 (t, J=7.2Hz, 3H).１３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 133.5, 133.2, 130.0, 128.2, 127.8, 126.4, 126.3, 126.2, 125.2, 121.8, 95.5, 78.6, 31.0, 22.1, 19.4, 13.7.

[0085] Manufacturing Example 24: Preparation of 6-phenyl-2-hexine Based on the description in Eur. J. Org. Chem. 35, 5839-5844, 2016, 6-phenyl-2-hexine was prepared from 5-phenyl-1-pentine (reagent, manufactured by Sigma-Aldrich Japan LLC) and methyl iodide (reagent, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). The NMR data for 6-phenyl-2-hexine is shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ ): 7.30-7.26 (m, 2H), 7.20-7.16 (m, 3H), 2.71 (t, J=7.6Hz, 2H), 2.17-2.12 (m, 2H), 1.83-1.76 (m, 5H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 141.9, 128.5, 128.3, 125.8, 78.8, 75.9, 34.8, 30.6, 18.2, 3.5.

[0086] Manufacturing Example 25: Production of Diphenylacetylene Based on the description in Current Organic Chemistry, 17, 1051-1057, 2013, diphenylacetylene was produced from 1-iodobenzene (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) and ethynylbenzene (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.). The NMR data for diphenylacetylene is shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ ): 7.56-7.52 (m, 4H), 7.38-7.31 (m, 6H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 131.6, 128.3, 128.2, 123.3, 89.4.

[0087] Manufacturing Example 26: Manufacturing of 1-Butoxy-4-[(4-chlorophenyl)ethynyl]benzene Referring to the description in ACS Nano, 10(7), 7023-7030, 2016, 1-butoxy-4-trimethylsilylethynylbenzene was manufactured from 1-butoxy-4-iodobenzene (reagent, Combi-Blocks) and trimethylsilylacetylene (reagent, Junsei Chemical Co., Ltd.). Subsequently, referring to the description in Angewandte Chemie, International Edition, 62, e202312633, 2023, 1-butoxy-4-ethynylbenzene was manufactured from 1-butoxy-4-trimethylsilylethynylbenzene. Furthermore, with reference to the description in Current Organic Chemistry, 17, 1051-1057, 2013, 1-butoxy-4-[(4-chlorophenyl)ethynyl]benzene was prepared from 1-chloro-4-iodobenzene (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) and 1-butoxy-4-ethynylbenzene. The NMR data for 1-butoxy-4-[(4-chlorophenyl)ethynyl]benzene is shown below. １ H-NMR (500MHz, CDCl ３ , δ ｐｐｍ ): 7.47 (d, J = 9.0 Hz, 2H), 7.45 (d, J = 8.5 Hz, 2H), 7.33 (d, J = 8.5 Hz, 2H), 6.89 (d, J = 8.5 Hz, 2H), 3.98 (t, J=6.5Hz, 2H), 1.83-1.77 (m, 2H), 1.55-1.50 (m, 2H), 1.01 (t, J=7.5Hz, 3H). １３ C-NMR (125.77MHz, CDCl ３ , δ ｐｐｍ ): 159.4, 133.8, 133.0, 132.6, 128.6, 122.2, 114.7, 114.6, 90.5, 86.9, 67.8, 31.2, 19.2, 13.8.

[0088] Manufacturing Example 27: Production of 1-(phenylethynyl)naphthalene Based on the description in Journal of the American Chemical Society, 132, 7905-7907, 2010, 1-(phenylethynyl)naphthalene was produced from 1-iodonaphthalene (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) and ethynylbenzene (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.). The NMR data for 1-(phenylethynyl)naphthalene is shown below. １ H-NMR (500MHz, CDCl ３ , δ ｐｐｍ ): 8.45 (d, J = 8.0 Hz, 1H), 7.87 (d, J = 8.0 Hz, 1H), 7.85 (d, J = 8.5 Hz, 1H), 7.77 (d, J = 7.0 Hz, 1H), 7.67- 7.64 (m, 2H), 7.62-7.58 (m, 1H), 7.56-7.52 (m, 1H), 7.47 (dd, J=7.5, 7.5Hz, 1H), 7.42-7.36 (m, 3H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 133.3, 133.2, 131.7, 130.4, 128.7, 128.4, 128.4, 128.3, 126.8, 126.4, 126.2, 125.3, 123.4, 120.9, 94.3, 87.5.

[0089] Manufacturing Example 28: Production of 1,4-diphenyl-1,3-butadiine Based on the description in Tetrahedron, 73, 5023-5028, 2017, 1,4-diphenyl-1,3-butadiine was produced from ethinylbenzene (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.). The NMR data for 1,4-diphenyl-1,3-butadiine is shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ ): 7.55-7.52 (m, 4H), 7.40-7.32 (m, 6H). １３ C-NMR (125MHz, CDCl ３ , δ ｐｐｍ ): 132.5, 129.2, 128.4, 121.8, 81.5, 73.9.

[0090] Production Example 29 3-Butoxy-1-iodobenzene was produced from 3-iodophenol (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) and 1-bromobutane (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) by Williamson ether synthesis of 1-ethynyl-3-butoxybenzene. Subsequently, 1-[2-(trimethylsilyl)ethynyl]-3-butoxybenzene was produced from 3-butoxy-1-iodobenzene and trimethylsilylacetylene (reagent, manufactured by Junsei Chemical Co., Ltd.), referring to the description in ACS Nano, 10(7), 7023-7030, 2016. Furthermore, with reference to the description in Angewandte Chemie, International Edition, 62, e202312633, 2023, 1-ethynyl-3-butoxybenzene was prepared from 1-[2-(trimethylsilyl)ethynyl]-3-butoxybenzene. The NMR data for 1-ethynyl-3-butoxybenzene is shown below. １ H-NMR (500MHz, CDCl ３ , δ ｐｐｍ ): 7.21 (dd, J=8.0, 8.0Hz, 1H), 7.08-7.05 (m, 1H), 7.02-7.01 (m, 1H), 6.91-6.88 (m, 1H), 3.9 5 (t, J=6.5Hz, 2H), 3.05 (s, 1H), 1.79-1.73 (m, 2H), 1.52-1.44 (m, 2H), 0.97 (t, J=7.5Hz, 3H). １３ C-NMR (125MHz, CDCl ３ , δ ｐｐｍ ): 158.8, 129.3, 124.4, 123.0, 117.6, 115.9, 83.6, 76.8, 67.7, 31.2, 19.2, 13.8.

[0091] Production Example 30 2-bromo-4-chloro-1-ethynylbenzene was produced from 2-bromo-4-chloroaniline (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) by the Sandmeyer reaction. Subsequently, 2-bromo-4-chloro-1-trimethylsilylethynylbenzene was produced from 2-bromo-4-chloro-1-iodobenzene and trimethylsilylacetylene (reagent, manufactured by Junsei Chemical Co., Ltd.), referring to the description in ACS Nano, 10(7), 7023-7030, 2016. Following the instructions in Angewandte Chemie, International Edition, 62, e202312633, 2023, 2-bromo-4-chloro-1-ethynylbenzene was produced from 2-bromo-4-chloro-1-trimethylsilylethynylbenzene. The NMR data for 2-bromo-4-chloro-1-ethynylbenzene is shown below. １ H-NMR (300MHz, CDCl ３ , δ ｐｐｍ ): 7.61 (d, J=2.1Hz, 1H), 7.45 (d, J=8.4Hz, 1H), 7.26 (dd, J=8.4, 2.1Hz, 1H), 3.40 (s, 1H). １３ C-NMR (125MHz, CDCl ３ , δ ｐｐｍ ): 135.3, 134.6, 132.3, 127.5, 126.0, 125.6, 122.9, 82.7, 81.0.

[0092] Manufacturing Example 31 2-(2-ethynylphenyl)-1,3-dioxane Based on the description in Angewandte Chemie, International Edition, 62, e202312633, 2023, 2-(2-ethynylphenyl)-1,3-dioxane was manufactured from 2-[2-(2-trimethylsilylethynylphenyl)]-1,3-dioxane. The NMR data for 2-(2-ethynylphenyl)-1,3-dioxane is shown below. １ H-NMR (300MHz, CDCl ３ , δ ｐｐｍ): 7.68 (dd, J = 7.5, 1.5 Hz, 1H), 7.49 (dd, J = 7.5, 1.2 Hz, 1H), 7.39 (ddd, J = 7.5, 7.5, 1.5 Hz, 1H), 7.29 (ddd, J = 7.5, 7.5 , 1.5Hz, 1H), 5.92 (s, 1H), 4.31-4.24 (m, 2H), 4.07-3.98 (m, 2H), 3.29 (s, 1H), 2.34-2.17 (m, 1H), 1.48-1.42 (m, 1H). １３ C-NMR (125MHz, CDCl ３ , δ ｐｐｍ ): 140.3, 132.6, 129.1, 128.6, 125.9, 120.4, 99.8, 81.3, 80.9, 67.6, 25.7.

[0093] Manufacturing Example 32 2-Ethynylnaphthalene 2-trimethylsilylethynylnaphthalene was prepared from 2-iodonaphthalene (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) and trimethylsilylacetylene (reagent, manufactured by Junsei Chemical Co., Ltd.) based on the description in ACS Nano, 10(7), 7023-7030, 2016. Subsequently, 2-ethynylnaphthalene was prepared from 2-trimethylsilylethynylnaphthalene based on the description in Angewandte Chemie, International Edition, 62, e202312633, 2023. The NMR data for 2-ethynylnaphthalene is shown below. １ H-NMR (500.03MHz, CDCl ３ , δ ｐｐｍ ): 8.03 (s, 1H), 7.83-7.78 (m, 3H), 7.54-7.48 (m, 3H), 3.15 (s, 1H). １３ C-NMR (125MHz, CDCl ３ , δ ｐｐｍ ): 133.0, 132.8, 132.3, 128.5, 128.0, 127.77, 127.76, 126.9, 126.6, 119.4, 84.0, 77.4.

[0094] Production Example 33: 2-bromo-1-iodobenzene was produced from 2-bromoaniline (reagent, manufactured by Kanto Chemical Co., Ltd.) by the 1-ethynyl-2-(3-methyl-2-butenyl)benzenezandemeyer reaction. Subsequently, (2-bromophenyl)ethynyltrimethylsilane was produced from 2-bromo-1-iodobenzene and trimethylsilylacetylene (reagent, manufactured by Junsei Chemical Co., Ltd.), referring to the description in ACS Nano, 10(7), 7023-7030, 2016. Furthermore, (2-bromophenyl)ethynyltrimethylsilane was reacted with a hexane solution of butyllithium (reagent, manufactured by Kanto Chemical Co., Ltd.) in the presence of tetramethylethylenediamine (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.), and then reacted with 1-bromo-3-methyl-2-butene (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) to produce 1-trimethylsilylethynyl-2-(3-methyl-2-butenyl)benzene. In addition, 1-ethynyl-2-(3-methyl-2-butenyl)benzene was produced from 1-trimethylsilylethynyl-2-(3-methyl-2-butenyl)benzene, with reference to the description in Angewandte Chemie, International Edition, 62, e202312633, 2023. The NMR data for 1-ethynyl-2-(3-methyl-2-butenyl)benzene is shown below. １ H-NMR (500MHz, CDCl ３ , δ ｐｐｍ ): 7.47 (dd, J=8.0, 1.5Hz, 1H), 7.27 (ddd, J=7.5, 7.5, 1.0Hz, 1H), 7.20 (d, J=7.5Hz, 1H), 7.14 (ddd, J=7.5, 7.5, 1.5Hz, 1H), 5.34-5.30 (m, 1H), 3.53 (d, J = 7.5Hz, 2H), 3.26 (s, 1H), 1.75 (d, J = 1.0Hz, 3H), 1.73 (s, 3H). １３ C-NMR (125MHz, CDCl ３ , δ ｐｐｍ ): 144.4, 132.9, 132.8, 128.9, 128.4, 125.6, 122.2, 121.4, 82.5, 80.9, 32.8, 25.7, 17.9.

[0095] Manufacturing Example 34: Manufacturing of 5-phenyl-1-pentine Referring to the description in ACS Nano, 10(7), 7023-7030, 2016, 1-(trimethylsilyl)-5-phenyl-1-pentine was manufactured from 3-phenylpropyl bromide (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) and trimethylsilylacetylene (reagent, manufactured by Junsei Chemical Co., Ltd.). Subsequently, referring to the description in Angewandte Chemie, International Edition, 62, e202312633, 2023, 5-phenyl-1-pentine was manufactured from 1-(trimethylsilyl)-5-phenyl-1-pentine. The NMR data for 5-phenyl-1-pentine is shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ ): 7.31-7.26 (m, 2H), 7.21-7.17 (m, 3H), 2.74 (t, J = 7.2Hz, 2H), 2.2 1 (td, J=7.2, 2.8Hz, 2H), 1.99 (t, J=2.8Hz, 1H), 1.89-1.81 (m, 2H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 141.5, 128.5, 128.4, 125.9, 84.2, 68.6, 34.6, 30.0, 17.8.

[0096] <Example 2> A deuterated alkene was produced from a substituted alkyne using a complex of cesium fluoride and diisobutylaluminum hydride by the method described below.

[0097] Example 2-1 (Preparation of 4-(1-deuterated vinyl)biphenyl from 4-ethynylbiphenyl) The hexane suspension of the complex of cesium fluoride and diisobutylaluminum hydride prepared in Example 1-1 was used as is, along with the reaction vessel. After removing the hexane from the hexane suspension of the complex of cesium fluoride and diisobutylaluminum hydride under reduced pressure, the reaction vessel was subjected to an argon atmosphere and 1.6 mL of diethylene glycol dimethyl ether was added. The complex of cesium fluoride and diisobutylaluminum hydride dissolved in the diethylene glycol dimethyl ether, giving a colorless and transparent solution. To this solution, 71.3 mg (0.40 mmol) of 4-ethynylbiphenyl prepared in Production Example 1 was added and stirred for 2 hours while heating in a silicone oil bath at 50°C. After the reaction mixture was cooled to room temperature, 1 mL of heavy water was added and stirred for 1 hour. To the reaction mixture, 3 mL of 1 M NaOH aqueous solution was added and the mixture was stirred for 15 minutes. The organic layer was extracted using a separatory funnel with a hexane / ethyl acetate (5 / 1 volume ratio) mixture, and the organic layer was dried over sodium sulfate. After removing the sodium sulfate from the organic layer by filtration, the organic layer was concentrated using an evaporator, and the resulting residue was purified by column chromatography using silica gel (Wako Gel® 60N, 63-212 μm, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (eluent: hexane) to obtain 4-(1-deuterated vinyl)biphenyl in 90% yield.

[0098] The NMR data for 4-(1-deuterated vinyl)biphenyl is shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ ): 7.63-7.56 (m, 4H), 7.50-7.42 (m, 4H), 7.34 (t, J=7.2Hz, 1H), 5.79 (d, J=2.0Hz, 1H), 5.27 (s, 1H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 140.7, 140.6, 136.5, 136.1 (t, J Ｃ－Ｄ =24.1Hz), 128.8, 127.3, 127.2, 127.0, 126.6, 113.7.

[0099] Example 2-2 (Production of 1-phenyl-(1-deuterated)-1-decene from 1-phenyl-1-decine) The same procedure as in Example 2-1 was followed, except that 4-ethynylbiphenyl (71.3 mg, 0.40 mmol) was replaced with 1-phenyl-1-decine (85.7 mg, 0.40 mmol). 1-phenyl-(1-deuterated)-1-decene and 1-phenyl-1-decene were obtained in yields of 94% and 4%, respectively. The E / Z ratio of the obtained 1-phenyl-(1-deuterated)-1-decene was 96 / 4. The NMR data for (E)-1-phenyl-(1-deuterated)-1-decene is shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ ): 7.35-7.31 (m, 2H), 7.30-7.26 (m, 2H), 7.21-7.16 (m, 1H), 6.36-6.20 (m, 1H), 2. 21 (q, J=6.8Hz, 2H), 1.50-1.43 (m, 2H), 1.40-1.20 (m, 10H), 0.89 (t, J=7.2Hz, 3H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 137.9, 131.2, 129.3 (t, J Ｃ－Ｄ =23.1Hz), 128.4, 126.7, 125.9, 33.0, 31.9, 29.5, 29.4, 29.3, 29.2, 22.7, 14.1.

[0100] The results from Examples 2-1 and 2-2 showed that the reduction of aromatic group-substituted alkynes using a complex of cesium fluoride and diisobutylaluminum hydride mainly proceeds via an intermediate in which aluminum atoms in the complex bond to the carbon atom substituted with the aromatic group.

[0101] <Example 3> A substituted alkene was produced from a substituted alkyne using a complex of cesium fluoride and diisobutylaluminum hydride by the method described below.

[0102] Example 3-1 (Preparation of 1-phenyl-1-decene from 1-phenyl-1-decine) The hexane suspension of the complex of cesium fluoride and diisobutylaluminum hydride prepared in Example 1-1 was used as is, along with the reaction vessel. After removing the hexane from the hexane suspension of the complex of cesium fluoride and diisobutylaluminum hydride under reduced pressure, the reaction vessel was subjected to an argon atmosphere and 1.6 mL of diethylene glycol dimethyl ether was added. The complex of cesium fluoride and diisobutylaluminum hydride dissolved in the diethylene glycol dimethyl ether, giving a colorless and transparent solution. To this solution, 85.7 mg (0.40 mmol) of 1-phenyl-1-decine prepared in the above-mentioned Production Example 2 was added and the mixture was stirred for 2 hours while heating in a silicone oil bath at 110°C. After the reaction mixture was cooled to room temperature, 3 mL of 1 M NaOH aqueous solution was added. The mixture was stirred for 15 minutes, and the organic layer was extracted using a separatory funnel with a hexane / ethyl acetate (10 / 1 volume ratio) mixture. The organic layer was then dried over sodium sulfate. After removing the sodium sulfate from the organic layer by filtration, the organic layer was concentrated using an evaporator. The resulting residue was purified by column chromatography using silica gel (Wako Gel® 60N, 63-212 μm, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) with hexane as the developing solvent to obtain 1-phenyl-1-decene. The yield and E / Z ratio are shown in Table 1.

[0103] Examples 3-2 to 3-26 In Example 3-1, 1-phenyl-1-decine was replaced with one of the substituted alkynes produced in Production Examples 3 to 24, as shown in Table 1, and the amount of the complex of cesium fluoride and diisobutylaluminum hydride relative to the substituted alkyne was changed as shown in Table 1. Substituted alkenes were obtained in the same manner. In Examples 3-8, 3-18, and 3-26, the reaction temperature was 150°C.

[0104] Example 3-27 Cesium fluoride (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) (182.3 mg, 1.20 mmol) was weighed into a 10 mL reaction vessel and dried by stirring at 100°C for 1 hour under reduced pressure using a vacuum pump. After the reaction vessel was subjected to an argon atmosphere, it was cooled to room temperature and diisobutylaluminum hydride (reagent, 1 M hexane solution, manufactured by Tokyo Chemical Industry Co., Ltd.) (1.20 mL, 1.20 mmol) was added. By stirring at room temperature for 30 minutes, a white complex of cesium fluoride and diisobutylaluminum hydride was obtained as a hexane suspension. Immediately after adding diisobutylaluminum hydride, precipitation of cesium fluoride was observed when stirring was stopped, but after stirring for 30 minutes, no precipitation was observed even when stirring was stopped. To a hexane solution of a complex of cesium fluoride and diisobutylaluminum hydride, diethylene glycol dimethyl ether (1.6 mL) and diphenylacetylene (71.3 mg, 0.40 mmol) prepared in the above-mentioned Production Example 25 were added, and the mixture was stirred for 16 hours while heating in a 40°C silicone oil bath. After the reaction mixture was cooled to room temperature, 1 mL of 1 M NaOH aqueous solution was added. The mixture was stirred for 15 minutes, and the organic layer was extracted with dichloromethane using a separatory funnel, and the organic layer was dried over sodium sulfate. After removing the sodium sulfate from the organic layer by filtration, the organic layer was concentrated using an evaporator, and the resulting residue was purified by column chromatography using silica gel (Wako Gel® 60N, 63-212 μm, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (eluent: hexane) to obtain stilbene. The yield and E / Z ratio are shown in Table 1.

[0105] Example 3-28 Stilbene was obtained in the same manner as in Example 3-27, except that the amount of the complex of cesium fluoride and diisobutylaluminum hydride relative to the substituted alkyne was changed from 3 equivalents to 2 equivalents. The yield and E / Z ratio are shown in Table 1.

[0106] Examples 3-29 to 3-35 In Example 3-27, diphenylacetylene was replaced with the substituted alkyne produced in Production Examples 26 to 28 as shown in Table 1, the amount of the complex of cesium fluoride and diisobutylaluminum hydride relative to the substituted alkyne was changed as shown in Table 1, and the reaction temperature was set to 40°C. Substituted alkenes were obtained in the same manner. In Example 3-29, commercially available 1,2-bis(4-chlorophenyl)acetylene was used, in Example 3-30, commercially available (4-chlorophenyl)phenylacetylene was used, in Example 3-32, commercially available 1,2-di(4-methylphenyl)acetylene (reagent, manufactured by Sigma-Aldrich Japan LLC) was used, and in Example 3-35, commercially available 6-dodecine (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) was used. The yield and E / Z ratio of the substituted alkenes are shown in Table 1.

[0107]

[0108] The NMR data for (E)-1-phenyl-1-decene produced in Example 3-1 is shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ ): 7.35-7.30 (m, 2H), 7.29-7.26 (m, 2H), 7.20-7.16 (m, 1H), 6.38 (d, J = 16.0Hz, 1H), 6.23 (dt, J = 1 6.0, 6.8Hz, 1H), 2.23-2.18 (m, 2H), 1.48-1.43 (m, 2H), 1.37-1.28 (m, 10H), 0.89 (t, J=6.8Hz, 3H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 138.0, 131.2, 129.7, 128.4, 126.7, 125.9, 33.1, 31.9, 29.5, 29.4, 29.29, 29.25, 22.7, 14.1.

[0109] The NMR data for (E)-1-phenyl-1-hexene produced in Example 3-2 is shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ): 7.37-7.31 (m, 2H), 7.30-7.26 (m, 2H), 7.20-7.16 (m, 1H), 6.38 (d, J = 15.6Hz, 1H), 6.2 3 (dt, J = 15.6, 6.8 Hz, 1H), 2.24-2.19 (m, 2H), 1.50-1, 33 (m, 4H), 0.94 (t, J = 7.2Hz, 3H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 138.0, 131.2, 129.7, 128.4, 126.7, 125.9, 32.7, 31.5, 22.3, 13.9.

[0110] The NMR data for (E)-1-phenyl-1-pentene produced in Example 3-3 is shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ ): 7.34 (d, J = 7.2 Hz, 2H), 7.29 (dd, J = 7.2, 7.2 Hz, 2H), 7.18 (dd, J = 7.2 Hz, 1H), 6.38 (d, J = 15.6 Hz, 1 H), 6.23 (dt, J=15.6, 6.8Hz, 1H), 2.19 (q, J=6.8Hz, 2H), 1.55-1.45 (m, 2H), 0.96 (t, J=7.2Hz, 3H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 138.0, 131.0, 129.9, 128.4, 126.7, 125.9, 35.1, 22.5, 13.7.

[0111] The NMR data for (E)-1-phenyl-1-octene produced in Example 3-4 is shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ ): 7.35-7.30 (m, 2H), 7.30-7.23 (m, 2H), 7.20-7.16 (m, 1H), 6.38 (d, J = 15.6Hz, 1H), 6.23 (dt, J = 1 5.6, 6.8Hz, 1H), 2.23-2.17 (m, 2H), 1.50-1.43 (m, 2H), 1.37-1.30 (m, 6H), 0.91 (t, J=6.8Hz, 3H). １３ C-NMR (100MHz, CDCl ３ , δｐｐｍ ): 138.0, 131.2, 129.7, 128.4, 126.7, 125.9, 33.0, 31.8, 29.4, 28.9, 22.6, 14.1.

[0112] The NMR data for (E)-(2-cyclohexylethenyl)benzene produced in Example 3-5 is shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ ): 7.35 (d, J = 8.0 Hz, 2H), 7.30-7.26 (m, 2H), 7.20-7.15 (m, 1H), 6.34 (d, J = 16.0Hz, 1H), 6.18 (dd, J=16.0, 6.8Hz, 1H), 2.18-2.08 (m, 1H), 1.84-1.72 (m, 4H), 1.72-1.64 (m, 1H), 1.38-1.12 (m, 5H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 138.1, 136.8, 128.4, 127.2, 126.7, 125.9, 41.1, 33.0, 26.2, 26.0.

[0113] The NMR data for (E)-3,3-dimethyl-1-buten-1-ylbenzene produced in Example 3-6 is shown below. １ H-NMR (500MHz, CDCl ３ , δ ｐｐｍ ): 7.37-7.35 (m, 2H), 7.31-7.27 (m, 2H), 7.20-7.17 (m, 1H), 6.32-6.24 (m, 2H), 1.12 (s, 9H). １３ C-NMR (125.61MHz, CDCl ３ , δ ｐｐｍ ): 141.8, 138.0, 128.5, 126.7, 126.0, 124.5, 33.3, 29.6.

[0114] The NMR data for (E)-1-(4-methylphenyl)-1-hexene produced in Examples 3-7 and 3-8 are shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ): 7.23 (d, J = 8.4 Hz, 2H), 7.09 (d, J = 8.4 Hz, 2H), 6.34 (d, J = 16.0 Hz, 1H), 6.17 (dt, J = 16. 0,6.8Hz, 1H), 2.32(s, 3H), 2.22-2.17(m, 2H), 1.49-1.32(m, 4H), 0.92(s, J=7.2Hz, 3H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 136.4, 135.2, 130.1, 129.5, 129.1, 125.8, 32.7, 31.6, 22.3, 21.1, 13.9.

[0115] The NMR data for (E)-1-(4-trifluoromethylphenyl)-1-hexene prepared in Example 3-9 is shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ ): 7.54 (d, J = 8.4 Hz, 2H), 7.42 (d, J = 8.4 Hz, 2H), 6.41 (d, J = 16.0 Hz, 1H), 6.34 (dt , J=16.0, 6.8Hz, 1H), 2.30-2.21 (m, 2H), 1.49-1.35 (m, 4H), 0.95 (t, J=7.2, 3H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 141.4, 135.4, 128.6 (q, ２ J Ｃ－Ｆ =21.6Hz), 128.6, 127.2, 126.0(q, ３ J Ｃ－Ｆ =2.9Hz), 124.4(q, １ J Ｃ－Ｆ =180.8Hz), 32.7, 31.3, 22.3, 13.9.

[0116] The NMR data for (E)-1-(4-bromophenyl)-1-hexene prepared in Example 3-10 is shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ): 7.40 (d, J = 8.8 Hz, 2H), 7.20 (d, J = 8.8 Hz, 2H), 6.31 (d, J = 15.6 Hz, 1H), 6.21 (dt, J = 15.6, 6 .8Hz, 1H), 2.23-2.17 (m, 2H), 1.49-1.42 (m, 2H), 1.42-1.32 (m, 2H), 0.92 (t, J=7.2Hz, 3H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 136.9, 132.1, 131.5, 128.6, 127.4, 120.3, 32.7, 31.4, 22.3, 13.9.

[0117] The NMR data for (E)-1-(3-bromophenyl)-1-hexene prepared in Example 3-11 is shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ ): 7.49 (s, 1H), 7.32-7.29 (m, 1H), 7.24 (d, J = 7.6Hz, 1H), 7.14 (dd, J = 7.6, 7.6Hz, 1H), 6.30 (d, J = 16. 0Hz, 1H), 6.23 (dt, J=16.0, 6.4Hz, 1H), 2.24-2.18 (m, 2H), 1.49-1.32 (m, 4H), 0.93 (t, J=7.2Hz, 3H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 140.2, 132.9, 129.9, 129.6, 128.8, 128.4, 124.6, 122.7, 32.6, 31.4, 22.2, 13.9.

[0118] The NMR data for (E)-1-(4-chlorophenyl)-1-hexene prepared in Example 3-12 is shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ ): 7.27-7.25 (m, 4H), 6.33 (d, J=15.6Hz, 1H), 6.21 (dt, J=15.6, 6.8Hz, 1H), 2. 24-2.19 (m, 2H), 1.50-1.43 (m, 2H), 1.42-1.34 (m, 2H), 0.93 (t, J=7.2Hz, 3H). １３ C-NMR (100MHz, CDCl３ , δ ｐｐｍ ): 136.5, 132.3, 132.0, 128.6, 128.6, 127.1, 32.7, 31.4, 22.3, 13.9.

[0119] The NMR data for (E)-1-(2-chlorophenyl)-1-hexene prepared in Example 3-13 is shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ ): 7.50 (dd, J=7.6, 1.6Hz, 1H), 7.32 (dd, J=8.0, 1.2Hz, 1H), 7.22-7.10 (m, 2H), 6.75 (d, J=16.0Hz , 1H), 6.21 (dt, J=16.0, 6.8Hz, 1H), 2.29-2.25 (m, 2H), 1.50-1.33 (m, 4H), 0.94 (t, J=7.2Hz, 3H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 136.0, 134.1, 132.5, 129.6, 127.8, 126.7, 126.6, 126.0, 32.9, 31.4, 22.3, 13.9.

[0120] The NMR data for (E)-1-(3-chlorophenyl)-1-hexene prepared in Example 3-14 is shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ ): 7.32 (s, 1H), 7.21-7.17 (m, 2H), 7.16-7.13 (m, 1H), 6.32 (d, J = 15.6Hz, 1H), 6.24 ( dt, J=15.6, 6.4Hz, 1H), 2.23-2.18 (m, 2H), 1.49-1.34 (m, 4H), 0.93 (t, J=7.2Hz, 3H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 139.9, 134.4, 132.8, 129.6, 128.5, 126.7, 125.8, 124.1, 32.6, 31.4, 22.2, 13.9.

[0121] The NMR data for (E)-1-(2-fluorophenyl)-1-hexene prepared in Example 3-15 is shown below.１ H-NMR (500MHz, CDCl ３ δ ｐｐｍ ): 7.43 (ddd, J=8.0, 8.0, 1.5Hz, 1H), 7.18-7.13 (m, 1H), 7.08-7.05 (m, 1H), 7.03-6.98 (m, 1H), 6.54 (d, J=16.0Hz, 1H), 6.31 (dt, J=16.0, 7.0Hz, 1H), 2.27-2.22 (m, 2H), 1.5 1-1.45 (m, 2H), 1.42-1.34 (m, 2H), 0.94 (t, J=7.5Hz, 3H). １３ C-NMR (125MHz, CDCl ３ δ ｐｐｍ ): 160.0 (d, １ J Ｃ－Ｆ =249.0Hz), 133.9 (d, ３ J Ｃ－Ｆ =3.8Hz), 127.9 (d, ３ J Ｃ－Ｆ =7.5Hz), 126.9(d, ３ J Ｃ－Ｆ =3.8Hz), 125.6 (d, ２ J Ｃ－Ｆ =12.6Hz), 123.9 (d, ４ J Ｃ－Ｆ =2.5Hz), 122.0 (d, ４ J Ｃ－Ｆ =3.8Hz), 115.6 (d, ２ J Ｃ－Ｆ =22.6Hz), 33.1, 31.4, 22.3, 13.9.

[0122] Example 3-16 The manufacturing method (E)-1-(3,5-ジクロロフェニル)-1-ヘキセンのNMRデータを is shown below. １ H-NMR (400MHz, CDCl ３ δ ｐｐｍ ): 7.17-7.29 (m, 3H), 6.27-6.25 (m, 2H), 2.24-2.1 9 (m, 2H), 1.47-1.34 (m, 4H), 0.93 (t, J=7.2Hz, 3H). １３ C-NMR (100MHz, CDCl ３ δ ｐｐｍ): 141.0, 135.0, 134.4, 127.4, 126.5, 124.3, 32.6, 31.2, 22.2, 13.9.

[0123] The NMR data for (E)-1-(4-n-butoxyphenyl)-1-hexene produced in Examples 3-17 and 3-18 are shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ ): 7.25 (d, J = 8.0 Hz, 2H), 6.82 (d, J = 8.4 Hz, 2H), 6.31 (d, J = 16.0 Hz, 1H), 6.07 (dt, J = 16.0, 7.2 Hz, 1H), 3.95 (t, J = 6 .8Hz, 2H), 2.21-2.16 (m, 2H), 1.77-1.72 (m, 2H), 1.51-1.33 (m, 6H), 0.97 (t, J=7.6Hz, 3H), 0.92 (t, J=7.2Hz, 3H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 158.2, 130.6, 129.1, 128.9, 126.9, 114.5, 67.7, 32.7, 31.7, 31.4, 22.3, 19.2, 14.0, 13.8.

[0124] The NMR data for (E)-1-(3-n-butoxyphenyl)-1-hexene prepared in Example 3-19 is shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ ): δ7.25 (d, J=8.0Hz, 2H), 6.82 (d, J=8.4Hz, 2H), 6.31 (d, J=16.0Hz, 1H), 6.07 (dt, J=16.0, 7.2Hz, 1H), 3.95 (t, J= 6.8Hz, 2H), 2.21-2.16 (m, 2H), 1.77-1.72 (m, 2H), 1.51-1.33 (m, 6H), 0.97 (t, J = 7.6Hz, 3H), 0.92 (t, J = 7.2Hz, 3H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): δ158.2, 130.6, 129.1, 128.9, 126.9, 114.5, 67.7, 32.7, 31.7, 31.4, 22.3, 19.2, 14.0, 13.8.

[0125] The NMR data for 2-((E)-1-hexenyl)benzo[b]thiophene prepared in Example 3-20 is shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ ): 7.78-7.71 (m, 1H), 7.67-7.62 (m, 1H), 7.30-7.22 (m, 2H), 7.04 (s, 1H), 6.60, (d, J = 15.6Hz, 1 H), 6.17 (dt, J = 15.6, 6.8 Hz, 1H), 2.27-2.21 (m, 2H), 1.50-1.36 (m, 4H), 0.94 (t, J = 7.2Hz, 3H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 143.3, 140.3, 138.5, 134.1, 124.3, 124.2, 123.7, 123.1, 122.1, 121.0, 32.6, 31.2, 22.3, 13.9.

[0126] The NMR data for 2-((E)-1-hexenyl)benzo[b]furan prepared in Example 3-21 is shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ ): 7.48 (dd, J = 8.0, 0.8 Hz, 1H), 7.41 (dd, J = 8.0, 0.4 Hz, 1H), 7.24-7.14 (m, 2H), 6.49 (dt, J = 16.0, 6.8 Hz, 1H), 6.4 6 (s, 1H), 6.32 (d, J = 16.0Hz, 1H), 2.29-2.23 (m, 2H), 1.51-1.45 (m, 2H), 1.44-1.36 (m, 2H), 0.94 (t, J = 7.2Hz, 3H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 155.2, 154.6, 134.0, 129.1, 123.9, 122.6, 120.5, 118.6, 110.7, 102.6, 32.6, 31.2, 22.3, 13.9.

[0127] The NMR data for 4-((E)-1-hexenyl)-1,1'-biphenyl prepared in Example 3-22 is shown below. １H-NMR (400MHz, CDCl ３ , δ ｐｐｍ ): 7.59 (d, J = 7.2 Hz, 2H), 7.53 (d, J = 8.0 Hz, 2H), 7.45-7.40 (m, 4H), 7.37-7.31 (m, 1H), 6.42 (d, J = 16.0Hz, 1H), 6.28 (dt, J=16.0, 6.8Hz, 1H), 2.27-2.21 (m, 2H), 1.50-1.43 (m, 2H), 1.42-1.34 (m, 2H), 0.94 (t, J=7.2Hz, 3H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 77.0ppm): δ140.9, 139.5, 137.0, 131.4, 129.3, 128.7, 127.2, 127.1, 126.9, 126.3, 32.8, 31.5, 22.3, 13.9.

[0128] The NMR data for (E)-1-(2-naphthyl)-1-hexene produced in Example 3-23 is shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ ): 7.80-7.74 (m, 3H), 7.67 (s, 1H), 7.58 (dd, J = 8.4, 1.6Hz, 1H), 7.46-7.39 (m, 2H), 6.54 (d, J = 16.0Hz , 1H), 6.36 (dt, J=16.0, 6.8Hz, 1H), 2.27 (q, J=6.4Hz, 2H), 1.50-1.36 (m, 4H), 0.95 (t, J=7.6Hz, 3H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 135.4, 133.7, 132.6, 131.7, 129.8, 128.0, 127.8, 127.6, 126.1, 125.4, 125.3, 123.6, 32.8, 31.6, 22.3, 14.0.

[0129] The NMR data for (E)-1-(1-naphthyl)-1-hexene produced in Example 3-24 is shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ): 8.13 (d, J = 8.2Hz, 1H), 7.86-7.82 (m, 1H), 7.77-7.73 (m, 1H), 7.56-7.40 (m, 4H), 7.11 (d, J = 15.6 Hz, 1H), 6.24 (dt, J=15.6, 6.8Hz, 1H), 2.37-2.31 (m, 2H), 1.57-1.39 (m, 4H), 0.97 (t, J=7.6Hz, 3H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 135.8, 134.6, 134.5, 133.6, 131.1, 128.4, 127.2, 126.9, 125.7, 125.6, 123.9, 123.5, 33.1, 31.6, 22.3, 14.0.

[0130] The NMR data for (E)-6-phenyl-2-hexene produced in Examples 3-25 and 3-26 are shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ ): 7.29-7.26 (m, 2H), 7.20-7.17 (m, 3H), 5.45-5.43 (m, 2H), 2.60 (t, J=8.0Hz, 2H), 2.04-2.02 (m, 2H), 1.83-1.66 (m, 5H). １３ C-NMR (125.77MHz, CDCl ３ , δ ｐｐｍ ): 142.6, 131.0, 128.4, 128.2, 125.6, 125.2, 35.4, 32.1, 31.3, 17.9.

[0131] The NMR data for (E)-stilbene produced in Examples 3-27 and 3-28 are shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ ): 7.53 (d, J=7.2Hz, 4H), 7.42 (dd, J=8.0, 8.0Hz, 4H), 7.28-7.24 (m, 2H), 7.12 (s, 2H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 137.5, 128.9, 128.8, 127.8, 126.7

[0132] The NMR data for (E)-1,2-bis(4-chlorophenyl)ethene produced in Example 3-29 is shown below. １ H-NMR (500MHz, CDCl ３ , δ ｐｐｍ ): 7.43 (d, J=8.5Hz, 4H), 7.33 (d, J=8.5Hz, 4H), 7.02 (s, 2H). １３ C-NMR (125MHz, CDCl ３ , δ ｐｐｍ ): 135.5, 133.4, 128.9, 128.0, 127.7.

[0133] The NMR data for (E)-1-(4-chlorophenyl)-2-phenylethene produced in Example 3-30 is shown below. １ H-NMR (500MHz, CDCl ３ , δ ｐｐｍ ): 7.51 (d, J = 7.5 Hz, 2H), 7.44 (d, J = 8.0 Hz, 2H), 7.38-7.26 (m, 5H), 7.07 (d, J = 20.5 Hz, 2H). １３ C-NMR (125MHz, CDCl ３ , δ ｐｐｍ ): 137.0, 135.8, 133.2, 129.3, 128.8, 128.7, 127.9, 127.6, 127.4, 126.5.

[0134] The NMR data for (E)-1-butoxy-4-[(4-chlorophenyl)-vinyl]benzene produced in Example 3-31 is shown below. １ H-NMR (500MHz, CDCl ３ , δ ｐｐｍ ): 7.43 (d, J = 8.5 Hz, 2H), 7.41 (d, J = 8.5 Hz, 2H), 7.30 (dd, J = 7.0, 2.0 Hz, 2H), 7.03 (d, J = 16.0, 1H), 6.91, (d, J = 16.0 Hz, 1H), 6.89 (d, J = 7.5Hz, 2H), 3.00 (t, J = 6.5Hz, 2H), 1.81-1.75 (m, 2H), 1.54-1.47 (m, 2H), 0.99 (t, J = 7.0Hz, 3H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ): 159.1, 136.2, 132.6, 129.5, 128.9, 128.8, 127.7, 127.4, 125.1, 114.7, 67.8, 31.3, 19.2, 13.8.

[0135] The NMR data for (E)-1,2-di(4-methylphenyl)ethene prepared in Example 3-32 is shown below. １ H-NMR (500MHz, CDCl ３ , δ ｐｐｍ ): 7.40 (d, J=6.5Hz, 2H), 7.41 (d, J=6.0Hz, 2H), 7.04 (s, 2H), 2.36 (s, 3H). １３ C-NMR (125MHz, CDCl ３ , δ ｐｐｍ ): 137.2, 134.7, 129.3, 127.6, 126.3, 21.2.

[0136] The NMR data for (E)-1-(2-phenylethenyl)naphthalene produced in Example 3-33 is shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ ): 8.23 ​​(d, J = 8.0 Hz, 1H), 7.88 (d, J = 16.0 Hz, 1H), 7.87 (dd, J = 2.0, 7.4 Hz, 1H), 7.80 (d, J = 8.2 Hz, 1H), 7.75 (d, J = 7.2 Hz, 1H), 7.61 (d, J = 7.2Hz, 2H), 7.56-7.46 (m, 3H), 7.40 (t, J = 7.6Hz, 2H), 7.32-7.28 (m, 1H), 7.16 (d, J = 16.0Hz, 1H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 137.6, 135.0, 133.7, 131.8, 131.4, 128.8, 128.6, 128.0, 127.8, 126.7, 126.1, 125.8, 125.8, 125.7, 123.8, 123.6.

[0137] The NMR data for 1,4-diphenylbuta-1-ene-3-yne produced in Example 3-34 is shown below. Note that 1,4-diphenylbuta-1-ene-3-yne was obtained as a mixture of the (E) and (Z) isomers. １H-NMR (300 MHz, CDCl ３ , δ ｐｐｍ ): (E)-isomer 7.51 - 7.27 (m, 10H), 7.05 (d, J = 16.2 Hz, 1H), 6.39 (d, J = 16.2 Hz, 1H); (Z)-isomer 7.94 (d, J = 7.0 Hz, 2H), 7.52 - 7.27 (m, 8H), 6.71 (d, J = 11.9 Hz, 1H), 5.93 (d, J = 11.9 Hz, 1H). １３ C-NMR (125 MHz, CDCl ３ , δ ｐｐｍ ): (E)-isomer and (Z)-isomer 141.2, 138.6, 136.5, 136.3, 131.5, 131.4, 128.7, 128.6, 128.5, 128.4, 128.3, 128.3, 128.2, 126.3, 123.4, 108.1, 107.4, 95.8, 91.7, 88.9, 88.2.

[0138] The NMR data of (E)-6-dodecene produced in Example 3 - 35 are shown below. １ H-NMR (400 MHz, CDCl ３ , δ ｐｐｍ ): 5.73 - 5.09 (m, 2H), 2.32 - 1.61 (m, 4H), 1.43 - 1.19 (m, 12H), 0.98 - 0.63 (m, 6H). １３ C-NMR (100 MHz, CDCl ３ , δ ｐｐｍ ): 130.5, 130.1, 32.8, 31.7, 31.6, 29.6, 29.5, 27.3, 22.8, 22.7, 14.3, 14.2.

[0139] As shown in Examples 3-1 to 3-35, it was found that by using a complex of cesium fluoride and diisobutylaluminum hydride, a disubstituted alkene can be produced from a disubstituted alkyne with E-selectivity. Further, it was found that when at least one of the substituents of the disubstituted alkyne is an aromatic group, the reactivity is enhanced and the disubstituted alkene can be obtained with high E-selectivity. From the results of Examples 3-7, 3-17, and 3-32, it was found that when an electron-donating group is present on the aromatic group which is a substituent of the disubstituted alkyne, the reactivity decreases. However, as shown in Examples 3-8 and 3-18, it was found that by increasing the complex of cesium fluoride and diisobutylaluminum hydride, both the reactivity and the geometric selectivity are improved. On the other hand, from the result of Example 3-31, it was found that even if one of the substituents on the two aromatic groups which are substituents of the disubstituted alkyne is an electron-donating group and the other is an electron-withdrawing group, the reactivity and the geometric selectivity are improved.

[0140] <Example 4-1>In Example 3-1, 1-phenyl-1-decene was produced from 1-phenyl-1-decyne in a yield of 16% and an E / Z ratio of 93 / 7 in the same manner except that the complex of cesium fluoride and diisobutylaluminum hydride was changed to the complex of sodium fluoride and diisobutylaluminum hydride produced in Example 1-2. The complex of sodium fluoride and diisobutylaluminum hydride was used as it was in the hexane suspension of the complex of sodium fluoride and diisobutylaluminum hydride produced in Example 1-2, together with the reaction vessel.

[0141] <Example 4-2>In Example 3-1, 1-phenyl-1-decene was produced from 1-phenyl-1-decyne in a yield of 33% and an E / Z ratio of 99 / 1 in the same manner except that the complex of cesium fluoride and diisobutylaluminum hydride was changed to the complex of potassium fluoride and diisobutylaluminum hydride produced in Example 1-3. The complex of potassium fluoride and diisobutylaluminum hydride was used as it was in the hexane suspension of the complex of potassium fluoride and diisobutylaluminum hydride produced in Example 1-3, together with the reaction vessel.

[0142] The results from Examples 3-1, 4-1, and 4-2 showed that 1-phenyl-1-decene can be E-selectively produced from 1-phenyl-1-decine by using a complex of an alkali metal fluoride salt and diisobutylaluminum hydride. It was also found that the reactivity increases as the period of the alkali metal increases, and that the reactivity becomes very high when the alkali metal fluoride salt is cesium fluoride. These findings are thought to be similar when producing substituted alkenes reductively from other substituted alkynes. Furthermore, when the complex of cesium fluoride and diisobutylaluminum hydride was changed to a complex of cesium chloride and diisobutylaluminum hydride, the complex did not react with 1-phenyl-1-decine, and 1-phenyl-1-decene could not be obtained. When the complex of cesium fluoride and diisobutylaluminum hydride was changed to a complex of cesium iodide and diisobutylaluminum hydride, (Z)-1-phenyl-1-decene was obtained from 1-phenyl-1-decine in a yield of 32%.

[0143] <Example 5> Example 5-1 (Production of 4-(1-bromoethenyl)biphenyl from 4-ethynylbiphenyl) Cesium fluoride (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) (97.2 mg, 0.64 mmol) was weighed into a 10 mL reaction vessel and stirred at 100°C for 1 hour under reduced pressure using a vacuum pump to dry. After the reaction vessel was subjected to an argon atmosphere, it was cooled to room temperature and diisobutylaluminum hydride (reagent, 1 M hexane solution, manufactured by Tokyo Chemical Industry Co., Ltd.) (0.8 mL, 0.8 mmol) was added. By stirring at room temperature for 30 minutes, a white complex of cesium fluoride and diisobutylaluminum hydride was obtained as a hexane suspension. Immediately after adding diisobutylaluminum hydride, precipitation of cesium fluoride was observed when stirring was stopped, but after stirring for 30 minutes, no precipitation was observed even when stirring was stopped. To a hexane solution of the complex of cesium fluoride and diisobutylaluminum hydride, diethylene glycol dimethyl ether (1.6 mL) and 4-ethynylbiphenyl (71.3 mg, 0.40 mmol) prepared in the above-mentioned Production Example 1 were added, and the mixture was heated in a 50°C silicone oil bath and stirred for 2 hours. After the reaction mixture was cooled to 0°C, N-bromosuccinimide (213.6 mg, 1.2 mmol) was added, and the mixture was heated from 0°C to room temperature and stirred for 2 hours. Then, 1.0 mL of 1 M NaOH aqueous solution was added, and the mixture was stirred for 15 minutes. The organic layer was extracted using a separatory funnel with a hexane / ethyl acetate (5 / 1, volume ratio) mixture, washed with saturated brine, and then dried over sodium sulfate. After removing sodium sulfate from the organic layer by filtration, the organic layer was concentrated using an evaporator. The resulting residue was purified by column chromatography using silica gel (Wako Gel® 60N, 63-212 μm, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) with hexane as the developing solvent to obtain 4-(1-bromoethenyl)biphenyl. The yield and the product (exo) / anti-Markovnikov ratio are shown in Table 2.

[0144] Examples 5-2 to 5-19 In Example 5-1, 4-ethynylbiphenyl was replaced with the substituted alkynes produced in Production Examples 29 to 34 and Production Example 2, as shown in Table 2, and the reaction temperature after adding N-bromosuccinimide was changed as shown in Table 2, otherwise a substituted alkene was obtained. In Example 5-2, commercially available phenylacetylene (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) was used; in Example 5-3, commercially available 4-chlorophenylacetylene (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) was used; in Example 5-4, commercially available 4-bromophenylacetylene (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) was used; in Example 5-5, commercially available 4-trifluoromethylphenylacetylene (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) was used; in Example 5-6, commercially available 4-nitrophenylacetylene (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) was used; in Examples 5-7 and 5-8, commercially available 4-butylphenylacetylene (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) was used; in Example 5-16, commercially available 1,4-di(ethynyl)benzene (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) was used; and in Examples 5-17 and 5-18, commercially available 1-ethynyl-1-cyclohexene (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) was used. The yields and exo / endo ratios of substituted alkenes are shown in Table 2.

[0145] Example 5-20 (Preparation of 1-bromo-1-phenyl-1-decene from 1-phenyl-1-decine) Cesium fluoride (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) (121.5 mg, 0.80 mmol) was weighed into a 10 mL reaction vessel and stirred at 100°C for 1 hour under reduced pressure using a vacuum pump to dry. After the reaction vessel was subjected to an argon atmosphere, it was cooled to room temperature and diisobutylaluminum hydride (reagent, 1 M hexane solution, manufactured by Tokyo Chemical Industry Co., Ltd.) (0.8 mL, 0.8 mmol) was added. By stirring at room temperature for 30 minutes, a white complex of cesium fluoride and diisobutylaluminum hydride was obtained as a hexane suspension. Immediately after adding diisobutylaluminum hydride, precipitation of cesium fluoride was observed when stirring was stopped, but after stirring for 30 minutes, no precipitation was observed even when stirring was stopped. To a hexane solution of a complex of cesium fluoride and diisobutylaluminum hydride, diethylene glycol dimethyl ether (1.6 mL) and 1-phenyl-1-decine (84.7 mg, 0.40 mmol) prepared in Production Example 2 were added and the mixture was heated in a 110°C silicone oil bath and stirred for 2 hours. After the reaction mixture was cooled to 0°C, N-bromosuccinimide (282.0 mg, 1.6 mmol) was added and the mixture was stirred for 1 hour while increasing the temperature from 0°C to room temperature. Then, water (1 mL) was added and the mixture was stirred for 15 minutes. The organic layer was extracted with hexane using a separatory funnel, washed with saturated brine, and then dried over sodium sulfate. After removing the sodium sulfate from the organic layer by filtration, the organic layer was concentrated using an evaporator, and the resulting residue was purified by column chromatography (eluent: hexane) using silica gel (Wako Gel® 60N, 63-212 μm, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) to obtain 1-bromo-1-phenyl-1-decene. The yields and the ratio of products (exo) based on Markovnikov's rule to products (endo) based on the anti-Markovnikov rule are shown in Table 2.

[0146]

[0147] The NMR data for 4-(1-bromoethenyl)biphenyl prepared in Example 5-1 is shown below. １ H-NMR (400MHz, CDCl３ , δ ｐｐｍ ): 7.67 (dd, J = 8.4, 1.6 Hz, 2H), 7.59 (dd, J = 8.4, 8.4 Hz, 4H), 7.45 (dd, J = 7.2, 7.2H z, 2H), 7.37 (dd, J = 7.6, 7.6Hz, 1H), 6.17 (d, J = 2.0Hz, 1H), 5.80 (d, J = 2.0Hz, 1H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 141.9, 140.2, 137.4, 130.7, 128.9, 127.74, 127.68, 127.1, 126.9, 117.6.

[0148] The NMR data for (1-bromoethenyl)benzene produced in Example 5-2 is shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ ): 7.61-7.58 (m, 2H), 7.37-7.32 (m, 3H), 6.12 (d, J=2.0Hz, 1H), 5.78 (d, J=2.0Hz, 1H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 138.6, 131.0, 129.1, 128.3, 127.3, 117.7.

[0149] The NMR data for 4-(1-bromoethenyl)-1-chlorobenzene prepared in Example 5-3 is shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ ): 7.53 (d, J = 8.4 Hz, 2H), 7.32 (d, J = 8.4 Hz, 2H), 6.10 (d, J = 2.0 Hz, 1H), 5.79 (d, J = 2.0 Hz, 1H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 137.0, 135.1, 129.6, 128.6, 128.4, 118.2.

[0150] The NMR data for 1-bromo-4-(1-bromoethenyl)benzene prepared in Example 5-4 is shown below. １ H-NMR (400MHz, CDCl３ , δ ｐｐｍ ): 7.49-7.44 (m, 4H), 6.11 (d, J=2.4Hz, 1H), 5.79 (d, 2.4Hz, 1H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 137.5, 131.4, 129.7, 128.8, 123.3, 118.3.

[0151] The NMR data for 1-(1-bromoethenyl)-4-trifluoromethylbenzene prepared in Example 5-5 is shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ ): 7.70 (d, J = 8.0 Hz, 2H), 7.61 (d, J = 8.0 Hz, 2H), 6.20 (d, J = 2.4 Hz, 1H), 5.89 (d, J = 2.4 Hz, 1H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 141.9, 131.0 (q, ２ J=32.2Hz), 129.2, 127.6, 125.3(q, ３ J=3.0Hz), 123.8(q, １ J=272.7Hz), 119.7.

[0152] The NMR data for 1-(1-bromoethenyl)-4-nitrobenzene prepared in Example 5-6 are shown below. １ H-NMR (300MHz, CDCl ３ , δ ｐｐｍ ): 8.21 (d, J = 9.0 Hz, 2H), 7.76 (d, J = 9.0 Hz, 2H), 6.29 (d, J = 2.4 Hz, 1H), 5.98 (d, J = 2.4 Hz, 1H). １３ C-NMR (125MHz, CDCl ３ , δ ｐｐｍ ): 147.9, 144.4, 128.23, 128.17, 123.6, 121.2.

[0153] The NMR data for 1-butyl-4-(1-bromoethenyl)benzene produced in Examples 5-7 and 5-8 are shown below. １ H-NMR (400MHz, CDCl３ , δ ｐｐｍ ): 7.50 (d, J = 8.4 Hz, 2H), 7.15 (d, J = 8.4 Hz, 2H), 6.08 (d, J = 2.0 Hz, 1H), 5.72 (d, J = 2.0 Hz, 1H), 2.62 (t, J=7.6Hz, 2H), 1.64-1.55 (m, 2H), 1.38-1.31 (m, 2H), 0.93 (t, J=7.2Hz, 3H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 144.2, 135.9, 131.1, 128.3, 127.2, 116.8, 35.3, 33.4, 22.3, 13.9.

[0154] The NMR data for 3-(1-bromoethenyl)-1-butoxybenzene produced in Examples 5-9 and 5-10 are shown below. １ H-NMR (500MHz, CDCl ３ , δ ｐｐｍ ): 7.24 (dd, J = 8.0, 8.0 Hz, 1H), 7.17-7.14 (m, 1H), 7.12-7.11 (m, 1H), 6.86 (dd, J = 8.0, 2.5Hz, 1H), 6.11 (d, J = 2.0H) z, 1H), 5.77 (d, J = 2.0Hz, 1H), 3.98 (t, J = 6.5Hz, 2H), 1.80-1.74 (m, 2H), 1.52-1.46 (m, 2H), 0.98 (t, J = 7.5Hz, 3H). １３ C-NMR (125MHz, CDCl ３ , δ ｐｐｍ ): 158.9, 139.9, 130.8, 129.2, 119.5, 117.8, 115.1, 113.8, 67.8, 31.3, 19.2, 13.8.

[0155] The NMR data for 2-bromo-1-(1-bromoethenyl)-4-chlorobenzene prepared in Example 5-11 is shown below. １ H-NMR (500MHz, CDCl ３ , δ ｐｐｍ ): 7.61 (s, 1H), 7.30 (d, J = 1.5Hz, 2H), 5.95 (d, J = 1.5Hz, 1H), 5.86 (d, J = 1.5Hz, 1H). １３ C-NMR (125MHz, CDCl ３, δ ｐｐｍ ): 139.7, 135.2, 132.8, 131.2, 127.7, 126.4, 123.1, 122.5.

[0156] The NMR data for 2-[2-(1-bromoethenyl)phenyl]-1,3-dioxane prepared in Example 5-12 are shown below. １ H-NMR (500MHz, CDCl ３ , δ ｐｐｍ ): 7.72-7.70 (m, 1H), 7.39-7.31 (m, 3H), 5.95 (d, J = 1.5Hz, 1H), 5.86 (d, J = 1.5Hz, 1H), 5 .75 (s, 1H), 4.25-4.21 (m, 2H), 4.01-3.95 (m, 2H), 2.30-2.22 (m, 1H), 1.47-1.42 (m, 1H). １３ C-NMR (125MHz, CDCl ３ , δ ｐｐｍ ): 138.7, 135.6, 129.2, 129.0, 128.7, 126.54, 126.45, 122.4, 99.1, 67.4, 25.7.

[0157] The NMR data for 2-(1-bromoethenyl)naphthalene produced in Example 5-13 is shown below. １ H-NMR (500MHz, CDCl ３ , δ ｐｐｍ ): 8.09 (d, J=1.5Hz, 1H), 7.88-7.86 (m, 1H), 7.84-7.79 (m, 2H), 7.69 (dd, J=8. 5, 2.0Hz, 1H), 7.53-7.48 (m, 2H), 6.27 (d, J = 2.0Hz, 1H), 5.88 (d, J = 2.0Hz, 1H). １３ C-NMR (125MHz, CDCl ３ , δ ｐｐｍ ): 135.6, 133.4, 132.9, 131.1, 128.5, 127.9, 127.5, 126.9, 126.6, 124.1, 118.0.

[0158] The NMR data for 1-(1-bromoethenyl)-2-(3-methyl-2-butenyl)benzene produced in Examples 5-14 and 5-15 are shown below. １ H-NMR (500MHz, CDCl３ , δ ｐｐｍ ): 7.28-7.20 (m, 2H), 7.20-7.15 (m, 2H), 5.88 (d, J = 1.5Hz, 1H), 5.73 (d, J = 1. 5Hz, 1H), 5.30-5.26 (m, 1H), 3.45 (d, J=7.5Hz, 2H), 1.74 (s, 3H), 1.72 (s, 3H). １３ C-NMR (125MHz, CDCl ３ , δ ｐｐｍ ): 140.0, 139.3, 132.7, 129.2, 129.1, 129.0, 128.9, 125.7, 122.7, 121.1, 31.6, 25.7, 17.9.

[0159] The NMR data for 1-(1-bromoethenyl)-4-(2-ethynyl)benzene produced in Example 5-16 is shown below. １ H-NMR (500MHz, CDCl ３ , δ ｐｐｍ ): 7.28-7.20 (m, 2H), 7.20-7.15 (m, 2H), 5.88 (d, J = 1.5Hz, 1H), 5.73 (d, J = 1. 5Hz, 1H), 5.30-5.26 (m, 1H), 3.45 (d, J=7.5Hz, 2H), 1.74 (s, 3H), 1.72 (s, 3H). １３ C-NMR (125MHz, CDCl ３ , δ ｐｐｍ ): 140.0, 139.3, 132.7, 129.2, 129.1, 129.0, 128.9, 125.7, 122.7, 121.1, 31.6, 25.7, 17.9.

[0160] The NMR data for 1-(1-bromoethenyl)cyclohexene prepared in Examples 5-17 and 5-18 are shown below. １ H-NMR (500MHz, CDCl ３ , δ ｐｐｍ ): 6.35 (t, J=4.0Hz, 1H), 5.75 (d, J=0.5Hz, 1H), 5.53 (d, J=0.5Hz, 1H), 2.26-2.19 (m, 4H), 1.71-1.66 (m, 2H), 1.60-1.57 (m, 2H). １３ C-NMR (125MHz, CDCl ３ , δ ｐｐｍ): 133.8, 132.6, 132.5, 114.3, 26.1, 25.9, 22.6, 21.8.

[0161] The NMR data for 2-bromo-5-phenyl-1-pentene prepared in Example 5-19 is shown below. １ H-NMR (500MHz, CDCl ３ , δ ｐｐｍ ): 7.32-7.28 (m, 2H), 7.23-7.18 (m, 3H), 5.59 (d, J=1.5Hz, 1H), 5.44 (d, J=1.5Hz, 1H), 2.65 (q, J=7.5Hz, 2H), 2.47 (t, J=7.5Hz, 2H), 1.92 (m, 2H). １３ C-NMR (125MHz, CDCl ３ , δ ｐｐｍ ): 141.7, 134.3, 128.43, 128.37, 125.9, 116.8, 40.7, 34.4, 29.5.

[0162] The NMR data for 1-bromo-1-phenyl-1-decene prepared in Example 5-20 is shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ ): 7.53-7.50 (m, 2H), 7.34-7.27 (m, 3H), 6.20 (t, J=7.2Hz, 1H), 2.39-2. 33 (m, 2H), 1.54-1.47 (m, 2H), 1.39-1.28 (m, 10H), 0.89 (t, J=6.8Hz, 3H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 140.2, 132.0, 128.2, 127.5, 125.2, 32.5, 31.9, 29.4, 29.32, 29.25, 28.4, 22.7, 14.1.

[0163] As shown in Examples 5-1 to 5-19, it was found that bromine-substituted alkenes can be selectively produced according to Markovnikov's rule by reacting a complex of cesium fluoride and diisobutylaluminum hydride with a monosubstituted alkyne and a brominating agent. Furthermore, as shown in Example 5-20, it was found that when bromine is introduced into a disubstituted alkyne in which one substituent is an aromatic group and the other is an aliphatic group, bromine is selectively introduced into the carbon atom substituted by the aromatic group. In addition, from the results of Examples 5-7, 5-9, and 5-14, it was found that the reactivity decreases when an electron-donating group is present on the aromatic group substituent of the disubstituted alkyne. Furthermore, from the results of Examples 5-17 and 5-19, it was found that the reactivity decreases when a disubstituted alkyne does not have an aromatic group as a substituent. However, as shown in Examples 5-8, 5-10, 5-15, and 5-18, it was found that the reactivity improves by increasing the reaction temperature.

[0164] <Example 6> (Production of 5-phenyl-4-tridecene from 1-phenyl-1-pentine) Cesium fluoride (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) (121.5 mg, 0.80 mmol) was weighed into a 10 mL reaction vessel and stirred at 100°C for 1 hour under reduced pressure using a vacuum pump to dry. After the reaction vessel was subjected to an argon atmosphere, it was cooled to room temperature and diisobutylaluminum hydride (reagent, 1 M hexane solution, manufactured by Tokyo Chemical Industry Co., Ltd.) (0.8 mL, 0.8 mmol) was added. By stirring at room temperature for 30 minutes, a white complex of cesium fluoride and diisobutylaluminum hydride was obtained as a hexane suspension. Immediately after adding diisobutylaluminum hydride, precipitation of cesium fluoride was observed when stirring was stopped, but after stirring for 30 minutes, no precipitation was observed even when stirring was stopped. To a hexane solution of a complex of cesium fluoride and diisobutylaluminum hydride, diethylene glycol dimethyl ether (1.6 mL) and 1-phenyl-1-pentine (361.6 mg, 0.42 mmol) prepared in the above-mentioned Production Example 2 were added, and the mixture was stirred for 2 hours while heating in a 50°C silicone oil bath. The reaction mixture was cooled to room temperature, and 1-iodooctane (40.5 mg, 1.69 mmol), prepared by the Finkelstein reaction from commercially available 1-bromooctane (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) and sodium iodide (reagent, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), was added, and the mixture was stirred for 18 hours while heating in a 120°C silicone oil bath. After the reaction mixture cooled to room temperature, water was added. The organic layer was then extracted with hexane using a separatory funnel, and the organic layer was dried over sodium sulfate. After removing sodium sulfate from the organic layer by filtration, the organic layer was concentrated using an evaporator. The resulting residue was purified by column chromatography using silica gel (Wako Gel® 60N, 63-212 μm, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) with hexane as the developing solvent, yielding (E)-5-phenyl-4-tridecene in 45% yield.

[0165] The NMR data for (E)-5-phenyl-4-tridecene produced in Example 6 is shown below. １ H-NMR (400MHz, CDCl ３ , δ ｐｐｍ): 7.35-7.28 (m, 4H), 7.20 (dd, J = 7.2Hz, 1H), 5.63 (t, J = 7.2Hz, 1H), 2.48 (t, J = 6.8Hz, 2H), 2.17 (q, J = 7.2Hz, 2H), 1.50-1.42 (m, 2H), 1.37-1.23 (m, 12H), 0.96 (t, J = 7.2Hz, 3H), 0.87 (t, J = 7.2Hz, 3H). １３ C-NMR (100MHz, CDCl ３ , δ ｐｐｍ ): 143.6, 140.3, 128.9, 128.1, 128.1, 126.3, 31.9, 30.6, 29.8, 29.6, 29.4, 29.3, 28.7, 23.1, 22.7, 14.1, 13.9.

[0166] The results from Example 6 showed that when introducing an alkyl group to a disubstituted alkyne, in which one substituent is an aromatic group and the other is an aliphatic group, using a complex of cesium fluoride and diisobutylaluminum hydride, the alkyl group is selectively introduced to the carbon atom substituted for the aromatic group.

[0167] <Example 7> (Production of 1-phenyl-1-(4-methylphenyl)ethene from phenylacetylene) Cesium fluoride (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) (97.2 mg, 0.64 mmol) was weighed into a 10 mL reaction vessel and stirred at 100°C for 1 hour under reduced pressure using a vacuum pump to dry. After the reaction vessel was subjected to an argon atmosphere, it was cooled to room temperature and diisobutylaluminum hydride (reagent, 1 M hexane solution, manufactured by Tokyo Chemical Industry Co., Ltd.) (0.8 mL, 0.8 mmol) was added. By stirring at room temperature for 30 minutes, a white complex of cesium fluoride and diisobutylaluminum hydride was obtained as a hexane suspension. Immediately after adding diisobutylaluminum hydride, precipitation of cesium fluoride was observed when stirring was stopped, but after stirring for 30 minutes, no precipitation was observed even when stirring was stopped. To a hexane solution of a complex of cesium fluoride and diisobutylaluminum hydride, diethylene glycol dimethyl ether (1.6 mL) and commercially available phenylacetylene (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) (39.8 mg, 0.39 mmol) were added, and the mixture was stirred for 2 hours while heating in a silicone oil bath at 50°C. The reaction mixture was cooled to room temperature, and tetrakistriphenylphosphine palladium (20.8 mg, 0.40 mmol) prepared using diethylene glycol dimethyl ether (1.6 mL), palladium chloride (reagent, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), triphenylphosphine (reagent, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and hydrazine (reagent, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 4-iodotoluene (175.0 mg, 0.80 mmol) were added, and the mixture was stirred at 70°C for 18 hours. After the reaction mixture cooled to room temperature, water was added, and the mixture was stirred for 15 minutes. The organic layer was extracted with hexane using a separatory funnel, and the organic layer was dried over sodium sulfate. After removing sodium sulfate from the organic layer by filtration, the organic layer was concentrated using an evaporator. The resulting residue was purified by column chromatography using silica gel (Wako Gel® 60N, 63-212 μm, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) with hexane as the developing solvent, yielding 1-phenyl-1-(4-methylphenyl)ethene in 70% yield.

[0168] The NMR data for 1-phenyl-1-(4-methylphenyl)ethene produced in Example 7 is shown below. １ H-NMR (500MHz, CDCl ３ , δ ｐｐｍ ): 7.35-7.30 (m, 5H), 7.24 (d, J = 8.0Hz, 2H), 7.14 (d, J = 8.0Hz, 2H), 5.43 (d, J = 2.0Hz, 1H), 5.41 (d, J = 2.0Hz, 1H), 2.37 (s, 3H). １３ C-NMR (125MHz, CDCl ３ , δ ｐｐｍ ): 149.9, 141.7, 138.6, 137.5, 128.8, 128.3, 128.13, 128.09, 127.6, 113.6, 21.2.

[0169] The results from Example 7 showed that when introducing an aromatic group to a monosubstituted alkyne using a complex of cesium fluoride and diisobutylaluminum hydride, the aromatic group is selectively introduced to the carbon atom substituted with the aromatic group.

[0170] According to the present invention, a complex of an alkali metal fluoride salt and an aluminum compound represented by general formula (1), and a method for producing a reductive substituted alkene from a substituted alkyne using the same can be provided. The method for producing a reductive substituted alkene from a substituted alkyne using a complex of an alkali metal fluoride salt and an aluminum compound represented by general formula (1) of the present invention can be suitably used compared to conventional methods for producing substituted alkenes using transition metals.

Claims

1. A complex of an alkali metal fluoride salt and an aluminum compound represented by the following general formula (1). (In general formula (1), R １ and R ２ These are each independently an alkyl group or an aromatic group.

2. The complex according to claim 1, wherein the alkali metal fluoride salt is cesium fluoride.

3. The complex according to claim 1 or 2, wherein the alkyl group is a branched alkyl group having 4 to 10 carbon atoms at the α or β position.

4. The aforementioned R １ and R ２ The complex according to claim 1 or 2, wherein the group is selected from isobutyl group, 2-methylbutyl group, 2-ethylbutyl group, 2-methylpentyl group, 2-ethylpentyl group, 2-propylpentyl group, cyclohexylmethyl group, and phenyl group.

5. The complex according to any one of claims 1 to 4, which is a complex of cesium fluoride and diisobutylaluminum hydride.

6. A method for producing a complex according to any one of claims 1 to 5, comprising mixing the alkali metal fluoride salt and the aluminum compound represented by the general formula (1) in an organic solvent.

7. A method for producing a substituted alkene reductively from a substituted alkyne using the complex described in any one of claims 1 to 5.

8. The method according to claim 7, wherein at least one substituent of the substituted alkyne is an aromatic group.

9. The method according to claim 8, wherein one substituent of the substituted alkyne is an aromatic group and the other substituent is an aliphatic group or an aromatic group.

10. The method according to claim 9, wherein the substituted alkene is an E-substituted alkene.

11. A method for reductively introducing a substituent to a substituted alkyne using the complex described in any one of claims 1 to 5.

12. The method according to claim 11, wherein the substituted alkyne is a substituted alkyne in which an aromatic group is substituted on one side, and the introduction of the substituent is the introduction to a carbon atom to which the aromatic group is bonded.

13. The method according to claim 11 or 12, wherein the introduction of the substituent is the introduction of a group selected from halogen atoms, alkyl groups, and aromatic groups.

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