JP2005232036A - Polysubstituted olefin and method for selectively producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for selectively producing a polysubstituted olefin suitable for a luminescent material, etc. <P>SOLUTION: The method for selectively producing a polysubstituted olefin comprises reacting a first carbon atom in an alkene compound in which an organic group containing an atom such as Si, etc., is bonded through the atom to a second carbon atom in the first carbon atom and the second carbon atom forming an alkene bond with a first aryl compound containing a first aryl group to bond the first aryl group to the first carbon atom, reacting the first carbon atom with a second aryl compound containing a second aryl group to bond the second aryl group to the first carbon atom and reacting the second carbon atom with a third aryl compound containing a third aryl group to bond the third aryl group to the second carbon atom. The reactions in which the first aryl group and the second aryl group are bonded to the first carbon atom are Mizoroki-Heck reactions and the reaction in which the third group is bonded to the second carbon atom is a cross coupling reaction. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a polysubstituted olefin suitable for various fields including a luminescent material and the like, an efficient selective production method thereof, and a luminescent material containing the polysubstituted olefin.

  A polysubstituted olefin obtained by substituting a number of substituents (preferably aryl groups) on carbon atoms forming an olefin bond can be suitably used in various fields, and is particularly promising as a luminescent material. Development of a new synthesis method is desired. Conventionally, the synthesis of the polysubstituted olefin has been performed by combining various known chemical synthesis methods, but the yield is poor and a desired substituent can be introduced at a desired position. However, it was difficult to synthesize a polysubstituted olefin having a desired structure, and there was a problem that it could not be synthesized efficiently and selectively (see Non-Patent Document 1).

C. Zhou, D.C. E. Emrich, R.M. C. Larock, Org. Lett. 2003, 5, 1579

  An object of the present invention is to solve the conventional problems and achieve the following objects. That is, the present invention provides a multi-substituted olefin suitable for various fields including a light-emitting material and the like, an efficient selective production method thereof, and a light-emitting material suitable for various fields including the multi-substituted olefin. For the purpose.

As a result of intensive studies by the present inventors in order to solve the above-mentioned problems, a specific alkenyl compound (for example, alkenylsilane) is used as a raw material, and a desired aryl group is desired to a carbon atom forming an olefin bond. It is possible to efficiently and selectively synthesize a desired polysubstituted olefin by introducing it at a site, and when the alkenyl compound is an alkenyl sulfide, the temperature conditions for introducing the desired aryl group are controlled. As a result, the inventors have obtained knowledge that the desired polysubstituted olefin can be synthesized efficiently and selectively. This invention is based on the said knowledge by the present inventors, and the means for solving the said subject are as follows. That is,
<1> A group 13 to a group 16 in the long-period periodic table of the element include an alkene bond and the second carbon atom of the first carbon atom and the second carbon atom forming the alkene bond. In an alkene compound in which an organic group containing an atom selected from the group is bonded through the atom,
The first aryl compound containing a first aryl group is reacted with the first carbon atom to bond the first aryl group, and the second aryl compound containing a second aryl group is reacted to react with the first carbon atom. After coupling the diaryl group,
A method for selectively producing a multi-substituted olefin, characterized in that a third aryl compound containing a third aryl group is reacted with the second carbon atom to bond the third aryl group.
<2> The method for selectively producing a polysubstituted olefin according to <1>, wherein the atom is any one of a Si atom, a Se atom, an O atom, a Ge atom, a Sn atom, a Pb atom, and a B atom.
<3> The method for selectively producing a polysubstituted olefin according to <1>, wherein the atom is a Si atom.
<4> After the first aryl group is bonded to the first carbon atom, the second aryl group is bonded at a higher temperature than when the first aryl group is bonded. 3> The method for selectively producing a multi-substituted olefin according to any one of 3>.
<5> An organic group containing an alkene bond, wherein a pyrimidine ring is bonded to an S atom to the second carbon atom of the first carbon atom and the second carbon atom forming the alkene bond, In an alkene compound bonded through an S atom,
After the first aryl compound containing the first aryl group is reacted with the first carbon atom to bond the first aryl group, the temperature is higher than when the first aryl group is bonded. After reacting a second aryl compound containing a second aryl group to bind the second aryl group,
A method for selectively producing a multi-substituted olefin, characterized in that a third aryl compound containing a third aryl group is reacted with the second carbon atom to bond the third aryl group.
<6> The method according to any one of <4> to <5>, wherein the second aryl group is bonded to the first carbon atom at a temperature 5 to 100 ° C. higher than when the first aryl group is bonded. This is a method for selectively producing a multi-substituted olefin.
<7> The method according to any one of <4> to <5>, wherein the second aryl group is bonded to the first carbon atom at a temperature 20 to 40 ° C. higher than when the first aryl group is bonded. This is a method for selectively producing a multi-substituted olefin.
<8> The reaction temperature for bonding the first aryl group to the first carbon atom is 45 ° C. or higher and lower than 75 ° C., and the reaction temperature for bonding the second aryl group is 75 ° C. or higher and lower than 105 ° C. The method for selectively producing a multi-substituted olefin according to any one of <4> to <7>.
<9> From the above <1>, the reaction of bonding the first aryl group to the first carbon atom and the reaction of bonding the second aryl group are a Mizoroki-Heck reaction. <8> A method for selectively producing a multi-substituted olefin according to any one of <8>.
<10> The polysubstituted olefin according to any one of <1> to <9>, wherein the reaction of bonding the third aryl group to the second carbon atom is a cross-coupling reaction. This is a selective manufacturing method.
<11> The organic compound bonded to the second carbon atom is substituted with a third aryl group, and the third aryl group is bonded to the second carbon atom. This is a method for selectively producing a polysubstituted olefin.
<12> The alkene compound in which the fourth aryl group is bonded to the second carbon atom before the first aryl group is bonded is used. This is a method for selectively producing a substituted olefin.
<13> After the third aryl group is bonded to the second carbon atom, the organic group bonded to the second carbon atom is replaced with the fifth aryl group, and the fifth aryl is bonded to the second carbon atom. The method for selectively producing a polysubstituted olefin according to any one of <1> to <12>, wherein a group is bonded.
<14> The method for selectively producing a polysubstituted olefin according to <13>, wherein the reaction of bonding the fifth aryl group to the second carbon atom is a cross-coupling reaction.
<15> The method for selectively producing a polysubstituted olefin according to <9>, wherein the Mizoroki-Heck reaction is performed in the presence of a transition metal catalyst and a base.
<16> The method for selectively producing a multi-substituted olefin according to any one of <10> and <14>, wherein the cross-coupling reaction is performed in the presence of a transition metal catalyst.
<17> The method for selectively producing a polysubstituted olefin according to any one of <15> to <16>, wherein the transition metal catalyst is a palladium catalyst.
<18> The method for selectively producing a polysubstituted olefin according to <17>, wherein the palladium catalyst is Pd [P (t-butyl) ₃ ] ₂ .
<19> Using the transition metal catalyst, base and reaction vessel used in the reaction of bonding the second aryl group to the first carbon atom, the reaction of bonding the first aryl group to the first carbon atom. It is the selective manufacturing method of the polysubstituted olefin as described in said <15> performed.
<20> The multi-substituted olefin according to any one of <1> to <19>, wherein the first aryl compound, the second aryl compound, and the third aryl compound are selected from halogenated aryl compounds. It is a manufacturing method.
<21> The method for selectively producing a polysubstituted olefin according to <13>, wherein the third aryl compound and the fifth aryl compound are selected from magnesium-containing aryl compounds.
<22> The aryl group in at least one of the first aryl compound, the second aryl compound, the third aryl compound, the fourth aryl compound, and the fifth aryl compound is any one of the following structural formulas a to q: The method for selectively producing a multi-substituted olefin according to any one of <20> to <21>, which is selected from those represented by formula (1).
<23> The polysubstituted olefin is
A first aryl group and a second aryl group are bonded to the first carbon atom of the first carbon atom and the second carbon atom that include the alkene bond and form the alkene bond, and the second carbon A trisubstituted product in which a tertiary aryl group is bonded to an atom, and
A first aryl group and a second aryl group are bonded to the first carbon atom of the first carbon atom and the second carbon atom that include the alkene bond and form the alkene bond, and Any one of <1> to <22>, wherein the carbon atom is at least one of a tetra-substituted product in which a third aryl group and any one of a fourth aryl group and a fifth aryl group are bonded. This is a method for selectively producing a polysubstituted olefin.
<24> A polysubstituted olefin produced by the method for selectively producing a polysubstituted olefin according to any one of <1> to <23>.
<25> A first aryl group and a second aryl group are bonded to the first carbon atom of the first carbon atom and the second carbon atom that include the alkene bond and form the alkene bond, A trisubstituted product in which a tertiary aryl group is bonded to two carbon atoms, and
A first aryl group and a second aryl group are bonded to the first carbon atom of the first carbon atom and the second carbon atom that include the alkene bond and form the alkene bond, and The polysubstituted olefin according to <24>, wherein the polysubstituted olefin is at least one of a tetrasubstituted product in which a third aryl group and any one of a fourth aryl group and a fifth aryl group are bonded to a carbon atom.
<26> The polysubstituted olefin according to any one of <24> to <25> represented by the following structural formula (4jab, 4cgb, 4iib, 4mmn, 4ggj, 4ijp, 4icq, 4igd, and 11cjo).
However, in the above structural formulas, Me represents a methyl group.
<27> A polysubstituted olefin represented by the following structural formula.
However, in the above structural formulas, Me represents a methyl group.
<28> A polysubstituted olefin represented by the following structural formula.
However, in the structural formula:
Ar ¹ and Ar ² are both a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-methoxyphenyl group, and a 1-naphthyl group,
Ar ¹ is a phenyl group and Ar ² is a 2-methylphenyl group, a 4-methylphenyl group or a 4-methoxyphenyl group,
Ar ¹ is a 4-methylphenyl group, Ar ² is a phenyl group or a 4-methoxyphenyl group,
Ar ¹ is a 4-methoxyphenyl group and Ar ² is a phenyl group, a 4-methylphenyl group or a 1-naphthyl group,
Ar ¹ is a 3-thienyl group, and Ar ² is a 4-methylphenyl group, a 4-methoxyphenyl group, or a 1-naphthyl group.
In the structural formula, Ph represents a phenyl group, p-Anis represents a 4-methoxyphenyl group, and Tol-p represents a 4-methylphenyl group.
<29> The polysubstituted olefin according to <24>, which is used as a light emitting material.
<30> A light emitting material comprising at least the polysubstituted olefin according to any one of <24> to <25>.
<31> The luminescent material according to <30>, containing at least one polysubstituted olefin represented by the following structural formula.
However, in the above structural formulas, Me represents a methyl group.

  According to the present invention, conventional problems can be solved, and a multi-substituted olefin suitable for various fields including a luminescent material and the like, an efficient selective production method thereof, A light-emitting material suitable in the field can be provided.

(Multi-substituted olefin and its selective production method, and luminescent material)
In the method for selectively producing a polysubstituted olefin of the present invention, a first aryl group is bonded to the first carbon atom in an alkene compound containing a first carbon atom and a second carbon atom forming an alkene bond. (First aryl group bonding step), after bonding the second aryl group (second aryl group bonding step), bonding the third aryl group to the second carbon atom (third aryl group) Bonding step) and further other steps as necessary.
The polysubstituted olefin of the present invention can be produced by the first aryl group bonding step and the second aryl group bonding step, preferably by the selective production method of the multisubstituted olefin of the present invention.
The light emitting material of the present invention contains at least the polysubstituted olefin of the present invention, and further contains other components appropriately selected as necessary.
Hereinafter, the contents of the multi-substituted olefin and the light-emitting material of the present invention will be clarified through the description of the method for selectively producing a multi-substituted olefin of the present invention.

-Alkene compounds-
The alkene compound is not particularly limited as long as it has a first carbon atom and a second carbon atom that form an alkene bond, and can be appropriately selected according to the purpose. Particularly preferred are the first alkene compound and the second alkene compound.

--First alkene compound--
The first alkene compound includes an alkene bond, and the second carbon atom of the first carbon atom and the second carbon atom forming the alkene bond is bonded to the second periodic table of the element. It has a structure in which an organic group containing an atom selected from Group 13 to Group 16 is bonded through the atom.
The atom is preferably selected from, for example, Si atom, Se atom, O atom, Ge atom, Sn atom, Pb atom and B atom, and among these, Si atom is particularly preferable. The first alkene compound in the case where the atom is a Si atom may be referred to as an alkenylsilane.

--Second alkene compound--
The second alkene compound includes an alkene bond, and a pyrimidine ring is bonded to the S atom to the second carbon atom of the first carbon atom and the second carbon atom forming the alkene bond. The organic group is formed by bonding through the S atom. The second alkene compound is sometimes referred to as an alkenyl sulfide.

-Primary aryl group binding step-
The first aryl group bonding step is a step of bonding the first aryl group by reacting the first aryl compound containing the first aryl group with the first carbon atom in the alkene compound.

There is no restriction | limiting in particular as said 1st aryl compound, Although it can select suitably according to the objective, For example, a halogenated aryl is mentioned especially suitably.
Examples of the halogen in the aryl halide include fluorine (F), chlorine (Cl), iodine (I), bromine (Br), and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, iodine (I), bromine (Br) and the like are particularly preferable.
The aryl in the aryl halide is not particularly limited and may be appropriately selected depending on the intended purpose. The aryl may contain a heteroatom and may be substituted with a known substituent. These may be used individually by 1 type and may use 2 or more types together. Among these, those represented by any one of the following structural formulas a to q are preferable.

--Reaction--
As the reaction for reacting the first aryl compound with the first carbon atom, for example, a Mizoroki-Heck reaction is particularly preferably exemplified.

  The Mizoroki-Heck reaction is, for example, (a) Mizoroki, T .; Mori, K .; Ozaki, A. Bull. Chem. Soc. Jpn. 1971, 44, 581. ) Heck, RF; Nolley, JPJ Org. Chem. 1972, 14, 2320., (c) Beletskaya, IP; Cheprakov, AV Chem. Rev. 2000, 100, 3009., (d) Cabri, W .; Candiani, I. Acc. Chem. Res. 1995, 28, 2., (e) de Meijere, A .; Meyer, FE Angew. Chem., Int. Ed. Engl. 1994, 33, 2379., (f) Heck, RF In Comprehensive Organic Synthesis; Trost, BM, Ed .; Pergamon: New York, 1991; Vol. 4, Chapter 4.3.

The conditions for the Mizooki-Heck reaction are not particularly limited and may be appropriately selected depending on the intended purpose. For example, the reaction is preferably performed in the presence of a transition metal catalyst and a base.
There is no restriction | limiting in particular as said transition metal catalyst, Although it can select suitably according to the objective, For example, a palladium catalyst is mentioned suitably. These may be used individually by 1 type and may use 2 or more types together. Among the palladium catalysts, Pd [P (t-butyl) ₃ ] ₂ is particularly preferable.
There is no restriction | limiting in particular as the usage-amount of the said transition metal catalyst, Although it can select suitably according to the objective, For example, it is 20 mass% or less normally, 10 mass% or less is preferable, and 3-7 mass% is preferable. More preferred.

There is no restriction | limiting in particular as said base, Although it can select suitably according to the objective, For example, an amine compound is mentioned suitably. These may be used individually by 1 type and may use 2 or more types together. Of the amine compounds, triethylamine is particularly preferable.
There is no restriction | limiting in particular as the usage-amount of the said base, Although it can select suitably according to the objective, For example, it is 10 equivalent or less normally with respect to the said transition gold catalyst, and 0.5-5 equivalent is preferable. 1.5 to 3.5 equivalents are more preferable.

  The temperature of the Mizooki-Heck reaction in the first aryl group bonding step is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the first alkene compound may be selected from When used, it is usually about 40 to 120 ° C., preferably 50 to 100 ° C., more preferably 45 ° C. or more and less than 75 ° C., and when the second alkene compound (alkenyl sulfide) is used, -80 degreeC is preferable and 45 degreeC or more and less than 75 degreeC are more preferable.

The reaction can be performed by mixing or stirring in a reaction vessel appropriately selected from known ones, and can be preferably performed in a state where the alkene compound is dissolved in an organic solvent.
There is no restriction | limiting in particular as said organic solvent, According to the objective, it can select suitably, For example, a dioxane, toluene, tetrahydrofuran, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these organic solvents, dioxane, toluene and the like are preferable.

  In the first aryl group bonding step, the first aryl group is selectively bonded (introduced) to the first carbon atom in the alkene compound.

-Second aryl group bonding step-
The second aryl group bonding step is a step of bonding the second aryl group by reacting the second aryl compound containing the second aryl group with the first carbon atom in the alkene compound.

There is no restriction | limiting in particular as said 2nd aryl compound, According to the objective, it can select suitably, The thing similar to said 1st aryl compound is mentioned, Among these, an aryl halide is mentioned especially suitably. .
Suitable examples of the halogen and aryl in the aryl halide include those described above. These halogens and aryls may be the same as or different from those in the first aryl group binding step.

--Reaction--
As the reaction at the time of reacting the second aryl compound with the first carbon atom, the above-described Mizoroki-Heck reaction is particularly suitable as in the first aryl group bonding step. It is mentioned in.

  As the conditions for the Mizooki-Heck reaction, it is preferable that the reaction is performed in the presence of the transition metal catalyst and the base described above, as in the first aryl group binding step. A transition metal catalyst and base other than the transition metal catalyst and base used in the coupling step may be used, or the transition metal catalyst and base used in the first aryl group coupling step may be used as they are in the second aryl group coupling. It can be suitably used in the process. Furthermore, this reaction can be performed in the same reaction vessel as that in which the first aryl group binding step was performed. In this case, there is no need to exchange the reaction vessel, catalyst, organic solvent, etc. between the first aryl group bonding step and the second aryl group bonding step, and this is efficient. (POT) process.

The temperature of the Mizooki-Heck reaction in the second aryl group binding step is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the first alkene compound may be selected from When used, it is usually about 40 to 120 ° C., preferably 70 to 110 ° C., more preferably 75 ° C. or more and less than 105 ° C., and when the second alkene compound (alkenyl sulfide) is used, 70 -110 degreeC is preferable and 75 degreeC or more and less than 105 degreeC are more preferable.
In addition, when the first alkene compound is used, the temperature is higher than when the first aryl group is bonded to the first carbon atom in the first aryl group bonding step. Preferably, the second aryl group is bonded to the first carbon atom, and the second aryl group is bonded to the first carbon atom at a temperature 5 to 100 ° C. higher than when the first aryl group is bonded. Preferably, the second aryl group is particularly preferably bonded at a temperature 20 to 40 ° C. higher than that when the first aryl group is bonded to the first carbon atom, and the second alkene compound is used. In this case, in the first aryl group bonding step, it is necessary to bond the second aryl group at a temperature higher than when the first aryl group is bonded to the first carbon atom. It is preferable that the second aryl group is bonded at a temperature 5 to 100 ° C. higher than that when the first aryl group is bonded to the carbon atom, and the first aryl group is bonded to the first carbon atom. More preferably, the second aryl group is bonded at a temperature 20 to 40 ° C. higher than that at the time.

  In the second aryl group bonding step, the second aryl group is further selectively bonded to the first carbon atom in which the first aryl group is selectively bonded (introduced) in the alkene compound ( be introduced.

  Of the first carbon atom and the second carbon atom forming the alkene bond by the first aryl group bonding step and the second aryl group bonding step, the first aryl group and the second carbon atom, The second aryl group is selectively bonded to obtain a trisubstituted alkenyl (trisubstituted product) in which the organic group remains bonded to the first carbon atom.

  Among such tri-substituted alkenyls (tri-substituted products), examples of novel compounds that can be used as they are in the third aryl group bonding step include alkenyl silanes and alkenyl sulfides shown below. Can be mentioned.

As said alkenylsilane, the compound which has the structure shown below is mentioned suitably, for example.
However, in the above structural formulas, Me represents a methyl group.

Suitable examples of the alkenyl sulfide include compounds having the following structures.
However, in the structural formula:
Ar ¹ and Ar ² are both a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-methoxyphenyl group, and a 1-naphthyl group,
Ar ¹ is a phenyl group and Ar ² is a 2-methylphenyl group, a 4-methylphenyl group or a 4-methoxyphenyl group,
Ar ¹ is a 4-methylphenyl group, Ar ² is a phenyl group or a 4-methoxyphenyl group,
Ar ¹ is a 4-methoxyphenyl group and Ar ² is a phenyl group, a 4-methylphenyl group or a 1-naphthyl group,
Ar ¹ is a 3-thienyl group, and Ar ² is a 4-methylphenyl group, a 4-methoxyphenyl group, or a 1-naphthyl group.
In the structural formula, Ph represents a phenyl group, p-Anis represents a 4-methoxyphenyl group, and Tol-p represents a 4-methylphenyl group.

-Third aryl group binding step-
The third aryl group bonding step is a step of bonding the third aryl group by reacting the second carbon atom in the alkene compound with a third aryl compound containing a third aryl group.

There is no restriction | limiting in particular as said 3rd aryl compound, According to the objective, it can select suitably, The aryl halide similar to said 1st aryl compound, a magnesium containing aryl compound, etc. are mentioned especially suitably. .
In addition, as a magnesium containing aryl compound, the compound etc. which are represented by the formula of Ar-MgX are mentioned suitably, for example. In the formula, Ar represents aryl, and those described above are preferably exemplified, Mg represents a magnesium atom, X represents halogen, and those described above are suitably exemplified. The aryl and halogen may be the same as or different from those in the first aryl group bonding step.

--Reaction--
As the reaction for reacting the third aryl compound with the second carbon atom, for example, a cross-coupling reaction is particularly preferable.
According to the cross-coupling reaction, the first aryl group bonded (substituted) to the first carbon atom in the alkene compound by the first aryl group bonding step and the second aryl group bonding step. And without attacking the second aryl group, the second aryl group is substituted with the organic group (silane-derived group, sulfide-derived group, etc.) bonded to the second carbon atom in the alkene compound. The tertiary aryl group can be bonded to any carbon atom.

  The cross-coupling reaction is, for example, (a) Yoshida, J .; Tamao, K .; Yamamoto, H .; Kakui, T .; Uchida, T .; Kumada, M. Organometallics 1982, 1 , 542., (b) Hatanaka, Y .; Hiyama, TJ Org. Chem 1988, 53, 918., (c) Tamao, K .; Kobayashi, K .; Ito, Y. Tetrahedron Lett. 1989, 30, 6051 , (D) Hatanaka, Y .; Hiyama, T. Synlett 1991, 845., (e) Hiyama, T .; Shirakawa, E. Top. Curr. Chem. 2002, 219, 61. It is as it is.

The conditions for the cross-coupling reaction are not particularly limited and may be appropriately selected depending on the intended purpose. For example, the reaction is preferably performed in the presence of a transition metal catalyst.
There is no restriction | limiting in particular as said transition metal catalyst, Although it can select suitably according to the objective, For example, a palladium catalyst is mentioned suitably. These may be used individually by 1 type and may use 2 or more types together. Among the palladium catalysts, Pd [P (t-butyl) ₃ ] ₂ is particularly preferable.
There is no restriction | limiting in particular as the usage-amount of the said transition metal catalyst, Although it can select suitably according to the objective, For example, it is 20 mass% or less normally, 10 mass% or less is preferable, and 3-7 mass% is preferable. More preferred.

  The temperature of the cross-coupling reaction in the third aryl group bonding step is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is usually about 40 to 120 ° C., 50-100 degreeC is preferable and 45 degreeC or more and less than 75 degreeC are more preferable.

The reaction can be performed by mixing or stirring in a reaction vessel appropriately selected from known ones, and can be suitably performed in the reaction solution in which the second aryl group bonding step has been performed. .
There is no restriction | limiting in particular as said organic solvent, According to the objective, it can select suitably, For example, a dioxane, toluene, tetrahydrofuran, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Of these organic solvents, toluene, tetrahydrofuran and the like are preferable.

  The second carbon atom, not the first carbon atom, in which the first aryl group and the second aryl group are selectively bonded (introduced) in the alkene compound by the third aryl group bonding step. In addition, the third aryl group is further selectively bonded (introduced) to the fifth aryl group described later.

  In the present invention, the first aryl group and the second carbon atom are bonded to the second carbon atom of the first carbon atom and the second carbon atom forming the alkene bond by the third aryl group bonding step. A trisubstituted alkenyl (trisubstituted) in which an aryl group is selectively bonded and the third aryl group is selectively bonded to the first carbon atom, or a tetrasubstituted alkenyl (tetrasubstituted) described below can get.

  Of the first and second carbon atoms forming the alkene bond, the first aryl group and the second aryl group are selectively bonded to the second carbon atom, and the first carbon atom In order to obtain a tetrasubstituted alkenyl (tetrasubstituted product) in which the third aryl group and the fourth aryl group are selectively bonded to atoms, the following two methods are preferably exemplified.

  One method is a method using the alkene compound in which the quaternary aryl group is previously bonded (introduced) to the second carbon atom. In addition, as the fourth aryl group, the above-mentioned aryl is preferably exemplified, and these may be the same as or different from the first aryl group, the second aryl group, the third aryl group, and the like. May be.

  In another method, the third aryl group is bonded to the second carbon atom in the alkene compound, and then the organic group bonded to the second carbon atom is substituted with a fifth aryl group. In this method, the fifth aryl group is bonded to two carbon atoms.

In this case, the conditions in the cross-coupling reaction for bonding the third aryl group to the second carbon atom are not particularly limited and can be appropriately selected depending on the purpose. For example, the treatment (pretreatment) with an organic metal is preferably performed in the presence of a transition metal catalyst, a metal halide, or the like.
There is no restriction | limiting in particular as said organic metal, According to the objective, it can select suitably, For example, an organic lithium compound etc. are mentioned, t-BuLi etc. are preferable (t-Bu represents a tertiary butyl group. ). In addition, there is no restriction | limiting in particular as temperature of the said process (pretreatment), Although it can select suitably according to the objective, For example, -78-25 degreeC is mentioned suitably.
There is no restriction | limiting in particular as said transition metal catalyst, Although it can select suitably according to the objective, For example, a palladium catalyst is mentioned suitably. These may be used individually by 1 type and may use 2 or more types together. Among the palladium catalysts, Pd [P (PPh) ₃ ] ₄ is particularly preferable (Ph represents a phenyl group).
There is no restriction | limiting in particular as the usage-amount of the said transition metal catalyst, Although it can select suitably according to the objective, For example, it is 20 mass% or less normally, 10 mass% or less is preferable, and 3-7 mass% is preferable. More preferred.
There is no restriction | limiting in particular as temperature of the said reaction, Although it can select suitably according to the objective, For example, it is about 0-50 degreeC normally, 10-40 degreeC is preferable and 20-30 degreeC is more preferable. The reaction can be performed by mixing or stirring in a reaction vessel appropriately selected from known ones, and can be suitably performed in the reaction solution in which the second aryl group bonding step has been performed. . There is no restriction | limiting in particular as an organic solvent used for this reaction, According to the objective, it can select suitably, For example, a dioxane, toluene, tetrahydrofuran, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Of these organic solvents, tetrahydrofuran and the like are preferable.

  In order to bond the fifth aryl group, a fifth aryl compound can be used, and the fifth aryl compound is not particularly limited and may be appropriately selected depending on the purpose. Particularly preferred examples include aryl halides and magnesium-containing aryl compounds similar to the three aryl compounds. In this case, as in the third aryl bonding step, a cross-coupling reaction can be preferably used, and preferable conditions thereof are also the same as those in the third aryl group bonding step. It is the same.

  According to the method for selectively producing a multi-substituted olefin of the present invention, (1) a first carbon atom that includes an alkene bond and forms the alkene bond, the first carbon atom is first bonded to the first carbon atom. An aryl group and a second aryl group are bonded, and a polysubstituted olefin (trisubstituted product) formed by bonding a third aryl group to the second carbon atom, (2) an alkene bond is formed, and the alkene bond is formed. A first aryl group and a second aryl group are bonded to the first carbon atom of the first carbon atom and the second carbon atom, and a third aryl group and a second aryl group are bonded to the second carbon atom. A polysubstituted olefin (tetrasubstituted product) formed by bonding with either a tetraaryl group or a fifth aryl group is selectively produced.

Among these polysubstituted olefins, preferred examples include compounds represented by the following structural formulas (4jab, 4cgb, 4iib, 4mmn, 4ggj, 4ijp, 4icq, 4igd and 11cjo).
However, in the above structural formulas, Me represents a methyl group.

  According to the method for selectively producing a polysubstituted olefin of the present invention, the first aryl group and the second aryl group are alkenyl-bonded (double bond) by the Mizoro-Heck reaction. Can be selectively and efficiently bonded (introduced) to one of the two carbon atoms forming the above, and the third aryl group is further required by the Cross-Coupling reaction. Accordingly, the fifth aryl group can be selectively and efficiently bonded (introduced) to the other carbon atom of the two carbon atoms. For this reason, the polysubstituted olefin which has a desired structure can be manufactured selectively and efficiently.

  The multi-substituted olefin of the present invention produced by the method for selectively producing the multi-substituted olefin of the present invention can be suitably used in various fields, but can be particularly suitably used as a light emitting material.

The luminescent material of the present invention contains at least the above-mentioned polysubstituted olefin of the present invention, and further contains other components appropriately selected as necessary. It is particularly preferred to contain at least one of the represented compounds.
In addition, this polysubstituted olefin (compound) shows blue light emission.
This polysubstituted olefin exhibits green light emission.
In the above structural formulas, Me represents a methyl group.

Here, the method for selectively producing the polysubstituted olefin of the present invention will be described more specifically.
As shown in the following reaction schemes (1) to (3), in the presence of the transition metal catalyst and the base, the first aryl compound and the second alkenyl silane or alkenyl sulfide as the alkene compound are When an organic halide (aryl halide) as an aryl compound is reacted, two aryl groups are selectively selected from the two carbon atoms that form an olefin bond but not a carbon atom to which a silane or sulfide is bonded. Can be bonded (introduced) to obtain a polysubstituted alkenylsilane or polysubstituted alkenyl sulfide. The obtained polysubstituted alkenylsilane or polysubstituted alkenyl sulfide is reacted with the organic halide (aryl halide) or organomagnesium compound (Ar-MgX) as the third aryl compound in the presence of the transition metal catalyst. By doing so, a polysubstituted olefin can be obtained with high yield and high stereoselectivity.

  Further, as shown in the following reaction scheme (4), when t-BuLi is allowed to act on the obtained polysubstituted alkenyl sulfide, a proton on the α-carbon of sulfur can be lithiated, where By reacting an organic halide (aryl halide) as the third aryl compound and an organomagnesium compound (Ar-MgX) as the fifth aryl compound, a polysubstituted olefin (tetrasubstituted product) is converted from vinyl sulfide. Can be obtained selectively.

Here, the aryl groups Ar ¹ , Ar ² , Ar ³ , Ar ⁴ and Ar are selected from those represented by any of the structural formulas a to q described above.

  Hereinafter, although the Example of this invention is described, this invention is not limited to this Example at all.

(Example 1)
A selective production method of a polysubstituted olefin was carried out using vinyl (2-pyrimidyl) silane or vinyl (2-pyridyl) silane as the alkene silane which is the alkene compound.

-First aryl group bonding step and second aryl group bonding step-
One-pot (ONE-POT) reaction of vinyl (2-pyrimidyl) silane or vinyl (2-pyridyl) silane with 4-methoxyphenyl-iodine is shown in the following reaction scheme in a Mizoroki-Heck reaction. ) The reaction was performed twice.
In the above reaction, the amount of vinyl (2-pyrimidyl) silane or vinyl (2-pyridyl) silane added is 1 equivalent, the amount of 4-methoxyphenyl-iodine added is 2 equivalents, and the amount of triethylamine added is 2.5 equivalents. , Pd [P (t-Bu) ₃ ] ₂ was 5%, and the solvents and reaction conditions shown in Table 1 below were used. The alkenylsilane shown below was synthesized as described above. In Table 1, the yield (%) is shown.

As shown in Table 1, as a result of comparing vinyl (2-pyridyl) silane and vinyl (2-pyrimidyl) silane as the alkene compound, the heteroaromatic ring bonded to the Si atom in the alkene compound is 2- A better result was obtained with the 2-pyrimidyl group than with the pyridyl group. As the palladium catalyst, good results were obtained with the Pd [P (t-Bu) ₃ ] ₂ used.

-Synthesis of vinyl (2-pyrimidyl) silane-
Vinyl (2-pyrimidyl) silane with good results was synthesized as follows by the above comparative experiment. That is, a solution of 19.0 g (51.4 mmol) of tributyl (2-pyrimidyl) stannane in 50 mL of tetrahydrofuran (THF) was added to an n-hexane solution of n-butyllithium (51.5 mmol) at −78 ° C. in an argon atmosphere. It was dripped. The mixture was stirred at -78 ° C for 2 hours. The obtained 2-pyrimidyllithium solution was added at −78 ° C. to a solution of 6.63 g (54.9 mmol) of chlorodimethylvinylsilane in 20 mL of tetrahydrofuran (THF). After stirring at room temperature for 2.5 hours, 100 mL of water was added to the mixture. The mixture was extracted with 3 × 100 mL of diethyl ether, and the organic solvent phase was dehydrated with MgSO ₄ . The organic solvent was distilled off under reduced pressure (96 to 98 ° C./22.6 mmHg) to obtain a colorless and transparent solution of 4.06 g (48% by mass) of vinyl (2-pyrimidyl) silane. Analytical data of ¹ H NMR (300 MHz, CDCl ₃ ) of vinyl (2-pyrimidyl) silane is shown. 0.44 (s, 6H), 5.86 (dd, J = 20.1, 3.6 Hz, 1H), 6.11 (dd, J = 14.4, 3.6 Hz, 1H), 6.37 (dd, J = 20.1, 14.4 Hz, 1H), 7.17 (t, J = 5.1 Hz, 1H), 8.75 (d, J = 5.1 Hz, 2H). ¹³ C NMR (75 MHz, CDCl ₃ ) d−3.9, 119.8, 133.8, 136.0, 155.2, 180.0. IR (neat ) 1547, 1393, 1248 cm ⁻¹ . HRMS (EI) m / z calcd for C ₈ H ₁₂ N ₂ Si: 164.0770, found 164.0773.

-First aryl group bonding step and second aryl group bonding step-
The vinyl (2-pyrimidyl) silane obtained above and the aryl halide (ArX) shown in Table 2 below are converted into a one-pot (ONE) by a Mizoroki-Heck reaction shown in the following reaction scheme. -POT) The reaction was performed twice. Specifically, 173.5 mg (1.06 mmol) of dimethyl (2-pyrimidyl) vinylsilane, 421.6 mg (2.07 mmol) of iodobenzene, 253.0 mg (2.50 mmol) of triethylamine, and Pd [P (t-Bu ₃ ) ₂ 25.6 mg (50.1 mol) in dry dioxane (3.0 mL) was stirred at 80 ° C. for 8 hours under an argon atmosphere. After the reaction, the solution was cooled to room temperature and the catalyst and salt were removed by filtration through a silica gel pad (ethyl acetate). For example, the yield of the crude product of alkenylsilane (3aa in Table 2) shown in Table 2 was evaluated as> 99% by ¹ H NMR. In gel permeation chromatography (CHCl ₃ ), the yield of 330.6 mg of alkenylsilane (3aa in Table 2) was 99%. The other alkenylsilanes shown in Table 2 were treated in the same manner as the alkenylsilane (3aa in Table 2).

In the above reaction, the addition amount of the vinyl (2-pyrimidyl) silane is 0.50 mmol, the addition amount of the aryl halide (ArX) is 1.25 mmol, the addition amount of trimethylamine is 1.25 mmol (2.5 equivalents), The addition amount of Pd [P (t-Bu) ₃ ] ₂ is 25 μmol (5%), and the addition amount of dioxane is 2 mL. The reaction conditions were 80 ° C. and 3 to 12 hours. The reaction is carried out in the presence of 2.5 mol% of Pd ₂ (dba) ₃ and 5 mol of tris (2,4-di-tert-butylphenyl) phosphite instead of Pd [P (t-Bu) ₃ ] _2. It was broken. Thus, the novel alkenylsilane shown in Table 2 was synthesized. The yield (%) in Table 2 is based on NMR analysis (% in parentheses refer to isolated yields).

Analytical data of ¹ H NMR (300 MHz, CDCl ₃ ) of alkenylsilane (3aa in Table 2) is shown. 0.21 (s, 6H), 6.59 (s, 1H), 7.12−7.16 (m, 3H), 7.23−7.34 (m, 8H), 8.72 (d, J = 5.1 Hz, 2H). ¹³ C NMR (125 MHz , CDCl ₃ ) d −2.2, 119.4, 125.6, 127.40, 127.44, 127.81, 127.83, 127.9, 129.5, 142.2, 142.8, 154.9, 159.0, 180.8.IR (neat) 1736, 1559, 1393 cm ⁻¹ .HRMS (EI ) m / z calcd for C ₂₀ H ₂₀ N ₂ Si: 316.1396, found 316.1398.

Analytical data of ¹ H NMR (300 MHz, CDCl ₃ ) of alkenylsilane (3bb in Table 2) is shown. 0.25 (s, 6H), 2.58 (s, 3H), 2.62 (s, 3H), 6.77 (s, 1H), 7.16 (t, J = 5.1 Hz, 1H), 7.24 (d, J = 8.1 Hz, 2H .), 7.35 (d, J = 8.1 Hz, 2H), 7.85 (d, J = 8.1 Hz, 4H), 8.70 (d, J = 5.1 Hz, 2H) 13 C NMR (125 MHz, CDCl 3) d - 2.3, 26.6 (two carbons), 119.6, 127.4, 128.0, 128.1, 129.7, 129.8, 136.24, 136.22, 146.36, 146.40, 155.0, 156.6, 179.8, 197.47, 197.48. IR (neat) 1682, 1603 cm ^-1 .HRMS (EI) m / z calcd for C ₂₄ H ₂₄ N ₂ O ₂ Si: 400.1607, found 400.1605.

Analytical data of ¹ H NMR (300 MHz, CDCl ₃ ) of alkenylsilane (3 cc in Table 2) is shown. 0.22 (s, 6H), 3.79 (s, 3H), 3.81 (s, 3H), 6.40 (s, 1H), 6.75−6.80 (m, 4H), 7.06 (d, J = 8.7 Hz, 2H), 7.14 (t, J = 4.8 Hz, 1H), 7.25 (d, J = 7.8 Hz, 2H), 8.71 (d, J = 4.8 Hz, 2H). ¹³ C NMR (75 MHz, CDCl ₃ ) d −2.1, 54.98 , 55.05, 113.00, 113.05, 119.3, 122.6, 128.7, 130.6, 134.8, 135.7, 154.8, 158.2, 158.9, 159.3, 181.0. IR (neat) 1547, 1248 cm ^-1 .HRMS (EI) m / z calcd for C ₂₂ H ₂₄ N ₂ O ₂ Si: 376.1607, found 376.1606.

Analytical data of ¹ H NMR (300 MHz, CDCl ₃ ) of alkenylsilane (3dd in Table 2) is shown. 0.24 (s, 6H), 3.71 (s, 3H), 3.76 (s, 3H), 6.56 (s, 1H), 6.67 (t, J = 2.4 Hz, 1H), 6.73 (d, J = 7.4 Hz, 1H ), 6.79 (dt, J = 8.4, 2.4 Hz, 2H), 6.88 (t, J = 2.4 Hz, 1H), 6.91 (dm, J = 7.4 Hz, 1H), 7.11−7.20 (m, 3H), 8.70 (d, J = 6.0 Hz, 2H). 13 C NMR (100 MHz, CDCl 3) d -2.0, 55.0, 55.2, 113.0, 113.1, 113.3, 114.6, 119.3, 119.9, 121.9, 125.5, 128.66, 128.68, 143.2 , 143.9, 154.7, 158.4, 158.8, 159.0, 180.4. IR (neat) 1738, 1559, 1547 cm ⁻¹ . HRMS (EI) m / z calcd for C ₂₂ H ₂₄ N ₂ O ₂ Si: 376.1607, found 376.1605.

Analytical data of ¹ H NMR (300 MHz, CDCl ₃ ) of alkenylsilane (3ee in Table 2) is shown. 0.23 (s, 6H), 2.93 (s, 6H), 2.95 (s, 6H), 6.27 (s, 1H), 6.58 (d, J = 8.7 Hz, 2H), 6.60 (d, J = 9.3 Hz, 2H ), 7.02 (d, J = 8.7 Hz, 2H), 7.11 (t, J = 4.8 Hz, 1H), 7.27 (d, J = 9.3 Hz, 2H), 8.71 (d, J = 4.8 Hz, 2H).

Analytical data of ¹ H NMR (300 MHz, CDCl ₃ ) of alkenylsilane (3ff in Table 2) is shown. 0.26 (s, 6H), 6.78 (s, 1H), 7.18 (t, J = 4.8 Hz, 1H), 7.23 (d, J = 8.7 Hz, 2H), 7.34 (d, J = 8.7 Hz, 2H), 7.55 (d, J = 6.6 Hz, 2H), 7.57 (d, J = 6.6 Hz, 2H), 8.69 (d, J = 4.8 Hz, 2H).

Analytical data of ¹ H NMR (300 MHz, CDCl ₃ ) of alkenylsilane ( ₃ gg in Table 2) is shown. 0.19 (s, 6H), 6.69 (s, 1H), 6.92 (t, J = 4.8 Hz, 1H), 7.1−7.24 (m, 3H), 7.30−7.35 (m, 1H), 7.39−7.62 (m, 4H), 7.68−7.74 (m, 3H), 7.82 (d, J = 8.1 Hz, 1H), 7.87 (dd, J = 8.1, 1.8 Hz, 1H), 8.49 (d, J = 4.8 Hz, 2H), 8.83 (d, J = 8.1 Hz, 1H). Analytical data of ¹ H NMR (125 MHz, CDCl ₃ ) of alkenylsilane ( ₃ gg in Table 2) is shown. 2.4, 119.0, 124.7, 124.9, 125.47, 125.52, 125.6, 125.8, 126.0, 126.2, 126.3, 127.7, 127.8, 127.9, 128.0, 128.5, 130.8, 131.8, 133.5, 134.4, 134.9, 141.1, 142.2, 154.4, 155.5, 180.0. IR (KBr) 1391, 1246 cm ⁻¹ .HRMS (EI) m / z calcd for C ₂₈ H ₂₄ N ₂ Si: 416.1709, found 416.1709.

Analytical data of ¹ H NMR (300 MHz, CDCl ₃ ) of alkenylsilane (3hh in Table 2) is shown. 0.28 (s, 6H), 6.61 (s, 1H), 6.85−6.95 (m, 4H), 7.17 (t, J = 6.4 Hz, 1H), 7.20−7.30 (m, 2H), 8.73 (d, J = 6.4 Hz, 2H). ¹³ C NMR (75 MHz, CDCl ₃ ) d −2.5, 119.5, 125.8, 126.1, 126.3, 126.6, 127.2, 127.3, 128.0, 141.9, 144.3, 147.9, 155.0, 180.3. IR (neat) 1559, 1547, 1393 cm ⁻¹ .HRMS (EI) m / z calcd for C ₁₆ H ₁₆ N ₂ SiS ₂ : 328.0524, found 328.0522.

Analytical data of ¹ H NMR (300 MHz, CDCl ₃ ) of alkenylsilane (3ii in Table 2) is shown. 0.25 (s, 6H), 6.50 (s, 1H), 6.85−6.93 (m, 2H), 7.15−7.25 (m, 4H), 7.31 (dd, J = 5.1, 1.2 Hz, 1H), 8.73 (d, J = 5.1 Hz, 2H). ¹³ C NMR (75 MHz, CDCl ₃ ) d −2.4, 119.4, 123.7, 124.0, 124.5, 124.9, 125.3, 126.0, 128.8, 142.4, 144.7, 148.1, 154.9, 180.7. neat) 1547, 1393 cm ⁻¹ .HRMS (EI) m / z calcd for C ₁₆ H ₁₆ N ₂ SiS ₂ : 328.0524, found 328.0519.

-First aryl group bonding step and second aryl group bonding step-
Next, vinyl (2-pyrimidyl) silane and two different aryl halides shown in Table 3 below (the numbers in Table 3 correspond to the compounds shown in Table 2) and the following reaction The reaction was carried out twice by one-pot (ONE-POT) treatment in the Mizoroki-Heck reaction shown in the scheme. And the novel alkenylsilane shown in Table 3 was synthesized. Specifically, dimethyl (2-pyrimidyl) vinylsilane (1b; 171.4 mg, 1.04 mmol), 4-iodoacetophenone (2b; 246.4 mg, 1.00 mmol), triethylamine (253.0 mg, 2.50 mmol) And Pd [P (t-Bu) ₃ ] ₂ (25.6 mg, 50.1 mol) in dry dioxane (2.0 mL) were stirred at 80 ° C. for 5 hours under an argon atmosphere. This mixture was added to 2-iodoanisole (2c; 286.1 mg, 1.22 mmol) and the reaction was further reacted at 80 ° C. for 19 hours. After cooling to room temperature, the catalyst and salt were removed by filtration through a short silica gel pad (ethyl acetate). The yield of alkenylsilane (3bc) was> 99% (3bc / 3cb = 98/2) as determined by ¹ H NMR of the crude product. The yield of alkenylsilane (3bc) was 318.5 mg (79%). The yield (%) in Table 3 is based on NMR analysis (% in parentheses refer to isolated yields).

^{a NMR yields. b Isolated yield was} 79%. c Isolated yield was 84%. d Isolated yield was 80%.

Analytical data of ¹ H NMR (300 MHz, CDCl ₃ ) of alkenylsilane (3bc in Table 3) is shown. 0.20 (s, 6H), 2.59 (s, 3H), 3.76 (s, 3H), 6.51 (s, 1H), 6.77 (d, J = 9.3 Hz, 2H), 7.11 (t, J = 5.4 Hz, 1H ), 7.18 (d, J = 9.3 Hz, 2H), 7.22 (d, J = 8.1 Hz, 2H), 7.81 (d, J = 8.1 Hz, 2H), 8.66 (d, J = 5.4 Hz, 2H). ¹³ C NMR (75 MHz, CDCl ₃ ) d −2.1, 26.5, 55.2, 113.3, 119.4, 124.2, 127.9, 128.6, 129.8, 134.7, 136.0, 147.5, 154.9, 157.2, 159.6, 180.4, 197.6. IR (neat) 1682, 1252 cm ⁻¹ .HRMS (EI) m / z calcd for C ₂₃ H ₂₄ N ₂ O ₂ Si: 388.1607, found 388.1604.

Analytical data of ¹ H NMR (300 MHz, CDCl ₃ ) of alkenylsilane (3cb in Table 3) is shown. 0.26 (s, 6H), 2.57 (s, 3H), 3.82 (s, 3H), 6.63 (s, 1H), 6.78 (d, J = 8.7 Hz, 2H), 7.05 (d, J = 8.7 Hz, 2H ), 7.16 (t, J = 5.1 Hz, 1H), 7.39 (d, J = 8.4 Hz, 2H), 7.85 (d, J = 8.4 Hz, 2H), 8.72 (d, J = 5.1 Hz, 2H). ¹³ C NMR (75 MHz, CDCl ₃ ) d −2.2, 26.6, 55.2, 113.3, 119.3, 127.7, 128.0, 128.3, 130.7, 133.9, 136.1, 147.7, 155.0, 157.7, 159.2, 180.5, 197.7. IR (neat) 1682, 1246 cm ⁻¹ .HRMS (EI) m / z calcd for C ₂₃ H ₂₄ N ₂ O ₂ Si: 388.1607, found 388.1606.

Analytical data of ¹ H NMR (300 MHz, CDCl ₃ ) of alkenylsilane (3ja in Table 3) is shown. 0.24 (s, 6H), 2.35 (s, 3H), 6.54 (s, 1H), 7.00−7.05 (m, 4H), 7.14 (t, J = 4.8 Hz, 1H), 7.21−7.29 (m, 3H) , 7.30-7.35 (m, 2H), 8.75 (d, J = 4.8 Hz, 2H). 13 C NMR (75 MHz, CDCl 3) d -1.9, 21.3, 119.1, 125.2, 127.3, 127.5, 127.7, 128.3, 129.3, 136.8, 139.1, 142.8, 154.6, 158.9, 180.6. IR (neat) 3023, 1393 cm ⁻¹ .HRMS (EI) m / z calcd for C ₂₁ H ₂₂ N ₂ Si: 330.1552, found 330.1551.

-Third aryl group binding step-
The alkenylsilane shown in Table 3 and the aryl halide shown in Table 4 were subjected to a cross-coupling reaction shown in the following reaction scheme. Then, novel alkenyl trisubstituted compounds shown in Table 4 were selectively synthesized. In the above reaction, the addition amount of the aryl halide (ArX) is 1.0 equivalent, the addition amount of the alkenylsilane is 1.5 equivalents, and the addition amount of tetrabutylammonium fluoride (Bu ₄ NF) is 1.5 equivalents. , PdCl ₂ (PhCN) ₂ and tetrahydrofuran (THF) were used, and the reaction temperature was 60 ° C. As described above, the five alkenyl trisubstituted compounds (4aak, 4cca, 4jab, 4cbg, 4iib) shown in Table 4 were synthesized. Specifically, alkenylsilane (compound represented by 3aa in Table 4) 47.0 mg (0.15 mmol), aryl halide (compound represented by 2k in Table 4) 27.5 mg (0.10 mmol) ) And 2.0 mg (5.2 mol) of PdCl ₂ (PhCN) _{2 in} 0.5 mL of a dry tetrahydrofuran solution (THF) was added to 0.15 mmol of Bu ₄ NF (1.0 M in tetrahydrofuran (THF) at room temperature. The mixture was stirred under an argon atmosphere for 3 hours at 60 ° C. The mixture was cooled to room temperature and the catalyst and salt were removed by filtration through short silica gel (ethyl acetate). By permeation chromatography, an alkenyl trisubstituted product (a compound represented by 4aak in Table 4) as a white crystal 31.5 g (96% yield). were also obtained other alkenyl trisubstituted in the same manner.

^a Reaction conditions: 2 (1.0 equiv), 3 (1.5 equiv), Bu ₄ NF (1.5 equiv), PdCl ₂ (PhCN) ₂ (5 mol%), THF, 60 ° C.

Analytical data of ¹ H NMR (400 MHz, CDCl ₃ ) of an alkenyl trisubstituted product (4aak in Table 4) is shown. 1.37 (t, J = 7.2 Hz, 3H), 4.33 (q, J = 7.2 Hz, 2H), 6.99 (s, 1H), 7.07 (d, J = 8.4 Hz, 2H), 7.17−7.19 (m, 2H ), 7.31-7.34 (m, 8H) , 7.80 (d, J = 8.4 Hz, 2H). 13 C NMR (100 MHz, CDCl 3) d 14.5, 60.8, 127.0, 127.59, 127.62, 127.8, 128.1, 128.2, 128.6, 129.1, 129.2, 130.1, 139.7, 141.8, 142.8, 144.8, 166.1.IR (neat) 1715, 1605, 1275 cm ^-1 .HRMS (EI) m / z calcd for C ₂₃ H ₂₀ O ₂ : 328.1463, found 328.1463.

Analytical data of ¹ H NMR (400 MHz, CDCl ₃ ) of an alkenyl trisubstituted product (4 cca in Table 4) is shown. 3.84 (s, 3H), 3.85 (s, 3H), 6.85 (s, 1H), 6.86 (d, J = 9.2 Hz, 2H), 6.87 (d, J = 8.8 Hz, 2H), 7.05−7.17 (m , 7H), 7.27 (d, J = 8.8 Hz, 2H). 13 C NMR (75 MHz, CDCl 3) d 55.2, 55.3, 113.5, 114.0, 126.2, 126.3, 127.9, 128.9, 129.4, 131.6, 132.7, 136.4 , 137.9, 141.8, 158.9, 159.2. IR (neat) 1605, 1509, 1246 cm ⁻¹ .HRMS (EI) m / z calcd for C ₂₂ H ₂₀ O ₂ : 316.1463, found 316.1463.

Analytical data of ¹ H NMR (400 MHz, CDCl ₃ ) of an alkenyl trisubstituted product (4jab in Table 4) is shown. 2.41 (s, 3H), 2.55 (s, 3H), 6.95 (s, 1H), 7.07 (d, J = 8.4 Hz, 2H), 7.12 (d, J = 8.0 Hz, 2H), 7.15 (d, J = 8.0 Hz, 2H), 7.30−7.36 (m, 5H), 7.73 (d, J = 8.4 Hz, 2H). ¹³ C NMR (100 MHz, CDCl ₃ ) d 21.5, 26.6, 126.6, 127.7, 127.8, 127.9 , 128.1, 129.3, 129.4, 130.0, 134.8, 136.6, 137.5, 142.4, 143.0, 145.1, 197.2.IR (neat) 1682, 1599, 1267 cm ^-1 .HRMS (EI) m / z calcd for C ₂₃ H ₂₀ O : 312.1514, found 312.1515.

Analytical data of ¹ H NMR (500 MHz, CDCl ₃ ) of an alkenyl trisubstituted product (4 cbg in Table 4) is shown. 2.55 (s, 3H), 3.87 (s, 3H), 6.93 (d, J = 8.8 Hz, 2H), 7.01 (d, J = 7.2 Hz, 1H), 7.17 (t, J = 8.0 Hz, 1H), 7.21 (d, J = 8.4 Hz, 2H), 7.33 (d, J = 8.8 Hz, 2H), 7.46 (s, 1H), 7.47-7.51 (m, 2H), 7.67 (d, J = 8.0 Hz, 1H ), 7.75 (d, J = 8.4 Hz, 2H), 7.80−7.85 (m, 1H), 8.12−8.16 (m, 1H). ¹³ C NMR (125 MHz, CDCl ₃ ) d 26.5, 55.3, 113.7, 124.5 , 125.3, 125.8, 126.06, 126.08, 127.3, 127.7, 128.1, 128.5, 129.3, 130.9, 132.4, 133.4, 134.8, 135.1, 135.6, 143.3, 145.7, 159.5, 197.7.IR (KBr) 1603, 1508 cm ^-1 . HRMS (EI) m / z calcd for C ₂₇ H ₂₂ O ₂ : 378.1620, found 378.1616.

Analytical data of ¹ H NMR (400 MHz, CDCl ₃ ) of an alkenyl trisubstituted product (4iib in Table 4) is shown. 2.55 (s, 3H), 6.93 (dd, J = 4.8, 1.2 Hz, 1H), 7.03 (s, 1H), 7.07 (dd, J = 2.8, 1.2 Hz, 1H), 7.11 (d, J = 8.8 Hz , 2H), 7.13 (dd, J = 2.8, 1.6 Hz, 1H), 7.30 (dd, J = 5.2, 1.6 Hz, 1H), 7.33 (dd, J = 4.8, 2.8 Hz, 1H), 7.35 (dd, J = 5.2, 2.8 Hz, 1H ), 7.75 (d, J = 8.8 Hz, 2H). 13 C NMR (100 MHz, CDCl 3) d 26.6, 123.7, 124.5, 125.7, 125.77, 125.85, 126.0, 127.9, 128.8 , 129.0, 134.2, 134.8, 139.3, 141.9, 144.0, 197.2. IR (neat) 1678, 1597 cm ⁻¹ . HRMS (EI) m / z calcd for C ₁₈ H ₁₄ OS ₂ : 310.0486, found 310.0483.

(Example 2)
First, the following experiment was conducted. That is, as the alkene sulfide as the alkene compound, a compound having a structure shown in Table 5 was used, and a selective production method of a polysubstituted olefin was carried out according to the reaction scheme shown in Table 5 below (similar to that in Example 1). The types and equivalents of aryl halide, equivalents of triethylamine, reaction temperature, reaction time, reaction yield, etc. are as shown in Table 5.

  From the results shown in Table 5, the case where the aryl group bonded to the S atom of the alkenyl sulfide is a pyrimidyl group (5d in Table 5) is the case of another group (5a to 5c in Table 5) (comparison experiment) ), The yield of the alkenyl sulfide (in which the first aryl group and the second aryl group were introduced) after the first aryl group bonding step and the second aryl group bonding step was found to be superior.

Next, for the alkenyl sulfide in which the aryl group bonded to the S atom is a pyrimidyl group (5d in Table 5), the first aryl group bonding step is performed at 60 ° C., and the second aryl group bonding step is performed at 90 ° C. In this order, a one-pot (ONE-POT) process was performed. The reaction scheme is as shown below, and the reaction conditions, the first aryl compound used, the second aryl compound, the reaction yield, etc. are as shown in Table 6. 2-pyrimidyl vinyl sulfide (compound represented by 5d in Table 6) 41.4 mg (0.30 mmol), 2-iodotoluene (compound represented by 2 l in Table 6) 131.1 mg (0. 60 mmol), triethylamine 119 mg (0.92 mmol) and Pd [P (t-Bu) ₃ ] ₂ 7.6 mg (14.9 mol) in dry toluene (1.5 mL) at 80 ° C. under argon atmosphere for 14 hours. Stir. After the mixture was cooled to room temperature, the catalyst and salt were removed by filtration using short silica gel (ethyl acetate). The filtrate was distilled off, the product was analyzed by chromatography on silica gel (hexane / ethyl acetate = 10/1 to 5/1), and the alkenyl introduced with the first aryl group and the second aryl group It was confirmed that 85.4 mg (yield 90%) of sulfide (compound represented by 7 ll in Table 6, pale yellow solid) was synthesized. Other novel alkenyl sulfides shown in the column “7” in Table 6 were synthesized in the same manner. A novel alkenyl sulfide (compound shown in the column “7” in Table 6) was obtained by the first aryl group bonding step and the second aryl group bonding step.

Analytical data of ¹ H NMR (300 MHz, CDCl ₃ ) of alkenyl sulfide (7aa in Table 6) is shown. 7.01 (t, J = 4.8 Hz, 1H), 7.22-7.50 (m, 10H), 7.79 (s, 1H), 8.56 (d, J = 4.8 Hz, 2H). ¹³ C NMR (75 MHz, CDCl ₃ ) d 117.1, 119.1, 127.3, 127.4, 127.9, 128.2, 128.4, 129.6, 139.3, 140.8, 141.2, 157.4, 170.3. HRMS (EI) m / z calcd for C ₁₈ H ₁₄ N ₂ S: 290.0878, found 290.0881.

Analytical data of ¹ H NMR (300 MHz, CDCl ₃ ) of alkenyl sulfide (7 ll in Table 6) is shown. 2.16 (s, 3H), 2.35 (s, 3H), 7.00 (t, J = 4.8 Hz, 1H), 7.10−7.35 (m, 8H), 7.53 (s, 1H), 8.53 (d, J = 4.8 Hz ¹³ C NMR (125 MHz, CDCl ₃ ) d 20.0, 21.2, 117.0, 122.8, 125.64, 125.65, 127.1, 127.9, 129.7, 130.1, 130.6, 130.9, 135.7, 136.1, 139.4, 140.4, 140.9, 157.4 HRMS (EI) m / z calcd for C ₂₀ H ₁₈ N ₂ S: 318.1191, found 318.1190.

Analytical data of ¹ H NMR (300 MHz, CDCl ₃ ) of alkenyl sulfide (7 mm in Table 6) is shown. 2.34 (s, 3H), 2.37 (s, 3H), 7.02 (t, J = 4.8 Hz, 1H), 7.07−7.35 (m, 8H), 7.73 (s, 1H), 8.57 (d, J = 4.8 Hz ¹³ C NMR (125 MHz, CDCl ₃ ) d 21.46, 21.47, 117.0, 118.7, 124.6, 126.7, 127.9, 128.1, 128.2, 128.3, 128.6, 130.2, 137.8, 138.0, 139.3, 141.2, 141.4, 157.4 HRMS (EI) m / z calcd for C ₂₀ H ₁₈ N ₂ S: 318.1191, found 318.1191.

Analytical data of ¹ H NMR (300 MHz, CDCl ₃ ) of alkenyl sulfide (7jj in Table 6) is shown. 2.35 (s, 3H), 2.40 (s, 3H), 7.00 (t, J = 4.8 Hz, 1H), 7.12 (d, J = 7.8 Hz, 2H), 7.18−7.30 (m, 6H), 7.67 (s , 1H), 8.55 (d, J = 4.8 Hz, 2H). 13 C NMR (75 MHz, CDCl 3) d 21.1, 21.2, 116.9, 117.6, 127.2, 128.9, 129.0, 129.5, 136.4, 137.1, 137.5, 138.7 140.8, 157.3, 170.5. HRMS (EI) m / z calcd for C ₂₀ H ₁₈ N ₂ S: 318.1191, found 318.1191.

Analytical data of ¹ H NMR (300 MHz, CDCl ₃ ) of alkenyl sulfide (7 cc in Table 6) is shown. 3.82 (s, 3H), 3.86 (s, 3H), 6.85 (d, J = 9.0 Hz, 2H), 6.94 (d, J = 8.7 Hz, 2H), 7.01 (t, J = 4.8 Hz, 1H), 7.25-7.32 (m, 4H), 7.55 (s, 1H), 8.56 (d, J = 4.8 Hz, 2H). ¹³ C NMR (75 MHz, CDCl ₃ ) d 55.1, 55.2, 113.5, 113.6, 116.2, 116.9 , 128.5, 130.9, 131.7, 134.3, 140.4, 157.3, 159.0, 159.1, 170.7. HRMS (EI) m / z calcd for C ₂₀ H ₁₈ N ₂ O ₂ S: 350.1089, found 350.1089.

Analytical data of ¹ H NMR (300 MHz, CDCl ₃ ) of alkenyl sulfide (7 gg in Table 6) is shown. 6.99 (t, J = 4.8 Hz, 1H), 7.30−7.60 (m, 8H), 7.75−7.80 (m, 1H), 7.82−7.90 (m, 3H), 7.93 (s, 1H), 8.03 (d, J = 8.1 Hz, 1H), 8.52 (d, J = 4.8 Hz, 2H), 8.63-8.70 (m, 1H). 13 C NMR (75 MHz, CDCl 3) d 117.0, 125.1, 125.3, 125.6, 125.7, 125.80, 125.83 (two carbons), 126.36, 126.41, 126.6, 127.7, 127.8, 128.50 (two carbons), 128.55, 130.7, 131.3, 134.0, 134.3, 137.6, 138.1, 140.0, 157.3, 170.4.HRMS (EI) m / z calcd for C ₂₆ H ₁₈ N ₂ S: 390.1191, found 390.1191.

Analytical data of ¹ H NMR (300 MHz, CDCl ₃ ) of alkenyl sulfide (7al in Table 6) is shown. 2.09 (s, 3H), 7.02 (t, J = 4.8 Hz, 1H), 7.15−7.40 (m, 9H), 7.43 (s, 1H), 8.55 (d, J = 4.8 Hz, 2H). ¹³ C NMR (125 MHz, CDCl ₃ ) d 20.5, 117.1, 120.1, 125.7, 127.5, 127.6, 128.2, 128.8, 130.32, 130.34, 136.4, 139.4, 140.8, 142.4, 157.4, 170.2.HRMS (EI) m / z calcd for C ₁₉ H ₁₆ N ₂ S: 304.1034, found 304.1034.

Analytical data of ¹ H NMR (300 MHz, CDCl ₃ ) of alkenyl sulfide (7aj in Table 6) is shown. 2.41 (s, 3H), 7.02 (t, J = 4.8 Hz, 1H), 7.22−7.40 (m, 9H), 7.74 (s, 1H), 8.57 (d, J = 4.8 Hz, 2H). ¹³ C NMR (125 MHz, CDCl ₃ ) d 21.1, 117.0, 118.1, 127.2, 127.9, 128.4, 129.0, 129.6, 137.3, 138.5, 139.5, 140.9, 157.4, 170.6.HRMS (EI) m / z calcd for C ₁₉ H ₁₆ N ₂ S: 304.1034, found 304.1034.

Analytical data of ¹ H NMR (300 MHz, CDCl ₃ ) of alkenyl sulfide (7ac in Table 6) is shown. 3.81 (s, 3H), 6.85 (d, J = 8.7 Hz, 2H), 7.01 (t, J = 4.8 Hz, 1H), 7.28 (d, J = 8.7 Hz, 2H), 7.30−7.43 (m, 5H ), 7.64 (s, 1H) , 8.56 (d, J = 4.8 Hz, 2H). 13 C NMR (125 MHz, CDCl 3) d 55.3, 113.6, 116.96, 117.02, 127.9, 128.4, 128.6, 129.7, 134.1, 139.5, 140.8, 157.4, 159.2, 170.8. HRMS (EI) m / z calcd for C ₁₉ H ₁₆ N ₂ OS: 320.0983, found 320.0984.

Analytical data of ¹ H NMR (300 MHz, CDCl ₃ ) of alkenyl sulfide (7ja in Table 6) is shown. 2.41 (s, 3H), 7.02 (t, J = 4.8 Hz, 1H), 7.22−7.40 (m, 9H), 7.74 (s, 1H), 8.57 (d, J = 4.8 Hz, 2H). ¹³ C NMR (125 MHz, CDCl ₃ ) d 21.3, 117.1, 118.7, 127.3, 127.4, 128.2, 129.1, 129.5, 136.3, 137.7, 140.9, 141.5, 157.4, 170.5.HRMS (EI) m / z calcd for C ₁₉ H ₁₆ N ₂ S: 304.1034, found 304.1034.

7jc: Stereochemistry was determined to be 97% E. ¹ H NMR (300 MHz, CDCl ₃ ) d 2.40 (s, 3H), 3.81 (s, 3H), 6.85 (d, J = 9.0 Hz, 2H), 7.00 ( t, J = 4.8 Hz, 1H), 7.20−7.30 (m, 6H), 7.59 (s, 1H), 8.55 (d, J = 4.8 Hz, 2H). ¹³ C NMR (75 MHz, CDCl ₃ ) d 21.3 , 55.2, 113.5, 116.5, 116.9, 128.5, 129.1, 129.5, 134.2, 136.5, 137.6, 140.7, 157.3, 159.1, 170.7.HRMS (EI) m / z calcd for C ₂₀ H ₁₈ N ₂ OS: 334.1140, found 334.1142 .

Analytical data of ¹ H NMR (300 MHz, CDCl ₃ ) of alkenyl sulfide (7ca in Table 6) is shown. 3.86 (s, 3H), 6.95 (d, J = 8.7 Hz, 2H), 7.02 (t, J = 4.8 Hz, 1H), 7.20−7.40 (m, 7H), 7.70 (s, 1H), 8.57 (d , J = 4.8 Hz, 2H) . 13 C NMR (125 MHz, CDCl 3) d 55.1, 113.7, 117.0, 118.4, 127.26, 127.29, 128.1, 130.8, 131.5, 140.4, 141.5, 157.3, 159.0, 170.3. HRMS ( EI) m / z calcd for C ₁₉ H ₁₆ N ₂ OS: 320.0983, found 320.0983.

Analytical data of ¹ H NMR (300 MHz, CDCl ₃ ) of alkenyl sulfide (7cj in Table 6) is shown. 2.35 (s, 3H), 3.85 (s, 3H), 6.94 (d, J = 9.0 Hz, 2H), 7.01 (t, J = 4.8 Hz, 1H), 7.12 (d, J = 8.1 Hz, 2H), 7.25 (d, J = 8.1 Hz, 2H), 7.28 (d, J = 9.0 Hz, 2H), 7.64 (s, 1H), 8.56 (d, J = 4.8 Hz, 2H). ¹³ C NMR (75 MHz, CDCl ₃ ) d 21.1, 55.2, 113.7, 116.9, 117.4, 127.3, 128.9, 130.9, 131.7, 137.2, 138.8, 140.6, 157.3, 159.1, 170.6.HRMS (EI) m / z calcd for C ₂₀ H ₁₈ N ₂ OS : 334.1140, found 334.1140.

Analytical data of ¹ H NMR (300 MHz, CDCl ₃ ) of alkenyl sulfide (7 cg in Table 6) is shown. 3.80 (s, 3H), 6.86 (d, J = 9.0 Hz, 2H), 7.01 (t, J = 4.8 Hz, 1H), 7.33−7.47 (m, 4H), 7.49−7.53 (m, 3H), 7.83 -7.86 (m, 2H), 7.94 (d, J = 8.1 Hz, 1H), 8.54 (d, J = 4.8 Hz, 2H). 13 C NMR (75 MHz, CDCl 3) d 55.2, 113.6, 117.1, 119.8 , 125.3, 125.6, 125.9, 126.3, 127.7, 128.0, 128.1, 130.1, 131.9, 132.5, 133.8, 139.1, 140.7, 157.4, 158.9, 170.3.HRMS (EI) m / z calcd for C ₂₃ H ₁₈ N ₂ OS ₂ : 370.1140, found 370.1141.

Analytical data of ¹ H NMR (300 MHz, CDCl ₃ ) of alkenyl sulfide (7ij in Table 6) is shown. 2.36 (s, 3H), 7.03 (t, J = 4.5 Hz, 1H), 7.09 (d, J = 4.8 Hz, 1H), 7.14 (d, J = 8.1 Hz, 2H), 7.27 (d, J = 8.1 Hz, 2H), 7.35 (dd, J = 4.8, 3.0 Hz, 1H), 7.40 (d, J = 3.0 Hz, 1H), 7.64 (s, 1H), 8.57 (d, J = 4.5 Hz, 2H). ¹³ C NMR (75 MHz, CDCl ₃ ) d 21.0, 117.0, 118.3, 125.1, 125.4, 127.2, 128.6, 128.8, 135.4, 137.2, 138.5, 139.5, 157.3, 170.1.HRMS (EI) m / z calcd for C ₁₇ H ₁₄ N ₂ S ₂ : 310.0598, found 310.0600.

Analytical data of ¹ H NMR (300 MHz, CDCl ₃ ) of alkenyl sulfide (7ic in Table 6) is shown. 3.83 (s, 3H), 6.87 (d, J = 9.0 Hz, 2H), 7.03 (t, J = 4.8 Hz, 1H), 7.09 (dd, J = 4.8, 1.5 Hz, 1H), 7.32 (d, J = 9.0 Hz, 2H), 7.37 (dd, J = 4.8, 3.3 Hz, 1H), 7.40 (dd, J = 3.3, 1.5 Hz, 1H), 7.56 (s, 1H), 8.57 (d, J = 4.8 Hz ¹³ C NMR (75 MHz, CDCl ₃ ) d 55.2, 113.5, 117.0, 117.3, 125.2, 125.5, 128.6, 128.7, 134.1, 135.4, 139.6, 157.4, 159.1, 170.4.HRMS (EI) m / z calcd for C ₁₇ H ₁₄ N ₂ OS ₂ : 326.0548, found 326.0543.

Analytical data of ¹ H NMR (300 MHz, CDCl ₃ ) of alkenyl sulfide (7 ig in Table 6) is shown. 7.03 (t, J = 4.8 Hz, 1H), 7.14 (dd, J = 5.4, 1.5 Hz, 1H), 7.26 (dd, J = 5.4, 3.0 Hz, 1H), 7.30-7.60 (m, 6H), 7.84 −7.90 (m, 3H), 8.55 (d, J = 4.8 Hz, 2H). ¹³ C NMR (125 MHz, CDCl ₃ ) d 117.3, 120.0, 125.0, 125.1, 125.4, 125.7, 126.0, 126.2, 127.2, 128.10 , 128.11, 128.2, 132.0, 133.7, 133.9, 140.5, 140.7, 157.5, 169.8. HRMS (EI) m / z calcd for C ₂₀ H ₁₄ N ₂ S ₂ : 346.0598, found 346.0601.

  Here, for the alkenyl sulfide in which the aryl group bonded to the S atom is a pyrimidyl group, the first aryl group bonding step is performed at 60 ° C. and the second aryl group bonding step is performed at 90 ° C. in this order. ONE-POT) (Example) was compared with the case where the first aryl group bonding step and the second aryl group bonding step were both performed at 80 ° C. (Comparative Example). The reaction scheme is as shown below, and the reaction conditions, the first aryl compound used, the second aryl compound, the reaction yield, etc. are as shown in Table 7. As shown in Table 7, when the first aryl group bonding step was performed at 60 ° C. and the second aryl group bonding step was performed at 90 ° C. in this order by one-pot (ONE-POT) treatment (Example). Compared with the case where the first aryl group bonding step and the second aryl group bonding step were both performed at 80 ° C. (Comparative Example), the yield was higher (improved by 30%).

The alkenylsilane and the aryl bromide / magnesium compound (third aryl compound) shown in Table 7 were subjected to a cross-coupling reaction shown in the following reaction scheme. Then, novel alkenyl trisubstituted compounds shown in Table 8 were selectively synthesized. In the above reaction, the addition amount of the aryl bromide / magnesium compound (Ar ³ MgBr) is 3.0 equivalents, Pd [P (t-Bu) ₃ ] ₂ 5% and toluene, the reaction temperature is 60 ° C., 15 Reacted for hours. Thus, 12 kinds of alkenyl trisubstituted compounds (4 mm, 4cco, 4ggj, 4ijp, 4ijp, 4icq, 4igd, 4ajc, 4acj, 4jac, 4jca, 4caj, 4cja) shown in Table 7 were synthesized.

Next, here, the relationship between the temperature and the catalyst equivalent in the cross-coupling reaction was examined. The results are as shown in Table 8.

Next, an alkenyl trisubstituted product was synthesized by the following reaction scheme. Here, the steps from the first aryl group bonding step to the third aryl group bonding step were performed using the same catalyst. Specifically, a toluene solution of p-toluylmagnesium bromide (8j; 1.50 mmol, 1.5 M, 1.0 mL) was added to alkenyl sulfide (7ac; 160.2 mg, 0.50 mmol), Pd [P (t-Bu ₃ ) ₂ (12.8 mg, 0.025 mmol) and dry toluene (1.0 mL) were added at room temperature. The mixture was stirred at 60 ° C. for 15 hours. After cooling to room temperature, water (ca. 5 mL) was added. Silica gel chromatography (hexane / ethyl acetate = 50/1) gave a white crystalline alkenyl trisubstituted product (4acj, 105.2 mg, 89%).

Similarly, an alkenyl tetra-substituted product was synthesized by the following reaction scheme. Here, the steps from the first aryl group bonding step to the third aryl group bonding step were performed using the same catalyst.

Analytical data of ¹ H NMR (400 MHz, CDCl ₃ ) of alkenyl sulfide (compound represented by 10 cj) is shown. 2.32 (s, 3H), 3.71 (s, 3H), 6.59 (d, J = 8.8 Hz, 2H), 6.82 (t, J = 4.8 Hz, 1H), 6.90 (d, J = 8.8 Hz, 2H), 7.00−7.07 (m, 5H), 7.23−7.25 (m, 2H), 7.44 (d, J = 8.4 Hz, 2H), 8.36 (d, J = 4.8 Hz, 2H). ¹³ C NMR (100 MHz, CDCl ₃ ) d 21.4, 55.1, 112.9, 116.5, 126.4, 127.2, 127.9, 128.5, 129.3, 130.9, 132.1, 132.2, 134.6, 137.1, 141.0, 149.7, 156.9, 158.3, 172.2.HRMS (EI) m / z calcd for C ₂₆ H ₂₂ N ₂ OS: 410.1453, found 410.1457.

  The following alkenyl trisubstituted product was synthesized as described above.

Analytical data of ¹ H NMR (300 MHz, CDCl ₃ ) of an alkenyl trisubstituted product (compound represented by 4 mmn) is shown. 2.30 (s, 3H), 2.36 (s, 3H), 7.00−7.25 (m, 10H), 7.35−7.42 (m, 2H), 7.52 (d, J = 8.4 Hz, 1H), 7.56−7.74 (m, ¹³ C NMR (125 MHz, CDCl ₃ ) d 21.4, 21.5, 124.9, 125.7, 125.8, 127.0, 127.1, 127.4, 127.6, 127.92, 127.94, 128.1, 128.21, 128.26, 128.31, 128.5, 129.1, 130.9, 132.2, 133.3, 135.2, 137.7, 138.2, 140.3, 143.1, 143.5. HRMS (EI) m / z calcd for C ₂₆ H ₂₂ : 334.1721, found 334.1721.

Analytical data of ¹ H NMR (300 MHz, CDCl ₃ ) of an alkenyl trisubstituted product (compound represented by 4cco) is shown. 3.82 (s, 3H), 3.84 (s, 3H), 6.78-6.87 (m, 7H), 6.97−7.02 (m, 2H), 7.08−7.11 (m, 2H), 7.23−7.26 (m, 2H). ¹³ C NMR (125 MHz, CDCl ₃ ) d 55.2, 55.3, 113.5, 114.0, 114.8 (d, J _CF = 21.1 Hz), 124.9, 128.8, 130.9 (d, J _CF = 7.5 Hz), 131.5, 132.4, 133.9 (d, J _CF = 3.6 Hz), 136.2, 141.5, 158.9, 159.2, 161.1 (d, J _CF = 246.4 Hz). HRMS (EI) m / z calcd for C ₂₂ H ₁₉ FO ₂ : 334.1369, found 334.1368.

Analytical data of ¹ H NMR (300 MHz, CDCl ₃ ) of an alkenyl trisubstituted product (compound represented by 4 ggj) is shown. 2.20 (s, 3H), 6.83 (s, 3H), 7.08 (s, 1H), 7.24−7.33 (m, 3H), 7.36−7.52 (m, 6H), 7.72−7.75 (m, 1H), 7.81− 8.01 (m, 3H), 8.02 (d, J = 8.4 Hz, 1H), 8.60−8.70 (m, 1H). ¹³ C NMR (125 MHz, CDCl ₃ ) d 21.1, 125.1, 125.6, 125.77, 125.80, 125.9 , 126.0, 126.1, 126.2, 126.3, 127.5, 127.8, 127.9, 128.3, 128.6, 128.7, 129.0, 131.4, 131.5, 134.1, 134.4, 134.85, 134.87, 136.8, 137.3, 139.5, 142.1.UV / Vis (CHCl ₃ ) : l _abs (e) = 238.0 (4.8 ´ 10 ⁴ ), 306.5 (2.6 ´ 10 ⁴ ) nm. FL (CHCl ₃ ): l _em = 395.5 nm.HRMS (EI) m / z calcd for C ₂₉ H ₂₂ : 370.1721, found 370.1724.

Analytical data of ¹ H NMR (300 MHz, CDCl ₃ ) of an alkenyl trisubstituted product (compound represented by 4ijp) is shown. 2.43 (s, 3H), 6.75 (dd, J = 4.8, 1.2 Hz, 1H), 6.97 (dd, J = 3.0, 1.2 Hz, 1H), 7.03 (dd, J = 4.8, 3.0 Hz, 1H), 7.22 (d, J = 8.1 Hz, 2H), 7.30 (s, 1H), 7.40−7.70 (m, 8H), 8.19 (dd, J = 8.1, 1.2 Hz, 1H), 8.66 (d, J = 8.1 Hz, 1H), 8.73 (d, J = 8.1 Hz, 1H). 13 C NMR (125 MHz, CDCl 3) d 21.2, 122.4, 122.9, 124.5, 125.3, 125.5, 125.9, 126.37, 126.45, 126.52, 126.57, 127.7, 128.0, 128.6, 129.5, 129.7, 130.3, 131.4, 131.6, 134.1, 134.1, 137.7, 139.5, 140.35, 140.39. HRMS (EI) m / z calcd for C ₂₇ H ₂₀ S: 376.1286, found 376.1287.

Analytical data of ¹ H NMR (300 MHz, CDCl ₃ ) of an alkenyl trisubstituted product (compound represented by 4 icq) is shown. 3.82 (s, 3H), 5.90 (s, 2H), 6.45 (s, 1H), 6.66 (s, 2H), 6.77−6.90 (m, 4H), 7.06−7.07 (m, 1H), 7.25−7.28 ( m, 2H), 7.31-7.34 (m , 1H). 13 C NMR (75 MHz, CDCl 3) d 55.3, 100.8, 107.9, 108.7, 113.5, 123.7, 124.6, 125.6, 126.8, 128.4, 129.4, 131.9, 135.3 , 135.7, 140.5, 146.2, 147.2, 159.2. HRMS (EI) m / z calcd for C ₂₀ H ₁₆ O ₃ S: 336.0820, found 336.0820.

Analytical data of ¹ H NMR (300 MHz, CDCl ₃ ) of an alkenyl trisubstituted product (compound represented by 4igd) is shown. 3.70 (s, 3H), 6.73 (s, 1H), 6.80 (dm, J = 8.4 Hz, 1H), 6.85 (s, 1H), 6.89−6.95 (m, 2H), 7.15−7.24 (m, 2H) , 7.30-7.50 (m, 5H), 7.80-7.90 (m, 2H), 7.97 (dm, J = 8.7 Hz, 1H). 13 C NMR (125 MHz, CDCl 3) d 55.0, 113.4, 113.8, 121.9, 124.8, 125.0, 125.3, 125.6, 125.9, 126.0, 126.9, 127.9, 128.2, 128.7, 129.2, 131.0, 131.8, 133.9, 136.4, 138.8, 141.3, 141.8, 159.3.HRMS (EI) m / z calcd for C ₂₃ H ₁₈ OS: 342.1078, found 342.1078.

Analytical data of ¹ H NMR (300 MHz, CDCl ₃ ) of an alkenyl trisubstituted product (compound represented by 4ajc) is shown. 2.35 (s, 3H), 3.75 (s, 3H), 6.67 (d, J = 8.7 Hz, 2H), 6.89 (s, 1H), 6.94 (d, J = 8.7 Hz, 2H), 7.11 (d, J = 8.4 Hz, 2H), 7.15-7.25 (m, 5H), 7.30-7.40 (m, 2H). 13 C NMR (125 MHz, CDCl 3) d 21.1, 55.1, 113.3, 126.8, 127.2, 127.3, 128.6, 128.9, 130.1, 130.4, 130.7, 137.0, 140.4, 140.74, 140.75, 158.2. HRMS (EI) m / z calcd for C ₂₂ H ₂₀ O: 300.1514, found 300.1514.

Analytical data of ¹ H NMR (300 MHz, CDCl ₃ ) of an alkenyl trisubstituted product (compound represented by 4acj) is shown. 2.26 (s, 3H), 3.81 (s, 3H), 6.80−7.00 (m, 7H), 7.20−7.40 (m, 7H). ¹³ C NMR (125 MHz, CDCl ₃ ) d 21.1, 55.2, 113.5, 126.4 127.2, 128.57, 128.61, 128.63, 129.3, 130.3, 134.7, 136.1, 136.2, 140.7, 141.1, 159.0. HRMS (EI) m / z calcd for C ₂₂ H ₂₀ O: 300.1514, found 300.1514.

Analytical data of ¹ H NMR (300 MHz, CDCl ₃ ) of an alkenyl trisubstituted product (compound represented by 4jac) is shown. 2.39 (s, 3H), 3.76 (s, 3H), 6.68 (d, J = 8.4 Hz, 2H), 6.88 (s, 1H), 6.98 (d, J = 9.0 Hz, 2H), 7.05−7.20 (m , 4H), 7.20-7.35 (m, 5H). 13 C NMR (125 MHz, CDCl 3) d 21.3, 55.1, 113.3, 127.1, 127.40, 127.41, 128.1, 129.4, 130.19, 130.23, 130.7, 136.9, 137.5, 140.5, 143.8, 158.2. HRMS (EI) m / z calcd for C ₂₂ H ₂₀ O: 300.1514, found 300.1513.

Analytical data of ¹ H NMR (300 MHz, CDCl ₃ ) of an alkenyl trisubstituted product (compound represented by 4jca) is shown. 2.38 (s, 3H), 3.82 (s, 3H), 6.80−6.90 (m, 3H), 7.00−7.20 (m, 7H), 7.25−7.30 (m, 4H). ¹³ C NMR (125 MHz, CDCl ₃ ) d 21.3, 55.2, 113.5, 126.25, 126.32, 127.9, 128.8, 129.3, 129.4, 130.2, 136.3, 137.0, 137.4, 137.7, 142.1, 159.1.HRMS (EI) m / z calcd for C ₂₂ H ₂₀ O: 300.1514 , found 300.1515.

Analytical data of ¹ H NMR (300 MHz, CDCl ₃ ) of an alkenyl trisubstituted product (compound represented by 4 caj) is shown. 2.27 (s, 3H), 3.84 (s, 3H), 6.87 (d, J = 8.7 Hz, 2H), 6.88 (s, 1H), 6.96 (s, 4H), 7.13 (d, J = 8.7 Hz, 2H ), 7.25-7.35 (m, 5H) . 13 C NMR (125 MHz, CDCl 3) d 21.2, 55.2, 114.0, 127.3, 127.6, 127.8, 128.1, 128.7, 129.4, 131.6, 132.7, 134.7, 136.4, 141.3, 143.9, 158.8. HRMS (EI) m / z calcd for C ₂₂ H ₂₀ O: 300.1514, found 300.1512.

Analytical data of ¹ H NMR (300 MHz, CDCl ₃ ) of an alkenyl trisubstituted product (compound represented by 4cja) is shown. 2.36 (s, 3H), 3.83 (s, 3H), 6.85 (d, J = 8.7 Hz, 2H), 6.87 (s, 1H), 7.00−7.20 (m, 8H), 7.20−7.30 (m, 3H) ¹³ C NMR (125 MHz, CDCl ₃ ) d 21.1, 55.1, 113.9, 126.4, 127.0, 127.6, 127.9, 128.8, 129.4, 131.6, 132.6, 137.3, 137.7, 141.0, 142.1, 158.8.HRMS (EI) m / z calcd for C ₂₂ H ₂₀ O: 300.1514, found 300.1518.

Analytical data of ¹ H NMR (300 MHz, CDCl ₃ ) of an alkenyl tri-substituted product (compound represented by 11 cjo) is shown. 2.26 (s, 3H), 3.72 (s, 3H), 6.61 (d, J = 8.0 Hz, 2H), 6.77 (dd, J = 8.4, 8.0 Hz, 2H), 6.87−7.01 (m, 9H), 7.02 −7.10 (m, 4H). ¹³ C NMR (125 MHz, CDCl ₃ ) d 21.2, 55.5, 113.0, 114.5 (d, J _CF = 21.4 Hz), 126.2, 127.7, 128.4, 131.2, 131.3, 132.5, 132.8 ( d, J _CF = 7.1 Hz), 136.1 (d, J _CF = 3.1 Hz), 138.4, 140.07, 140.10, 140.6, 140.8, 144.0, 158.0, 161.2 (d, J _CF = 244.1 Hz) .HRMS (EI) m / z calcd for C ₂₈ H ₂₃ FO: 394.1733, found 394.1732.

The polysubstituted olefin of the present invention can be used, for example, in various fields, can be suitably used as a luminescent material, and can be particularly suitably used for the luminescent material of the present invention.
The method for selectively producing a multi-substituted olefin according to the present invention is capable of selectively and efficiently synthesizing, for example, those having a desired structure such as an alkenyl tri-substituted product and an alkenyl tetra-substituted product. It can be suitably used.
The light emitting material of the present invention can be used as, for example, a photoluminescence material.

Claims (31)

The first carbon atom that contains an alkene bond and forms the alkene bond, and the second carbon atom of the second carbon atom is selected from Groups 13 to 16 in the long-period periodic table of elements In an alkene compound in which an organic group containing an atom is bonded through the atom,
The first aryl compound containing a first aryl group is reacted with the first carbon atom to bond the first aryl group, and the second aryl compound containing a second aryl group is reacted to react with the first carbon atom. After coupling the diaryl group,
A method for selectively producing a multi-substituted olefin, comprising reacting the second carbon atom with a third aryl compound containing a third aryl group to bond the third aryl group.   The method for selectively producing a polysubstituted olefin according to claim 1, wherein the atom is any one of Si atom, Se atom, O atom, Ge atom, Sn atom, Pb atom and B atom.   The method for selectively producing a multi-substituted olefin according to claim 1, wherein the atom is a Si atom.   The first aryl group is bonded to the first carbon atom, and then the second aryl group is bonded at a higher temperature than when the first aryl group is bonded. A method for selectively producing the polysubstituted olefin as described. An organic group containing an alkene bond, wherein a pyrimidine ring is bonded to an S atom, is bonded to the second carbon atom of the first and second carbon atoms forming the alkene bond. In the alkene compound formed by bonding via
After the first aryl compound containing the first aryl group is reacted with the first carbon atom to bond the first aryl group, the temperature is higher than when the first aryl group is bonded. After reacting a second aryl compound containing a second aryl group to bind the second aryl group,
A method for selectively producing a multi-substituted olefin, comprising reacting the second carbon atom with a third aryl compound containing a third aryl group to bond the third aryl group.   The selective of the multi-substituted olefin according to any one of claims 4 to 5, wherein the second aryl group is bonded to the first carbon atom at a temperature 5 to 100 ° C higher than when the first aryl group is bonded. Production method.   The selective of the multi-substituted olefin according to any one of claims 4 to 5, wherein the second aryl group is bonded to the first carbon atom at a temperature 20 to 40 ° C higher than that when the first aryl group is bonded. Production method.   The reaction temperature for bonding the first aryl group to the first carbon atom is 45 ° C. or more and less than 75 ° C., and the reaction temperature for bonding the second aryl group is 75 ° C. or more and less than 105 ° C. Item 8. A method for selectively producing a multi-substituted olefin according to any one of Items 4 to 7.   The reaction for bonding the first aryl group and the reaction for bonding the second aryl group to the first carbon atom is a Mizooki-Heck reaction. The method for selectively producing a multi-substituted olefin as described in 1. above.   The method for selectively producing a multi-substituted olefin according to any one of claims 1 to 9, wherein the reaction for bonding the third aryl group to the second carbon atom is a cross-coupling reaction.   The selection of the polysubstituted olefin according to any one of claims 1 to 10, wherein the organic group bonded to the second carbon atom is substituted with a third aryl group to bond the third aryl group to the second carbon atom. Manufacturing method.   The selective production of a polysubstituted olefin according to any one of claims 1 to 11, wherein the alkene compound is one in which a quaternary aryl group is bonded to the second carbon atom before the first aryl group is bonded. Method.   After the third aryl group is bonded to the second carbon atom, the organic group bonded to the second carbon atom is replaced with the fifth aryl group, and the fifth aryl group is bonded to the second carbon atom. The method for selectively producing a polysubstituted olefin according to any one of claims 1 to 12.   The method for selectively producing a multi-substituted olefin according to claim 13, wherein the reaction for bonding the fifth aryl group to the second carbon atom is a cross-coupling reaction.   The method for selectively producing a multi-substituted olefin according to claim 9, wherein the Mizoroki-Heck reaction is carried out in the presence of a transition metal catalyst and a base.   The method for selectively producing a multi-substituted olefin according to any one of claims 10 and 14, wherein the cross-coupling reaction is performed in the presence of a transition metal catalyst.   The method for selectively producing a polysubstituted olefin according to any one of claims 15 to 16, wherein the transition metal catalyst is a palladium catalyst. The method for selectively producing a multi-substituted olefin according to claim 17, wherein the palladium catalyst is Pd [P (t-butyl) ₃ ] ₂ .   The reaction for bonding the second aryl group to the first carbon atom is performed using the transition metal catalyst, base and reaction vessel used in the reaction for bonding the first aryl group to the first carbon atom. Item 16. A method for selectively producing a multi-substituted olefin according to Item 15.   The method for selectively producing a multi-substituted olefin according to any one of claims 1 to 19, wherein the first aryl compound, the second aryl compound, and the third aryl compound are selected from halogenated aryl compounds.   The method for selectively producing a multi-substituted olefin according to claim 13, wherein the third aryl compound and the fifth aryl compound are selected from magnesium-containing aryl compounds. The aryl group in at least one of the first aryl compound, the second aryl compound, the third aryl compound, the fourth aryl compound, and the fifth aryl compound is represented by any one of the following structural formulas a to q. The method for selectively producing a multi-substituted olefin according to any one of claims 20 to 21, which is selected from those described above.
Multi-substituted olefins
A first aryl group and a second aryl group are bonded to the first carbon atom of the first carbon atom and the second carbon atom that include the alkene bond and form the alkene bond, and the second carbon A trisubstituted product in which a tertiary aryl group is bonded to an atom, and
A first aryl group and a second aryl group are bonded to the first carbon atom of the first carbon atom and the second carbon atom that include the alkene bond and form the alkene bond, and The polysubstituted group according to any one of claims 1 to 22, which is at least one of a tetra-substituted product in which a third aryl group and any one of a fourth aryl group and a fifth aryl group are bonded to a carbon atom. A method for selective production of olefins.   A multi-substituted olefin produced by the method for selectively producing a multi-substituted olefin according to any one of claims 1 to 23. A first aryl group and a second aryl group are bonded to the first carbon atom of the first carbon atom and the second carbon atom that include the alkene bond and form the alkene bond, and the second carbon A trisubstituted product in which a tertiary aryl group is bonded to an atom, and
A first aryl group and a second aryl group are bonded to the first carbon atom of the first carbon atom and the second carbon atom that include the alkene bond and form the alkene bond, and The multi-substituted olefin according to claim 24, wherein the poly-substituted olefin is at least one of a tetra-substituted product in which a carbon atom is bonded to a third aryl group and any one of a fourth aryl group and a fifth aryl group. The polysubstituted olefin according to any one of claims 24 to 25 represented by the following structural formula (4jab, 4cgb, 4iib, 4mmn, 4ggj, 4ijp, 4icq, 4igd and 11cjo).
However, in the above structural formulas, Me represents a methyl group. A polysubstituted olefin represented by the following structural formula.
However, in the above structural formulas, Me represents a methyl group. A polysubstituted olefin represented by any one of the following structural formulas.
However, in the structural formula:
Ar ¹ and Ar ² are both a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-methoxyphenyl group, and a 1-naphthyl group,
Ar ¹ is a phenyl group and Ar ² is a 2-methylphenyl group, a 4-methylphenyl group or a 4-methoxyphenyl group,
Ar ¹ is a 4-methylphenyl group, Ar ² is a phenyl group or a 4-methoxyphenyl group,
Ar ¹ is a 4-methoxyphenyl group and Ar ² is a phenyl group, a 4-methylphenyl group or a 1-naphthyl group,
Ar ¹ is a 3-thienyl group, and Ar ² is a 4-methylphenyl group, a 4-methoxyphenyl group, or a 1-naphthyl group.
In the structural formula, Ph represents a phenyl group, p-Anis represents a 4-methoxyphenyl group, and Tol-p represents a 4-methylphenyl group.   The multi-substituted olefin according to claim 24, which is used as a luminescent material.   A luminescent material comprising at least the polysubstituted olefin according to any one of claims 24 to 25. The luminescent material according to claim 30, comprising at least one of polysubstituted olefins represented by the following structural formula.
However, in the above structural formulas, Me represents a methyl group.