WO2007105622A1

WO2007105622A1 - Method for producing heterocyclic compound

Info

Publication number: WO2007105622A1
Application number: PCT/JP2007/054644
Authority: WO
Inventors: Kazuhiko Takai; Yoichiro Kuninobu
Original assignee: National University Corporation Okayama University
Priority date: 2006-03-10
Filing date: 2007-03-09
Publication date: 2007-09-20
Also published as: JP5181190B2; JPWO2007105622A1

Abstract

Disclosed is a method for producing a heterocyclic compound represented by the formula (III) below, wherein an aromatic imine is reacted with an aldehyde. (In the formula, R1, R2, R3, R4, R5 and R7 respectively represent a hydrogen atom, an alkyl group, an aryl group or the like; and X represents O, S, Se or Te.) Consequently, an isobenzofuran and similar compounds can be synthesized from an easily available raw material through a short reaction process.

Description

Specification

Method for producing heterocyclic compound

Technical field

[0001] The present invention relates to a method for producing a heterocyclic compound, in particular, isobenzofuran or a similar heterocyclic compound.

Background art

[0002] Heterocyclic compounds having a π-conjugated system are also attracting interest as materials for organic electroluminescence (EL) devices, organic field effect transistor (FET) devices, fluorescent dyes, and the like. One such heterocyclic compound is isobenzofuran or a similar compound. So far, several methods have been reported for synthesizing isobenzofuran and its compounds in which oxygen atoms are replaced by sulfur atoms or selenium atoms.

[0003] For example, Non-Patent Document 1 describes a method of synthesizing 1,3-diphenylisobenzofuran by reducing orthodibenzoylbenzene with potassium borohydride and then dehydrating it using an acid catalyst. Is described. Then, 1,3-diphenylisobenzofuran obtained by this method is reacted with pentasulfurium diphosphorusen to produce 1,3-diphenylbenzo [c] thiophene (isothianaphthene). Is also obtained. Non-Patent Document 2 describes a method of synthesizing 1,3-diphenylisobenzofuran by oxidizing 2,2-dimethyl-1,3-diphenylisoindene in air. Non-Patent Document 3 describes a method of synthesizing 1,3-diphenylisobenzofuran by reacting benzoyl chloride to a dilithium salt of benzophenosylhydrazone and then reacting with lithium bromide. Yes. In Non-Patent Document 4, benzo [c] selenophene (isoselenanaphthene) is obtained by reacting isobenzofuran with Woollins reagent ([PhP (Se) (μ-Se)]).

2

A method of synthesis is described.

[0004] However, as shown in these examples, the conventional synthesis methods often require special raw materials as shown in these examples. Therefore, the synthesis of the raw materials required multiple steps, which required a long time and high manufacturing costs. In addition, it was not easy to introduce a substituent at an arbitrary position of the ring skeleton of the obtained heterocyclic compound. In addition, the reactant In many cases, there were problems such as safety, the need for a large amount of solvent, and the formation of a large amount of by-products.

[0005] In Non-Patent Document 5, a method of synthesizing an indene derivative by reacting with an acetylene after activating a CH bond at the ortho-position of an aromatic ring to which an imino group is bonded with a rhodium compound, Similarly, a method for synthesizing a phthalimidine derivative by reacting with an isocyanate after being activated has already been reported by the inventors of the present application.

[0006] Non-Patent Document 1: M. P. Cava, 2 others, Journal of Organic Chemistry, 1960, Vol. 25, p. 1481-1484

Non-Patent Document 2: E. Johansson, 1 other, Journal of Organic Chemistry, 1981, Vol. 46, p. 3752-3754

Non-Patent Document 3: J. T. Sharp, 1 other, Tetrahedron Letters, 1986, Vol. 27, p. 869 -872

Non-Patent Document 4: A. K. Mohanakrishnan, 1 other, Tetrahedron Letters, 2005, 46, p. 7201-7204

Non-Patent Document 5: Y. Kuninobu, 3 others, Journal of the American Chemical Society, 2006, No. 128, p. 202-209

Disclosure of the invention

Problems to be solved by the invention

[0007] The present invention has been made to solve the above-described problems, and provides a method for synthesizing isobenzofuran and similar heterocyclic compounds in a short reaction step that is easily available. It is the purpose.

Means for solving the problem

[0008] The above object is to provide an aromatic imine having at least one aromatic ring bonded to a carbon atom of an imino group and having at least one hydrogen atom at the position of imino group ortho in the aromatic ring, an aldehyde, A group consisting of thioaldehyde, selenaldehyde, and terucaldehyde also selected from the group consisting of isobenzofuran, isothianaphthene, isoselenanaphthene and isotellananaphthene, characterized by reacting with one compound It is solved by providing a process for the preparation of one kind of heterocyclic compound in which force is also selected. Specifically, the above problem is solved by the following formula (I)

[Chemical 1]

[Wherein, R \ R ² , R ³ and R ⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. An alkyl group, an aryl group that may have a substituent, an aryl group that may have a substituent, an arylalkyl group that may have a substituent, and a substituent. May have an aryl alkyl group, an optionally substituted cycloalkyl group, an optionally substituted heterocyclic group, an optionally protected hydroxyl group, an alkoxy group, an aryloxy group, an aldehyde Group, an optionally protected carboxyl group or a salt thereof, an alkyl carbo group, an aryl carbo group, an alkyloxy carbo group, an aryloxy carbo ol group, an alkyl group, a hydroxy group, an ally carbo group. -Mouthoxy group, even if protected Good amino group, alkylamino group, arylamino group, ammonia group, alkylammonium group, arylamine group, optionally protected thiol group, alkylthio group, arylthio group, protected Sulfinic acid group or salt thereof, alkyl sulfier group, aryl sulfiel group, sulfonic acid group or salt thereof which may be protected, alkyl sulfonyl group, aryl sulfonyl group, alkyl azo group, aralkyl azo group, protected A phosphoric acid group or a salt thereof, which may be protected, a phosphorous acid group or a salt thereof which may be protected, a cyano group, a -ortho group or an azide group; R ⁵ and R ⁶ are each independently , A hydrogen atom, an alkyl group which may have a substituent, an alkyl group which may have a substituent, an alkyl group which may have a substituent, or a substituent. An aryl group which may have a substituent, an aryl group which may have a substituent, an aryl group which may have a substituent, an aryl group which may have a substituent, or a substituent. It may have a cycloalkyl group or a substituent, R \ R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be bonded to each other to form a ring. And a compound of the following formula (II)

[Chemical 2]

[Wherein R ⁷ has an aryl group that may have a substituent, an aromatic heterocyclic group that may have a substituent, an aryl group that may have a substituent, or a substituent. An alkenyl group which may have a substituent, a alkenyl group or an alkyl group which may have a substituent; and X is an oxygen atom, a sulfur atom, a selenium atom and It is one selected from the group of tellurium nuclear power. ]

Which is reacted with a compound represented by the following formula (III)

[Chemical 3]

[Where

R ⁴ , R ⁵ , R ⁷ and X are the same as those in the above formulas (I) and (II). It is solved by providing the manufacturing method of the heterocyclic compound shown by these.

At this time, R ⁵ may have a substituent, may have a aryl group, or may have a substituent !, an aromatic heterocyclic group, an optionally substituted aryl group or substituent. An aryl group that may have an alkyl group, a substituent, a alkenyl group, or a substituent, which is an alkyl group, is preferable. It is also preferred that X is an oxygen atom. Such catalysts that are preferably reacted in the presence of a catalyst comprising a transition metal compound include transition metal compounds belonging to Group 7, Group 8, Group 9 or Group 10 of the Periodic Table, among them. However, rhenium compounds, particularly rhenium (I) compounds are preferably used. In the reaction, it is represented by the formula (I). It is preferable that the molar ratio (πΖι) of the compound represented by the formula (II) to the compound to be reacted is 1.5 or more. In addition, when X is an oxygen atom, it is preferable to proceed the reaction while removing generated water from the reaction system.

The invention's effect

[0011] According to the production method of the present invention, it is possible to synthesize isobenzofuran and similar heterocyclic compounds in a reaction process that is easily available and has a short reaction time. It is also easy to introduce various substituents at any position of the ring skeleton of the heterocyclic compound, and it is possible to obtain compounds useful as functional materials, pharmaceuticals, or intermediates thereof. .

BEST MODE FOR CARRYING OUT THE INVENTION

[0012] The present invention relates to an aromatic imine having at least one aromatic ring bonded to a carbon atom of an imino group and having at least one hydrogen atom at the position of the imino group ortho in the aromatic ring, and an aldehyde , Thioaldehyde, selenoaldehyde, and terucaldehyde are also selected. This is a method for producing one kind of selected heterocyclic compound.

[0013] First, an aromatic imine that is one of raw materials and composites in the production method of the present invention will be described. The aromatic imine may have an arbitrary substituent that does not inhibit the progress of the reaction of the present invention. Specifically, a compound represented by the following formula (I) is preferably used.

[0014] [Chemical 4]

[Where

R ^2, R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, which may have a substituent Alkyl group, aryl group which may have a substituent, aryl alkyl group which may have a substituent, aryl hydrocarbon group which may have a substituent, aryl which may have a substituent An alkyl group, an optionally substituted cycloalkyl group, an optionally substituted heterocyclic group, an optionally protected hydroxyl group, an alkoxy group, an aryloxy group, an aldehyde group, and a protected group; Good carboxyl group or salt thereof, alkyl carbo group, aryl carbo group, alkyloxy carbo group, aryloxy carbo ol group, alkyl group, carboxy group, ally carboxy group, protective group Amino group, alkylamino group, arylamino group, ammonia group, alkylammonium group, arylamine group, optionally protected thiol group, alkylthio group Group, arylthio group, sulfinic acid group or salt thereof which may be protected, alkylsulfier group, arylsulfur group, sulfonic acid group or salt thereof which may be protected, alkylsulfonyl group, arylsulfol group , An alkylazo group, an arylazo group, an optionally protected phosphoric acid group or a salt thereof, an optionally protected phosphorous acid group or a salt thereof, a cyano group, a -ortho group or an azide group; R ⁵ And R ⁶ are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkyl group which may have a substituent, or an alkyl group which may have a substituent. An aryl group that may have a substituent, an aryl group that may have a substituent, an aryl group that may have a substituent, an aryl group that may have a substituent, a substituted group With group It, has a cycloalkyl group or a substituent Yo, a heterocyclic group

R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be bonded to each other to form a ring. ]

Here, the monovalent substituents RR ² , R ³ and R ⁴ bonded to the aromatic ring in the formula (I) are not particularly limited as long as they do not inhibit the progress of the reaction of the present invention. Instead, the above-mentioned various substituents can be employed. However, as shown in the formula (I), it is necessary that at least one hydrogen atom is bonded to the ortho position as viewed from the imino group in the aromatic ring. This is because it is presumed that the reaction proceeds by activating the CH bond at the ortho position as viewed from the force imino group that explains the estimation mechanism of the reaction of the present invention.

[0016] The substituents R ¹ R ² , R ³ and R ⁴ may have a substituent !, an alkyl group, an optionally substituted alkenyl group, and a substituent. It may have an alkyl group or a substituent. An aryl group, an aryl group that may have a substituent, an aryl group that may have a substituent, an aryl group that may have a substituent, and a substituent. A cycloalkyl group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxy group, an aryloxy group, an alkylcarbonyl group, an arylylcarbonyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylcarbo group; Nyloxy group, aryl-carboxyl group, alkylamino group, arylamino group, alkyl ammonium group, aryl ammonium group, alkylthio group, arylthio group, alkylsulfier group, arylsulfyl group, alkylsulfo group The number of carbon atoms of the thiol group, arylsulfol group, alkylazo group and allylazo group is not particularly limited, and may be a polymer chain. However, it is usually 1 to 20, and preferably 1 to 10.

[0017] In the formula (I), R ⁵ may have a hydrogen atom, a substituent, an alkyl group, a substituent, an alkyl group, or a substituent. An alkyl group that may have a substituent, an aryl group that may have a substituent, an aryl group that may have a substituent, an arylalkyl group that may have a substituent, and a substituent. An arylalkyl group which may be substituted, a cycloalkyl group which may have a substituent, or a heterocyclic group which may have a substituent. However, from the viewpoint of the stability of the reaction product, R ⁵ is preferably not a hydrogen atom. That is, the compound represented by the formula (I) is preferably ketimine rather than aldimine. In addition, from the viewpoint of the stability of the obtained heterocyclic compound, R ⁵ has an aryl group which may have a substituent, an aromatic heterocyclic group or a substituent which may have a substituent. A arylalkenyl group which may have a substituent, an alkenyl group which may have a substituent, or an alkyl group which may have a substituent. More preferably, it has an aryl group which may have a substituent, an aromatic heterocyclic group which may have a substituent, an arylalkyl group which may have a substituent or a substituent. Further preferred is an arylalkyl group which may be used. The carbon number of each substituent of R ⁵ is not particularly limited, and may be a polymer chain, but is usually 1 to 20, preferably 6 to 20, more preferably 6 to 10. It is. Preferable specific examples thereof include a phenyl group which may have a substituent, a naphthyl group which may have a substituent, a substituent which may have a substituent, and a cinnamyl group.

In the formula (I), R ⁶ may have a hydrogen atom, a substituent, an alkyl group, or a substituent. Alkyl group, alkyl group which may have a substituent, aryl group which may have a substituent, aryl alkyl group which may have a substituent, and substituent An arylalkyl group that may be substituted, an arylalkyl group that may have a substituent, a cycloalkyl group that may have a substituent, or a heterocyclic group that may have a substituent. However, in terms of reactivity, it is preferable that R ⁶ is not a hydrogen atom. The carbon number of each substituent of R ⁶ is not particularly limited and may be a polymer chain, but is usually 1 to 20, preferably 6 to 20, more preferably 6 to: LO. R ⁶ is a substituent that is not finally incorporated into the target product but is incorporated into the by-product amine or aldimine. Preferable specific examples include a phenyl group and a benzyl group.

In the formula (I), R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be bonded to each other to form a ring.

For example,

Of R ³ and R ⁴ , adjacent substituents may be bonded to form a ring, or distant substituents may be bonded to form a ring. R ⁵ is

It may be bonded to R ² , R ³ or R ⁴ . Furthermore, R ⁶ is

In this case, it may be bonded to R ³ , R ^4, or R ^5, and in this case, there is an amine produced as a by-product of the reaction, and aldimine is incorporated into the heterocyclic compound shown by the formula (III). Become. Also,

Three or more substituents of R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be bonded to each other. The ring thus formed may be an aromatic ring or a non-aromatic ring. Further, it may be a carbocyclic ring or a heterocyclic ring. The number of carbon atoms of the substituent in the case of forming a ring is not particularly limited, and the ring may be bonded to the polymer chain, but is usually 1 to 20, preferably 6 to 20, Preferably it is 6-10. The carbon number here is the total number of carbon atoms of the substituents that are bonded to each other to form a ring. For example, when a naphthalene ring is formed by condensing a benzene ring at the R ¹ and R ² positions, the carbon number is counted as 4.

[0020] Next, one compound selected from the group power consisting of aldehyde, thioaldehyde, selenoaldehyde, and teraldehyde aldehyde, which is the other raw material compound in the production method of the present invention, will be described. The compound may have an arbitrary substituent that does not inhibit the progress of the reaction of the present invention. Specifically, a compound represented by the following formula (Π) is preferably used.

[0021] [Chemical 5] R ⁷ Η

[0022] Te you, expression (Π), R ⁷ is, I may have a substituent!, Have Ariru group, the substituents!ヽ芳 Aromatic heterocyclic group, optionally substituted aryl alkenyl group, optionally substituted aryl hydrocarbon group, optionally substituted, alkenyl group or substituent An alkynyl group which may have That is, it has an aromatic ring or an unsaturated bond that can be conjugated with a C = X bond. Among them, from the viewpoint of stability of the product, those having an aromatic ring that can be conjugated with a C = X bond, that is, R ⁷ may have an aryl group or a substituent which may have a substituent. However, it may preferably have an aromatic heterocyclic group, a substituent, an arylalkyl group or a substituent, and may be an arylalkyl group. Preferable specific examples of R ⁷ include a phenyl group which may have a substituent, a naphthyl group which may have a substituent, a cinnamyl group which may have a substituent. As will be shown later in Examples, according to the method of the present invention, a good yield can be obtained regardless of whether R ⁷ is a phenyl group having an electron-withdrawing group or a phenyl group having an electron-donating group. As a result, it is possible to introduce various substituents.

[0023] In the formula (II), X is an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atomic force, which is one kind selected. When X is an oxygen atom, the compound represented by the formula (II) is an aldehyde. When X is a sulfur atom, the compound represented by the formula (II) is thioaldehyde. When X is a selenium atom, the compound represented by the formula (II) is selenoaldehyde. When X is a tellurium atom, the compound represented by the formula (Π) is a tellurium aldehyde. These compounds may form stable trimers. For example, in the case of thioaldehyde, a trithian ring is formed to form a trimer. In the production method of the present invention, this In this case, the reaction proceeds via the monomer produced in the reaction system.

[0024] By reacting the compound represented by the above formula (I) with the compound represented by the above formula (Π), a heterocyclic compound represented by the formula (III) is obtained. The heterocyclic compound represented by the formula (III) has a molecular structure shown below.

[0025] [Chemical 6]

[Where

R ⁷ and X are the same as the above formulas (I) and (II). ]

In the formula (III), X is one selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, and tellurium atomic energy. When X is an oxygen atom, the heterocyclic compound represented by the formula (ΠΙ) is isobenzofuran (2-benzofuran: benzo [c] furan). When X is a sulfur atom, the heterocyclic compound represented by the formula (ΠΙ) is isothianaphthene (2-benzothiophene (benzo [c] thiophene). When X is a selenium atom, the formula (III The heterocyclic compound represented by) is isoselenanaphthene (2-benzoselenophene: benzo [c] selenophene) When X is a tellurium atom, the heterocyclic compound represented by formula (III) is Isotellanaphthene (2-benzoterphene: benzo [c] terphene).

In the heterocyclic compound represented by the formula (III), the substituents of RR ² , R ³ , R ⁴ , R ⁵ and R ⁷ are each a compound represented by the formula (I) as a raw material And from a compound represented by the formula (Π). Both the compound represented by the formula (I) and the compound represented by the formula (ことが) are compounds that can be easily introduced with various substituents, and as a result, have various substituents at desired positions. The heterocyclic compound represented by the formula (ΠΙ) can be easily produced in one step.

[0028] The reaction described above is represented by a reaction formula by taking the case where X is an oxygen atom as an example. (1) That is, by reacting 1 mol of the compound represented by the formula (I) with 2 mol of the compound represented by the formula (Ila), 1 mol of the heterocyclic compound represented by the formula (Ilia) is obtained. As a result, 1 mol of the compound represented by the formula (IV) (aldimine) and 1 mol of water are by-produced. Half of the compound represented by the formula (Ila) reacts directly with the compound represented by the formula (I), and the other half captures the by-produced amine during the reaction to obtain the compound represented by the formula (IV) Is consumed to form). Here, R ⁶ and R ⁷ in the compound represented by the formula (IV) have the same meanings as the formula (I) and the formula (II).

[0029] [Chemical 7]

(I) (H a) (m a) (IV)

[0030] In the production method of the present invention, it is preferable to use an excess of the compound represented by the formula (I) relative to the compound represented by the formula (I). Specifically, the reaction is preferably performed with the molar ratio (πΖι) of the compound represented by the formula (II) to the compound represented by the formula (I) being 1.5 or more. It is more preferable. The molar ratio (πΖι) is usually 10 or less, preferably 5 or less.

[0031] The method of mixing and reacting the compound represented by the formula (I) and the compound represented by the formula (Π) is not particularly limited. You may make it react in a solution using a solvent, and you may make it react without a solvent. The solvent that can be used is not particularly limited, but an aprotic organic solvent such as hexane, benzene, toluene, dichloroethane, and tetrahydrofuran is preferable. Of these, hydrocarbon solvents or halogen-containing hydrocarbon solvents are preferably used. When X in the formula (II) is an oxygen atom, water is by-produced as the reaction proceeds. Therefore, it is preferable to proceed the reaction while removing the produced water from the reaction system. This is because the presence of water in the reaction system may cause hydrolysis of the compound represented by the formula (I) as a raw material. The method for removing water from the reaction system is not particularly limited. A water-absorbing agent such as molecular sieves may coexist in the reaction system, and water is removed when the solvent is heated to reflux. You may leave. The reaction temperature is not particularly limited, but a temperature of 0 to 300 ° C is usually employed. Preferably, it is 50 ° C or higher and 200 ° C or lower.

[0032] When the compound represented by the formula (I) and the compound represented by the formula (Π) are reacted, it is preferably reacted in the presence of a catalyst composed of a transition metal compound. The amount of the transition metal compound used is not particularly limited, but the transition metal compound is used in an amount of 0.001 to 0.5 times the number of moles of the compound represented by the formula (I) on a metal atom basis. Is preferred. From the viewpoint of the reaction rate and yield, the amount of the transition metal compound used is more preferably 0.005 times or more, more preferably 0. 0,5 times the number of moles of the compound represented by formula (I). 01 times or more. On the other hand, from the viewpoint of reducing manufacturing costs and waste, the amount of transition metal compound used is more preferably 0.2 times or less the number of moles of the compound represented by formula (I). Is less than 0.1 times.

[0033] The transition metal compound used as the catalyst is preferably a transition metal compound belonging to Group 7, Group 8, Group 9 or Group 10 of the periodic table. This is because these transition metal compounds are generally considered to have the ability to activate C—H bonds. In particular, compounds of rhenium, ruthenium, rhodium, iridium and palladium are suitable. Of these, rhenium compounds, particularly monovalent rhenium compounds (rhenium (I) compounds) are preferably used. The rhenium compound is not particularly limited, but is preferably a compound containing a ligand (complex). In this case, the ligand includes halogen atoms such as bromine and chlorine, carbon monoxide, tetrahydrofuran (thf ) And the like. Specific examples of the rhenium compound include [ReBr (CO) (thf)], ReBr (CO), and ReCl (CO). here

3 2 5 5

When the rhenium (I) compound is used, the valence of the rhenium compound to be added may be different as long as the rhenium (I) compound is present in the reaction system. For example, a zero-valent rhenium compound may be oxidized in the reaction system, and a polyvalent rhenium compound may be reduced in the reaction system.

[0034] Although the reaction mechanism of the present invention is not necessarily clear, when a rhenium catalyst is used and an aldehyde is used as the compound represented by the formula (II), a mechanism such as the following formula (2) is used. Is estimated. First, the CH bond at the ortho position of the aromatic ring is activated by a rhenium catalyst, and an aldehyde is inserted into the formed C—Re bond. Next, find it in the molecule. A cyclization reaction proceeds nuclearly, rhenium salt is reductively eliminated, and amine is eliminated. The released amine reacts with the aldehyde and dehydrates to form aldimine.

[0035] [Chemical 8]

[0036] Since the heterocyclic compound represented by the formula (III) thus obtained has a long and π-conjugated system, it is an organic electroluminescence (EL) device, an organic field effect transistor (FET) device, an organic compound. It is promising as a material for light emitting diodes and fluorescent dyes. According to the production method of the present invention, a heterocyclic compound having various substituents at desired positions can be easily produced in one step. Therefore, it becomes easy to adjust the physical properties of the heterocyclic compound represented by the formula (III), and the target compound based on the molecular design can be easily obtained.

[0037] For example, the compound (B1553) represented by the following formulas (3) and (4) has an electron transport capability and a hole transfer capacity of 1 ^ 1 ^ In addition, since it emits intensely in a solid state and can be easily vacuum-deposited on a hole transport layer (HT layer), it is preferably used for an organic light emitting diode. As for the production method, the method of the following formula (3) has been reported (J. Am. Chem. Soc. 1967, 89, 6091). On the other hand, according to the manufacturing method of the present invention, B1553 can be easily manufactured by the method shown in the equation (4). [0038] [9]

[0040] The heterocyclic compound represented by the formula (III) is also useful as a reaction intermediate. For example, it is also preferred that the heterocyclic compound represented by the formula (III) is reacted with olefin (V) or acetylene (VII) to advance the Diels-Alder reaction. At this time, the diels-alder reaction may proceed by reacting olefin (V) or acetylene (VII) with a bicyclic compound synthesized in advance. However, the reaction is allowed to proceed in the presence of a compound represented by the formula (I), a compound represented by the formula (、), olefin (V) or acetylene (VII), and represented by the formula (III) produced. The heterocyclic compound is preferably captured by olefin (V) or acetylene (VII) in the reaction system. This is a particularly effective technique when the heterocyclic compound represented by the formula (III) is unstable. In this case, it is preferable that olefin (V) or acetylene (VII) is blended in an excessive amount with respect to the compound represented by formula (I). When the olefin represented by the following formula (V) is reacted with the heterocyclic compound represented by the formula (III), the Diels-Alder attached product represented by the following formula (VI) is obtained. can get. In addition, when the acetylene represented by the following formula (VII) is reacted with the heterocyclic compound represented by the formula (III), a diels-alder-attached product represented by the following formula (VIII) Is obtained. Here, as the substituents for R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ R ¹² and R ¹³ , the same substituents as those for R ² , R ³ and R ⁴ can be used.

[0041] [Chemical 11]

[0043] [Chemical 13]

[0044] [Chemical 14]

[0045] The compound obtained by the Diels-Alder reaction as described above has a skeleton in which a large number of rings are bonded, and often has a long π-conjugated system. Therefore, an organic electroluminescence (EL) device or It is promising as a material for organic field-effect transistor (FET) elements, organic light-emitting diodes, and fluorescent dyes. According to the production method of the present invention, a polycyclic compound having various substituents at desired positions can be easily produced. For example, a new blue light-emitting substance, 7, 16-dihydroheptacene derivative, has been reported to be synthesized by the method of the following formula (5). (J. Org. Chem. 2006, 71, 4085), but requires a multi-step reaction. On the other hand, according to the manufacturing method of the present invention, as shown in the equation (6), the number of steps can be greatly reduced.

[0046] [Chemical 15]

Ar = Ar '= Ph, 82%

mesityl, 86%

7,6-dihydroheptacene Ar = Ar '= Ph, 38%

[0047] [Chemical 16]

heptacene (6)

Example

[0048] Example 1 The compound represented by formula (I) is an aromatic imine, N- (diphenylmethylene) benzenamine 129 mg (0.500 mmol), and the compound represented by formula (II) is benzaldehyde 1 02 (1. OOmmol). ), [ReBr (CO) (thf)] 10.6 mg (0.O125 mmol) as a catalyst,

3 2

A mixture of molecular sieves 4A 0.2 g and toluene 1. OmL was heated at 115 ° C. under reflux conditions. After 24 hours, 1,3-diphenylisobenzofuran was produced as a heterocyclic compound represented by the formula (III) in a yield of 95% (^ H-NMR yield). At this time, by-production of N- (phenylmethylene) benzeneamine was confirmed. When isolated and purified by silica gel column chromatography, 123 mg (91)% of 1,3-diphenylisobenzofuran was obtained. The structure of the product was identified by 'H-NMR, ¹³ C-NMR and IR. The catalyst [ReBr (CO) (thf)] was found in Vitali, D .; Calderazzo, F. Gazz. Chim. Ital. 1972, 102, 587.

3 2

Prepared according to the method described. The chemical reaction formula of this example is shown in the following formula (3). Table 1 summarizes the yield of the heterocyclic compound represented by the formula (III).

[0049] The chemical structure of 1,3-diphenylisobenzofuran obtained in Example 1 is as shown in the following formula (IX).

[0050] [Chemical 17]

[0051] The structural data of 1,3-diphenylisobenzofuran obtained in Example 1 is as follows.

^J H NMR (400 MHz, CDC1) δ 7.01-7.04 (m, 2Η), 7.30 (t, J = 7.8 Hz, 2H), 7.49 (t

Three

, J = 7.8 Hz, 4H), 7.83-7.87 (m, 2H), 7.95 (d, J = 7.8 Hz, 4H); ¹³ C NMR (100 MHz, CDC1) δ 120.17 (2C), 122.08 (2C), 124.77 (4C), 125.14 (2C), 126.88 (4C), 128.9

Three

4 (2C), 131.63 (2C), 143.72 (2C); IR (nujol, v I cm '' ¹ ) 1653 (m), 1597 (m), 1492 (m), 1205 (m), 1068 (m), 1028 (m), 910 (m), 765 (s), 741 (m), 691 (s), 658 (s).

[0052] Examples 2-7 A heterocycle represented by the formula (ΠΙ) in the same manner as in Example 1 except that the compound represented by the formula (I) and the compound represented by the formula (Π) were each changed to the compounds shown in Table 1 below. The formula compound was obtained. The chemical reaction formula at that time is shown in the following formula (7). Table 1 summarizes the yield of the heterocyclic compound represented by the formula (III).

[0053] [Chemical 18]

(1 equiv) (2 equiv)

[0054] [Table 1]

R ⁵ R ⁶ R ⁷ Yield Example 1 Ph Ph Ph 91 (95) Example _{2 Ph PhCH 2 Ph - (95} ) Example 3 Ph Ph - (85) Example _{4 Ph Ph p-MeC 6 H} 4 - (83) example _{5 Ph Ph o-MeC 6 H} 4 - (86) example _{6 Ph Ph p- (CF 3)} C 6 H 4 (98)

Example 7

One ¹ numbers in parentheses ¹ H-NMR Yield. “One” indicates unmeasured.

[0055] Example 8

As the compound represented by the formula (I), N- (diphenylmethylene) benzenamine 129 mg (0.500 mmol) which is an aromatic imine, and benzaldehyde 1002 μL · (l. OOmmol), cyclooctene 130 μL (l.OOmmol) as olefin, [ReBr (CO) (thf)] 10.6 mg (0.O125 mmol), molecular sieves 4A0.2

3 2 A mixture of g and toluene 1. OmL was heated at 115 ° C. under reflux conditions. After 24 hours, a 1,3-diphenylisobenzofuran diels-Alder product was produced in 90% yield (^ H-NMR yield). At this time, by-production of N- (fermethylene) benzeneamine was confirmed. When isolated and purified by silica gel chromatography and gel filtration chromatography, 158 mg (83%) of a Diels-Alder-attached koji product was obtained. The structure of the product was identified by ¹ H-NMR, ¹³ C-NMR and IR. The chemical reaction formula of this example is shown in the following formula (4). In addition, Table 2 summarizes the yield of the Diels-Alder-added cocoon product.

[0056] The chemical structure of the Diels-Alder addition product obtained in Example 8 is as shown in the following formula (X).

[0057] [Chemical 19]

[0058] The structural data of the Diels-Alder-attached product represented by the above formula (X) is as follows: JH NMR (400 MHz, CDC1) δ 0.46—0.54 (m, 2H), 1.29—1.38 (m, 2H), 1.42—1.62 (

Three

m, 8H), 2.95-3.01 (m, 2H), 7.04 (dd, J = 5.3, 3.0 Hz, 2H), 7.21 (dd, J = 5.3, 3.0 Hz, 2H), 7.36-7.45 (m, 6H) ; 7.66 (d, J = 6.9 Hz, 4H); ¹³ C NMR (100 MHz, CDC1) δ

Three

25.35 (2C), 26.19 (2C), 30.37 (2C), 46.82 (2C), 91.40 (2C), 121.32 (2C), 126.10 (2 C), 128.34 (4C), 128.41 (2C), 128.59 (4C) , 137.30 (2C), 146.79 (2C); IR (nujol, v I cm " ¹ ) 3055 (w), 1734 (w), 1700 (w), 1684 (w), 1635 (w), 1601 (w) , 1521 (w), 1506 (w), 1445 (s), 1364 (m), 1315 (m), 1015 (m), 979 (m), 972 (m), 771 (m), 753 (s) , 798 (s), 666 (m), 642 (m).

[0059] Examples 9-12

A Diels-Alder addition product was obtained in the same manner as in Example 8, except that the compound represented by the formula (I) and the compound represented by the formula (Π) were each changed to the compounds shown in Table 2 below. . So The chemical reaction formula at this time is shown in the following formula (8). In addition, ¹ H—NM of the cocoon product with Diels-Alder

The R yield is summarized in Table 2.

[0060] The chemical structure of the Diels-Alder addition product obtained in Example 9 is as shown in the following formula (XI).

[0061] [Chemical 20]

[0062] The structural data of the Diels-Alder-attached product represented by the above formula (XI) is as follows.

^J H NMR (400 MHz, CDCl) δ 0.42—0.52 (m, 2Η), 1.21—1.58 (m, 10H), 2.53 (t, J

Three

= 10.2 Hz, IH), 2.94 (t, J = 10.2 Hz, IH), 6.84 (d, J = 16.2 Hz, IH), 6.98 (d, J = 7.2 Hz, IH), 7.04 (d, J = 16.2 Hz, IH), 7.17-7.29 (m, 4H), 7.35 (t, J = 7.8 Hz, 2H), 7.40-7.46 (m, 3H), 7.50 (d, J = 7.8 Hz, 2H), 7.64 (d, J = 7.8 Hz, 2H); ¹³ C NMR (10 0 MHz, CDCl) δ 25.14 (IC), 25.30 (IC), 26.10 (IC), 26.17 (IC), 30.21 (IC), 30.7

Three

2 (IC), 46.26 (IC), 50.57 (IC), 89.36 (IC), 91.51 (IC), 120.34 (IC), 121.52 (IC), 1 24.75 (IC), 126.17 (2C), 126.65 (2C) , 127.88 (IC), 128.43 (2C), 128.52 (IC), 128.5 5 (2C), 128.63 (2C), 133.37 (IC), 136.75 (IC), 137.22 (IC), 145.59 (IC), 146.55 (1 C); IR (nujol, v I cm "1) 3025 (w), 1734 (w), 1684 (w), 1653 (w), 1600 (w), 1576 (w), 1559 (w), 1360 ( m), 1018 (m), 967 (s), 755 (s), 698 (s), 666 (m), 639 (m).

[0063] The chemical structure of the Diels-Alder addition product obtained in Example 10 is as shown in the following formula (ΧΠ).

[0064] [Chemical 21]

[0065] The structural data of the Diels-Alder addition product represented by the above formula (XII) is as follows.

^J H NMR (400 MHz, CDCl) δ 0.44—0.52 (m, 2H), 1.28—1.61 (m, 10H), 2.38 (s, 3

Three

H), 2.93-3.00 (m, 2H), 7.01-7.06 (m, 2H), 7.18-7.24 (m, 4H), 7.36-7.44 (m, 3H), 7.54 (d, J = 8.1 Hz, 2H), 7.65 (d, J = 7.7 Hz, 2H); 13 C NMR (100 MHz, CDCl) δ 21

Three

.25 (IC), 25.37 (2C), 26.21 (2C), 30.41 (2C), 46.81 (IC), 46.90 (IC), 91.31 (2C), 1 21.26 (IC), 121.39 (2C), 126.03 (2C) ), 128.32 (2C), 128.35 (IC), 128.54 (2C), 128.5 7 (2C), 129.05 (2C), 134.19 (IC), 138.17 (2C), 146.81 (IC); IR (nujol, v / cm " ¹ ) 17 34 (w), 1700 (w), 1684 (w), 1635 (w), 1541 (w), 1506 (w), 1365 (m), 1317 (m), 981 (m), 821 (s), 762 (s), 697 (s).

[0066] [Chemical 22]

[0067] [Table 2] Yield I Example 8 Ph Ph 83 (90) Example 9 Ph 77 (83)

Example 10 Ph p-MeC ₆ H ₄ 81 (85) Example 11 Ph-MeC ₆ H ₄ 56 (62) Example 12 Ph p- (CF ₃ ) C ₆ H ₄ 86 (92)

) ¹ Numbers in parentheses ¹ H-NMR Yield.

Claims

Claims [1] An aromatic imine having at least one aromatic ring bonded to the carbon atom of the imino group and having at least one hydrogen atom at the position of the imino group ortho in the aromatic ring; A group consisting of isobenzofuran, isothianaphthene, isoselenanaphthene and isotellananaphthenca, characterized by reacting with one compound selected from the group consisting of aldehyde, thioaldehyde, selenaldehyde and terucaldehyde Force A method for producing one selected polycyclic compound. [2] The following formula (I)

[Chemical 1]

[Wherein, R \ R ² , R ³ and R ⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. An alkyl group, an aryl group that may have a substituent, an aryl group that may have a substituent, an arylalkyl group that may have a substituent, and a substituent. May have an aryl alkyl group, an optionally substituted cycloalkyl group, an optionally substituted heterocyclic group, an optionally protected hydroxyl group, an alkoxy group, an aryloxy group, an aldehyde Group, an optionally protected carboxyl group or a salt thereof, an alkyl carbo group, an aryl carbo group, an alkyloxy carbo group, an aryloxy carbo ol group, an alkyl group, a hydroxy group, an ally carbo group. -Mouthoxy group, even if protected Good amino group, alkylamino group, arylamino group, ammonia group, alkylammonium group, arylamine group, optionally protected thiol group, alkylthio group, arylthio group, protected Sulfinic acid group or salt thereof, alkyl sulfier group, aryl sulfier group, sulfonic acid group which may be protected or salt thereof, alkyl sulfone group Group, arylsulfol group, alkylazo group, allylazo group, phosphoric acid group which may be protected or a salt thereof, phosphorous acid group which may be protected or a salt thereof, cyano group, -to-oral group or Each of R ⁵ and R ⁶ independently has a hydrogen atom, an alkyl group that may have a substituent, an alkyl group that may have a substituent, or a substituent. An alkyl group that may have a substituent, an aryl group that may have a substituent, an aryl group that may have a substituent, an aryl group that may have a substituent, and a substituent. May be an arylalkynyl group, a substituent, a cycloalkyl group or a substituent, and a heterocyclic group.

R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be bonded to each other to form a ring. ] And the following formula (II)

[Chemical 2]

Which is reacted with a compound represented by the following formula (III)

[Chemical 3]

[Where

R ⁷ and X are the same as the above formulas (I) and (II). ] The manufacturing method of the heterocyclic compound shown by these. [3] R ⁵ may have a substituent, may have a aryl group, may have a substituent, may have an aromatic heterocyclic group, a substituent, an arylalkyl group, The heterocyclic ring according to claim 2, wherein the heterocyclic group is an aryl group, a cycloalkyl group, a substituent, a alkenyl group, or a substituent. A method for producing a formula compound.

[4] The method for producing a heterocyclic compound according to [2] or [3], wherein X is an oxygen atom.

[5] The reaction according to claims 1 to 4, wherein the reaction is carried out in the presence of a catalyst comprising a transition metal compound! A method for producing a heterocyclic compound according to any one of the above.

6. The method for producing a heterocyclic compound according to claim 5, wherein the catalyst is a transition metal compound belonging to Group 7, Group 8, Group 9, or Group 10 of the periodic table.

7. The method for producing a heterocyclic compound according to claim 6, wherein the catalyst comprises a rhenium compound.

8. The method for producing a heterocyclic compound according to claim 7, wherein the rhenium compound is a rhenium (I) compound.

[9] The heterocyclic compound according to any one of claims 2 to 8, which is reacted at a molar ratio (ΠΖΙ) of the compound represented by the formula (Π) to the compound represented by the formula (I) of 1.5 or more. Production method.

10. The method for producing a heterocyclic compound according to claim 4, wherein the reaction is allowed to proceed while removing generated water from the reaction system.