JP2009235009A - Method for producing fluorine compound and fluorine compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a means for producing a new fluorine-containing heteroaryl compound from an easily available raw material by an industrially advantageous method and a new fluorine-containing pyrazole compound useful as a synthetic raw material of an organic electroluminescent element (or an organic EL element). <P>SOLUTION: The method for producing a compound represented by general formula (2) (wherein R<SB>1</SB>and R<SB>2</SB>are each a heteroaryl group or an aryl group with the proviso that at least one of R<SB>1</SB>and R<SB>2</SB>is a heteroaryl group; and n is an integer of ≥1) comprises reacting a compound represented by general formula (1) with a fluorine gas in a halogen-containing solvent. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a novel fluorine-containing compound useful as a synthetic intermediate for light-emitting materials and electronic materials, and a method for producing the same.

  Fluorine-containing heteroaryl compounds are known to be useful as synthetic intermediates for light-emitting materials and electronic materials (for example, see Patent Document 1) and pharmaceutical / agrochemical synthetic intermediates (for example, see Non-Patent Document 1). Yes. In addition, heteroaryl compounds having a crosslinked structure are used as ligands for transition metal atoms such as rhenium and chromium, and are used in the pharmaceutical field (for example, see Non-Patent Document 2) and catalysts in polymer synthesis (for example, patents). Its usefulness is shown as Reference 2).

  In particular, among the platinum complex compounds exemplified in Patent Document 1, the compound represented by the following formula (5) exemplified by the number 216 on page 38 is highly durable due to its structural characteristics. Sex is expected. However, for this compound, the predicted maximum wavelength of phosphorescence emission using semi-empirical molecular orbital method calculation is from 455 to 460 nm, which is an ideal blue color, at 451 nm on the slightly lower wavelength side. When an organic electroluminescent element is produced by using it, it is predicted that the violet-colored blue light is emitted.

  On the other hand, the compound represented by the following formula (6) has a predicted maximum wavelength of phosphorescence emitted by semi-empirical molecular orbital calculation, which is 460 nm close to an ideal blue color. When an organic electroluminescent element is produced, it is predicted to emit blue light. For this reason, development of the compound represented by Formula (6) has been eagerly desired.

  However, a pyrazole compound having a structure crosslinked with a tetrafluoroethylene group represented by the following formula (7), which is a synthesis intermediate of the compound represented by the above formula (6), has been synthesized so far. There are no reports.

  As a known pyrazole compound having a structure crosslinked with a tetrafluoroethylene group, a compound represented by the following formula (8) is known (for example, see Non-Patent Document 3). However, in this method for producing a compound, a compound bonded to the tetrafluoroethylene group at the 3-position of the pyrazole ring is obtained, and a compound bonded to the tetrafluoroethylene group at the 4-position of the pyrazole ring cannot be essentially obtained. .

  Under such circumstances, it is also conceivable to newly synthesize a compound represented by the above formula (7) by applying a known synthesis method of a similar compound. As a known synthesis method, a method of converting an aryl compound having a structure crosslinked with an ethynylene group into an aryl compound having a structure crosslinked with a tetrafluoroethylene group is known.

For example, a conversion method using xenon difluoride as shown in the following reaction formula (i) is known (see, for example, Non-Patent Document 4). However, this method requires xenon difluoride, which is very expensive and difficult to obtain, and requires the use of a large amount of anhydrous hydrogen fluoride, which is highly toxic and corrosive and difficult to handle. Not suitable for manufacturing. In addition to this, there is no known example of fluorinating an ethynylene compound substituted with a heteroaryl group by this method.

Moreover, the conversion method using the nitrosyl tetrafluoroborate as shown to following reaction formula (ii) is known (for example, refer nonpatent literature 5). However, this method has to use a large amount of pyridine / hydrogen fluoride double salt, which is highly toxic and corrosive and difficult to handle, and is not suitable for industrial production. In addition to this, there is no known example of fluorinating an ethynylene compound substituted with a heteroaryl group by this method. Although details are given in the examples described later, synthesis of the compound represented by the above formula (7) was attempted by applying this method, but the target product could not be obtained.

Similarly, a method of fluorination using a fluorine-halogen compound as shown in the following reaction formula (iii) is known (for example, see Non-Patent Document 6). However, this method requires expensive iodine, and in addition, it is difficult to implement industrially because it is necessary to synthesize unstable and high-risk iodine fluoride in advance. There is no known example of fluorinating an ethynylene compound substituted with a heteroaryl group.

Further, a method of fluorinating an ethynylene compound substituted with an aromatic group using a fluorine gas as shown in the following reaction formula (iv) is known (for example, see Non-Patent Document 7). However, since this production method uses fluorotrichloromethane (CFC-11), which is an ozone-depleting substance and is currently difficult to obtain, it can be said that it is very difficult to implement at present. In addition to this, there is no known example in which an ethynylene compound substituted with a heteroaryl group is fluorinated by this method. This is because when a compound having a heteroaryl group is reacted with fluorine gas, a heteroatom on the heteroaryl ring, which has the highest electron density in the molecule, is reacted under normal reaction conditions. This is because it has been considered that a heteroaryl compound crosslinked with a tetrafluoroethylene group cannot be obtained and has not been tried. In fact, the details will be shown in the comparative example described later, but the present inventors tried to fluorinate an acetylene compound substituted with a heteroaryl group under the general fluorination conditions in acetonitrile solvent and acetic acid solvent. The target tetrafluoroethylene was not obtained.

JP 2007-19462 A US Patent Application Publication No. 2005/0288464 G. W. Walle, D.C. M.M. By Whitacre, “An Introduction to Insecticides, 4th edition” University of Minnesota, Minnesota, 2004 W. Krause, “Contrast Agents III Radiopharmaceuticals From Diagnostics to Therapeutics, Topics in Current Chemistry 252” Springer Berlin Heidelhead “Journal Husesoyutsunogo Kimikeskogo of Kestkeswa im Day I Mendeleev”, page 26, 1986, Vol. 26, 1985. D. Mendeleeva. “Journal of Organic Chemistry”, Vol. 39, 1974, p. 2646. “Journal of Organic Chemistry” Vol. 59, 1994, p. 6493. Journal of Organic Chemistry, Volume 51, 1986, p. 222. “Journal of Fluorine Chemistry”, Volume 25, 1984, page 169.

  An object of the present invention is to provide means for producing a novel fluorine-containing heteroaryl compound from readily available raw materials by an industrially advantageous method. Another object of the present invention is to provide a novel fluorine-containing pyrazole compound that is useful as a raw material for synthesizing an organic electroluminescent element (or organic EL element) material.

  As a result of intensive studies to solve the above problems, the present inventors have found conditions for producing a heteroaryl compound crosslinked with a tetrafluoroethylene group from an easily available raw material by an industrially advantageous method. It came to complete. That is, the said subject was solved by the following means.

1. A method for producing a compound represented by the following general formula (2), which comprises reacting a compound represented by the following general formula (1) with a fluorine gas in a halogen-containing solvent.

(In General Formula (1) and General Formula (2), R ₁ and R ₂ represent a heteroaryl group or an aryl group, provided that at least one represents a heteroaryl group, and n represents an integer of 1 or more. )
2. _2. The production method according to 1 above, wherein R ₁ and R ₂ in the general formulas (1) and (2) are both heteroaryl groups.
3. 3. The production method according to 1 or 2 above, wherein the halogen-containing solvent is a halogen-containing saturated hydrocarbon solvent or a halogen-containing saturated hydrocarbon ether solvent.
4). The compound represented by the general formula (1) is a compound represented by the following general formula (3), and the compound represented by the general formula (2) is represented by the following general formula (4). 4. The production method according to any one of 1 to 3 above, which is a compound.

(In General Formula (3) and General Formula (4), R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ each independently represents a hydrogen atom or a substituent.)
5. A compound represented by the following general formula (4).

(In the general formula (4), R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ each independently represents a hydrogen atom or a substituent.)

  According to the production method of the present invention, a novel fluorine-containing heteroaryl compound can be produced from a readily available raw material by an industrially advantageous method. The present invention also provides a novel fluorine-containing pyrazole compound useful as a raw material for synthesizing organic electroluminescent device (or organic EL device) materials.

  The method for producing a compound represented by the following general formula (2) of the present invention is characterized by reacting a compound represented by the following general formula (1) with a fluorine gas in a halogen-containing solvent.

In the general formulas (1) and (2), R ₁ and R ₂ represent a heteroaryl group or an aryl group. However, at least one represents a heteroaryl group. Preferably both are heteroaryl groups, and these heteroaryl groups may be the same or different. N is an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 1 to 5, still more preferably an integer of 1 to 2, and particularly preferably 1. .

  The heteroaryl group is an optionally substituted monocyclic or bicyclic ring having 1 to 2 kinds of heteroatoms and containing 1 to 4 heteroatoms, preferably 3 to 14 members, preferably 5 to 10 members. Of the heteroaryl group. A heteroatom is an atom of an element other than carbon. The element other than carbon is preferably the 15th periodic element or the 16th periodic element, more preferably an element selected from the group consisting of nitrogen, phosphorus, arsenic, oxygen, sulfur, selenium, and tellurium, and further preferably Is an element selected from the group consisting of nitrogen, oxygen and sulfur.

  Examples of heteroaryl groups include pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolyl, isoindolyl, indazolyl, benzimidazolyl, benzotriazolyl, imidazolopyridyl, purinyl, quinolyl, isoquinolyl, quinoxalinyl , Quinazolinyl, cinnolinyl, phthalazinyl, naphthyridinyl, pteridinyl, furyl, oxazolyl, isoxazolyl, oxadiazolyl, oxatriazolyl, benzofuryl, isobenzofuryl, benzoxazolyl, benzoisoxazolyl, flopridyl, thienyl, thiazolyl, isothiazolyl, thiadiazolyl , Thiatriazolyl, benzothienyl, isobenzothienyl, benzothiazolyl, benzoiso Azolyl, thienopyridyl, and the like, but preferably pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolyl, indazolyl, benzimidazolyl, quinolyl, isoquinolyl, quinoxalinyl, furyl, oxazolyl, oxazolyl, oxazolyl, Benzoxazolyl, benzisoxazolyl, thienyl, thiazolyl, isothiazolyl, thiadiazolyl, benzothienyl, benzothiazolyl, benzisothiazolyl, more preferably pyrrolyl, imidazolyl, pyrazolyl, pyridyl, indolyl, indazolyl, benzimidazolyl, Quinolyl, furyl, oxazolyl, isoxazolyl, oxadiazolyl, benzofuryl, benzoxazolyl Thienyl, thiazolyl, isothiazolyl, benzothienyl, benzothiazolyl, more preferably, pyrrolyl, pyrazolyl, pyridyl, indolyl, furyl, isoxazolyl, oxadiazolyl, benzofuryl, thienyl, isothiazolyl, benzothienyl, particularly preferably pyrazolyl.

  The bond between the heteroaryl group and the ethynylene group or tetrafluoroethylene group may form a bond at any atom on the heteroaryl ring, but preferably forms a bond at a carbon atom on the heteroaryl ring.

  The aryl group is an aryl group having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, which may have a substituent. Examples of the aryl group include a phenyl group, a naphthyl group, and a biphenylyl group.

  Although the specific example of the compound represented by General formula (1) which does not have a substituent below is shown, this invention is not limited to these. A compound in which a substituent is introduced in such a manner that a hydrogen atom is substituted at a carbon atom on the heteroaryl ring or aryl ring or at any position on the heteroatom can be obtained by those skilled in the art without showing the structural formula of the compound. Since the chemical structure can be estimated easily, only specific examples of the form having no substituent are given here.

  Although the specific example of the compound represented by General formula (2) which does not have a substituent below is shown, this invention is not limited to these. A compound in which a substituent is introduced in such a manner that a hydrogen atom is substituted at a carbon atom on the heteroaryl ring or aryl ring or at any position on the heteroatom can be obtained by those skilled in the art without showing the structural formula of the compound. Since the chemical structure can be estimated easily, only specific examples of the form having no substituent are given here.

  Examples of the substituent that the heteroaryl group and the aryl group may have include an alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms, For example, methyl, ethyl, iso-propyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, etc.), an alkenyl group (preferably having 2 to 30 carbon atoms, more preferred). Has 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include vinyl, allyl, 2-butenyl, 3-pentenyl and the like, and an alkynyl group (preferably having 2 to 30 carbon atoms, more preferably Has 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as propargyl, 3-pentynyl and the like. And alkylidene groups (preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, such as methylidene, ethylidene, isopropylidene, cyclohexylidene, and cyclopentadienylidene). A haloalkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms such as fluoromethyl, chloromethyl, bromomethyl, iodomethyl, difluoromethyl, trifluoromethyl, Examples include trichloromethyl, 2,2,2-trifluoroethyl, 2,2,3,3-tetrafluoro-n-propyl, 1,1,1,3,3,3-hexafluoro-2-propyl and the like. ), An alkoxyalkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, Preferably it is C1-C10, for example, methoxymethyl, methoxyethyl, ethoxyethyl, 2- (methoxyethoxy) ethyl etc.), an aryl group (preferably C6-C30, more preferably carbon number) 6 to 20, particularly preferably 6 to 12 carbon atoms, such as phenyl, p-methylphenyl, naphthyl, anthranyl, etc.), arylidene groups (preferably 7 to 31 carbon atoms, more preferably 7 carbon atoms) To 11 and includes, for example, benzylidene), an amino group (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, and particularly preferably 0 to 10 carbon atoms, such as amino and methylamino). Dimethylamino, diethylamino, dibenzylamino, diphenylamino, ditolylamino, etc. The ), An alkoxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, and examples thereof include methoxy, ethoxy, butoxy, 2-ethylhexyloxy and the like. ), An aryloxy group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenyloxy, 1-naphthyloxy, 2-naphthyloxy and the like. Heterocyclic oxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy, piperidyloxy, etc. An acyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms). Particularly preferably, it has 1 to 12 carbon atoms, and examples thereof include acetyl, benzoyl, formyl, pivaloyl, etc.), an alkoxycarbonyl group (preferably 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably C2-C12, for example, methoxycarbonyl, ethoxycarbonyl, etc.), aryloxycarbonyl groups (preferably C7-30, more preferably C7-20, particularly preferably C7-C7) 12 such as phenyloxycarbonyl), an acyloxy group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms such as acetoxy and benzoyl). Oxy, etc.), acylamino groups (preferably having 2 to 30 carbon atoms) More preferably, it has 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include acetylamino, benzoylamino and the like, and an alkoxycarbonylamino group (preferably 2 to 30 carbon atoms, more preferably carbon atoms). 2-20, particularly preferably having 2-12 carbon atoms, such as methoxycarbonylamino, and the like, an aryloxycarbonylamino group (preferably having 7-30 carbon atoms, more preferably having 7-20 carbon atoms, Particularly preferably, it has 7 to 12 carbon atoms, and examples thereof include phenyloxycarbonylamino, etc.), a sulfonylamino group (preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 carbon atom). -12, for example, methanesulfonylamino, benzenesulfonylamino, etc. . ), Sulfamoyl groups (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 12 carbon atoms, such as sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl) ), A carbamoyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl, etc. An alkylthio group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms such as methylthio and ethylthio), an arylthio group. (Preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms. Particularly preferably, it has 6 to 12 carbon atoms, and examples thereof include phenylthio.), A heterocyclic thio group (preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms). For example, pyridylthio, 2-benzimidazolylthio, 2-benzoxazolylthio, 2-benzthiazolylthio, piperidinylthio and the like, sulfonyl group (preferably having 1 to 30 carbon atoms, more preferably carbon 1 to 20, particularly preferably 1 to 12 carbon atoms, such as mesyl and tosyl), sulfinyl group (preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably C1-C12, for example, methanesulfinyl, benzenesulfinyl, etc.), ureido group (preferably Has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include ureido, methylureido, phenylureido and the like, and a phosphoric acid amide group (preferably carbon). 1 to 30, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as diethyl phosphoric acid amide and phenyl phosphoric acid amide)), hydroxy group, oxo group, mercapto group , Thioxo group, halogen atom (including fluorine atom, chlorine atom, bromine atom and iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, hydroxy Imino group, hydrazono group, heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, Hetero atoms include, for example, nitrogen atoms, oxygen atoms, sulfur atoms, specifically imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, carbazolyl, azepinyl, tetrahydropyrani. And tetrahydrofuranyl. ), A silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, such as trimethylsilyl, triphenylsilyl, etc.), a silyloxy group (preferably Are those having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, and particularly preferably 3 to 24 carbon atoms, and examples thereof include trimethylsilyloxy, triphenylsilyloxy, and the like. These substituents may be further substituted.

The compound represented by the general formula (1) can be synthesized by a known method (for example, Tetrahedron Letters Vol. 50, 1975, page 4467, and Journal of Organic Chemistry). (Journal of Organic Chemistry) Vol. 62, 1997, page 1491, and Organic Letters, Vol. 3, 2001, page 2883, etc.). By referring to this method, those skilled in the art can easily synthesize compounds having the same or different R ₁ and R ₂ in the compound represented by the general formula (1) with good yield. it can.

As shown below, the method for producing the compound represented by the general formula (2) includes a step of reacting the compound represented by the general formula (1) with a fluorine gas in a halogen-containing solvent. R ₁ , R ₂ and n in the following general formula (1) and general formula (2) have the same meanings as described above.

  The fluorine gas may be used as it is, but may be used after being diluted with a gas inert to the fluorine gas, or may be used by being dissolved or dispersed in a liquid inert to the fluorine gas. Preferably, fluorine gas diluted with an inert gas is used. Examples of the inert gas include nitrogen, helium, and neon, but nitrogen is more preferable for economical reasons. The degree of dilution of the fluorine gas is preferably 0.01 to 80%, more preferably 0.1% to 40% as the volume concentration of the fluorine gas in the dilution gas.

  The temperature at which the reaction with the fluorine gas is carried out may be any temperature within the feasible temperature range, but it is more preferably −100 ° C. to + 100 ° C. from the point of industrial implementation, and −80 to + 60 ° C. Further, it is more preferable to carry out at a temperature not lower than the melting point of the solvent and not higher than the boiling point of the solvent.

  Although the pressure which performs reaction with fluorine gas is not specifically limited, In normal cases, it is preferably performed in the pressure range of atmospheric pressure to 1 MPa from the point of industrial implementation.

  The amount of fluorine used for the fluorination reaction needs to be 2 mol or more per 1 mol of ethynylene group in the compound represented by the general formula (1), and preferably 2 to 2 mol per 1 mol of ethynylene group. 100 moles are used, more preferably 2 to 20 moles per mole of ethynylene group.

  The reaction mode with the fluorine gas may be a batch type or a continuous type. In the embodiment of the present invention, it is performed in a batch system.

  The reaction vessel used for the reaction with fluorine gas is preferably made of resin, metal or earthenware that is not subject to corrosion by fluorine gas and hydrogen fluoride which may be by-produced, but coexist with a hydrogen fluoride scavenger. When the reaction is carried out, a glass reaction vessel or a metal vessel lined with a material containing glass and capable of being corroded by fluorine gas and hydrogen fluoride which may be by-produced can be used.

As the hydrogen fluoride scavenger, any substance capable of capturing hydrogen fluoride can be used, but preferably a metal fluoride salt (for example, sodium fluoride, calcium fluoride, etc.), metal carbonate ( Examples thereof include sodium carbonate and calcium carbonate), metal hydroxide salts (for example, potassium hydroxide and magnesium hydroxide), and metal oxide salts (for example, aluminum oxide). Is a scavenger selected from the group consisting of lithium fluoride, sodium fluoride, potassium fluoride, calcium fluoride, and aluminum oxide, or a combination of two or more, more preferably lithium fluoride, sodium fluoride, or fluorine. Potassium halide is used alone. In addition, the hydrogen fluoride scavenger can be used only in the minimum amount necessary to supplement the produced hydrogen fluoride, but usually an excellent amount is obtained by using an excess amount. In Examples of the present invention described later, an excess amount of sodium fluoride is allowed to coexist as a hydrogen fluoride scavenger, and synthesis is performed using a glass container.
The hydrogen fluoride scavenger is preferably used in an amount of 1 to 500 mol with respect to 1 mol of the compound represented by the general formula (1).

  The reaction with the fluorine gas is performed in the liquid phase. In the reaction in the liquid phase, when the compound represented by the general formula (1) is a halogen-containing compound and is a liquid at a temperature at which the reaction with the fluorine gas is performed, the solvent itself acts as a solvent. Although it may not be used, it is preferably carried out using a halogen-containing solvent.

  Here, the halogen is preferably fluorine, chlorine, bromine or iodine, more preferably fluorine or chlorine. The halogen-containing solvent indicates a compound that has at least one or more types of halogen atoms in the molecule and is liquid at the reaction temperature with fluorine gas. The halogen-containing compound is a compound having at least one or more types of halogen atoms in the molecule.

  The reaction may be performed in a state in which the compound represented by the general formula (1) is not dissolved at all in the halogen-containing solvent used for the reaction with the fluorine gas, but preferably in a state in which 1% or more is dissolved. The reaction is performed, and more preferably 5% or more is dissolved.

  The halogen-containing solvent used for the reaction with the fluorine gas is preferably a halogen-containing saturated hydrocarbon (chain, branched or cyclic saturated having at least one kind of halogen atom or two or more kinds in the molecule. A compound, preferably a saturated hydrocarbon compound having 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, still more preferably 1 to 10 carbon atoms, such as carbon tetrachloride, chloroform, fluoroform, dichloromethane, fluorotrichloro. Methane, dichlorodifluoromethane, tetrachloroethane, trichloroethane, dichlorotetrafluoroethane, trichlorotrifluoroethane, dichlorohexafluoropropane, dichloropentafluoropropane, hexafluorocyclopropane, perfluoroisobutane, tetrachlorooctafluoroiso , Perfluoro (methylcyclohexane), etc.), halogen-containing saturated hydrocarbon ethers (having at least one or two or more halogen atoms in the molecule and at least one etheric oxygen atom) A linear, branched or cyclic saturated compound, preferably having 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, still more preferably 1 to 10 carbon atoms, such as chloromethyl methyl ether, Chloromethyldichloromethyl ether, trichloromethyl methyl ether, trifluoromethyl methyl ether, trichloromethyl trifluoromethyl ether, trifluoroethyl methyl ether, dichlorotrifluoroethyl ethyl ether, heptafluoropropyl methyl ether, nonafluorobutyl methyl ether , Perfluoro (2-butyltetrahydrofuran), etc.), halogen-containing alcohols (having at least one halogen atom of one kind or two or more kinds in the molecule and at least one alcoholic hydroxyl group, It is a chain, branched or cyclic alcohol compound, preferably having 1 to 15 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 8 carbon atoms. For example, trifluoroethanol, chloroethanol, trichloro Ethanol, hexafluoroisopropanol, nonafluoro-t-butanol, etc.), halogenated aromatic compounds (having at least one or two or more halogen atoms in the molecule, and at least one aromatic ring) Preferably 1 to 15 carbon atoms, more preferably carbon The number is from 1 to 13, more preferably from 1 to 8, and examples thereof include chlorobenzene, dichlorobenzene, trichlorobenzene, fluorobenzene, hexafluorobenzene, and trifluoromethylbenzene. ), Halogen-containing ester compounds (compounds having at least one halogen atom in the molecule and at least one ester group, preferably having 1 to 20 carbon atoms, more preferably carbon atoms) 1 to 15, more preferably 1 to 10 carbon atoms, such as ethyl chloroacetate, methyl dichloroacetate, ethyl trifluoroacetate, trifluoroethyl trichloroacetate, trifluoroethyl acetate, methyl trifluoromethanesulfonate, nonafluorobutanesulfone Ethyl acrylate, trifluoroethyl chlorosulfonate, chloroethyl toluenesulfonate, etc.), halogen-containing carboxylic acid (having at least one or two or more halogen atoms in the molecule, and at least one carboxyl A compound having a group, preferably Has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, still more preferably 1 to 10 carbon atoms, and examples thereof include chloroacetic acid, trichloroacetic acid, pentachloropropanoic acid, trifluoroacetic acid, and pentachlorobenzoic acid. ), Halogen-containing sulfonic acid (a compound having at least one halogen atom in the molecule and at least one sulfo group, preferably having 0 to 15 carbon atoms, more preferably carbon number) 0 to 12, more preferably 0 to 10 carbon atoms, such as chlorosulfonic acid, fluorosulfonic acid, trifluoromethanesulfonic acid, nonafluorobutanesulfonic acid, pentachlorobenzenesulfonic acid, etc.), halogen-containing carboxylic acid Anhydride (less than one or more halogen atoms in the molecule And having at least one carboxylic acid anhydride partial structure, preferably having 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, still more preferably 2 to 12 carbon atoms, Chloroacetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, acetyl pentachlorobenzoate, etc.), halogen-containing sulfonic anhydride (at least one or more types of halogen atoms in the molecule) And a compound having at least one sulfonic anhydride partial structure, preferably having 0 to 20 carbon atoms, more preferably 0 to 15 carbon atoms, still more preferably 0 to 12 carbon atoms, such as chlorosulfonic acid Anhydride, fluorosulfonic anhydride, trifluoromethanesulfonic anhydride, pentachlorobenzenesulfonic anhydride, etc. And so on. ), Acid halides (compounds having at least one halogen atom in the molecule and at least one halogen atom and having at least one halocarbonyl group or halosulfonyl group, preferably having 1 to 20 carbon atoms, more preferably Is a C1-C18, more preferably C1-C15, and examples thereof include acetyl chloride, acetyl fluoride, trichloroacetyl chloride, trifluoroacetyl chloride, pentachlorobenzoic acid chloride, phthalic acid chloride, and the like. Examples thereof include hydrogen fluoride compounds (for example, anhydrous hydrogen fluoride, hydrofluoric acid, hydrogen fluoride-triethylamine complex compounds, hydrogen fluoride-pyridine complex compounds, etc.), and more preferably halogen-containing saturated hydrocarbons. , Halogen-containing saturated hydrocarbon ethers, halogenated aromatic compounds Halogen-containing ester compounds, halogen-containing carboxylic acid anhydrides, halogen-containing sulfonic acid anhydrides, acid halides, hydrogen fluoride compounds, more preferably halogen-containing saturated hydrocarbons, halogen-containing saturated hydrocarbon ethers, halogenated aromatic compounds And halogen-containing ester compounds, particularly preferably halogen-containing saturated hydrocarbons and halogen-containing saturated hydrocarbon ethers. Specific examples of particularly preferred solvents include carbon tetrachloride, chloroform, fluoroform, dichloromethane, fluorotrichloromethane, tetrachloroethane, trichloroethane, trichlorotrifluoroethane, trichloropentafluoropropane, dichloropentafluoropropane, methyl nonafluorobutyl ether, ethyl Nonafluorobutyl ether, trifluoromethylbenzene, fluorobenzene, chlorobenzene, dichlorobenzene, and trichlorobenzene are exemplified.

  Due to the reaction between the compound represented by the general formula (1) and fluorine gas, a small amount of a compound in which a fluorine atom is substituted on a hetero atom of a heteroaryl group may be formed as a by-product. Although this may be post-treated as it is, such compounds generally generate strong fluoride and highly toxic and corrosive hydrogen fluoride in addition to having strong oxidizing properties. It is preferable to add the process of processing with a reducing agent after making it react with gas.

  As the reducing agent, any compound having a reducing property (for example, aluminum hydride compound, alkali metal or alkaline earth metal hydride, borohydride compound, sulfurous acid and sulfite, hypophosphite, alkali metal / alkali It is also possible to use earth metals, simple metals such as zinc, iron (II) salts, oxalic acid and oxalate). Among them, an aluminum hydride compound, an alkali metal or alkaline earth metal hydride or a borohydride compound is preferable from the viewpoint of reactivity, and a borohydride compound (for example, sodium borohydride, for example) from the viewpoint of ease of handling and economy. And diborane.) Is more preferable. The reducing agent is preferably used in an amount of 0.1 to 20 mol with respect to 1 mol of the compound represented by the general formula (1).

  Next, the compound represented by the general formula (3) and the compound represented by the general formula (4) will be described.

In general formulas (3) and (4), R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ each independently represents a hydrogen atom or a substituent. As the substituent, an alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as methyl, ethyl, iso-propyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, etc.), an alkenyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 carbon atoms). For example, vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), alkynyl groups (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 carbon atoms). -10, such as propargyl and 3-pentynyl), haloalkyl groups (preferably carbon 1 to 30, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms. For example, fluoromethyl, chloromethyl, bromomethyl, iodomethyl, difluoromethyl, trifluoromethyl, trichloromethyl, 2,2,2 -Trifluoroethyl, 2,2,3,3-tetrafluoro-n-propyl, 1,1,1,3,3,3-hexafluoro-2-propyl and the like), an alkoxyalkyl group (preferably Is a carbon number of 1-30, more preferably a carbon number of 1-20, and particularly preferably a carbon number of 1-10, and examples thereof include methoxymethyl, methoxyethyl, ethoxyethyl, 2- (methoxyethoxy) ethyl and the like. An aryl group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms). Yes, for example, phenyl, p-methylphenyl, naphthyl, anthranyl, etc.), amino group (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 10 carbon atoms). For example, amino, methylamino, dimethylamino, diethylamino, dibenzylamino, diphenylamino, ditolylamino, etc.), an alkoxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably C1-C10, for example, methoxy, ethoxy, butoxy, 2-ethylhexyloxy, etc.), aryloxy groups (preferably C6-C30, more preferably C6-C20, particularly preferably Has 6 to 12 carbon atoms, such as phenyloxy, 1-naphthyloxy, 2-naphth Tiloxy and the like. ), A heterocyclic oxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy, piperidyloxy and the like. An acyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include acetyl, benzoyl, formyl, pivaloyl). An alkoxycarbonyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, etc.), an aryloxycarbonyl group ( Preferably 7-30 carbons, more preferably 7-20 carbons, especially Preferably, it has 7 to 12 carbon atoms, such as phenyloxycarbonyl.), An acyloxy group (preferably 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms). For example, acetoxy, benzoyloxy, etc.), an acylamino group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms such as acetylamino, Benzoylamino and the like), an alkoxycarbonylamino group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino). ), Aryloxycarbonylamino group (preferably having 7 to 30 carbon atoms, more preferably carbon 7 to 20, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonylamino, and the like, and a sulfonylamino group (preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, especially Preferably it has 1 to 12 carbon atoms, such as methanesulfonylamino, benzenesulfonylamino, etc.), sulfamoyl group (preferably 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably carbon numbers). 0-12, for example, sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl, etc.), carbamoyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, Particularly preferred are those having 1 to 12 carbon atoms, such as carbamoyl, methylcarbamoyl, di- Examples thereof include ethylcarbamoyl and phenylcarbamoyl. ), An alkylthio group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methylthio and ethylthio), an arylthio group (preferably carbon). 6 to 30, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio, etc.), a heterocyclic thio group (preferably 1 to 30 carbon atoms, more preferably C1-C20, Most preferably, it is C1-C12, for example, pyridylthio, 2-benzimidazolylthio, 2-benzoxazolylthio, 2-benzthiazolylthio, piperidinylthio etc. are mentioned), sulfonyl. Group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, Mesyl, tosyl, etc.), sulfinyl groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfinyl, benzenesulfinyl, etc.) Ureido group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include ureido, methylureido, and phenylureido). A phosphoric acid amide group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as diethyl phosphoric acid amide and phenylphosphoric acid amide); Hydroxy group, mercapto group, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom can be mentioned) A cyano group, a sulfo group, a carboxyl group, a nitro group, a hydroxamic acid group, a sulfino group, a hydrazino group, a hydrazono group, a heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, As, for example, nitrogen atom, oxygen atom, sulfur atom, specifically imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, carbazolyl, azepinyl, tetrahydropyranyl, Tetrahydrofuranyl, etc.), silyl groups (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, such as trimethylsilyl and triphenylsilyl). ), Silyloxy groups (preferably Has 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, and examples thereof include trimethylsilyloxy and triphenylsilyloxy. ) And the like. These substituents may be further substituted.

R ₃ and R ₄ are preferably a hydrogen atom, an alkyl group, a haloalkyl group, an alkoxyalkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a halogen atom, a heterocyclic group, and a silyl group, and more preferably Is a hydrogen atom, an alkyl group, an alkoxyalkyl group, an aryl group, an acyl group, or a heterocyclic group.

R ₅ , R ₆ , R ₇ and R ₈ are preferably a hydrogen atom, alkyl group, haloalkyl group, alkoxyalkyl group, aryl group, amino group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkoxycarbonyl Group, aryloxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, heterocyclic thio group, sulfonyl group, sulfinyl group Hydroxy group, mercapto group, halogen atom, cyano group, sulfo group, carboxyl group, nitro group, sulfino group, heterocyclic group, silyl group, silyloxy group.

  Although the specific example of a compound represented by General formula (4) below is shown, this invention is not limited to these. In addition, Ph represents a phenyl group, Me represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, and nPr represents a normal propyl group. When nothing is written at the tip of the bond line, it indicates that the tip is a methyl group, and when nothing is written at the apex of the zigzag line, it represents an unsubstituted methylene group.

  The method for obtaining the compound represented by the general formula (3) is not particularly limited. For example, Journal of Organic Chemistry Vol. 62, 1997, page 1491, Organic Letters. ) Volume 3, 2001, page 2883. Below, the example of the manufacturing method is shown.

The platinum complex compound represented by the following general formula (9) is obtained by using a compound represented by the general formula (4) of the present invention in which R ₅ and R ₇ are both hydrogen atoms. Synthesis is possible with reference to the method described in Japanese Unexamined Patent Publication No. 2007-19462. However, R < ₆ >, R < ₈ > of General formula (9) is synonymous with those in General formula (3) and (4).

When R ₃ and R ₄ of the compound represented by the general formula (4) are not hydrogen atoms, in the production of the compound represented by the general formula (9), both R ₃ and R ₄ are converted to hydrogen atoms. Is preferred. This can be easily accomplished by one skilled in the art using known methods. For example, when R ₃ and R ₄ are a methoxymethyl group or a tetrahydropyranyl group, they can be easily replaced with a hydrogen atom by heat treatment under acidic conditions of hydrochloric acid. When R ₃ and R ₄ are acyl groups, they can be easily replaced with hydrogen atoms by treatment under basic conditions such as aqueous sodium hydroxide. When R ₃ and R ₄ are methyl groups, they can be replaced with hydrogen atoms according to known methods (for example, Journal of Heterocyclic Chemistry 28, 1991, p. 1837).

  An organic electroluminescent element using the platinum complex compound represented by the general formula (9) can be produced by a method described in a literature (JP 2007-19462 A). From the result of the above theoretical calculation, the produced organic electroluminescent device is predicted to have a maximum wavelength at 460 nm, and is useful as a blue phosphorescent light emitting device.

Examples that specifically illustrate the present invention are given below, but the present invention is not limited thereto. Here, GC is referred to as gas chromatography, GC-MS as gas chromatography mass spectrometry, TLC as thin layer chromatography, and NMR as nuclear magnetic resonance. ^{In 1} H-NMR, tetramethylsilane was used as an internal standard, and in ¹⁹ F-NMR, measurement was performed using fluorotrichloromethane as an external standard. Dichloropentafluoropropane was designated as HCFC-225, which was used as a mixture of two types of structural isomers (HCFC-225ca and HCFC-225cb).

(1) GC analysis conditions GC used GC-14B made by Shimadzu Corporation and DB-1 made by J & WS Scientific (diameter 0.25 mm × length 15 m) as a capillary column. As for the temperature raising condition, after holding at 100 ° C. for 10 minutes, the temperature was raised to 280 ° C. at a rate of 20 ° C./min. A flame ionization detector (FID) was used as a detector.
(2) GC-MS analysis conditions For GC-MS, Shimadzu GCMS-QP2010 and J & WS Scientific DB-1HT (diameter 0.25 mm × length 15 m) were used as the capillary column. As for the temperature raising condition, after holding at 100 ° C. for 10 minutes, the temperature was raised to 280 ° C. at a rate of 20 ° C./min. Unless otherwise stated, CI was used as the ionization method, and the detector voltage was measured at 70 eV.

  The compounds (10) and (12), which are raw materials used in the examples, were obtained by referring to the synthesis method described in Journal of Organic Chemistry Vol. 62, 1997, page 1491. Were produced according to the following reaction formula. (In the formula, A represents a tetrahydropyranyl group {compound (10)} or an acetyl group {compound (12)}).

[Example 1: Production of compound (11) in HCFC-225 solvent]

Into a glass reaction vessel equipped with a reflux condenser connected to a gas inlet pipe, a gas outlet pipe, and a thermometer, take 2.19 g of compound (10), 7.04 g of sodium fluoride, 670 mL of HCFC-225, and a nitrogen atmosphere. It was immersed in a bath cooled to −80 ° C. and stirred. Nitrogen gas was blown into this at a rate of 150 mL / min for 0.5 hour, and then diluted with nitrogen gas to a volume ratio of 2% (hereinafter, fluorine gas diluted with nitrogen gas to a volume ratio of n% was converted to n% (Referred to as diluted fluorine gas) was blown in at a rate of 200 mL / min for 2 hours. The amount of 2% diluted fluorine gas blown was 25.0 L. Nitrogen gas was blown in at a rate of 180 mL / min for 0.75 hours to drive out the remaining fluorine gas in the reaction vessel, and then the reaction vessel was taken out of the bath and heated to room temperature. The disappearance of compound (10) and the formation of compound (11) were confirmed by GC and GC-MS analysis. From the GC analysis, the yield of the compound (11) was 79%. After solid was filtered off from the reaction solution, the solvent was distilled off, and 10 mL of isopropanol was added to the residue.
In a glass reaction vessel, 0.74 g of sodium borohydride and 25 mL of isopropanol were taken and stirred at room temperature. The above residue solution was added dropwise thereto, and the mixture was stirred as it was for 0.5 hour. After adding 50 mL of water and 18 mL of 1 mol / L hydrochloric acid and stirring well, a saturated aqueous sodium hydrogen carbonate solution was added to adjust the pH of the solution from 7 to 8. To this solution, 80 mL of methylene chloride was added for extraction, and the resulting organic layer was dried and the solvent was distilled off to obtain 2.53 g of a pale brown liquid crude product. This was purified by silica gel column chromatography to obtain 0.82 g of white crystals of compound (11).
¹ H-NMR [TMS, CDCl ₃ ]: δ [ppm] = 7.80 (s, 2H), 7.65 (s, 2H), 5.42-5.38 (m, 2H), 4.08 -4.03 (m, 2H), 3.75-3.66 (m, 2H), 2.12 to 1.60 (m, 6H); ¹⁹ F-NMR [CFCl ₃ , CDCl ₃ ]: δ [ ppm] = − 105.2 (m); GC-MS [CI, 70 eV]: m / z = 403 [M + H] ⁺ .

[Example 2: Production of compound (11) in methylene chloride solvent]
In a glass reaction vessel, 0.083 g of compound (10), 0.513 g of sodium fluoride and 20 mL of methylene chloride were taken, immersed in a bath cooled to −80 ° C. under a nitrogen atmosphere, and stirred. Nitrogen gas was blown into this at a rate of 40 mL / min for 0.5 hours, and then 4% diluted fluorine gas was blown at a rate of 50 mL / min for 0.28 hours. The amount of 4% diluted fluorine gas blown was 0.85 L. Nitrogen gas was blown in at a rate of 40 mL / min for 0.75 hours to expel residual fluorine gas in the reaction vessel, and then the reaction vessel was taken out of the bath and heated to room temperature. From the GC analysis, the yield of the compound (11) was 61%.

[Example 3: Production of compound (11) in chloroform solvent]
The reaction was performed in the same manner as in Example 2 except that methylene chloride was changed to chloroform and the bath temperature was changed to -40 ° C. According to GC analysis, the yield of the compound (11) was 55%.

[Example 4: Production of compound (11) in nonafluorobutyl methyl ether solvent]
The reaction was performed in the same manner as in Example 2 except that methylene chloride was changed to chloroform. According to GC analysis, the yield of compound (11) was 53%.

[Example 5: Production of compound (11) in ethyl trifluoroacetate solvent]
The reaction was conducted in the same manner as in Example 2 except that methylene chloride was changed to ethyl trifluoroacetate and the bath temperature was changed to -40 ° C. According to GC analysis, the yield of the compound (11) was 44%.

[Example 6: Production of compound (11) in ethyl trichloroacetate]
The reaction was conducted in the same manner as in Example 2 except that methylene chloride was changed to ethyl trifluoroacetate and the bath temperature was changed to -15 ° C. According to GC analysis, the yield of the compound (11) was 30%.

[Example 7: Production of compound (13) in HCFC-225 solvent]

In a glass reaction vessel, 0.061 g of compound (12), 0.520 g of sodium fluoride, and 20 mL of HCFC-225 were taken, immersed in a bath cooled to −80 ° C. in a nitrogen atmosphere, and stirred. Nitrogen gas was blown into this at a rate of 40 mL / min for 0.5 hours, and then 4% diluted fluorine gas was blown at a rate of 50 mL / min for 0.16 hours. The amount of 4% diluted fluorine gas blown was 0.49 L. Nitrogen gas was blown in at a rate of 40 mL / min for 0.75 hours to expel residual fluorine gas in the reaction vessel, and then the reaction vessel was taken out of the bath and heated to room temperature. From the GC analysis, the yield of the compound (13) was 70%.
To the reaction vessel, 20 mL of a 3% aqueous sodium hydrogen carbonate solution was added for liquid separation, and the resulting organic layer was dried and the solvent was distilled off to obtain 0.066 g of a light brown liquid crude product. A part of this was purified by TLC to confirm the formation of the target compound (13).
¹ H-NMR [TMS, CDCl ₃ ]: δ [ppm] = 7.81 (s, 2H), 7.65 (s, 2H), 2.66 (s, 6H); ¹⁹ F-NMR [CFCl ₃ , CDCl ₃ ]: δ [ppm] = − 105.1 (m); GC-MS [CI, 70 eV]: m / z = 319 [M + H] ⁺ .

[Comparative Example 1: Production of compound (11) in acetonitrile solvent]
The reaction was performed in the same manner as in Example 2 except that methylene chloride was changed to acetonitrile and the bath temperature was changed to -40 ° C. Although the production | generation of compound (11) was able to be confirmed by GC and GC-MS analysis, the yield was 5% or less, and the several product with unknown structure was confirmed as a main product. ^{From 19} F-NMR, a plurality of peaks were observed in the vicinity of +40 to +20 ppm, and it is considered that a compound in which the nitrogen atom of the pyrazole ring was fluorinated was produced.

[Comparative Example 2: Production of Compound (11) in Acetic Acid Solvent]
The reaction was performed in the same manner as in Example 2 except that methylene chloride was changed to acetic acid and the bath temperature was changed to 5 ° C. The formation of compound (11) could not be confirmed by GC and GC-MS analysis. A plurality of products with unknown structures were confirmed as main products. ^{From 19} F-NMR, a plurality of peaks were observed in the vicinity of +40 to +10 ppm, and it is considered that a compound in which the nitrogen atom of the pyrazole ring was fluorinated was produced.

[Comparative Example 3: Production of Compound (11) Using Nitrosyl Tetrafluoroborate]

In a reaction vessel made of HDPE (high density polyethylene), 0.011 g of nitrosyltetrafluoroborate (NOBF ₄ ) and 0.5 mL of pyridine polyhydrofluoride (pyridine (HF) _n ) are taken and stirred in an ice-water bath under a nitrogen atmosphere. I let you. To this was added a solution of 0.010 g of Compound (10) in 0.5 mL of dichloromethane, and the mixture was stirred for 7 hours. The bath was removed, and the mixture was stirred at room temperature for 11 hours.
After completion of the reaction, a small amount was extracted, neutralized by adding to a saturated aqueous sodium hydrogen carbonate solution, extracted with ethyl acetate, and the solvent was distilled off. ^{From 19} F-NMR, there was no peak in the vicinity of −105 ppm, and formation of a difluoroethylene group was not observed.
[Example 8: Synthesis of compound (14)]

A glass reaction vessel was charged with 2.2 g of compound (11), 6.6 g of ion exchange resin (DOWEX® 50W × 2-100), and 100 mL of methanol, and the mixture was heated to reflux for 6 hours with stirring. After confirming the completion of the reaction by NMR, the mixture was cooled to room temperature, the ion exchange resin was filtered, the solvent was distilled off, and recrystallization was performed using ethyl acetate-hexane to obtain 1.01 g of compound (14) as white crystals. It was.
¹ H-NMR [TMS, MeOH-d4]: δ [ppm] = 7.80 (s, 4H); ¹⁹ F-NMR [CFCl ₃ , MeOH-d4]: δ [ppm] = − 106.9 (m ).
[Example 9: Synthesis of compound (16)]

Under a nitrogen atmosphere, 736 mg of salicylaldoxime, 192 mg of copper oxide, 18.9 g of cesium carbonate, 250 mL of N, N-dimethylformamide were charged in a glass reaction vessel, heated to 150 ° C., and then 2.39 g of compound (14) and A solution prepared by dissolving 1.57 g of compound (16) in 200 mL of N, N-dimethylformamide was added dropwise over 6 hours. While stirring as it was, refluxing was performed for 16 hours.
After completion of the reaction, the mixture is filtered through celite and concentrated, followed by extraction with water and ethyl acetate. The organic layer is dried over sodium sulfate, filtered and concentrated, and the residue is purified by silica gel column chromatography. Compound (16) was obtained as a white solid, 0.54 g.
[Example 10: Synthesis of compound (17)]

Under a nitrogen atmosphere, 433 mg of Compound (6), 269 mg of platinum platinum and 25 mL of benzonitrile were charged into a glass reaction vessel, and the reaction was performed by gradually raising the temperature from 140 ° C. to 200 ° C. over 6 hours.
After completion of the reaction, the reaction solution was allowed to cool to room temperature and concentrated, and the residue was purified by silica gel column chromatography to obtain 59.5 mg of Compound (17) as a yellow solid.

[Example 11: Creation of light-emitting element]
The cleaned ITO substrate was put into a vapor deposition apparatus, and copper phthalocyanine was vapor-deposited by 10 nm, and NPD (N, N′-di-α-naphthyl-N, N′-diphenyl) -benzidine) was vapor-deposited thereon by 40 nm. On top of this, mCP and the exemplified compound (17) of the present invention were vapor-deposited at a ratio of 90:10 (mass ratio) of 67 nm, and BAlq was vapor-deposited thereon at 40 nm. On top of this, 3 nm of lithium fluoride was deposited, and then 60 nm of aluminum was deposited to produce a device. As a result of emitting light by applying a DC constant voltage to the above device using a source measure unit type 2400 manufactured by Toyo Technica, blue light emission derived from the compound (17) was obtained.

Claims (5)

A method for producing a compound represented by the following general formula (2), which comprises reacting a compound represented by the following general formula (1) with a fluorine gas in a halogen-containing solvent.

(In General Formula (1) and General Formula (2), R ₁ and R ₂ represent a heteroaryl group or an aryl group, provided that at least one represents a heteroaryl group, and n represents an integer of 1 or more. ) _2. The production method according to claim 1, wherein R ₁ and R ₂ in the general formulas (1) and (2) are both heteroaryl groups.   The method according to claim 1 or 2, wherein the halogen-containing solvent is a halogen-containing saturated hydrocarbon solvent or a halogen-containing saturated hydrocarbon ether solvent. The compound represented by the general formula (1) is a compound represented by the following general formula (3), and the compound represented by the general formula (2) is represented by the following general formula (4). It is a compound, The manufacturing method in any one of Claims 1-3 characterized by the above-mentioned.

(In General Formula (3) and General Formula (4), R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ each independently represents a hydrogen atom or a substituent.) A compound represented by the following general formula (4).

(In the general formula (4), R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ each independently represents a hydrogen atom or a substituent.)