Pyran derivative, method for production thereof and photoelectric converter

Abstract

To provide a compound demonstrating high external quantum efficiency suitable as a photoelectric conversion material for blue light, a method for synthesizing the compound, and a photoelectric converter containing the compound.SOLUTION: The present invention provides a pyran derivative represented by a formula (1) and a method for producing the same. In the formula (1), A1 represents an electron-withdrawing double-bond functional group. R1-R3 independently represent a hydrogen atom or an alkyl group. R4 independently represent a hydrogen atom, an alkyl group, an aryl group, a dialkylamino group, a diarylamino group or a trialkylsilyl group. The dialkylamino group and diarylamino group may form an integrated ring by incorporating a nitrogen atom, or may form an integrated ring by incorporating a nitrogen atom bonded through an oxygen atom or sulfur atom. Ar1 independently represent an arylene group or a heteroarylene group, each of which may be optionally substituted with an alkyl group. n represents an integer of 0-2, excluding the case where n is 0 and R4 is a hydrogen atom.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a pyran derivative, a method for producing the same, and a photoelectric conversion element.

[0002] Photoelectric conversion elements are used in sensors such as optical sensors and image sensors, and in photovoltaic devices such as solar cells. A photoelectric conversion element using an organic photoelectric conversion material is disclosed in Patent Document 1 and the like.

[0003] As photoelectric conversion elements, elements using silicon semiconductors are widely used, and silicon photodiodes are mainly used as imaging elements. Since such silicon photodiodes have sensitivity over the entire visible light range, a color filter with RGB arranged in a mosaic pattern is placed on top of the photodiode, and each pixel is assigned as a light receiving section for each RGB, thereby performing color imaging. In this method, the efficiency of light utilization is low due to the loss of incident light in the color filter, and it is feared that this will become a barrier to increasing the sensitivity of imaging elements. Therefore, an imaging element in which organic photoelectric conversion films of each color of RGB are stacked (hereinafter referred to as a stacked organic imaging element) has been proposed (see, for example, Non-Patent Document 1). In this method, there is no light loss due to the color filter compared to when a color filter is used, and the efficiency of light utilization is several times higher, so it is expected to be used in high-sensitivity devices that have an advantage in miniaturizing pixels accompanying the high pixel count of devices such as cameras.

[0004] The photoelectric conversion film of the stacked organic imaging element is required to exhibit high external quantum efficiency in the wavelength region corresponding to each color. That is, in the case of the B layer (blue photoelectric conversion film), it is required to exhibit high external quantum efficiency in the blue light region of 400 to 500 nm.

[0005] Patent Documents 1 to 3 describe blue photoelectric conversion elements containing perylene derivatives, coumarin derivatives, dipyrromethene derivatives, and the like, but all of them are different from the photoelectric conversion element containing the pyran derivative of the present invention. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2020 / 195935 [Patent Document 2] International Publication No. 2020 / 196029 [Patent Document 3] International Publication No. 2021 / 029223 [Non-patent literature]

[0007] [Non-Patent Document 1] Japanese Journal of Applied Physics, 2011, Vol. 50, p. 024103 Summary of the Invention [Problem to be solved by the invention]

[0008] An object of the present invention is to provide a compound exhibiting high external quantum efficiency suitable as a blue light photoelectric conversion material, a method for simply synthesizing the compound, and a photoelectric conversion element containing the compound. [Means for solving the problem]

[0009] As a result of intensive research aimed at solving the above problems, the present inventors discovered that a photoelectric conversion element containing a novel pyran derivative exhibits high external quantum efficiency in the wavelength range of blue light, and thus completed the present invention.

[0010] That is, the present invention is [1] A pyran derivative represented by the following formula (1):

[0011] [ka]

[0012] {In formula (1), A 1represents an electron-withdrawing double-bond functional group. R 1 ~R 3 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R 4 each independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, a dialkylamino group having 2 to 8 carbon atoms, a diarylamino group having 12 to 24 carbon atoms, or a trialkylsilyl group having 3 to 12 carbon atoms. In the dialkylamino group and diarylamino group, two alkyl groups or aryl groups may be bonded together through an oxygen atom or a sulfur atom and formed together with a nitrogen atom to form a ring. In the dialkylamino group and diarylamino group, two alkyl groups or aryl groups may be bonded together through an oxygen atom or a sulfur atom and formed together with a nitrogen atom to form a ring. Ar 1 each independently represents an arylene group having 6 to 18 carbon atoms or a heteroarylene group having 2 to 12 carbon atoms, and the arylene group and heteroarylene group may be substituted with an alkyl group having 1 to 4 carbon atoms. n represents an integer of 0 to 2. where n is 0 and R 4 Except when is a hydrogen atom.}; [2] In formula (1), Ar 1 each independently represents a phenylene group, a furanylene group, a thienylene group, a benzofuranylene group, or a benzothienylene group, each of which may be substituted by an alkyl group having 1 to 4 carbon atoms; [3] In formula (1), A 1 is a dicyanomethylidene group, a 1,3-indanedion-2-ylidene group, or a 1,3-cyclopenta[b]naphthalenedion-2-ylidene group; [4] In formula (1), R 1 ~R 3 is a hydrogen atom. The present invention also provides a method for producing a semiconductor device comprising the steps of: [5] The following formula (2)

[0013] [ka]

[0014] (In formula (2), A 1 R represents an electron-withdrawing double bond functional group. 1 ~R 3 Each of X independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 1 and X 2 each independently represents a halogen atom; and a pyran compound represented by the following formula (3):

[0015] [ka]

[0016] (In formula (3), R 4 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, a dialkylamino group having 2 to 8 carbon atoms, a diarylamino group having 12 to 24 carbon atoms, or a trialkylsilyl group having 3 to 12 carbon atoms. In the dialkylamino group and diarylamino group, two alkyl groups or aryl groups may be bonded together through an oxygen atom or a sulfur atom to form a ring together with a nitrogen atom. In the dialkylamino group and diarylamino group, two alkyl groups or aryl groups may be bonded together through an oxygen atom or a sulfur atom to form a ring together with a nitrogen atom. Ar 1 each independently represents an arylene group having 6 to 18 carbon atoms or a heteroarylene group having 2 to 12 carbon atoms, and the arylene group and heteroarylene group may be substituted with an alkyl group having 1 to 4 carbon atoms. a represents an integer of 1 to 2. 1 ZnY 1 , MgY 2 , Sn(Y 3 ) 3 Or B(OY 4 ) 2 Represents Y. 1 and Y 2each independently represents an alkyl group having 1 to 4 carbon atoms or a phenyl group; Y 3 each independently represents an alkyl group having 1 to 4 carbon atoms or a phenyl group; Y 4 Each of (OY) independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group. 4 ) groups may be taken together with the boron atom to form a ring.

[0017] [ka]

[0018] (In formula (4), R 4a represents a dialkylamino group having 2 to 8 carbon atoms or a diarylamino group having 12 to 24 carbon atoms. In the dialkylamino group and diarylamino group, two alkyl groups or aryl groups may be bonded together through an oxygen atom or a sulfur atom to form a ring together with a nitrogen atom. In the dialkylamino group and diarylamino group, two alkyl groups or aryl groups may be bonded together through an oxygen atom or a sulfur atom to form a ring together with a nitrogen atom.

[0019] [ka]

[0020] (In formula (1), A 1 , R 1 ~R 4 and Ar 1 has the same meaning as above. 4 is R 4aand each independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, a dialkylamino group having 2 to 8 carbon atoms, a diarylamino group having 12 to 24 carbon atoms, or a trialkylsilyl group having 3 to 10 carbon atoms. In the dialkylamino group and diarylamino group, two alkyl groups or aryl groups may be bonded together through an oxygen atom or a sulfur atom to form a ring together with a nitrogen atom. In the dialkylamino group and diarylamino group, two alkyl groups or aryl groups may be bonded together through an oxygen atom or a sulfur atom to form a ring together with a nitrogen atom. n represents an integer of 0 to 2. The present invention also provides a method for producing a semiconductor device comprising the steps of: [6] Formula (5)

[0021] [ka]

[0022] (In formula (5), A 1 R represents an electron-withdrawing double bond functional group. 1 ~R 3 Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 2 ZnY 1 , MgY 2 , Sn(Y 3 ) 3 Or B(OY 4 ) 2 Represents Y. 1 and Y 2 each independently represents an alkyl group having 1 to 4 carbon atoms or a phenyl group; Y 3 each independently represents an alkyl group having 1 to 4 carbon atoms or a phenyl group; Y 4 Each of (OY) independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group. 4 ) groups may be united to form a ring together with the boron atom.

[0023] [ka]

[0024] (In formula (6), R 4 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, a dialkylamino group having 2 to 8 carbon atoms, a diarylamino group having 12 to 24 carbon atoms, or a trialkylsilyl group having 3 to 10 carbon atoms. In the dialkylamino group and diarylamino group, two alkyl groups or aryl groups may be bonded together through an oxygen atom or a sulfur atom to form a ring together with a nitrogen atom. In the dialkylamino group and diarylamino group, two alkyl groups or aryl groups may be bonded together through an oxygen atom or a sulfur atom to form a ring together with a nitrogen atom. Ar 1 each independently represents an arylene group having 6 to 18 carbon atoms or a heteroarylene group having 2 to 12 carbon atoms, and the arylene group and heteroarylene group may be substituted with an alkyl group having 1 to 4 carbon atoms. a represents an integer of 1 to 2. 3 represents a halogen atom.) is reacted with a compound represented by the following formula (1a):

[0025] [ka]

[0026] (In formula (1a), A 1 , R 1 ~R 3 , Ar 1 and n a has the same meaning as above. 4each independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, a dialkylamino group having 2 to 8 carbon atoms, a diarylamino group having 12 to 24 carbon atoms, or a trialkylsilyl group having 3 to 10 carbon atoms. In the dialkylamino group and diarylamino group, two alkyl groups or aryl groups may be bonded together with a nitrogen atom to form a ring. In addition, in the dialkylamino group and diarylamino group, two alkyl groups or aryl groups may be bonded together with an oxygen atom or a sulfur atom to form a ring together with a nitrogen atom. The present invention also provides a method for producing a semiconductor device comprising the steps of: [7] A photoelectric conversion element comprising the pyran derivative according to any one of the above [1] to [4]; [8] A photoelectric conversion device comprising a photoelectric conversion layer containing the pyran derivative according to any one of the above [1] to [4]; [9] The photoelectric conversion element according to [8], wherein the photoelectric conversion layer further contains a fullerene derivative;

[10] The fullerene derivative is

[60] fullerene (C 60 ) or

[70] fullerene (C 70 ) the photoelectric conversion element according to [9],

[11] A material for a photoelectric conversion device, comprising the pyran derivative according to any one of the above [1] to [4].

[12] The material for photoelectric conversion elements according to

[11] , which is a material for photoelectric conversion layers. Effect of the Invention

[0027] In this specification, a numerical range indicated using "~" indicates a range including the numerical values ​​described before and after "~" as the minimum and maximum values, respectively. In addition, unless specifically stated otherwise, the units of the numerical values ​​described before and after "~" are the same. In the numerical ranges described in stages in this specification, the upper limit or lower limit of a certain numerical range may be replaced with the upper limit or lower limit of a numerical range of another stage. In addition, in the numerical ranges described in this specification, the upper limit or lower limit of the numerical range may be replaced with a value shown in the examples. In addition, the upper limit and lower limit values ​​described individually can be combined arbitrarily.

[0028] The pyran derivative (1) of the present invention exhibits high external quantum efficiency in the blue light region, and is therefore expected to be used as an organic electronic material, such as a material for a blue light organic photoelectric conversion element. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0029] The present invention will be described in detail below.

[0030] In the pyran derivative (1) of the present invention, A 1 , R 1 ~R 4 , Ar 1 The definition of is explained below.

[0031] A 1 The electron-withdrawing double-bond functional group represented by the formula (I) is not particularly limited, and specific examples thereof include a difluoromethylidene group, a cyanofluoromethylidene group, a carboxycyanomethylidene group, a dicyanomethylidene group, a 1,3-indandione-2-ylidene group, and a 1,3-cyclopenta[b]naphthalenedion-2-ylidene group. In terms of ease of synthesis of the pyran derivative (1), a dicyanomethylidene group, a 1,3-indandione-2-ylidene group, and a 1,3-cyclopenta[b]naphthalenedion-2-ylidene group are preferred.

[0032] R 1 ~R 3The alkyl group having 1 to 4 carbon atoms represented by the formula (I) is not particularly limited, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a 1-methylethyl group, a cyclopropyl group, a butyl group, a 2-butyl group, a tert-butyl group, and a cyclobutyl group. A methyl group is preferred in terms of ease of synthesis of the pyran derivative (1). R 1 ~R 3 is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. R 4 The alkyl group having 1 to 18 carbon atoms represented by the formula (I) may be any of a linear, branched, or cyclic alkyl group, and specific examples thereof include a methyl group, a cyclohexylmethyl group, an ethyl group, a 2-cyclopentylethyl group, a 1-propyl group, a 2-propyl group, a 2-methylpropyl group, a 2,2-dimethylpropyl group, a 3-cyclopropylpropyl group, a 1-methylethyl group, a cyclopropyl group, a butyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 2-butyl group, a 3-methylbutan-2-yl group, a tert-butyl group, a cyclobutyl group, a pentyl group, a 2-methylpentyl group, a 3-ethylpentyl group, a 2,4-dimethylpentyl group, a 2-pentyl group, a 2-methylpentan-2-yl group, a 4,4-dimethylpentan-2-yl group, a 3-pentyl group, a 3-ethylpentan-3-yl group, a cyclopentyl group, a 2,5-dimethylcyclopentyl group, a 3-ethyl ethylcyclopentyl, hexyl, 2-methylhexyl, 3,3-dimethylhexyl, 4-ethylhexyl, 2-hexyl, 2-methylhexan-2-yl, 5,5-dimethylhexan-2-yl, 3-hexyl, 2,4-dimethylhexan-3-yl, cyclohexyl, 4-ethylcyclohexyl, 4,4-dimethylcyclohexyl, heptyl, 2-heptyl, 3-heptyl , 4-heptyl group, bicyclo[2.2.1]heptyl group, octyl group, 2-octyl group, 3-octyl group, 4-octyl group, cyclooctyl group, bicyclo[2.2.2]octyl group, hexadecyl group, heptadecyl group, octadecyl group, 1-adamantyl group, and the like can be illustrated. From the viewpoint of ease of synthesis of the pyran compound (1), a methyl group, an ethyl group, a tert-butyl group, a hexyl group, and an adamantyl group are preferred.

[0033] R 4 Examples of the aryl group having 6 to 14 carbon atoms represented by the formula (I) include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-biphenylyl group, a 3-biphenylyl group, a 4-biphenylyl group, a 3,5-terphenylyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthrenyl group, a 2-phenanthrenyl group, a 3-phenanthrenyl group, a 4-phenanthrenyl group, a 9-phenanthrenyl group, a 1-fluorenyl group, a 2-fluorenyl group, a 3-fluorenyl group, a 4- Examples include a fluorenyl group, a 9,9-dimethyl-9H-fluoren-1-yl group, a 9,9-dimethyl-9H-fluoren-2-yl group, a 9,9-dimethyl-9H-fluoren-3-yl group, a 9,9-dimethyl-9H-fluoren-4-yl group, a 1-pyrenyl group, a 2-pyrenyl group, a 9-pyrenyl group, a 1-triphenylenyl group, and a 2-triphenylenyl group. From the viewpoint of ease of synthesis of the pyran compound (1), a phenyl group, a 1-naphthyl group, and a 2-naphthyl group are preferred. R 4 In the dialkylamino group having 2 to 8 carbon atoms represented by the formula (I), the two alkyl groups may be either linear or branched, and specific examples thereof include a dimethylamino group, a diethylamino group, a dipropylamino group, a diisopropylamino group, and a dibutylamino group. The two alkyl groups may form a ring together by incorporating a nitrogen atom, or may be bonded via an oxygen atom or a sulfur atom to form a ring together by incorporating a nitrogen atom, and specific examples thereof include a 1-pyrrolidinyl group, a 1-piperidinyl group, an N-morpholyl group, and an N-thiomorpholyl group. A dimethylamino group or an N-morpholyl group is preferred in terms of ease of synthesis of the pyran derivative (1). R 4Specific examples of the diarylamino group having 12 to 24 carbon atoms represented by the formula (1) include a diphenylamino group, a 1-naphthyl(phenyl)amino group, a 2-naphthyl(phenyl)amino group, and a bis(biphenylyl)amino group. The two aryl groups may form a ring together by including a nitrogen atom, or may be bonded via an oxygen atom or a sulfur atom to form a ring together by including a nitrogen atom, and specific examples thereof include a 9-carbazoyl group, an N-phenoxazinyl group, and an N-phenothiazinyl group. A diphenylamino group is preferred in terms of ease of synthesis of the pyran derivative (1). R 4 Examples of the trialkylsilyl group having 3 to 12 carbon atoms represented by the formula (I) include a trimethylsilyl group, an ethyldimethylsilyl group, a dimethylpropylsilyl group, an isopropyldimethylsilyl group, a tert-butyldimethylsilyl group, a triethylsilyl group, a diethylpropylsilyl group, a diethylisopropylsilyl group, a tripropylsilyl group, a tri(isopropyl)silyl group, a tributylsilyl group, and a tri(isobutyl)silyl group. In terms of high solubility of the pyran compound (1), a trimethylsilyl group and a triethylsilyl group are preferred. R 4 is preferably a hydrogen atom, a methyl group, an ethyl group, a tert-butyl group, a hexyl group, an adamantyl group, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a dimethylamino group, an N-morpholyl group, a diphenylamino group, a trimethylsilyl group, or a triethylsilyl group, and more preferably a hydrogen atom, an adamantyl group, a phenyl group, an N-morpholyl group, a diphenylamino group, or a trimethylsilyl group. Ar 1Specific examples of the arylene group having 6 to 18 carbon atoms represented by the formula (1) include a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, a 1,4-naphthylene group, a 1,5-naphthylene group, a 2,6-naphthylene group, a 2,7-naphthylene group, a 1,4-anthrylene group, a 2,6-anthrylene group, a 1,8-phenanthrylene group, a 2,7-phenanthrylene group, a 2,6-fluorenylene group, a 2,7-fluorenylene group, etc. The arylene group may be substituted with an alkyl group having 1 to 4 carbon atoms, specific examples of which include a 2-methyl-1,4-phenylene group, a 9,9-dimethyl-9H-fluoren-2,6-ylene group, a 9,9-dimethyl-9H-fluoren-2,7-ylene group, etc. In view of ease of synthesis of the pyran compound (1), a 1,4-phenylene group and a 2-methyl-1,4-phenylene group are preferred. Ar 1Specific examples of the heteroarylene group having 2 to 12 carbon atoms represented by the formula (I) include a 2,5-furanylene group, a 2,5-thienylene group, a 2,5-pyrrolylene group, a 2,5-pyridylene group, a 2,6-quinolylene group, a 3,7-quinolylene group, a 2,5-benzofuranylene group, a 2,6-benzofuranylene group, a 2,5-benzothienylene group, a 2,6-benzothienylene group, a 2,5-indolylene group, Examples include a 2,6-indolylene group, a 2,7-carbazolyle group, a 3,7-dibenzofuranylene group, and a 3,7-dibenzothienylene group. From the viewpoint of ease of synthesis of the pyran compound (1), a 2,5-furanylene group, a 2,5-thienylene group, a 2,5-benzofuranylene group, a 2,6-benzofuranylene group, a 2,5-benzothienylene group, and a 2,6-benzothienylene group are preferred. The heteroarylene group may be substituted with an alkyl group having 1 to 4 carbon atoms. Specific examples include 3-methyl-2,5-furanylene, 3-methyl-2,5-thienylene, 3-methyl-2,5-benzofuranylene, 3-methyl-2,6-benzofuranylene, 3-methyl-2,5-benzothienylene, and 3-methyl-2,6-benzothienylene groups. From the viewpoint of ease of synthesis of pyran compound (1), 3-methyl-2,5-benzofuranylene, 3-methyl-2,6-benzofuranylene, 3-methyl-2,5-benzothienylene, and 3-methyl-2,6-benzothienylene groups are preferred. Ar 1 As the alkyl group, a 1,4-phenylene group, a 2,5-furanylene group, a 2,5-thienylene group, a 2,5-benzofuranylene group, a 2,6-benzofuranylene group, a 2,5-benzothienylene group, a 2,6-benzothienylene group, a 3-methyl-2,5-benzofuranylene group, a 3-methyl-2,6-benzofuranylene group, a 3-methyl-2,5-benzothienylene group, and a 3-methyl-2,6-benzothienylene group are preferable, and a 1,4-phenylene group, a 2,5-furanylene group, a 2,5-benzofuranylene group, a 2,6-benzofuranylene group, a 3-methyl-2,5-benzofuranylene group, and a 3-methyl-2,6-benzofuranylene group are more preferable.

[0034] The pyran compound (1) of the present invention is not particularly limited, and specific examples thereof include the compounds having the structures shown in the following 1-1 to 1-35.

[0035] [ka]

[0036] [ka]

[0037] TIFF2025006993000011.tif82168

[0038] In this specification, Me represents a methyl group.

[0039] Among the compounds represented by 1-1 to 1-35, the pyran derivative (1) of the present invention is preferably a compound represented by 1-1, 1-5, 1-6, 1-7, 1-8, 1-9, 1-10, 1-14, 1-15, 1-18, 1-19, 1-22, 1-25, 1-26, 1-27, 1-28, 1-29, 1-30, 1-31 or 1-32 in terms of ease of synthesis, and more preferably a compound represented by 1-5, 1-7, 1-22, 1-25, 1-29, 1-30, 1-31 or 1-32.

[0040] Next, a method for producing the pyran derivative (1) of the present invention (hereinafter referred to as the production method of the present invention) will be described.

[0041] The pyran derivative (1) of the present invention can be produced by step 1A, step 1B or step 2 shown in the following reaction scheme.

[0042] [ka]

[0043] [ka]

[0044] [ka] In the formula, A 1 R represents an electron-withdrawing double bond functional group. 1 ~R 3 R each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 4 R each independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, a dialkylamino group having 2 to 8 carbon atoms, a diarylamino group having 12 to 24 carbon atoms, or a trialkylsilyl group having 3 to 12 carbon atoms. In the dialkylamino group and diarylamino group, two alkyl groups or aryl groups may be bonded together through an oxygen atom or a sulfur atom to form a ring together with a nitrogen atom. In the dialkylamino group and diarylamino group, two alkyl groups or aryl groups may be bonded together through an oxygen atom or a sulfur atom to form a ring together with a nitrogen atom. 4a represents a dialkylamino group having 2 to 8 carbon atoms or a diarylamino group having 12 to 24 carbon atoms. In the dialkylamino group and diarylamino group, two alkyl groups or aryl groups may be bonded together through an oxygen atom or a sulfur atom to form a ring together with a nitrogen atom. In the dialkylamino group and diarylamino group, two alkyl groups or aryl groups may be bonded together through an oxygen atom or a sulfur atom to form a ring together with a nitrogen atom. Ar 1 each independently represents an arylene group having 6 to 18 carbon atoms or a heteroarylene group having 2 to 12 carbon atoms, and the arylene group and heteroarylene group may be substituted with an alkyl group having 1 to 4 carbon atoms. a represents an integer of 1 to 2. 1 , X 2 and X 3 Each independently represents a halogen atom. 1 and M 2 are each independently ZnY 1 , MgY 2 , Sn(Y 3 ) 3 Or B(OY 4 ) 2 Represents Y.1 and Y 2 each independently represents an alkyl group having 1 to 4 carbon atoms or a phenyl group; Y 3 each independently represents an alkyl group having 1 to 4 carbon atoms or a phenyl group; Y 4 Each of (OY) independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group. 4 ) groups may be joined together to form a ring with the boron atom.

[0045] Step 1A is a step of producing a pyran derivative (1a) by reacting a compound (2) with a compound (3). Examples of the substituents in the compounds (2) and (3) include the same ones as those in the pyran derivative represented by the general formula (1).

[0046] Specific examples of the compound (2) used in step 1A include compounds having structures shown in the following structures 2-1 to 2-6. 1 and X 2 has the same definition as in equation (2).

[0047] [ka]

[0048] X 1 and X 2 Specific examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0049] Compound (2) can be produced by a general method well known to those skilled in the art, and for example, compound (2) can be obtained in good yield by following the method disclosed in Tetrahedron, vol. 28, pp. 1001-1008, 1972, or the methods described in Reference Synthesis Examples 1 and 3. Alternatively, a commercially available product may be used.

[0050] Specific examples of the compound (3) used in step 1A include compounds having the structures shown in the following structures 3-1 to 3-24. 1has the same definition as equation (3).

[0051] [ka] M 1 The group represented by the formula (I) is not particularly limited, but may be, for example, ZnY 1 , MgY 2 , Sn(Y 3 ) 3 , B(OY 4 ) 2 etc., and B(OY 4 ) 2 is preferred.

[0052] ZnY 1 , MgY 2 Although there is no particular limitation to the above, examples of the oxide include ZnCl, ZnBr, ZnI, MgCl, MgBr, and MgI.

[0053] Sn(Y 3 ) 3 is not particularly limited, but for example, Sn(Me) 3 , Sn(Bu) 3 Examples include:

[0054] B(OY 4 ) 2 is not particularly limited, but may be, for example, B(OH) 2 , B(OMe) 2 , B(O i Pr) 2 , B(OBu) 2 , B(OPh) 2 Me is a methyl group, i Pr represents an isopropyl group, Bu represents a butyl group, and Ph represents a phenyl group.

[0055] In addition, two (OY 4 ) groups together with the boron atom form a ring, 4 ) 2Examples of the group are not particularly limited, but include the following groups represented by (I) to (VI), and the group represented by (II) is preferred in terms of good yield.

[0056] [ka]

[0057] Compound (3) can be produced by a general method well known to those skilled in the art, and for example, compound (3) can be obtained in good yield according to the method disclosed in The Journal of Organic Chemistry, 1995, vol. 60, p. 7508, The Journal of Organic Chemistry, 2000, vol. 65, p. 164, or Journal of the chemical Society, Perkin Transactions 1, 2000, p. 3786, etc. Alternatively, a commercially available product may be used.

[0058] In step 1A, a catalyst and a base are preferably reacted with compound (2) and compound (3).

[0059] The catalyst used in step 1A is not particularly limited, but may be, for example, a palladium catalyst. Palladium chloride, palladium acetate, palladium trifluoroacetate, palladium nitrate, etc. Radium salts; Complex compounds such as π-allylpalladium chloride dimer, palladium acetylacetonate, tris(dibenzylideneacetone)dipalladium, bis(dibenzylideneacetone)palladium, dichlorobis(acetonitrile)palladium, and dichlorobis(benzonitrile)palladium; and Palladium complexes having a tertiary phosphine as a ligand, such as dichlorobis(triphenylphosphine)palladium, tetrakis(triphenylphosphine)palladium, dichloro(1,1'-bis(diphenylphosphino)ferrocene)palladium, bis(tri-tert-butylphosphine)palladium, bis(tricyclohexylphosphine)palladium, and dichlorobis(tricyclohexylphosphine)palladium; Examples include:

[0060] Palladium complexes having a tertiary phosphine as a ligand can also be prepared in the reaction system by adding a tertiary phosphine to a palladium salt or complex compound. Examples of tertiary phosphines that can be used in this case include triphenylphosphine, trimethylphosphine, tributylphosphine, tri(tert-butyl)phosphine, tricyclohexylphosphine, tert-butyldiphenylphosphine, 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene, 2-(diphenylphosphino)-2'-(N,N-dimethylamino)biphenyl, 2-(di-tert-butylphosphino)biphenyl, 2-(dicyclohexylphosphino)biphenyl, bis(diphenylphosphine), and tertiary phosphino. Examples of the 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl phosphine include 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl phosphine, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl phosphine, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl phosphine, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl phosphine, and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl phosphine.

[0061] Palladium complexes having a tertiary phosphine as a ligand are preferred in terms of good yield, and palladium complexes having 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl or triphenylphosphine as a ligand are more preferred.

[0062] The molar ratio of the tertiary phosphine to the palladium salt or complex compound is preferably in the range of 1:10 to 10:1, and more preferably in the range of 1:2 to 3:1 in terms of good yield. There is no limitation on the amount of the palladium catalyst used in step 1A, but in terms of good yield, the molar equivalent of the palladium catalyst is preferably in the range of 0.005 to 0.5 molar equivalents relative to compound (3).

[0063] The base used in step 1A is not particularly limited, but examples thereof include metal hydroxide salts such as sodium hydroxide, potassium hydroxide, and calcium hydroxide; metal carbonate salts such as sodium carbonate, potassium carbonate, lithium carbonate, and cesium carbonate; metal acetate salts such as potassium acetate and sodium acetate; metal phosphate salts such as potassium phosphate and sodium phosphate; metal fluoride salts such as sodium fluoride, potassium fluoride, and cesium fluoride; and metal alkoxides such as sodium methoxide, potassium methoxide, sodium ethoxide, sodium tert-butoxide, potassium isopropyl oxide, and potassium tert-butoxide. Among these, metal carbonates, metal phosphates, and metal alkoxides are preferred in terms of good reaction yield, and potassium carbonate, potassium phosphate, or sodium tert-butoxide is more preferred. There is no particular limit to the amount of base, but in terms of good reaction yield, the molar ratio of the base to compound (3) is preferably in the range of 1:2 to 10:1, and more preferably in the range of 1:1 to 4:1.

[0064] Step 1A can be carried out in a solvent. There is no particular limit to the solvent that can be used, and any solvent that does not inhibit the reaction may be used. Specific examples of such solvents include aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, anisole, and tetralin; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, and cyclohexane; ethers such as diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether (CPME), tetrahydrofuran (THF), 2-methyltetrahydrofuran, 1,4-dioxane, dimethoxyethane, and 4-methyltetrahydropyran (MTHP); halogenated solvents such as chloroform, dichloromethane, chlorobenzene, and orthodichlorobenzene; and amides such as N,N-dimethylformamide (DMF), dimethylacetamide (DMAc), and N-methylpyrrolidone (NMP); and the like, which may be mixed in any ratio. There is no particular limit to the amount of solvent used. Among these, aromatic hydrocarbons, ethers, halogenated solvents or mixed solvents thereof are preferred in terms of the good reaction yield of the pyran derivative (1a) of the present invention, and toluene, THF, dimethoxyethane or mixed solvents thereof are more preferred.

[0065] The reaction temperature when carrying out step 1A is not particularly limited, and the reaction can usually be carried out at a temperature appropriately selected from -80 to 180°C. In terms of the good reaction yield of the pyran derivative (1a) of the present invention, the reaction is preferably carried out at a temperature appropriately selected from 20°C to 140°C, and more preferably at a temperature appropriately selected from 20°C to 120°C.

[0066] In step 1A, the pyran derivative (1a) of the present invention can be obtained by carrying out a normal treatment after the completion of the reaction. If necessary, it may be purified by recrystallization, column chromatography, sublimation, preparative HPLC, or the like.

[0067] Step 1B is a step of producing a pyran derivative (1b) by reacting compound (2) with compound (4). Examples of the substituents in compound (2) and compound (4) include the same as the substituents in the pyran derivative represented by general formula (1).

[0068] As the compound (2) used in step 1B, the same compounds as those exemplified in step 1A can be used.

[0069] Specific examples of the compound (4) used in step 1B include compounds having the structures shown in the following 4-1 to 4-12.

[0070] [ka]

[0071] Compound (4) can be produced by a general method well known to those skilled in the art, or a commercially available product may be used.

[0072] Examples of the catalyst, base, solvent, reaction temperature, and post-treatment (purification) that can be used in step 1B are the same as those exemplified in step 1A, and the preferred configurations thereof are also the same.

[0073] Step 2 is a step of producing a pyran derivative (1a) by reacting a compound (5) with a compound (6). Examples of the substituents in the compounds (5) and (6) include the same ones as those in the pyran derivative represented by the general formula (1).

[0074] The compound (5) used in step 2 is X in the compounds represented by formulae 2-1 to 2-6. 1 and X 2 M 2 Examples of structures in which M is replaced with 2 is defined as in formula (5), and M in compound (3) 1 The same can be mentioned.

[0075] The compound (6) used in step 2 is M in the compounds represented by formulas 3-1 to 3-24. 1 X 3 An example of the structure is X. 3 is defined as the same as in formula (6), and X in compound (2) 1 and X 2 The same can be mentioned.

[0076] Examples of the catalyst, base, solvent, reaction temperature, and post-treatment (purification) that can be used in step 2 are the same as those exemplified in step 1A, and the preferred configurations thereof are also the same.

[0077] Further, a photoelectric conversion element containing the pyran derivative (1) of the present invention (hereinafter referred to as "the photoelectric conversion element of the present invention") will be described. The photoelectric conversion element of the present invention includes a substrate, a negative electrode layer, a photoelectric conversion layer, and a positive electrode layer. If necessary, a hole transport layer and / or an electron blocking layer may be provided between the negative electrode layer and the photoelectric conversion layer, and an electron transport layer and / or a hole blocking layer may be provided between the positive electrode layer and the photoelectric conversion layer.

[0078] In the photoelectric conversion element of the present invention, the pyran derivative (1) of the present invention may be used in any layer, but is preferably used in the photoelectric conversion layer.

[0079] The photoelectric conversion layer may contain a fullerene derivative. The fullerene derivative is, for example,

[60] fullerene (C 60 ),

[70] Fullerene (C 70 ), Phenyl-C 61 -Methyl butyrate (

[60] PCBM), phenyl-C 71 -Methyl butyrate (

[70] PCBM), phenyl-C 85 3-methylbutyrate (

[84] PCBM), and

[60] fullerene (C 60 ) or

[70] fullerene (C 70 ) is preferred.

[0080] When the photoelectric conversion layer contains a fullerene derivative, the mixing ratio of the pyran derivative (1) of the present invention to the fullerene derivative is preferably 1:0.01 to 1:100, and more preferably 1:0.1 to 1:10.

[0081] In the photoelectric conversion element of the present invention, a hole transport layer may be provided between the negative electrode and the photoelectric conversion layer, and an electron transport layer may be provided between the positive electrode and the photoelectric conversion layer, in order to improve carrier transportability. The hole transport layer is not particularly limited, and has either hole injection or transport, or electron barrier properties, and may be either an organic or inorganic material, and specifically includes triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline-based copolymers, and conductive polymer oligomers. The electron transport layer is not particularly limited, and has either electron injection or transport or hole blocking properties. Specific examples include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidene methane derivatives, anthraquinodimethane, and anthrone derivatives or oxadiazole derivatives. In addition, for the purpose of suppressing dark current generation, an electron blocking layer may be provided between the negative electrode and the photoelectric conversion layer, and a hole blocking layer may be provided between the positive electrode and the photoelectric conversion layer. Examples of the electron blocking layer include triarylamines such as 2,7-bis(9-carbazolyl)-9,9-spirobifluorene (Spiro-2CBP) and 3,7-bis[4-(9H-carbazol-9-yl)phenyl]-2,6-diphenylbenzo[1,2-b:4,5-b']difuran (CZBDF). The hole blocking layer may be made of naphthalene tetracarboxylic acid diimides such as N,N'-di(4-pyridyl)-1,4,5,8-naphthalene tetracarboxylic acid diimide, tris(8-quinolinolato)aluminum (Alq 3The hole transport layer may also function as an electron blocking layer, and the electron transport layer may also function as a hole blocking layer.

[0082] There is no particular limitation on the method for producing the photoelectric conversion layer, hole transport layer, electron transport layer, hole blocking layer and electron blocking layer (hereinafter referred to as "organic layers") of the photoelectric conversion element of the present invention, but film formation by vacuum deposition is possible. Film formation by vacuum deposition can be performed by using a general-purpose vacuum deposition device. The degree of vacuum in the vacuum chamber when forming a film by vacuum deposition is 1×10, which can be achieved by a commonly used diffusion pump, turbomolecular pump, cryopump, etc., taking into consideration the production takt time and production cost for producing an organic electroluminescent device. -6 Pa or more 1×10 -2 The deposition rate is preferably 0.005 nm / sec or more and 1.0 nm / sec or less, depending on the thickness of the film to be formed. Film formation can also be performed by a spin coating method, an inkjet method, a casting method, a dipping method, or the like using a general-purpose device.

[0083] The positive electrode layer and the negative electrode layer of the photoelectric conversion element of the present invention are connected to a power source via an electrical conductor such as a conducting wire. Either the positive electrode layer or the negative electrode layer can be in contact with the substrate of the photoelectric conversion element of the present invention. For convenience, the electrode in contact with the substrate is called the lower electrode. In the photoelectric conversion element of the present invention, either the positive electrode layer or the negative electrode layer may be the lower electrode.

[0084] As for the positive electrode layer and the negative electrode layer (hereinafter referred to as "electrode") of the photoelectric conversion element of the present invention, at least one of them, which is the light receiving surface, is preferably light transmissive. As the light transmissive electrode, a general transparent electrode material can be used, and examples thereof include metal oxides such as indium-tin oxide (ITO), indium-zinc oxide (IZO), tin oxide, aluminum or indium-doped tin oxide, magnesium-indium oxide, or nickel-tungsten oxide, metal nitrides such as gallium nitride, metal selenides such as zinc selenide, or metal sulfides such as zinc sulfide. Metal oxides are preferred in terms of good light transmissivity and electrical conductivity, and ITO, IZO, and tin oxide are more preferred. In addition, the electrode can be modified with plasma-deposited fluorocarbon.

[0085] For the other electrode that is not the light receiving surface, in addition to the transparent electrode materials exemplified above, an opaque or reflective electrode material can be used. Examples of the opaque or reflective electrode material include gold, silver, iridium, molybdenum, palladium, platinum, sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum, and aluminum / aluminum oxide (Al 2 O 3 ) mixtures, indium, lithium / aluminum mixtures, rare earth metals, etc.

[0086] There is no particular limitation on the method for producing the electrodes of the photoelectric conversion element of the present invention, but film formation by vacuum deposition, sputtering, electron beam deposition, chemical reaction methods (such as the sol-gel method), coating methods, etc. are possible.

[0087] The photoelectric conversion element of the present invention is formed on a substrate. The substrate may be light-transmitting or opaque depending on the intended light receiving direction. Light-transmitting is preferred for receiving light through the substrate, and examples of the substrate include transparent glass, quartz, and plastic. Examples of opaque substrates include silicon and silicon oxide. The substrate may also be a composite structure including multiple material layers.

[0088] The method for producing the photoelectric conversion element of the present invention is not particularly limited, but the element can be produced by successively forming an electrode layer, an organic layer, and an electrode layer on a substrate. Alternatively, an organic layer and an electrode layer may be successively formed on a substrate on which an electrode layer has been formed in advance. EXAMPLES

[0089] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention should not be construed as being limited to these. [ 1 H-NMR measurement] 1 H-NMR measurements were performed using a Bruker AVANCE III 400 or AVANCE III HD 400 NMR. 1 H-NMR was measured using a deuterated solvent as the measurement solvent and tetramethylsilane (TMS) as the internal standard. [Thin film preparation and film thickness measurement] The thin film was prepared by vacuum deposition using ELORA-500 (manufactured by ULVAC KIKOU Co., Ltd.). The substrate was cleaned in advance with isopropyl alcohol and then cleaned with oxygen plasma. The film thickness was measured using a stylus film thickness measuring instrument DektakXT (manufactured by BRUKER). [Absorption spectrum measurement] The absorption spectrum was measured using a spectrophotometer V-750 (manufactured by JASCO Corporation). The measurement was performed at a scan speed of 400 nm / min. The measurement sample was a thin film prepared on a quartz substrate by vacuum deposition. [Light current measurement] The photocurrent was measured using a solar cell spectral response measurement device (manufactured by Soma Optical Co., Ltd.). The irradiated light intensity was 50 μW / cm 2 Measurements were performed. [Dark current measurement] The dark current was measured using a Source Measure Unit 2636B (manufactured by Keithley).

[0090] The reagents used were commercially available. Synthesis reference example-1 2-(2-(4-bromophenyl)-6-(4-chlorophenyl)-4H-pyran-4-ylidene)malononitrile

[0091] [ka]

[0092] 2-(4-bromophenyl)-6-(4-chlorophenyl)-4H-pyran-4-one (6.6 g, 18 mmol) and malononitrile (1.3 g, 20 mmol) were suspended in acetic anhydride (90 mL) and refluxed for 18 hours. Water was added to the reaction solution, and the resulting solid was filtered and washed with water, methanol, and hexane to obtain 2-(2-(4-bromophenyl)-6-(4-chlorophenyl)-4H-pyran-4-ylidene)malononitrile (6.2 g, 83%). 1 H-NMR (CDCl 3 ):δ7.83(brd,J=8.8Hz,2H),7.76(brd,J=8.8Hz,2H),7.71(brd,J=8.8Hz,2H),7.56(brd,J=8.8Hz,2H).7.19(d,J=2.0Hz,1H),7.18(d,J=2.0Hz,1H). Synthesis Example 1 2-(2,6-bis(4-(benzofuran-2-yl)phenyl)-4H-pyran-4-ylidene)malononitrile (1-5)

[0093] [ka]

[0094] Under an argon atmosphere, 2-(2-(4-bromophenyl)-6-(4-chlorophenyl)-4H-pyran-4-ylidene)malononitrile (0.30 g, 0.73 mmol), benzofuran-2-ylboronic acid (0.29 g, 1.8 mmol), palladium acetate (5.0 mg, 0.022 mmol) and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (21 mg, 0.044 mmol) were suspended in THF (15 mL). 2M potassium carbonate aqueous solution (1.0 mL, 2.0 mmol) was added to this suspension and stirred at 80°C for 18 hours. The precipitate was collected by filtration from the reaction solution and washed with water, methanol and hexane. The obtained solid was dissolved in hot toluene and allowed to stand at room temperature, and the resulting solid was purified by column chromatography (CHCl 3 ) to obtain 2-(2,6-bis(4-(benzofuran-2-yl)phenyl)-4H-pyran-4-ylidene)malononitrile (0.050 g, 5%). 1 H-NMR (CDCl 3 ):δ8.07(brd,J=8.6Hz,4H),8.02(brd,J=8.6Hz,4H),7.65(brd,J=8.3Hz,2H),7.58(brd,J=8.3 Hz,2H),7.37(brdd,J=8.3,7.6Hz,2H),7.29(brdd,J=8.3,7.6Hz,2H),7.28(s,2H),7.24(s,2H). Synthesis reference example-2 2-(2,6-bis(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-4H-pyran-4-ylidene)malononitrile

[0095] [ka]

[0096] Under an argon atmosphere, 2-(2-(4-bromophenyl)-6-(4-chlorophenyl)-4H-pyran-4-ylidene)malononitrile (2.6 g, 6.3 mmol), bis(pinacolato)diboron (3.8 g, 15 mmol), palladium acetate (43 mg, 0.19 mmol), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (0.18 g, 0.38 mmol) and potassium acetate (4.5 g, 45 mmol) were suspended in THF (60 mL). 2M potassium carbonate aqueous solution (1.0 mL, 2.0 mmol) was added to this suspension and stirred at 80°C for 18 hours. Water and hexane were added to the reaction solution to form a precipitate, which was collected by filtration and washed with water, methanol, and hexane to obtain 2-(2,6-bis(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-4H-pyran-4-ylidene)malononitrile (3.0 g, 87%). 1 H-NMR (CDCl 3 ):δ7.80(brd,J=8.6Hz,4H),7.89(brd,J=8.6Hz,4H),7.26(s,2H),1.38(s,24H). Synthesis Example 2 2-(2,6-bis(4-(5-(4-(trimethylsilyl)phenyl)furan-2-yl)phenyl)-4H-pyran-4-ylidene)malononitrile (1-29)

[0097] [ka]

[0098] Under an argon atmosphere, 2-(2,6-bis(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-4H-pyran-4-ylidene)malononitrile (1.4 g, 2.5 mmol), (4-(5-bromofuran-2-yl)phenyl)trimethylsilane (1.8 g, 6.1 mmol) and tetrakis(triphenylphosphine)palladium (0.15 g, 0.13 mmol) were suspended in THF (25 mL). 2M potassium carbonate aqueous solution (6.5 mL, 13 mmol) was added to this suspension and stirred at 80° C. for 18 hours. The precipitate was collected by filtration from the reaction solution, washed with water, methanol, and hexane, and then purified by column chromatography (CHCl3) to obtain 2-(2,6-bis(4-(5-(4-(trimethylsilyl)phenyl)furan-2-yl)phenyl)-4H-pyran-4-ylidene)malononitrile (0.17 g, 9%). 1 H-NMR (CDCl 3 ):δ7.98(brd,J=8.6Hz,4H),7.92(brd,J=8.6Hz,4H),7.76(brd,J=8.3Hz,4H),7.60(brd ,J=8.3Hz,4H),7.25(s,2H),6.96(d,J=3.7Hz,2H),6.84(d,J=3.7Hz,2H),0.31(s,18H). Synthesis Example 3 2-(2,6-bis(4-(5-morpholinofuran-2-yl)phenyl)-4H-pyran-4-ylidene)malononitrile (1-25)

[0099] [ka]

[0100] Under an argon atmosphere, 2-(2-(4-bromophenyl)-6-(4-chlorophenyl)-4H-pyran-4-ylidene)malononitrile (1.3 g, 3.2 mmol), 4-(5-(trimethylstannyl)furan-2-yl)morpholine (2.4 g, 7.6 mmol), palladium acetate (72 mg, 0.16 mol), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (0.30 g, 0.32 mmol) and cesium fluoride (2.4 g, 16 mmol) were suspended in dimethoxyethane (30 mL) and stirred at 90°C for 18 hours. The precipitate was collected by filtration from the reaction solution, washed with water, methanol, and hexane, and then purified by column chromatography (CHCl3) to obtain 2-(2,6-bis(4-(5-morpholinofuran-2-yl)phenyl)-4H-pyran-4-ylidene)malononitrile (0.14 g, 7%). 1 H-NMR (CDCl 3 ):δ7.86(brd,J=8.6Hz,4H),7.64(brd,J=8.6Hz,4H),7.16(s,2H),6.80(d, J=3.6Hz,2H),5.34(d,J=3.6Hz,2H),3.91-3.85(m,8H),3.31-3.24(m,8H). Synthesis Example 4 2-(2,6-bis(4-(5-(4-adamantylphenyl)furyl)phenyl)-4H-pyran-4-ylidene)malononitrile (1-22)

[0101] [ka]

[0102] Under an argon atmosphere, 2-(2,6-bis(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-4H-pyran-4-ylidene)malononitrile (0.7 g, 2.0 mmol), 2-bromo-3-methylbenzofuran (0.5 g, 0.83 mmol) and tetrakis(triphenylphosphine)palladium (69 mg, 60 μmol) were dissolved in THF (10 mL). To this mixture, 2M potassium carbonate aqueous solution (3.0 mL, 6.0 mmol) was added and stirred at 80° C. for 22 hours. The suspension was then filtered while still hot, and the solid was washed with water, methanol, hexane, and toluene to obtain a yellow-orange solid, 2-(2,6-bis(4-(5-(4-adamantylphenyl)furyl)phenyl)-4H-pyran-4-ylidene)malononitrile (0.33 g, yield 20%). 1 H-NMR (CDCl 3 ):δ7.97(d,J=8.6Hz, 4H),7.91(d,J=8.6Hz,4H),7.74(d,J=8.6Hz,4H),7.45(d,J=8.4Hz,4H),7.24(m,2H),6.9 5(d,J=3.5Hz,2H),6.77(d,J=3.3Hz,2H),2.13(brs,6H),1.96(brs,12H),1.80(brs,12H). Synthesis Example 5 2-(2,6-bis(4-(diphenylamino)phenyl)-4H-pyran-4-ylidene)malononitrile (1-31)

[0103] [ka]

[0104] Under an argon atmosphere, 2-(2-(4-bromophenyl)-6-(4-chlorophenyl)-4H-pyran-4-ylidene)malononitrile (1.7 g, 4.2 mmol), diphenylamine (2.1 g, 12 mmol), palladium acetate (47 mg, 0.21 mmol), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (0.20 g, 0.42 mmol) and sodium tert-butoxide (1.2 g, 12 mmol) were suspended in toluene (40 mL) and refluxed for 18 hours. Hexane was added to the reaction solution to collect the resulting precipitate, which was then purified by column chromatography (CHCl 3 The solid obtained after distilling off the solvent was dissolved in hot toluene and allowed to stand at room temperature to obtain 2-(2,6-bis(4-(diphenylamino)phenyl)-4H-pyran-4-ylidene)malononitrile (0.52 g, 20%). 1 H-NMR (CDCl 3 ):δ7.70(brd,J=9.0Hz,4H),7.34(dd,J=8.6,7.3Hz,8H),7.19-7.13(m,12H),7.06(brd,J=9.0Hz,4H),7.02(s,2H). Synthesis Example 6 2-(2,6-bis(4-(3-methylbenzofuran-2-yl)phenyl)-4H-pyran-4-ylidene)malononitrile (1-7)

[0105] [ka]

[0106] Under an argon atmosphere, 2-(2,6-bis(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-4H-pyran-4-ylidene)malononitrile (1.7 g, 3.1 mmol), 2-bromo-3-methylbenzofuran (1.2 g, 7.3 mmol) and tetrakistriphenylphosphine palladium (0.3 g, 0.22 mmol) were dissolved in THF (30 mL). 2M potassium carbonate aqueous solution (11 mL, 22 mmol) was added to this mixture and stirred at 80° C. for 19 hours. The suspension was then filtered while still hot, and the solid was washed with water, methanol, hexane, and toluene to obtain an orange-yellow solid, 2-(2,6-bis(4-(3-methylbenzofuran-2-yl)phenyl)-4H-pyran-4-ylidene)malononitrile (1.0 g, yield 58%). 1 H-NMR (CDCl 3 ):δ8.05(s,8H),7.61(brd,J=8.2Hz,2H),7.54(brd,J=8.5Hz,2H),7.39-7.36(m,2H),7.30-7.24(m,4H),2.59(s,6H). Synthesis reference example-3 2-(2-(4-bromophenyl)-6-(4-chlorophenyl)-4H-pyran-4-ylidene)-1H-indene-1,3(2H)-dione

[0107] [ka]

[0108] 2-(4-bromophenyl)-6-(4-chlorophenyl)-4H-pyran-4-one (2.0 g, 5.5 mmol) and 1,3-indandione (0.81 g, 5.5 mmol) were suspended in acetic anhydride (55 mL) and refluxed for 6 hours. Water was added to the reaction solution, and the resulting solid was filtered and washed with water, methanol, and hexane to obtain 2-(2-(4-bromophenyl)-6-(4-chlorophenyl)-4H-pyran-4-ylidene)-1H-indene-1,3(2H)-dione (2.1 g, 79%). 1H-NMR (CDCl 3 ):δ9.09(d,J=1.8Hz,1H),9.08(d,J=1.8Hz,1H),7.95(brd,J=8.7Hz,2H),7.88(brd,J=8.7Hz ,2H),7.84-7.80(m,2H),7.71(brd,J=8.7Hz,2H),7.68-7.65(m,2H),7.55(brd,J=8.7Hz,2H). Synthesis Example 7 2-(2,6-bis(4-(diphenylamino)phenyl)-4H-pyran-4-ylidene)-1H-indene-1,3(2H)-dione (1-32)

[0109] [ka]

[0110] Under an argon atmosphere, 2-(2-(4-bromophenyl)-6-(4-chlorophenyl)-4H-pyran-4-ylidene)-1H-indene-1,3(2H)-dione (1.0 g, 2.0 mmol), diphenylamine (1.0 g, 6.1 mmol), palladium acetate (23 mg, 0.10 mmol), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (95 mg, 0.20 mmol) and sodium tert-butoxide (0.59 g, 6.1 mmol) were suspended in toluene (20 mL) and refluxed for 18 hours. Hexane was added to the reaction solution, and the resulting precipitate was collected by filtration and purified by column chromatography (CHCl3). The solid obtained after distilling off the solvent was dissolved in hot toluene and allowed to stand at room temperature to obtain 2-(2,6-bis(4-(diphenylamino)phenyl)-4H-pyran-4-ylidene)-1H-indene-1,3(2H)-dione (0.49 g, 33%). 1 H-NMR (CDCl 3):δ8.98(s,2H),7.84(brd,J=8.9Hz,4H),7.77-7.74(m,2H),7.1-7.58(m,2H ),7.34(dd,J=8.4,7.4Hz,8H),7.20-7.12(m,12H),7.09(brd,J=8.9Hz,4H). Synthesis Example 8 2-(2,6-bis(4-morpholinophenyl)-4H-pyran-4-ylidene)malononitrile (1-30)

[0111] [ka]

[0112] Under an argon atmosphere, 2-(2-(4-bromophenyl)-6-(4-chlorophenyl)-4H-pyran-4-ylidene)malononitrile (0.10 g, 0.24 mmol), morpholine (63 μL, 0.73 mmol), palladium acetate (1.6 mg, 7.3 μmol), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (6.8 mg, 15 μmol) and sodium tert-butoxide (70 mg, 0.73 mmol) were suspended in toluene (2 mL) and refluxed for 18 hours. The reaction solution was analyzed by NMR to confirm the production of 2-(2,6-bis(4-morpholinophenyl)-4H-pyran-4-ylidene)malononitrile. 1 H-NMR (CDCl 3 ):δ7.81(d,J=8.8Hz,4H),7.04(s,2H),6.96(d,J=8.8Hz,4H),3.92-3.83(m,8H),3.38-3.27(m,8H). Evaluation Example 1 A photoelectric conversion element containing the pyran derivative of the present invention as a constituent component was prepared, and its performance was evaluated.

[0113] The substrate used was a glass substrate with an ITO transparent electrode on which a 2 mm wide ITO film was patterned in a stripe shape. This substrate was washed with isopropyl alcohol and then oxygen plasma cleaned. After cleaning, the substrate was coated with 3,7-bis[4-(9H-carbazol-9-yl)phenyl]-2,6-diphenylbenzo[1,2-b:4,5-b']difuran (CZBDF, film thickness 10 nm) as a hole transport layer and a photoelectric conversion layer composed of the pyran derivative (1-31) of the present invention and fullerene (C 60 A co-evaporation film of N,N'-di(4-pyridyl)-1,4,5,8-naphthalenetetracarboxylic diimide (thickness 10 nm) was then formed as an electron transport layer by vacuum deposition (thickness 140 nm, equivalent film thickness ratio 2:1). A metal mask was then placed on the substrate so as to be perpendicular to the ITO stripes, and aluminum was vacuum-deposited at a deposition rate of 0.2 nm / sec as a positive electrode layer. After deposition, the multilayer film was sealed in a nitrogen atmosphere glove box with oxygen and moisture concentrations of 1 ppm or less, and the light-receiving area of ​​the multilayer film was 4 mm2. 2 The photoelectric conversion element was produced using a glass sealing cap and an epoxy type UV-curable resin (manufactured by Nagase ChemteX Corporation).

[0114] Evaluation comparison example-1 A photoelectric conversion element was prepared in the same manner as in Evaluation Example 1, except that the commercially available 2-tert-butyl-4-(dicyanomethylene)-6-[2-(1,1,7,7-tetramethyljulolidin-9-yl)vinyl]-4H-pyran (DCJTB) was used instead of the pyran derivative (1-31).

[0115] Table 1 shows the 1×10 5 The results of measuring the external quantum efficiency (irradiation light wavelength 450 nm) and dark current when V / cm was applied are shown. The photoelectric conversion element of the present invention was operated as a photoelectric conversion element having sensitivity in the blue light region, and showed a high external quantum efficiency and a low dark current compared to Evaluation Comparative Example-1. For a photoelectric conversion element, a high external quantum efficiency, which is an index of sensitivity, is preferable, and a low dark current, which is an index of noise, is preferable. Therefore, it was found that the photoelectric conversion element of the present invention showed superior performance compared to Evaluation Comparative Example-1.

[0116] [Table 1] [Industrial Applicability]

[0117] The pyran compound (1) of the present invention can be used in electronic materials such as organic photodiode materials, organic thin-film solar cell materials, organic semiconductor laser materials, organic EL display materials, and photonic crystal materials.

Claims

1. A pyran derivative represented by formula (1): 【Chemistry 1】 In formula (1), A １ represents an electron-withdrawing double-bond functional group. R １ ~R ３ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ４ each independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, a dialkylamino group having 2 to 8 carbon atoms, a diarylamino group having 12 to 24 carbon atoms, or a trialkylsilyl group having 3 to 12 carbon atoms. In the dialkylamino group and diarylamino group, two alkyl groups or aryl groups may be bonded together through an oxygen atom or a sulfur atom and formed together with a nitrogen atom to form a ring. In the dialkylamino group and diarylamino group, two alkyl groups or aryl groups may be bonded together through an oxygen atom or a sulfur atom and formed together with a nitrogen atom to form a ring. Ar １ each independently represents an arylene group having 6 to 18 carbon atoms or a heteroarylene group having 2 to 12 carbon atoms, and the arylene group and heteroarylene group may be substituted with an alkyl group having 1 to 4 carbon atoms. n represents an integer of 0 to 2. where n is 0 and R ４ Except when is a hydrogen atom.

2. In formula (1), Ar １ The pyran derivative according to claim 1, wherein each of the groups independently represents a phenylene group, a furanylene group, a thienylene group, a benzofuranylene group, or a benzothienylene group, each of which may be substituted with an alkyl group having 1 to 4 carbon atoms.

3. In formula (1), A １ The pyran derivative according to claim 1, wherein is a dicyanomethylidene group, a 1,3-indanedion-2-ylidene group, or a 1,3-cyclopenta[b]naphthalenedion-2-ylidene group.

4. In formula (1), R １ ~R ３ The pyran derivative according to claim 1 , wherein is a hydrogen atom.

5. The following formula (2) 【Chemistry 2】 (In formula (2), R １ ~R ３ Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. １ represents an electron-withdrawing double bond functional group. １ and X ２ each independently represents a halogen atom; and 【Chemistry 3】 (In formula (3), R ４ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, a dialkylamino group having 2 to 8 carbon atoms, a diarylamino group having 12 to 24 carbon atoms, or a trialkylsilyl group having 3 to 12 carbon atoms. In the dialkylamino group and diarylamino group, two alkyl groups or aryl groups may be bonded together through an oxygen atom or a sulfur atom and formed together with a nitrogen atom to form a ring. In the dialkylamino group and diarylamino group, two alkyl groups or aryl groups may be bonded together through an oxygen atom or a sulfur atom and formed together with a nitrogen atom to form a ring. １ each independently represents an arylene group having 6 to 18 carbon atoms or a heteroarylene group having 2 to 12 carbon atoms, and the arylene group and the heteroarylene group may be substituted with an alkyl group having 1 to 4 carbon atoms. ａ represents an integer of 1 to 2. １ ZnY １ , MgY ２ , Sn(Y ３ ) ３ Or B(OY ４ ) ２ Represents Y. １ and Y ２ each independently represents an alkyl group having 1 to 4 carbon atoms or a phenyl group; Y ３ each independently represents an alkyl group having 1 to 4 carbon atoms or a phenyl group; Y ４ Each of (OY) independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group. ４ ) groups may be taken together to form a ring with the boron atom. 【Chemistry 4】 (In formula (4), R ４ａ represents a dialkylamino group having 2 to 8 carbon atoms or a diarylamino group having 12 to 24 carbon atoms. In the dialkylamino group and diarylamino group, two alkyl or aryl groups may be bonded together with a nitrogen atom to form a ring. In the dialkylamino group and diarylamino group, two alkyl or aryl groups may be bonded together with an oxygen atom or a sulfur atom to form a ring together with a nitrogen atom. 【Chemistry 5】 (In the formula, R １ ~R ３ , A １ and Ar １ has the same meaning as above. ４ is R ４ａ and each independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, a dialkylamino group having 2 to 8 carbon atoms, a diarylamino group having 12 to 24 carbon atoms, or a trialkylsilyl group having 3 to 10 carbon atoms. In the dialkylamino group and diarylamino group, two alkyl groups or aryl groups may be bonded together with a nitrogen atom to form a ring. In the dialkylamino group and diarylamino group, two alkyl groups or aryl groups may be bonded together with an oxygen atom or a sulfur atom to form a ring together with a nitrogen atom. n represents an integer of 0 to 2.

6. The following formula (5) 【Chemistry 6】 (In formula (5), R １ ~R ３ Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. １ represents an electron-withdrawing double bond functional group. ２ ZnY １ , MgY ２ , Sn(Y ３ ) ３ Or B(OY ４ ) ２ Represents Y. １ and Y ２ each independently represents an alkyl group having 1 to 4 carbon atoms or a phenyl group; Y ３ each independently represents an alkyl group having 1 to 4 carbon atoms or a phenyl group; Y ４ Each of (OY) independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group. ４ ) groups may be united to form a ring together with the boron atom. 【Chemistry 7】 (In formula (6), R ４ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, a dialkylamino group having 2 to 8 carbon atoms, a diarylamino group having 12 to 24 carbon atoms, or a trialkylsilyl group having 3 to 10 carbon atoms. In the dialkylamino group and diarylamino group, two alkyl groups or aryl groups may be bonded together through an oxygen atom or a sulfur atom and formed together with a nitrogen atom to form a ring. In the dialkylamino group and diarylamino group, two alkyl groups or aryl groups may be bonded together through an oxygen atom or a sulfur atom and formed together with a nitrogen atom to form a ring. Ar １ each independently represents an arylene group having 6 to 18 carbon atoms or a heteroarylene group having 2 to 12 carbon atoms, and the arylene group and the heteroarylene group may be substituted with an alkyl group having 1 to 4 carbon atoms. ａ represents an integer of 1 to 2. ３ represents a halogen atom; and 【Chemistry 8】 (In formula (1a), R １ ~R ３ , A １ , Ar １ and n ａ has the same meaning as above. ４ each independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, a dialkylamino group having 2 to 8 carbon atoms, a diarylamino group having 12 to 24 carbon atoms, or a trialkylsilyl group having 3 to 10 carbon atoms. In the dialkylamino group and diarylamino group, two alkyl groups or aryl groups may be bonded together with a nitrogen atom to form a ring. In addition, in the dialkylamino group and diarylamino group, two alkyl groups or aryl groups may be bonded together with an oxygen atom or a sulfur atom to form a ring together with a nitrogen atom.

7. A photoelectric conversion element comprising the pyran derivative according to any one of claims 1 to 4.

8. A photoelectric conversion element comprising a photoelectric conversion layer containing the pyran derivative according to any one of claims 1 to 4.

9. The photoelectric conversion element according to claim 8 , wherein the photoelectric conversion layer further contains a fullerene derivative.

10. The fullerene derivative is [60]fullerene (C ６０ ) or [70]fullerene (C ７０ 10. The photoelectric conversion element according to claim 9 .

11. A material for a photoelectric conversion device, comprising the pyran derivative according to any one of claims 1 to 4.

12. The material for a photoelectric conversion element according to claim 11 , which is a material for a photoelectric conversion layer.

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