Compound and material for generating singlet oxygen

Abstract

Provided is a compound represented by general formula (I). In general formula (I), X1 to X8 each independently represent a hydrogen atom or a substituent (which is not a halogen atom), X1 and X2, X3 and X4, X5 and X6, and X7 and X8 each may independently be bonded to each other via a substituent to form a benzene ring, Y represents an oxygen atom or a sulfur atom, and R1 to R8 each independently represent an organic group, with the proviso that when Y is an oxygen atom, not all of R1 to R8 are phenyl groups.

Description

Compounds and singlet oxygen generating materials

[0001] The present disclosure relates to compounds and singlet oxygen generating materials.

[0002] Singlet oxygen is a type of reactive oxygen and has high reactivity. Utilizing the high reactivity of singlet oxygen, studies are underway to develop therapeutic drugs and new medicines, as well as to apply it to the environmental field. Phthalocyanine compounds are being studied as one of the materials that generate singlet oxygen (see, for example, Patent Document 1).

[0003] Patent Document 1: Japanese Patent Application Laid-Open No. 2001-064284

[0004] Porphyrinoid compounds such as phthalocyanine compounds and naphthalocyanine compounds have absorption peaks in the visible to near-infrared region, and singlet oxygen is generated by irradiating the porphyrinoid compound with light in this region. It is preferable that the porphyrinoid compound has a high singlet oxygen generation efficiency or is capable of generating singlet oxygen by long-wavelength absorption, and more preferably satisfies both requirements. The present disclosure has been made in view of the above-described conventional circumstances, and one aspect of the present disclosure aims to provide a compound that has a high singlet oxygen generation efficiency or is capable of generating singlet oxygen by long-wavelength absorption, and a singlet oxygen-generating material containing the compound.

[0005] Specific means for achieving the above object are as follows: <1> A compound represented by the following general formula (I):

[0006] (In general formula (I), X １ ~X ８ each independently represents a hydrogen atom or a substituent (excluding a halogen atom). １ and X ２ , X ３ and X ４ , X ５ and X ６ and X ７ and X ８ may each independently be linked to each other via a substituent to form a benzene ring. Y represents an oxygen atom or a sulfur atom. R １ ~R ８each independently represents an organic group, provided that when Y is an oxygen atom, R １ ~R ８ In the general formula (I), X cannot all be phenyl groups. １ ~X ８ <3> The compound according to <1>, wherein in general formula (I), R is a hydrogen atom and Y is an oxygen atom. １ ~R ８ <4> The compound according to <2>, wherein at least one of the organic groups represented by the general formula (I) has a hydroxy group. １ ~R ８ <5> The compound according to <2> or <3>, wherein at least one of the organic groups represented by the general formula (I) has a carboxy group or an alkali metal salt thereof. １ ~R ８ <6> The compound according to any one of <2> to <4>, wherein at least one of the organic groups represented by the general formula (I) has a maleimide group. １ ~R ８ The organic group represented by -(R ９ O) ｎ -R １０ (wherein R ９ represents an alkylene group, and R １０ represents an alkyl group; and n represents an integer of 1 or more. １ ~R ８ <8> The compound according to <2>, wherein in general formula (I), X １ ~X ８ are each independently an alkoxy group or an aryloxy group, and Y is an oxygen atom. １ ~R ８ <10> The compound according to <8>, wherein at least one of the organic groups represented by the general formula (I) has a hydroxy group. １ ~R ８<11> The compound according to <8> or <9>, wherein at least one of the organic groups represented by the general formula (I) has a carboxy group or an alkali metal salt thereof. １ ~R ８ <12> The compound according to any one of <8> to <10>, wherein at least one of the organic groups represented by the general formula (I) has a maleimide group. １ ~R ８ The organic group represented by -(R ９ O) ｎ -R １０ (wherein R ９ represents an alkylene group, and R １０ represents an alkyl group; and n represents an integer of 1 or more. １ ~X ８ and each independently represent a thioalkoxy group or a thioaryloxy group, and Y is an oxygen atom. １ and X ２ , X ３ and X ４ , X ５ and X ６ and X ７ and X ８ are bonded to each other via a substituent to form a benzene ring, and Y is an oxygen atom. １ ~R ８ <16> The compound according to <14>, wherein at least one of the organic groups represented by the general formula (I) has a hydroxy group. １ ~R ８ <17> The compound according to <14> or <15>, wherein at least one of the organic groups represented by the general formula (I) has a carboxy group or an alkali metal salt thereof. １ ~R ８ <18> The compound according to any one of <14> to <16>, wherein at least one of the organic groups represented by the general formula (I) has a maleimide group. １ ~R ８ The organic group represented by -(R９ O) ｎ -R １０ (wherein R ９ represents an alkylene group, and R １０ represents an alkyl group; and n represents an integer of 1 or more. １ ~X ８ <20> The compound according to <1>, wherein: is a hydrogen atom, and Y is a sulfur atom. <21> The compound according to <1>, wherein: ２ <21> The compound according to any one of <1> to <20>, which is a dye. <22> A singlet oxygen-generating material comprising the compound according to any one of <1> to <20>.

[0007] According to one aspect of the present disclosure, there are provided a compound that has excellent singlet oxygen generation efficiency or is capable of generating singlet oxygen by long wavelength absorption, and a singlet oxygen-generating material containing this compound.

[0008] 1 is an absorption spectrum of Compound 1. 2 is an absorption spectrum of Compound 2. 3 is an absorption spectrum of Compound 3. 4 is an absorption spectrum of Compound 5. 5 is an absorption spectrum of Compound 6. 6 is an absorption spectrum of Compound 8. 7 is an absorption spectrum of Compound 9. 8 is an absorption spectrum of Compound 10. 9 is an absorption spectrum of Compound 13. 10 is an absorption spectrum of Compound 19. 11 is an absorption spectrum of Compound 20. 12 is an absorption spectrum of Comparative Compound 1. 13 is an absorption spectrum of Comparative Compound 2. 14 is an absorption spectrum of Comparative Compound 3. 15 is a diagram showing absorption spectra obtained after each irradiation time when a mixed solution of Compound 1 and DPBF is irradiated with excitation light. 16 is a plot of the change in absorbance (410 nm) derived from DPBF versus each irradiation time when a mixed solution of Compound 1 and DPBF is irradiated with excitation light. 17 is a plot of the change in absorbance (410 nm) derived from DPBF versus each irradiation time when a mixed solution of Comparative Compound 1 and DPBF is irradiated with excitation light. 1 is a plot of the change in absorbance (410 nm) derived from DPBF versus each irradiation time when a mixed solution of compound 2 and DPBF is irradiated with excitation light. 2 is a plot of the change in absorbance (410 nm) derived from DPBF versus each irradiation time when a mixed solution of compound 3 and DPBF is irradiated with excitation light. 3 is a plot of the change in absorbance (410 nm) derived from DPBF versus each irradiation time when a mixed solution of compound 4 and DPBF is irradiated with excitation light. 4 is a plot of the change in absorbance (410 nm) derived from DPBF versus each irradiation time when a mixed solution of compound 5 and DPBF is irradiated with excitation light. 5 is a plot of the change in absorbance (410 nm) derived from DPBF versus each irradiation time when a mixed solution of compound 8 and DPBF is irradiated with excitation light. 1 is a plot of the change in absorbance (410 nm) derived from DPBF versus each irradiation time when a mixed solution of compound 9 and DPBF is irradiated with excitation light. 2 is a plot of the change in absorbance (410 nm) derived from DPBF versus each irradiation time when a mixed solution of compound 10 and DPBF is irradiated with excitation light. 3 is a plot of the change in absorbance (410 nm) derived from DPBF versus each irradiation time when a mixed solution of compound 13 and DPBF is irradiated with excitation light. 4 is a plot of the change in absorbance (410 nm) derived from DPBF versus each irradiation time when a mixed solution of compound 19 and DPBF is irradiated with excitation light.1 is a plot of the change in absorbance (410 nm) derived from DPBF versus each irradiation time when a mixed solution of Compound 20 and DPBF is irradiated with excitation light. 2 is a plot of the change in absorbance (410 nm) derived from DPBF versus each irradiation time when a mixed solution of Comparative Compound 2 and DPBF is irradiated with excitation light. 3 is a plot of the change in absorbance (410 nm) derived from DPBF versus each irradiation time when a mixed solution of Comparative Compound 3 and DPBF is irradiated with excitation light.

[0009] The present disclosure will be described in detail below. However, the present disclosure is not limited to the following embodiments. In the following embodiments, the components (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and do not limit the present disclosure.

[0010] In the present disclosure, numerical ranges indicated using "to" include the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In numerical ranges described in stages in the present disclosure, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another staged numerical range. Furthermore, in numerical ranges described in the present disclosure, the upper or lower limit value of that numerical range may be replaced with a value shown in the examples. In the present disclosure, each component may contain multiple corresponding substances. When multiple substances corresponding to each component are present in the composition, the content or amount of each component means the total content or amount of the multiple substances present in the composition, unless otherwise specified. In the present disclosure, the compound represented by the following general formula may be a mixture of positional isomers.

[0011] <Compound> The compound of the present disclosure is represented by the following general formula (I).

[0012]

[0013] In general formula (I), １ ~X ８ each independently represents a hydrogen atom or a substituent (excluding a halogen atom). １ and X ２ , X ３ and X４ , X ５ and X ６ and X ７ and X ８ may each independently be linked to each other via a substituent to form a benzene ring. Y represents an oxygen atom or a sulfur atom. R １ ~R ８ each independently represents an organic group, provided that when Y is an oxygen atom, R １ ~R ８ Not all of the groups are phenyl groups.

[0014] The compound represented by formula (I) will be described in detail below. １ ~X ８ each independently represents a hydrogen atom or a substituent (excluding a halogen atom). １ ~X ８ The substituent represented by X is not particularly limited. １ ~X ８ Examples of the substituent represented by the formula (I) include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, a thioaryloxy group, a hydroxy group, a mercapto group, an amino group, a ureido group, a formyl group, an acyl group, a carboxy group or an alkali metal salt thereof, a cyano group, a nitro group, a sulfo group or an alkali metal salt thereof, -(R ９ O) ｎ -R １０ (wherein R ９ represents an alkylene group, and R １０ represents an alkyl group. n represents an integer of 1 or more. Hereinafter, this may be referred to as a specific alkylated alkyleneoxy group.) or a substituent formed by combining two or more of these substituents. ９ The alkylene group represented by the formula (I) is preferably an alkylene group having 2 to 6 carbon atoms, and examples thereof include an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group. １０The alkyl group represented by the formula (I) is preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, an isopentyl group, a sec-pentyl group, a t-pentyl group, and an n-hexyl group. １ ~X ８ is preferably a hydrogen atom, an alkoxy group, an aryloxy group, a thioalkoxy group, or a thioaryloxy group. These substituents may further have a substituent. １ ~X ８ Substituents that further substitute the substituent represented by the formula (I) may include a hydroxy group; an amino group; a carboxy group; a mercapto group; a ureido group; a group having a hydroxy group; a group having a carboxy group or an alkali metal salt thereof; a group having a maleimide group; an alkoxy group; a halogen atom, etc. The hydroxy group, amino group, carboxy group, etc. may be protected by a protecting group. Examples of the protecting group for the hydroxy group include a tert-butyldimethylsilyl (TBDMS) group, etc.

[0015] Furthermore, the compound represented by general formula (I) may be a complex substituted with a modified substance such as an antibody, glycoprotein, polypeptide, polynucleotide, polysaccharide, liposome, micelle, or polymer resin. When the compound represented by general formula (I) is a complex substituted with the above-mentioned modified substance, X １ ~X ８ Examples of the substituent represented by X include the groups containing the modified compounds described above. １ ~X ８ is a group containing the above-mentioned modified compound, X １ ~X ８ The substituent represented by the formula (I) may contain a linking structure that links the modified product with the aromatic ring in the compound represented by the formula (I). １ ~X ８ When the substituent represented by the formula １ ~X ８ The modified entity may be bonded to the terminal of the linking structure contained in the substituent represented by the formula:

[0016] In general formula (I), １ and X ２ , X ３ and X ４ , X ５ and X ６ and X ７ and X ８ may each independently be linked to each other via a substituent to form a benzene ring. １ and X ２ , X ３ and X ４ , X ５ and X ６ and X ７ and X ８ It is preferred that all of the groups be linked to each other via a substituent to form a benzene ring.

[0017] In general formula (I), R １ ~R ８ each independently represents an organic group, provided that when Y is an oxygen atom, R １ ~R ８ Not all of R are phenyl groups. １ ~R ８ The organic group represented by R is not particularly limited. １ ~R ８ The organic group represented by the formula (I) is the above-mentioned X １ ~X ８ or a group in which the position to be bonded to Y is a carbon atom, among the specific examples of the substituent represented by formula (I) or a substituent formed by combining two or more of the above-mentioned substituents. When the compound represented by formula (I) is a complex with the above-mentioned modified substance, R １ ~R ８ Examples of the organic group represented by R include the groups containing the above-mentioned modified compounds. １ ~R ８ is a group containing the above-mentioned modified substance, R １ ~R ８ The organic group represented by R may contain a linking structure that links the modified substance and the aromatic ring in the compound represented by general formula (I) via Y. １ ~R ８ When the organic group represented by the formula (I) contains a linking structure, R １ ~R ８The modified substance may be bonded to the terminal of the linking structure contained in the organic group represented by the formula:

[0018] In the compound represented by formula (I), X １ ~X ８ , Y and R １ ~R ８ The compound represented by general formula (I) may be, for example, a compound represented by general formula (I) in which X １ ~X ８ may be a combination in which X is a hydrogen atom and Y is an oxygen atom; １ ~X ８ may be a combination in which each independently represents an alkoxy group or an aryloxy group, and Y represents an oxygen atom; １ ~X ８ may be a combination in which each independently represents a thioalkoxy group or a thioaryloxy group, and Y represents an oxygen atom; １ and X ２ , X ３ and X ４ , X ５ and X ６ and X ７ and X ８ may be a combination in which X are linked to each other via a substituent to form a benzene ring, and Y is an oxygen atom; １ ~X ８ may be a combination in which X is a hydrogen atom and Y is a sulfur atom; １ ~X ８ may be a combination in which each independently represents an alkoxy group or an aryloxy group, and Y represents a sulfur atom, １ ~X ８ may be a combination in which each independently represents a thioalkoxy group or a thioaryloxy group, and Y represents a sulfur atom, １ and X ２ , X ３ and X ４ , X ５ and X ６ and X ７ and X ８may be a combination in which each of them is linked to each other via a substituent to form a benzene ring, and Y is a sulfur atom. １ ~X ８ and Y, R １ ~R ８ is not particularly limited.

[0019] (First embodiment) The compound of the first embodiment represented by general formula (I) is a compound represented by general formula (I) in which X １ ~X ８ is a hydrogen atom, Y is an oxygen atom, and R １ ~R ８ At least one of the organic groups represented by R has a hydroxy group. １ ~R ８ The organic group having a hydroxy group represented by the formula (I) includes a group in which a hydrogen atom of an alkyl group is substituted with a hydroxy group. In this case, the alkyl group is preferably an alkyl group having a total of 1 to 4 carbon atoms, and more preferably an ethyl group. In the compound of the first embodiment, R １ ~R ８ At least one of the organic groups represented by R １ ~R ８ All of the organic groups represented by R may be groups having a hydroxy group. １ ~R ８ When the organic group represented by R １ ~R ８Examples of the organic group represented by the formula (I) include an alkyl group, an aryl group, and a specific alkylated alkyleneoxy group, and the specific alkylated alkyleneoxy group and an alkyl group are preferred, and the specific alkylated alkyleneoxy group and an alkyl group having a total carbon number of 1 to 4 are more preferred. Specific examples of the compound of the first embodiment are shown below, but the compound of the first embodiment is not limited to the following specific examples. Furthermore, the compound of the first embodiment may form a modified entity-compound complex, such as an antibody-compound complex (conjugate with an antibody), a glycoprotein-compound complex (conjugate with a glycoprotein), a polypeptide-compound complex (conjugate with a polypeptide), a polynucleotide-compound complex (conjugate with a polynucleotide), a polysaccharide-compound complex (conjugate with a polysaccharide), a liposome-compound complex (conjugate with a liposome), a micelle-compound complex (conjugate with a micelle), or a polymer resin-compound complex (conjugate with a polymer resin), via a hydroxyl group contained in the compound of the first embodiment.

[0020]

[0021] The compound of the first embodiment is R １ ~R ８ At least a part of the hydroxy groups contained in the organic group represented by the formula (I) may be protected with a protecting group. Specific examples of the compound of the first embodiment in which the hydroxy groups are protected with a protecting group are shown below, but the compound of the first embodiment in which the hydroxy groups are protected with a protecting group is not limited to the following specific examples. In the following specific examples, TBDMS represents a tert-butyldimethylsilyl group.

[0022]

[0023] (Second embodiment) In the compound of the second embodiment represented by general formula (I), １ ~X ８ is a hydrogen atom, Y is an oxygen atom, and R １ ~R８ At least one of the organic groups represented by R is a group having a carboxy group or an alkali metal salt thereof. １ ~R ８ Examples of the organic group having a carboxy group or an alkali metal salt thereof represented by the formula (I) include a group obtained by reacting a group in which an alkyl group is substituted with a hydroxy group with a carboxylic acid anhydride, or an alkali metal salt thereof. In this case, the alkyl group is preferably an alkyl group having a total of 1 to 4 carbon atoms, more preferably an ethyl group. Examples of the carboxylic acid anhydride include succinic anhydride, maleic anhydride, and phthalic anhydride. In the compound of the second embodiment, R １ ~R ８ At least one of the organic groups represented by R １ ~R ８ All of the organic groups represented by R may be groups having a carboxy group or an alkali metal salt thereof. １ ~R ８ When the organic group represented by the formula (I) has a group other than a carboxy group or a group having an alkali metal salt thereof, R １ ~R ８Examples of the organic group represented by the formula (I) include an alkyl group, an aryl group, and a specific alkylated alkyleneoxy group, with the specific alkylated alkyleneoxy group and an alkyl group being preferred, and the specific alkylated alkyleneoxy group and an alkyl group having a total carbon number of 1 to 4 being more preferred. Specific examples of the compound of the second embodiment are shown below, but the compound of the second embodiment is not limited to these specific examples. Furthermore, the compound of the second embodiment may form a modified entity-compound complex, such as an antibody-compound complex (conjugate with an antibody), glycoprotein-compound complex (conjugate with a glycoprotein), polypeptide-compound complex (conjugate with a polypeptide), polynucleotide-compound complex (conjugate with a polynucleotide), polysaccharide-compound complex (conjugate with a polysaccharide), liposome-compound complex (conjugate with a liposome), micelle-compound complex (conjugate with a micelle), or polymer resin-compound complex (conjugate with a polymer resin), via a carboxy group or an alkali metal salt thereof contained in the compound of the second embodiment, with the modified entity such as an antibody, glycoprotein, polypeptide, polynucleotide, polysaccharide, liposome, micelle, polymer resin, or polymer resin.

[0024]

[0025] (Third embodiment) In the compound of the third embodiment represented by the general formula (I), １ ~X ８ is a hydrogen atom, Y is an oxygen atom, and R １ ~R ８ At least one of the organic groups represented by R １ ~R ８ Examples of the organic group having a maleimide group represented by the formula (I) include a group in which a structure having a maleimide group is bonded via an ester to a group in which a hydrogen atom of an alkyl group is substituted with a hydroxy group. For example, an organic group having a maleimide group is formed by reacting a group in which a hydrogen atom of an alkyl group is substituted with a hydroxy group with 3-maleimidopropionic acid or the like. In the compound of the third embodiment, R１ ~R ８ At least one of the organic groups represented by R １ ~R ８ All of the organic groups represented by R may be groups having a maleimide group. １ ~R ８ is a group other than a group having a maleimide group, R １ ~R ８ Examples of the organic group represented by the formula (I) include an alkyl group, an aryl group, and a specific alkylated alkyleneoxy group, with the specific alkylated alkyleneoxy group and an alkyl group being preferred, and the specific alkylated alkyleneoxy group and an alkyl group having a total carbon number of 1 to 4 being more preferred. Specific examples of the compound of the third embodiment are shown below, but the compound of the third embodiment is not limited to these specific examples. Furthermore, the compound of the third embodiment may form a modified entity-compound conjugate, such as an antibody-compound conjugate (conjugate with an antibody), glycoprotein-compound conjugate (conjugate with a glycoprotein), polypeptide-compound conjugate (conjugate with a polypeptide), polynucleotide-compound conjugate (conjugate with a polynucleotide), polysaccharide-compound conjugate (conjugate with a polysaccharide), liposome-compound conjugate (conjugate with a liposome), micelle-compound conjugate (conjugate with a micelle), or polymer resin-compound conjugate (conjugate with a polymer resin), via the maleimide group contained in the compound of the third embodiment, with a modified entity such as an antibody, glycoprotein, polypeptide, polynucleotide, polysaccharide, liposome, micelle, polymer resin, or polymer resin.

[0026]

[0027] (Fourth embodiment) In the compound of the fourth embodiment represented by the general formula (I), １ ~X ８ is a hydrogen atom, Y is an oxygen atom, and R １ ~R ８ The organic group represented by the formula (I) is a combination of specific alkylated alkyleneoxy groups. １ ~R８ The specific alkylated alkyleneoxy groups represented by the formula (I) may all be the same or different. ９ As R in the specific alkylated alkyleneoxy group, an ethylene group or a trimethylene group is preferable. １０ is preferably a methyl group or an ethyl group. n in the specific alkylated alkyleneoxy group is preferably an integer of 1 to 6, more preferably an integer of 1 to 5, and even more preferably an integer of 1 to 4. Specific examples of the compound of the fourth embodiment are shown below, but the compound of the fourth embodiment is not limited to the specific examples below.

[0028]

[0029]

[0030] (Fifth embodiment) In the compound of the fifth embodiment represented by the general formula (I), １ ~X ８ is a hydrogen atom, Y is an oxygen atom, and R １ ~R ８ The organic group represented by the formula (I) is a combination of alkyl groups having a total of 1 to 18 carbon atoms. １ ~R ８ Examples of the alkyl group having a total of 1 to 18 carbon atoms represented by the formula (I) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, an isopentyl group, a sec-pentyl group, a t-pentyl group, an n-hexyl group, an n-heptyl group, an isoheptyl group, a sec-heptyl group, a 2,4-dimethylpentyl group, an n-octyl group, a 2-ethylhexyl group, and a cyclohexyl group. １ ~R ８ The alkyl group having a total of 1 to 18 carbon atoms, represented by the formula (I), preferably has 2 to 10 carbon atoms in total, and more preferably has 4 to 8 carbon atoms in total.

[0031] (Sixth embodiment) In the compound of the sixth embodiment represented by the general formula (I), １ ~X ８are each independently an alkoxy group or an aryloxy group, and Y is an oxygen atom. １ ~R ８ The organic group represented by X is not particularly limited. １ ~X ８ Examples of the alkoxy group represented by X include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an n-amyloxy group, an n-octyloxy group, and an n-decyloxy group. １ ~X ８ The alkoxy group represented by the following formula may further have a substituent. １ ~X ８ Substituents that further substitute the alkoxy group represented by the formula (I) may include a hydroxy group, an amino group, a carboxy group, a mercapto group, a ureido group, a group having a hydroxy group, a group having a carboxy group or an alkali metal salt thereof, a group having a maleimide group, an alkoxy group, a halogen atom, etc. The hydroxy group, amino group, carboxy group, etc. may be protected by a protecting group. An example of a protecting group for a hydroxy group is a tert-butyldimethylsilyl (TBDMS) group, etc. X １ ~X ８ Examples of the aryloxy group represented by X include a phenoxy group and a naphthoxy group. １ ~X ８ The aryloxy group represented by the following formula may further have a substituent. １ ~X ８ Substituents that further substitute the aryloxy group represented by the formula (I) may include a hydroxy group, an amino group, a carboxy group, a mercapto group, a ureido group, a group having a hydroxy group, a group having a carboxy group or an alkali metal salt thereof, a group having a maleimide group, an alkoxy group, a halogen atom, etc. The hydroxy group, amino group, carboxy group, etc. may be protected by a protecting group. An example of a protecting group for a hydroxy group is a tert-butyldimethylsilyl (TBDMS) group, etc. X １ ~X ８ The substituent represented by R is preferably an alkoxy group having a substituent. １ ~R８ The organic group represented by the formula (I) is preferably a specific alkylated alkyleneoxy group, a group having a hydroxy group, a group having a carboxy group or an alkali metal salt thereof, or a group having a maleimide group, and more preferably a specific alkylated alkyleneoxy group.

[0032] In the compound of the sixth embodiment represented by general formula (I), R １ ~R ８ At least one of the organic groups represented by the general formula (I) may be a group having a hydroxy group. １ ~R ８ The organic group having a hydroxy group represented by the formula (I) may be a group in which a hydrogen atom of an alkyl group is substituted with a hydroxy group. In this case, the alkyl group is preferably an alkyl group having a total of 1 to 4 carbon atoms, more preferably an ethyl group. In the compound of the sixth embodiment, R １ ~R ８ At least one of the organic groups represented by R may be a group having a hydroxy group, １ ~R ８ All of the organic groups represented by R may be groups having a hydroxy group. １ ~R ８ When the organic group represented by R １ ~R ８ Examples of the organic group represented by R include an alkyl group, an aryl group, and a specific alkylated alkyleneoxy group, and the specific alkylated alkyleneoxy group and an alkyl group are preferred, and the specific alkylated alkyleneoxy group and an alkyl group having a total carbon number of 1 to 4 are more preferred. １ ~R ８ At least a part of the hydroxy groups contained in the organic group represented by the formula (I) may be protected with a protecting group. Examples of the protecting group for the hydroxy group include a tert-butyldimethylsilyl (TBDMS) group.

[0033] In the compound of the sixth embodiment represented by general formula (I), R １ ~R ８At least one of the organic groups represented by the general formula (I) may be a group having a carboxy group or an alkali metal salt thereof. １ ~R ８ Examples of the group having a carboxy group represented by the formula (I) or an alkali metal salt thereof include a group obtained by reacting a group in which an alkyl group is substituted with a hydroxy group with a carboxylic acid anhydride, or an alkali metal salt thereof. In this case, the alkyl group is preferably an alkyl group having a total of 1 to 4 carbon atoms, more preferably an ethyl group. Examples of the carboxylic acid anhydride include succinic anhydride, maleic anhydride, and phthalic anhydride. In the compound of the sixth embodiment, R １ ~R ８ At least one of the organic groups represented by R may be a group having a carboxy group or an alkali metal salt thereof, １ ~R ８ All of the organic groups represented by R may be groups having a carboxy group or an alkali metal salt thereof. １ ~R ８ When the organic group represented by the formula (I) has a group other than a carboxy group or a group having an alkali metal salt thereof, R １ ~R ８ Examples of the organic group represented by the formula (I) include an alkyl group, an aryl group, and a specific alkylated alkyleneoxy group. Of these, the specific alkylated alkyleneoxy group and an alkyl group are preferred, and the specific alkylated alkyleneoxy group and an alkyl group having a total of 1 to 4 carbon atoms are more preferred.

[0034] In the compound of the sixth embodiment represented by general formula (I), R １ ~R ８ In the compound of the sixth embodiment represented by general formula (I), at least one of the organic groups represented by R １ ~R ８ Examples of the organic group having a maleimide group represented by the formula (I) include a group in which a structure having a maleimide group is bonded via an ester to a group in which a hydrogen atom of an alkyl group is substituted with a hydroxy group. １ ~R ８At least one of the organic groups represented by R may be a group having a maleimide group, １ ~R ８ All of the organic groups represented by R may be groups having a maleimide group. １ ~R ８ is a group other than a group having a maleimide group, R １ ~R ８ Examples of the organic group represented by the formula (I) include an alkyl group, an aryl group, and a specific alkylated alkyleneoxy group. Of these, the specific alkylated alkyleneoxy group and an alkyl group are preferred, and the specific alkylated alkyleneoxy group and an alkyl group having a total of 1 to 4 carbon atoms are more preferred.

[0035] In the compound of the sixth embodiment represented by general formula (I), R １ ~R ８ The organic group represented by the formula (I) may be a specific alkylated alkyleneoxy group. ９ As R in the specific alkylated alkyleneoxy group, an ethylene group or a trimethylene group is preferable. １０ As for n in the specific alkylated alkyleneoxy group, an integer of 1 to 6 is preferred, an integer of 1 to 4 is more preferred, and an integer of 1 to 2 is even more preferred. １ ~R ８ The specific alkylated alkyleneoxy groups represented by the formula (I) may all be the same or different.

[0036] Specific examples of the compound of the sixth embodiment are shown below, but the compound of the sixth embodiment is not limited to the following specific examples. In the following specific examples, Ph represents a phenyl group.

[0037]

[0038]

[0039]

[0040] (Seventh embodiment) In the compound of the seventh embodiment represented by the general formula (I), １ ~X８ In the seventh embodiment, R is a thioalkoxy group or a thioaryloxy group, and Y is an oxygen atom. １ ~R ８ The organic group represented by X is not particularly limited. １ ~X ８ Examples of the thioalkoxy group represented by the formula (X) include a thiomethoxy group, a thioethoxy group, a thio-n-propoxy group, a thioisopropoxy group, a thio-n-butoxy group, and a thio-t-butoxy group. １ ~X ８ The thioalkoxy group represented by the following formula may further have a substituent. １ ~X ８ Substituents that further substitute the thioalkoxy group represented by the formula (I) may include a hydroxy group, an amino group, a carboxy group, a mercapto group, a ureido group, a group having a hydroxy group, a group having a carboxy group or an alkali metal salt thereof, a group having a maleimide group, an alkoxy group, a halogen atom, etc. The hydroxy group, amino group, carboxy group, etc. may be protected by a protecting group. An example of a protecting group for a hydroxy group is a tert-butyldimethylsilyl (TBDMS) group, etc. X １ ~X ８ Examples of the thioaryloxy group represented by the formula (X) include a thiophenoxy group and a thionaphthoxy group. １ ~X ８ The thioaryloxy group represented by the following formula may further have a substituent. １ ~X ８ Substituents that further substitute the thioaryloxy group represented by the formula (I) may include a hydroxy group, an amino group, a carboxy group, a mercapto group, a ureido group, a group having a hydroxy group, a group having a carboxy group or an alkali metal salt thereof, a group having a maleimide group, an alkoxy group, a halogen atom, etc. The hydroxy group, amino group, carboxy group, etc. may be protected by a protecting group. An example of a protecting group for a hydroxy group is a tert-butyldimethylsilyl (TBDMS) group, etc. X １ ~X ８The substituent represented by R is preferably a thioaryloxy group, more preferably a thiophenoxy group. １ ~R ８ The organic group represented by the formula (I) is preferably a specific alkylated alkyleneoxy group, a group having a hydroxy group, a group having a carboxy group or an alkali metal salt thereof, or a group having a maleimide group, and more preferably a specific alkylated alkyleneoxy group.

[0041] In the compound of the seventh embodiment represented by general formula (I), R １ ~R ８ In the compound of the seventh embodiment represented by general formula (I), at least one of the organic groups represented by R １ ~R ８ The organic group having a hydroxy group represented by the formula (I) includes a group in which a hydrogen atom of an alkyl group is substituted with a hydroxy group. In this case, the alkyl group is preferably an alkyl group having a total of 1 to 4 carbon atoms, and more preferably an ethyl group. In the compound of the seventh embodiment, R １ ~R ８ At least one of the organic groups represented by R may be a group having a hydroxy group, １ ~R ８ All of the organic groups represented by R may be groups having a hydroxy group. １ ~R ８ When the organic group represented by R １ ~R ８ Examples of the organic group represented by R include an alkyl group, an aryl group, and a specific alkylated alkyleneoxy group, and the specific alkylated alkyleneoxy group and an alkyl group are preferred, and the specific alkylated alkyleneoxy group and an alkyl group having a total carbon number of 1 to 4 are more preferred. １ ~R ８ At least a part of the hydroxy groups contained in the organic group represented by the formula (I) may be protected with a protecting group. Examples of the protecting group for the hydroxy group include a tert-butyldimethylsilyl (TBDMS) group.

[0042] In the compound of the seventh embodiment represented by general formula (I), R １ ~R ８ In the compound of the seventh embodiment represented by general formula (I), at least one of the organic groups represented by R １ ~R ８ Examples of the group having a carboxy group represented by the formula (I) or an alkali metal salt thereof include a group obtained by reacting a group in which an alkyl group is substituted with a hydroxy group with a carboxylic acid anhydride, or an alkali metal salt thereof. In this case, the alkyl group is preferably an alkyl group having a total of 1 to 4 carbon atoms, more preferably an ethyl group. Examples of the carboxylic acid anhydride include succinic anhydride, maleic anhydride, and phthalic anhydride. In the compound of the seventh embodiment, R １ ~R ８ At least one of the organic groups represented by R may be a group having a carboxy group or an alkali metal salt thereof, １ ~R ８ All of the organic groups represented by R may be groups having a carboxy group or an alkali metal salt thereof. １ ~R ８ When the organic group represented by the formula (I) has a group other than a carboxy group or a group having an alkali metal salt thereof, R １ ~R ８ Examples of the organic group represented by the formula (I) include an alkyl group, an aryl group, and a specific alkylated alkyleneoxy group. Of these, the specific alkylated alkyleneoxy group and an alkyl group are preferred, and the specific alkylated alkyleneoxy group and an alkyl group having a total of 1 to 4 carbon atoms are more preferred.

[0043] In the compound of the seventh embodiment represented by general formula (I), R １ ~R ８ At least one of the organic groups represented by the general formula (I) may be a group having a maleimide group. １ ~R ８The organic group having a maleimide group represented by the formula (I) can be a group in which a structure having a maleimide group is bonded via an ester to a group in which a hydrogen atom of an alkyl group is substituted with a hydroxy group. １ ~R ８ At least one of the organic groups represented by R may be a group having a maleimide group, １ ~R ８ All of the organic groups represented by R may be groups having a maleimide group. １ ~R ８ is a group other than a group having a maleimide group, R １ ~R ８ Examples of the organic group represented by the formula (I) include an alkyl group, an aryl group, and a specific alkylated alkyleneoxy group. Of these, the specific alkylated alkyleneoxy group and an alkyl group are preferred, and the specific alkylated alkyleneoxy group and an alkyl group having a total of 1 to 4 carbon atoms are more preferred.

[0044] In the compound of the seventh embodiment represented by general formula (I), R １ ~R ８ The organic group represented by the formula (I) may be a specific alkylated alkyleneoxy group. ９ As R in the specific alkylated alkyleneoxy group, an ethylene group or a trimethylene group is preferable. １０ As for n in the specific alkylated alkyleneoxy group, an integer of 1 to 6 is preferred, an integer of 1 to 4 is more preferred, and an integer of 1 to 2 is even more preferred. １ ~R ８ The specific alkylated alkyleneoxy groups represented by the formula (I) may all be the same or different.

[0045] Specific examples of the compound of the seventh embodiment are shown below, but the compound of the seventh embodiment is not limited to the following specific examples. In the following specific examples, Ph represents a phenyl group.

[0046]

[0047]

[0048]

[0049] Eighth Embodiment In the compound of the eighth embodiment represented by the general formula (I), X １ and X ２ , X ３ and X ４ , X ５ and X ６ and X ７ and X ８ are linked to each other via a substituent to form a benzene ring, and Y is an oxygen atom. １ ~R ８ The organic group represented by X is not particularly limited. １ and X ２ , X ３ and X ４ , X ５ and X ６ and X ７ and X ８ When each of R and R forms a benzene ring, the compound of the eighth embodiment corresponds to a naphthalocyanine compound. The hydrogen atoms on the formed benzene ring may be substituted with a hydroxy group, an amino group, a carboxy group, a mercapto group, a ureido group, a group having a hydroxy group, a group having a carboxy group or an alkali metal salt thereof, a group having a maleimide group, an alkoxy group, a halogen atom, or the like. The hydroxy group, amino group, carboxy group, or the like may be protected with a protecting group. An example of a protecting group for a hydroxy group is a tert-butyldimethylsilyl (TBDMS) group. R １ ~R ８ Examples of the organic group represented by the formula include a group having a hydroxy group, a group having a carboxy group or an alkali metal salt thereof, a group having a maleimide group, an alkyl group, an aryl group, and a specific alkylated alkyleneoxy group.

[0050] In the compound of the eighth embodiment represented by general formula (I), R １ ~R ８ In the compound of the eighth embodiment represented by general formula (I), at least one of the organic groups represented by R１ ~R ８ The organic group having a hydroxy group represented by the formula (I) can be a group in which a hydrogen atom of an alkyl group is substituted with a hydroxy group. In this case, the alkyl group is preferably an alkyl group having a total of 1 to 4 carbon atoms, more preferably an ethyl group. In the compound of the eighth embodiment, R １ ~R ８ At least one of the organic groups represented by R may be a group having a hydroxy group, １ ~R ８ All of the organic groups represented by R may be groups having a hydroxy group. １ ~R ８ When the organic group represented by R １ ~R ８ Examples of the organic group represented by R include an alkyl group, an aryl group, and a specific alkylated alkyleneoxy group, and the specific alkylated alkyleneoxy group and an alkyl group are preferred, and the specific alkylated alkyleneoxy group and an alkyl group having a total carbon number of 1 to 4 are more preferred. １ ~R ８ At least a part of the hydroxy groups contained in the organic group represented by the formula (I) may be protected with a protecting group. Examples of the protecting group for the hydroxy group include a tert-butyldimethylsilyl (TBDMS) group.

[0051] In the compound of the eighth embodiment represented by general formula (I), R １ ~R ８ In the compound of the eighth embodiment represented by general formula (I), at least one of the organic groups represented by R １ ~R ８Examples of the group having a carboxy group represented by the formula (I) or an alkali metal salt thereof include a group obtained by reacting a group in which an alkyl group is substituted with a hydroxy group with a carboxylic acid anhydride, or an alkali metal salt thereof. In this case, the alkyl group is preferably an alkyl group having a total of 1 to 4 carbon atoms, more preferably an ethyl group. Examples of the carboxylic acid anhydride include succinic anhydride, maleic anhydride, and phthalic anhydride. In the compound of the eighth embodiment, R １ ~R ８ At least one of the organic groups represented by R may be a group having a carboxy group or an alkali metal salt thereof, １ ~R ８ All of the organic groups represented by R may be groups having a carboxy group or an alkali metal salt thereof. １ ~R ８ When the organic group represented by the formula (I) has a group other than a carboxy group or a group having an alkali metal salt thereof, R １ ~R ８ Examples of the organic group represented by the formula (I) include an alkyl group, an aryl group, and a specific alkylated alkyleneoxy group. Of these, the specific alkylated alkyleneoxy group and an alkyl group are preferred, and the specific alkylated alkyleneoxy group and an alkyl group having a total of 1 to 4 carbon atoms are more preferred.

[0052] In the compound of the eighth embodiment represented by general formula (I), R １ ~R ８ In the compound of the eighth embodiment represented by general formula (I), at least one of the organic groups represented by R １ ~R ８ An example of the organic group having a maleimide group represented by the formula (I) is a group in which a structure having a maleimide group is bonded via an ester to a group in which a hydrogen atom of an alkyl group is substituted with a hydroxy group. １ ~R ８ At least one of the organic groups represented by R may be a group having a maleimide group, １ ~R ８ All of the organic groups represented by R may be groups having a maleimide group. １ ~R８ is a group other than a group having a maleimide group, R １ ~R ８ Examples of the organic group represented by the formula (I) include an alkyl group, an aryl group, and a specific alkylated alkyleneoxy group. Of these, the specific alkylated alkyleneoxy group and an alkyl group are preferred, and the specific alkylated alkyleneoxy group and an alkyl group having a total of 1 to 4 carbon atoms are more preferred.

[0053] In the compound of the eighth embodiment represented by general formula (I), R １ ~R ８ In the eighth embodiment, at least one of the organic groups represented by R １ ~R ８ Preferably, at least one of the organic groups represented by R is a specific alkylated alkyleneoxy group. １ ~R ８ All of the organic groups represented by the formula (I) are specific alkylated alkyleneoxy groups (i.e., in the general formula (I), １ ~R ８ It is more preferable that the organic group represented by the formula (I) is a specific alkylated alkyleneoxy group. ９ As R in the specific alkylated alkyleneoxy group, an ethylene group or a trimethylene group is preferable. １０ As for n in the specific alkylated alkyleneoxy group, an integer of 1 to 6 is preferred, an integer of 1 to 5 is more preferred, and an integer of 1 to 4 is even more preferred. １ ~R ８ When the organic group represented by R １ ~R ８ Examples of the organic group represented by R include an alkyl group, an aryl group, and a group having a maleimide group. １ ~R ８The specific alkylated alkyleneoxy groups represented by the following formula (I) may all be the same or different. Specific examples of the compound of the eighth embodiment are shown below, but the compound of the eighth embodiment is not limited to these specific examples.

[0054]

[0055]

[0056]

[0057]

[0058] Ninth Embodiment In the compound of the ninth embodiment represented by the general formula (I), １ ~X ８ In the ninth embodiment, R is a hydrogen atom and Y is a sulfur atom. １ ~R ８ The organic group represented by R is not particularly limited. １ ~R ８ Examples of the organic group represented by R include a group having a hydroxy group, a group having a carboxy group or an alkali metal salt thereof, a group having a maleimide group, an alkyl group, an aryl group, and a specific alkylated alkyleneoxy group. Among these, an alkyl group or an aryl group is preferred, and an aryl group is more preferred. １ ~R ８ Examples of the alkyl group represented by the formula (I) include alkyl groups having a total of 1 to 18 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, an isopentyl group, a sec-pentyl group, a t-pentyl group, an n-hexyl group, an n-heptyl group, an isoheptyl group, a sec-heptyl group, a 2,4-dimethylpentyl group, an n-octyl group, a 2-ethylhexyl group, and a cyclohexyl group. １ ~R ８ Examples of the aryl group represented by R include a phenyl group and a naphthyl group. １ ~R ８The organic group represented by the formula (I) is preferably an aryl group, more preferably a phenyl group. Specific examples of the compound of the ninth embodiment are shown below, but the compound of the ninth embodiment is not limited to the following specific examples. In the following specific examples, Ph represents a phenyl group.

[0059]

[0060] (Tenth embodiment) In the compound of the tenth embodiment represented by the general formula (I), １ ~X ８ are each independently an alkoxy group or an aryloxy group, and Y is a sulfur atom. １ ~R ８ The organic group represented by X in the compound of the tenth embodiment is not particularly limited. １ ~X ８ and an alkoxy group or aryloxy group represented by R １ ~R ８ The details, preferred ranges, preferred combinations, etc. of the organic group represented by the formula (I) are the same as those in the sixth embodiment. Specific examples of the compound of the tenth embodiment include compounds in which the oxygen atom corresponding to Y in general formula (I) in the specific examples of the compound of the sixth embodiment is substituted with a sulfur atom.

[0061] Eleventh Embodiment In the compound of the eleventh embodiment represented by the general formula (I), １ ~X ８ In an eleventh embodiment, R is a combination in which each independently represents a thioalkoxy group or a thioaryloxy group, and Y is a sulfur atom. １ ~R ８ The organic group represented by X in the compound of the eleventh embodiment is not particularly limited. １ ~X ８ and a thioalkoxy group or a thioaryloxy group represented by R １ ~R ８The details, preferred ranges, preferred combinations, etc. of the organic group represented by the formula (I) are the same as those in the seventh embodiment. Specific examples of the compound of the eleventh embodiment include compounds in which the oxygen atom corresponding to Y in general formula (I) in the specific examples of the compound of the seventh embodiment is substituted with a sulfur atom.

[0062] (Twelfth embodiment) In the compound of the twelfth embodiment represented by the general formula (I), １ and X ２ , X ３ and X ４ , X ５ and X ６ and X ７ and X ８ are linked to each other via a substituent to form a benzene ring, and Y is a sulfur atom. １ ~R ８ The organic group represented by X in the compound of the twelfth embodiment is not particularly limited. １ ~X ８ and a benzene ring represented by R １ ~R ８ The details, preferred ranges, preferred combinations, etc. of the organic group represented by the formula (I) are the same as those in the above-mentioned eighth embodiment. Specific examples of the compound of the twelfth embodiment include compounds in which the oxygen atom corresponding to Y in general formula (I) in the specific examples of the compound of the eighth embodiment is substituted with a sulfur atom.

[0063] (Solubility) The compound represented by the general formula (I) has a solubility in water at 25°C of 0.1 g / 100 g-H in order to enable its use as an aqueous solution. ２ It is preferable that the density is 0 or more, and 0.3 g / 100 g-H ２ More preferably, it is 0 or more, and 0.5 g / 100 g-H ２ The solubility of the compound represented by formula (I) in water at 25°C is preferably 0.1 g / 100 g-H ２ From the viewpoint of being 0 or more, in the general formula (I), X １ ~X ８ or a substituent represented by R １~R ８ It is preferable that the organic group represented by the formula (I) has a carboxy group or an alkali metal salt thereof, or contains a specific alkylated alkyleneoxy group. In the present disclosure, the solubility in water at 25°C refers to the concentration at which the dissolution of the compound in water is confirmed by visual observation.

[0064] The compound represented by general formula (I) can be produced by a standard method, for example, by referring to the methods described in JP-A-3-62878, JP-A-3-215466, and JP-A-4-226390.

[0065] The compound represented by general formula (I) exhibits a high singlet oxygen generation quantum yield or can generate singlet oxygen by long-wavelength absorption, and can function as a singlet oxygen generating material. Therefore, the compound represented by general formula (I) can be applied to photodynamic therapy (PDT), photoimmunotherapy (PIT), and the like. Furthermore, since the compound represented by general formula (I) exhibits color, it can be used as a dye. Furthermore, when the compound represented by general formula (I) emits light, the luminescence can be used for cell imaging, disease diagnosis, and in vivo pharmacokinetic observation. Furthermore, by incorporating the compound represented by general formula (I) into a resin, it becomes possible to generate singlet oxygen in the resin at any timing by irradiating it with light, thereby controlling the timing of resin decomposition.

[0066] The absorption peak of the compound represented by general formula (I) is not particularly limited, but is preferably 650 nm or more, more preferably 700 nm or more, even more preferably 720 nm or more, and particularly preferably 820 nm or more.

[0067] The singlet oxygen generation quantum yield for the compound represented by general formula (I), calculated using the comparative compound 1 described below as a standard, is preferably 15% or more, more preferably 30% or more, even more preferably 50% or more, and particularly preferably 70% or more. The singlet oxygen generation quantum yield for the compound represented by general formula (I) may be 100% or less. In the present disclosure, the singlet oxygen generation quantum yield refers to a value measured by the following method using 1,3-diphenylisobenzofuran (DPBF) as a singlet oxygen quencher. A mixed solution of DPBF and a substance to be measured for singlet oxygen generation quantum yield in dimethylformamide is irradiated with excitation light, and the change in absorbance at 410 nm derived from DPBF is tracked and plotted. The singlet oxygen generation quantum yield Φ Δ Similar measurements are performed on a reference compound with known values, and the slope obtained from the plot is substituted into equation (1) to determine the singlet oxygen production quantum yield Φ Δ Calculate Φ Δ =Φ Δ ｓｔｄ × (m × F ｓｔｄ ×n ｓｔｄ / m ｓｔｄ ×F×n) Equation (1) where std is the value for the reference compound, m is the slope of the plot, and F is the absorbance correction factor (1-10 －Ａｂｓ where Abs is the absorbance at the excitation wavelength, and n is the relative photon number calculated from the excitation light intensity. Measurement of the singlet oxygen generation quantum yield using DPBF is described in detail in Aagata B. et al., J. Photochem. Photobiol. A: Chem. 2020, 388, 112161. and Tsuga Y. et al., Chem. Asian J. 2019, 14, 2067-2071. In the present disclosure, Comparative Compound 1 described below was used as a reference compound. The singlet oxygen generation quantum yield (Φ) for Comparative Compound 1 was Δ ｓｔｄ ) is 0.49 (49%) according to Muller S. et al., J. Photochem. Photobiol. B Biol. 1996, 35, 167.

[0068] <Singlet Oxygen Generating Material> The singlet oxygen generating material of the present disclosure includes a compound represented by general formula (I). The singlet oxygen generating material of the present disclosure may contain other components in addition to the compound represented by general formula (I). Examples of other components include porphyrinoid compounds other than the compound represented by general formula (I), organic solvents, inorganic fillers, and organic fillers. When the singlet oxygen generating material of the present disclosure contains other components, the proportion of the compound represented by general formula (I) in the entire singlet oxygen generating material of the present disclosure is preferably 90% by mass or more but less than 100% by mass, more preferably 99% by mass or more but less than 100% by mass, and even more preferably 99.9% by mass or more but less than 100% by mass. The singlet oxygen generating material of the present disclosure may consist solely of the compound represented by general formula (I) (i.e., contain no other components). The singlet oxygen generating material of the present disclosure may contain one compound represented by general formula (I) alone, or two or more compounds in combination.

[0069] The present disclosure will be described in more detail below using examples, but the present disclosure is not limited to the following examples.

[0070] <Preparation of Compounds> [Synthesis of Compound 1] (Synthesis of Intermediate 1) 1-Bromo-3-methoxypropane (3.26 mL, 29.2 mmol) was added to a suspension of 2,3-dicyanohydroquinone (1.79 g, 11.2 mmol) and potassium carbonate (5.44 g, 40.2 mmol) in dimethylformamide (22 mL), and the mixture was heated and stirred at 100°C under a nitrogen atmosphere for 4 hours. Water was then added to the reaction solution, and the precipitated solid was filtered and washed with water. The solid was recrystallized from toluene to obtain Intermediate 1 (3.12 g, 92%) represented by the following formula as a white solid. １ H-NMR (400MHz, CDCl ３ ) δ (ppm) 2.05-2.12 (m, 4H), 3.36 (s, 6H), 3.58 (t, 4H, J=5,9Hz), 4.16 (t, 4H, J=6.2Hz), 7.19 (s, 2H).

[0071]

[0072] (Synthesis of Compound 1) A suspension of intermediate 1 (1.02 g, 3.35 mmol), diazabicycloundecene (0.5 mL, 3.32 mmol), and palladium chloride (0.183 g, 1.03 mmol) in 1-pentanol (6 mL) was heated and stirred at 110°C for 18 hours under a nitrogen atmosphere. The reaction solution was then filtered through Celite, and the filtrate was concentrated. The residue was purified using a silica gel column (chloroform-acetone) and recycling preparative HPLC (chloroform) to obtain compound 1 (0.187 g, 17%) as a dark green oil. １ H-NMR (400MHz, CDCl ３ ) δ (ppm) 2.42-2.52 (m, 16H), 3.37 (s, 24H), 3.77 (t, 16H, J = 6.1Hz), 4.97 (t, 16H, J = 6.9Hz), 7.62 (s, 8H).

[0073]

[0074] [Synthesis of Compound 2] (Synthesis of Intermediate 2) Using 2,3-dicyanohydroquinone (3.05 g, 19.1 mmol), potassium carbonate (9.56 g, 69.2 mmol), and triethylene glycol-2-bromoethyl methyl ether (11 mL, 52.5 mmol) as raw materials and reaction reagents, a white solid intermediate 2 (6.67 g, 65%) represented by the following formula was obtained in the same synthetic method as for Intermediate 1. １ H-NMR (400MHz, CDCl ３ ) δ (ppm) 3.37 (s, 6H), 3.52-3.57 (m, 4H), 3.62-3.69 (m, 16H), 3.72-3. 76 (m, 4H), 3.89 (t, 4H, J=4.6Hz), 4.23 (t, 4H, J=4.6Hz), 7.25 (s, 2H).

[0075]

[0076] (Synthesis of Compound 2) Compound 2 (0.192 g, 6%) was obtained as a dark green oil by a synthetic method similar to that for Compound 1 using Intermediate 2 (2.82 g, 5.22 mmol), diazabicycloundecene (0.781 mL, 5.18 mmol), and palladium chloride (0.288 g, 1.63 mmol) as raw materials and reaction reagents. １H-NMR (400MHz, CDCl ３ ) δ (ppm) 3.31 (s, 24H), 3.44-3.50 (m, 16H), 3.55-3.61 (m, 32H), 3.61-3. 68 (m, 32H), 4.19 (t, 16H, J=5.1Hz), 5.11 (t, 16H, J=5.1Hz), 7.7 (s, 8H).

[0077]

[0078] [Synthesis of Compound 3] (Synthesis of Intermediate 3) (2-Bromoethoxy)(tert-butyl)dimethylsilane (11 mL, 51.6 mmol) was added to a suspension of 2,3-dicyanohydroquinone (3.42 g, 21.3 mmol) and potassium carbonate (8.82 g, 63.8 mmol) in dimethylformamide (40 mL), and the mixture was heated and stirred at 50°C under a nitrogen atmosphere for 6 hours. Water was then added to the reaction solution, and the precipitated solid was filtered and washed with water. The solid was recrystallized from ethanol to obtain Intermediate 3 (6.82 g, 67%) represented by the following formula as a white solid. １ H-NMR (400MHz, CDCl ３ ) δ (ppm) 0.10 (s, 12H), 0.88 (s, 18H), 4.00 (t, 4H, J = 4.9Hz), 4.17 (t, 4H, J = 4.9Hz), 7.25 (s, 2H).

[0079]

[0080] (Synthesis of Compound 3) A suspension of intermediate 3 (7.00 g, 14.7 mmol) and diazabicycloundecene (2.21 mL, 14.7 mmol) in 1-pentanol (28 mL) was stirred at 125°C to dissolve intermediate 3. Palladium chloride (1.18 g, 6.67 mmol) was added to the solution, and the mixture was heated and stirred at 125°C to 130°C for 36 hours under a nitrogen atmosphere. The reaction solution was then filtered through Celite, and the filtrate was concentrated. The residue was purified by a silica gel column (toluene-ethyl acetate) and reprecipitation (dichloromethane-methanol) to obtain compound 3 (0.838 g, 11%) as a dark green solid. １ H-NMR (400MHz, CDCl ３) δ (ppm) 0.08 (s, 48H), 0.91 (s, 72H), 4.32 (t, 16H, J = 5.9Hz), 5.03 (t, 16H, J = 5.7Hz), 7.73 (s, 8H).

[0081]

[0082] [Synthesis of Compound 4] Triethylamine trihydrofluoride (2 mL, 12.3 mmol) was added to a solution of Compound 3 (0.838 g, 0.416 mmol) in tetrahydrofuran (4 mL), and the mixture was stirred at room temperature overnight. The solid precipitated from the reaction solution was then filtered and washed with tetrahydrofuran to obtain Compound 4 (0.479 g, quant.) as a dark green solid. １ H-NMR (400MHz, d-DMSO) δ (ppm) 4.01-4.08 (m, 16H), 4.86 (t, 16H, J = 5.6Hz), 5.09 (t, 8H, J = 5.6Hz), 7.84 (s, 8H).

[0083]

[0084] [Synthesis of Compound 5] Succinic anhydride (0.043 g, 0.430 mmol) was added to a solution of compound 4 (0.0467 g, 0.0450 mmol) and triethylamine (0.111 mL, 0.800 mmol) in dimethylformamide (1 mL), and the mixture was stirred at room temperature overnight. The reaction solution was then concentrated. The resulting residue was washed with tetrahydrofuran to give compound 5 (0.0281 g, 35%) as a dark green solid. １ H-NMR (400MHz, d-DMF) δ (ppm) 2.50-2.58 (m, 16H), 2.60-2.67 (m, 16H), 4.81 (t, 16H, J = 5.2Hz), 5.26 (t, 16H, J = 4.8Hz), 7.90 (s, 8H).

[0085]

[0086] [Synthesis of Compound 6] Compound 5 (0.0758 g, 0.0399 mmol) was dissolved in 40 mM aqueous sodium hydroxide solution (8 mL, 0.32 mmol), and the water was then removed by lyophilization to obtain Compound 6 (0.0805 g, 97%) as a dark green solid.

[0087]

[0088] [Synthesis of Compound 7] N,N'-Dicyclohexylcarbodiimide (0.478 g, 2.32 mmol) and 4-dimethylaminopyridine (0.0455 g, 0.372 mmol) were added to a dichloromethane (2.0 mL) suspension of compound 4 (0.253 g, 0.23 mmol) and 3-maleimidopropionic acid (0.320 g, 1.892 mmol), and the mixture was stirred at room temperature under a nitrogen atmosphere for 28 hours. The reaction solution was then concentrated. The residue was purified using a silica gel column (chloroform) to obtain compound 7 (0.107 g, 20%) as a dark green oil. １ H-NMR (400MHz, d-DMSO) δ (ppm) 2.65-2.72 (m, 16H), 4.81-4.87 (m, 32H), 5.26 (t, 16H, J = 4.8Hz), 7.86 (d, 16H, J=8.0Hz), 7.91(s, 8H).

[0089]

[0090] [Synthesis of Compound 8] (Synthesis of Intermediate 4) To a suspension of 2,3-dicyanohydroquinone (10.0 g, 62.7 mmol) and potassium carbonate (13.3 g, 96.1 mmol) in dimethylformamide (120 mL) was added (2-bromoethoxy)(tert-butyl)dimethylsilane (13.5 mL, 63.1 mmol), and the mixture was heated and stirred at 60°C under a nitrogen atmosphere for 11.5 hours. Water was then added to the reaction solution, and the organic layer was extracted with chloroform. The organic layer was dried over sodium sulfate, filtered, and concentrated to obtain a crude product. Iodomethane (3.0 mL, 48.2 mmol) was added to a suspension of the crude product and potassium carbonate (9.04 g, 65.4 mmol) in dimethylformamide (60 mL), and the mixture was stirred at room temperature under a nitrogen atmosphere for 18 hours. Water was then added to the reaction solution, and the organic layer was extracted with chloroform. The organic layer was dried over sodium sulfate, filtered, and concentrated. The residue was purified by a silica gel column (toluene-ethyl acetate) and recrystallization (ethanol) to obtain intermediate 4 (1.34 g, 6%) represented by the following formula as a white solid. １ H-NMR (400MHz, CDCl ３) δ (ppm) 0.10 (s, 6H), 0.89 (s, 9H), 3.93 (s, 3H) 4.00 (t, 2H, J = 5.4Hz), 4.17 (t, 2H, J = 4.9Hz), 7.15 (d, 1H, J = 9.5Hz), 7.29 (d, 1H, J=9.5Hz).

[0091]

[0092] (Synthesis of Compound 8) Compound 8 (0.204 g, 6%) was obtained as a dark green solid by a synthetic method similar to that for Compound 1 using intermediate 4 (0.899 g, 2.70 mmol), 3,6-bis(2-ethoxyethoxy)1,2-benzene-dicarbonitrile) (2.48 g, 8.14 mmol), diazabicycloundecene (2.21 mL, 14.7 mmol), and palladium chloride (0.583 g, 3.29 mmol) as raw materials and reaction reagents. １ H-NMR (400MHz, CDCl ３ ) δ (ppm) 0.07 (s, 6H), 0.90 (s, 9H), 1.19-1.32 (m, 18H), 3.62-3.77 (m, 12H), 4.08-4.18 (m, 10H), 4.24 (t, 2H, J = 5.4Hz), 4.31 (t, 2H, J = 5.6Hz), 4.58 (s, 3H), 5.03-5.19 (m, 14H), 7.55 (d, 1H, J = 9.0Hz) 7.66-7.75 (m, 7H), 7.78 (d, 1H, J = 9.0Hz).

[0093]

[0094] [Synthesis of Compound 9] Compound 9 (0.0868 g, 38%) was obtained as a dark green solid by a synthetic method similar to that for Compound 4, except that Compound 8 (0.250 g, 0.185 mmol) and triethylamine trihydrofluoride (0.09 mL, 0.555 mmol) were used as raw materials and reaction reagents. １ H-NMR (400MHz, CDCl ３) δ (ppm) 1.17-1.32 (m, 18H), 3.60-3.78 (m, 12H), 3.99-4.07 (m, 2H), 4.08-4.16 (m, 8H), 4.18-4.27 (m, 4H), 4.59 (s, 3H), 4.82 (t, 2H, J = 4.1Hz), 5.04 (t, 2H, J = 5.4Hz), 5.08-5.18 (m, 10H), 5.40 (t, 1H, J = 6.7Hz), 7.59 (d, 1H, J = 8.8Hz), 7.67-7.77 (m, 7H).

[0095]

[0096] [Synthesis of Compound 10] Compound 10 (0.0257 g, 30%) was obtained as a dark green solid by a synthetic method similar to that for Compound 5, using Compound 9 (0.0786 g, 0.0635 mmol), triethylamine (0.02 mL, 0.144 mmol), and succinic anhydride (0.0208 g, 0.208 mmol) as raw materials and reaction reagents. １ H-NMR (400MHz, d-DMSO) δ (ppm) 1.21-1.29 (m, 18H), 2.45 (t, 2H, J = 6.7 Hz), 2.54 (t, 2H, J=7.2Hz), 3.63-3.75 (m, 12H), 4.12-4.15 (m, 10H), 4. 22 (t, 2H, J = 5.6Hz), 4.56 (s, 3H), 4.73 (t, 2H, J = 4.6Hz), 5.09-5.14 (m, 12H), 5.24 (t, 2H, J = 10.0Hz), 7.53 (d, 1H, J = 8.5Hz), 7.68-7.71 (m, 7H)

[0097]

[0098] [Synthesis of Compound 11] Compound 11 (0.0039 g, 89%) was obtained as a dark green solid by a synthesis method similar to that for Compound 6 using Compound 10 (0.0043 g, 0.00321 mmol) and a 3.2 mM aqueous sodium hydroxide solution as raw materials and reaction reagents.

[0099]

[0100] [Synthesis of Compound 12] Compound 12 (0.0967 g, 42%) was obtained as a dark green oil by a synthetic method similar to that for Compound 7, using compound 9 (0.203 g, 0.164 mmol), 3-maleimidopropionic acid (0.0391 g, 0.231 mmol), N,N'-dicyclohexylcarbodiimide (0.0431 g, 0.209 mmol), and 4-dimethylaminopyridine (0.0052 g, 0.0426 mmol) as raw materials and reaction reagents. １ H-NMR (400MHz, CDCl ３ ) δ (ppm) 1.20-1.28 (m, 18H), 2.40-2.45 (m, 2H), 3.63-3.75 (m, 12H), 4.12-4.15 (m, 10H), 4.22 (t, 2H, J = 5.6Hz), 4.5 6 (s, 3H), 4.70-4.80 (m, 4H), 5.10-5.14 (m, 12H), 5.21 (t, 2H, J = 10.0Hz), 7.58 (d, 1H, J = 8.5Hz), 7.70-7.85 (m, 7H), 7.90 (d, 2H, J=10.6Hz).

[0101]

[0102] [Synthesis of Compound 13] (Synthesis of Intermediate 5) Tetrafluorophthalonitrile (1.99 g, 9.95 mmol) was added to a suspension of 2-ethoxyethanol (4.7 mL, 48.5 mmol) and potassium carbonate (13.8 g, 99.9 mmol) in dimethylformamide (20 mL), and the mixture was heated and stirred at 100°C for 10 hours under a nitrogen atmosphere. The reaction solution was then diluted with water, and the organic layer was extracted with chloroform. The organic layer was dried over sodium sulfate, filtered, and concentrated. The residue was purified using a silica gel column (chloroform-acetone) to obtain Intermediate 5 (4.10 g, 86%) as a white solid. １ H-NMR (400MHz, CDCl ３ ) δ (ppm) 1.16-1.22 (m, 12H), 3.48-3.59 (m, 8H), 3.69-3.79 (m, 8H), 4.32-4.38 (m, 8H).

[0103]

[0104] (Synthesis of Compound 13) Compound 13 (0.0675 g, 6%) was obtained as a dark green oil by a synthetic method similar to that for Compound 1 using intermediate 5 (1.02 g, 2.11 mmol), diazabicycloundecene (0.31 mL, 2.06 mmol), and palladium chloride (0.120 g, 0.674 mmol) as raw materials and reaction reagents. １ H-NMR (400MHz, CDCl ３ ) δ (ppm) 1.09 (t, 24H, J=6.8Hz), 1.34 (t, 24H, J=6.8Hz), 3.55 (dd, 18H, J=6.8, 7.2 Hz), 3.75 (dd, 18H, J=6.8, 7.2 Hz), 4.05 (t, 16H, J=5.2 Hz), 4.14 (t, 16H, J=4.8 Hz), 4.74 (t, 16H, J=5.2 Hz), 5.10 (t, 16H, J=5.6 Hz).

[0105]

[0106] [Synthesis of Compound 14] (Synthesis of Intermediate 6) Using tetrafluorophthalonitrile (7.03 g, 9.95 mmol), potassium carbonate (48.5 g, 350 mmol), and 2-(tetrahydro-2H-pyran-2-yloxy)ethanol (23 mL, 169 mmol) as raw materials and reaction reagents, a crude product of Intermediate 6 was obtained as a colorless oil by the same synthetic method as for Intermediate 5. In Intermediate 6, THP means a tetrahydropyranyl group.

[0107]

[0108] (Synthesis of Intermediate 7) Pyridinium p-toluenesulfonate (0.965 g, 3.84 mmol) was added to a solution of the crude product of Intermediate 6 in methanol (70 mL), and the mixture was heated and stirred at 60°C for 19 hours. The reaction solution was then concentrated. The residue was purified using a silica gel column (chloroform-methanol) and suspension washing (ethyl acetate) to obtain Intermediate 7 (7.24 g, 56%, 2 steps) as a white solid. １H-NMR (400MHz, d-DMSO) δ (ppm) 3.66-3.73 (m, 8H), 4.17-4.25 (m, 8H), 4.90 (t, 2H, J = 5.2Hz), 4.95 (t, 2H, J = 5.6Hz).

[0109]

[0110] (Synthesis of Intermediate 8) To a solution of Intermediate 7 (7.24 g, 22.4 mmol) and imidazole (13.1 g, 192 mmol) in dimethylformamide (20 mL) was added tert-butyldimethylchlorosilane (14.4 g, 95.9 mmol), and the mixture was stirred overnight at room temperature under a nitrogen atmosphere. The reaction solution was then diluted with water and extracted with dichloromethane. The organic layer was dried over sodium sulfate, filtered, and concentrated. The residue was purified using a silica gel column (chloroform) to obtain Intermediate 8 (15.4 g, 83%) as a colorless oil. １ H-NMR (400MHz, CDCl ３ ) δ (ppm) 0.06 (s, 12H), 0.06 (s, 12H), 0.85 (s, 18H), 0.88 (s, 18H), 3.90 (t, 4H, J=4.8Hz), 3.95 (t, 4H, J=4.4Hz), 4.27 (dd, 8H, J=4.0, 5.6 Hz).

[0111]

[0112] (Synthesis of Compound 14) Compound 14 (0.02 g, 3%) was obtained as a dark green solid by a synthetic method similar to that for Compound 1 using Intermediate 8 (0.595 g, 0.721 mmol), diazabicycloundecene (0.108 mL, 0.717 mmol), and palladium chloride (0.0383 g, 0.231 mmol) as raw materials and reaction reagents. １ H-NMR (400MHz, CDCl ３ ) δ (ppm) - 0.14 (s, 48H), 0.19 (s, 48H), 0.66 (s, 72H), 0.97 (s, 72H), 4.20 (t, 16H, J=6.0Hz), 4.32 (t, 16H, J=6.0Hz), 4.61 (t, 16H, J=6.0Hz), 5.00 (t, 16H, J=6.0Hz).

[0113]

[0114] (Synthesis of Compound 15) Compound 15 (0.0427 g, 96%) was obtained as a dark green solid by a synthetic method similar to that for Compound 4, using compound 14 (0.0957 g, 0.0281 mmol) and triethylamine trihydrofluoride (0.23 mL, 1.41 mmol) as raw materials and reaction reagents. １ H-NMR (400MHz, d-DMSO) δ (ppm) 3.97-4.14 (m, 32H), 4.59 (t, 16H, J = 4.4Hz), 4.93 (t, 16H, J = 5.2Hz), 5.06 (t, 8H, J = 5.6Hz), 5.26 (t, 8H, J=5.6Hz).

[0115]

[0116] (Synthesis of Compound 16) Compound 16 (0.0309 g, 38%) was obtained as a dark green solid by a synthetic method similar to that for Compound 5 using compound 15 (0.0401 g, 0.0253 mmol), triethylamine (0.123 mL, 0.891 mmol), and succinic anhydride (0.0446 g, 0.446 mmol) as raw materials and reaction reagents. １ H-NMR (400MHz, d-DMSO) δ (ppm) 2.56-2.76 (m, 64H), 4.39-4.50 (m, 64H).

[0117]

[0118] (Synthesis of Compound 17) Compound 17 (0.00113 g, 93%) was obtained as a dark green solid by a synthesis method similar to that for Compound 6 using Compound 16 (0.0109 g, 0.00342 mmol) and 3.4 mM aqueous sodium hydroxide solution as raw materials and reaction reagents.

[0119]

[0120] [Synthesis of Compound 18] Compound 18 (0.0245 g, 48%) was obtained as a dark green oil by a synthetic method similar to that for Compound 7, using compound 15 (0.0201 g, 0.0127 mmol), 3-maleimidopropionic acid (0.0378 g, 0.223 mmol), N,N'-dicyclohexylcarbodiimide (0.0513 g, 0.249 mmol), and 4-dimethylaminopyridine (0.0056 g, 0.0458 mmol) as raw materials and reaction reagents. １ H-NMR (400MHz, CDCl ３ ) δ (ppm) 2.34-2.42 (m, 32H), 4.40-4.56 (m, 64H), 4.89 (t, 32H, J=5.2 Hz), 7.92 (d, 32H, J=10.6 Hz).

[0121]

[0122] [Synthesis of Compound 19] (Synthesis of Intermediate 9) Using 1,4-dihydroxy-2,3-dicyanonaphthalene (0.500 g, 2.38 mmol), potassium carbonate (0.824 g, 5.96 mmol), and 1-bromo-2-ethoxyethane (0.64 mL, 5.73 mmol) as raw materials and reaction reagents, a pale yellow solid, Intermediate 9 (0.60 g, 71%), represented by the following formula, was obtained in the same manner as for Intermediate 1. １ H-NMR (400MHz, CDCl ３ ) δ (ppm) 1.22 (t, 6H, J = 6.9Hz), 3.60 (q, 4H, J = 7.1Hz), 3.86-3.90 (m, 4H), 4.55-4.59 (m, 4H), 7.74-7.81 (m, 2H), 8.37-8.44 (m, 2H).

[0123]

[0124] (Synthesis of Compound 19) Compound 19 (0.0361 g, 6%) was obtained as a dark yellow solid by a synthetic method similar to that for Compound 1 using Intermediate 9 (0.590 g, 1.69 mmol), diazabicycloundecene (0.26 mL, 1.73 mmol), and palladium chloride (0.095 g, 0.536 mmol) as raw materials and reaction reagents. １ H-NMR (400MHz, CDCl３ ) δ (ppm) 1.23 (t, 24H, J = 6.9Hz), 3.61 (q, 16H, J = 7.0Hz), 4.08 (t, 16H, J = 4.6Hz) ), 5.45 (t, 16H, J=4.5Hz), 7.73 (s, 8H), 7.85-7.91 (m, 8H), 9.11-9.17 (m, 8H).

[0125]

[0126] [Synthesis of Compound 20] (Synthesis of Intermediate 10) Using 1,4-dihydroxy-2,3-dicyanonaphthalene (1.05 g, 4.98 mmol), potassium carbonate (2.42 g, 17.5 mmol), and triethylene glycol 2-bromoethyl methyl ether (2.8 mL, 13.3 mmol) as raw materials and reaction reagents, a brown oily intermediate 10 (1.53 g, 52%) represented by the following formula was obtained by the same synthetic method as for Intermediate 1. １ H-NMR (400MHz, CDCl ３ ) δ (ppm) 3.37 (s, 6H), 3.52-3.56 (m, 4H), 3.62-3.70 (m, 16H), 3.72-3.76 (m, 4H), 3.93-3.97 (m, 4H), 4.55-4.59 (m, 4H), 7.78 (dd, 2H, J=3.3, 6.5Hz), 8.41 (dd, 2H, J=3.3, 6.5Hz).

[0127]

[0128] (Synthesis of Compound 20) Compound 20 (0.0115 g, 1%) was obtained as a dark yellow oil by a synthetic method similar to that for Compound 1 using Intermediate 10 (0.779 g, 1.32 mmol), diazabicycloundecene (0.191 mL, 1.27 mmol), and palladium chloride (0.0712 g, 0.402 mmol) as raw materials and reaction reagents. １H-NMR (400MHz, d-DMSO) δ (ppm) 3.12 (s, 24H), 3.28-3.32 (m, 16H), 3.38-3.43 (m, 32H), 3.43-3.47 (m, 16H), 3.49-3.54 (m, 16H), 3.59-3.64 (m, 16H), 4.14 (t, 16H, J=5.0Hz), 5.33 (t, 16H, J=4.9Hz), 7.94 (dd, 8H, J=3.2, 6.6Hz), 9.05 (dd, 8H, J=3.3, 6.5Hz).

[0129]

[0130] [Synthesis of Compound 21] (Synthesis of Intermediate 11) Using 1,4-dihydroxy-2,3-naphthalenedicarbonitrile (2.49 g, 11.9 mmol), potassium carbonate (4.94 g, 35.7 mmol), and (2-bromoethoxy)(tert-butyl)dimethylsilane (6 mL, 28.0 mmol) as raw materials and reaction reagents, a pale yellow oily intermediate 11 (4.37 g, 70%) was obtained by the same synthetic method as for Intermediate 1. １ H-NMR (400MHz, CDCl ３ ) δ (ppm) 0.09 (s, 12H), 0.88 (s, 18H), 4.07 (t, 4H, J = 4.4 Hz), 4.49 (t, 4H, J = 4.8 Hz), 7.71-7.77 (m, 2H), 8.43-8.49 (m, 2H).

[0131]

[0132] (Synthesis of Compound 21) Compound 21 (0.109 g, 3%) was obtained as a dark yellow solid by a synthetic method similar to that for Compound 1 using intermediate 11 (3.30 g, 14.7 mmol), diazabicycloundecene (0.950 mL, 6.30 mmol), and palladium chloride (0.336 g, 1.90 mmol) as raw materials and reaction reagents. １ H-NMR (400MHz, CDCl ３ ) δ (ppm) 0.23 (s, 48H), 0.99 (s, 72H), 4.64 (t, 16H, J = 4.4 Hz), 5.23 (t, 16H, J = 4.8 Hz), 7.73-7.78 (m, 8H), 8.45-8.51 (m, 8H).

[0133]

[0134] (Synthesis of Compound 22) Compound 22 (0.0468 g, 86%) was obtained as a dark yellow solid by a synthetic method similar to that for Compound 4 using compound 21 (0.0925 g, 0.0418 mmol) and triethylamine trihydrofluoride (0.159 mL, 0.976 mmol) as raw materials and reaction reagents. １ H-NMR (400MHz, d-DMSO) δ (ppm) 4.12 (t, 16H, J = 4.4 Hz), 4.98 (t, 16H, J = 4.8 Hz), 5.06 (t, 8H, J = 4.8 Hz), 7.72-7.77 (m, 8H), 8.43-8.49 (m, 8H).

[0135]

[0136] (Synthesis of Compound 23) Compound 23 (0.0284 g, 66%) was obtained as a dark yellow solid by a synthetic method similar to that for Compound 5 using compound 22 (0.0267 g, 0.0205 mmol), triethylamine (0.047 mL, 0.339 mmol), and succinic anhydride (0.0180 g, 0.180 mmol) as raw materials and reaction reagents. １ H-NMR (400MHz, d-DMSO) δ (ppm) 2.61-2.78 (m, 32H), 4.56 (t, 16H, J = 4.4 Hz), 5.21 (t, 16H, J = 4.8 Hz), 7.70-7.77 (m, 8H), 8.40-8.47 (m, 8H).

[0137]

[0138] (Synthesis of Compound 24) Compound 24 (0.0099 g, 90%) was obtained as a dark yellow solid by a synthesis method similar to that for Compound 6 using Compound 23 (0.0101 g, 0.00481 mmol) and 4.8 mM aqueous sodium hydroxide solution as raw materials and reaction reagents.

[0139]

[0140] (Synthesis of Compound 25) Compound 25 (0.0187 g, 56%) was obtained as a dark yellow oil by a synthetic method similar to that for Compound 7 using compound 22 (0.0211 g, 0.0134 mmol), 3-maleimidopropionic acid (0.0178 g, 0.105 mmol), N,N′-dicyclohexylcarbodiimide (0.0278 g, 0.135 mmol), and 4-dimethylaminopyridine (0.0041 g, 0.0336 mmol) as raw materials and reaction reagents. １ H-NMR (400MHz, CDCl ３ ) δ (ppm) 2.71 (t, 16H, J=7.1 Hz), 4.49-4.61 (m, 32H), 5.15 (t, 16H, J=4.8 Hz), 7.71-7.77 (m, 8H), 7.92 (d, 16H, J=10.6Hz), 8.42-8.47 (m, 8H).

[0141]

[0142] [Synthesis of Compound 26] (Synthesis of Intermediate 12) Using 1,4-dihydroxy-2,3-naphthalenedicarbonitrile (5.08 g, 24.2 mmol), potassium carbonate (10.0 g, 72.3 mmol), (2-bromoethoxy)(tert-butyl)dimethylsilane (6.1 mL, 28.6 mmol), and iodomethane (1.8 mL, 28.9 mmol) as raw materials and reaction reagents, a pale yellow oily intermediate 12 (3.69 g, 40%) represented by the following formula was obtained in the same synthetic method as for Intermediate 4. １ H-NMR (400MHz, CDCl ３ ) δ (ppm) 0.11 (s, 6H), 0.88 (s, 9H), 3.94 (s, 3H), 4.01 (t, 2H, J = 5.4Hz), 4.15 (t, 2H, J = 4.9Hz), 7.12-7.21 (m, 2H), 8.01-8.07 (m, 1H), 8.18-8.22 (m, 1H).

[0143]

[0144] (Synthesis of Compound 26) Compound 26 (0.0750 g, 7%) was obtained as a dark yellow solid by a synthetic method similar to that for Compound 1 using intermediate 12 (1.043 g, 2.72 mmol), intermediate 9 (2.78 g, 7.85 mmol), diazabicycloundecene (1.6 mL, 10.6 mmol), and palladium chloride (0.565 g, 3.19 mmol) as raw materials and reaction reagents. １ H-NMR (400MHz, CDCl ３ ) δ (ppm) 0.08 (s, 6H), 0.91 (s, 9H), 1.18-1.30 (m, 18H), 3.63-3.77 (m, 12H), 4.07-4.17 (m, 10H), 4.26 (t, 2H) , J=5.4Hz), 4.31 (t, 2H, J=5.6Hz), 4.59 (s, 3H), 5.05-5.20 (m, 14H), 7.86-7.97 (m, 8H), 8.18-8.24 (m, 1H), 8.36-8.48 (m, 7H).

[0145]

[0146] (Synthesis of Compound 27) Compound 27 (0.0263 g, 60%) was obtained as a dark yellow solid by a synthetic method similar to that for Compound 4 using Compound 26 (0.0472 g, 0.0304 mmol) and triethylamine trihydrofluoride (0.014 mL, 0.0868 mmol) as raw materials and reaction reagents. １ H-NMR (400MHz, CDCl ３ ) δ (ppm) 1.20-1.30 (m, 18H), 3.61-3.75 (m, 12H), 4.08-4.18 (m, 10H), 4.29 (t, 2H, J = 5.4Hz), 4 .33 (t, 2H, J=5.6Hz), 4.61 (s, 3H), 5.06-5.20 (m, 14H), 7.86-7.97 (m, 8H), 8.20-8.24 (m, 1H), 8.31-8.47 (m, 7H).

[0147]

[0148] (Synthesis of Compound 28) Compound 28 (0.0145 g, 56%) was obtained as a dark yellow solid by a synthetic method similar to that for Compound 5 using Compound 27 (0.0243 g, 0.0169 mmol), triethylamine (0.005 mL, 0.0361 mmol), and succinic anhydride (0.004 g, 0.0400 mmol) as raw materials and reaction reagents. １ H-NMR (400MHz, CDCl ３ ) δ (ppm) 1.18-1.29 (m, 18H), 2.47 (t, 2H, J = 6.7Hz), 2.55 (t, 2H, J = 7.2Hz), 3.61-3.74 (m, 12H), 4.09-4.17 (m, 10H), 4 .28 (t, 2H, J=5.4Hz), 4.33 (t, 2H, J=5.6Hz), 4.60 (s, 3H), 5.07-5.22 (m, 14H), 7.86-7.97 (m, 8H), 8.21-8.25 (m, 1H), 8.31-8.46 (m, 7H).

[0149]

[0150] (Synthesis of Compound 29) Compound 29 (0.007 g, 90%) was obtained as a dark yellow solid by a synthetic method similar to that for Compound 6 using Compound 28 (0.0076 g, 0.00494 mmol) and 4.9 mM aqueous sodium hydroxide solution as raw materials and reaction reagents.

[0151]

[0152] (Synthesis of Compound 30) Compound 30 (0.0121 g, 54%) was obtained as a dark yellow oil by a synthetic method similar to that for Compound 7, using compound 27 (0.0203 g, 0.0141 mmol), 3-maleimidopropionic acid (0.0043 g, 0.0254 mmol), N,N′-dicyclohexylcarbodiimide (0.0054 g, 0.0262 mmol), and 4-dimethylaminopyridine (0.001 g, 0.00819 mmol) as raw materials and reaction reagents. １ H-NMR (400MHz, CDCl ３) δ (ppm) 1.18-1.29 (m, 18H), 2.48 (t, 2H, J = 6.7Hz), 3.61-3.75 (m, 12H), 4.09-4.18 (m, 10H), 4.12 (t, 2H, J = 5.6Hz), 4 .28 (t, 2H, J=5.4Hz), 4.36 (t, 2H, J=5.6Hz), 4.62 (s, 3H), 5.10-5.22 (m, 14H), 7.88-7.97 (m, 8H), 8.21-8.26 (m, 1H), 8.33-8.47 (m, 7H).

[0153]

[0154] The following comparative compounds 1 and 2 were purchased commercially, and comparative compound 3 was synthesized according to the examples in JP 2001-064284 A. Comparative compound 1 is a compound with a known singlet oxygen generation quantum yield and was prepared as a standard for calculating the singlet oxygen generation quantum yield of the compounds of the present disclosure. Comparative compound 2 has been widely studied as a commercially available singlet oxygen-generating dye (photosensitizer) and is approved by the U.S. Food and Drug Administration (FDA), and was therefore prepared as a representative example of a dye for photodynamic therapy (PDT) / photoimmunotherapy (PIT). Comparative compound 3 was prepared as prior art for technology using the compounds of the present disclosure. In the following specific examples, Ph represents a phenyl group.

[0155]

[0156]

[0157]

[0158] <Solubility Test> Distilled water was added to a sample in a flask at 25°C, and the flask was shaken to stir. After stirring, it was visually confirmed whether the sample had dissolved. A sample was judged to be soluble in water when the concentration was equal to or higher than the concentration at which dissolution was confirmed visually. Compound 6 was used as a sample, and when it was dissolved in 1 g of water at 25°C, it was found that 10 mg or more of the compound dissolved. The solubility in water at 25°C was 1 g / 100 g-H ２ It was above O.

[0159] <Measurement of Absorption Spectra> Compounds 1 to 30 and Comparative Compounds 1 to 3 were each dissolved in dimethylformamide (DMF) or water to prepare solutions, and the absorption spectra were measured using a spectrophotometer (V-770, manufactured by JASCO Corporation). The absorption spectra of representative compounds 1 to 6, 8 to 10, 13, 19, and 20 are shown in Figures 1 to 12. The absorption spectra of Comparative Compounds 1 to 3 are also shown in Figures 13 to 15.

[0160] <Measurement of Singlet Oxygen Generation Quantum Yield> The singlet oxygen generation quantum yield was measured using 1,3-diphenylisobenzofuran (DPBF) as a singlet oxygen detector according to the following method. A mixed solution of DPBF and Compound 1 in dimethylformamide was prepared and placed in a quartz cell with an optical path length of 1 cm. The cell containing the solution was placed in a spectrofluorometer (FP8650, manufactured by JASCO Corporation) and irradiated with excitation light. The excitation light intensity was measured using an optical power meter (8230E+82311B, manufactured by ADC Corporation). The absorption spectrum of the solution was measured every 5 seconds of irradiation. The absorption spectra obtained after each irradiation time are shown in Figure 16. The change in absorbance at 410 nm derived from DPBF was tracked. The absorbance at 410 nm at 0 seconds of irradiation was used as a reference, and the difference between the absorbance at 410 nm at each irradiation time and the absorbance at 0 seconds of irradiation (change in absorbance at 410 nm) was plotted against the irradiation time. The results are shown in Figure 17.

[0161] Singlet oxygen production quantum yield Φ Δ is known (Φ Δ ｓｔｄ The same measurement was performed on the comparative compound 1 (=49%), and a plot was obtained. The results are shown in Figure 18. The slope m obtained from Figure 17 and the slope m obtained from Figure 18 ｓｔｄ By substituting each of these into equation (1), the singlet oxygen production quantum yield Φ of compound 1 can be calculated. Δ The calculated value was 87%. Δ =Φ Δ ｓｔｄ × (m × F ｓｔｄ ×n ｓｔｄ / m ｓｔｄ×F×n) Equation (1) In the equation, std is the value for Comparative Compound 1, m is the slope of the plot, and F is the absorbance correction factor (1-10 －Ａｂｓ where Abs is the absorbance at the excitation wavelength, and n is the relative photon number calculated from the excitation light intensity.

[0162] The singlet oxygen production quantum yield Φ of each compound was measured in the same manner except that other synthetic compounds and comparative compounds 2 and 3 were used instead of compound 1 and the excitation wavelength was set to the absorption maximum wavelength of each compound. Δ The change in absorbance at 410 nm was plotted against irradiation time when representative compounds 2 to 5, 8 to 10, 13, 19, and 20 and comparative compounds 2 and 3 were used, and these are shown in Figures 19 to 30. The singlet oxygen production quantum yield Φ of each compound was calculated from the obtained plots. Δ and the absorption maximum wavelength (excitation wavelength) λ ａｂｓ are summarized in Table 1.

[0163] The compounds of the present disclosure exhibited absorption bands at longer wavelengths than comparative compounds 1 to 3. Among these, some compounds exhibited absorption bands at wavelengths 100 nm or longer than the comparative compounds. It is known that in the visible to near-infrared light region, the longer the wavelength of light, the deeper the tissue penetration. Compounds of the present disclosure, which function at wavelengths longer than the comparative compounds, are expected to improve PDT / PIT efficiency and apply PDT / PIT to deep-seated cancers. Furthermore, some compounds exhibited higher singlet oxygen generation quantum yields than comparative compounds 1 to 3, and are expected to improve PDT / PIT efficiency.

[0164] The disclosure of Japanese Patent Application No. 2024-099173, filed on June 19, 2024, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards mentioned herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A compound represented by the following general formula (I): (In general formula (I), X １ ~X ８ each independently represents a hydrogen atom or a substituent (excluding a halogen atom). １ and X ２ , X ３ and X ４ , X ５ and X ６ and X ７ and X ８ may each independently be linked to each other via a substituent to form a benzene ring. Y represents an oxygen atom or a sulfur atom. R １ ~R ８ each independently represents an organic group, provided that when Y is an oxygen atom, R １ ~R ８ Not all of the groups are phenyl groups.) 2. In general formula (I), X １ ~X ８ 2. The compound according to claim 1, wherein is a hydrogen atom and Y is an oxygen atom.

3. In general formula (I), R １ ~R ８ The compound according to claim 2, wherein at least one of the organic groups represented by the formula (I) has a hydroxy group.

4. In general formula (I), R １ ~R ８ The compound according to claim 2, wherein at least one of the organic groups represented by the formula (I) has a carboxy group or an alkali metal salt thereof.

5. In general formula (I), R １ ~R ８ The compound according to claim 2, wherein at least one of the organic groups represented by the formula (I) has a maleimide group.

6. In general formula (I), R １ ~R ８ The organic group represented by -(R ９ O) ｎ -R １０ (wherein R ９ represents an alkylene group, and R １０ represents an alkyl group; and n represents an integer of 1 or more.

7. In general formula (I), R １ ~R ８ The compound according to claim 2, wherein the organic group represented by the formula (I) is an alkyl group having a total of 1 to 18 carbon atoms.

8. In general formula (I), X １ ~X ８ The compound according to claim 1, wherein each of the groups independently represents an alkoxy group or an aryloxy group, and Y represents an oxygen atom.

9. In general formula (I), R １ ~R ８ The compound according to claim 8, wherein at least one of the organic groups represented by the formula (I) has a hydroxy group.

10. In general formula (I), R １ ~R ８ The compound according to claim 8, wherein at least one of the organic groups represented by the formula (I) has a carboxy group or an alkali metal salt thereof.

11. In general formula (I), R １ ~R ８ The compound according to claim 8, wherein at least one of the organic groups represented by the formula (I) has a maleimide group.

12. In general formula (I), R １ ~R ８ The organic group represented by -(R ９ O) ｎ -R １０ (wherein R ９ represents an alkylene group, and R １０ represents an alkyl group; and n represents an integer of 1 or more.

13. In general formula (I), X １ ~X ８ The compound according to claim 1, wherein each of the groups independently represents a thioalkoxy group or a thioaryloxy group, and Y represents an oxygen atom.

14. In general formula (I), X １ and X ２ , X ３ and X ４ , X ５ and X ６ and X ７ and X ８ The compound according to claim 1, wherein each of the groups is linked to each other via a substituent to form a benzene ring, and Y is an oxygen atom.

15. In general formula (I), R １ ~R ８ The compound according to claim 14, wherein at least one of the organic groups represented by the formula (I) has a hydroxy group.

16. In general formula (I), R １ ~R ８ The compound according to claim 14, wherein at least one of the organic groups represented by the formula (I) has a carboxy group or an alkali metal salt thereof.

17. In general formula (I), R １ ~R ８ The compound according to claim 14, wherein at least one of the organic groups represented by the formula (I) has a maleimide group.

18. In general formula (I), R １ ~R ８ The organic group represented by -(R ９ O) ｎ -R １０ (wherein R ９ represents an alkylene group, and R １０ represents an alkyl group; and n represents an integer of 1 or more.

19. In general formula (I), X １ ~X ８ 2. The compound according to claim 1, wherein is a hydrogen atom and Y is a sulfur atom.

20. The solubility in water at 25°C is 0.1 g / 100 g-H ２ 2. The compound of claim 1, wherein the aryl group is O or more.

21. The compound according to any one of claims 1 to 20, which is a dye.

22. A singlet oxygen generating material comprising the compound according to any one of claims 1 to 20.

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