WO2017155042A1 - Composé de dithiénophosphorine et colorant fluorescent produit à l'aide de celui-ci - Google Patents

Composé de dithiénophosphorine et colorant fluorescent produit à l'aide de celui-ci Download PDF

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WO2017155042A1
WO2017155042A1 PCT/JP2017/009490 JP2017009490W WO2017155042A1 WO 2017155042 A1 WO2017155042 A1 WO 2017155042A1 JP 2017009490 W JP2017009490 W JP 2017009490W WO 2017155042 A1 WO2017155042 A1 WO 2017155042A1
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group
compound
optionally substituted
general formula
dithienophosphorine
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PCT/JP2017/009490
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Japanese (ja)
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愛子 中
山口　茂弘
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国立大学法人名古屋大学
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6578—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and sulfur atoms with or without oxygen atoms, as ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials

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  • the present invention relates to a dithienophosphorine compound and a fluorescent dye using the same.
  • organic molecules having absorption and fluorescence maximum wavelengths in this region (620 nm or more) are attracting attention in deep observation of living tissue.
  • Organic molecules that exhibit fluorescence in the near-infrared region have high importance beyond the framework of applications such as bioimaging fluorescent probes and fluorescent materials for organic EL devices. So far, many near-infrared fluorescent organic molecules are known based on the skeletons of classic fluorescent dyes such as cyanine dyes, squalin dyes, porphyrin dyes, and phthalocyanine dyes.
  • indocyanine green is one of the most widely used near-infrared fluorescent dyes from the viewpoint of a fluorescent probe.
  • ICG indocyanine green
  • a fluorescein dye has an absorption maximum wavelength of 491 nm, a fluorescence maximum wavelength of 510 nm, and a quantum yield of 0.85 (Non-Patent Document 1), but for bioimaging, it has a wavelength in the deep red to near infrared region.
  • Non-Patent Document 1 Non-Patent Document 1
  • it since it is necessary to show absorption and fluorescence, it is required to further increase the absorption maximum wavelength and the fluorescence maximum wavelength.
  • the present invention provides a fluorescent dye having an absorption maximum and a fluorescence maximum at a high wavelength, a high fluorescence quantum yield, high stability to light, and capable of introducing various substituents. With the goal.
  • the present inventors have replaced the benzene ring portion of the rhodamine dye with a thiophene skeleton, and also replaced the oxygen atom in the skeleton with a phosphorus-containing group, thereby achieving an absorption maximum and a fluorescence maximum at a high wavelength. And having high fluorescence quantum yield, high stability to light, and found that various substituents can be introduced.
  • the present invention has been completed by further research based on such knowledge. That is, the present invention includes the following configurations.
  • R 1 represents the general formula (2A) or (2B):
  • R 7 is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted aryl group, or a substituted group;
  • Ar represents an optionally substituted aromatic hydrocarbon ring or an optionally substituted heteroaromatic ring.
  • R 2 is the general formula (3A), (3B) or (3C):
  • R 8 is the same or different and is a hydroxy group, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkenyl group, or an optionally substituted alkynyl group.
  • R 9 represents a hydrogen atom or an optionally substituted alkyl group
  • Y represents an oxygen atom or a sulfur atom.
  • R 3 and R 4 are the same or different and each represents a hydrogen atom, a halogen atom, a sulfonyl group, an optionally substituted alkyl group, or an optionally substituted aryl group.
  • R 5 and R 6 are the same or different and each represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group.
  • X represents an anion.
  • n represents 1 or 2, and is 1 when R 2 is a group represented by the general formula (3A) or (3C), and 2 when R 2 is a group represented by the general formula (3B).
  • Item 2 The dithienophosphorine compound according to Item 1, wherein R 1 in the general formula (1) is a group represented by the general formula (2A).
  • Item 3 The dithienophosphorine according to Item 2, wherein in the general formula (1), R 7 is an aryl group which may be substituted.
  • Item 4 The dithienophosphorine compound according to any one of Items 1 to 3, wherein, in the general formula (1), R 2 is a group represented by the general formula (3A), and n is 1.
  • Item 5 The dithienophosphorine compound according to Item 4, wherein Y in the general formula (1) is an oxygen atom.
  • Item 6 The dithienophosphorine compound according to Item 4 or 5, wherein, in the general formula (1), R 8 is an optionally substituted aryl group.
  • Item 7. The dithienophosphorine compound according to any one of Items 1 to 6, wherein in the general formula (1), R 3 and R 4 are both hydrogen atoms.
  • Item 8 The dithienophosphorine compound according to any one of Items 1 to 7, wherein, in the general formula (1), R 5 and R 6 are the same or different and each is a hydrogen atom or an optionally substituted alkyl group.
  • Item 9 The dithienophosphorine compound according to any one of Items 1 to 8, which has an absorption maximum wavelength at 650 to 850 nm.
  • Item 10 The dithienophosphorine compound according to any one of Items 1 to 9, which has a fluorescence maximum wavelength at 750 to 1000 nm.
  • Item 11 A fluorescent dye containing the dithienophosphorine compound according to any one of Items 1 to 10.
  • the thiophene-containing compound of the present invention has an absorption maximum and a fluorescence maximum at a high wavelength by replacing the benzene ring portion of the rhodamine dye with a thiophene skeleton and replacing the oxygen atom in the skeleton with a phosphorus-containing group, and has a high fluorescence. Has quantum yield and high stability to light.
  • various groups can be introduced according to the required characteristics.
  • FIG. 4 shows an ultraviolet-visible near-infrared absorption spectrum and a fluorescence spectrum of the dithienophosphorine compound of Example 1 (compound 1 + .TFA ⁇ ) at pH 4.0.
  • FIG. 4 is an ultraviolet-visible near-infrared absorption spectrum of the dithienophosphorine compound of Example 2 (compound 6 + .TFA ⁇ ) at pH 4.0.
  • FIG. 4 shows an ultraviolet-visible near-infrared absorption spectrum and a fluorescence spectrum of the dithienophosphorine compound of Example 3 (compound 8a + .TFA ⁇ ) at pH 7.4.
  • FIG. 4 shows an ultraviolet-visible near-infrared absorption spectrum and a fluorescence spectrum of the dithienophosphorine compound of Example 1 (compound 1 + .TFA ⁇ ) at pH 4.0.
  • FIG. 4 is an ultraviolet-visible near-infrared absorption spectrum of the dithienophosphorine compound of Example 2 (compound 6 + .TF
  • FIG. 4 shows an ultraviolet-visible near-infrared absorption spectrum and a fluorescence spectrum of the dithienophosphorine compound of Example 3 (compound 8b + .TFA ⁇ ) at pH 7.4.
  • FIG. 4 shows an ultraviolet-visible near-infrared absorption spectrum and a fluorescence spectrum of the dithienophosphorine compound of Example 3 (compound 8c + .TFA ⁇ ) at pH 7.4.
  • FIG. 4 shows an ultraviolet-visible near-infrared absorption spectrum and a fluorescence spectrum of the dithienophosphorine compound of Example 3 (compound 8d + .TFA ⁇ ) at pH 7.4.
  • FIG. 4 shows an ultraviolet-visible near-infrared absorption spectrum and a fluorescence spectrum of the dithienophosphorine compound of Example 3 (compound 8d + .TFA ⁇ ) at pH 7.4.
  • Example 4 is an ultraviolet-visible near-infrared absorption spectrum of the dithienophosphorine compound of Example 4 (compound 11 + .TFA ⁇ ) at pH 4.0.
  • 2 is a graph showing the transition of relative absorbance with the irradiation time of ICG and the dithienophosphorine compound of Example 1 (compound 1 + .TFA ⁇ ).
  • Dithienothiophene phospholine compound of Example 3 (Compound 8a + ⁇ TFA -, 8b + ⁇ TFA -, 8c + ⁇ TFA -, and 8d + ⁇ TFA -) and a graph showing a change in the relative absorbance due to the irradiation time of ICG It is.
  • FIG. 2 is a graph showing the change in absorbance of the dithienophosphorine compound of Example 1 (compound 1 + .TFA ⁇ ) with pH.
  • (A) shows the change in absorption spectrum with pH
  • (b) shows the change in absorbance with pH.
  • 2 is a graph showing the change in absorbance of the dithienophosphorine compound of Example 2 (compound 6 + .TFA ⁇ ) with pH.
  • (A) shows the change in absorption spectrum with pH
  • (b) shows the change in absorbance with pH.
  • 4 is a graph showing the change in absorbance of the dithienophosphorine compound of Example 3 (compound 8a + .TFA ⁇ ) with pH.
  • (A) shows the change in absorption spectrum with pH
  • (b) shows the change in absorbance with pH
  • 4 is a graph showing the change in absorbance of the dithienophosphorine compound of Example 4 (compound 11 + .TFA ⁇ ) with pH.
  • (A) shows changes in absorption spectrum with pH
  • (b) and (c) show changes in absorbance with pH.
  • the thiophene compound of the present invention has the general formula (1):
  • R 1 represents the general formula (2A) or (2B):
  • R 7 is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted aryl group, or a substituted group;
  • Ar represents an optionally substituted aromatic hydrocarbon ring or an optionally substituted heteroaromatic ring.
  • R 2 is the general formula (3A), (3B) or (3C):
  • R 8 is the same or different and is a hydroxy group, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkenyl group, or an optionally substituted alkynyl group.
  • R 9 represents a hydrogen atom or an optionally substituted alkyl group
  • Y represents an oxygen atom or a sulfur atom.
  • R 3 and R 4 are the same or different and each represents a hydrogen atom, a halogen atom, a sulfonyl group, an optionally substituted alkyl group, or an optionally substituted aryl group.
  • R 5 and R 6 are the same or different and each represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group.
  • X represents an anion.
  • n represents 1 or 2, and is 1 when R 2 is a group represented by the general formula (3A) or (3C), and 2 when R 2 is a group represented by the general formula (3B).
  • It is a dithienophosphorine compound represented by these.
  • the dithienophosphorine compound represented by the general formula (1) is a novel compound not described in any literature.
  • R 1 represents the general formula (2A) or (2B):
  • R 7 represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted aryl group, or a substituted group;
  • the heteroaryl group which may be sufficient is shown.
  • Ar represents an aromatic hydrocarbon ring which may be substituted or a heteroaromatic ring which may be substituted. ] It is group represented by these.
  • alkyl group represented by R 7 either a linear alkyl group or a branched alkyl group can be employed.
  • a linear alkyl group having 1 to 6 carbon atoms (particularly 1 to 4) is preferable.
  • a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, n -A hexyl group etc. are mentioned.
  • branched alkyl group a branched alkyl group having 3 to 6 carbon atoms (particularly 3 to 5) is preferable.
  • Examples of the substituent that the alkyl group represented by R 7 may have include, for example, a hydroxy group, a halogen atom described later, an alkoxy group described later, an alkenyl group described later, an alkynyl group described later, an aryl group described later, Heteroaryl group, carboxy group, amide group (dimethylamide group, diethylamide group, acetamido group, etc.), ester group (methoxycarbonyl group, ethoxycarbonyl group, etc.) and the like.
  • the number in the case of having a substituent is not particularly limited and is preferably 1 to 6, more preferably 1 to 3.
  • the alkenyl group represented by R 7 is preferably an alkenyl group having 2 to 6 (particularly 2 to 4) carbon atoms, and examples thereof include a vinyl group, an allyl group, a 1-butenyl group, and a 2-butenyl group.
  • alkenyl group represented by R 7 may have include, for example, a hydroxy group, a halogen atom described below, the above alkyl group, an alkoxy group described below, an alkenyl group described below, an alkynyl group described below, and an aryl described below. Groups, heteroaryl groups described later, carboxy groups, amide groups (dimethylamide groups, diethylamide groups, acetamide groups, etc.), ester groups (methoxycarbonyl groups, ethoxycarbonyl groups, etc.) and the like.
  • the number in the case of having a substituent is not particularly limited and is preferably 1 to 6, more preferably 1 to 3.
  • the alkynyl group represented by R 7 is preferably an alkynyl group having 2 to 6 carbon atoms (particularly 2 to 4 carbon atoms), such as ethynyl group, 1-propynyl group, propargyl group, 1-butynyl group, 2-butynyl group and the like. Is mentioned.
  • alkynyl group represented by R 7 may have include, for example, a hydroxy group, a halogen atom described below, the above alkyl group, an alkoxy group described below, the alkenyl group, the alkynyl group, and an aryl group described below. And a later-described heteroaryl group, carboxy group, amide group (dimethylamide group, diethylamide group, acetamide group, etc.), ester group (methoxycarbonyl group, ethoxycarbonyl group, etc.) and the like.
  • the number in the case of having a substituent is not particularly limited and is preferably 1 to 6, more preferably 1 to 3.
  • any of a monocyclic aryl (phenyl group) group and a polycyclic aryl group can be employed.
  • Examples of the substituent that the aryl group represented by R 7 may have include, for example, a hydroxy group, a halogen atom described later, the alkyl group, an alkoxy group described later, the alkenyl group, the alkynyl group, the aryl group, Examples thereof include a heteroaryl group, a carboxy group, an amide group (dimethylamide group, diethylamide group, acetamide group, etc.), an ester group (methoxycarbonyl group, ethoxycarbonyl group, etc.) and the like described later.
  • the number in the case of having a substituent is not particularly limited and is preferably 1 to 6, more preferably 1 to 3.
  • heteroaryl group represented by R 7 examples include a thienyl group, a furyl group, a pyridyl group, and the like.
  • Examples of the substituent that the heteroaryl group represented by R 7 may have include, for example, a hydroxy group, a halogen atom described later, the alkyl group, an alkoxy group described later, the alkenyl group, the alkynyl group, and the aryl group. And the above heteroaryl group, carboxy group, amide group (dimethylamide group, diethylamide group, acetamide group, etc.), ester group (methoxycarbonyl group, ethoxycarbonyl group, etc.) and the like.
  • the number in the case of having a substituent is not particularly limited and is preferably 1 to 6, more preferably 1 to 3.
  • an aryl group which may be substituted is preferable from the viewpoint of having a higher fluorescence quantum yield and facilitating recognition during bioimaging, and an optionally substituted monocyclic aryl Group (optionally substituted phenyl group) is more preferable, monocyclic aryl group having a substituent at ortho position (phenyl group having a substituent at ortho position) is more preferable, o-tolyl group, 2,6- A dimethoxyphenyl group and the like are particularly preferable.
  • any of a monocyclic aromatic hydrocarbon ring (benzene ring) and a polycyclic aromatic hydrocarbon ring can be adopted.
  • Examples of the substituent that the aromatic hydrocarbon ring represented by Ar may have include, for example, a hydroxy group, a halogen atom described later, the alkyl group, an alkoxy group described later, the alkenyl group, the alkynyl group, and the aryl.
  • the number in the case of having a substituent is not particularly limited and is preferably 1 to 6, more preferably 1 to 3.
  • heteroaromatic ring represented by Ar examples include a thiophene ring, a furan ring, and a pyridine ring.
  • Examples of the substituent that the heteroaromatic ring represented by Ar may have include, for example, a hydroxy group, a halogen atom described later, the alkyl group, an alkoxy group described later, the alkenyl group, the alkynyl group, the aryl group, Examples include the heteroaryl group, carboxy group, amide group (dimethylamide group, diethylamide group, acetamido group, etc.), ester group (methoxycarbonyl group, ethoxycarbonyl group, etc.) and the like.
  • the number in the case of having a substituent is not particularly limited and is preferably 1 to 6, more preferably 1 to 3.
  • Ar is preferably an aromatic hydrocarbon ring which may be substituted from the viewpoint of having a higher fluorescence quantum yield and making it easier to recognize during bioimaging.
  • a ring aromatic hydrocarbon ring (an optionally substituted benzene ring) is more preferable.
  • R 1 is preferably a group represented by the general formula (2A) from the viewpoint of easier synthesis.
  • R 1 is a group represented by the general formula (2B) it is expected that a function of switching fluorescence properties (on / off) by ring opening and ring closing will appear.
  • R 2 represents the general formula (3A), (3B) or (3C):
  • R 8 is the same or different and is a hydroxy group, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkenyl group, or an optionally substituted alkynyl group.
  • R 9 represents a hydrogen atom or an optionally substituted alkyl group.
  • Y represents an oxygen atom or a sulfur atom.
  • alkyl group alkenyl group, alkynyl group, aryl group and heteroaryl group represented by R 8 , those described above can be adopted.
  • the kind and number of substituents are the same.
  • an alkoxy group having 1 to 6 (particularly 1 to 4) carbon atoms is preferable.
  • a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentoxy group, and n-hexoxy group is preferable.
  • Examples of the substituent that the alkoxy group represented by R 8 may have include, for example, a hydroxy group, a halogen atom described later, the alkyl group, the alkoxy group, the alkenyl group, the alkynyl group, the aryl group, and the above. Examples include heteroaryl group, carboxy group, amide group (dimethylamide group, diethylamide group, acetamido group, etc.), ester group (methoxycarbonyl group, ethoxycarbonyl group, etc.) and the like.
  • the number in the case of having a substituent is not particularly limited and is preferably 1 to 6, more preferably 1 to 3.
  • an optionally substituted aryl group is preferable, an optionally substituted monocyclic aryl group (an optionally substituted phenyl group) is more preferable, and an unsubstituted phenyl group is further preferable.
  • alkyl group represented by R 9 those described above can be adopted.
  • the kind and number of substituents are the same.
  • Y may be either an oxygen atom or a sulfur atom, but an oxygen atom is preferred from the viewpoint of higher water solubility and ease of use during bioimaging.
  • the absorption maximum wavelength and the fluorescence maximum wavelength can be made longer, and furthermore, the electron withdrawing property is higher, and the HOMO level (the energy level of the highest occupied orbit)
  • the group represented by the general formula (3A) or (3B) is preferable from the viewpoint of easily improving the stability to light because the LUMO level (the energy level of the lowest orbital orbit) is more easily reduced.
  • a group represented by the formula (3A) is more preferable.
  • examples of the halogen atom represented by R 3 and R 4 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable from the viewpoint of further improving light resistance.
  • the sulfonyl group represented by R 3 and R 4 includes not only a sulfo group (a group represented by —SO 3 H) but also a methanesulfonyl group, an ethanesulfonyl group, a phenylsulfonyl group, p -Toluenesulfonyl group, trifluoromethanesulfonyl group, etc. are also mentioned.
  • R 3 and R 4 a hydrogen atom is preferable from the viewpoint of easier synthesis.
  • alkyl group alkenyl group and aryl group represented by R 5 and R 6 , those described above can be adopted.
  • the kind and number of substituents are the same.
  • R 5 and R 6 are easy to synthesize, easily cationized, and can acquire high stability in a wider pH range, and have longer absorption maximum wavelengths and fluorescence maximum wavelengths.
  • a hydrogen atom or an alkyl group is more preferable.
  • R 5 and R 6 are alkyl groups, even when R 5 and R 6 are hydrogen atoms, the absorption maximum wavelength and the fluorescence maximum wavelength can be further increased, and a wider range High stability without decomposition in the pH range.
  • R 5 and R 6 are alkyl groups, they have high stability without being decomposed even in the neutral region (about pH 6 to 8) that is usually used for bioimaging. Can be maintained. Therefore, in the dithienophosphorine compound of the present invention, compounds in which R 5 and R 6 are alkyl groups are particularly useful for bioimaging applications.
  • examples of the anion represented by X include halogen ions (fluoride ions, chloride ions, bromide ions, iodide ions, etc.), cyanide ions, acetate ions, trifluoroacetate ions, and the like.
  • N the number of moles of the anion is a 2 for group R 2 is in the case of the group represented by the general formula (3A) or (3C) of 1, R 2 is represented by the general formula (3B) is there.
  • the dithienophospholine compound of the present invention that satisfies such conditions is easier to synthesize, has higher light resistance and water solubility, has a higher fluorescence quantum yield, and has a wider range of pH values. From the viewpoint of achieving high stability, making it easier to increase the absorption maximum wavelength and the fluorescence maximum wavelength, and making it easier to recognize during bioimaging, the general formula (1A):
  • R 2 , R 3 , R 4 , R 7 , X and n are the same as defined above.
  • R 5a and R 6a are the same or different and each represents an optionally substituted alkyl group.
  • the dithienophosphorine compound represented by these is more preferable.
  • dithienophosphorine compound of the present invention examples include, for example,
  • a dithienophosphorine compound represented by the above formula is more preferred.
  • the dithienophosphorine compound of the present invention can have an absorption maximum wavelength of preferably 650 to 850 nm, more preferably 700 to 800 nm, and a fluorescence maximum wavelength of 750 to 1000 nm, more preferably 800 to 950 nm.
  • the light resistance can be drastically improved over conventional fluorescent dyes in the pH range of about 3-12. Therefore, it is possible to dramatically improve the light resistance compared to the ICG while making the absorption maximum wavelength and the fluorescence maximum wavelength as long as the conventional ICG. For this reason, it is possible to increase the absorption maximum wavelength and the fluorescence maximum wavelength even compared with conventional fluorescent dyes, and it is useful for applications such as a fluorescent probe for bioimaging and a fluorescent material for organic EL elements.
  • R 5 and R 6 are alkyl groups
  • the absorption maximum wavelength and the fluorescence maximum wavelength can be further increased even when R 5 and R 6 are hydrogen atoms. Furthermore, it has high stability without decomposition over a wide pH range. For this reason, when R 5 and R 6 are alkyl groups, they have high stability without being decomposed even in the neutral region (about pH 6 to 8) that is usually used for bioimaging. Can be maintained. Therefore, in the dithienophosphorine compound of the present invention, compounds in which R 5 and R 6 are alkyl groups are particularly useful for bioimaging applications.
  • the dithienophosphorine compound of the present invention may exist as a hydrate or a solvate, and any of these substances is included in the scope of the present invention.
  • the dithienophospholine compound of the present invention is not particularly limited, and can be synthesized by various methods.
  • the dithienophospholine compounds (1A) of the present invention in which R 1 is a group represented by the general formula (2A) is a group represented by the general formula (2A)
  • the dithienophospholine compound (1A2) in which R 5 and R 6 are hydrogen atoms is The following reaction formula 1:
  • R 2 , R 7 , X and n are the same as defined above.
  • X 1 is the same or different and represents a halogen atom.
  • R 10 is the same or different and represents an optionally substituted aryl group.
  • examples of the halogen atom represented by X 1 include a chlorine atom, a bromine atom, and an iodine atom, and a bromine atom is preferable from the viewpoint of yield.
  • dithienophosphorine compound (1A1) of the present invention in which R 1 is a group represented by the general formula (2A) and R 5 and R 6 are optionally substituted alkyl groups has the following reaction Formula 2:
  • compound (4) can be obtained by reacting compound (4) with an organolithium compound, then reacting with an electrophilic halogenating agent, and then adding an acid.
  • Compound (4) can be synthesized, for example, according to a report (Angew. Chem. Int. Ed. 2013, 52, 8990-8994.).
  • Examples of the organic lithium compound include alkyllithium such as ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, pentyllithium, and hexyllithium; and cycloalkyl such as cyclohexyllithium.
  • Lithium One or two or more kinds of aryllithium such as phenyllithium may be used. Among these, in this step, alkyllithium is preferable and sec-butyllithium is more preferable from the viewpoint of yield.
  • the amount of the organic lithium compound used is usually preferably from 1 to 10 mol, more preferably from 2 to 5 mol, based on 1 mol of the compound (4), from the viewpoint of ease of synthesis, yield, and the like.
  • electrophilic halogenating agent examples include iodine (I 2 ), bromine (Br 2 ), iodine monochloride (ICl), N-iodosuccinimide (NIS), N-bromosuccinimide (NBS), 1,2- One such as diiodoethane (ICH 2 CH 2 I), 1,2-dibromoethane (BrCH 2 CH 2 Br), 1,2-dibromo-1,1,2,2-tetrachloroethane (BrCl 2 CCCl 2 Br) Or 2 or more types are mentioned.
  • the amount of the electrophilic halogenating agent to be used is generally preferably 1 to 10 mol, more preferably 2 to 5 mol, per 1 mol of compound (4).
  • the acid examples include hydrogen chloride (hydrochloric acid), sulfuric acid, hydrogen peroxide, formic acid, acetic acid, trifluoroacetic acid (TFA), trifluoroacetic anhydride, boron trifluoride diethyl ether complex, trifluoromethanesulfonic acid and the like. Or 2 or more types are mentioned.
  • the amount of the acid to be used is preferably 0.2 to 3.0 mol, more preferably 0.5 to 1.5 mol with respect to 1 mol of the compound (4), from the viewpoint of ease of synthesis, yield and the like.
  • an excess amount for example, a solvent amount can be used.
  • reaction solvents include, for example, diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran (THF), 1,4-dioxane, dimethoxyethane (DME), diglyme, cyclopentyl methyl ether (CPME), tert-butyl methyl ether ( TBME), ethers such as anisole; aromatic hydrocarbons such as benzene, toluene, and xylene, and the like. Ethers are preferable and tetrahydrofuran is more preferable from the viewpoint of ease of synthesis and yield. These reaction solvents can be used alone or in combination of two or more.
  • the reaction atmosphere can usually be an inert gas atmosphere (argon gas atmosphere, nitrogen gas atmosphere, etc.).
  • the reaction temperature can be any of heating, normal temperature, and cooling.
  • the reaction with the organolithium compound and the electrophilic halogenating agent is ⁇ 150 to 0 ° C. (particularly ⁇ 100 to ⁇ 50 ° C.).
  • the reaction with the acid is preferably carried out at -50 to 100 ° C (especially 0 to 50 ° C).
  • the reaction time is not particularly limited, and is preferably a time for which the reaction proceeds sufficiently.
  • purification can be performed according to a conventional method if necessary. Moreover, the following process can also be performed without performing a refinement
  • the compound (6) or the compound (11) can be obtained by reacting the compound represented by the formula (1) with a Suzuki-Miyaura coupling reaction.
  • the compound (8) is preferably used in an amount of 1.5 to 5.0 mol (particularly 2.0 to 3.0 mol) per mol of the compound (5) or the compound (10).
  • a palladium catalyst usually used for Suzuki-Miyaura coupling is used. Specifically, palladium acetate (Pd (OAc) 2 ), tetrakis (triphenylphosphine) palladium (0) (Pd (PPh 3 ) 4 ), palladium trifluoroacetate, palladium chloride, palladium bromide, palladium iodide, Tris (dibenzylideneacetone) dipalladium (0) (Pd 2 (dba) 3 ) and the like.
  • palladium acetate (Pd (OAc) 2 ) is used from the viewpoint of ease of synthesis and yield. preferable.
  • the amount of the palladium catalyst used is usually preferably 0.02 to 0.50 mol, more preferably 0.05 to 0.20 mol with respect to 1 mol of the compound (5) or compound (10), from the viewpoint of ease of synthesis, yield, and the like. .
  • a ligand compound can be used as necessary.
  • ligand compounds that can be used include triphenylphosphine, trimethoxyphosphine, triethylphosphine, triisopropylphosphine, tri (tert-butyl) phosphine, tri (n-butyl) phosphine, triisopropoxyphosphine, and tricyclopentylphosphine.
  • Tricyclohexylphosphine 2,2'-bipyridyl, diphenylphosphinomethane, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,5-bis (diphenylphosphino) ) Pentane, 1,5-cyclooctadiene, 2,2′-bis (diphenylphosphino) -1,1′-binaphthyl (BINAP) and the like.
  • 2,2'-bis (diphenylphosphino) -1,1'-binaphthyl is preferable in this step from the viewpoint of yield and ease of synthesis.
  • the amount of the ligand compound used is usually preferably from 0.5 to 5.0 mol, more preferably from 1.0 to 3.0 mol, based on 1 mol of the palladium catalyst, from the viewpoint of ease of synthesis, yield, and the like.
  • a base can be used as necessary.
  • the base include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, potassium phosphate, sodium acetate and the like.
  • cesium carbonate is used from the viewpoint of yield and ease of synthesis. preferable.
  • the amount used is preferably 1 to 5 mol, more preferably 1.5 to 3 mol with respect to 1 mol of compound (5) or compound (10) from the viewpoint of ease of synthesis, yield and the like. preferable.
  • the reaction can usually be performed in the presence of a reaction solvent.
  • the reaction solvent that can be used include diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran (THF), 1,4-dioxane, dimethoxyethane (DME), diglyme, cyclopentyl methyl ether (CPME), tert-butyl methyl ether ( TBME), ethers such as anisole; aromatic hydrocarbons such as benzene, toluene and xylene; nitrile solvents such as acetonitrile; amide solvents such as dimethylformamide, etc., from the viewpoint of ease of synthesis, yield, etc. Aromatic hydrocarbons are preferred, and toluene is more preferred. These reaction solvents can be used alone or in combination of two or more.
  • the reaction atmosphere can usually be an inert gas atmosphere (argon gas atmosphere, nitrogen gas atmosphere, etc.).
  • the reaction temperature can be any of heating, room temperature and cooling, and it is usually preferably 0 to 150 ° C. (especially 50 to 100 ° C.).
  • the reaction time is not particularly limited, and is preferably a time for which the reaction proceeds sufficiently.
  • purification can be performed according to a conventional method if necessary. Moreover, the following process can also be performed without performing a refinement
  • compound (9) or compound (10) can be obtained by reacting compound (5) with a dialkylamine compound.
  • the dialkylamine compound is preferably a dithienophospholine compound (1A1) or dithienophospholine compound (1A3) according to the present invention in which desired R 5a and, if necessary, R 6a can be introduced, dimethylamine, diethylamine , Di (n-propyl) amine, diisopropylamine, di (n-butyl) amine, diisobutylamine, di (sec-butyl) amine, di (tert-butyl) amine, methylethylamine, isopropylethylamine, etc. From the viewpoint of ease of synthesis, diethylamine is preferable.
  • the amount of the dialkylamine compound used is preferably an excess amount relative to the compound (5) from the viewpoint of yield and the like, and can also be a solvent amount.
  • the reaction can usually be performed in the presence of a reaction solvent.
  • the reaction solvent that can be used include ethers such as dibutyl ether, diisopropyl ether, 1,4-dioxane, dimethoxyethane (DME), and diglyme; aromatic hydrocarbons such as toluene and xylene; amide solvents such as dimethylformamide From the viewpoints of ease of synthesis, yield, etc., amide solvents are preferred, and dimethylformamide is more preferred.
  • ethers such as dibutyl ether, diisopropyl ether, 1,4-dioxane, dimethoxyethane (DME), and diglyme
  • aromatic hydrocarbons such as toluene and xylene
  • amide solvents such as dimethylformamide From the viewpoints of ease of synthesis, yield, etc., amide solvents are preferred, and dimethylformamide is more preferred.
  • These reaction solvents can be used alone or in combination of two
  • the reaction atmosphere can usually be an inert gas atmosphere (argon gas atmosphere, nitrogen gas atmosphere, etc.).
  • the reaction temperature can be any of heating, room temperature and cooling, and it is usually preferably 50 to 150 ° C. (especially 80 to 130 ° C.). When reacted at a high temperature (100 to 150 ° C., etc.), compound (9) is obtained, and when reacted at a low temperature (50 to 100 ° C., etc.), compound (10) is obtained.
  • the reaction time is not particularly limited, and is preferably a time for which the reaction proceeds sufficiently.
  • purification can be performed according to a conventional method if necessary. Moreover, the following process can also be performed without performing a refinement
  • Grignard reagent those capable of introducing a desired R 7 in the dithienophospholine compound (1A2) or dithienophospholine compound (1A3) of the present invention are preferable, and R 7 MgX 2 (R 7 is the same as above) X 2 represents a halogen atom).
  • halogen atom represented by X 2 those described above can be adopted. The same applies to preferred embodiments.
  • Grignard reagents that satisfy these conditions include:
  • organolithium compound those capable of introducing the desired R 7 in the dithienophospholine compound (1A2) or dithienophospholine compound (1A3) of the present invention are preferable, and R 7 Li (R 7 is the same as above) .) Is preferred.
  • organolithium compounds that satisfy these conditions include:
  • the amount of the organometallic nucleophile used is preferably 0.2 to 30.0 mol (especially 0.5 to 15.0 mol) with respect to 1 mol of compound (6) or compound (11) from the viewpoint of yield and the like.
  • it is preferably used in a large amount (5.0 to 30.0 mol, etc.), and when it is intended to obtain the compound (1A3), it is preferably used in a small amount (0.2 to 5.0 mol, etc.). preferable.
  • Examples of the acid reagent that can be used include hydrogen chloride (hydrochloric acid), sulfuric acid, formic acid, acetic acid, trifluoroacetic acid (TFA), trifluoroacetic anhydride, boron trifluoride diethyl ether complex, trifluoromethanesulfonic acid, and the like.
  • the amount of the acid reagent to be used is preferably 0.2 to 3.0 mol, more preferably 0.5 to 1.5 mol, relative to 1 mol of compound (6), from the viewpoint of ease of synthesis, yield and the like.
  • the acid reagent is a liquid, it may be in an excess amount, for example, a solvent amount.
  • reaction can usually be performed in the presence of a reaction solvent.
  • reaction solvents include diethyl ether, dibutyl ether, diisopropyl ether, tetrahydrofuran (THF), 1,4-dioxane, dimethoxyethane (DME), diglyme, cyclopentyl methyl ether (CPME), tert-butyl methyl ether ( TBME), ethers such as anisole; aromatic hydrocarbons such as benzene, toluene, and xylene, and the like. Ethers are preferable and tetrahydrofuran is more preferable from the viewpoint of ease of synthesis and yield. These reaction solvents can be used alone or in combination of two or more.
  • the reaction atmosphere can usually be an inert gas atmosphere (argon gas atmosphere, nitrogen gas atmosphere, etc.).
  • the reaction temperature can be any of heating, room temperature, and cooling, and it is usually preferably -50 to 150 ° C (particularly 0 to 100 ° C).
  • the reaction time is not particularly limited, and is preferably a time for which the reaction proceeds sufficiently.
  • the dithienophosphorine compound (1A2) or dithienophospholine compound (1A3) of the present invention can be obtained by purifying according to a conventional method if necessary.
  • this process is not limited only to the above, but the compound (6) or the compound (11) is reacted with a first acid reagent (hydrochloric acid, etc.) to give a general formula (7) or (12):
  • R 2 , R 3 , R 4 and R 5a are the same as defined above.
  • the compound represented by formula (1) the compound (7) or the compound (12) is reacted with a Grignard reagent, and then reacted with a second acid reagent (hydrochloric acid, trifluoroacetic acid, etc.). It is also possible to obtain a dithienophosphorine compound (1A2) or a dithienophospholine compound (1A3).
  • the anion contained in the second acid reagent constitutes the anion X of the dithienophosphorine compound (1A2) or dithienophospholine compound (1A3) of the present invention.
  • organic halogen compound examples include one or more halogenated silanes such as trichlorosilane, diphenyldichlorosilane, and triphenylchlorosilane.
  • the amount of the organic halogen compound used is preferably from 2.0 to 20.0 mol, more preferably from 3.0 to 10.0 mol, based on 1 mol of the compound (9), from the viewpoint of ease of synthesis, yield and the like.
  • the amount of the acid reagent to be used is preferably 0.2 to 3.0 mol, more preferably 0.5 to 1.5 mol, per 1 mol of compound (9), from the viewpoints of ease of synthesis, yield and the like.
  • the acid reagent is a liquid, it may be in an excess amount, for example, a solvent amount.
  • reaction can usually be performed in the presence of a reaction solvent.
  • reaction solvents include diethyl ether, dibutyl ether, diisopropyl ether, tetrahydrofuran (THF), 1,4-dioxane, dimethoxyethane (DME), diglyme, cyclopentyl methyl ether (CPME), tert-butyl methyl ether ( TBME), ethers such as anisole; aromatic hydrocarbons such as benzene, toluene, and xylene, and the like. Ethers are preferable and cyclopentylmethyl ether (CPME) is more preferable from the viewpoint of ease of synthesis and yield.
  • reaction solvents can be used alone or in combination of two or more.
  • the reaction atmosphere can usually be an inert gas atmosphere (argon gas atmosphere, nitrogen gas atmosphere, etc.).
  • the reaction temperature can be any of heating, room temperature, and cooling, and it is usually preferably -50 to 150 ° C (particularly 0 to 100 ° C).
  • the reaction time is not particularly limited, and is preferably a time for which the reaction proceeds sufficiently.
  • the dithienophosphorine compound (1A1) of the present invention can be obtained by purifying according to a conventional method if necessary.
  • the dithienophospholine compound (1A) of the present invention is not limited to the above method, and may be produced by various methods. Can do.
  • the dithienophospholine compound of the present invention in which R 1 is a group represented by the general formula (2B) is, for example, a Grignard derived from an o-halogenated alkyl benzoate (such as methyl o-bromobenzoate).
  • a Grignard derived from an o-halogenated alkyl benzoate such as methyl o-bromobenzoate.
  • Fluorescent dye contains the above-described dithienophosphorine compound of the present invention.
  • the fluorescent dye of the present invention has an absorption maximum wavelength of preferably 650 to 850 nm, more preferably 700 to 800 nm because the benzene ring portion of the rhodamine dye is replaced with a thiophene skeleton and the oxygen atom in the skeleton is replaced with a phosphorus-containing group. It can have a fluorescence maximum wavelength in the range of 750 to 1000 nm, more preferably 800 to 950 nm, and dramatically improve the light resistance over conventional fluorescent dyes in the pH range of about 3 to 12. Is possible.
  • the fluorescent dye of the present invention is particularly useful for uses such as a fluorescent probe for bioimaging and a fluorescent material for organic EL elements.
  • the dithienophosphorine compound of the present invention has a high absorption wavelength and a fluorescence maximum wavelength that are not found in conventional fluorescent dyes having an absorption maximum wavelength and a fluorescence maximum wavelength in a high wavelength region.
  • the fluorescent dye of the present invention When used for bioimaging applications, it is preferably dissolved in an organic solvent to form a solution.
  • the content of the dithienophosphorine compound of the present invention is 1 ⁇ 10 ⁇ 8 to 1 ⁇ 10 ⁇ 4 mol / L is preferable, and 1 ⁇ 10 ⁇ 7 to 1 ⁇ 10 ⁇ 5 mol / L is more preferable.
  • content of a dithienophosphorin compound can be restrained low.
  • the organic solvent that can be used is not particularly limited, and either a polar solvent or a nonpolar solvent can be used.
  • polar solvents examples include ether compounds (tetrahydrofuran, anisole, 1,4-dioxane, cyclopentyl methyl ether, etc.), alcohols (methanol, ethanol, allyl alcohol, etc.), ester compounds (ethyl acetate, etc.), ketones (acetone, etc.) , Halogenated hydrocarbons (dichloromethane, chloroform), dimethyl sulfoxide, amide solvents (N, N-dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, etc.) .
  • nonpolar solvent examples include aliphatic organic solvents such as pentane, hexane, cyclohexane and heptane; aromatic solvents such as benzene, toluene, xylene and mesitylene.
  • Buffers Hepes buffer, Tris buffer, tricine-sodium hydroxide buffer, phosphate buffer, phosphate buffered saline, etc. are used to adjust the pH of the cell detection agent of the present invention. You can also
  • LC-Forte / R (YMC Technos Co., Ltd.) or Nippon Analytical Industry Co., Ltd. LC-9201 was used for preparative recycling HPLC.
  • a UV-visible near-infrared spectrophotometer UV-3150 (Shimadzu Corporation) was used for the measurement of the UV-visible absorption spectrum.
  • the fluorescence spectrum was measured using a fluorometer Fluorolog-3 (HORIBA).
  • the absolute fluorescence quantum yield was measured using an absolute PL quantum yield measuring apparatus (Hamamatsu Photonics Co., Ltd.) equipped with a multichannel spectrometer PMA-12. Unless otherwise specified, the reaction was carried out under a nitrogen atmosphere using a commercially available dehydrated solvent (Kanto Chemical Co., Ltd.) purified with a Glass Contour organic solvent purifier (Nikko Hansen Co., Ltd.).
  • n-BuLi n-butyllithium.
  • THF represents tetrahydrofuran.
  • Et 2 O represents diethyl ether.
  • PhPCl 2 represents phenyldichlorophosphine.
  • sec-BuLi represents sec-butyllithium.
  • Ph 2 C ⁇ NH represents benzophenone imine.
  • Pd (OAc) 2 represents palladium acetate.
  • BINAP represents 2,2′-bis (diphenylphosphino) -1,1′-binaphthyl. Ph represents a phenyl group. The same applies hereinafter. ]
  • a tetrahydrofuran (THF) solution (0.27M, 2.10 mL) of 2,6-dimethoxyphenyllithium prepared from 2,6-dimethoxybromobenzene was added, and the temperature was slowly returned to room temperature.
  • 0.2% aqueous trifluoroacetic acid (TFA) solution (10 mL) was added, and the mixture was stirred for 1 hour.
  • n-BuLi n-butyllithium.
  • THF represents tetrahydrofuran.
  • Et 2 O represents diethyl ether.
  • PhPCl 2 represents phenyldichlorophosphine. Ph represents a phenyl group.
  • sec-BuLi represents sec-butyllithium.
  • Et 2 NH represents diethylamine.
  • DMF represents dimethylformamide.
  • CPME represents cyclopentyl methyl ether.
  • iPr represents an isopropyl group. The same applies hereinafter.
  • the reaction mixture was heated to 70 ° C. and stirred for 18 hours. The mixture was then cooled to room temperature and 34.5% aqueous H 2 O 2 (0.05 mL) was added. After stirring for 5 minutes, the reaction was quenched with Na 2 SO 3 aqueous solution. The resulting solution was extracted with CHCl 3 and the solvent was removed under reduced pressure. The resulting solid was purified by reverse phase HPLC (YMC-DispoPack AT, 30/80 to 80/20 CH 3 CN / H 2 O containing 0.1% TFA as eluent). The eluent was extracted with CHCl 3 . The solvent was removed from the combined solution under reduced pressure.
  • the reaction mixture was heated to 70 ° C. and stirred for 13 hours. The mixture was then cooled to room temperature and 34.5% aqueous H 2 O 2 (0.1 mL) was added. After stirring for 5 minutes, the reaction was quenched with Na 2 SO 3 aqueous solution. The resulting solution was extracted with CHCl 3 and the solvent was removed under reduced pressure. The resulting solid was purified by reverse phase HPLC (YMC-DispoPack AT, 30/80 to 80/20 CH 3 CN / H 2 O containing 0.1% TFA as eluent). The eluent was extracted with CHCl 3 . The solvent was removed from the combined solution under reduced pressure.
  • the resulting solution was extracted with CHCl 3 and the solvent was removed under reduced pressure.
  • the resulting solid was purified by reverse phase HPLC (YMC-DispoPack AT, 30/80 to 80/20 CH 3 CN / H 2 O containing 0.1% TFA as eluent).
  • the eluent was extracted with CHCl 3 .
  • the solvent was removed from the combined solution under reduced pressure.
  • the resulting solid was purified by reverse phase HPLC (YMC-Actus Triart, 30/80 to 80/20 CH 3 CN / H 2 O containing 0.1% TFA as eluent), and compound 8d + ⁇ TFA - was obtained as a green solid. Obtained (25.5 mg, 34.3 ⁇ mol, 39%).
  • Ph represents a phenyl group.
  • Et 2 NH represents diethylamine.
  • DMF represents dimethylformamide.
  • Ph 2 C ⁇ NH represents benzophenone imine.
  • Pd (OAc) 2 represents palladium acetate.
  • BINAP represents 2,2′-bis (diphenylphosphino) -1,1′-binaphthyl.
  • THF represents tetrahydrofuran. The same applies hereinafter.
  • the resulting solution was extracted with CHCl 3 and the solvent was removed under reduced pressure.
  • the resulting solid was purified by reverse phase HPLC (YMC-DispoPack AT, 30/80 to 80/20 CH 3 CN / H 2 O containing 0.1% TFA as eluent).
  • the eluent was extracted with CHCl 3 .
  • the solvent was removed from the combined solution under reduced pressure.
  • the resulting solid was purified by reverse phase HPLC (YMC-Actus Triart, 30/80 to 80/20 CH 3 CN / H 2 O containing 0.1% TFA as eluent), and compound 11 + • TFA - was obtained as a green solid. Obtained (11.3 mg, 19.2 ⁇ mol, 21%).
  • the dithienophosphorine compound of the present invention can increase the absorption maximum wavelength and the fluorescence maximum wavelength to the same extent as ICG, which is a typical near-infrared fluorescent dye, and the fluorescence quantum yield. Can be understood to be sufficiently high.
  • the measurement was carried out by measuring the absorbance immediately after irradiation (A 0 ) and the absorbance after a certain period of time (A), and evaluating A / A 0 as the maintenance rate.
  • DMSO dimethyl sulfoxide
  • water Na 2 HPO 4 / NaH 2 PO 4
  • DMSO / water 1/99% by volume
  • ICG which is a representative near-infrared fluorescent dye
  • the dithienophosphorine compound of the present invention is high stability to light
  • compound 1 + ⁇ TFA - is the relative absorbance of about 0.95 hardly decreased absorbance even after the elapse 8 hours or more from the start of irradiation dramatically the stability under acidic conditions It can be understood that it was able to be improved.

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Abstract

L'invention concerne un colorant fluorescent qui présente un maximum d'absorption et un maximum de fluorescence à des longueurs d'onde plus élevées, qui présente un rendement quantique en fluorescence élevé et qui présente une stabilité élevée à la lumière et dans lequel différents substituants peuvent être introduits. Dans un colorant de type rhodamine, le fragment de cycle benzénique est substitué par une structure de type thiophène et un atome d'oxygène dans le squelette est substitué par un groupe contenant du phosphore, tel que représenté dans la formule générale (1) [dans laquelle R2 représente un groupe représenté par la formule générale (3A), (3B) ou (3C)].
PCT/JP2017/009490 2016-03-09 2017-03-09 Composé de dithiénophosphorine et colorant fluorescent produit à l'aide de celui-ci WO2017155042A1 (fr)

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WO2021176755A1 (fr) 2020-03-04 2021-09-10 国立大学法人京都大学 Composé de dithiénophosphorine, et matériau incolore absorbant le proche infrarouge et matériau électrochromique utilisant chacun celui-ci
WO2023219010A1 (fr) * 2022-05-13 2023-11-16 富士フイルム株式会社 Composition de résine, film, filtre optique, élément d'imagerie à l'état solide, dispositif d'affichage d'images, capteur infrarouge, module d'appareil de prise de vue, et composé
DE102022116865A1 (de) 2022-07-06 2024-01-11 PhoSuMa Photonic & Sustainable Materials Heteroaromatische ketone und ihre verwendung in der radikalischen und kationischen polymerisation

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021176755A1 (fr) 2020-03-04 2021-09-10 国立大学法人京都大学 Composé de dithiénophosphorine, et matériau incolore absorbant le proche infrarouge et matériau électrochromique utilisant chacun celui-ci
WO2023219010A1 (fr) * 2022-05-13 2023-11-16 富士フイルム株式会社 Composition de résine, film, filtre optique, élément d'imagerie à l'état solide, dispositif d'affichage d'images, capteur infrarouge, module d'appareil de prise de vue, et composé
DE102022116865A1 (de) 2022-07-06 2024-01-11 PhoSuMa Photonic & Sustainable Materials Heteroaromatische ketone und ihre verwendung in der radikalischen und kationischen polymerisation
WO2024008805A1 (fr) 2022-07-06 2024-01-11 Phosuma Photonic & Sustainable Materials Gmbh Cetones hétéroaromatiques et leur utilisation dans la polymerisation radicalaire et cationique

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