JP6638948B2 - New oxocarbon compounds - Google Patents

Description

  The present invention relates to a novel oxocarbon-based compound having a squarylium skeleton or a croconium skeleton.

  Conventionally, oxocarbon compounds having a squarylium skeleton or a croconium skeleton in the compound have been provided. These oxocarbon compounds are generally produced by using squaric acid or croconic acid as a raw material and introducing a heterocyclic group at both ends of the raw material (Patent Documents 1 to 5).

  As a compound in which pyrrole is bonded to a squarylium skeleton or a croconium skeleton, for example, there is a compound represented by the following formula disclosed in Patent Document 6 (compound 1A).

  Patent Document 7 describes a compound represented by the following formula (Example 1 and the like).

  Patent Document 8 discloses a compound represented by the following formula and the like.

  Further, Non-Patent Document 1 discloses a compound represented by the following formula and the like.

  Non-Patent Document 2 discloses a compound represented by the following formula and the like.

  Non-Patent Document 3 discloses a compound represented by the following formula.

  Further, Non-Patent Document 4 discloses a compound represented by the following formula.

Japanese Patent Application Laid-Open No. Hei 1-230674 JP 2008-308602 A JP 2011-208101 A JP 2007-169315 A JP 2008-1754 A JP 2001-183522 A JP-T-2005-520835 JP 2008-184606 A

Raymond, 2 others, "Squaraines based on 2-arylpyrroles", Tetrahedron, August 23 (2004), 60, pp 8913-8918. Luca, 14 others, “Assessment of Water-Soluble π-Extended Squaraines as One-and Two-Photon Singletted Oxygen Photon, Cancer, Cancer, J.A., 1980. Fabio, et al., "A squaraine-phthalocyanine ensemble: towards molecular pancreatic sensitizers in solar cells", Chem. Commun. , April 20 (2009), pp 4500-4502. Michael, 3 others, "Redox-Switchable Squaraines with Extended Conjugation", Org. Lett. , July 19 (2003), 5 (17), pp 2975-2978.

  However, in each of Patent Documents 6 to 8 and Non-Patent Documents 1 to 4, in compounds in which a pyrrole ring is directly bonded to a squarylium skeleton, a molecule is designed by introducing a substituent at the α-position of the pyrrole ring. However, studies on the β-position of the pyrrole ring have not been sufficiently conducted. In addition, conventional compounds sometimes have insufficient light resistance.

  Under such circumstances, the present invention provides a novel oxocarbon by introducing a new substituent at the β-position carbon of the pyrrole ring in a compound in which a pyrrole ring is directly bonded to a squarylium skeleton or a croconium skeleton. The object of the present invention is to provide a system compound. Improving light fastness is another task.

  The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, by introducing a cyclic substituent into the two β-position carbons of the pyrrole ring, a new oxo which has not been known before The present inventors have found that it is possible to obtain a carbon-based compound and that the compound is hardly deteriorated even when irradiated with light, thereby completing the present invention.

  That is, the oxocarbon compound according to the present invention is characterized by being represented by the following formula (1) having a squarylium skeleton or the following formula (2) having a croconium skeleton.

(In the formulas (1) and (2), R ^{a1 to} R ^a4 are each independently a structural unit represented by the following formula (3).)

(In equation (3),
A represents a ring structure formed by two carbon atoms at the β-position of the pyrrole ring together with other atoms;
X is a hydrogen atom or an organic group,
Y is a hydrogen atom, an electron-withdrawing group or an organic substituent,
* Represents a binding site. )

  A is an aromatic ring, an alicyclic hydrocarbon ring, at least one or more carbon atoms constituting an aromatic ring or an alicyclic hydrocarbon ring is at least one or more selected from N, S and O It is preferable that the heterocyclic ring is replaced with an atom, and that these rings are condensed with another ring. Further, it is more preferable that X is a hydrogen atom and Y is an alkyl group having 1 to 4 carbon atoms which may have a substituent or an aryl group which may have a substituent. It is an aspect.

  According to the present invention, a novel oxocarbon-based compound having excellent light resistance can be obtained.

It is a peak comparison result of Formulation 1 measured before and after the light fastness test. It is a peak comparison result of Formulation 2 measured before and after the light resistance test. It is a peak comparison result of Formulation 3 measured before and after the light fastness test. It is a peak comparison result of the prescription 4 measured before and after the light resistance test. It is a peak comparison result of the prescription 5 measured before and after the light resistance test.

<Oxocarbon compounds>
The novel oxocarbon-based compound according to the present invention is characterized by being represented by the following formula (1) having a squarylium skeleton or the following formula (2) having a croconium skeleton.

(In the formulas (1) and (2), R ^{a1 to} R ^a4 are each independently a structural unit represented by the following formula (3).)

(In equation (3),
A represents a ring structure formed by two carbon atoms at the β-position of the pyrrole ring together with other atoms;
X is a hydrogen atom or an organic group,
Y is a hydrogen atom, an electron-withdrawing group or an organic substituent,
* Represents a binding site. )

  The novel oxocarbon-based compound according to the present invention has a squarylium skeleton or a croconium skeleton, and the compound represented by the formula (1) or (2) has a conjugate relationship with these compounds, respectively. The compound may be present. Examples of the compound having a conjugate relationship include the following (1a), (1b), (2a), (2b), and (2c). Hereinafter, in the specification of the present application, a compound represented by the formula (1) (may be referred to as a compound (1)) even if an oxocarbon-based compound in which such a compound having a conjugate relationship exists. And a compound represented by the formula (2) (sometimes referred to as a compound (2)). The compound (1) includes compounds represented by the following formulas (1a) and (1b). The compound (2) also includes the following formulas (2a), (2b), and (2c).

  First, a structural unit represented by the formula (3) that can be bonded to a squarylium skeleton or a croconium skeleton will be described. In the structural unit represented by the formula (3), A is a ring structure formed by two carbon atoms at the β-position of the pyrrole ring together with other atoms. A is preferably, for example, a 5- to 7-membered ring, more preferably a 5- or 6-membered ring.

  In the following, when A is described as a ring, it is assumed that the ring includes two carbon atoms located at the β-position of the pyrrole ring.

  A is not particularly limited as long as the two carbon atoms at the β-position of the pyrrole ring form a ring together with other atoms, but is preferably an aromatic ring or an alicyclic hydrocarbon ring. As the aromatic ring, for example, an aromatic ring having 6 to 10 carbon atoms such as a benzene ring is preferable. Examples of the alicyclic hydrocarbon ring include cycloalkane having 3 to 10 carbon atoms such as cyclopentane, cyclohexane, and cycloheptane; cyclopentene, cyclopentadiene, cyclohexene, cyclohexadiene (for example, 1,3-cyclohexadiene); A monocyclic ring such as cycloalkene having 3 to 10 carbon atoms such as cycloheptene and cycloheptadiene; or bicyclo [2.2.1] pentane, bicyclo [2.2.1] penta-2-ene, bicyclo [2 2.2.2] octane, bicyclo [2.2.2] oct-2-ene, and the like, and a cyclic alkane having a bridge. Among them, an aromatic ring having 6 to 7 carbon atoms, a cycloalkane having 5 to 7 carbon atoms, a cycloalkene having 5 to 7 carbon atoms, and a cyclic alkane having 5 to 9 carbon atoms having a bridge are preferable. Also preferably, a five-membered ring (for example, cyclopentene (A-1 below) or the like), a six-membered ring (for example, cyclohexane (A-2 below), cyclohexene (A-3 below), cyclohexadiene (A-4 below)) , Bicyclo [2.2.2] octane (A-5 below), bicyclo [2.2.2] oct-2-ene (A-6 below), bicyclo [2.1.2] heptane (A- 7), bicyclo [2.1.2] hepta-2-ene (A-8 below), etc.). Among them, a structural formula selected from the following formulas (A-1) to (A-8) is preferable. In the following formulas (A-1) to (A-8), * represents a bond to the β carbon atom of the pyrrole ring, and may be any of the two β carbon atoms. The bond is bonded to two carbon atoms located at the β-position of the pyrrole ring to form a ring.

  In the ring A, at least one or more of carbon atoms constituting the above-described aromatic ring or alicyclic hydrocarbon ring (excluding a carbon atom shared with a pyrrole ring) includes N (nitrogen atom), S ( It may be a heterocycle substituted with at least one or more atoms selected from a sulfur atom) and O (oxygen atom). As such a heterocyclic ring, for example, at least one of carbon atoms constituting a cycloalkane having 5 to 7 carbon atoms or a cycloalkene having 5 to 7 carbon atoms is at least one kind selected from N, S and O A heterocyclic ring substituted with the above atoms is preferable, and more preferably, at least one or more of carbon atoms constituting cyclohexane, cyclohexene, and cyclohexadiene is at least one or more atoms selected from N, S, and O. Substituted heterocycles are preferred. The number of N, S and O per A1 ring depends on the skeleton constituting A, but is 1 or more (especially 1 to 2), and may be 2 or more (especially 2). When the number of N, S, and O contained in the ring A1 is two or more, each of N, S, and O may be the same or different. Such heterocycles include, for example, heterocycles in which the atom bonded to the carbon atom at the β-position of the pyrrole ring is N, S or O (for example, (B-1), (B-3), (B- 5) to (B-17) and the like, and heterocycles in which the other carbon atoms are N, S or O (for example, the following (B-2) and (B-4)). Among them, a structural formula selected from the following formulas (B-1) to (B-17) is preferable. In the following formulas (B-1) to (B-17), * represents a bond to the β carbon atom of the pyrrole ring, and may be any of the two β carbon atoms. The bond is bonded to two carbon atoms located at the β-position of the pyrrole ring to form a ring.

  Further, ring A may be condensed with another ring B. By condensing another ring B, the resulting oxocarbon-based compound can have a longer wavelength, which facilitates molecular design according to the color tone of the compound. For the ring B, for example, an aromatic ring, an alicyclic hydrocarbon ring, or a heterocyclic ring described in detail in the section of the ring A can be appropriately selected. Among them, an aromatic ring having 6 to 10 carbon atoms, Cycloalkanes having 5 to 10 carbon atoms, cycloalkenes having 5 to 10 carbon atoms, cyclic alkanes having 5 to 12 carbon atoms having a bridge, and at least one of carbon atoms constituting these rings has N, S And a heterocyclic ring substituted by at least one atom selected from O. In addition, what is described as a ring in the column of A is read in B as including any two adjacent carbon atoms present in A. Further, the structure exemplified using a bond is read as B in the case where the bond is bonded to any two adjacent carbon atoms present in A to form a ring.

  Examples of the ring A in which the ring B is condensed include condensed polycyclic hydrocarbons and (for example, (C-1), (C-2), (C-5), (C-6), (C- 8), (C-9), etc.) and condensed heteropolycyclic compounds (for example, (C-3), (C-4), (C-7) and the like below), among which the following formula (C- Structural formulas selected from 1) to (C-9) are preferred. In the following formulas (C-1) to (C-9), * represents a bond to the β carbon atom of the pyrrole ring, and may be any of the two β carbon atoms. The bond is bonded to two carbon atoms located at the β-position of the pyrrole ring to form a ring.

  The hydrogen atom of the ring A and / or ring B may be substituted with an electron-withdrawing group and / or an organic substituent.

  The electron withdrawing group is not particularly limited as long as it is a substituent that can be introduced by an electrophilic substitution reaction. In the electron-withdrawing group, as an index of electron-withdrawing property, a substituent constant σ of Hammett's rule and the like are known, and a functional group whose substituent constant σ of Hammett's rule is positive is regarded as an electron-withdrawing group. No. Examples of the electron-withdrawing group include halogens such as fluorine, chlorine, bromine and iodine, a cyano group, a nitro group, a thiocyanate group, a trifluoromethyl group, an acyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, Examples include a sulfo group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfamoyl group.

  Examples of the acyl group include a substituted or unsubstituted alkanoyl group such as an acetyl group, a propanoyl group, a butanoyl group, a pentanoyl group, a hexanoyl group, a heptanoyl group, an octanoyl group, a nonanoyl group, a decanoyl group, and a trifluoroacetyl group; A substituted or unsubstituted aroyl group such as a group, a 1-naphthoyl group or a 2-naphthoyl group; Among these, an acyl group having 2 to 15 carbon atoms is preferable, and an acyl group having 2 to 10 carbon atoms is more preferable.

  Examples of the alkyloxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a pentyloxycarbonyl group, a hexyloxycarbonyl group, a heptyloxycarbonyl group, an octyloxycarbonyl group, and a decyloxycarbonyl group. And a substituted or unsubstituted alkyloxycarbonyl group such as octadecyloxycarbonyl group and trifluoromethyloxycarbonyl group. The alkyl group in the alkyloxycarbonyl group may be linear or branched.

  Examples of the aryloxycarbonyl group include a phenoxycarbonyl group, a 4-dimethylaminophenyloxycarbonyl group, a 4-diethylaminophenyloxycarbonyl group, a 2-chlorophenyloxycarbonyl group, a 2-methylphenyloxycarbonyl group, and a 2-methoxyphenyl group. Oxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-fluorophenyloxy A substituted or unsubstituted phenyloxycarbonyl group such as a carbonyl group, a 4-cyanophenyloxycarbonyl group or a 4-methoxyphenyloxycarbonyl group; 1-naphthyloxy Carbonyl group, a substituted or unsubstituted naphthyl oxycarbonyl group such as a 2-naphthyloxycarbonyl group; and the like.

  Examples of the carbamoyl group include substituted or unsubstituted carbamoyl groups such as a carbamoyl group, an N-ethylcarbamoyl group, an N-phenylcarbamoyl group, an N, N-dibutylcarbamoyl group, and an N- (2-dodecyloxyethyl) carbamoyl group. Groups.

  Examples of the alkylsulfinyl group include, for example, methylsulfinyl group, ethylsulfinyl group, propylsulfinyl group, isopropylsulfinyl group, butylsulfinyl group, hexylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, octylsulfinyl group, cyanomethylsulfinyl group And a substituted or unsubstituted alkylsulfinyl group of a methoxymethylsulfinyl group or the like. The alkyl group in the alkylsulfinyl group may be linear or branched.

  Examples of the arylsulfinyl group include a phenylsulfinyl group, a 2-chlorophenylsulfinyl group, a 2-methylphenylsulfinyl group, a 2-methoxyphenylsulfinyl group, a 2-butoxyphenylsulfinyl group, a 2-fluorophenylsulfinyl group, and a 3-methyl Phenylsulfinyl, 3-chlorophenylsulfinyl, 3-trifluoromethylphenylsulfinyl, 3-cyanophenylsulfinyl, 3-nitrophenylsulfinyl, 4-methylphenylsulfinyl, 4-fluorophenylsulfinyl, 4-cyano A substituted or unsubstituted phenylsulfinyl group such as a phenylsulfinyl group, a 4-methoxyphenylsulfinyl group and a 4-dimethylaminophenylsulfinyl group; 1-naphthylsulfur Iniru group, 2-naphthylsulfinyl substituted or unsubstituted naphthylsulfinyl group such as Le group; and the like.

  Examples of the alkylsulfonyl group include, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, hexylsulfonyl, cyclohexylsulfonyl, 2-ethylhexylsulfonyl, octylsulfonyl, cyanomethylsulfonyl Group, methoxymethylsulfonyl group, trifluoromethylsulfonyl group and the like. The alkyl group in the alkylsulfonyl group may be linear or branched.

  Examples of the arylsulfonyl group include a phenylsulfonyl group, a 2-chlorophenylsulfonyl group, a 2-methylphenylsulfonyl group, a 2-methoxyphenylsulfonyl group, a 2-butoxyphenylsulfonyl group, a 2-fluorophenylsulfonyl group, and a 3-methyl Phenylsulfonyl, 3-chlorophenylsulfonyl, 3-trifluoromethylphenylsulfonyl, 3-cyanophenylsulfonyl, 3-nitrophenylsulfonyl, 3-fluorophenylsulfonyl, 4-methylphenylsulfonyl, 4-fluoro A substituted or unsubstituted phenylsulfonyl group such as a phenylsulfonyl group, a 4-cyanophenylsulfonyl group, a 4-methoxyphenylsulfonyl group, a 4-dimethylaminophenylsulfonyl group; 1-naphthylsulfo Group, a substituted or unsubstituted naphthylsulfonyl group and a 2-naphthylsulfonyl group; and the like.

The sulfamoyl group may be a monosubstituted sulfamoyl group in which one hydrogen atom in the sulfamoyl group (—SOONH ₂ ) is substituted, or a disubstituted sulfamoyl group in which two hydrogen atoms are substituted. Examples of the monosubstituted sulfamoyl group include a sulfamoyl group; N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, and N-hexylsulfamoyl. A sulfamoyl group substituted by an alkyl group such as a group, N-cyclohexylsulfamoyl group, N-octylsulfamoyl group, N-2-ethylhexylsulfamoyl group, N-decylsulfamoyl group; N-phenylsulfur Famoyl group, N-2-methylphenylsulfamoyl group, N-2-chlorophenylsulfamoyl group, N-2-methoxyphenylsulfamoyl group, N-2-isopropoxyphenylsulfamoyl group, N- 3-chlorophenylsulfamoyl group, N-3-nitrophenylsulfamoyl group, N-3- Anophenylsulfamoyl group, N-4-methoxyphenylsulfamoyl group, N-4-cyanophenylsulfamoyl group, N-4-dimethylaminophenylsulfamoyl group, N-4-methylsulfanylphenylsulfa A sulfamoyl group substituted with a substituted or unsubstituted aryl group such as a moyl group or an N-4-phenylsulfanylphenylsulfamoyl group; Examples of the disubstituted sulfamoyl group include N-methyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl group, N, N-dibutylsulfamoyl group, N, N-diphenylsulfamoyl group And the like.

  Examples of the organic substituent capable of substituting a hydrogen atom of the ring A and / or ring B include an alkyl group, an alkoxy group, a thioalkoxy group, an aryl group, an aralkyl group, an aryloxy group, an arylthiooxy group, and the like. Is mentioned.

  Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, Examples thereof include linear or branched alkyl groups such as dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and icosyl group. Among them, an alkyl group having 1 to 20 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable, and a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group or t-butyl is more preferable. And more preferably a propyl group, an isopropyl group, a butyl group, an isobutyl group or a t-butyl group, and more preferably a t-butyl group. This alkyl group may have a substituent. Examples of the substituent of the alkyl group include a halogen and an alkoxy group.

  Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, and a dodecyloxy group. , Tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy, nonadecyloxy, icosyloxy, methoxyethoxy, ethoxyethoxy and the like. Among them, an alkoxy group having 1 to 20 carbon atoms is preferable, and an alkoxy group having 1 to 10 carbon atoms is more preferable. Further, the alkyl group in the alkoxy group may be linear or branched.

  Examples of the thioalkoxy group include a methylthiooxy group, an ethylthiooxy group, a propylthiooxy group, a butylthiooxy group, a pentylthiooxy group, a hexylthiooxy group, a heptylthiooxy group, an octylthiooxy group, and a nonylthio group. Oxy, decylthiooxy, undecylthiooxy, dodecylthiooxy, tridecylthiooxy, tetradecylthiooxy, pentadecylthiooxy, hexadecylthiooxy, heptadecylthiooxy, octadecyl A thiooxy group, a nonadecylthiooxy group, an icosylthiooxy group and the like. Among these, a thioalkoxy group having 1 to 20 carbon atoms is preferable, and one having 1 to 10 carbon atoms is more preferable. The alkyl group in the thioalkoxy group may be linear or branched.

  As the aryl group, for example, phenyl group, biphenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, indenyl group, azulenyl group, fluorenyl group, terphenyl group, quarterphenyl group, pentalenyl group, heptalenyl group, biphenylenyl Group, indacenyl group, acenaphthylenyl group, phenalenyl group, fluorenyl group, phenanthryl group and the like. Among these, an aryl group having 6 to 30 carbon atoms is preferable, and an aryl group having 6 to 15 carbon atoms is more preferable. This aryl group may have a substituent. Examples of the substituent of the aryl group include an alkyl group, an alkoxy group, a halogen, a cyano group, a nitro group, a thiocyanate group, an acyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfo group, an alkylsulfinyl group, and an aryl group. Examples include a sulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfamoyl group.

  The aralkyl group is preferably an aralkyl group having 7 to 18 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a phenylpropyl group, a phenylbutyl group, and a phenylpentyl group. This aralkyl group may have a substituent, as the substituent, an alkyl group, an alkoxy group, a halogen, a cyano group, a nitro group, a thiocyanate group, an acyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, Examples include a carbamoyl group, a sulfo group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfamoyl group.

  Examples of the aryloxy group include a phenyloxy group, a biphenyloxy group, a naphthyloxy group, an anthryloxy group, a phenanthryloxy group, a pyrenyloxy group, an indenyloxy group, an azulenyloxy group, a fluorenyloxy group, Phenyloxy group, quarter phenyloxy group, pentalenyloxy group, heptalenyloxy group, biphenylenyloxy group, indacenyloxy group, acenaphthylenyloxy group, phenalenyloxy group, fluorenyloxy Group, phenanthryloxy group and the like. Among these, an aryloxy group having 1 to 25 carbon atoms is preferable, and one having 1 to 15 carbon atoms is more preferable.

  Examples of the arylthiooxy group include a phenylthiooxy group, a biphenylthiooxy group, a naphthylthiooxy group, an anthrylthiooxy group, a phenanthrylthiooxy group, a pyrenylthiooxy group, an indenylthiooxy group, Renylthiooxy group, fluorenylthiooxy group, terphenylthiooxy group, quarterphenylphenylthiooxy group, pentalenylthiooxy group, heptalenylthiooxy group, biphenylenylthiooxy group, indacenylthiooxy group, acenaphthyleni And a luthiooxy group, a phenalenylthiooxy group, a fluorenylthiooxy group, and a phenanthrylthiooxy group. Among these, an arylthiooxy group having 1 to 25 carbon atoms is preferable, and one having 1 to 15 carbon atoms is more preferable.

  As the organic substituent, an alkyl group, an alkoxy group, a thioalkoxy group, an aryl group, and an aryloxy group are preferable, more preferably an alkyl group, and particularly when A is a poorly soluble ring such as acenaphthene, From the viewpoint of improving the solubility, a bulky group such as a t-butyl group or an isobutyl group is particularly preferable.

The bonding position of the organic substituent is not particularly limited. For example, it is preferable that the organic substituent be bonded to ring B (for example, when represented by formulas (C-1) to (C-9), R ^{c2 to} R ^c5 , R ^{c8 ~R c11, R c13 ~R c40} , R c42 ~R c47, R c50 ~R c57).

Note that R ^a1 and R ^a2 in the compound (1) having a squarylium skeleton may be the same or different. It is preferable that R ^a1 and R ^a2 are the same because of easy production. Similarly, in the compound (2) having a croconium skeleton, R ^a3 and R ^a4 may be the same or different, and it is a more preferable embodiment that they are the same.

  Next, X in Expression (3) will be described. X is a hydrogen atom or an organic group, and examples of the organic group include an alkyl group, an aryl group, an aralkyl group, an alkylsulfonyl group, an arylsulfonyl group, and an alkoxyalkyl group.

  As the alkyl group, for example, an alkyl group having 1 to 20 carbon atoms is preferable, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a tert-butyl group, and a sec-butyl group. Group, pentyl group, isopentyl group, neopentyl group, hexyl group, 2-methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, heptyl group, 2-methylhexyl group A 3-methylhexyl group, a 2,2-dimethylpentyl group, a 2,3-dimethylpentyl group, a 2,4-dimethylpentyl group, a 3-ethylpentyl group, a 2,2,3-trimethylbutyl group, an octyl group, Methylheptyl group, dimethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, trimethylpentyl group, 3-ethyl-2-methyl Rupentyl group, 2-ethyl-3-methylpentyl group, 2,2,3,3-tetramethylbutyl group, nonyl group, methyloctyl group, 3,7-dimethyloctyl group, dimethylheptyl group, 3-ethylheptyl group And 4-ethylheptyl, trimethylhexyl, 3,3-diethylpentyl, decyl, undecyl, dodecyl and the like.

  As the aryl group, for example, phenyl group, biphenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, indenyl group, azulenyl group, fluorenyl group, terphenyl group, quarterphenyl group, pentalenyl group, heptalenyl group, biphenylenyl Group, indacenyl group, acenaphthylenyl group, phenalenyl group, fluorenyl group, phenanthryl group and the like. Among these, an aryl group having 6 to 30 carbon atoms is preferable, and an aryl group having 6 to 15 carbon atoms is more preferable. This aryl group may have a substituent. Examples of the substituent of the aryl group include an alkyl group, an alkoxy group, a halogen, a cyano group, a nitro group, a thiocyanate group, an acyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfo group, an alkylsulfinyl group, and an aryl group. Examples include a sulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfamoyl group.

  The aralkyl group is preferably an aralkyl group having 7 to 18 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a phenylpropyl group, a phenylbutyl group, and a phenylpentyl group. This aralkyl group may have a substituent, as the substituent, an alkyl group, an alkoxy group, a halogen, a cyano group, a nitro group, a thiocyanate group, an acyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, Examples include a carbamoyl group, a sulfo group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfamoyl group.

  Examples of the alkylsulfonyl group include, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, hexylsulfonyl, cyclohexylsulfonyl, 2-ethylhexylsulfonyl, octylsulfonyl, cyanomethylsulfonyl Group, methoxymethylsulfonyl group, trifluoromethylsulfonyl group and the like. The alkyl group in the alkylsulfonyl group may be linear or branched.

  Examples of the arylsulfonyl group include a phenylsulfonyl group, a 2-chlorophenylsulfonyl group, a 2-methylphenylsulfonyl group, a 2-methoxyphenylsulfonyl group, a 2-butoxyphenylsulfonyl group, a 2-fluorophenylsulfonyl group, and a 3-methyl Phenylsulfonyl, 3-chlorophenylsulfonyl, 3-trifluoromethylphenylsulfonyl, 3-cyanophenylsulfonyl, 3-nitrophenylsulfonyl, 3-fluorophenylsulfonyl, 4-methylphenylsulfonyl, 4-fluoro A substituted or unsubstituted phenylsulfonyl group such as a phenylsulfonyl group, a 4-cyanophenylsulfonyl group, a 4-methoxyphenylsulfonyl group, a 4-dimethylaminophenylsulfonyl group; 1-naphthylsulfo Group, a substituted or unsubstituted naphthylsulfonyl group and a 2-naphthylsulfonyl group; and the like.

  Examples of the alkoxyalkyl group include the following formula (5):

(Wherein, Z ¹ and Z ² are each independently an alkylene group, Z ³ is an alkyl group, and n represents an integer of 0 to 4).
Z ¹ and Z ² are preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 to 5 carbon atoms. To illustrate the preferred alkylene group _{include, -CH 2 -, - CH 2} CH 2 -, - CH 2 CH 2 CH 2 -, - CH 2 CH 2 CH 2 CH 2 -, - CH (CH 2) CH 2 - _{, -CH (C 2 H 5)} CH 2 -, - C (CH 2) 2 CH 2 -, - CH 2 CH 2 CH 2 CH 2 CH 2 -, - CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -, And the like. Among them, -CH ₂ - _{(methylene), - CH 2 CH 2 -} ( ethylene _{group), - CH (CH 2)} CH 2 - ( propylene), or -CH ₂ CH ₂ CH ₂ - (trimethylene group) are preferred, more preferably -CH ₂ - (ethylene group) - (methylene) or -CH ₂ CH _2.
Z ³ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms. Preferred examples of the alkyl group include, for example, a methyl group, an ethyl group, and an n-propyl group. Group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group and n-pentyl group, more preferably methyl group or ethyl group.
n is an integer of 0 to 4, more preferably 0 to 2, and still more preferably 0 or 1.
Examples of such an alkoxyalkyl group include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxymethyl group, a methoxyethoxymethyl group, an ethoxyethoxyethyl group, and the like.

  Among these, in the present invention, X is preferably a hydrogen atom, an alkyl group, or an alkoxyalkyl group, and more preferably a hydrogen atom.

  Next, Y in Expression (3) will be described. Y is a hydrogen atom, an electron-withdrawing group or an organic substituent; examples of the electron-withdrawing group include the aforementioned halogen, cyano, nitro, thiocyanate, trifluoromethyl, acyl, and alkyl groups. It is preferable to select an oxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfo group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, or the like. Similarly, as the organic substituent, for example, the above-described alkyl group, alkoxy group, thioalkoxy group, aryl group, aralkyl group, aryloxy group, arylthiooxy group, etc. may be selected. Among them, an alkyl group having 1 to 4 carbon atoms or an aryl group which may have a substituent is preferable, and an aryl group having 6 to 10 carbon atoms substituted with a methyl group, an ethyl group, or an alkoxy group is more preferable. And more preferably a phenyl group substituted with a methyl group, an ethyl group, or an alkoxy group, and particularly preferably a methyl group, an ethyl group, (o-, m-, p-) methoxyphenyl, or (o) -, M-, p-) ethoxyphenyl.

  Examples of particularly preferred compounds as such oxocarbon-based compounds include, for example, compounds having a squarylium skeleton.

Examples of the compound having a croconium skeleton include, for example,

Etc. can be exemplified.

  The maximum absorption wavelength (λmax) of the novel oxocarbon-based compound according to the present invention is 550 to 1,000 nm for a squarylium-based dye. For example, the maximum absorption wavelength (λmax) is obtained by converting a bridged cyclic alkane in the molecule into an aromatic ring. By increasing the wavelength of the compound, the wavelength can be set to 600 to 800 nm. In the case of a croconium-based dye, the maximum absorption wavelength (λmax) of the dye is 700 to 1200 nm, and the compound is made to have a longer wavelength by, for example, converting a bridged cyclic alkane in the molecule into an aromatic ring. , 800 to 950 nm.

  Further, the novel oxocarbon-based compound according to the present invention is excellent in light resistance. When the coating film containing the oxocarbon-based compound according to the present invention was set on a xenon weather meter and subjected to a light resistance test of irradiating light at 60 ° C. for 24 hours, the peak was obtained before and after the light resistance test. The obtained peak residual ratio can achieve 30% or more, more preferably 50% or more, and still more preferably 60% or more.

<Method for producing oxocarbon compound>
The oxocarbon compound according to the present invention has the following formula (4):

(Wherein A, X and Y in the formula (4) are the same as above) and squaric acid or croconic acid.

  In the step of reacting squaric acid or croconic acid with the pyrrole derivative (4) (hereinafter referred to as “step 1”), the amount of the pyrrole derivative (4) used is 0.8 It is preferably at least 1.2 times mol, more preferably at least 1.5 times mol, preferably at most 5 times mol, more preferably at most 4 times mol, even more preferably at least 4 times mol. It is 3 times or less mol.

  This reaction is preferably carried out in the presence of a solvent. Examples of usable solvents include chlorinated hydrocarbons such as chloroform and methylene chloride; aromatic hydrocarbons such as benzene, toluene and xylene; THF, Ethers such as dioxane, cyclopentylmethyl ether, diisopropyl ether and diethyl ether; alcohols such as methanol, ethanol, propanol and butanol; amides such as dimethylformamide and dimethylacetamide. These solvents may be used alone or in combination of two or more.

  The amount (total) of the solvent used is preferably at least 1 weight, more preferably at least 10 weight, even more preferably at least 20 weight, with respect to squaric acid or croconic acid, and the upper limit is, for example, The weight is 100 times or less.

  The reaction temperature may be appropriately set, and is, for example, preferably 0 ° C or higher, more preferably 25 ° C or higher, preferably 170 ° C or lower, more preferably 140 ° C or lower. This reaction may be performed in a reflux state in order to remove water produced by the reaction. The reaction time is not particularly limited, and is, for example, preferably 0.1 hour or more, more preferably 0.5 hour or more, preferably 24 hours or less, more preferably 12 hours or less.

  It is recommended that Step 1 be performed in an atmosphere of an inert gas (such as nitrogen or argon).

  The oxocarbon-based compound obtained by the above reaction may be appropriately purified after the reaction. Examples of the purification means include filtration, silica gel column chromatography, alumina column chromatography, recrystallization, crystallization, and reprecipitation.

  When A and / or B in the formula (3) contains a cyclic alkane having a bridge, after the step 1 produces an oxocarbon compound having a cyclic alkane in the molecule, The bridged cyclic alkane can be converted to an aromatic ring by subjecting the obtained oxocarbon-based compound to a heat treatment (hereinafter, referred to as “step 2”).

  The heat treatment temperature at this time is preferably 160 ° C. or higher, more preferably 210 ° C. or higher, preferably 280 ° C. or lower, more preferably 270 ° C. or lower. The heat treatment time is preferably at least 0.2 hour, more preferably at least 0.5 hour, preferably at most 10 hours, more preferably at most 6 hours.

  It is recommended that Step 2 be performed in an atmosphere of an inert gas (nitrogen, argon, or the like).

  Hereinafter, the present invention will be described more specifically with reference to Examples. However, the present invention is not limited to the following Examples, and may be appropriately modified within a range that can conform to the purpose of the preceding and the following. It is, of course, possible to implement them, and all of them are included in the technical scope of the present invention. In the following, “parts” means “parts by mass” and “%” means “% by mass” unless otherwise specified.

The following apparatus was used for the analysis of the synthesized compound.
UV-visible absorption spectrum; model "U-2810" manufactured by Hitachi High-Technologies Corporation, model "v-570" manufactured by JASCO Corporation
Infrared absorption spectrum; Model “FT-720” manufactured by Horiba, Ltd.
NMR spectrum; JNM-AL400, JEOL; JNM-EX400, JEOL; Mercury 2000, Varian Technologies
Mass spectrum: Model "JMS-MS 700" manufactured by JEOL Ltd.
(MALDI-TOF) mass spectrum; manufactured by Applied Biosystems, model “Voyager-DE ^™ -PRO”

  Compound 20 used in this example was manufactured by Tetsuo and nine others, "Acenaphthylene-Fused Cyclo [8] pyrroles with Intense Near-IR-Region Absorption Options Bands, Chemistry-Aug. (41)), produced by a method similar to the method of synthesizing compound 5 on page 13971 described in pp 13970-13978.

  Compound 4 used in this example was Yuya, 6 others, “Synthesis of π-expanded O-chelated boron-dipyrromethene as an NIR dye”, Tetrahedron, May 6 (2001), 67 (18) -87. The compound was prepared in the same manner as in the method for synthesizing compound 3b on page 3188 described in 3193.

  The pyrrole 13 used in the present example is Schultz, and one other person, “Application of In Situ-Generated Rh-Bound Trimethylenemethane Variant to the Synthesis of 3, 4-Fused Pyrroles”. Am. Chem. Soc. (2013), 135, pp 4696-4699, and prepared in the same manner as in the method for synthesizing compound 13a on page 4697.

≪Squarylium dye≫
Example 1 Synthesis of squarylium dye having acenaphthopyrrole

[Step1]
Acenaphthopyrrole 20 (413 mg, 1.1 mmol) was added to the reaction vessel, and the atmosphere in the vessel was replaced with nitrogen. 30 mL of dryTHF was added to shield light, LiAlH ₄ (213 mg, 5.6 mmol) was added, and the mixture was heated under reflux overnight. After returning to room temperature, the mixture was quenched with a saturated aqueous solution of sodium tartrate, extracted with ethyl acetate, and washed with water and saturated saline. After drying over Na ₂ SO ₄ and concentration under reduced pressure, the desired acenaphthopyrrole 2 was obtained (yield 356 mg, 1.1 mmol, quant.).
Mol. Form. : (Exact Mass: 317.2143, Mol. Wt .: 317.4672)
Appearance: pale yellow-green solid
¹ H NMR (CDCl ₃ , 400 MHz): δ = 7.72 (brs, 1H), 7.60 (d, J = 1.2 Hz, 1H), 7.52 (m, 2H), 7.50 (m , 1H), 6.85 (d, J = 2.3 Hz, 1H), 2.54 (s, 3H), 1.45 (s, 9H), 1.43 (s, 9H).

[Step2]
Squaric acid 1 (62.4 mg, 0.547 mmol) and acenaphthopyrrole 2 (0.356 g, 1.13 mmol) were added to the reaction vessel and the atmosphere was replaced with nitrogen. 20 mL of n-BuOH and toluene were added at a ratio of 1: 1 and heated under reflux. After 1 hour, it was confirmed by TLC that acenaphthopyrrole as a raw material had disappeared. Then, the heating was stopped, the temperature was returned to room temperature, and the mixture was concentrated under reduced pressure. After washing with MeOH, a dark green solid which was considered to be a product was obtained, and further recrystallized from CHCl ₃ / MeOH to obtain compound 3 (yield 0.2744 g, 0.383 mmol, 70%). The rotational isomer abundance ratio at the time of dissolution in chloroform was 5: 3.
Mol. Form. : (Exact Mass 712.4020: Mol. Wt .: 712.99601)
Appearance: green powder
¹ H NMR (CDCl ₃ , 400 MHz): δ = 10.19 (brs, 1H, minor), 9.97 (brs, 1H, major), 9.42 (s, 1H, major), 9.24 (s) , 1H, minor), 7.80-7.78 (m, 2H), 7.73-7.68 (m, 4H), 2.76 (s, 3H, minor), 2.64 (s, 3H) , Major), 1.63-1.48 (m, 36H).
UV-vis (CHCl ₃ ) λmax, 709 nm
MS (MALDI-TOF MS): 713.0355 (M ^<+> )

  Example 2 Synthesis of squarylium dye having o-methoxyphenylbicyclopyrrole

Squaric acid 1 (29.5 mg, 0.26 mmol) and o-methoxyphenylbicyclopyrrole 4 (126.3 mg, 0.5 mmol) were added to the reaction vessel and the atmosphere was replaced with nitrogen. 10 mL of n-BuOH and toluene were added at a ratio of 1: 1 and the mixture was heated under reflux. After confirming by TLC that o-methoxyphenylbicyclopyrrole as a raw material had disappeared 30 minutes later, heating was stopped, the temperature was returned to room temperature, and the mixture was concentrated under reduced pressure. After washing with isopropanol, Compound 5 was obtained (yield 0.0925 g, 0.16 mmol, 62% yield).
Mol. Form. : (Exact Mass: 580.2362, Mol. Wt .: 580.6722)
Appearance: green powder
¹ H NMR (CDCl ₃ , 400 MHz): δ = 10.66 (brs, 1H), 10.38 (brs, 1H), 7.78 (m, 2H), 7.36 (m, 2H), 7. 09 (m, 2H), 7.04 (m, 2H), 6.63 (m, 2H), 6.53 (m, 2H), 5.06 (m, 1H), 4.92 (m, 1H) ), 4.38 (m, 2H), 4.07 (s, 3H), 4.03 (s, 3H), 1.79-1.56 (m, 8H).
UV-vis (CHCl ₃ ) λmax, 639 nm
MS (MALDI-TOF MS): 581.8236 (M ⁺ ), 553.88042 (M ⁺ -28), 524.78111 (M ⁺ -56).

  Example 3 Synthesis of squarylium dye having o-methoxyphenyl-isoindole

Compound 5 (15.6 mg, 0.027 mmol) was added to the reaction vessel, followed by purging with nitrogen. The mixture was heated at 230 ° C. for 1 hour and allowed to cool to room temperature to obtain Compound 6 (14 mg, 0.027 mmol, quant). The rotational isomer abundance ratio at the time of dissolution in chloroform was 2: 1.
Mol. Form. : (Exact Mass: 524.1736, Mol. Wt .: 524.5654)
Appearance: Black powder
¹ H NMR (CDCl ₃ , 400 MHz): δ = 12.38 (brs, 1H, major), 12.12 (brs, 1H, minor), 8.94 (d, J = 8.1 Hz, 1H, minor) , 8.80 (d, J = 8.1 Hz, 1H, major), 8.14-8.06 (m, 4H), 7.51-7.38 (m, 6H), 7.20-7. 10 (m, 4H), 4.19 (s, 3H, major), 4.10 (s, 3H, minor)
UV-vis (CHCl ₃ ) λmax, 740 nm
MS (MALDI-TOF MS): 546.03 (M ⁺⁺ 23)

  Example 4 Synthesis of squarylium dye having α-methylbicyclopyrrole

Squaric acid 1 (57.9 mg, 0.5 mmol) and α-methylbicyclopyrrole 7 (160 mg, 1.0 mmol) were added to the reaction vessel, and the atmosphere in the reaction vessel was replaced with nitrogen. 10 mL of n-BuOH and toluene were added at a ratio of 1: 1 and the mixture was heated under reflux. After confirming by TLC that pyrrole as a raw material disappeared after 30 minutes, the heating was stopped, the temperature was returned to room temperature, the mixture was concentrated under reduced pressure, and recrystallized from chloroform / hexane to obtain Compound 8 (yield 0.3133 g, 0%). .787 mmol, 78% yield).
Mol. Form. : (Exact Mass: 580.2362, Mol. Wt .: 396.4810)
Appearance: Color powder
¹ H NMR (CDCl ₃ , 400 MHz): δ = 9.61 (brs, 1H), 9.39 (brs, 1H), 6.56-6.46 (m, 4H), 4.94 (m, 1H) ), 4.80 (m, 1H), 3.90 (s, 2H), 2.36 (s, 6H), 1.65-1.26 (m, 8H).
UV-vis (CHCl ₃ ) λmax, 563 nm
MS (MALDI-TOF): 368.84 (M ⁺ -28)
MS (FAB): 396 (M ⁺ ), 340 (M ⁺ -56)

  Example 5 Synthesis of squarylium dye having α-methylisoindole

Compound 8 (12.0 mg, 0.03 mmol) was added to the reaction vessel, followed by purging with nitrogen. The mixture was heated at 230 ° C. for 1 hour and allowed to cool to room temperature to obtain Compound 9 (yield 10 mg, 0.03 mmol, quant.).
Mol. Form. : (Exact Mass: 340.1212, Mol. Wt .: 340.3746)
Appearance: black powder UV-vis (CHCl ₃ ) λmax, 650 nm

  Example 6

Squaric acid (56 mg, 0.493 mmol) and pyrrole 13 (295 mg, 0.985 mol) were put in a reaction vessel, n-BuOH / toluene (1: 1, 10 mL) was added, and the mixture was refluxed for 30 minutes. After the completion of the reaction, the mixture was returned to room temperature, concentrated under reduced pressure, and washed with MeOH to obtain the intended product 14. The rotational isomer abundance ratio at the time of dissolution in chloroform was 2: 1.
yield: 109 mg (41%)
Mol. Form. _{: C 34 H 34 N 2 O} 4 (Exact Mass: 534.25, Mol.Wt:. 534.64)
Appearance: green powder
UV-vis (CHCl ₃ ): 651 nm

≪ Croconium dye ≫
Example 7 Synthesis of croconium dye having o-methoxyphenyl-bicyclopyrrole

Croconic acid (101 mg, 0.402 mmol) and o-methoxyphenylbicyclopyrrole 4 (30.3 mg, 0.213 mol) are put in a reaction vessel, n-BuOH / toluene (1: 1, 5 mL) is added, and the mixture is added for 2 hours. Refluxed. After completion of the reaction, the mixture was returned to room temperature, concentrated under reduced pressure, and washed with IPA to obtain Compound 10 (yield 105 mg, 81%). The rotational isomer abundance ratio at the time of dissolution in chloroform was 1: 1.
Mol. Form. : C ₃₉ H ₃₂ N ₂ O ₅ (Exact Mass: 608.23, Mol. Wt .: 608.68)
Appearance: brown-red powder
1H NMR: (CDCl ₃ , 400 MHz): δ = 13.14 (brs, 1H), 12.83 (brs, 1H), 12.76 (brs, 1H), 12.60 (brs, 1H), 7. 94-7.83 (m, 2H + 2H), 7.47-7.40 (m, 2H + 2H), 7.15-7.06 (m, 4H + 4H), 6.71-6.52 (m, 4H + 4H), 5.81 (m, 1H), 5.72 (m, 1H), 5.65 (m, 1H), 4.47-4.41 (m, 2H + 2H), 4.17 (s, 3H), 4 .16 (s, 3H), 4.14 (s, 3H), 4.10 (s, 3H), 1.69-1.56 (m, 8H + 8H)
MS (MALDI-TOF): 579.49 (M ⁺ -28)
UV-vis (CHCl ₃ ) λmax, 794 nm

  Example 8 Synthesis of Croconium Dye Having o-Methoxyphenyl-isoindole

Compound 10 (6.5 mg, 0.011 mmol) was placed in a reaction vessel, and heated in a vacuum at 230 ° C. for 2 hours. The temperature was returned to room temperature to obtain the target product 11.
yield: trace (trace)
Mol. Form. : C ₃₉ H ₃₂ N ₂ O ₅ (Exact Mass: 552.17, Mol. Wt .: 552.58)
Appearance: block solid
UV-vis (CHCl ₃ ) λmax, 866 nm

  Example 9 Synthesis of Croconium Dye Having Acenaphthopyrrole

Croconic acid (243 mg, 1.71 mmol) and acenaphthopyrrole 2 (1.09 g, 3.42 mol) were put in a reaction vessel, n-BuOH / toluene (1: 1, 10 mL) was added, and the mixture was refluxed for 1.5 hours. . After completion of the reaction, the temperature was returned to room temperature, concentrated under reduced pressure, and washed with IPA to obtain the desired product 12 (yield 1.15 g, 91%). The rotational isomer abundance ratio at the time of dissolution in chloroform was 10: 7.
Mol. Form. : C ₅₁ H ₅₄ N ₂ O ₃ (Exact Mass: 742.41; Mol. Wt .: 742.99)
Appearance: brown-red powder
1H NMR: (CDCl ₃ , 400 MHz): δ (syn) = 12.60 (brs, 2H, major), 9.67 (s, 2H, major), 7.82 (s, 2H, major), 7. 68 (s, 2H, major), 7.43 (s, 2H, major), 2.55 (s, 6H, major), 1.62 (s, 18H, major), 1.41 (s, 18H, major) major), δ (anti) = 13.41 (brs, 1H, minor), 11.76 (brs, 1H, minor), 9.74 (s, 1H, minor), 9.64 (s, 1H, minor) ), 7.86 (s, 1H, minor), 7.83 (s, 1H, minor), 7.77 (s, 1H, minor), 7.72 (s, 1H, minor), 7.69 ( s, 1H, mino r), 7.63 (s, 1H, minor), 2.82 (s, 3H, minor), 2.57 (s, 3H, minor), 1.64 (s, 9H, minor), 1.60. (S, 9H, minor), 1.50 (s, 9H, minor), 1.47 (s, 9H, minor)
MS (FAB): 742 (M ⁺ )
UV-vis (CHCl ₃ ) λmax, 854 nm

  Example 10

Croconic acid (182 mg, 1.28 mmol) and pyrrole 13 (582 mg, 2.56 mol) were put in a reaction vessel, n-BuOH / toluene (1: 1, 10 mL) was added, and the mixture was stirred at room temperature for 2 hours. After completion of the reaction, the mixture was concentrated under reduced pressure, and washed with MeOH to obtain the intended product 15. The rotational isomer abundance ratio at the time of dissolution in chloroform was 1: 1.
yield: 408 mg (57%)
Mol. Form. : C ₃₅ H ₃₂ N ₂ O ₅ (Exact Mass: 560.23, Mol. Wt .: 560.64)
Appearance: brown-red powder
UV-vis (CHCl ₃ ): 800 nm

<Light fastness test>
The coating films obtained by the following prescriptions 1 to 5 were set on a xenon weather meter (X75SC, manufactured by Suga Test Instruments Co., Ltd.), and a light resistance test was performed. The evaluation condition was a light irradiation for 24 hours in a 60 ° C. atmosphere.

製造 Method for producing resin composition≫
Production Example 1 (Dimethylacetamide solution of polyimide)
5 parts of 1,2,4,5-cyclohexanetetracarboxylic acid (manufactured by Tokyo Chemical Industry, purity 98%, mw = 260.20) and 44 parts of acetic anhydride (manufactured by Wako Pure Chemical Industries) are charged into a flask and reacted while stirring. The inside of the vessel was replaced with nitrogen gas. The temperature was raised to the reflux temperature of the solvent under a nitrogen gas atmosphere, and the solvent was refluxed for 10 minutes. The mixture was cooled to room temperature with stirring to precipitate crystals. The precipitated crystals were subjected to solid-liquid separation and dried to obtain crystals of the desired product (1,2,4,5-cyclohexanetetracarboxylic dianhydride). In a flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, a dropping funnel with a side tube, Dean Stark, and a cooling tube, 4,4′-diaminodiphenyl ether (manufactured by Wako Pure Chemical, mw = 200.24) under a nitrogen stream. After 8.9 parts and 76 parts of dimethylacetamide as a solvent were charged and dissolved, 10 parts of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (mw = 224.17) was solid at room temperature. The mixture was dividedly charged over 1 hour while stirring, and stirred at room temperature for 2 hours. 26 parts of toluene was added as an azeotropic dehydrating agent, and the mixture was reacted at 130 ° C. for 3 hours, and refluxed by Dean-Stark to separate azeotropically generated water. After evaporating xylene while raising the temperature to 194 ° C., the mixture was cooled to obtain a dimethylacetamide solution of polyimide.

Production Example 2 (Acrivure in dioxane)
Ten parts of Nippon Shokubai's Acrybure (registered trademark: “RN”) were mixed with 90 parts of dioxane and stirred to obtain a dioxane solution of Acrybure (RN).

≪Coating film manufacturing method≪
Formulation 1 (resin composition containing compound 3)
The polyimide dimethylacetamide solution obtained in Production Example 1 was diluted with dimethylacetamide to adjust the concentration to 8%. 12.31 parts of this solution and 0.015 part of compound (3) obtained in Example 1 were mixed to dissolve the compound. After the solution was filtered to remove insolubles and the like, it was spin-coated on a glass substrate and baked at 150 ° C. for 20 minutes to obtain a coating film.

Formulation 2 (resin composition containing compound 3)
9.85 parts of the dichroic acid solution of Acribure obtained in Production Example 2 and 0.015 part of the compound (3) obtained in Example 1 were mixed to dissolve the compound. After the solution was filtered to remove insolubles and the like, it was spin-coated on a glass substrate and baked at 150 ° C. for 20 minutes to obtain a coating film.

Formulation 3 (resin composition containing compound 12)
9.85 parts of the dichroic acid solution of Acribure obtained in Production Example 2 and 0.015 part of the compound (12) obtained in Example 9 were mixed to dissolve the compound. After the solution was filtered to remove insolubles and the like, it was spin-coated on a glass substrate and baked at 150 ° C. for 20 minutes to obtain a coating film.

Prescription 4
The polyimide dimethylacetamide solution obtained in Production Example 1 was diluted with dimethylacetamide to adjust the concentration to 8%. 12.31 parts of this solution and 0.015 part of a squarylium dye represented by the following formula were mixed to dissolve the dye. After the solution was filtered to remove insolubles and the like, it was spin-coated on a glass substrate and baked at 150 ° C. for 20 minutes to obtain a coating film.

Prescription 5
The polyimide dimethylacetamide solution obtained in Production Example 1 was diluted with dimethylacetamide to adjust the concentration to 8%. 12.31 parts of this solution and 0.015 part of a croconium dye represented by the following formula were mixed to dissolve the dye. After the solution was filtered to remove insolubles and the like, it was spin-coated on a glass substrate and baked at 150 ° C. for 20 minutes to obtain a coating film.

The peaks obtained before and after the light resistance test were measured, and the results are shown in FIGS. 1 to 5 (the solid line in the attached chart shows the spectrum before the test and the dotted line shows the spectrum after the test). The peak tops obtained before and after the light resistance test were determined, and (the value of the peak top before the test-the value of the peak top after the test) was divided by the value of the peak top before the test to obtain a peak residual ratio. The results of the peak residual ratio are shown below.
Prescription 1 (Fig. 1) 44%
Prescription 2 (Fig. 2) 72%
Prescription 3 (Fig. 3) 92%
Formula 4 (Figure 4) 2%
Prescription 5 (Fig. 5) 56%

  From the results of Formulations 1 and 2 and Formula 4, from the compounds in which a pyrrole ring is bonded to a squarylium skeleton, a compound in which a cyclic substituent is introduced at the two β-position carbons of a pyrrole ring is a compound that is not so, that is, methine It was found that the peak residual ratio was higher and the light resistance was excellent as compared with a compound having a group. Similarly, from the results of Formulations 3 and 5, it was found that among compounds having a croconium skeleton, a compound in which a cyclic substituent was introduced at the two β-position carbons of the pyrrole ring was excellent in light resistance.

  The novel oxocarbon-based compound according to the present invention has an excellent color tone, and as a dye absorbing visible light and near infrared rays, an optical filter for a semiconductor light receiving element having a function of absorbing and cutting visible light and near infrared rays. A near-infrared absorbing film or a near-infrared absorbing plate that blocks heat rays for energy saving; an information display material as a security ink or an invisible barcode ink; a solar cell material using visible light and near-infrared light; a plasma display panel ( Specific wavelength absorption filters for PDPs and CCDs; Photothermal conversion materials for laser welding; Light fixing method using light that does not easily cause problems due to pressure or heating (toner for electrostatic charge development for flash fixing method); Can be used.

Claims (1)

Formula that having a squarylium skeleton (1) or an oxo carbon-based compound characterized by being represented by the following formula (2) having a croconium skeleton.
(In the formulas (1) and (2), R ^{a1 to} R ^a4 are each independently a structural unit represented by the following formula (3).)
(In equation (3),
A represents a 5- or 6-membered ring structure formed by two carbon atoms at the β-position of the pyrrole ring together with other atoms;
A is an aromatic ring or an alicyclic hydrocarbon ring, A may be fused with another carbon ring,
X is a hydrogen atom,
Y is an alkyl group having 1 to 4 carbon atoms, or an aryl group which may have a substituent,
* Represents a binding site.
However, A is an aromatic ring, A is an alicyclic hydrocarbon ring and is condensed with another aromatic ring, and Y is an aryl group which may have a substituent. )