JP2003171571A - Cyanine compound, its intermediate, cyanine dye, optical recording material and optical information record medium - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cyanine compound, a cyanine dye, an optical recording material and an optical information recording medium which have a light fastness against laser light and natural light and a moisture resistance. <P>SOLUTION: This cyanine compound is a compound obtained by making a substitution with a metallocene-bonded group of the general formula, wherein R<SB>03</SB>is a straight chain or branched alkyl group, R<SB>04</SB>and R<SB>05</SB>are each hydrogen or a substituent and M is a transition metal such as iron or the like, on a cyanine compound such as an indolenine or the like. This cyanine compound is used for the cyanine dye, the optical recording material and the optical information recording medium. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel cyanine compound obtained by chemically bonding a metallocene group to the molecular skeleton of a cation of a cyanine compound, an intermediate thereof, and a cyanine dye comprising the cyanine compound. , An optical recording material containing each of these substances, and an optical information recording medium having a recording layer containing the optical recording material.

[0002]

2. Description of the Related Art As means for recording information and reproducing the recorded information, an optical information recording medium for recording and reproducing information with a laser beam having a high energy density is a CD.
-R / RW, DVD-RAM, DVD-R / RW, etc. are widely known. Further, in recent years, there has been a report on an optical information recording medium capable of recording and reproducing with a blue laser aiming at higher density recording. Among these, as a so-called write-once type optical information recording medium in which recording can be performed only once and reproduction can be repeated, C
D-R and DVD-R are in widespread use. These CD-R
As a recording material used for a recording layer of a write-once type optical information recording medium such as a DVD-R or the like, a cyanine dye, which is an organic dye that has been used as a sensitizer for silver salt photography, has been known for a long time. In particular, indocarbocyanine dyes are widely used because of their high sensitivity. For example, the trimethine-based cyanine-based dyes mentioned in Comparative Examples below are well known as a dye material for recording layers of DVD-R. Further, ferrocene, which is a complex of two molecules of cyclopentadiene and iron, and metallocene in which the iron is replaced with a metal such as other transition metal are also well known, and in JP-A-4-31434, ferrocene is improved in combustion. Not only is it available as an additive, but JP-A-11-86337 discloses that a recording layer is formed by using ferrocene as a light stabilizer mixed with a cyanine dye as a dye material. It is also disclosed to manufacture an optical information medium that can obtain a stabilizing effect. In addition to this, JP-A-10-147
The use of ferrocene as a photostabilizer is also disclosed in JP-A-062, JP-A-2001-47740 and the like, and it is already known that a stable ferrocene compound has a function of photostabilization and the like. There is.

By the way, among the organic dyes used in the recording layer of the write-once type recording medium typified by CD-R and DVD-R, which can be written only once, the cyanine dye is the sensitivity at the time of recording by laser light, It has good thermal decomposability, that is, the dye is exposed to laser light and decomposes when it is irradiated with laser light, resulting in excellent pit-forming performance. Also used when forming the recording layer. It is often used because it has good solubility in a solvent when producing a dye solution. In order to enable higher density recording / reproducing, a semiconductor laser having a wavelength of 630 to 690 nm is usually used in an optical recording medium such as a DVD-R. It is also attracting attention as a dye material for the recording layer. However, since cyanine dyes are generally susceptible to photodegradation, when used as a dye material for a recording layer of an optical recording medium such as a CD-R or a DVD-R, irradiation with a short wavelength laser is performed for recording or reproduction. Durability that can withstand irradiation during recording and repeated reproduction, and storage stability during storage that prevents the signals of images recorded on the recording layer from being altered, especially repeated exposure to natural light. Many opportunities,
As a result, there is a problem in light resistance when it is stored such that it is exposed to the light for a long period of time. In addition, some cyanine dyes having a relatively small molecular weight generally tend to be easily dissolved in water, and when such a cyanine dye is used in the recording layer, moisture penetrates into the recording layer under high humidity, There is also a problem that the cyanine dye easily diffuses as if it oozes out, resulting in poor storage stability. Further, in order to realize high-speed recording on a write-once type optical recording medium such as a CD-R or a DVD-R, it has been proposed to reduce the optimum recording power (Japanese Patent Laid-Open No. HEI-2).
No. 000-276767), an optical recording material capable of forming sharp pits with low laser power, that is, low energy is desired.

Therefore, for the purpose of preventing photo-deterioration in the recording layer of the optical recording medium, an aminium salt or an immonium salt (JP-A-6-321872 and JP-A-10-316632).
JP-A 6-1).
99045) in combination with an organic dye, or an ionic bond dye in which a dye cation and a stabilizer are ionically bonded (JP-A-6-320869, WO9).
Proposals have been made for improving the light resistance, such as the use of recording materials including Japanese Patent Laid-Open No. 8/234988), and some have been put to practical use. In addition, as an example in which the above-mentioned metallocene is used in an optical information recording medium, an example in which a recording layer is formed by using a metal stabilizer mixed with an organic dye as a light stabilizer so that a light stabilizing effect can be obtained (Japanese Patent Laid-Open No. Hei 10-1999) No. 11-86337, No. 10-147062, No. 2001-4774.
No. 0) or an example in which a recording layer is formed by using it as a thermal decomposition accelerator mixed with an organic dye in order to improve the thermal decomposition property (JP-A-10-116).
No. 443) is known.

[0005]

However, even when a stable ferrocene is used as the stabilizer, and also when any of the other stabilizers mentioned above is used, in particular DV
High-density recording / reproducing is performed by using a laser beam having a short wavelength like an optical recording medium such as D-R, and an optical recording medium after recording is often stored for a long period of time and is exposed to natural light for a long period of time. In many cases, the light stabilization is not sufficient,
It is desired to improve durability against laser light and light resistance against natural light. Further, the above-mentioned aminium salt, immonium salt, nickel dithiol complexes, and further a stabilizer comprising an ion-bonding dye have low solubility in a solvent when producing a dye solution used for forming a recording layer. Therefore, the amount of the cyanine dye dissolved is limited, and as a result, only the dye layer with a reduced content of the cyanine dye can be obtained, which affects the absorbance and refractive index of the recording layer made of the dye, and In some cases, the sensitivity may be lowered, an appropriate modulation degree may not be obtained, and the thermal decomposition characteristics may be affected, making it difficult to form sharp pits. Further, even if any stabilizer is used in combination, the above-mentioned moisture resistance, that is, a cyanine dye having a relatively small molecular weight generally tends to be soluble in water, and such a cyanine dye is used for a recording layer. In the case of the optical information recording medium, when it is stored under high humidity, the dye easily bleeds due to the moisture that has entered the recording layer, and the storage property is deteriorated such that the dye diffuses and the recording characteristics and reproducing characteristics deteriorate. Not only is this problem not improved, but it takes time and effort to mix a plurality of materials when forming the recording layer, an extra step is required, and the uniformity of the mixing varies. This is unavoidable, and the effect thereof may affect the recording and reproducing characteristics, resulting in a problem such as variation in quality. From these facts, as described above, the write-once type optical recording medium has thermal decomposability suitable for recordability, has optical characteristics suitable for recording and reproducing characteristics, and has sufficient light resistance and moisture resistance. The emergence of a single compound cyanine dye (cyanine compound) is desired.

A first object of the present invention is to provide a novel cyanine compound obtained by chemically bonding a metallocene group to the molecular skeleton of the cation of the cyanine compound, an intermediate thereof, a cyanine dye, an optical recording material and An object is to provide an optical information recording medium. A second object of the present invention is to provide a novel cyanine compound, a cyanine dye, which has optical properties peculiar to a cyanine dye, has good solubility in a solvent, is excellent in thermal decomposability, and is particularly excellent in light stabilizing effect and moisture resistance. Another object of the present invention is to provide an optical recording material and an optical information recording medium. A third object of the present invention is that it has excellent sensitivity, is suitable for high-speed recording, has excellent light resistance, and can be used alone without being combined with other light stabilizers, etc. Another object of the present invention is to provide an optical information recording medium that can be used.

[0007]

Means for Solving the Problems The present inventors have found that when ferrocene is chemically bonded to the cation molecular skeleton of a cyanine compound, the light resistance and moisture resistance are remarkably improved. The present invention has been completed. The present invention provides (1), a cyanine compound represented by the following general formula [Formula 1].

[Chemical 1] [In the formula, L is 1, 3, 5 or 7 methine groups (-CH
=) Represents a methine chain bound by forming a conjugated double bond.
The hydrogen atom on the methine chain is a halogen atom or its
It may be substituted with other substituents, and the substituents are linked to each other.
To form a ring, and it may extend over a plurality of carbons.
It may have a cyclic side chain, Y₀₁And Y₀₂Are each
Represents a group of atoms necessary to form a heterocycle,
May have a substituent, and Z is represented by the following general formula [Chemical formula 2].
Represents a substituted or bonded substituent, i is 1 to
Is an integer of 4, and when i is 2 to 4, Z's are the same.
May or may not be different, R₀₁And R₀₂
Represents a hydrogen atom, a substituted or unsubstituted alkyl group
, They may be the same or different, uX^r-Is X^r-Is the r value (r
Represents a positive integer) organic or inorganic anion, and u is
R is the number that makes the entire molecule neutral.₀₁And R₀₂Less
When either one has an anion group, uX ^r-Is
You don't have to.

[Chemical 2] (In the formula, R₀₃Is a single bond or linear or branched alkyl
Group, -CH = CH-,-(CO)-, -NH-, -O
-, -S-, -N = C-, -C₆H_Four-,-(SO ₂)
Represents a linking group in which-and the like are combined, and hydrogen in the linking group
Atoms may be substituted with halogen atoms or other substituents
Well, R₀₄And R₀₅Are hydrogen atoms or substituents, respectively.
I, same or different, M is titanium, iron, lute
Represents transition metals such as nickel, osmium, and nickel
You )] Further, the present invention provides (2), the following general formula [Chemical formula 3]
A cyanine compound represented by

[Chemical 3] (In the formula, L, Y ₀₁ and Y ₀₂ , and uX ^r- represent the same as those in the general formula [Chemical formula 1] of the above (1), and Z ₁ and Z ₂ respectively represent the above general formula of the above (1). Represents a substituent represented by [Chemical Formula 2], j and k each represent an integer of 0 to 2 and j + k ≧ 1, and when j and k are not 0, Z ₁ and Z ₂ may be the same or different. Alternatively, when j and k are each 2, Z ₁ and Z ₂ may be the same or different, and R ₀₁ and R ₀₂ represent a hydrogen atom, a substituted or unsubstituted alkyl group, and are the same or different. (3), a cyanine compound represented by the following general formula [Chemical Formula 4],

[Chemical 4] (In the formula, L, Y ₀₁ and Y ₀₂ , and uX ^r- represent the same as those in the general formula [Chemical formula 1] of the above (1), and at least one of Z ₃ and Z ₄ has the above-mentioned formula (1). Represents a substituent represented by the general formula [Chemical Formula 2], and when only one of them is substituted with the substituent represented by the general formula [Chemical Formula 2],
The other represents a substituted or unsubstituted alkyl group. ) (4), a cyanine compound represented by the following general formula [Chemical formula 5],

[Chemical 5] (In the formula, Y ₁ and Y ₂ each represent a carbon atom or a heteroatom necessary for forming a heterocycle, and may have a substituent, and R ₁ and R ₂ are each a hydrogen atom or a halogen atom. A benzene ring fused through atoms or other substituents or adjacent carbons (may have one or more halogen atoms or other substituents, in the case of multiple, the substituents may be the same And R ₁ and R ₂ may be singular or plural in each case, and in the case of plural, they may be the same or different. , R ₁ and R ₂ may be the same or different, and the substitution positions of R ₁ and R ₂ may be symmetrical or asymmetrical, and Z ₃ and Z ₄ Is at least one of the above-mentioned general formula (1) And represents a substituent represented, when only one of which is substituted with a substituent represented by the general formula [2], the other represents a substituted or unsubstituted alkyl group, uX ^r- is claimed And the cyanine compound represented by the following general formula [Chemical formula 6]:

[Chemical 6] (In the formula, R ₁ and R ₂ , Z ₃ and Z ₄ , and uX ^r- represent the same as those described in the general formula [Chemical Formula 5] of (4) above, and R ₃ , R ₄ , R ₅ and R ₆ represents an alkyl group having 1 to 11 carbon atoms, adjacent substituents may be linked to each other to form a ring, and A represents a hydrogen atom, a halogen atom or another substituent.) 6), a cyanine compound represented by the following general formula [Chemical formula 7],

[Chemical 7] (In the formula, R ₁ and R ₂ , Z ₃ and Z ₄ , R ₃ , R ₄ , and R
₅ and R ₆ , A and uX ^r- are the general formula of the above (5)
The same as those described in. (7) The cyanine compound according to any one of (1) to (6), wherein M is an iron (Fe) atom in the substituent represented by the general formula [Chemical Formula 2] in (1) above. R in the substituent represented by the general formula [Chemical Formula 2] in the above (1) is R
A cyanine compound of any one of the above (1) to (7), wherein ₀₃ is a linear or branched alkylene group having 1 to 22 carbons, (9), represented by the general formula [Chemical Formula 2] of the above (1). In the substituent, R ₀₃ is a linear or branched alkylene group having 1 to 8 carbon atoms, and the cyanine compound according to any one of (1) to 7 above, (10), the general formula of (1) ] The cyanine compound according to any one of (1) to (7) above, wherein the substituent represented by the following is a substituent represented by the following general formula [Chemical formula 8],

[Chemical 8] (In the formula, R ₀₄ and R ₀₅ represent the same as those described in the general formula [Chemical Formula 2] in (1) above, and R ₇ and R ₈ represent a hydrogen atom, a straight chain or branched chain having 1 to 8 carbon atoms. Represents an alkyl group (a hydrogen atom may be substituted with a halogen atom or other substituent) and other substituents, and n represents an integer of 1 to 8) (11), the general formula of (1) above. A cyanine compound according to any one of the above (1) to (7), wherein the substituent represented by [Chemical Formula 2] is a substituent represented by the following general formula [Chemical Formula 9],

[Chemical 9] (In the formula, R ₀₄ and R ₀₅ represent the same as those described in the general formula [Chemical Formula 2] of the above (1), and n and m are 0 respectively.
Or R 1, R ₉ represents a single bond or an alkylene group having 11 carbon atoms, R ₁₀ represents a single bond, —CH═CH—, —C
_{H 2 -C (= O) -} , - CH 2 CH 2 -C (= O) - or an alkylene group having a carbon number of 1 to 11, R ₁₁ represents an alkylene group having 1 to 11 carbon atoms. (12) The cyanine-based compound according to any one of (1) to (7) above, wherein the substituent represented by the general formula [Chemical Formula 2] in the above (1) is a substituent represented by the following general formula [Chemical Formula 10]. Compound,

[Chemical 10] (In the formula, R ₀₄ and R ₀₅ represent the same as those described in the general formula [Chemical Formula 2] in the above (1), m is 1 to 8 and n is 0 to
Represents an integer of 8. (13) The above (1) represented by the following general formula [Chemical formula 11]
A cyanine-based compound represented by the general formula [Chemical Formula 1] or an intermediate of the cyanine-based compound represented by the general formula [Chemical Formula 3] of the above (2),

[Chemical 11] (In the formula, Y ₀₁ , R ₀₁ , Z, and uX ^r- represent the same as those in the general formula [Chemical formula 1] of the above (1), i represents an integer of 1 or 2, and R ₁₂ represents -CH. ₃ or -OCH ₃ , -SCH
It is a substituent capable of forming a chemical bond by elimination reaction such as ₃ . (14), an intermediate of the cyanine compound represented by the general formula [Chemical Formula 4] of the above (3) represented by the following general formula [Chemical Formula 12],

[Chemical 12] (In the formula, Y ₀₁ , Z ₃ , and uX ^r- represent the same as those in the general formula [Chemical formula 4] of the above (3), and R ₁₂ represents the general formula [Chemical formula 11] in claim 13. (15), an intermediate of the cyanine compound represented by the general formula [Chemical Formula 6] of the above (5) represented by the following general formula [Chemical Formula 13],

[Chemical 13] (In the formula, R ₁ , R ₃ , R ₄ , Z ₃ , and uX ^r- are the same as those in the above (3).
Of the general formula [Chemical formula 4] and R ₁₂ is the same as that of the general formula [Chemical formula 11] of the above (13). (16), Z and Z ₃ are the substituents represented by the general formula [Chemical Formula 2] in (1) above, wherein R ₀₃ is a linear or branched alkylene group having 1 to 22 carbon atoms. An intermediate of the cyanine compound according to any one of (15), (1
7) Z and Z ₃ are the substituents represented by the general formula [Chemical Formula 2] in (1) above, and R ₀₃ is a linear or branched alkylene group having 1 to 8 carbon atoms, and the above (13) to (15) An intermediate of the cyanine compound of any of (18), Z,
Z ₃ is an intermediate of the cyanine compound of any of the above (13) to (15), wherein Z ₃ is a substituent represented by the general formula [10], and (19), Z and Z ₃ are the above. (1
The intermediate of the cyanine compound of any one of the above (13) to (15), which is a substituent represented by the general formula [Chem. 9] of 1), (20), Z, and Z ₃ are the same as those of the above (12). An intermediate of the cyanine compound of any of the above (13) to (15), which is a substituent represented by the formula [Chemical Formula 10],
(21) A cyanine dye comprising the cyanine compound of any of (1) to (12), (22), the cyanine compound of any of (1) to (12), or the cyanine of (21). Recording material containing an optical dye or an intermediate of the cyanine compound of any one of (13) to (20), (23), and optical information recording having a recording layer containing the optical recording material of (22). It provides a medium.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to "an indolenine-based, thiazole-based, imidazole-based, oxazole-based or selenazole-based cyanine compound having a substituted or unsubstituted metallocene-bonding group, and an intermediate of the cyanine compound. , A cyanine dye containing the cyanine compound, an optical dye material containing each of these substances, and an optical information recording medium having a recording layer containing the optical dye material ", but the above (1) to (22) Invention is preferable. In the invention of the above (1), a cyanine compound is obtained in which 1 to 4 metallocene-bonding groups of the general formula [Chemical formula 2] represented by Z are substituted to obtain one compound. It may be any of the above, for example, for the methine chain of L, or for the heterocycles on both sides of the methine chain and its substituents. When the heterocycles on both sides of the methine chain and the substituents thereof are substituted with 0 to 2 metallocene-bonding groups of the general formula [Chemical Formula 2] represented by Z, the cyanine compound of the general formula [Chemical Formula 3] is obtained. Further, the cyanine of the general formula [Chemical Formula 4] is obtained by substituting the metallocene bonding groups of the general formula [Chemical Formula 2] represented by Z ₁ and Z ₂ in the general formula [Chemical Formula 3] with R ₀₁ and R ₀₂ , respectively. It becomes a system compound. In the above general formulas [Chemical Formula 1], [Chemical Formula 3] and [Chemical Formula 4], L is a methine chain consisting of 1, 3, 5 or 7 methine groups (-CH =), but a conjugated double bond Form. That is, even when L is one methine group, a conjugated double bond is formed between one carbon and the other carbon bonded to both sides of the methine group and N ⁺ bonded thereto, and in other cases, a conjugated double bond is also formed. The methine chain is formed so as to form Preferably, the trimethine cyanine compound in which L is composed of three methine groups is a recording material for DVD-R (hereinafter, also referred to as "dye material"),
A pentamethine cyanine compound in which L is composed of 5 methine groups is used as a recording material for CD-R, but is not limited to this, and a less methine group is more suitable for recording and reproduction with a laser having a shorter wavelength, for example, The monomethine cyanine compound in which L is composed of one methine group may be used in the same manner as the above-mentioned trimethine cyanine compound, but both of them are used for recording and reproducing for a laser having a shorter wavelength such as a blue laser. It can be used for. The hydrogen atom on the methine chain may be substituted with a halogen atom or another substituent, and the methine chain or its substituent may be linked to each other to form a ring. Examples of the halogen atom include a fluorine atom, a bromine atom and a chlorine atom,
Examples of the substituent include an alkyl group, an aryl group, a nitro group, a cyano group, an alkoxy group, a hydroxy group and a carbonyl group.

[Formula 1], [Formula 3], [Formula 4]
In the above, each of Y ₀₁ and Y ₀₂ represents an atomic group necessary for forming a heterocycle, and examples of the heterocycle include an indolenine ring, a benzoindolenine ring, a thiazole ring, a thiazoline ring, a benzothiazole ring and a naphtho group. Thiazole ring, imidazole ring, benzimidazole ring, naphthimidazole ring, oxazole ring, oxazoline ring,
Examples thereof include a benzoxazole ring, a naphthoxazole ring, a selenazole ring, a selenazoline ring, a benzoselenazole ring, a naphthoselenazole ring, a quinoline ring, and a pyridine ring, and preferably an indolenine ring, a benzoindolenine ring, a thiazole ring, a thiazoline ring. , Benzothiazole ring and benzoxazole ring. These rings may be other carbon rings (benzene ring etc.) or heterocycles (viridin ring etc.).
To form a condensed ring, and on the ring, as a substituent, an alkyl group, an aryl group, a halogen atom, a nitro group,
A cyano group, an alkoxy group, a hydroxyl group, a carbonyl group and the like may be substituted, and an alkyl group, a halogen atom, a nitro group and an alkoxy group are preferable. The alkyl group is preferably a linear or branched alkyl group having 1 to 6 carbon atoms. The halogen atom is preferably a fluorine atom or a chlorine atom. The alkoxy group is preferably a lower alkoxy group having 1 to 4 carbon atoms such as methoxy group, isopropyloxy group, and n-butoxy group. In the above general formulas [Chemical Formula 1] and [Chemical Formula 3], each of R ₀₁ and R ₀₂ represents a hydrogen atom or a substituted or unsubstituted alkyl group, and preferably has a straight or branched chain having 1 to 22 carbon atoms or It is a cyclic alkyl group, more preferably having 1 to 8 carbon atoms.
Is a linear or branched alkyl group. Examples of the substituent include an aryl group having 6 to 10 carbon atoms (phenyl group, naphthyl group, etc.), halogen atom (fluorine atom, chlorine atom, etc.) and the like. Further, the substituent may be an acid group bonded to an alkali metal ion or an alkyl group, for example, an alkylsulfonic acid group.

In the above general formulas [Chemical formula 1] and [Chemical formula 3],
Z, Z ₁ and Z ₂ represent the above-mentioned general formula [Chemical formula 2]. In the above-mentioned general formula [Chemical formula 1], _i of (Z) i is an integer of 1 to 4, and It is shown that at least one substituent and at most four substituents can be substituted. Further, in the above general formula [Chemical Formula 3], _j of (Z ₁ ) _j , (Z ₂ ) _k ,
k is an integer of 0 to 2 and j + k ≧ 1, which means that the substituent represented by the general formula [Chemical formula 2] can be substituted at a minimum of 1 and a maximum of 4, and The number of substitutions on one of the heterocycles on both sides is 0, 1, 2, 3,
In the case of 4, the number of substitutions on the other heterocycle side is 4, 3, 2,
It shows that it is 1,0. Note that j or k is 0, that is, the number of substitutions of 0 indicates non-substitution. In the above general formula [Chemical formula 4], both Z ₃ and Z ₄ may be a substituent represented by the above general formula [Chemical formula 2], but only one of them is represented by the above general formula [Chemical formula 2]. May be a substituent, in which case the other represents a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms.

The metallocene represented by the above general formula [Chemical Formula 2]
In the substituents of the group ₀₄And R₀₅Is above
The metals and substituents listed above are represented by two metallocenes.
It is a complex of cyclopentadiene and its metal (transition metal).
And unsubstituted cyclopentadiene for both of them
A ring compound is preferred, in which case the substituent is a hydrogen atom.
But at least one of them, that is, R₀₄Over
And R₀₅Have a substituent other than a hydrogen atom on at least one of the
It may be one. These substituents are two cyclopenta
In the diene ring, the types of the substituents may be the same or different.
The number of the substituents may be single or the same or different.
There may be plural, and the substitution position of the substituent is symmetric or asymmetric.
May be In this general formula [Chemical formula 2], R₀₃Is
Groups obtained by combining the groups listed above such as single bonds
There is this R₀₃As a straight chain having 1 to 22 carbon atoms
Or a branched alkylene group, especially having 1 to 8 carbon atoms
Is preferably a linear or branched alkylene group of
Yes. Also, R₀₃Is the above-mentioned general formula [Chemical formula 8], [Chemical formula 9], [Chemical formula 9]
And a substituent represented by the formula [10] is also preferable.
In each general formula, the symbols are the above-mentioned substituents and numbers
, But especially R₀₄And R₀₅Is a hydrogen atom
preferable. Further, in the above general formula [Chem. 9],
When n = 0 and m = 0, the linking group with the rosene is R₉And R_TenWhen
R₁₁The linking group of can be an alkylene group, and the carbon
You can match the above case by limiting the prime number
Where n = 1, m = 0, R₉Is a single bond or having 1 to 8 carbon atoms
An alkylene group, R_TenIs a single bond and R₁₁Is carbon
Carbon containing an ester bond which is an alkylene group of the numbers 1 to 8
Number 2 to 16 connecting group (-R₉-COO-R₁₁−)
Is also preferable. [Formula 1], [Formula 3], [Formula 1]
4], X^r-Is an r-valent organic or inorganic anion
As shown, a monovalent (r = 1) is, for example, halo.
Gen ion, ClO_Four ^-Perhalogenate ion such as BF
_Four ^-, PF₆ ^-, SbF₆ ^-Toluenesulfonate Io
And methanesulfonate ion, etc., and divalent (r =
Examples of 2) include naphthalene disulfonic acid,
Examples include benzenedisulfonic acid and ferrocenedisulfonic acid.
But preferably ClO_Four ^-, BF_Four ^-, PF ₆
^-, SbF₆ ^-Is. u is the number that makes the whole molecule neutral
Of the structure of the above general formulas [Chemical formula 1] and [Chemical formula 3]
Of which, uX^r-On the main skeleton other than
It has one acid group that can bind to on and its main bone
If the case is neutral, u is 0 (R₀₁And R₀₂of
At least one of them binds to an acid group, especially an alkali metal ion
UX when having an acid group capable of^r-Even without
It can be said that it is good. ), Having no acid groups on its main skeleton,
Is 1 or 2, u is 1 or 0.5, respectively.
Becomes

In the above general formula [Chemical Formula 4], Y₀₁And Y
₀₂Is preferably represented by the above general formula [Chemical formula 5]
Cyanine compounds. Where L and Z₃Over
And Z _Four, UX^r-Is the above general formula [Chemical formula 1]
Represents the same as Y₁And Y₂Are both carbon atoms,
Those that are sulfur atom, nitrogen atom, oxygen atom, selenium atom
Each has a substituent
, But indolenin, thiazole
System, imidazole system, oxazole system, selenazole system
It is a compound called a cyanine compound. R₁as well as
R₂Each represents a substituent listed above,
The “other substituent” in the substituent is an alkyl group,
Alkoxy, aryl, cyano and nitro groups are listed.
You can Of these, represented by the above general formula [Chemical formula 6]
Trimethine indolenine cyanine compounds
Is preferably used as a recording material for DVD-R and the like.
It In addition, the pentamethyene represented by the general formula [Chem. 7]
Indolenine-based cyanine compounds are CD-R
It is preferably used as a recording material. This general formula
6] and [Chemical 7], Z₃And Z_Four, UX^r-, R₁
And R₂Is the same as the above general formula [Chemical Formula 5]
And A, R₃~ R₆Include the substituents listed above
However, as for A, "the other substituent" in the substitution
Is an alkyl group, an alkoxy group, an aryl group, a sialic group.
And a nitro group. R₁And R₂Little
Lower alkyl when at least one of them is an alkyl group
A group (having 1 to 5 carbon atoms) is preferable, and when it is an alkoxy group,
A lower alkoxy group (having 1 to 5 carbon atoms) is preferable. R₁When
R₂Can be the same or different types of listed substituents
The number of substituents may be singular, and may be the same or different.
There may be a plurality of substitutions, and the number of substitutions may be any of 0-4.
The substitution position of both may be symmetrical or asymmetrical.
Yes. R₁And R₂Is a pair condensed at the 4, 5 and 4 ', 5'positions
A cyanine compound having a benzene ring is preferable,
Having a halogen atom instead of a benzene ring on one side
The thing is also preferable. In the above general formulas [Chemical formula 6] and [Chemical formula 7], Z
₃And Z_FourAre both the above metallocene-bonding groups,
May be a preferred metallocene-bonding group,
One is this metallocene linking group and the other is
It is an exemplified group, and it may be a lower alkyl group.
preferable.

The compound of the general formula [Chemical formula 1] belongs to the compound of the general formula [Chemical formula 3], and the compound of the general formula [Chemical formula 3] belongs to the compound of the general formula [Chemical formula 4]. The compound of the general formula [Chemical formula 4] belongs to the compound of the general formula [Chemical formula 5], and the compound of the general formula [Chemical formula 6] and [Chemical formula 7] belongs to the compound of the general formula [Chemical formula 5]. These compounds are derived from the compounds represented by the above general formula [Chemical Formula 11] or specific compounds belonging thereto, and can be synthesized by the reactions exemplified below. In the following reactions, symbols of chemical formulas have the same meanings as those in the above general formulas [Chemical formula 1] to [Chemical formula 10]. (A) Synthesis example (I) Production method of forming a cyanine skeleton from a heterocyclic compound (intermediate) having a metallocene-bonding group as a substituent (II) Production method of directly introducing metallocene into an existing cyanine compound It can be produced by the method shown below. In the case of the above method (I) (I) -1. Production of Heterocyclic Compound (Intermediate) Having Metallocene Bonding Group as Substituent The cyanine compound represented by the above general formula [Chemical Formula 1], that is, the above general intermediate which is an intermediate of a cyanine compound chemically bound with metallocene Formula [Chemical formula 1
The heterocyclic compounds belonging to [1] are mainly represented by the following (1) to
It is prepared by the three methods of (3), but is not limited to these specific methods. (1) As shown in the following reaction formula [Chemical Formula 14], a metallocene obtained by reacting a heterocyclic compound (a) having a reaction site W with a metallocene derivative (b) having a reaction site V is chemically bonded. N-alkylated heterocyclic compound (d) in which the heterocyclic compound (c) is N-alkylated with alkyl halide (X′-R ₁₃ ) or the like to bond a metallocene bonding group.
When X ′ is not a desired anion after preparing the above, it can be converted to a desired anion to prepare a specific compound (Formula 11a) belonging to the above [Formula 11]. The reaction site W may be a substitutable hydrogen of a heterocyclic ring or a substituent thereof, but by the reaction of W and V, i = 1 and Z in the above general formula A specific compound (Chemical formula 11a) which is a metallocene-bonding group represented by [2] is obtained. At that time, the above W and V each include a halogen atom, a hydroxyl group, a carboxyl group, a carbonyl group, an aryl group, an amino group, or the like reaction site (reaction point) or a side chain having a reaction site (hereinafter referred to as “reaction site etc.”). ), And each of V and W can be bonded using a coupling reaction, a substitution reaction, an alkylation reaction, or the like, and after the reaction, a connecting chain such as an alkyl, ester, amide, amine, or ether bond is formed. Those that can be formed are preferable, and R ₀₃ in the above general formula [Chemical Formula 2] is formed in this way. The same applies when i = 2, in which case Z may be the same or different. Depending on the type of reaction between V and W and the type of connecting chain after the reaction, a compound in which a plurality of the same or different metallocene bonding groups in the general formula [Chem. 11] are substituted can be obtained. The conversion of the anion can be performed by reacting with the corresponding inorganic salt or organic salt.
The heterocyclic compound having a reactive site W and the metallocene derivative having a reactive site V are, for example, "Large Organic Chemistry Vol. 14 Heterocyclic Compound I (Asakura Shoten)", "Experimental Chemistry Course 24 Organic Synthesis IV Heterocycle". Compound Synthesis Nos. 463-549
Pp. (Maruzen) "and" Large Organic Chemistry Vol. 13 Non-Benzene Aromatic Ring Compound-28 Cyclopentadienyl Compound (Asakura Shoten) "and the like.

[0014]

[Chemical 14] (In the formula, Y ₀₁ and R ₁₂ are the same as those described in the above general formula [Chemical Formula 11], and R ₀₃ , R ₀₄ , R ₀₅ and M
Represents the same as the one represented by the above general formula [Chemical Formula 2] represented by Z of the same [Chemical Formula 11], and V and W represent a halogen atom, a hydroxyl group, a carboxyl group, a carbonyl group, an aryl group, an amino group or the like. It may be a reaction site containing, and may have a linear or branched alkyl group, a linking group such as —CH═CH—, —C ₆ H ₄ —, R ₁₂ is a substituted or unsubstituted alkyl group, X 'Represents an atom or an atomic group that can be eliminated and become an anion after the reaction such as a halogen atom, a methanesulfonyl group and a toluenesulfonyl group. )

(2) As shown in the following reaction formula [Chemical formula 15], the same reaction site W as that used in the above reaction formula [Chemical formula 14]
A heterocyclic compound (a) (hereinafter referred to as a heterocyclic compound (a)
Etc., the same symbols and the same chemical formulas represent the same thing in the above reaction formulas [Chem. 14] and [15]. ) Is N-alkylated with an alkyl halide (X′-R ₁₃ ), etc. to prepare an N-alkylated heterocyclic compound (e), which is then reacted with a metallocene derivative (b) to subsequently give a desired anion. By conversion, a compound (Formula 11a) in which the metallocene bonding group is substituted in the above-mentioned General Formula [Formula 11] similar to the case of the above Formula [Formula 14] is obtained.

[0016]

[Chemical 15] (In the formula, Y ₀₁ , R ₁₂ , R ₀₃ , R ₀₄ , R _O5 , R ₁₃ , X ′,
V and W are the same as those described in the above reaction formula [Chemical formula 14]. (3) For example, 1 of a complex compound such as indolenine, thiazole, imidazole, oxazole, and selenazole
When a metallocene is introduced at the position, the following reaction formula
6], in the heterocyclic compound (a ′) and the metallocene derivative (b ′) (metallocene derivative (b), for example, V is halogen having an alkylene linking group, and the linking group and R ₀₃ are the same. And the N-alkylation reaction is used to replace the metallocene-bonding group with hydrogen of the N-alkyl group to prepare a metallocene-bonding-group-N-alkyl-group-containing heterocyclic compound (f), followed by the desired anion. In the above general formula [Chemical Formula 12], Z ₃ is a metallocene-bonding group having R ₀₃ as a linking group, and a compound (Chemical formula 12a) in which the metallocene-bonding group is bonded to an N-alkyl group is obtained.

[0017]

[Chemical 16] (In the formula, Y ₀₁ , R ₀₃ , R ₀₄ , R _O5 , R ₁₂ and X ′ are the same as those described in the above reaction formula [Chemical Formula 14].)

(I) -2. Synthesis of cyanine compound (I) -1. Specific compounds (Chemical formula 11a) and (Chemical formula 12a) obtained by substituting the metallocene bonding groups in the above general formulas [Chemical formula 11] and [Chemical formula 12] prepared as in (1) to (3), respectively. As an intermediate, and using these, the above general formulas [Chemical Formula 1], [Chemical Formula 3], [Chemical Formula 4],
A specific cyanine compound belonging to each of [Chemical Formula 5] can be synthesized. As a synthetic method thereof, a methine group (-CH =) in which L is 1, 3, 5 and 7 in these general formulas is used. Is a methine chain linked via a conjugated double bond, shown below in each case (1)
To the synthesis method according to (4). (1) In the general formulas [Chemical Formula 1] and [Chemical Formula 3], L is a cyanine compound in which one methine group (—CH =) is a methine chain bonded by forming a conjugated double bond, and a sequence thereof. As shown in the following reaction formula [Chemical formula 17], for example, as shown in the following reaction formula [Chemical formula 17], R ₁₂ in the general formula [Chemical formula 11] is a methyl group. And a heterocyclic compound (g) in which (Z) _i is (Z ₁ ) _j in the above-mentioned general formula [Chemical Formula 3] and R ₁₂ is bonded to another atom by an elimination reaction such as —SCH _3. By reacting the compound (h), which is a group and (Z) _i is (Z ₂ ) _k in the above-mentioned general formula [Chemical Formula 3], in the presence of a base such as pyridine or triethylamine in an equimolar amount, L Is a monomethine group (-CH
A cyanine compound (Chemical formula 3a) which is =) is obtained. At this time, a solvent such as alcohol or dimethylformamide may be used. The cyanine compound (Chemical Formula 3a) is Z ₁ ,
By selecting the substitution position of Z ₂ , the cyanine compound of the above general formula [Chemical formula 4] in which L is one methine group, and further by selecting the type of Y ₀₁ and Y ₀₂ , the above general formula The cyanine compound of 5] can be synthesized.

[0019]

[Chemical 17] (In the formula, Y ₀₁ , R ₀₁ , and uX ^r- represent the same as those described in the general formula [Chemical Formula 11], and (Z ₁ ) _j , that is, Z ₁ and _j are each represented by the general formula [Chemical Formula 11]. ] Described in],
_{i 02 of} the heterocyclic compound (h),
R ₀₂ is Y ₀₁ or R described in the general formula [Chem. 11].
Y _{01 01} belonged and heterocyclic compounds (g), and R ₀₁ represents what may be different the same as the respective other of these, (Z _{2) k,} i.e. Z _{2, k,} respectively the general The same as or different from Z ₁ and _{j of the} above-mentioned heterocyclic compound (g), which belong to Z and _i described in the formula [Chemical Formula 11], may be the same or different. According to the above reaction formula [Chemical formula 17], instead of one or both of the heterocyclic compounds (g) and (h), the above-mentioned compounds (Chemical formula 11a) and (Chemical formula 12a) (wherein R ₁₂ is a methyl group or H ₃ CS- or the like as a leaving group), a cyanine compound (Chemical Formula 3a) obtained by combining various heterocyclic compounds has a metallocene-bonding group in one molecule or It is possible to substitute a plurality of molecules, and it is possible to obtain a methine chain having symmetrical or asymmetrical molecular structures on both sides, and various novel metallocene-bonding group-substituted cyanine compounds can be produced. Incidentally, the cyanine compound (Formula 3a) is, using the compound (Formula 12a) on one or both, the specific cyanine compound belonging to the general formula [4], also further types of Y _01, Y ₀₂ Depending on the selection, the above general formula
The specific cyanine compound belonging to the cyanine compound can be synthesized.

(2) In the general formulas [Chemical formula 1] and [Chemical formula 3], L is a cyanine compound in which three methine groups (-CH =) are methine chains bonded by forming a conjugated double bond. And a method of synthesizing the compounds of the general formulas [Chemical Formula 4] to [Chemical Formula 6] which are sequentially embodied, for example, as shown in the following reaction formula [Chemical Formula 18], in the general formula [Chemical Formula 11], R ₁₂ is methyl. A heterocyclic compound (g) which is a group and (Z) _i is (Z ₁ ) _j of the above-mentioned general formula [Chemical Formula 3], and a condensing agent (diphenylformamidine derivative (i )) Is reacted with acetic anhydride (Ac ₂ O) or the like as a solvent to obtain a precursor (j) of a cyanine compound. The precursor (j) and the compound heterocyclic compound H ₃ CS- is H ₃ C-(methyl group) in (h) (h ') (the (g) may be the same or different from the compound) By reacting and in the presence of a base such as pyridine or triethylamine in an equimolar amount, a cyanine compound (Chemical Formula 3b) having a trimethine group (-CH = CA-CH =) can be produced.

[0021]

[Chemical 18] (In the formula, Y ₀₁ , R ₀₁ , uX ^r- , (Z ₁ ) _j , Y ₀₂ ,
R ₀₂ and (Z ₂ ) _k each represent the same one as described in the above reaction formula [Chemical Formula 17], Ph represents a phenyl group (hereinafter, the same), Ac represents an acetyl group (hereinafter,
Similarly, A represents the same one as described in the above general formula [Chemical formula 6]. As the condensing agent (diphenylformamidine-derived mono (i)), a commercially available product can be used, or it can be prepared by a conventional method using aniline and an orthoester compound such as an orthoformate ester. That is, with respect to 1 mol of orthoesters such as ethyl orthoformate and ethyl orthoacetate, alcohols such as methanol, ethanol, and isopropanol with 2 to 5 mol, preferably 2 to 2.5 mol of aniline, It can be obtained by reacting in a solvent such as dimethylformamide, dimethylsulfoxide, dioxane, toerne and xylene. The above reaction formula [Chemical formula 1
8], the condensing agent (i) is used in an amount of 1 to 5 mol, preferably 1.5 to 2.5 mol, or the acetic anhydride (Ac ₂ O) is used in an amount of 5 to 30 mol, based on the heterocyclic compound (g). It is advisable to add them in an amount of preferably 10 to 20 mol. When it is desired to obtain a cyanine compound having a symmetric structure as the above cyanine compound (Chemical Formula 3b), as shown in the following reaction formula [Chemical Formula 19], as described above, the complex compound can be obtained without passing through the cyanine compound precursor (j). A cyclic compound (g) is reacted with a diphenylformamidine derivative (i) or an orthoester compound (k) in a solvent such as pyridine or acetic anhydride, and cyanine has a symmetrical molecular structure on both sides as viewed from the methine chain. The compound (Chemical Formula 3c) may be synthesized, and preferably the compound (k) and the like are mixed and reacted in an amount of 0.5 to 6 mol, more preferably 0.5 to 3 mol.

[0022]

[Chemical 19] (In the formula, Y ₀₁ , R ₀₁ , uX ^r- , (Z ₁ ) j, and A are the same as those described in the above reaction formula [Chemical Formula 18], j is 1 or 2, and R ₁₄ Represents a methyl group, an alkyl group such as an ethyl group.) In addition, cyanine compounds (Chemical Formula 3b) and (Chemical Formula 3c) are Z ₁ ,
By selecting the substitution position of Z ₂ , the cyanine compound of the above general formula [Chemical formula 4] in which L is three methine groups, and further by selecting the types of Y ₀₁ and Y ₀₂ , the above general formula 5],
The cyanine compound of [Chemical Formula 6] can be synthesized.
According to the above reaction formulas [Chemical Formula 18] and [Chemical Formula 19], instead of the heterocyclic compounds (g) and (h ′), the above-mentioned compounds (Chemical formula 11a) and (Chemical formula 12a) (provided that R ₁₂ is a methyl group). Of one or both of the above), the cyanine compound obtained by combining various heterocyclic compounds can be substituted with a metallocene-bonding group in one molecule or a plurality of molecules in the molecule, and a symmetric or Asymmetric metallocene-substituted cyanine compounds can be synthesized, and various novel metallocene-bonded group-substituted cyanine compounds can be produced. The cyanine compound (Chemical formula 3b), (Chemical formula 3)
c) is a specific cyanine compound belonging to the above general formula [Chemical formula 4], if the above compound (Chemical formula 11b) is used for one or both, and further by the selection of the types of Y ₀₁ and Y ₀₂ , the above general formula Specific cyanine compounds belonging to the cyanine compounds of [Chemical Formula 5] and [Chemical Formula 6] can be synthesized.

(3) L in the general formulas [Chemical formula 1] and [Chemical formula 3]
Is a cyanine compound which is a methine chain in which five methine groups (-CH =) are bound by forming a conjugated double bond, and the above-indicated general formulas [Chemical Formula 4] and [Chemical Formula 5], A method for synthesizing the compound of [Chemical Formula 7], for example, as shown in the following reaction formula [Chemical Formula 20],
In the above reaction formula [Chemical Formula 18] shown in the section 1, by using a condensing agent (malonaldehyde phenylimine (l)) shown below in place of the condensing agent (diphenylformamidine derivative (i)), cyanine A compound precursor (m) was prepared and reacted with the compound (h ′), and L was a pentamethine group (—CH═CH—CA═CH—).
A cyanine compound (CH3) (Chemical Formula 3d) can be produced.

[0024]

[Chemical 20] (In the formula, Y ₀₁ , R ₀₁ , uX ^r- , (Z ₁ ) _j , Y ₀₂ ,
R ₀₂ , (Z ₂ ) _k and A are each represented by the above reaction formula
The same as those described in [8]. A commercially available product can be used as the condensing agent (malonaldehyde phenylimines (l)), and can also be prepared by a standard method using aniline and malonaldehyde bisdialkyl acetals such as tetramethoxypropane. When it is desired to obtain a cyanine compound having a symmetric structure as the above cyanine compound (Chemical Formula 3d), as shown in the following reaction formula [Chemical Formula 21], as described above, the complex compound can be obtained without passing through the cyanine compound precursor (m). The ring compound (g) is reacted with the above malonaldehyde phenylimines (l) or malonaldehyde bisdialkylacetal derivative (n) in a solvent such as pyridine or acetic anhydride to obtain a molecular structure on both sides of the methine chain. A cyanine compound (Chemical Formula 3e) having a symmetric structure may be synthesized, and the compound (n) or the like is preferably added in an amount of 0.5 to
It is advisable to add 6 moles, more preferably 0.5 to 3 moles, for reaction.

[0025]

[Chemical 21] (In the formula, Y ₀₁ , R ₀₁ , uX ^r- , (Z ₁ ) _j , R ₁₄ and A
Are the same as those described in the above reaction formula [Chemical Formula 19]. ) Incidentally, the cyanine compounds (Chemical formula 3d) and (Chemical formula 3e) are Z ₁ ,
By selecting the substitution position of Z ₂ , the cyanine compound of the above general formula [Chemical formula 4] in which L is 5 methine groups, and further by selecting the types of Y ₀₁ and Y ₀₂ , the above general formula 5],
The cyanine compound of [Chemical Formula 7] can be synthesized.
According to the above reaction formulas [Chemical Formula 20] and [Chemical Formula 21], instead of the heterocyclic compounds (g) and (h ′), the above-mentioned compounds (Chemical formula 11a) and (Chemical formula 12a) (wherein R ₁₂ is a methyl group). Of one or both of the above), the cyanine compound obtained by combining various heterocyclic compounds can be substituted with a metallocene-bonding group in one molecule or a plurality of molecules in the molecule, and a symmetric or Asymmetric metallocene-substituted cyanine compounds can be synthesized, and various novel metallocene-bonded group-substituted cyanine compounds can be produced. The cyanine compound (Chemical formula 3d), (Chemical formula 3
e) is a specific cyanine compound belonging to the above general formula [Chemical formula 4], if the above compound (Chemical formula 11b) is used for one or both, and further by the selection of the types of Y ₀₁ and Y ₀₂ , the above general formula Specific cyanine compounds belonging to the cyanine compounds of [Chemical Formula 5] and [Chemical Formula 7] can be synthesized. (4) In the general formulas [Chemical Formula 1] and [Chemical Formula 3], L is a cyanine compound in which seven methine groups (-CH =) are combined to form a conjugated double bond, and a cyanine compound and the order thereof. As shown in the following reaction formula [Chemical formula 22], the above-mentioned (2)
In the above-mentioned reaction formula [Chemical Formula 18] shown in the paragraph, the precursor (p) of the cyanine compound is obtained by using the following condensing agent (o) instead of the condensing agent (diphenylformamidine derivative) (i). Is prepared, and this is reacted with the above compound (h ′), and L is a heptamethine group (—CH═CH—CH
= CA-CH = CH-CH =) can be produced.

[0026]

[Chemical formula 22] (In the formula, Y ₀₁ , R ₀₁ , uX ^r- , (Z ₁ ) _j , Y ₀₂ ,
R ₀₂ , (Z ₂ ) _k and A are each represented by the above reaction formula
The same as those described in [8]. ) When obtaining a cyanine compound having a symmetrical structure as the above cyanine compound (Chemical Formula 3f), as shown in the following reaction formula [Chemical Formula 23], a precursor (p) of the cyanine compound as described above is obtained.
Without reacting with the heterocyclic compound (g) and the condensing agent (o) in a solvent such as pyridine or acetic anhydride, the cyanine compound having a symmetric molecular structure on both sides as viewed from the methine chain (3g ) May be synthesized, preferably 0.5 to 6 mol of the compound (o) and the like, more preferably 0.5 to 6 mol.
It is advisable to mix and react so as to be 3 mol.

[0027]

[Chemical formula 23] (In the formula, Y ₀₁ , R ₀₁ , uX ^r- , (Z ₁ ) _j and A are the same as those described in the above reaction formula [Chemical Formula 19].) Incidentally, the cyanine compound (Chemical Formula 3f), (Chemical formula 3g) is Z ₁ ,
By selecting the substitution position of Z ₂ , the cyanine compound of the above general formula [Chemical formula 4] in which L is 7 methine groups, and further by selecting the types of Y ₀₁ and Y ₀₂ , the above general formula [Chemical formula 4] The cyanine compound of 5] can be synthesized. According to the above reaction formulas [Chemical Formula 22] and [Chemical Formula 23], instead of the heterocyclic compounds (g) and (h ′), the above compound (Chemical formula 11)
a), (Chemical formula 12a) (provided that R ₁₂ is a methyl group.)
When one or both of the above are used, the cyanine compound obtained by combining various heterocyclic compounds is capable of substituting a metallocene-bonding group in one molecule or a plurality of molecules in the molecule, and a symmetric or asymmetric metallocene group. A substituted cyanine compound can be synthesized, and various novel metallocene-bonded group-substituted cyanine compounds can be produced. Cyanine compound (Chemical formula 3f), (Chemical formula 3g)
When one or both of the above compounds (Chemical formula 11b) are used, is a specific cyanine compound belonging to the above general formula [Chemical formula 4], and further, by selecting the types of Y ₀₁ and Y ₀₂ , the above general formula [5] A specific cyanine compound belonging to the cyanine compound of [5] can be synthesized.

In the case of the above method (II) (method in which metallocene is directly introduced into a cyanine compound), many known cyanine compounds have a functional group (reactive site), and such a cyanine compound is used directly. A metallocene linking group can be introduced. As a method for synthesizing various cyanine compounds, “FM Hamer
Written by Heterocyclic Compounds,
Cyanine Dyes and Related
Compounds (John Wiley & So
ns) ”and the like, and various cyanine compounds having a reactive site can be prepared by known methods.

A method for directly reacting a cyanine compound with a metallocene is, for example, a cyanine compound having a reactive group W (known) as shown in the following reaction formula [Chemical Formula 24].
A method of reacting (c1) with a metallocene compound (m1) having a reactive group V that reacts with this reactive group W to obtain a cyanine compound (mc1) substituted with a metallocene-bonding group can be mentioned.

[0030]

[Chemical formula 24] (In the formula, L, Y ₀₁ , Y ₀₂ , R ₀₁ , R ₀₂ , uX ^r- , (Z)
_i represents the same as in the above general formula [Chemical Formula 1] (Z
Represents the above general formula [Chemical Formula 2], V and W are reaction sites containing a halogen atom, a hydroxyl group, a carboxyl group, a carbonyl group, an aryl group, an amino group, and the like, and a linear or branched alkylene group, -CH It may have a connecting group such as ═CH—, —C ₆ H ₄ — and the like. )

(B) More specific synthesis of cyanine compound than in the case of (A) The cyanine compound represented by the above general formula [Chem. 5] has one or two metallocene-bonding groups in the cyanine compound. It can also be said that it is a compound bonded, specifically, the case where the metallocene-bonding group is a ferrocene-bonding group can be mentioned, but its production method is not limited to a particular production method, and for example, It can be manufactured by the method shown in the examples. (1) When one molecule of ferrocene-bonding group is bonded to a cyanine compound When the metallocene-bonding group of the above general formula [Chemical formula 2] is a ferrocene-bonding group and the linking group with ferrocene is an alkylene group, the following general formula [Chemical formula 25] A cyanine compound represented by the following general formula [Chemical formula 5], wherein L has a substituent A with three methine groups and Z ₃ is a general formula [Chemical formula 8] ], And when R ₇ and R ₈ are hydrogen atoms (in the general formula [Chem. 9], n = 0, m = 0, -R ₉ -R ₁₀ -R
_{When 11} -is an alkylene group), a cyanine compound such as an indolenine compound, a thiazole compound, an oxazole compound, or a selenazole compound)

[0032]

[Chemical 25] (In the formula, uX ^r- , Y ₁ , Y ₂ , R ₀₄ , R ₀₅ , R ₁ ,
R ₂ and Z ₄ represent the same as those in the above general formula [Chemical formula 5], A represents the same as those in the above general formula [Chemical formula 6], n represents 1 to 22, and particularly 1 to 8 Is preferred. (A) First, a ferrocene derivative (haloalkylferrocene) (f1) is prepared as shown in the following reaction formula [Chemical Formula 26].

[0033]

[Chemical formula 26] (In the formula, X'is the same as that in the above reaction formula [Chemical formula 14].
Represents the same thing, that is, a halogen atom, methanesulfo
Anionic groups such as nyl group and toluenesulfonyl group (animated
Represents a group which can be on or anion,
n, R₀₄, R₀₅Are those represented by the above general formula
Represent the same. ) That is, first, ferrocene alcohols as raw materials
Regarding (f01) (commercially available), when n is 1, a conventional method is used.
Follow the procedure below tosyl hydroxyl groups of commercially available ferrocenemethanol
(When X'is a toluenesulfonyl group), mesylation
(When X'is a methanesulfonyl group) or halogenated
(When X ′ is a halogen atom)
(F1) (when n = 1) is obtained. When n is 2 or more
If you use commercially available ferrocene alcohols,
And the compound of the above (f1) (when n is larger than 1)
May be obtained, but ferrocene (f02) and ha are used as raw materials.
Rocarboxylic acid halide (Hal- (CH₂)_n-1-C
Belongs to OHal (Hal represents a halogen atom)
For example, halocarboxylic acid chloride (X '-(CH₂)
_n-1-COCl (X 'represents a halogen atom)
(F03) was reacted according to the conventional method in the presence of aluminum chloride.
Acylation by so-called Friedel-Crafts reaction
To give intermediate (f04)
Aluminum groups (--CO groups among them) with aluminum chloride and NaB
H_Four, AlLiH_FourIt is obtained by reducing with a reducing agent such as. Profit
In the compound of (f1) above, X ′ is
Iodine atom, methanesulfonyl group, toluenesulfonyl
In the case of a group, uX of the above general formula ^r-Is that
Halogen ion, methanesulfonate ion, toluene
It becomes a sulfonate ion. The halogen ion is iodine
UX in all other cases^r-Iodide
React with inorganic iodine salts such as sodium and potassium iodide
Can be obtained. Other desired organic or inorganic salt
It can be replaced with the desired anion.

(B) As shown in the following reaction formula [Chemical Formula 27], a ferrocene-bonded group-substituted heterocyclic compound (intermediate of cyanine compound) (fc1) is prepared.

[0035]

[Chemical 27] (In the formula, Y ₁ , R ₁ , R ₀₄ , R ₀₅ and n represent the same as those in the above general formula [Chemical formula 25].) That is, first, the heterocyclic ring on the left side of the above general formula [Chemical formula 25]. To prepare a compound (hc1) necessary for constituting the above, that is, compounds such as indolenines, thiazoles, oxazoles, and selenazoles. Note that these are available off-the-shelf (known). Next, the compound (hc1) and the compound (f1) are passed through an N-ferrocene-bonded group-substituted hetero compound (intermediate) (fc01) to undergo anion conversion (as shown in the reaction formula [Chemical Formula 14]). X'is uX ^r-
The above compound (fc1) is prepared. That is, each compound of the compound (f1) and the compound (hc1) is treated with alcohol, acetone, dichloromethane, chloroform, carbon tetrachloride, toluene, xylene,
The reaction is carried out in a solvent such as dimethylformamide or dimethylsulfoxide at about room temperature to about 150 ° C. to carry out N alkylation (substitutional alkylation with a substituted alkyl group, the same applies hereinafter). When uX ^r- is not the desired anion, it is converted to the desired anion by subsequent reaction with an inorganic salt or organic salt corresponding to the desired anion.

(C) As shown in the following reaction formula [Chemical Formula 28], a methine chain-bonded heterocyclic compound (an intermediate of a cyanine compound) (hc2 ') is prepared.

[0037]

[Chemical 28] (In the formula, uX ^r- , Y ₂ , R ₂ , Z ₄ and A represent the same as those in the above-mentioned general formula [Chemical formula 25].) As the condensing agent for bonding the methine chain between the rings to the heterocycle on the right side thereof, the above-mentioned diphenylformamidine derivative (i)
To use. A heterocyclic compound (hc2), which is a compound having a heterocyclic ring on the right side of the compound represented by the general formula [Chem. Off-the-shelf (known) products are available for these compounds. Next, the diphenylformamidine derivative (i) and the heterocyclic compound (hc
An intermediate (hc2 ′) of a cyanine compound is prepared with 2). That is, 1 of the above heterocyclic compound (hc2)
The diphenylformamidine derivative condensing agent is mixed in an amount of 1 to 5 mol, preferably 1.5 to 2.5 mol, and acetic anhydride in an amount of 5 to 30 mol, preferably 10 to 20 mol. It is obtained by reacting. At this time, acetic acid or the like may be used as the solvent. (D) As shown in the following reaction formula [Chemical Formula 29], a cyanine compound (Chemical Formula 25a) of the above general formula [Chemical Formula 25] is prepared.

[0038]

[Chemical 29] Intermediates (fc1) and (hc) of the above cyanine compounds
2 ') prepares the cyanine compound (Formula 25a) of the above-mentioned general formula [Formula 25]. That is, the intermediate (fc
It is obtained by reacting the respective compounds 1) and (hc2 ′) in the presence of a base such as pyricin or triethylamine in equimolar amounts. At this time, a solvent such as alcohol or dimethylformamide may be used.

The specific method for producing a cyanine compound belonging to the above-mentioned general formula [Chemical formula 6] belonging to the above-mentioned general formula [Chemical formula 5] is, of course, the concrete method belonging to the above-mentioned general formula [Chemical formula 5]. Although the method for producing a cyanine compound can be applied, it can be summarized as in the following reaction formulas [30], [31] and [32].

[0040]

[Chemical 30]

[Chemical 31]

[Chemical 32] (In [Chemical Formula 30], [Chemical Formula 31] and [Chemical Formula 32], R ₃ ,
R ₄ , R ₅ and R ₆ are the same as those described in the above general formula [Chemical formula 6], and other abbreviations are the above-mentioned general formula [Chemical formula 2]
5], the same as those described in the above reaction formulas [Chemical formula 26] to [Chemical formula 29]. )

In the above general formula [Chemical formula 5], L is 5
Indolenine-based cyanine compound represented by the above general formula [Chemical Formula 7] when the number of methine groups is the same, and similar indolenine-based compound when L is 7 methine groups in the above general formula [Chemical Formula 5] With respect to the cyanine compound, the method for forming each methine chain has been described above, but the above reaction formula [Chemical Formula 2] is used in the same manner except that a condensing agent therefor is used.
6] to [Chemical Formula 32]. The same applies to the case (2) described later. When the metallocene-bonding group of the general formula [Chemical Formula 2] is a ferrocene-bonding group and the linking group with ferrocene is a connecting chain of an ester group and an alkylene group, a cyanine compound represented by the following general formula [Chemical Formula 33] In the formula [Chemical formula 5], L is three methine groups having no substituents, and Z ₃ is a general formula [Chemical formula 2] in which the above formula [Chemical formula 10] is n = q, m = n. In the case of, an indolenine-based, thiazole-based, oxazole-based, or selenazole-based cyanine-based compound) production method.

[0042]

[Chemical 33] (In the formula, uX ^r- , Y ₁ , Y ₂ , R ₀₄ , R ₀₅ , R ₁ ,
R ₂ , Z ₄ and A represent the same as those described in the above general formula [Formula 25], n is preferably 1 to 22, particularly 1 to 8, q is an integer, and 0 to 7 is particularly preferable. . )

(A) As shown in the following general formula [Chemical Formula 34], a precursor (c) of a ferrocene-bonded group-substituted cyanine compound
01) is prepared.

[0044]

[Chemical 34] (In the formula, uX ^r- , Y ₁ , Y ₂ , R ₁ , R ₂ , Z ₄ , A,
n represents the same one as described in the above general formula [Chemical Formula 33], and X ′ represents an anionic group (anion or a group capable of becoming an anion) such as a halogen atom, a methanesulfonyl group or a toluenesulfonyl group. . )

First, as shown in the lower stage of the reaction formula [Chemical Formula 34], the heterocyclic compound (hc1) and X '-(CH ₂ )
n-OH (alcohols having a leaving group that is eliminated by the reaction of iodoalcohol) (al1),
The reaction product is subjected to anion conversion as shown in the above reaction formula [Formula 26] to prepare an N-alkylene hydroxyheterocyclic compound (hc1 ′). That is, the alcohol (al1) and the heterocyclic compound (h
c1) indolenines, thiazoles, oxazoles, selenazoles and the like in a solvent such as alcohol, acetone, dichloromethane, chloroform, carbon tetrachloride, toluene, xylene, dimethylformamide, dimethylsulfoxide at room temperature to about 150 ° C. The reaction is followed by N alkylation. When X'is not the desired anion,
Subsequently, the desired anion is converted into the desired anion of uX ^r- by reacting with an inorganic salt or an organic salt corresponding to the desired anion. On the other hand, the above compound (hc2) and the above reaction formula
8] The condensing agent (diphenylformamidine derivative) (i) shown in 8] is reacted in the presence of Ac ₂ O (acetic anhydride) to prepare a methine chain-bonded heterocyclic compound (hc2 ′).

(B) In order to form the skeleton of the cyanine compound, the above compound (hc1 ') and the above compound (hc
2 ′) is reacted to prepare the above compound (c01).
That is, the compound (hc1 ′) and the compound (hc1)
It is obtained by reacting 2 ') with equimolar amounts in the presence of a base such as pyridine or triethylamine. At this time, a solvent such as alcohol or dimethylformamide may be used. (C) As shown in the following reaction formula [Chemical Formula 35], a compound of the above general formula [Chemical Formula 33a] is prepared from the above compound (c01) and ferrocenecarboxylic acids.

[0047]

[Chemical 35] (In the formula, uX ^r- , Y ₁ , Y ₂ , R ₁ , R ₂ , Z ₄ , A,
n and q are the same as those described in the above general formula [Chemical Formula 33]. That is, a hydroxyl group of the compound (c01) and a ferrocenecarboxylic acid (ferrocene having a carboxyl group-containing group as a substituent) (fcr1) are bound by an ester bond by a coupling reaction to form a cyanine compound of the general formula [Chemical Formula 33]. A system compound (Chemical Formula 33a) is prepared. At this time, for the ester formation, a DCC (dicyclohexylcarbodiimide) method or an esterification formation reaction with an acid chloride of ferrocenecarboxylic acid or an anhydride of ferrocenecarboxylic acid in the presence of a base can be used. At this time DC
When method C is used, a base such as dimethylaminopyridine may be added.

The specific method for producing a cyanine compound belonging to the above-mentioned general formula [Chemical formula 6] belonging to the above-mentioned general formula [Chemical formula 5] is, of course, the concrete method belonging to the above-mentioned general formula [Chemical formula 5]. Although the method for producing a cyanine compound can be applied, it can be summarized as in the following reaction formulas [36] and [37].

[0049]

[Chemical 36]

[Chemical 37] (In [Chemical 36] and [Chemical 37], R ₃ , R ₄ , R ₅ , R ₆
Represents the same one as described in the above general formula [Chemical Formula 6],
Other abbreviations are the same as those described in the above general formula [Chemical Formula 33] and the above reaction formulas [Chemical Formula 34] to [Chemical Formula 35]. )

In the above general formula [Chemical formula 5], L is 5
Indolenine-based cyanine compound represented by the above general formula [Chemical Formula 7] when the number of methine groups is 1, or an indolenine-based cyanine type compound when L is 7 methine groups in the above general formula [Chemical Formula 5] Regarding the compound, the method for forming each methine chain was also described above for the same indolenine-based cyanine-based compound as described above, but the above reaction formula [Chemical Formula 34] was performed in the same manner except that a condensing agent for that purpose was used.
~ It can be manufactured according to [Chemical Formula 37]. The same applies to the case (2) described later. (2) When two molecules of ferrocene-bonding group are bonded to a cyanine compound When the metallocene-bonding group of the above general formula [Formula 2] is a ferrocene-bonding group and the linking group of the ferrocene-bonding group with ferrocene is an alkylene group A cyanine compound represented by the general formula [Chemical Formula 38] (in the general formula [Chemical Formula 5], L is a methine group and a substituent A
And Z ₃ and Z ₄ are both in the general formula [Chemical formula 8] belonging to the general formula [Chemical formula 2], and R ₇ and R ₈ are hydrogen atoms, an indolenine-based, thiazole-based, and oxazole System or selenazole-based cyanine compound)

[0051]

[Chemical 38] (In the formula, uX ^r- , Y ₁ , Y ₂ , R ₁ and R ₂ are the same as those described in the above general formula [Chemical Formula 5], and R ₀₄ , R ₀₅
Is the same as the one represented by the above general formula [Chemical formula 2] represented by Z ₁ and Z ₂ in the above general formula [Chemical formula 5],
R ^_'04, R' ₀₅ is respectively the same meaning as R _04, R _05, which may be the same or different and each also may be the same or different from each other, n, n 'are be the same or different Well, n and n ′ are preferably 1 to 22, and particularly preferably 1 to 8. ) It can be produced as shown in the following reaction formula [Chemical Formula 39].

[0052]

[Chemical Formula 39] (In the formula, uX ^r− , Y ₁ , Y ₂ , R ₁ , R ₂ , R ₀₄ ,
R ₀₅ , R ′ ₀₄ , R ^′ ₀₅ , n, n ′ and A represent the same as those represented by the above general formula [Chemical Formula 38], and X ′ represents the one represented by the above reaction formula [Chemical Formula 26]. Represent the same. )

First, the above reaction formulas [Formula 26] and [Formula 27]
And an N-ferrocene-bonded heterocyclic compound (fc1) prepared according to the above, and a diphenylformamidine derivative (i)
From the above, a precursor (fc1 ′) of a ferrocene-bonded group-substituted cyanine compound is prepared. That is, 1 to 5 mol of the condensing agent of the diphenylformamidine derivative (i) is added to 1 mol of the N-ferrocene-bonded heterocyclic compound (fc1),
Preferably, it is 1.5 to 2.5 mol, and acetic anhydride is 5 to 5 mol.
It is obtained by mixing and reacting so as to be 30 mol, preferably 10 to 20 mol. At this time, acetic acid or the like may be used as the solvent. Then, in the same manner as in the above-mentioned reaction formula [Chemical formula 27], the compound (hc3) necessary for constituting the right heterocycle of the above-mentioned general formula [Chemical formula 38], that is, indolenines, thiazoles, oxazoles, etc. And a compound (f1 ′) necessary for constituting the ferrocene-bonding group on the right side of the general formula [Chemical Formula 38] prepared by the same procedure as the above-mentioned reaction formula [Chemical Formula 26]. A group-substituted heterocyclic compound (fc3) is prepared. That is, each compound of the above compounds (hc3) and (f1 ′) is treated at room temperature to 150 ° C. in a solvent such as alcohol, acetone, dichloromethane, chloroform, carbon tetrachloride, toluene, xylene, dimethylformamide and dimethylsulfoxide.
After reacting to some extent to carry out N-alkylation, it is converted into a desired anion by reacting with an inorganic salt or organic salt corresponding to the desired anion. The above general formula [Formula 38a] is adjusted by the intermediate (fc1 ′) of the ferrocene-bonding group-substituted cyanine compound and the N-ferrocene-bonding group-substituted heterocyclic compound (fc3). That is, it can be obtained by reacting the respective compounds of the intermediates (fc1 ′) and (fc3) in the presence of a base such as pyridine or triethylamine in an equimolar amount. At this time, a solvent such as alcohol or dimethylformamide may be used. When it is desired to obtain a cyanine compound having a symmetric structure as the above general formula [Chemical Formula 38], the above reaction formula [Chemical Formula 26] is used without passing through the precursor (fc1 ′) of the ferrocene-bonding group-substituted cyanine compound as described above. ] The diphenylformamidine derivative (i) or the orthoester compound is preferably added in an amount of 0.5 to 6 mol, and more preferably 0.1% to 1 mol of the N-ferrocene-bonding group heterocyclic compound (fc1) prepared according to [Chemical Formula 27]. 5-3
It is mixed in a molar amount and reacted in the presence of a base such as pyridine or triethylamine to give a compound of the above general formula
Among the compounds belonging to the category II, those having a symmetric structure in the molecular structure on both sides of the methine chain can be obtained. At this time, a solvent such as alcohol or dimethylformamide may be used.

When the metallocene-bonding group of the general formula [Chemical Formula 2] is a ferrocene-bonding group and the linking group of the ferrocene-bonding group to ferrocene is a connecting chain of an ester group and an alkylene group, the following general formula [Chemical Formula 40] A cyanine compound represented by the formula (L in the above general formula [Chem. 5] is a methine group having three substituents A
In the above general formula [Chemical formula 10] in which Z ₃ and Z ₄ both belong to the general formula [Chemical formula 2], one of them is n = q, m = n,
The other is a method of producing an indolenine-based, thiazole-based, oxazole-based, or selenazole-based cyanine-based compound) where n = q ′ and m = n ′.

[0055]

[Chemical 40] (In the formula, uX ^r- , Y ₁ , Y ₂ , R ₁ and R ₂ are the same as those in the above general formula [Chemical formula 5], and R ₀₄ and R ₀₅ are described in the above general formula [Chemical formula 5]. of Z _1, Z ₂ represent the same as those described in the formula 2 indicated, R _'04, R
_^'05 are respectively the same meaning as R _04, R _05, which may be the same or different and each also may be the same or different from each other, n, n' may be the same or different,
n and n ′ are preferably 1 to 22, particularly preferably 1 to 8, and q is an integer of 0 or more, particularly preferably 0 to 8. ) It can be produced as shown in the following reaction formula [Chemical Formula 41].

[0056]

[Chemical 41] (In the formula, uX ^r− , Y ₁ , Y ₂ , R ₁ , R ₂ , R ₀₄ ,
R ₀₅ , R ′ ₀₄ , R ^′ ₀₅ , n, n ′, A and q are the same as those described in the above general formula [Chemical formula 40], and X ′ is the same as those in the above reaction formula [Chemical formula 26]. Represents the same thing. )

First, a precursor (hc1 ″) of a cyanine compound is prepared from the compound (hc1 ′) shown in the above reaction formula [Chemical Formula 34] and the diphenylformamidine derivative (i). That is, with respect to 1 mol of the compound (hc1 ′), 1 to 5 mol, preferably 1.5 to 2.5 mol, of a condensing agent of the diphenylformamidine derivative (i), and 5 to 30 mol of acetic anhydride are used. , Preferably 10 to 20 mol, and obtained by reacting. At this time, acetic acid or the like may be used as the solvent. Then, by the same procedure as in the above-mentioned reaction formula [Chemical Formula 34], the compound (hc3) necessary for constituting the right heterocycle of the above-mentioned General Formula [Chemical Formula 40], that is, indolenines, thiazoles, oxazoles, etc. Compounds and alcohols having leaving groups (al1 ')
From the, N-alkylene hydroxy heterocyclic compound (hc
3 ') is prepared. That is, each of the above compounds (hc3) and (al1 ′) is reacted at room temperature to about 150 ° C. in a solvent such as alcohol, acetone, dichloromethane, chloroform, carbon tetrachloride, toluene, xylene, dimethylformamide, dimethylsulfoxide and the like. Then, after performing N-alkylation, an inorganic salt or an organic salt corresponding to the desired anion is reacted to convert into the desired anion. Furthermore, in order to form the skeleton of the cyanine compound, the above compounds (hc1 ″) and (hc3 ′)
And are reacted to prepare the above compound (c01 ′). That is, it can be obtained by reacting each of the above intermediates (hc1 ″) and (hc3 ′) in the presence of a base such as pyridine or triethylamine in an equimolar amount. At this time, a solvent such as alcohol or dimethylformamide may be used. As shown in the following reaction formula [Chemical Formula 42], the compound (c01 ′) and the ferrocenecarboxylic acid (fcr1)
Then, the compound of the above general formula [40a] is prepared. That is, the hydroxyl group of the above (c01 ′) and the above reaction formula
The ferrocenecarboxylic acid (fcr1) shown in (4) can be bound by an ester bond by a coupling reaction in the same manner as in the above reaction formula [Chemical Formula 35] to obtain the compound of the above general formula [Chemical Formula 40a]. When it is desired to obtain a cyanine compound having a symmetric structure represented by the general formula [Chemical Formula 40], the compound (hc1 ″) can be obtained without going through the compound (hc1 ″).
1 ') 1 mole of the diphenylformamidine derivative (i) or orthoester compound is added in an amount of 0.5 to 6 moles, preferably 0.5 to 3 moles to prepare a base such as pyridine or triethylamine. Among the compounds belonging to the above compound (c01 ′), a compound having a symmetric structure on both sides of the methine chain is obtained by reacting in the presence of the compound (c01 ′). At this time, a solvent such as alcohol or dimethylformamide may be used. Subsequently, in the same manner as described above, an ester forming reaction is carried out with ferrocenecarboxylic acids (fcr1), and among the compounds belonging to the above general formula [Chemical Formula 40a],
A methine chain whose molecular structure on both sides is symmetrical is obtained.

[0058]

[Chemical 42]

A cyanine compound of the above general formula [Chemical Formula 1],
A cyanine compound of the above general formula [Chemical Formula 3]
The cyanine-based compound of the general formula [Chemical formula 4] belonging to the general formula [Chemical formula 3] and the cyanine-based compound of the general formula [Chemical formula 5] belonging to the general formula [Chemical formula 4]
4] to [Chemical Formula 23] and [Chemical Formula 24], and the cyanine compound (Z ₁
And Z ₂ in which at least one of the groups of the general formula [Chemical formula 2] is substituted)
5], [Chemical Formula 33], and [Chemical Formula 38], the cyanine compound can be produced, and the obtained cyanine compound can be identified by, for example, an NMR analyzer. That is, a specific analysis value of a ferrocene-bonding group such as a ferrocene-bonding group bonded to an N-alkyl group, and a balance of a cyanine compound (dye), that is, a structure in which a heterocycle is bonded to both sides of a methine chain, It can be identified by a specific analytical value. The above general formula [Chemical formula 1] that can be identified in this way
Since the cyanine-based compound belonging to (1) has a basic skeleton similar to that of the cyanine-based dye conventionally used in the optical recording medium, it is absorbed in a solution, for example, between 550 and 600 nm, as shown in Examples described later. To have a maximum,
It is a novel compound having a sharp absorption spectrum and a high molar extinction coefficient, and by binding a metallocene to a cation molecular skeleton, it is possible to realize high light resistance and moisture resistance which cannot be obtained by a conventional cyanine dye alone. Further, suitable conditions and qualities for producing an optical recording medium are, for the dye material to be used, solubility in a solvent when obtaining the solution, light resistance, water resistance and sensitivity of a recording layer obtained by coating and drying the solution. The cyanine compound belonging to the above-mentioned general formula [Chemical formula 1] is sufficient to achieve the object in terms of solubility and sensitivity, though it is greatly affected by thermal decomposition characteristics and the like.

Not only that, the cyanine compound of the general formula [Chemical formula 1] substituted with the group of the above-mentioned general formula [Chemical formula 2] has a metallocene-bonding group such as a ferrocene-bonding group in the molecule. For example, as compared with the case of being substituted with another substituent such as an alkyl group, some can lower the thermal decomposition temperature, and some can improve the weight loss rate during thermal decomposition. As described above, the light resistance and the humidity resistance can be remarkably improved while the thermal decomposition property is at least equivalent to this, and the solubility in a solvent is also good. From this, as described above, in place of ferrocene as a combustion improving additive described in JP-A-4-31434, etc., the above general formula [Chemical Formula 2] is substituted. 1]
It is also possible to use the cyanine compound. Further, this cyanine compound is used as an optical recording material, a colorant-related other spectral sensitizer, a fluorescent labeling agent, etc., alone or together with other dye materials as a cyanine dye, or together with other dye materials or other materials as an additive. It can also be used. In particular, application to an optical recording medium is epoch-making because it is possible to utilize these characteristics, and this point will be described in more detail below. Generally, write-once type optical recording media (CD-R, DVD-R, etc.) in which an organic dye represented by a cyanine dye or an azo dye is used as a material for the recording layer, the dye in the recording layer absorbs laser light during recording. , The recording layer (dye layer) in the portion where the temperature is locally raised and
A part (pit) whose optical characteristics are changed due to chemical and physical changes of the substrate of the recording medium and their interface, and to detect the optical difference between that part and the part which is not changed during reproduction. Is a mechanism for reading the presence or absence of the pit. For such laser light,
Laser light having a wavelength of about 780 nm is used for the CD-R, and laser light having a wavelength of 635 to 660 nm is used for the DVD-R. Further, as an optical recording medium having a recording density higher than that of the CD-R and DVD-R, an optical recording medium using a laser beam of 530 nm or less, for example, a blue semiconductor laser is being studied for practical use. -13747
No. 8 and the like report on these high-density write-once type optical recording media using organic dyes. As described in the section "Prior Art", conventional cyanine dyes widely used as recording layer materials for these write-once type optical recording media are generally used because they have poor light resistance and moisture resistance. Similarly, the optical recording medium also has low light resistance and moisture resistance, which may cause problems in long-term storage and storage under high temperature and high humidity. When using a conventional cyanine dye, generally, a stabilizer is added to improve light resistance and moisture resistance, but even in this case, the stabilizing effect is not sufficient, and the cyanine dye alone is used. In some cases, the optical characteristics and thermal decomposition characteristics of the recording layer tended to change as compared with those used in, and as a result, the recording characteristics of the optical recording medium deteriorated.

When the cyanine compound of the present invention is used as a means for solving these problems, the optical recording medium used as a recording material using the same has the same light resistance because of its excellent light resistance and moisture resistance. Since it has excellent moisture resistance, it has excellent storage stability under long-term storage, high temperature, and high humidity, and it has optical characteristics and thermal decomposition characteristics equivalent to or better than conventional cyanine dyes. The recording medium can have excellent recording characteristics. In addition, as a more practical aspect, the novel cyanine compound and the like can be used alone as a recording material without adding or mixing a stabilizer as an additive. Can be prevented, and the workability during production and the stability of quality can be improved.

The cyanine compound and the like of the present invention are prepared by using the above-mentioned CD
When used as a material for a recording layer in a write-once type optical recording medium such as -R or DVD-R, a compound having an appropriate structure should be selected according to the wavelength of the laser beam used, and the absorption wavelength of the compound should be adjusted. It is also possible to find practical characteristics. Generally, in the above-mentioned optical recording media, in a CD-R using a laser beam having a wavelength near 780 nm, the absorption wavelength (maximum absorption wavelength) of a thin film used as a recording layer is 650 to 800 nm.
And more preferably 700 to 75
The novel cyanine compound of the present invention represented by the above general formula [Chemical formula 1] has a pentamethine chain in which the methine chain has 5 carbon atoms, and the heterocycle is an indolenine ring. Those represented by the above general formula (Formula 7) are suitable, but the present invention is not limited thereto. Further, in a DVD-R using a laser beam having a wavelength of 635 to 660 nm, the absorption wavelength (maximum absorption wavelength) of the thin film used as the recording layer is preferably 550 to 660 nm, more preferably 570 to 640 nm,
Corresponding to this, a novel cyanine compound of the present invention has a methine chain having a trimethine chain of 3 carbon atoms,
The heterocycle having an indolenine ring (the one represented by the general formula [Chemical Formula 6] above is suitable, but the heterocycle is not limited thereto. In addition, laser light of shorter wavelength (wavelength 530
It is considered that it is desirable that the absorption wavelength (maximum absorption wavelength) of the thin film be in the range of 350 to 530 nm in a high density recording medium using a wavelength of not more than 350 nm). Those having a monomethine chain in which the carbon number of the methine chain is 1 and those having a trimethine chain in which the carbon number of the methine chain is 3 are suitable for this. Also,
It is also possible to use laser light having a plurality of wavelengths by mixing several kinds of compounds each having an absorption maximum in each wavelength range described above, for example, CD-R and DV.
It can be commonly used for D-R and the like.

Especially as a cyanine dye, alone or together with other dye materials or other materials, or as an additive (a light stabilizer and / or a thermal decomposition accelerator, both) together with other dye materials in an optical recording material, For example, wavelengths 630-6
When a recording layer of an optical recording medium such as a DVD-R, which is required to have a high-density recording capacity of 3.95 GB or 4.7 GB, is formed by recording / reproducing with a 90 nm semiconductor laser, Especially when used alone as a cyanine dye, the recording sensitivity at the time of recording by laser light can be significantly improved by improving its thermal decomposability, and there is a demand for higher recording sensitivity for high-speed recording. In addition to being able to respond, it is possible to dramatically improve durability against laser light irradiation at the time of recording / reproducing and light resistance which is excellent in preservability even when stored for a long time under natural light.

In particular, in order to realize high-speed recording on the optical recording medium such as the DVD-R, it has been proposed to reduce the optimum recording power (Japanese Patent Laid-Open No. 2000-276767 etc.), and a low laser power, that is, An optical recording material capable of forming sharp pits (concave recording portions) even with low energy is preferred. That is, when the thermal decomposition temperature is very high (for example, 400 ° C. or higher), the temperature rise must be increased by absorbing the laser light, and high laser power is required, so high-speed recording is required. It is considered to be unsuitable, and when the thermal decomposition temperature is too low (for example, 100 ° C. or less), the thermal stability is too low, resulting in destabilization of pit formation and deterioration of long-term storage stability after recording. There is a problem. Therefore, it is considered that the thermal decomposition temperature of the recording material is preferably 100 to 400 ° C., and more preferably 150 to 350 ° C., but the cyanine-based compound of the general formula [Chemical formula 1] substituted with the group of the general formula [Chemical formula 2] is used. When the compound is used in an optical recording material as a cyanine dye or an additive, it has a thermal decomposition temperature in the range of 150 to 320 ° C. and has good thermal decomposability as a cyanine dye, as shown in Examples described later. alone, especially if used in thermal degradability is improved, in particular X ^- a is an anion of peroxide such as dye anion is perchlorate (ClO ₄ ^{- -)} or periodate (IO ₃₎ When used, it shows a very sharp thermal decomposition peak (the rate of weight loss with respect to temperature changes is sharp), and also shows a relatively low thermal decomposition temperature,
An optical recording material having excellent thermal decomposition characteristics can be provided.

Further, in particular, the cyanine compound of the above-mentioned general formula [Chemical formula 1] substituted by the above-mentioned general formula [Chemical formula 2], its dye, the optical recording material containing them, and the optical recording using this optical recording material. When M in the general formula [Chemical Formula 2] is iron (Fe) and R ₀₄ and R ₀₅ are both ferrocenes which are hydrogen, the medium is industrially widely used in other fields. It is more preferable because it is used as an inexpensive material and has less influence on environmental pollution as compared with other transition metals when it is disposed of. Further, in particular, an optical recording material using the cyanine compound represented by the general formula [Chemical Formula 1] substituted by the general formula [Chemical Formula 2] alone as a cyanine dye, and an optical recording medium using the same are light-proofing agents. When it is not necessary to add various dyes or mix various dyes, adjustment of the composition of the optical recording material and its optical adjustment are made to simplify the work process in the production of the optical recording medium and enable recycling for cost reduction. There are many advantages such as extremely easy quality control of the performance of the recording layer made of the recording material. Particularly in the case of an optical recording medium, addition of a stabilizer and mixing of other dyes can be suppressed, so that deterioration of recording characteristics can be prevented, and workability and quality stability can be improved. .

The cyanine compound of the above general formula [Chemical formula 1] substituted by the above general formula [Chemical formula 2] can be used in combination with other dye materials as a cyanine dye or an additive. Is other cyanine dye other than the above-mentioned cyanine compound to be used,
At least one of polymethine dyes, quinoline dyes, azo dyes, styryl dyes and phthalocyanine dyes can be used. Further, since the cyanine compound of the present invention has excellent light resistance, it can be used alone without adding a light stabilizer, but if necessary, singlet oxygen quencher, radical scavenger, etc. Can also be used by adding as a stabilizer, as those stabilizers,
Nitroso compounds, aminium salts, immonium salts, diimonium salts, transition metal chelate complexes (dithiol type, acetylacetonate type), metallocenes, azo type metal complexes, and the like, and as a sensitizer other than these additives Other compounds having a function such as a light absorber and a flame retardant accelerator may be added. The above general formulas [Chemical formula 11] to [Chemical formula 1]
The intermediate represented by [3] also has excellent light resistance and moisture resistance, and exhibits the same effect as when the cyanine compound of the present invention is used by using it together with the cyanine compound of the present invention or with other coloring materials. You can also let it.

When the cyanine compound of the general formula [Chemical Formula 1] or an intermediate thereof is used as an optical recording material, a transparent substrate such as polycarbonate or polymethylmethacrylate is used, and the cyanine compound is cyanine compound on the surface thereof. Solvents alone or as a mixture with other materials as a system dye (for example, alcohols such as methanol, propanol, fluorinated alcohols, cellosolves such as methyl cellosolve,
1-20 obtained by dissolving in diacetone alcohol, etc.
% (Mass%, the same applies hereinafter) solution (when the cyanine compound is used as a dye mixed with other materials, it is preferable to use 50 to 100% of the cyanine compound in the mixture) as easily as spin coating. It is applied by various coating methods and dried to form a recording layer having a thickness of, for example, 0.1 to 5 μm. An optical recording medium is obtained by forming a reflective layer of gold, silver, aluminum or the like on the coating film by vapor deposition, and coating a protective layer made of an ultraviolet curable resin on the reflective layer. As the above-mentioned substrate, in addition to polycarbonate and polymethylmethacrylate, a resin substrate such as polyethylene terephthalate or a glass substrate is preferable, and the surface thereof is, for example, 0.
A guide groove (pre-groove) for 63 to 0.8 μm or other laser light may be formed. In addition to the spin coating method, the recording layer may be formed by a vacuum deposition method, a sputtering method, a molecular beam growth method, a casting method, a dipping method, or the like. The spin coating method is particularly preferable from the viewpoint of cost and mass productivity. preferable. When a coating method such as a spin coating method is used, examples of the solvent include those exemplified above, alcohols such as methanol, propanol, and isopropanol, tetrafluoroalcohol, octafluoropentanol. Fluorinated alcohols such as, cellosolves such as methyl cellosolve, esters such as butyl acetate and cellosolve acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ketone alcohols such as diacetone alcohol, chlorination of dichloromethane, chloroform, etc. Hydrocarbons, amides such as dimethylformamide and dimethylacetamide, and the like can be used. Further, these solvents, including those exemplified above, are used alone or in combination of two or more as described above in consideration of the solubility of the cyanine compound of the present invention, its intermediates and other materials to be mixed. be able to. Further, using the above solvent, as described above, 1 to 20% of the cyanine compound of the present invention or an intermediate thereof or a mixture thereof (preferably using 50 to 100% of the cyanine compound in the mixture) is dissolved. It is possible to form a recording layer by forming a film using the above solution and further drying.
Further, in the film formation when forming the recording layer, if necessary, a binder may be added in addition to the above-mentioned materials, and as the binder, cellulose acetate, nitrocellulose, polymethyl methacrylate, polyvinyl alcohol, Examples include polycarbonate.

A reflective layer may be provided on the recording layer as described above. As the material for the reflective layer, in addition to the above-mentioned gold, silver and aluminum, a metal such as copper, platinum or palladium, or the like can be used. It is also possible to use that alloy, or an alloy to which a trace amount component other than these is added, and the reflective layer can be formed by vapor deposition, sputtering, or the like. Also,
A protective layer using an ultraviolet curable resin may be provided on the reflective layer as described above, but another dummy substrate may be further laminated thereon via an adhesive layer. It is also possible to obtain an optical recording medium having a layer structure in which double-sided recording is possible by adhering another substrate having a layer structure so that the recording layer is on the inside.

In order to perform recording on the optical recording medium obtained as described above, a laser beam is normally irradiated along the guide groove with a specific pulse signalized by reading information such as an image. The recording layer formed on the guide groove absorbs the energy of the laser light as described above, and the temperature locally rises, whereby the dye in the recording layer is decomposed, dissolved, Chemical changes such as chemical changes,
Micropores (pits) whose optical characteristics are changed by physical or both causes are formed. By scanning with a laser beam having a power smaller than that at the time of recording at the time of reproduction, a signal can be read by utilizing an optical difference such as reflectance, and the signal can be converted to read information.

In addition to the optical recording materials used in the optical recording medium as described above, the cyanine compound and the intermediate thereof of the present invention are not limited in their applications and may be used alone or in combination with other materials. In addition to the above-described combustion improving additive and fluorescent labeling agent, it may be used as a visible light absorber for solar cells, a filter for various information display devices, and the like.

[0071]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples. Example 1 Cyanine compound (Cyanine dye) of the following [Chemical Formula 43]
Was produced by the following procedure.

[0072]

[Chemical 43]

(Formula 25a) '(where
25] in the reaction formula [Chemical Formula 32]), A =
H, R₃= R_Four= R_Five= R₆= CH₃, R₁= R₂=
Condensed benzene ring at the 4th and 5th positions, R₀₄= R₀₅=
H, Z_Four= CH₃, UX^r-= ClO _Four ^-, N = 3)   3-iodopropylferrocene (the above general formula (f
1) (reaction formula [product in Chemical formula 26])_Four= R_Five=
H, X '= I, n = 3) 2-Chloropropylferrocene 27.6 g, sodium iodide
22.5 g of helium was mixed in 100 ml of acetone, and 1
The mixture was heated under reflux for one day. After the reaction was completed, the insoluble salt was filtered,
The filtrate is treated with an evaporator to remove acetone and leave behind.
Dissolve the residue in ethyl acetate, wash with water and then saturated saline.
It was After dehydrating the organic layer with sodium sulfate,
And 35.5 g of 3-iodopropylferrose were removed.
I got it. Yield 95%. The obtained 3-iodopropyl
The NMR analysis values for the identification of erosen are as follows.
is there.¹ H-NMR (CDCl₃, TMS) δ 4.12-4.
04 (m, 9H), 3.19 (t, 2H), 2.46.
(T, 2H), 2.00-1.96 (m, 2H)

In 2,3,3-trimethyl-4,5-benzindolenin (the above-mentioned general formula (hc1) ′ (raw material in the reaction formula [Chemical Formula 30]), R ₁ = benzene ring at the 4- and 5-positions Was condensed, R ₃ ═R ₄ ═CH ₃ ) was prepared, and a ready-made product (known) was obtained.

1-ferrocenepropyl-2,3,3
In trimethyl-4,5-benzindolenin perchlorate (the above general formula (fc1) '(the product in the reaction formula [Chemical Formula 30], the starting material in the reaction formula [Chemical Formula 32]), R ₁ = 4,5
Condensed with a benzene ring at the position, R ₃ = R ₄ = CH ₃ ,
Preparation of uX ^r− = ClO ₄ ⁻ , n = 3) 25.0 g of 3-iodopropylferrocene obtained above
Then, 14.2 g of 2,3,3-trimethyl-4,5-benzindolenin obtained above was dissolved in 100 ml of toluene, and heated under reflux for 8 hours in the presence of nitrogen. After the reaction, the mixture was cooled to room temperature and 100 ml of diethyl ether was gradually added to precipitate a salt. The obtained salt was dissolved by heating in 100 ml of methanol, 25 g of a 60% sodium perchlorate aqueous solution was added, and then the mixture was heated and stirred at 70 ° C. for 1 hour. The solution was cooled to room temperature, 100 ml of water was added and the resulting salt was filtered off,
Recrystallized from methanol and ethyl acetate to give 26.3 g of 1-ferrocenepropyl-2,3,3-trimethyl-
4,5-Benzindolenin perchlorate was obtained. Yield 7
2%. Obtained 1-ferrocenepropyl-2,3,3-
The NMR analysis values for the identification of trimethyl-4,5-benzindolenine perchlorate are as follows. ¹ H-NMR (DMSO, TMS) δ 8.38 (d, 1
H), 8.31 (d, 1H), 8.22 (d, 1H),
8.14 (d, 1H), 7.77 (m, 2H), 4.6
3 (m, 2H), 4.15 (m, 9H), 2.94
(S, 3H), 2.54 (m, 2H), 2.15 (m,
2H), 1.78 (s, 6H)

1,2,3,3-tetramethyl-4,
5-benzindolenine perchlorate (the above general formula (hc
2) ′ (raw material in reaction formula [Chemical Formula 31]), R ₂ =
Condensation of a benzene ring at the 4- and 5-positions, R ₅ = R ₆ = C
_{H 3, Z 4 = CH 3} , uX r- = ClO 4 -) was obtained in the Preparation above 2,3,3-trimethyl-4,5-benz isopropyl indolenine 24g and p- toluenesulfonic acid methyl ester 28g It was dissolved in 60 ml of alcohol and heated under reflux in the presence of nitrogen for 4 hours. After the reaction, the mixture was cooled to room temperature, 50 ml of dimethylformamide and 30 g of 60% sodium perchlorate solution were added, and the mixture was further heated and refluxed for 1 hour. Then, the mixture was cooled to room temperature and 100 ml of water was gradually added to precipitate crude crystals. The crude crystals were filtered off and recrystallized from methanol and ethyl acetate to give 26.8 g of 1,2,
3,3-Tetramethyl-4,5-benzindolenine perchlorate was obtained. Yield 72%. Obtained 1, 2, 3, 3-
The NMR analysis values for the identification of tetramethyl-4,5-benzindolenine perchlorate are as follows. ¹ H-NMR (DMSO, TMS) δ 8.37 (d, 1
H), 8.30 (d, 1H), 8.24 (d, 1H),
8.10 (d, 1H), 7.79 (t, 1H), 7.7
3 (t, 1H), 4.09 (s, 3H), 2.86
(S, 3H), 1.75 (s, 6H)

2- (2-acetanilide vinyl)-
1,3,3-Trimethyl-4,5-benzindolenine perchlorate (the above general formula (hc2 ′) ′ (reaction formula [Chemical Formula 3
2) in which the benzene ring is condensed at the A = H, R ₂ = 4,5 positions, R ₅ = R ₆ = CH ₃ , Z ₄ = C
Preparation of H ₃ , uX ^r− = ClO ₄ ⁻ ) 1,2,3,3-tetramethyl-4, obtained above
26.3 g of 5-benzindolenine perchlorate and diphenylformamidine (compound of the above general formula (i)) 2
70 g of 7.0 g while introducing nitrogen into 200 ml of acetic acid
The solution was dissolved in, and 120 ml of acetic anhydride was added all at once, and the mixture was heated and stirred for 5 hours. After the reaction, it was cooled to room temperature and ethyl acetate 250m
1, isopropyl alcohol (250 ml) were added in this order, and the crystals were stirred overnight at room temperature and filtered to separate them as yellow crystals.
3.6 g of 2- (2-acetanilide vinyl) -1,
3,3-Trimethyl-4,5-benzindolenin perchlorate was obtained. Yield 90%. Obtained 1, 2, 3, 3-
The NMR analysis values for the identification of tetramethyl-4,5-benzindolenine perchlorate are as follows. ¹ H-NMR (CDCl ₃ , TMS) δ9.28 (d,
1H), 8.13 (d, 1H), 7.98 (d, 2
H), 7.73-7.54 (m, 6H), 7.46.
(D, 2H), 5.59 (d, 1H), 3.80 (s,
3H), 2.12 (s, 3H), 2.01 (s, 6H)

The cyanine compound (cyanine dye) of the above [Chemical Formula 43] (the above general formula (Chemical Formula 25a) ′ (the product in the reaction formula [Chemical Formula 32] belonging to the general formula (Chemical Formula 25))
_{Among, A = H, R 3 =} R 4 = R 5 = R 6 = CH 3, R 1 =
R ₂ = condensed with a benzene ring at the 4- and 5-positions, R ₀₄ = R
_{05 = H, Z 4 = CH} 3, uX r- = ClO 4 -, n = 3)
Preparation of 1-ferrocenepropyl-2,3,3 obtained above
14.4 g of trimethyl-4,5-benzindolenine perchlorate and 2- (2-acetanilide vinyl) -1,3,3-trimethyl-4,5-benzindolenine perchlorate obtained above 12.9 g was dissolved in 50 ml of dimethylformamide in the presence of nitrogen to give triethylamine 5
Add g. As a result of tracking the progress of the reaction by high performance liquid chromatography, the reaction was almost completed in 2 hours. 1 more
After stirring for 100 hours, 100 ml of isopropyl alcohol was added to obtain 17.2 g of brown-colored crude crystals of the dye. The crystals were washed with 50% aqueous methanol and dried well,
It was completely dissolved in 50 ml of dimethylformamide and filtered through a filter paper. 200 ml of methanol is added to the filtrate while stirring.
ml was added slowly and allowed to slowly stir overnight at room temperature. The obtained crystals are separated by filtration and well dried to obtain purple crystals as the cyanine compound (cyanine dye) 1 of the above [Chemical Formula 43].
2.2 g was obtained. Using high performance liquid chromatography,
As a result of detection with a light source having a wavelength of 590 nm, the purity is 99.8.
%Met. Yield 62%. The NMR analysis values for identifying the obtained cyanine compound are as follows. ¹ H-NMR (CDCl ₃ , TMS) δ8.62 (t,
1H), 8.11 (d, 2H), 7.97-7.88.
(M, 4H), 7.63 (m, 2H), 7.49 (m,
2H), 7.41 (d, 1H), 7.15 (d, 1
H), 6.86 (d, 2H), 4.28-4.10.
(M, 11H), 3.85 (s, 3H), 2.67
(T, 2H), 2.10-2.02 (m, 14H)

Example 2 Cyanine compound (Cyanine dye) of the following [Chemical Formula 44]
Was produced by the following procedure.

[0080]

[Chemical 44]

In the above general formula (Formula 25a) '(the product in the reaction formula [Formula 32] belonging to the general formula [Formula 25]), A =
H, R ₃ = R ₄ = R ₅ = R ₆ = CH ₃ , R ₁ = R ₂ =
Condensation of benzene ring at the 4th and 5th positions, R ₀₄ = R ₀₅ =
_{H, Z 4 = C 4 H} 9, uX r- = ClO 4 -, in n = 3) Example 1, in accordance with ~, in the place of p- toluenesulfonic acid methyl, 1-butyl using iodobutane -2,3,3 trimethyl-4,5-benzindolenine perchlorate was obtained, and in the place of 1,2,3,3-tetramethyl-4,5-benzindolenine perchlorate, this 1 -Butyl-2,3,3-trimethyl-
Using 4,5-benzindolenin perchlorate
(2-acetanilide vinyl) -1-n-butyl-3,
3-Dimethyl-4,5-benzindolenine perchlorate is obtained, and then 2- (2-acetanilidovinyl) -1,
Instead of 3,3-trimethyl-4,5-benzindolenine perchlorate, this 2- (2-acetanilidovinyl) -1-n-butyl-3,3-dimethyl-4,5-benzindolenine perchlorate was used. Using the chlorate, the cyanine compound (cyanine dye) of [Formula 44] was obtained. The purity was 99.5% as a result of detection with a light source having a wavelength of 590 nm using high performance liquid chromatography. Yield 63%.
The NMR analysis values for identifying the cyanine compound are as follows. ¹ H-NMR (CDCl ₃ , TMS) δ8.62 (t,
1H), 8.12 (m, 2H), 7.98-7.87.
(M, 4H), 7.63 (m, 2H), 7.48 (m,
2H), 7.38 (d, 1H), 7.15 (d, 1
H), 6.84 (m, 2H), 4.32-4.12.
(M, 13H), 2.64 (m, 2H), 2.14
2.04 (m, 14H), 1.90 (m, 2H), 1.
64-1.54 (m, 2H), 1.01 (t, 3H)

Example 3 Cyanine compound (cyanine dye) of the following [Chemical Formula 45]
Was produced by the following procedure.

[0083]

[Chemical formula 45]

(Formula 25a) '(where
25] in the reaction formula [Chemical Formula 32]), A =
H, R₃= R_Four= R_Five= R₆= CH₃, R₁= R₂=
Condensed benzene ring at the 4th and 5th positions, R₀₄= R₀₅=
H, Z_Four= CH₃, UX^r-= ClO _Four ^-, N = 4) In Example 1, according to
4-chlorobutylferro instead of propylferrocene
To obtain 4-iodobutylferrocene using sen,
4-iodobut instead of 3-iodopropylferrocene
1-ferrocenebutyl-2, using tilferrocene
3,3-Trimethyl-4,5-benzindolenine persalt
1-ferrocenepropyl-2,3 is obtained.
3-Trimethyl-4,5-benzindoleum perchloric acid
Instead of salt, this 1-ferrocenebutyl-2,3,3-
Trimethyl-4,5-benzindolenine perchlorate
Using the above-mentioned [Chemical 45] cyanine compound (cyanine compound
Dye) was obtained. High-speed liquid chromatography
As a result of detection with a long 590 nm light source, the purity is 99.6%.
Met. Yield 63%. Of the obtained cyanine compound
The NMR analysis values for the determination are as follows.¹ H-NMR (CDCl₃, TMS) δ8.63 (t,
1H), 8.12 (d, 2H), 7.95 (m, 4
H), 7.63 (t, 2H), 7.49 (t, 2H),
7.41 (d, 1H), 7.34 (d, 1H), 6.8
7 (t, 2H), 4.27 (m, 2H), 4.10-
3.98 (m, 9H), 3.85 (s, 3H), 2.4
2 (t, 2H), 2.13-1.89 (m, 14H),
1.75 (m, 2H)

Example 4 Cyanine compound (cyanine dye) of the following [Chemical Formula 46]
Was produced by the following procedure.

[0086]

[Chemical formula 46]

(The above general formula (formula 25a) '(general formula [formula 25a]'
25] in the reaction formula [Chemical Formula 32]), A =
H, R₃= R_Four= R_Five= R₆= CH₃, R₁= R₂=
Condensed benzene ring at the 4th and 5th positions, R₀₄= R₀₅=
H, Z_Four= CH₃, UX^r-= PF₆ ^-, N = 3) In Example 1, according to
Use potassium hexafluorophosphate instead of sodium
1,2,3,3-tetramethyl-4,5-benzii
Andrendenine hexafluorophosphate is obtained, then 1, 2, 3,
3-tetramethyl-4,5-benzindoleum perchlorine
This 1,2,3,3-tetramethyl-
Using 4,5-benzindoleum hexafluorophosphate
2- (2-acetanilide vinyl) -1,3,3-tri
Methyl-4,5-benzindolenine hexafluorophosphate
And then 2- (2-acetanilide vinyl) -1,
3,3-Trimethyl-4,5-benzindoleum persalt
This 2- (2-acetanilide vinylidin
) -1,3,3-Trimethyl-4,5-benzindo
Using the renin hexafluorophosphate,
A nin compound (cyanine dye) was obtained. High speed liquid black
Using a totography and detecting with a light source with a wavelength of 590 nm.
As a result, the purity was 99.3%. Yield 76%. Got
The NMR analysis values for identifying the cyanine compound
It is as below.¹ H-NMR (CDCl₃, TMS) δ8.63 (t,
1H), 8.12 (d, 2H), 7.95 (m, 4
H), 7.63 (m, 2H), 7.52-7.46.
(M, 2H), 7.41 (d, 1H), 7.16 (d,
1H), 6.86 (d, 2H), 4.28-4.10.
(M, 11H), 3.85 (s, 3H), 2.67
(T, 2H), 2.10-2.00 (m, 14H)

Example 5 A cyanine compound (cyanine dye) represented by the following chemical formula [Chemical Formula 47] was produced by the following procedure.

[0089]

[Chemical 47]

In the above general formula (Formula 25a) '(the product in the reaction formula [Formula 32] belonging to the general formula [Formula 25]), A =
H, R ₃ = R ₄ = R ₅ = R ₆ = CH ₃ , R ₁ = condensed with a benzene ring at the 4- and 5-positions, R ₂ = Cl at the 5-position, R _{04
= R 05 = H, Z 4} = CH 3, uX r- = PF 6 -, n =
3) In 5-chloro-2,3,3-trimethylindolenine (the above-mentioned general formula (hc1) ′ (the starting material in the reaction formula [Chemical Formula 30]), ═C (CH ₃ ) ₂ , R ₁ = 5 position Cl, R _{3
= R 4 = CH 3, Z} 4 = CH 3, uX r- = PF 6 -) of the preparation, it was obtained off the shelf.

5-Chloro-1,2,3,3-tetramethyl-4,5-benzindolenin hexafluorophosphate (the above general formula (hc2) '(raw material of reaction formula [Chemical Formula 31]) Among them, R ₂ = Cl at the ₅ -position, R ₅ = R ₆ = CH ₃ , Z _{4
^{= CH 3, uX r- = PF}} 6 -) Preparation obtained above 5-chloro-2,3,3-trimethyl indolenine 16.0g and p- toluenesulfonic acid methyl ester 21.2g of isopropyl alcohol 160m
It was dissolved in 1 and heated to reflux for 8 hours in the presence of nitrogen. After the reaction, the mixture was cooled to room temperature, 24 ml of dimethylformamide and 20 g of potassium hexafluorophosphate were added, and the mixture was further heated and refluxed for 1 hour. The resulting solution was cooled to room temperature and 100 ml of water was gradually added to precipitate crude crystals. The crude crystals were filtered off and recrystallized from acetone and ethyl acetate to give 24.5 g of 5-
Chloro-1,2,3,3-tetramethyl-4,5-benzindolenin hexafluorophosphate was obtained. Yield 83%.
Obtained 5-chloro-1,2,3,3-tetramethyl-
The NMR analysis values for the identification of 4,5-benzindolenine hexafluorophosphate are as follows. ¹ H-NMR (DMSO, TMS) δ 8.10 (s, 1
H), 8.01 (d, 1H), 7.80 (d, 1H),
4.03 (s, 3H), 2.82 (s, 3H), 1.6
2 (s, 6H)

2- (2-acetanilide vinyl)-
In 5-chloro-1,3,3-trimethylindolenine hexafluorophosphate (the above-mentioned general formula (hc2 ′) ′ (raw material in the reaction formula [Chemical Formula 32]), A = H, R ₅ = R ₆ = C
H ₃ , R ₂ = Cl at the 5th position, R ₀₄ = R ₀₅ = H, Z ₄ = CH
^{_{3, uX r- = PF 6 -}} ) obtained in the Preparation above 5-chloro--1,2,3,3- tetramethyl-4,5 benzindolenine hexafluorophosphate 9.
5 g and diphenylformamidine (the compound of the above (i)) 8.4 g were introduced into 40 ml of acetic acid while introducing nitrogen.
After dissolving at 0 ° C, 18 ml of acetic anhydride was added all at once, and the mixture was heated and stirred for 6 hours. After the reaction, the mixture was cooled to room temperature, 100 ml of isopropyl alcohol and 60 ml of ethyl acetate were added in this order, and the crystals stirred overnight at room temperature were filtered off to give 9.9 as yellow crystals.
g of 2- (2-acetanilide vinyl) -5-chloro-
1,3,3-Trimethylindolenine hexafluorophosphate was obtained. Yield 74%. The NMR analysis values for identifying the obtained 2- (2-acetanilidovinyl) -5-chloro-1,3,3-trimethylindolenine hexafluorophosphate are as follows. ¹ H-NMR (CDCl ₃ , TMS) δ9.18 (d,
1H), 8.66 (m, 3H), 7.47-7.30.
(M, 5H), 5.47 (d, 1H), 3.57 (s,
3H), 2.11 (s, 3H), 1.77 (s, 6H)

1-ferrocenepropyl-2,3,3-trimethyl-4,5-benzindolenin perchlorate (17.4 g) obtained in Example 1 and 2 obtained above
-(2-acetanilide vinyl) -5-chloro-1,
3,3-Trimethylindolenine hexafluorophosphate 1
5.0 g is dissolved in 60 ml of dimethylformamide in the presence of nitrogen, and 5 g of triethylamine is added. The progress of the reaction was monitored by high performance liquid chromatography, and as a result, the reaction was almost completed in 2 hours. After stirring for an additional 1 hour, 100 ml of 50% methanol water was added to the mixture to give brown-colored crude crystals of dye 1.
8.7 g was obtained. The crystals were washed with 50% methanol water, dried well, and then 42 ml of dimethylformamide.
Completely dissolved in water and filtered through a filter paper. 200 ml of isopropyl alcohol was gradually added to the filtrate while stirring, and the mixture was slowly stirred overnight at room temperature. The crystals obtained are filtered off and dried thoroughly to give the above-mentioned [Chemical Formula 47] as red-purple crystals.
14.3 g of the cyanine compound (cyanine dye) was obtained. Using high performance liquid chromatography, wavelength 570n
As a result of detection with a light source of m, the purity was 99.5%.
Yield 56%. The NMR analysis values for identifying the obtained cyanine compound are as follows. ¹ H-NMR (CDCl ₃ , TMS) δ8.43 (t,
1H), 6.79 (d, 2H), 8.09 (d, 1
H), 7.95 (m, 2H), 7.75-7.20.
(M, 5H), 7.01 (d, 1H), 6.65 (m,
2H), 4.18-4.03 (m, 11H), 3.62.
(M, 3H), 2.65 (t, 2H), 2.41 (t,
2H)

Example 6 Cyanine compound (Cyanine dye) of the following [Chemical Formula 48]
Was produced by the following procedure.

[0095]

[Chemical 48]

(In the general formula [Chemical Formula 38] above, A = H, R ₁
= R ₂ = one in which a benzene ring is condensed at the 4, 5 positions, R ₀₄ =
R ₀₅ = H, Y ₁ = Y ₂ = C (CH ₃ ) ₂ , Z ₄ = C
H ₃ , uX ^r− = PF ₆ ⁻ , n = n ′ = 3) According to the method in Example 1, 4-chlorobutylferrocene was used in place of 3-chloropropylferrocene, and 4-iodobutylferrocene was used. According to the method of Example 1, 4-iodobutylferrocene and potassium hexafluorophosphate were used in place of 4-iodopropylferrocene and 60% sodium perchlorate to prepare 1-ferrocenebutyl- 2,3,3-trimethyl-
4,5-benzindolenine hexafluorophosphate was obtained.
Yield 63%. The NMR analysis values for the identification are as follows. ¹ H-NMR (DMSO, TMS) δ 8.06 (m, 3
H), 7.68 (m, 3H), 4.55 (t, 2H),
4.08 (m, 9H), 2.85 (s, 3H), 2.4
4 (t, 2H), 1.94 (t, 2H), 1.79
(S, 6H), 1.63 (t, 2H) 1-ferrocenebutyl-2,3,3-obtained above
Trimethyl-4,5-benzindolenine hexafluorophosphate (5.6 g) and triethyl orthoformate (1.5 g) were refluxed in 20 ml of pyridine for 5 hours in the presence of nitrogen. After completion of the reaction, the mixture was cooled and 30 ml of methanol was added to precipitate crystals. 100 ml of the obtained crude crystals are dimethylformamide.
And was filtered through a filter paper. Methanol 1 in the filtrate
00 ml was gradually added, and the mixture was slowly stirred overnight. The obtained crystals are separated by filtration and well dried to give brown crystals as the cyanine compound (Cyanine dye) of [Chemical Formula 48] above.
6.9 g was obtained. Using high performance liquid chromatography,
As a result of detection with a light source having a wavelength of 590 nm, the purity is 99.9.
%Met. Yield 70%. The NMR analysis values for identifying the obtained cyanine compound are as follows. ¹ H-NMR (CDCl ₃ , TMS) δ 8.63 (t,
1H), 8.12 (d, 2H), 7.96 (m, 4
H), 7.63 (t, 2H), 7.49 (m, 2H),
7.34 (d, 2H), 6.68 (d, 2H), 4.1
3 (m, 22H), 2.39 (m, 4H), 2.05
(S, 12H), 1.94 (m, 4H), 1.68
(M, 4H)

Example 7 Cyanine compound (Cyanine dye) of the following [Chemical formula 49]
Was produced by the following procedure.

[0098]

[Chemical 49]

(The above general formula (Formula 32b) (reaction formula [Formula 3]
7)], A = H, R ₁ = R ₂ = a benzene ring condensed at the 4 and 5 positions, R ₃ = R ₄ = R ₅ = R ₆ =
CH ₃ , R ₀₄ = R ₀₅ = H, Z ₄ = C ₄ H ₉ , uX ^r- = C
^{_{lO 4 -, n = 2,}} q = 0) 1- hydroxyethyl 2,3,3 trimethyl benzindolenine perchlorate (the general formula (hc1 ')'
In the (intermediate of the reaction formula [Chemical Formula 36]), R ₁ == a benzene ring condensed at the 4- and 5-positions, R ₃ = R ₄ = CH ₃ , uX
^{_{r- = ClO 4 -, n =}} 2) Preparation of 2-iodo-ethanol 50.0g of were obtained in in Example 1 2,3,3-trimethyl benzindolenine 5
0.0 g was dissolved in 50 ml of toluene and heated under reflux for 3 hours in the presence of nitrogen. After the reaction, the mixture was cooled to room temperature and ethyl acetate 5
0 ml, ether 50 ml, diethyl ether 50 ml
Was added. The salt obtained was filtered off, mixed with 50 g of 60% sodium perchlorate solution and 200 ml of methanol and refluxed for 1 hour. After cooling to room temperature, water 20
0 ml was added for dilution, and the generated crystals were filtered off. The crystals were recrystallized from methanol-ethyl acetate to give 52.4 g.
1-hydroxyethyl-2,3,3-trimethyl-
4,5-Benzindolenin perchlorate was obtained. Yield 5
5%. The NMR analysis values for identifying the obtained 1-hydroxyethyl-2,3,3-trimethyl-4,5-benzindolenin perchlorate are as follows. ¹ H-NMR (DMSO, TMS) δ 8.39 (d, 1
H), 8.28 (d, 1H), 8.22 (d, 1H),
8.13 (d, 1H), 7.84-7.72 (m, 2
H), 4.71 (t, 2H), 3.94 (t, 2H),
2.92 (s, 3H), 1.59 ((s, 6H)

1-hydroxyethyl-1′-butyl-3,3,3 ′, 3′-tetramethyl-4,5,4 ′,
5'dibenz 2,2 'indocarbocyanine perchlorate (in the above general formula (c01)' (product of the reaction formula [Chemical Formula 36]), A = H, R ₁ = R ₂ = 4,5 positions. Condensed benzene ring, R ₃ = R ₄ = R ₅ = R ₆ = CH ₃ , Z ₄
= C ₄ H ₉ , uX ^r− = ClO ₄ ⁻ , n = 2) (Cyanine compound (cyanine dye)) 1-hydroxyethyl-2,3,3-trimethyl-4,5 obtained above -Benzindolenin perchlorate 7.8
g and 2- (2-acetanilidovinyl) -1-butyl-3,3-dimethylbenzindolenine perchlorate (11.2 g) used in Example 2 were dissolved in dimethylformamide (40 ml) in the presence of nitrogen to give triethylamine (4 g). Was added and stirred for 3 hours, then 200 ml of 50% methanol water was added.
Was added to obtain 6.3 g of a dark brown crude crystal of the pigment. After drying the crystals well, 36 ml of dimethylformamide
Was completely dissolved in the mixture, 144 ml of isopropyl alcohol was gradually added with stirring, and the mixture was slowly stirred overnight at room temperature. The precipitated dye crystals were separated by filtration and dried to give the above-mentioned 1-hydroxyethyl-1′-butyl-3 as violet crystals,
3,3 ', 3'-Tetramethyl-4,5,4', 5'-
Dibenz 2,2 ′ indocarbocyanine perchlorate 9.
6 g was obtained. Yield 69%. Identification of the obtained 1-hydroxyethyl-1'-butyl-3,3,3 ', 3'-tetramethyl-4,5,4', 5'-dibenz2,2'indocarbocyanine perchlorate The NMR analysis values for are as follows. ¹ H-NMR (CDCl ₃ , TMS) δ8.65 (t,
1H), 8.13 (m, 2H), 7.97 (m, 4
H), 7.64 (m, 2H), 7.53-7.36.
(M, 4H), 6.78 (d, 1H), 6.64 (d,
1H), 4.39 (t, 2H), 4.21 (d, 2)
H), 4.10 (m, 1H), 2.76 ((t, 1
H), 2.07 (m, 12H), 1.88 (m, 2
H), 1.58 (m, 2H), 1.01 (t, 3H)

In the cyanine compound (cyanine dye) of the above [Chemical Formula 49] (the above general formula (Chemical Formula 33b) (the product in the reaction formula [Chemical Formula 37]), A = H, R ₁ = R ₂ = 4 ，
A condensed benzene ring at the 5-position, R ₃ = R ₄ = R ₅ =
R ₆ = CH ₃ , R ₀₄ = R ₀₅ = H, Z ₄ = C ₄ H ₉ , uX
^{_{r- = ClO 4 -, n =}} 2, q = 0) 1- hydroxyethyl prepared obtained by the above-1'-butyl -
3,3,3 ', 3'-tetramethyl-4,5,4',
5.6 g of 5'-dibenz 2,2 'indocarbocyanine perchlorate, 2.4 g of ferrocenecarboxylic acid and 1.2 g of 4-dimethylaminopyridine were dissolved in 50 ml of methylene chloride, and dicyclohexylcarbodiimide was stirred with an ice bath. 2.1 g of (DCC) was added. The mixture was stirred in an ice bath for 2 hours and then at room temperature overnight. After filtering the solution, the filtrate was transferred to a separatory funnel and washed with water and saturated brine.
Then, after dehydration with anhydrous sodium sulfate, the solution was concentrated to obtain a residue. The residue was heated and dissolved in 15 ml of dimethylformamide, and filtered with filter paper. 100 ml of methanol was gradually added to the filtrate while stirring, and the mixture was slowly stirred overnight at room temperature. The precipitated crystals were separated by filtration and dried well to obtain 5.1 g of the cyanine compound (cyanine dye) of [Formula 49] as brown crystals. As a result of analysis by high performance liquid chromatography at a wavelength of 590 nm, the purity was 99.1%. Yield 58%. The NMR analysis values for identifying the obtained cyanine compound (cyanine dye) are as follows. ¹ H-NMR (CDCl ₃ , TMS) δ8.62 (t,
1H), 8.11 (m, 2H), 7.95 (m, 4
H), 7.62 (m, 2H), 7.56-7.39.
(M, 4H), 6.70 (m, 2H), 4.79 (m,
2H), 4.62 (m, 4H), 4.25 (m, 4
H), 4.03 (m, 5H), 2.04 (m, 12)
H), 1.90 (m, 2H), 1.60 (m, 2H),
1.03 (t, 3H)

Example 8 Cyanine compound (cyanine dye) of the following [Chemical Formula 50]
Was produced by the following procedure.

[0103]

[Chemical 50]

(The above general formula (Formula 33b) (reaction formula [Formula 3b]
7)], A = H, R ₁ = R ₂ = a benzene ring condensed at the 4 and 5 positions, R ₃ = R ₄ = R ₅ = R ₆ =
CH ₃ , R ₀₄ = R ₀₅ = H, Z ₄ = CH ₃ , uX ^r- = PF
₆ ^-, in n = 2, q = 0) Example 7, in accordance with ~, in the place of 60% sodium perchlorate, using six potassium fluoride, 1-hydroxyethyl 2,3,3 -Trimethyl-
4,5-benzindolenine hexafluorophosphate is obtained,
Then 1-hydroxyethyl-2,3,3-trimethyl-
4,5-benzindolenine perchlorate and 2- (2-
Acetanilide vinyl) -1-butyl-3,3-dimethyl-4,5-benzindolenine perchlorate instead of 1-hydroxyethyl-2,3,3-trimethyl-
4,5-benzindolenine hexafluorophosphate and 2- (2-acetanilidovinyl) -1, used in Example 4
Using 3,3-trimethyl-4,5-benzindolenine hexafluorophosphate, 1-hydroxyethyl-1 ′,
3,3,3 ', 3'-pentamethyl-4,5,4',
5'-dibenz-2,2'-indocarbocyanine hexafluorophosphate is obtained, and 1-hydroxyethyl-1 '
-Butyl-3,3,3 ', 3'-tetramethyl-4,
Instead of 5,4 ', 5' dibenz 2,2'-indocarbocyanine perchlorate, this 1-hydroxyethyl-
1 ', 3,3,3', 3'-pentamethyl-4,5,
Using 4 ', 5'-dibenz-2,2'-indocarbocyanine hexafluorophosphate, the cyanine compound (Cyanine dye) of the above [Chemical Formula 50] was obtained. Yield 43%. The NMR analysis values for identifying the obtained cyanine compound (cyanine dye) are as follows. ¹ H-NMR (CDCl ₃ , TMS) δ8.61 (t,
1H), 8.11 (m, 2H), 7.93 (m, 4
H), 7.70-7.42 (m, 6H), 6.71.
(M, 2H), 4.78 (m, 2H), 4.67-4.
61 (m, 4H), 4.28 (m, 2H), 4.06
(M, 5H), 3.82 (s, 3H), 2.04 (m,
12H)

Example 9 Cyanine compound (cyanine dye) of the following [Chemical Formula 51]
Was produced by the following procedure.

[0106]

[Chemical 51]

(The above general formula (formula 33b) (reaction formula [formula 3]
7)], A = H, R ₁ = R ₂ = a benzene ring condensed at the 4 and 5 positions, R ₃ = R ₄ = R ₅ = R ₆ =
CH ₃ , R ₀₄ = R ₀₅ = H, Z ₄ = C ₄ H ₉ , uX ^r- = P
F ₆ ⁻ , n = 2, q = 0) According to Examples 6 and 7, the cyanine compound (cyanine dye) of [Chemical Formula 51] was obtained. Its yield is 62%, and the NMR analysis values for its identification are as follows. ¹ H-NMR (CDCl ₃ , TMS) δ8.62 (t,
1H), 8.11 (m, 2H), 7.96 (m, 4
H), 7.63 (m, 2H), 7.49 (m, 4H),
6.70 (m, 2H), 4.78 (m, 2H), 4.6
4 (m, 4H), 4.26 (m, 4H), 4.04
(M, 5H), 2.04 (s, 12H), 1.91
(M, 2H), 1.59 (m, 2H), 1.04 (t,
3H)

Example 10 Cyanine compound (Cyanine dye) of the following [Chemical Formula 52]
Was produced by the following procedure.

[0109]

[Chemical 52]

(In the general formula [Chem. 7] above, A = H, R₁=
R₂= R condensed with a benzene ring at the 4- and 5-positions, R₃= R
_Four= R_Five= R₆= CH₃, Z₃= In the above general formula [Chemical formula 8]
In R₇= R₈= R₀₄= R₀₅= H and n = 3,
Z_Four= C_FourH₉, UX^r-= PF ₆ ^-) In Example 1 above, according to
Methyl ruene sulfonate and 60% sodium perchlorate
Instead of iodobutane and potassium hexafluorophosphate
With 1-butyl-2,3,3 trimethyl-4,5
-Obtaining benzindolenine hexafluorophosphate,
1,2,3,3-tetramethyl-4,5-benzindo
Alternatives to renin perchlorate and diferformamidine
The 1-butyl-2,3,3 trimethyl-4,5-
Benzindolenin hexafluorophosphate and malon alde
Hydobisphenylimine (for which off-the-shelf (public)
Knowledge) was used) to obtain 2- (4-acetanilide
-1,3-Butadienyl) -1,3,3-trimethyl ester
Insulindrenine hexafluorophosphate is obtained, then 2-
(2-acetanilide vinyl) -1,3,3-trimethyl
In place of rubenzindolenine perchlorate, this 2-
(4-acetanilide-1,3-butadienyl) -1,
3,3-Trimethylbenzindolenine hexafluorophosphate
Using a salt, the cyanine compound (Cyanide) of the above [Chemical 52]
Dye) was obtained. For high performance liquid chromatography
As a result of analysis with a light source having a wavelength of 680 nm, the purity is 9
It was 9.5%. Yield 71%. Obtained cyanine system
The NMR analysis values for identifying the compound are as follows.
It¹ H-NMR (CDCl₃, TMS) δ8.23-8.
08 (m, 4H), 7.90 (m, 4H), 7.62
(M, 2H), 7.48 (m, 2H), 7.31 (d,
2H), 7.15 (d, 2H), 6.62 (t, 1
H), 6.19-6.07 (m, 2H), 4.19-
4.03 (m, 13H), 2.57 (t, 2H), 2.
05 (m, 14H), 1.87 (m, 2H), 1.52
(M, 2H), 1.02 (t, 3H)

Example 11 Cyanine compound (cyanine dye) of the following [Chemical Formula 53]
Was produced by the following procedure.

[0112]

[Chemical 53]

(In the general formula [Chem. 7], A = H, R ₁ =
R ₂ = a benzene ring condensed at the 4- and 5-positions, R ₃ = R
₄ = R ₅ = R ₆ = CH ₃ , Z ₃ = Z ₄ = R ₇ = R ₈ = R ₀₄ = R ₀₅ = H and n = 4 in the general formula [Chem. 8], Z ₄ = C _{4 ^{H 9, uX r- = BF 4}} -) 1- ferrocene butyl-2,3,3-trimethyl -
Preparation of 4,5-benzindolenin tetrafluoroborate According to the method in Example 1, 4-chloropropylferrocene was used in place of 3-chloropropylferrocene to obtain 4-iodopropylferrocene, According to the method of Example 1, using 4-iodobutylferrocene and sodium borofluoride instead of 3-iodopropylferrocene and 60% sodium perchlorate,
1-ferrocenebutyl-2,3,3-trimethyl-4,
5-Benzindolenin tetrafluoroborate was obtained. Yield 60%. The NMR analysis values for identifying the obtained compound are as follows. ¹ H-NMR (DMSO, TMS) δ 8.38 (d, 1
H), 8.31 (d, 1H), 8.22 (d, 1H),
8.16 (d, 1H), 7.79 (t, 1H), 7.7
3 (t, 1H), 4.61 (t, 2H), 4.05
(M, 9H), 2.95 (s, 3H), 2.34 (t,
2H), 1.94 (m, 2H), 1.76 (s, 6
H), 1.67 (m, 2H) Preparation of the cyanine compound (Cyanine dye) of [Chemical Formula 53] 1-ferrocenebutyl-2,3,3-trimethyl-4,5-benzindone obtained above 2.7 g of renin tetrafluoroborate and 2.0 g of tetramethoxypropane were refluxed in 7.5 ml of pyridine in the presence of nitrogen for 7 hours. After completion of the reaction, the mixture was cooled and 25 ml of methanol and 5 ml of water were added to precipitate crystals. The obtained crude crystals were dissolved in 12 ml of acetone and filtered with filter paper. 50 ml of isopropyl alcohol was gradually added to the filtrate, and the mixture was slowly stirred overnight. The obtained crystals were separated by filtration and well dried to obtain 1.5 g of the cyanine compound (cyanine dye) of [Chemical Formula 53] as a brown crystal. High-performance liquid chromatography analysis using a light source with a wavelength of 680 nm revealed that the purity was 9
It was 9.8%. Yield 59%. The NMR analysis values for identifying the obtained cyanine compound are as follows. ¹ H-NMR (CDCl ₃ , TMS) δ 8.33 (t,
2H), 8.21 (d, 2H), 7.92 (t, 4
H), 7.62 (t, 2H), 7.47 (t, 2H),
7.28 (d, 2H), 6.66 (t, 1H), 6.1
9 (d, 2H), 4.13-4.03 (m, 22H),
2.43 (t, 4H), 2.07 (s, 12H), 1.
89 (m, 4H), 1.66 (m, 4H)

Example 12 Cyanine compound (cyanine dye) of the following [Chemical Formula 54]
Was produced by the following procedure.

[0115]

[Chemical 54]

(In the above general formula [Chem. 5], L = CH, R ₁
= R ₂ = H, Y ₁ = Y ₂ = S, Z ₃ = Z ₄ = R ₇ = R ₈ = R ₀₄ = R ₀₅ = H and n = in the above general formula [Formula 8]
1 ^{_{thing, uX r- = PF 6 -)}} 1- ferrocene-methyl-2-ethylthio-4,5
Benzthiazole hexafluorophosphate (the above general formula [Chemical Formula 1
2], R ₁₂ = SC ₂ H ₅ , Z ₃ = the above general formula [Chemical formula 8]
In which R ₇ = R ₈ = R ₀₄ = R ₀₅ = H and n = 1, Y ₀₁ = an atomic group forming a benzenethiazole ring, u
According) a conventional method for preparation of iodomethyl ferrocene (which the, ^- X ^r- = PF ₆
Ferrocenemethanol was prepared by reacting chlorotrimethylsilane and sodium iodide in acetonitrile. ) 39.1 g and 2-ethylthio-4,5
-Benzthiazole (for this, according to the conventional method, 2-
Prepared from mercapto-4,5-benzthiazole and iodoethane. ) 19.5 g of acetonitrile 50 ml
Mix at room temperature for 30 minutes. Further, 23.9 g of potassium hexafluorophosphate and water were added in appropriate amounts and stirred for 30 minutes, and then the precipitated crude crystals were filtered off and recrystallized from dimethylformamide and methanol to give 1-ferrocenemethyl-2-ethylthio-4, 5-benzthiazole hexafluorophosphate 3
9.0 g was obtained. Yield 72%. The NMR analysis values for identifying the obtained 1-ferrocenemethyl-2-ethylthio-4,5-benzthiazole hexafluorophosphate are as follows. ¹ H-NMR (DMSO, TMS) δ 8.40-8.3
6 (m, 2H), 7.88-7.84 (t, 1H),
7.75-7.71 (t, 1H), 5.63 (s, 2
H), 4.59 (m, 2H), 4.33 (s, 5H),
4.24 (m, 2H), 3.71-3.66 (m, 2
H), 1.60-1.56 (t, 3H) Preparation of cyanine compound (cyanine dye) of the above [Chemical 54] 1-ferrocenemethyl-2-ethylthio-obtained above
4,5-Benzthiazole hexafluorophosphate 10.8g
And 6.1 g of 1-ethyl-2-methyl-4,5-benzthiazole hexafluorophosphate (prepared from 2-methyl-4,5-benzthiazole and iodoethane according to the usual procedure for this). In the presence of 50 ml of dimethylformamide and 4.0 g of triethycamine were added, and the mixture was stirred at room temperature for 1 hour, 150 ml of methanol was added to obtain yellow crude crystals of the precipitated dye. The crude crystals were recrystallized from dimethylformamide-methanol to obtain 7.6 g of the cyanine compound (cyanine dye) of [Chemical Formula 54]. As a result of analysis by a high-performance liquid chromatography using a light source having a wavelength of 430 nm, the purity was 99.0%. Yield 77
%. The NMR analysis values for identifying the obtained cyanine compound are as follows. ¹ H-NMR (DMSO, TMS) δ 8.23-8.1
9 (m, 2H), 8.17 (d, 1H), 7.92
(D, 1H), 7.77 (m, 2H), 7.48 (m,
2H), 6.87 (s, 1H), 5.68 (s, 2
H), 4.77-4.71 (m, 2H), 4.94.
(M, 2H), 4.34 (s, 5H), 4.18 (m,
2H), 1.45-1.42 (t, 3H)

The cyanine compounds (cyanine dyes) obtained in the above examples were evaluated as follows according to the length of the methine chain. The light resistance and the moisture resistance were collectively evaluated for Examples 1 to 11 except Example 12. Evaluation Method 1 Evaluation (Solubility, Optical Properties, Thermal Decomposition Properties, and Optical Recording Properties) of each cyanine compound (cyanine dye) obtained in Examples 1 to 9 (the above [Chemical Formula 43] to [Chemical Formula 51]) (A) Solubility 100 mg of each cyanine compound (Cyanine dye) of [Chemical Formula 43] to [Chemical Formula 51] is added to 10 ml of 1H, 1H, 3
The mixture was mixed with H-tetrafluoropropanol (manufactured by Daikin Fine Chemicals Co., Ltd.), stirred at room temperature for 24 hours, and then filtered using filter paper. It was confirmed that each cyanine compound (cyanine dye) was dissolved and no crystalline solid remained. (B) Optical Properties Each of the cyanine compounds (Cyanine dyes) of the above [Chemical formula 43] to [Chemical formula 51] and the following [Chemical formula 55] known as a comparative example.
Cyanine-based dye (Comparative Example 1) and cyanine-based dye of the following [Chemical Formula 56] (Comparative Example 2) (the cyanine-based dyes of these Comparative Examples have good recording characteristics as a dye material for a recording layer of an optical recording medium. Each of the above) was dissolved in methanol to prepare a solution having a solution concentration of 1 mg / 250 ml, and the absorption spectrum maximum and the molar absorption coefficient of each solution were determined. The absorption spectrum maximum was measured with a UV-VIS spectrometer (manufactured by Shimadzu Corporation). In addition, each cyanine compound (cyanine dye) was added to 1H, 1H, 3
H-tetrafluoropropanol (manufactured by Daikin Fine Chemical Co., Ltd.) was dissolved in the range of 1 to 2% by weight, and each of the resulting solutions was 0.2 μm siridi filter (material: PTF).
After filtering with E (polytetrafluoroethylene), a 25 mm square (25 m) using a spinner coater (manufactured by Mikasa)
It was uniformly coated on a glass substrate (m square). At this time, the rotation speed is 500 to 1000 rpm
Adjust in the range of (revolutions per minute), UV-VIS
It was prepared by a spectrometer (manufactured by Shimadzu Corporation) so that the absorbance of the dye film was about 0.8, and dried at 50 ° C. for 1 hour. With respect to the dye film thus obtained, the absorption spectrum maximum of each cyanine compound (cyanine dye) in the film state was measured in the same manner as above. The results are shown in Table 1. From the results in Table 1, it was found that the compounds (dyes) obtained in Examples 1 to 9 exhibited almost the same level of absorptivity as the two dyes of Comparative Examples. It can be said that the dye material exhibits good recording characteristics.

[0118]

[Chemical 55]

[0119]

[Chemical 56]

(C) Thermal decomposition characteristics The thermal decomposition characteristics of the cyanine compounds (cyanine dyes) of [Chemical formula 43] to [Chemical formula 51] and the cyanine dyes of Comparative Examples 1 and 2 are shown in TG-DTA. It investigated using the thermal analyzer (made by Seiko Instruments Inc.). Table 1 shows the resulting thermal decomposition start temperature (° C.). The thermal decomposition starting temperature of each of the cyanine compounds (cyanine dyes) of [Chemical Formula 43] to [Chemical Formula 51] is in the range of 150 ° C. to 300 ° C. The cyanine-based dye of (1) and the cyanine-based compound (cyanine-based dye) of the above-mentioned [Chemical formula 43] to [Chemical formula 51] of the example have equivalent thermal decomposition characteristics,
It turns out that the latter is superior. Also, TG-D
Comparative examples in which the absorption peak of thermal decomposition is sharp in the TA curve and can be compared with this are shown in FIGS.
(The above [Chemical formula 43] to [Chemical formula 5 obtained in Examples 1 to 9 above]
1] corresponds to those of [Chemical 43], FIG. 2 corresponds to [Chemical 44], FIG. 3 corresponds to [Chemical 45], and FIG. 4 corresponds to [Chemical 49]. As a comparative example, FIG.
Corresponds to that of [formula 55]. ). In the figure, the horizontal axis represents time (minutes) and the left vertical axis represents temperature (° C), T
G (weight reduction) (%) is shown, and the right vertical axis shows DTA (differential heat) (μV). From these results, Examples 1-9
It can be seen that, among the cyanine compounds (cyanine dyes), the perchlorate compound has a particularly sharp weight loss curve and has the property of decomposing at a low temperature.

[0121]

[Table 1]

(D) Optical recording characteristics Each of the cyanine compounds (cyanine dyes) of [Chemical formula 43] to [Chemical formula 51] is added to 1 to 2 of 1H, 1H, 3H-tetrafluoropropanol (manufactured by Daikin Fine Chemical Co., Ltd.).
Polycarbonate in which a pre-groove indicating a synchronizing signal and track and sector addresses was transferred to the inner circumference of the track, according to a conventional method, in a solution obtained by dissolving in a range of wt% and then filtered through a 0.1 μm silid filter (described above). A recording layer is formed by spin-coating on a substrate (diameter 12 cm, thickness 0.6 mm) and then drying it, and then silver is sputtered on the recording layer to form a reflective layer. Further, a known layer is formed on the reflective layer. After spin coating the UV curable resin of
UV (ultraviolet) irradiation is performed to form a protective layer, and finally another polycarbonate substrate (diameter 12 cm, thickness 0.6 mm) is attached by an adhesive layer formed by spin coating, and an optical recording medium (DVD-R (2) was produced, the optical recording medium could be recorded and reproduced by a laser beam having a wavelength near 650 nm.

Evaluation Method 2 Evaluation of each cyanine compound (cyanine dye) obtained in Examples 10 and 11 (the above [Chemical Formula 52] to [Chemical 53]) (solubility, optical properties, thermal decomposition properties and Optical recording characteristics) (a) Solubility The cyanine compound (cyanine dye) of [Chemical Formula 52] and [Chemical Formula 53] is used in (a) in "Evaluation Method 1" above.
When dissolved in 1H, 1H, 3H-tetrafluoropropanol according to the method of 1., it was confirmed that each of these cyanine compounds (cyanine dye) was dissolved and no crystalline solid remained. (B) Optical Properties Each cyanine compound (Cyanine dye) of [Chemical Formula 52] and [Chemical Formula 53] and a cyanine dye of the following [Chemical Formula 57] known as a comparative example (Comparative Example 3) are dissolved in methanol. Then, a solution having a solution concentration of 1 mg / 400 ml was prepared, and the absorption spectrum maximum and molar absorption coefficient of each solution and the absorption spectrum maximum in the film state were measured according to the method (b) in the above “Evaluation method 1”. Was measured. The results are shown in Table 2. From the results of Table 2, Examples 10 and 11
It was found that each of the cyanine compounds (cyanine dyes) obtained in 1. exhibited almost the same level of absorption characteristics as the cyanine dye of Comparative Example 3, and when used in an optical recording medium, good recording characteristics as a dye material for a recording layer. Can be said to indicate.

[0124]

[Chemical 57]

(C) Pyrolysis property According to the method of (c) in the above "Evaluation method 1", the cyanine compounds (cyanine dyes) of the above [Chemical Formula 52] and [Chemical Formula 53] and the comparative examples thereof are described above. Table 2 shows the results of examining the thermal decomposition characteristics of the cyanine dye of [Chemical Formula 57].
Both compounds have a thermal decomposition starting temperature of 150 ° C to 300 ° C.
And is within the range of
It can be seen that the cyanine-based compound (cyanine-based dye) of No. 1 has a thermal decomposition property comparable to or equivalent to the cyanine dye of the above [Chemical Formula 57] of Comparative Example 3.

[0126]

[Table 2]

(D) Optical recording characteristics 1 to 2 of each of the cyanine compounds (cyanine dyes) of [Chemical Formula 52] and [Chemical Formula 53] in 1H, 1H, 3H-tetrafluoropropanol (manufactured by Daikin Fine Chemical Co., Ltd.).
Polycarbonate in which a pre-groove indicating a synchronizing signal and track and sector addresses was transferred to the inner circumference of the track, according to a conventional method, in a solution obtained by dissolving in a range of wt% and then filtered through a 0.1 μm silid filter (described above). A recording layer is formed by spin-coating on a substrate (diameter 12 cm, thickness 1.2 mm) and then drying, and silver is sputtered on the recording layer to form a reflective layer. Further, a known layer is formed on the reflective layer. After spin coating the UV curable resin of
When an optical recording medium (CD-R) was prepared by irradiating with UV (ultraviolet rays) to form a protective layer, the optical recording medium could be recorded and reproduced by a laser beam having a wavelength near 780 nm.

Evaluation method 3 [Chemical formula 5] having the monomethine chain obtained in Example 12
4] Evaluation of Cyanine Compound (Cyanine Dye) (Optical Properties, Thermal Degradation Properties) Cyanine compound (Cyanine Dye) of [Chemical Formula 54] above
Is dissolved in chloroform and the solution concentration is 1 mg / 250 m
The solution of 1 was prepared, and the absorption characteristics in a solution state were measured according to the method (b) in the above “Evaluation method 1”. The absorption spectrum maximum was 536.0 nm, and the molar absorption coefficient was 0.74 ×. 10 is a ^5, also, the absorption maximum wavelength of the film state was 431.0Nm. Further, the thermal decomposition characteristics were measured in the same manner as in (c) in the above "Evaluation method 1".
The thermal decomposition starting temperature was 195.5 ° C. From these facts, the write-once type optical recording medium using the cyanine compound (cyanine dye) of [Chemical formula 54] obtained in Example 12 as the recording layer was found to have absorption characteristics, a thermal decomposition starting temperature and a wavelength of 530 nm. The following short wavelength laser light (eg 405 nm)
It can be said that recording and reproduction can be performed by a blue semiconductor laser light in the vicinity).

Evaluation method 4 Evaluation of light resistance of each cyanine compound (cyanine dye) obtained in Examples 1 to 11 and the cyanine dyes in Comparative Examples 1 to 3 and Comparative Examples 4 and 5 below. [Chemical Formula 43] to [Chemical Formula 5]
3] Each cyanine compound (cyanine dye), each cyanine dye of [Chemical Formula 55] to [Chemical Formula 57] in Comparative Examples 1 to 3 above, and ferrocene as a stabilizer are added. 4 as a mixture of the above [Chemical 55] cyanine dye: ferrocene = 1: 1 (molar ratio) and Comparative Example 5 as a mixture of the above [Chemical 56] cyanine dye: ferrocene = 1: 1 (molar ratio) Each dye film prepared according to the method (b) in the above "Evaluation method 1" was used as a test piece, and a xenon lamp (manufactured by Suga Test Instruments Co., Ltd.) was used to irradiate the film with xenon light to perform a light resistance test. . The criteria for the evaluation are that the cyanine dye of the above [Chemical Formula 56] (Comparative Example 2) is irradiated with light for the same time as the half-life (half-life) of the absorbance (time at which the absorbance is 50% of the original), and each cyanine system is used. The decrease rate of the absorbance of the test piece coated with the compound (cyanine dye), that is, the dye deterioration rate (or the dye residual rate) was used. At this time, the dye deterioration rate = (1- (absorbance after irradiation / absorbance before irradiation)) × 100%,
Further, the residual dye rate = (absorbance after irradiation / absorbance before irradiation) × 100%. The results are shown in Table 3. From the results of Table 3, the cyanine compounds (Cyanine dyes) of the above [Chemical 43] to [Chemical 53] obtained in Examples 1 to 11 are dye-reduced as compared with the cyanine dyes in Comparative Examples 1 to 3. The ratio is about a fraction to a few tenths, has a sufficiently high light resistance, and is equivalent to or higher than the light resistance of Comparative Examples 4 and 5 when a stabilizer is added. You can see that

Evaluation Method 5 Evaluation of Moisture Resistance of Each Cyanine Compound (Cyanine Dye) Obtained in Examples 1 to 11 and Cyanine Dyes in Comparative Examples 1 to 3 The above obtained in Examples 1 to 11 above. [Chemical 43] to [Chemical 5
[3] Each cyanine compound (cyanine dye) and each cyanine dye of [Chemical Formula 55] to [Chemical Formula 57] in Comparative Examples 1 to 3 described above (b) in "Evaluation Method 1".
Each of the dye films prepared according to the method of 1. was used as a test piece, and immersed in warm water of 50 ° C. for 30 minutes to perform a moisture resistance test. The evaluation standard was represented by the rate of decrease in absorbance of the test piece coated with each cyanine compound (cyanine dye), that is, the dye reduction rate (or dye residual rate). At this time, the dye reduction rate = (1- (absorbance after immersion / absorbance before immersion)) × 100%, and the residual dye rate = (absorbance after immersion / absorbance before immersion) × 100% expressed. The results are shown in Table 3. From the results of Table 3, the above [Chemical formula 43] to [Chemical formula 53] obtained in Examples 1 to 11 were obtained.
It can be seen that the cyanine-based compound (cyanine-based dye) in (1) has a low dye reduction rate and has sufficiently high moisture resistance.

[0131]

[Table 3]

[0132]

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a novel cyanine compound and a cyanine dye represented by the above general formula [Chemical Formula 1], and the excellent solubility of conventional cyanine dyes, While maintaining or improving properties such as optical properties and thermal decomposability, it shows excellent properties in light resistance and humidity resistance, which are generally inferior to conventional cyanine dyes. Utilizing these physical properties, it can be used in various materials. In particular, by utilizing these excellent physical properties, there are some which are excellent in light resistance and moisture resistance, and also have excellent sensitivity and are suitable for high-speed recording. Furthermore, a conventional cyanine compound and a stabilizer are mixed and used. It is possible to provide an easy-to-use optical recording material that does not have the inconvenience of such mixing work, is easy to control quality, and is durable in recording and reproducing with laser light. There, it is possible to provide an optical recording medium having a low recording layer deterioration in long-term storage in natural light or under high humidity conditions.

[Brief description of drawings]

FIG. 1 is a TG-DTA curve (pyrolysis curve, the same applies hereinafter) of a cyanine compound (cyanine dye) of Example 1 (Example 1) of the present invention.

FIG. 2 is a TG-DTA curve of the cyanine compound (cyanine dye) of the second example (Example 2) of the present invention.

FIG. 3 is a TG-DTA curve of a cyanine compound (cyanine dye) of a third example (Example 3) of the present invention.

FIG. 4 is a TG-DTA curve of a cyanine compound (cyanine dye) of a seventh example (Example 7) of the present invention.

FIG. 5 is a TG-DTA curve of a cyanine compound (cyanine dye) of a first comparative example (Comparative Example 1).

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G11B 7/24 516 B41M 5/26 Y (72) Inventor Masahiro Tsuchiya 16 Sayamagahara, Iruma City, Saitama Prefecture 2 F-term in Tamura Chemical Co., Ltd. (reference) 2H111 EA03 EA22 EA25 EA39 FB43 4C204 BB04 BB05 CB13 DB03 DB13 EB10 FB03 FB06 GB01 4H056 CA01 CC02 CC08 CE03 CE06 DD03 DD19 5D029 JA04 JC17

Claims (23)

[Claims] 1. A cyanide represented by the following general formula [Chemical formula 1]
Compounds. [Chemical 1] [In the formula, L is 1, 3, 5 or 7 methine groups (-CH
=) Represents a methine chain bound by forming a conjugated double bond.
The hydrogen atom on the methine chain is a halogen atom or its
It may be substituted with other substituents, and the substituents are linked to each other.
To form a ring, and it may extend over a plurality of carbons.
It may have a cyclic side chain, Y₀₁And Y₀₂Are each
Represents a group of atoms necessary to form a heterocycle,
May have a substituent, and Z is represented by the following general formula [Chemical formula 2].
Represents a substituted or bonded substituent, i is 1 to
Is an integer of 4, and when i is 2 to 4, Z's are the same.
May or may not be different, R₀₁And R₀₂
Represents a hydrogen atom, a substituted or unsubstituted alkyl group
, They may be the same or different, uX^r-Is X^r-Is the r value (r
Represents a positive integer) organic or inorganic anion, and u is
R is the number that makes the entire molecule neutral.₀₁And R₀₂Less
When either one has an anion group, uX ^r-Is
You don't have to. [Chemical 2] (In the formula, R₀₃Is a single bond or linear or branched alkyl
Group, -CH = CH-,-(CO)-, -NH-, -O
-, -S-, -N = C-, -C₆H_Four-,-(SO ₂)
Represents a linking group in which-and the like are combined, and hydrogen in the linking group
Atoms may be substituted with halogen atoms or other substituents
Well, R₀₄And R₀₅Are hydrogen atoms or substituents, respectively.
I, same or different, M is titanium, iron, lute
Represents transition metals such as nickel, osmium, and nickel
You )] 2. A cyanine compound represented by the following general formula [Chemical Formula 3]. [Chemical 3] (In the formula, L, Y ₀₁ and Y ₀₂ , and uX ^r- represent the same as those in the general formula [Chemical Formula 1] described in claim 1, Z ₁ and Z _1
2 represents a substituent represented by the general formula [Chemical Formula 2] described in claim 1, j and k each represent an integer of 0 to 2 and j + k ≧ 1, and j and k are 0 respectively.
Otherwise, Z ₁ and Z ₂ may be the same or different,
When j and k are 2, Z ₁ and Z ₂ may be the same or different, and R ₀₁ and R ₀₂ represent a hydrogen atom or a substituted or unsubstituted alkyl group and may be the same or different. ) 3. A cyanine compound represented by the following general formula [Chemical Formula 4]. [Chemical 4] (In the formula, L, Y ₀₁ and Y ₀₂ , and uX ^r- represent the same as those in the general formula [Chemical Formula 1] described in claim 1, Z ₃ and Z
_At least one of ₄ represents a substituent represented by the general formula [Chemical Formula 2] of claim 1, and when only one of them is substituted with a substituent represented by the general formula [Chemical Formula 2], , The other represents a substituted or unsubstituted alkyl group. ) 4. A cyanine compound represented by the following general formula [Chemical formula 5]. [Chemical 5] (In the formula, Y ₁ and Y ₂ each represent a carbon atom or a heteroatom necessary for forming a heterocycle, and may have a substituent, and R ₁ and R ₂ are each a hydrogen atom or a halogen atom. A benzene ring fused through atoms or other substituents or adjacent carbons (may have one or more halogen atoms or other substituents, in the case of multiple, the substituents may be the same And R ₁ and R ₂ may be singular or plural in each case, and in the case of plural, they may be the same or different. , R ₁ and R ₂ may be the same or different, and the substitution positions of R ₁ and R ₂ may be symmetrical or asymmetrical, and Z ₃ and Z ₄ At least one of the above general formulas [Chemical Formula 2] And represents a substituent in shown, when only one of which is substituted with a substituent represented by the general formula [2] and the other represents a substituted or unsubstituted alkyl group, uX ^r- is The same thing as the thing of General formula [Chemical formula 1] of Claim 1 is represented.) 5. A cyanine compound represented by the following general formula [Chemical Formula 6]. [Chemical 6] (In the formula, R ₁ and R ₂ , Z ₃ and Z ₄ , and uX ^r- represent the same as those in the general formula [Chemical Formula 5] described in claim 4, and R ₃ , R ₄ , R ₅ And R ₆ represent an alkyl group having 1 to 11 carbon atoms, adjacent substituents may be linked to each other to form a ring, and A represents a hydrogen atom, a halogen atom or other substituents.) 6. A cyanine compound represented by the following general formula [Chemical formula 7]. [Chemical 7] (In the formula, R ₁ and R ₂ , Z ₃ and Z ₄ , R ₃ , R ₄ , and R
₅ and R ₆ , A and uX ^r- represent the same as those described in the general formula [Chemical Formula 6] described in claim 5. ) 7. The cyanine compound according to claim 1, wherein M is an iron (Fe) atom in the substituent represented by the general formula [Chemical Formula 2] according to claim 1. 8. The substituent represented by the general formula [Chemical Formula 2] according to claim 1, wherein R ₀₃ is a linear or branched alkylene group having 1 to 22 carbon atoms. The cyanine compound described. 9. The substituent represented by the general formula [Chemical Formula 2] according to claim 1, wherein R ₀₃ is a linear or branched alkylene group having 1 to 8 carbon atoms. The cyanine compound described. 10. The cyanine-based compound according to claim 1, wherein the substituent represented by the general formula [Chemical formula 2] according to claim 1 is a substituent represented by the following general formula [Chemical formula 8]. Compound. [Chemical 8] (In the formula, R ₀₄ and R ₀₅ are the same as those described in the general formula [Chemical Formula 2] described in claim 1, R ₇ and R ₈ are a hydrogen atom, a straight chain having 1 to 8 carbon atoms, or A branched alkyl group (a hydrogen atom may be substituted with a halogen atom or another substituent) represents another substituent, and n represents an integer of 1 to 8.) 11. The cyanine-based compound according to claim 1, wherein the substituent represented by the general formula [Chemical Formula 2] according to claim 1 is a substituent represented by the following general formula [Chemical Formula 9]. Compound. [Chemical 9] (In the formula, R ₀₄ and R ₀₅ represent the same as those described in the general formula [Chemical Formula 2] described in claim 1, n and m each represent 0 or 1, and R ₉ represents a single bond or carbon. Represents an alkylene group of the formula 11, R ₁₀ is a single bond, —CH═CH
_{-, - CH 2 -C (=} O) -, - CH 2 CH 2 -C (=
O)-or an alkylene group having 1 to 11 carbon atoms, R
₁₁ represents an alkylene group having 1 to ₁₁ carbon atoms. ) 12. The cyanine-based compound according to claim 1, wherein the substituent represented by the general formula [Chemical Formula 2] according to claim 1 is a substituent represented by the following general formula [Chemical Formula 10]. Compound. [Chemical 10] (In the formula, R ₀₄ and R ₀₅ are the same as those in the general formula [Chemical Formula 2] described in claim 1, m is 1 to 8, and n is
Represents an integer of 0-8. ) 13. A cyanine-based compound represented by the general formula [Chemical Formula 1] according to claim 1 represented by the following general formula [Chemical Formula 11] or a general formula [Chemical Formula 3] according to claim 2. Cyanine compound intermediate [Chemical 11] (In the formula, Y ₀₁ , R ₀₁ , Z, and uX ^r- represent the same as those in the general formula [Chemical Formula 1] described in claim 1, i is 1 or 2;
Represents an integer of R ₁₂ is —CH ₃ or —OCH ₃ , —S
It is a substituent capable of forming a chemical bond by elimination reaction such as CH ₃ . ) 14. An intermediate of the cyanine compound represented by the general formula [Chemical Formula 4] according to claim 3 represented by the following general formula [Chemical Formula 12]. [Chemical 12] (In the formula, Y ₀₁ , Z ₃ and uX ^r- represent the same as those in the general formula [Chemical Formula 4] described in claim 3, and R ₁₂ represents
The same as those of the general formula [Chem. 11] described in ) 15. An intermediate of the cyanine compound represented by the general formula [Chemical Formula 6] according to claim 5, which is represented by the following general formula [Chemical Formula 13]. [Chemical 13] (In the formula, R ₁ , R ₃ , R ₄ , Z ₃ , and uX ^r- represent the same as those in the general formula [Chemical Formula 4] described in claim 3, and R ₁₂
Are the same as those in the general formula [Chemical Formula 11]. ) 16. Z and Z ₃ are the substituents represented by the general formula [Chemical Formula 2] according to claim 1, wherein R ₀₃ has 1 to 1 carbon atoms.
22 is a linear or branched alkylene group of 22.
An intermediate of the cyanine compound according to any one of 3 to 15. 17. Z and Z ₃ are the substituents represented by the general formula [Chemical Formula 2] according to claim 1, wherein R ₀₃ has 1 to 1 carbon atoms.
The linear or branched alkylene group of 8
An intermediate of the cyanine compound according to any one of 1 to 15. 18. Z or Z ₃ is a substituent represented by the general formula [Chemical Formula 8] of claim 10.
An intermediate of the cyanine compound according to any one of 5 above. 19. Z or Z ₃ is a substituent represented by the general formula [Chemical Formula 9] of claim 11.
An intermediate of the cyanine compound according to any one of 5 above. 20. The intermediate of the cyanine compound according to claim 13, wherein Z and Z ₃ are the substituents represented by the general formula [Chemical Formula 10] according to claim 12. 21. A cyanine dye comprising the cyanine compound according to claim 1. 22. A cyanine compound according to any one of claims 1 to 12, a cyanine dye according to claim 21, or an intermediate of the cyanine compound according to any one of claims 13 to 20. Optical recording material. 23. An optical information recording medium having a recording layer containing the optical recording material according to claim 22.