JPH05311083A - Production of cyanine dye - Google Patents

Abstract

PURPOSE:To perform the color formation reaction at good efficiency by adding an alkali metal salt and/or an alkaline earth metal salt to the reaction system in synthesizing a six-membered 2,4-cross-linked methine-chain pentamethinecyanine color from a quat. ammonium salt and a cyclic ketone. CONSTITUTION:An alkali metal salt and/or an alkaline earth metal salt are added to the reaction system in synthesizing a cyanine dye of formula IV by reacting a compound of formula I and/or a compound of formula II with a compound of formula III. In the formulas, Z1 and Z2 are each an atomic group necessary to form a five- or six-membered nitrogenous heterocyclic ring; Q is an atomic group necessary to form a five- or six-membered ring; R1 and R2 are each alkyl; R3 is hydrogen or alkyl; L1 to L7 are each a methine group; L1a and L3a are each an active methyl group; n1 and n2 are each 0 or 1; M1 to M3 are each an ion which neutralizes the charge; and m1 to m3 are each a number of 0 or greater necessary for neutralizing the molecule.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a cyanine dye.

[0002]

2. Description of the Related Art General formula (I) and / or general formula (II)
The conventional method for synthesizing the cyanine dye represented by the general formula (IV) by reacting the compound represented by the formula (III) with the compound represented by the general formula (III) is described in US Pat. No. 2,481,022 (R ₃ =
H) or Japanese Patent Application No. 2-270164 (R ₃ = alkyl).

[0003]

However, in the above conventional method, the desired dye may not be obtained in good yield depending on the kind of the quaternary salt used. For example, it is a case where an electron-donating group (eg, methyl group, ethoxy group, etc.) is substituted as a nuclear substituent of the quaternary salt, or a sterically bulky substituent is substituted. Therefore, it has been desired to develop an efficient method for synthesizing the methine dye represented by the general formula (IV).

[0004]

The inventors of the present invention have conducted various studies in order to overcome the drawbacks of the above-mentioned conventional methods, and as a result, added a salt compound of an alkali metal and / or an alkaline earth metal to obtain a dye. The inventors have found that the chemical reaction can be carried out efficiently, and have completed the present invention. That is, in the present invention, the compound represented by the general formula (I) is prepared by reacting the compound represented by the general formula (I) and / or the compound represented by the general formula (II) with the compound represented by the general formula (III).
The present invention provides a process for producing a cyanine dye represented by V), which comprises adding a salt of an alkali metal and / or an alkaline earth metal. General formula (I)

[0005]

[Chemical 5]

General formula (II)

[0007]

[Chemical 6]

General formula (III)

[0009]

[Chemical 7]

General formula (IV)

[0011]

[Chemical 8]

Where Z₁And Z₂Is a 5 or 6 member nitrogen containing
Represents a group of atoms necessary to form an elementary heterocycle. Q is 5
Or represents an atomic group necessary for forming a 6-membered ring. R₁as well as
R₂Represents an alkyl group. R₃Is a hydrogen atom or an alk
Represents a radical. L₁, L₂, L ₃, L_Four, L_Five, L₆as well as
L₇Represents a methine group. L_1aAnd L_3aAre each active methyl
Represents a group. n₁And n₂Each represents 0 or 1.
M₁, M₂And M₃Represents a charge neutralizing ion, m₁, M
₂And m₃Is 0 necessary to neutralize the charge in the molecule
The above is the number.

Next, the general formulas (I) to (IV) will be described in detail. The nucleus formed by Z ₁ and Z ₂ includes a thiazole nucleus (thiazole nucleus (eg, thiazole,
4-methylthiazole, 4-phenylthiazole, 4,
5-dimethylthiazole, 4,5-diphenylthiazole), benzothiazole nucleus (eg, benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 5-nitrobenzothiazole, 4-methylbenzo) Thiazole, 5-methylbenzothiazole, 6-methylbenzothiazole,
5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-ethoxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5 -Carboxybenzothiazole, 5-phenethylbenzothiazole, 5-fluorobenzothiazole, 5-chloro-
6-methylbenzothiazole, 5,6-dimethylbenzothiazole, 5,6-dimethoxybenzothiazole, 5
-Hydroxy-6-methylbenzothiazole, tetrahydrobenzothiazole, 4-phenylbenzothiazole), naphthothiazole nucleus (for example, naphtho [2,1-
d] thiazole, naphtho [1,2-d] thiazole, naphtho [2,3-d] thiazole, 5-methoxynaphtho [1,2-d] thiazole, 7-ethoxynaphtho [2,2]
1-d] thiazole, 8-methoxynaphtho [2,1-
d] thiazole, 5-methoxynaphtho [2,3-d] thiazole)}, thiazoline nucleus (for example, thiazoline, 4
-Methylthiazoline, 4-nitrothiazoline),

Oxazole nucleus {Oxazole nucleus (eg, oxazole, 4-methyloxazole, 4-nitroxazole, 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4
-Ethyloxazole), a benzoxazole nucleus (for example, benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-
Phenylbenzoxazole, 5-methoxybenzoxazole, 5-nitrobenzoxazole, 5-trifluoromethylbenzoxazole, 5-hydroxybenzoxazole, 5-carboxybenzoxazole,
6-methylbenzoxazole, 6-chlorobenzoxazole, 6-nitrobenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole, 5,6-dimethylbenzoxazole, 4,6-
Dimethylbenzoxazole, 5-ethoxybenzoxazole), naphthoxazole nucleus (for example, naphtho [2,1-d] oxazole, naphtho [1,2-d] oxazole, naphtho [2,3-d] oxazole, 5-
Nitronaphtho [2,1-d] oxazole)}, an oxazoline nucleus (eg, 4,4-dimethyloxazoline),

Selenazole nuclei {selenazole nuclei (eg 4-methylselenazole, 4-nitroselenazole, 4-phenylselenazole), benzoselenazole nuclei (eg benzoselenazole, 5-chlorobenzoselenazole, 5- Nitrobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, 6-nitrobenzoselenazole, 5-chloro-
6-nitrobenzoselenazole, 5,6-dimethylbenzoselenazole), naphthoselenazole nucleus (for example, naphtho [2,1-d] selenazole, naphtho [1,2-
d] selenazole)}, a selenazoline nucleus (eg, selenazoline, 4-methylselenazoline), a quinoline nucleus {quinoline nucleus (eg, 2-quinoline, 3-methyl-2-quinoline, 5-ethyl-2-quinoline, 6- Methyl-2-
Quinoline, 6-nitro-2-quinoline, 8-fluoro-
2-quinoline, 6-methoxy-2-quinoline, 6-hydroxy-2-quinoline, 8-chloro-2-quinoline, 4
-Quinoline, 6-ethoxy-4-quinoline, 6-nitro-4-quinoline, 8-chloro-4-quinoline, 8-fluoro-4-quinoline, 8-methyl-4-quinoline, 8-
Methoxy-4-quinoline, 6-methyl-4-quinoline,
6-methoxy-4-quinoline, 6-chloro-4-quinoline), and the like. The nucleus formed by Z ₁ and Z ₂ is preferably a benzothiazole nucleus, a naphthothiazole nucleus, a benzoxazole nucleus or a naphthoxazole nucleus.

Q is preferably formed by a carbon atom, an oxygen atom, a sulfur atom and a nitrogen atom, and the carbon atom and the nitrogen atom may be further substituted. As the substituent, an unsubstituted alkyl group (for example, methyl, ethyl, propyl, butyl group), a substituted alkyl group (for a substituent, for example, a carboxy group, a sulfo group, a phenyl group, a methoxy group, a hydroxy group), a halogen atom ( For example, chlorine atom, fluorine atom, bromine atom), acyl group (eg acetyl group, benzoyl group), acyloxy group (eg,
Acetyloxy group), alkoxycarbonyl group (for example, methoxycarbonyl group), carbamoyl group (for example, carbamoyl group, N, N-dimethylcarbamoyl group),
Sulfamoyl group (eg, sulfamoyl group, N, N
-Dimethylsulfamoyl group), carboxy group, cyano group, hydroxy group, amino group, acylamino group, alkoxy group (eg, methoxy group, ethoxy group), sulfonic acid group, aryl group and the like. More preferably, Q is dimethylene group, trimethylene group, 2,2-dimethyltrimethylene group, 2-methyltrimethylene group, 2
-Ethyltrimethylene group, 2-phenyltrimethylene group, tetramethylene group, and 2-methyl-2-phenyltrimethylene group. R ₁ and R ₂ are preferably
An unsubstituted alkyl group having 18 or less carbon atoms (for example, methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, octadecyl), or a substituted alkyl group (for example, as a substituent, a carboxy group, a sulfo group, a cyano group, a halogen) Atoms (eg, fluorine, chlorine, bromine), hydroxy groups (alkoxycarbonyl groups having 8 or less carbon atoms (eg, methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl), alkoxy groups having 8 or less carbon atoms (eg, methoxy) ,
Ethoxy, benzyloxy, phenethyloxy), monocyclic aryloxy groups having 10 or less carbon atoms (eg, phenoxy, p-tolyloxy), acyloxy groups having 3 or less carbon atoms (eg, acetyloxy, propionyloxy),
Acyl groups having 8 or less carbon atoms (eg acetyl, propionyl, benzoyl, mesyl), carbamoyl groups (eg carbamoyl, N, N-dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl), sulfamoyl groups (eg sulfamoyl, N, N-). Dimethylsulfamoyl, morpholinosulfonyl, piperidinosulfonyl), an aryl group having 10 or less carbon atoms (eg, phenyl,
4-chlorophenyl, 4-methylphenyl, α-naphthyl) -substituted alkyl groups having 18 or less carbon atoms}. Preferably, an unsubstituted alkyl group (eg, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group), carboxyalkyl group (eg, 2-carboxyethyl group, carboxymethyl group) ), A sulfoalkyl group (for example, 2-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, 3-
Sulfobutyl group). R ₃ is a hydrogen atom or an alkyl group, and examples of the alkyl group include those described for R ₁ and R ₂ . Of these, a hydrogen atom, a methyl group and an ethyl group are preferable. L ₁ , L ₂ , L ₃ , L ₄ ,
L ₅ , L ₆ and L ₇ are a methine group or a substituted methine group (eg, a substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, 2-carboxyethyl group), a substituted or unsubstituted aryl group (eg, phenyl) Group, o-carboxyphenyl group), halogen atom (eg chlorine atom, bromine atom), alkoxy group (eg methoxy group,
An ethoxy group), an amino group (for example, an N, N-diphenylamino group, an N-methyl-N-phenylamino group, an N-methylpiperazino group), and the like}, and other methine groups. It may form a ring, or may form a ring with the auxochrome. L ₁ , L ₂ , L
₃ , L ₄ , L ₅ , L ₆ and L ₇ are preferably unsubstituted methine groups. L _1a and L _3a are active methyl groups. That is, it is a group capable of exhibiting nucleophilicity by abstracting H ⁺ by a base, and specifically, a methyl group or a substituted methyl group. For example, examples of the substituent include those which form a 5-, 6-, or 7-membered ring with the N-position substituents R ₁ and R ₂ of the nitrogen-containing heterocycle. n ₁ and n ₂ are 0 or 1. Preferably, n ₁ = n ₂ = 0. M ₁ ,
_{m 1, M 2, m 2} , M 3, m 3, M 4, m 4 and M _5, m _5, when it is necessary to the ion charge of the dye neutral, cationic or anionic Included in the formula to indicate presence or absence. Whether a dye is a cation, an anion, or has a net ionic charge depends on its auxochrome and substituents. Typical cations are ammonium ions and alkali metal ions, while the anions can be either inorganic or organic anions,
For example, a halogen anion (eg, fluorine ion, chlorine ion, bromide ion, iodine ion), a substituted aryl sulfonate ion (eg, p-toluene sulfonate ion, p
-Chlorobenzenesulfonate ion), aryldisulfonate ion (for example, 1,3-benzenesulfonate ion, 1,5-naphthalenedisulfonate ion, 2,6-
Examples thereof include naphthalene disulfonate ion), alkylsulfate ion (for example, methylsulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate salt, acetate ion, and trifluoromethanesulfonate ion. Preferred are perchlorate ion, iodine ion, and substituted aryl sulfonate ion (for example, p-toluene sulfonate ion).
Preferred salts of alkali metals and alkaline earth metals include halides such as lithium, sodium, potassium and cesium, sulfates, carbonates, perchlorates and BF.
₄ salts, PF ₆ salts, organic acid salts, etc. or halides such as magnesium, calcium, strontium, barium, sulfates, carbonates, perchlorates, BF ₄ salts, PF
₆ salts, organic acid salts, etc. More preferred are salts of lithium, magnesium and barium, such as lithium chloride, lithium iodide, magnesium chloride, magnesium sulfate, barium chloride and the like. Alkali metal and /
Alternatively, the amount of the alkaline earth metal salt added may be a catalytic amount or an equivalent amount or more. The amount is preferably 0.05 to 10 molar equivalents, more preferably 0.5 to 3 molar equivalents, relative to the compound represented by the general formula (I). The alkali metal and / or alkaline earth metal salt to be added may be one kind or two or more kinds.

In the present invention, when the compound represented by the general formula (IV) is a so-called symmetrical dye (that is, Z ₁
= Z ₂ , R ₁ = R ₂ , L ₄ = L ₆ , L ₅ = L ₇ , and n
₁ = n ₂ ), the compound represented by the general formula (I) and the general formula (I
The compound represented by II) may be reacted. in this case,
The intermediate represented by the general formula (V) may be once isolated and further reacted with the compound represented by the general formula (I),
The reaction may be performed without isolating the intermediate represented by the general formula (V). General formula (V)

[0018]

[Chemical 9]

Where Z ₁ , R ₁ , R ₃ , Q, L ₁ ,
_{L 2, L 4, L 5} , n 1, M 3, m 3 is the same meaning as defined in formula (I) ~ (IV), respectively.

When the compound represented by the general formula (IV) is a so-called asymmetric dye (that is, Z ₁ ≠ Z ₂ ,
R ₁ ≠ R ₂ , L ₄ ≠ L ₆ , L ₅ ≠ L ₇ , and n ₁ ≠ n ₂ ), the compound represented by the general formula (I) and the general formula (III It is necessary to obtain the intermediate (V) by reacting the compound represented by At this time,
The intermediate (V) may or may not be isolated, and may be further reacted with a compound represented by the general formula (II) to obtain a compound represented by the general formula (IV). Next, the reaction conditions will be described.

The compound represented by the general formula (III) is preferably used in an amount of 0.5 to 10 molar equivalents relative to the compound represented by the general formula (I) to carry out the reaction, and 0.5 to 3 It is more preferable to use a molar equivalent. The reaction temperature is preferably 0 to 200 ° C, more preferably 20 to 180 ° C,
If the temperature is lower than 0 ° C, the progress of the reaction is slow and it is difficult to completely eliminate the raw materials. If the temperature exceeds 200 ° C, the product is decomposed and the yield is low.

A solvent is not always necessary for the reaction.
However, depending on the reaction compound used, a solvent can be used if necessary. Examples of the solvent include aromatic hydrocarbons (eg, benzene, toluene, xylene, ethylbenzene, etc.), ethers (eg, anisole, etc.), aliphatic hydrocarbons (eg, hexane, ligroin, etc.).
Decalin etc.), halogenated hydrocarbons (eg chloroform, dichloroethane etc.), N-alkyl lactams,
Examples thereof include dialkyl amides, dialkyl sulfoxides, nitro compounds, halogenated benzenes, nitrile compounds (eg acetonitrile, benzonitrile) and the like.

The reaction conditions may be neutral, acidic or alkaline. As the acid, for example, substituted benzenesulfonic acid, hydrochloric acid, sulfuric acid and the like can be used, and as the base, an organic base (eg triethylamine etc.) and the like can be used.

Next, the general formula (I) used in the present invention,
Specific examples of the compounds represented by (II) and (III) are shown below, but the present invention is not limited thereto.

[0025]

[Chemical 10]

[0026]

[Chemical 11]

Next, the general formula (I
V) or specific examples of the compound represented by the general formula (V) include Japanese Patent Application Nos. 2-270161, 2-270162,
2-270163, 2-270164, 3-26138
Examples thereof include the compounds described in 9 and the like, but the present invention is not limited thereto. A specific example is shown below.

[0028]

[Chemical formula 12]

[0029]

[Chemical 13]

[0030]

EXAMPLES The present invention will be described in more detail based on examples. Example 1 Dye (1) based on compound (T-1) and compound (M-1)
Synthesis of

[0031]

[Chemical 14]

[0032]

[Chemical 15]

0.379 g (2 mmo of compound (T-1)
l), 0.104 g (1 mmol) of the compound (M-1) and 1 mmol of the additive were heated and stirred at 160 ° C. for 3.5 hours. The reaction solution was cooled and diluted with methanol, and the resulting dye (1) was subjected to visible absorption measurement (λ max = 650 nm, ε = 1.72 × 1).
0 ⁵ ). Table 1 shows the production rate of the dye (1) when the additives were changed. As additives, in addition to alkali metal and alkaline earth metal salts, as comparative examples, Lewis acid catalysts such as TiCl ₄ , FeCl ₃ , and AlCl are used.
₃ , BF ₃ , Et ₂ O, and molecular sieve 3A as a dehydrating agent were used.

[0034]

[Table 1]

From the results of Table 1, alkali metal and alkaline earth metal salts (MgSO ₄ , MgCl ₂ , LiCl,
It can be seen that when CaCl ₂ or BaCl ₂ ) is added, the dye formation rate is improved as compared with the case where no addition is made. On the other hand, Lewis acid catalysts such as TiCl ₄ , FeCl ₃ , AlCl ₃ ,
It was found that when BF ₃ and Et ₂ O were added, no dye was formed, and when the dehydrating agent Molecular Sieve 3A was added, no noticeable change was observed in the reaction system. Example 2 Dye (1) based on compound (T-1) and compound (M-2)
Synthesis of

[0036]

[Chemical 16]

Magnesium sulfate is selected as an additive,
The same comparative experiment as in Example 1 was conducted. The results are shown in Table 2.

[0038]

[Table 2]

As a result, it can be seen that the addition of magnesium sulfate improves the dye formation rate as in Example 1. Example 3 (Synthesis of Dye (2))

[0040]

[Chemical 17]

[0041]

[Chemical 18]

Magnesium sulfate is selected as an additive,
The same comparative experiment as in Example 1 was conducted. The results are shown in Table 3.

[0043]

[Table 3]

As a result, it is found that the dye formation rate is improved by adding magnesium sulfate. Example 4 (Synthesis of Dye (3))

[0045]

[Chemical 19]

[0046]

[Chemical 20]

Magnesium sulfate is selected as an additive,
The same comparative experiment as in Example 1 was conducted. The results are shown in Table 4.

[0048]

[Table 4]

As a result, it can be seen that the dye formation rate is improved by adding magnesium sulfate. Example 5 (Synthesis of Dye (4))

[0050]

[Chemical 21]

[0051]

[Chemical formula 22]

70.0 g of compound (T-3), compound (M
-2) 18.8 g and 12.0 g of magnesium sulfate to 16
It was heated to 5 ° C. and allowed to stir for 3.5 hours. After that, outside temperature 1
100 ml of xylene was added to the reaction solution at 60 ° C, and the external temperature was 1
20 ml of triethylamine was added at 00 ° C. Then, an aqueous sodium iodide solution (NaI 40.0
g, MeOH 200 ml, EtOH 50 ml, water 100 ml)
Was added, and the mixture was stirred under water cooling for 30 minutes. The precipitated crystals were filtered off and washed with 200 ml of water and 200 ml of MeOH. The obtained crude crystals are heated at 150 ° C. in 240 ml of benzyl alcohol.
After heating and dissolving in ethyl acetate and filtering, ethyl acetate 36
0 ml was added at room temperature. The precipitated crystals are filtered off and washed with MeOH
Washed with 200 ml. Air-dried at 40 ° C. for 1 day to obtain 27.2 g of the target compound (4). Yield 44% λ = 646 nm (MeOH) ε = 1.78 × 10 ⁵ mp = 273 ° C. (decomposition)

[0053]

INDUSTRIAL APPLICABILITY When synthesizing the compound represented by the general formula (IV) from the general formulas (I), (II) and (III), the reaction rate can be improved by adding salts of alkali metal and / or alkaline earth metal. Can be improved. The compound represented by the general formula (IV) is also used as a spectral sensitizer for photographic emulsions, as a dye for preventing irradiation, antihalation, and filters of silver halide photographic light-sensitive materials, or for other uses. Can be used.

Claims (1)

[Claims] 1. The following general formula (I) and / or general formula
A compound represented by (II) and a compound represented by general formula (III)
To react with the cyanine dye represented by the general formula (IV)
When synthesizing, alkali metal and / or alkaline earth metal
Of cyanine dyes, characterized by adding salt of
Law. General formula (I):General formula (II)General formula (III)General formula (IV):In the formula, Z₁And Z₂Is a 5- or 6-membered nitrogen-containing heterocycle
Represents the atomic group necessary to form. Q is a 5- or 6-membered ring
Represents the atomic group required to form. R₁And R₂Is Archi
Represents a radical. R₃Represents a hydrogen atom or an alkyl group.
L₁, L₂, L ₃, L_Four, L_Five, L₆And L₇Is methine
Represents a group. L_1aAnd L_3aEach represents an active methyl group. n
₁And n₂Each represents 0 or 1. M₁, M₂And M
₃Represents a charge neutralizing ion, m₁, M₂And m₃Is the molecule
It is a number of 0 or more necessary for neutralizing the electric charge in the inside.