JPH10195319A - Production of polymethinecyanine compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymethinecyanine compound part of the methine chain of which is replaced by a ring structure, showing excellent fastness when used for laser recording stably in good yields by using an intermediate obtained by using an aromatic amine such as aniline as the starting material. SOLUTION: A polymethinecyanine compound of formula II is obtained by using a compound of formula I (wherein T is an alkylene group necessary to form a ring structure; a is an aryl; and X is a halogen or a substituted amino) as the reaction intermediate. In the formula, L<1> and L<2> are each a non-metal atomic group necessary to form a ring together with the carbon in position 3 of the nitrogenous ring; Z<1> and Z<2> are each an atomic group necessary to form an aromatic or heterocyclic ring; R<1> and R<2> are each an alkyl; R is a halogen or a substituted amino, alkoxyl or like group derivable from a halogen; T is as defined above; B is an anion; and m is a number necessary to adjust the change of the molecule to 0. The compound of formula I can be easily isolated and purified and can be stored stably for a long time. The compound of formula II has an absorption maximum near 800nm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polymethinecyanine compound frequently used in industrial dyes and dyes, particularly in the field of laser recording materials, in which a part of the methine chain is replaced by a cyclic structure and has excellent robustness. It is intended to provide an industrial production method of a compound of the type described above, which is excellent in production stability.

[0002]

2. Description of the Related Art Polymethine cyanine compounds have characteristics such as that they can cover a wide range of absorption wavelengths depending on the length of the methine chain, types of heterocycles and substituents thereof, and have a large absorption coefficient at the maximum absorption. Dyes and dyes, especially sensitizing dyes and filter dyes for recording materials such as silver salt photographic materials.

In recent years, in such recording material systems, types of writing and reading by a scanning exposure method using a laser beam have been increasing. As a laser light source used in this method, a semiconductor laser (LD), which is inexpensive, can be downsized, and can directly convert an electric signal into an optical signal, is mainly used. Currently, the wavelength of this semiconductor laser light is mainly in the near-infrared region of 700 to 1000 nm, in particular, AlG.
A heptamethine cyanine compound is used as a dye or dye at 780 nm or 830 nm using an aAs alloy as an oscillation source and suitable for the laser light source.

[0004] Among them, in particular, indolenine heptamethine cyanine compounds have advantages such as relatively easy synthesis and excellent solubility in organic solvents. However, a compound having a 3,3-dimethylindolenine nucleus and a linear polymethine chain, which is the most common of this type, has a disadvantage that the wavelength of the maximum absorption is as short as about 730 nm (in methanol). On the other hand, a dye having an indolenine nucleus having a spiro-cyclic structure at the 3-position has a maximum absorption shifted to a longer wavelength and a large extinction coefficient, which is advantageous for LD.

In general, polymethine cyanine compounds have a drawback that they are easily oxidized by air or the like and have poor stability. As a means for improving the stability, there is a method of introducing a cyclic structure into a part of the polymethine chain. For example, Christ
ian Jutz et al., Justus LiebigsAnnalen der Chemie, 874
-900, (1975), etc., have been reported. Dyes having these structures have high stability, but have a long synthesis step and a low yield.

[0006] Also, GARynolds et al., Journal of Org
anic Chemistry, 42,885-888 (1977), Narasimhachari Na
rayanan et al., Journal of Organic Chemistry, 60,2391-
2395 (1995) describes a method using a diformyl form of a cycloalkene. This is a method in which a cyclic saturated ketone such as cyclopentanone is used as a starting material to form a diformyl compound by a Vilsmeier-Haack reaction, and this is condensed with a nitrogen-containing heterocyclic quaternary salt having an active methyl group. Compounds synthesized by this method are not only excellent in stability but also characterized in that the maximum absorption shifts to a longer wavelength of about 30 nm. By combining with the above-mentioned spiro structure, an ideal maximum absorption wavelength for LD can be obtained.

[0007]

However, in the above-mentioned synthesis method, although the desired product can be obtained in high yield, the diformyl compound is generally very unstable, so that it is difficult to isolate and purify it, and There is a problem in storage, and it is disadvantageous for mass production, for example, the yield depends on the purity of the diformyl form. An object of the present invention is to provide a method for producing a polymethinecyanine compound having a cyclic structure represented by the general formula 2 in a stable and high yield.

[0008]

According to the present invention, instead of using the diformyl compound, the diformyl compound is used as a raw material intermediate represented by the general formula 1 by using an aromatic amine such as aniline. This intermediate is easily isolated and purified and can be stably stored for a long period of time. The object of the present invention has been achieved by using this intermediate as a raw material for synthesizing a polymethinecyanine compound represented by the general formula 2.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention provides a polymethinecyanine compound having a cyclic structure as shown in the general formula 2 and having maximum absorption and excellent stability suitable for LD. Further, the present invention provides a method for producing the above-mentioned polymethinecyanine compound in a stable and high yield using the compound represented by the general formula 1 as a reaction intermediate.

[0010]

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In the formula, T is a substituted or unsubstituted alkylene group necessary for forming a cyclic structure, even if one or more of the carbon atoms constituting the ring is substituted with another atom or atomic group. good. A represents a substituted or unsubstituted aryl group. X represents a halogen atom or a substituted amino group.

T is a substituted or unsubstituted alkylene group, which forms a ring together with the carbon atom bonded to X and the three carbon atoms on both sides thereof. One or more of the methylene groups constituting the ring in T may be substituted with another atom or atomic group. Specific examples of T include ethylene, propylene,
Butylene, 2-oxapropylene, 2-thiapropylene, 2-methylpropylene, 2-tert-butylpropylene and the like.

A is a substituted or unsubstituted aryl group. Specific examples include phenyl, 4-tolyl, 3-tolyl, 2-tolyl, 1-naphthyl, 2-naphthyl, 4-te
rt-butylphenyl, 4-chlorophenyl, 3-chlorophenyl, 4-methoxyphenyl and the like. Specific examples other than the halogen atom for X include a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a di-n-butylamino group, a di-isobutylamino group, a 1-pyrrolidinyl group, a 1-piperidyl group, Examples include a 4-morpholinyl group and a 4-thiomorpholinyl group.

[0014]

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In the formula, L ¹ and L ² may be the same or different from each other, and are a group of non-metallic atoms necessary for forming a ring together with the carbon atom at the 3-position of the nitrogen-containing ring. One or more of the atoms may be replaced with another atom or group. Z ¹ and Z ² may be the same or different from each other, and represent a group of atoms necessary to form a substituted or unsubstituted aromatic or heterocyclic ring. R ¹ and R ² are a substituted or unsubstituted alkyl group, and R is a halogen atom or a substituent that can be substituted or introduced from a halogen atom, and represents a substituted amino group, an alkoxy group, or an alkylthio group. T is a substituted or unsubstituted alkylene group necessary for forming a cyclic structure, and one or more of the carbon atoms constituting the ring may be substituted with another atom or atomic group.
B is an anion, and m represents a number necessary to adjust the intramolecular charge to zero.

The cyclic structures formed together with the carbon atom at the 3-position of the nitrogen-containing ring represented by L ¹ and L ² may be the same or different, and are preferably a 4- to 7-membered hydrocarbon ring. Specific examples of the hydrocarbon ring include cyclobutane, cyclopentane, cyclohexane, cycloheptane and the like. Further, one or more of methylene in the hydrocarbon ring may be substituted with a hetero atom, and specific examples include pyran and piperidine. The hydrocarbon ring of L ¹ and L ² may have a substituent, and specific examples of the substituent include a lower group having 3 or less carbon atoms such as a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Alkyl groups can be mentioned.

Z ¹ and Z ² may be the same or different from each other, and represent an atomic group necessary for forming a substituted or unsubstituted aromatic or heterocyclic ring. Z ¹ and Z ² may have a substituent, and specific examples of the substituent include a sulfo group, a carboxy group, an alkyl group, an aralkyl group, an aryl group, a halogen atom, a cyano group, a nitro group, an alkoxy group, Examples include a hydroxy group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfonamide group, and a carboxamide group. When the substituent is an acid substituent, an organic metal salt such as an alkali metal salt such as Na or K, an alkaline earth metal salt such as Mg or Ca, an ammonium salt, a triethylammonium salt, a tributylammonium salt or a pyridinium salt; It may be in the form of

R ¹ and R ² are a substituted or unsubstituted alkyl group. Specific examples include ethyl, n-propyl, n-
Butyl, n-octyl, n-octadecyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 3-
Sulfobutyl, 2-carboxyethyl, 3-carboxy-n-propyl, 4-carboxy-n-butyl, 5-carboxy-n-pentyl, benzyl, (4-carboxyphenyl) methyl, (4-hydroxyphenyl) methyl, -Tolylmethyl, 3-tolylmethyl, 2-hydroxyethyl, 3-hydroxy-n-propyl, 2-methoxyethyl, 2-ethoxyethyl, 2- (methoxycarbonyl) ethyl, 3- (phenoxycarbonyl) -n-
Propyl, 2- (acetyloxy) ethyl and the like. When the substituent of the substituted alkyl group is an acid substituent, an alkali metal salt such as Na or K, Mg, C
It may be in the form of an alkaline earth metal salt such as a, an ammonium salt, a triethylammonium salt, a tributylammonium salt, an organic ammonium salt such as a pyridinium salt.

R is a halogen atom or a substituent which can be substituted / introduced from a halogen atom, and represents a substituted amino group, an alkoxy group or an alkylthio group. Specific examples include a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a di-n-butylamino group, a di-isobutylamino group, a 1-pyrrolidinyl group,
-Piperidyl group, 4-acetyl-1-piperidyl group, 4
-Methoxycarbonyl-1-piperidyl group, 4-morpholinyl group, 4-thiomorpholinyl group, methoxy group,
Examples include ethoxy, phenoxy, ethylthio, n-propylthio, phenylthio, and tolylthio groups.

The anion represented by B includes a halogen ion, a perchlorate ion, an arylsulfonate ion,
Alkyl sulfate ions and the like can be mentioned. here,
m represents the number necessary to adjust the intramolecular charge to zero.

Specific examples of the compound represented by the general formula 2 which can be produced by the present invention are shown below.
It is not limited to these.

[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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The compound represented by the general formula 1 is
nic Synthesis, collect vol.5,215 (1973), GAReynold
s et al., Journal of Organic Chemistry, 42, 885-888 (197
It can be easily obtained by reacting a diformyl form of a cycloalkene which can be synthesized by the method described in 7) with an aromatic amine such as aniline. In many cases, this compound can be easily synthesized with a structure represented by the general formula 1 by adding an aromatic amine to the reaction mixture as described above. At that time, an appropriate acid and amine salt may be used, or the acid may be added to the reaction solution to obtain the target compound in the form of an acid salt. The acid used is hydrochloric acid, hydrobromic acid, sulfuric acid,
Hydroiodic acid, perchloric acid and the like, preferably hydrochloric acid,
It is sulfuric acid.

[0043]

EXAMPLES Specific examples of the synthesis method of the present invention are described in detail below. (Synthesis Example 1) A synthesis reaction scheme of the compound represented by the general formula 1 is shown in Scheme 1.

[0044]

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Chloroform 4 in a 300 ml three-necked flask
0 ml and N, N-dimethylformamide (40 ml) were added, and a mixed solution of phosphorus oxychloride (37 ml) and chloroform (40 ml) was added dropwise on an ice water bath with stirring under a nitrogen atmosphere. After completion of the dropwise addition, the ice water bath was removed, and the mixture was stirred at room temperature for 1 hour. After dropping a mixed solution of 10 g of cyclohexanone and 10 ml of chloroform at an internal temperature of 20 ° C. or lower, an oil bath (70 mL) was added.
° C) and heated and stirred for 2 hours. After confirming the completion of the reaction by TLC, transfer the contents to a 1-liter three-necked flask,
Under a nitrogen atmosphere, an aqueous sodium acetate solution was added dropwise on an ice water bath with stirring. After confirming the completion of the neutralization of the solution with pH test paper, the ice water bath was removed, and the mixture was stirred at room temperature for 1 hour. After standing, the lower layer (chloroform layer) of the reaction solution was washed with water, dried over anhydrous sodium sulfate, filtered with a desiccant, and then a methanol solution of aniline hydrochloride was added. After stirring for 3 hours, the precipitated crystals were collected by filtration and washed with acetone and then with ethanol. Dry,
27.7 g of compound (a) (77% yield based on cyclohexanone) was obtained. After the synthesis, the solution was put in a glass container, sealed, and stored at room temperature for one month. Its purity was analyzed by HPLC to be 98%. Melting point: 231.5-232.5 ° C. Nuclear magnetic resonance spectrum ( ¹ H, DMSO-d ₆ , δ ppm): 1.87 (t, 2
H), 2.72 (t, 4H), 7.28 (d, 2H), 7.47 (dd, 4H), 7.56 (d, 4
H), 8.55 (s, 2H)

(Synthesis Example 2) The reaction scheme is shown in Scheme 2.

[0047]

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The same treatment was carried out using cyclopentanone instead of cyclohexanone, and the compound (c) 13.2 was obtained.
g (yield 38% based on cyclopentanone) was obtained. After the synthesis, the solution was put in a glass container, sealed, and stored at room temperature for one month. It was 97% pure by HPLC.
Met. Melting point: 221.4-222.3 ° C. Nuclear magnetic resonance spectrum ( ¹ H, DMSO-d ₆ , δ ppm): 2.98 (t, 4
H), 7.28 (d, 2H), 7.46 (dd, 4H), 7.54 (d, 4H), 8.32 (s, 2
H)

Synthesis Example 3 Synthesis of Exemplified Compound 4 The reaction scheme is shown in Scheme 3.

[0050]

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54.0 g of phenylhydrazine and 63.0 g of acetylcyclohexane were dissolved in 150 ml of glacial acetic acid and heated under reflux for 2 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, ethyl acetate was added to the residue, and the mixture was washed three times with a 5% aqueous sodium hydrogen carbonate solution and once with a saturated saline solution. After the organic layer was dried over anhydrous magnesium sulfate, insolubles were removed by filtration, and the filtrate was concentrated under reduced pressure to obtain 92.2 g of a crude purified compound (d). This crude product (d) was subjected to the next reaction without purification by distillation under reduced pressure.

In a 500 ml flask, 92.2 g of a crude product of the above compound (d), 151.2 g of ethyl iodide
g and ethyl acetate (90 ml), and the mixture was heated and refluxed for 6 hours while stirring on an oil bath at 90 ° C. The mixture was allowed to cool at room temperature overnight, and the precipitated crystals were collected by filtration. The extract was washed with ethyl acetate and then with diisopropyl ether and dried to obtain 90.8 g of compound (e).
(A yield of 51% based on phenylhydrazine) was obtained. Nuclear magnetic resonance spectrum ( ¹ H, DMSO-d ₆ , δ ppm): 1.46 (t, 3
H), 1.9 (m, 10H), 2.93 (s, 3H), 4.55 (q, 2H), 7.66 (ddd, 2
H), 8.11 (dd, 2H)

In a 100 ml flask, add compound (e)
2.13 g, methanol 10.0 ml, triethylamine 6.0 ml, compound (a) (one month or more after synthesis)
After adding 1.08 g, stirring and dissolving uniformly, 20.0 ml of acetic anhydride was gradually added dropwise over 30 minutes while cooling on a water bath. Thereafter, the mixture was stirred at room temperature for 3 hours, and the precipitate was collected by filtration.
After washing with acetone and then with isopropyl ether, 1.74 g (yield 81%) of Exemplified Compound 4 was obtained. Yellow-green powder, λmax = 786 nm (methanol) Nuclear magnetic resonance spectrum ( ¹ H, DMSO-d ₆ , δppm): 1.49 (t, 6)
H), 2.0 (m, 20H), 2.0 (t, 2H), 2.76 (t, 4H), 4.28 (q, 4
H), 6.16 (d, 2H), 7.25 (dd, 4H), 7.47 (d, 2H), 7.85 (d, 2
H), 8.57 (d, 2H)

Synthesis Example 4 Synthesis of Exemplified Compound 9 The reaction scheme is shown in Scheme 4.

[0055]

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Acetic acid 70 ml in a 200 ml three-necked flask
And 17.5 g of p-methoxyphenylhydrazine hydrochloride were added, and 13.8 g of acetylcyclohexane was added while stirring on an oil bath (70 ° C.). Raise the bath temperature to 85 ° C 3
After 0 minutes of reaction and the rise in internal temperature subsided,
C. and reacted for a further 2 hours. After cooling to room temperature, 5
Transfer to a 00 ml beaker, add 120 ml of water, and add
0 g was gradually added, and the mixture was stirred until foaming stopped. After extraction with ethyl acetate, the extract was washed with an aqueous sodium hydrogen carbonate solution and dried over anhydrous sodium sulfate. After filtering off the drying agent, about half of the ethyl acetate was distilled off under reduced pressure using an evaporator. After 31.2 g of ethyl iodide was added, the mixture was heated and refluxed for 4 hours on an oil bath (90 ° C.), and then allowed to cool to room temperature. The resulting precipitate was collected by filtration, washed with methyl ethyl ketone and then with diisopropyl ether, and dried to obtain 17.6 g of compound (f) (46% yield based on hydrazine). Nuclear magnetic resonance spectrum ( ¹ H, DMSO-d ₆ , δ ppm): 1.41 (t, 3
H), 1.9 (m, 10H), 2.81 (s, 3H), 3.90 (s, 3H), 4.46 (q, 2
H), 7.23 (dd, 1H), 7.54 (d, 1H), 7.95 (d, 1H)

In a 50 ml flask, compound (f) 1.
16 g, methanol 5.0 ml, triethylamine 2.
2 g, compound (c) (one month or more after synthesis) 0.52
g was added thereto, and the mixture was stirred and uniformly dissolved. Then, 10 ml of acetic anhydride was gradually added dropwise over 30 minutes while cooling on a water bath. Then, after stirring at room temperature for 2 hours, 50 ml of ethyl acetate was gradually added, and after stirring for 1 hour, the precipitate was collected by filtration. After washing with acetone and then with diisopropyl ether, the above exemplified compound 9
Was obtained (yield 72%). Yellowish brown powder, λmax = 835 nm (methanol) Nuclear magnetic resonance spectrum ( ¹ H, CDCl ₃ , δppm): 1.44 (t, 6H),
2.0 (m, 20H), 3.03 (t, 4H), 3.96 (s, 6H), 4.24 (q, 4H), 5.
95 (d, 2H), 6.95 (dd, 2H), 7.14 (d, 2H), 7.38 (d, 2H), 7.9
3 (d, 2H)

Synthesis Example 5 Synthesis of Exemplified Compound 12 A reaction scheme is shown in Scheme 5.

[0059]

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In a 100 ml flask, add compound (e)
0.36 g, methanol 5.0 ml, triethylamine 0.11 g, compound (a) (one month or more after synthesis)
After adding 0.36 g and stirring to dissolve uniformly, 3.0 ml of acetic anhydride was added while cooling on a water bath, and the mixture was stirred for 1 hour. Further, 0.11 g of triethylamine and 2.0 m of acetic anhydride
1, 0.39 g of compound (f) was added, and the mixture was stirred at room temperature for 3 hours. 50 ml of water was added, and the mixture was stirred for 1 hour, allowed to stand, and then decanted to remove the aqueous solution. The obtained precipitate was dissolved in methanol, the solvent was distilled off under reduced pressure, and the residue was dried. The residue was subjected to silica gel column chromatography (chloroform + methanol 10: 1), and then recrystallized and purified from a mixed solvent of acetone + diisopropyl ether 1: 2 to obtain 0.22 g of the above exemplified compound 12 (yield: 29%). Was. Red-brown powder, λmax = 797 nm (methanol) Nuclear magnetic resonance spectrum ( ¹ H, DMSO-d ₆ , δppm): 1.45 (t, 3
H), 1.49 (t, 3H), 2.0 (m, 20H), 1.99 (t, 2H), 2.73 (m, 4
H), 3.87 (s, 3H), 4.28 (m, 4H), 6.01 (d, 1H), 6.14 (d, 1
H), 7.11 (dd, 1H), 7.28 (dd, 2H), 7.5 (m, 3H), 7.88 (d, 1
H))

(Comparative Synthesis Example) The reaction scheme is shown in Scheme 6.
Shown in

[0062]

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Compound (A) was converted to Organic Synthesis, coll
ect vol.5, 215 (1973), etc., and isolated and purified by recrystallization (yellow crystals, 58% yield). When opened, it turned brown. Its purity was analyzed by HPLC to be 70%.

Compound (a) 0.62 containing this impurity
g, compound (e) 2.13 g, potassium acetate 0.59
g, 10 ml of acetic anhydride and 1.0 ml of acetic acid were placed in a 50 ml flask, and heated and stirred on an oil bath (90 ° C.) for 20 minutes. After allowing to cool to room temperature, the precipitate was collected by filtration, washed with acetic acid, acetone, and diisopropyl ether in that order, and dried to obtain 1.23 g of Exemplified Compound 4 (57% yield).

[0065]

As described above, according to the present invention, 800 n
a polymethinecyanine compound having a cyclic structure as shown in general formula 2 having an absorption maximum in the near infrared region near m
It can be synthesized under mild and easy-to-control conditions. This synthesis method has excellent production stability and a relatively high yield.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI G02B 5/22 G02B 5/22 G03C 1/20 G03C 1/20

Claims (1)

[Claims] 1. A method for producing a polymethine cyanine compound represented by the following general formula 2, wherein a compound represented by the following general formula 1 is used as a raw material intermediate. Embedded image (In the formula, T is a substituted or unsubstituted alkylene group necessary for forming a cyclic structure, and one or more of the carbon atoms constituting the ring may be substituted with another atom or atomic group. A represents a substituted or unsubstituted aryl group, and X represents a halogen atom or a substituted amino group. (In the formula, L ¹ and L ² may be the same or different from each other, and are a group of nonmetallic atoms necessary to form a ring together with the carbon atom at the 3-position of the nitrogen-containing ring. or one is optionally substituted with another atom or atomic group .Z ^1,
Z ² may be the same or different and represents an atom group necessary to form a substituted or unsubstituted aromatic or heterocyclic ring. R ¹ and R ² are a substituted or unsubstituted alkyl group, and R is a halogen atom or a substituent that can be substituted or introduced from a halogen atom, and represents a substituted amino group, an alkoxy group, or an alkylthio group. T is a substituted or unsubstituted alkylene group necessary for forming a cyclic structure, and one or more of the carbon atoms constituting the ring may be substituted with another atom or atomic group. B is an anion, and m represents a number necessary to adjust the intramolecular charge to zero. )