JP2000256364A - Substituted benzene dithiol metal complex and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a novel substituted benzene thiol metal complex that is useful as a singlet oxygen quencher as well as can function as an optical information-recording medium. SOLUTION: This is a metal complex represented by formula I [R is a group of formula II or formula III (R1 is a 1-4C alkyl); M is a transition metal, preferably Cu, Co, Ni; A+ is quaternary ammonium or quaternary phosphonium group], typically 4-thiomorpholinosulfonyl-1,2-benzenedithiol nickel complex of formula IV. The metal complex of formula I is prepared, for example, by using a 1,2-dihalogenobenzene as a starting material to prepare a 3,4- dihalogenobenzenesulfonyl chloride, allowing thiomorpholine or a 4- alkylpiperidine to react with the resultant sulfonyl chloride to give a 4- substituted sulfonyl-1,2-dihalogenobenzene, substituting the halogen group with mercapto group, followed by reaction of the resultant mercaptan compound with a transition metal salt and a quaternary ammonium salt or quaternary phosphonium salt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a metal complex and a method for producing the same, and more particularly to a substituted benzenedithiol metal complex and a method for producing the same.

[0002]

2. Description of the Related Art An indolenine-based cyanine dye having good heat resistance and water resistance is preferably used as an optical information recording medium constituting a recording layer of various optical recording disks (JP-A-59-5959). 24692, etc.). However, since indolenine-based cyanine dyes are liable to undergo reproduction deterioration due to repeated irradiation of reproduction light and light deterioration under storage in a bright room, it is difficult to use a recording layer using the dye stably for a long period of time. . Therefore, when forming a recording layer using an indolenine-based cyanine dye, a metal complex that can function as a singlet oxygen quencher is mixed with the dye, and a coating solution obtained by dissolving this mixture in a solvent is used as an optical recording disk. To form a recording layer (for example, JP-A-59-55794).

[0003] By the way, such a metal complex as described above can function not only as a singlet oxygen quencher but also as an optical information recording medium itself.
Broader usefulness can be expected. For example, with such a metal complex, it becomes possible to form a recording layer of an optical recording disk only with the metal complex without using the indolenine-based cyanine dye as described above.

An object of the present invention is to realize a novel metal complex which can function not only as a singlet oxygen quencher but also as an optical information recording medium itself.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found a substituted benzenedithiol metal complex represented by the following general formula (1).

That is, the substituted benzenedithiol metal complex according to the present invention is represented by the following general formula (1).

[0007]

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In the general formula (1), R represents a thiomorpholino group represented by the following formula (2):

[0009]

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Alternatively, a compound represented by the following general formula (3):
Represents an alkylpiperazino group,

[0011]

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(R ¹ represents an alkyl group having 1 to 4 carbon atoms) M represents a transition metal, and A ⁺ represents a quaternary ammonium group or a quaternary phosphonium group.

Specific examples of such a substituted benzenedithiol metal complex represented by the general formula (1) include, for example, 4-thiomorpholinosulfonyl-1,2-benzenedithiol metal represented by the following general formula (1-a). The complex is a 4-methylpiperidinosulfonyl-1,2-benzenedithiol metal complex represented by the following general formula (1-b).

[0014]

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[0015]

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In the general formulas (1-a) and (1-b), M
And A ⁺ are the same as in the case of the general formula (1).

The method for producing a substituted benzenedithiol metal complex represented by the general formula (1) according to the present invention comprises:

3,4-Dihalogenobenzenesulfonyl chloride is reacted with thiomorpholine represented by the following formula (4) and one of 4-alkylpiperidines represented by the general formula (5) to react with the following general formula: A step of synthesizing a 4-substituted sulfonyl-1,2-dihalogenobenzene represented by (6),

[0019]

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[0020]

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(R ¹ represents an alkyl group having 1 to 4 carbon atoms)

[0022]

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(Wherein X ¹ and X ² represent a chlorine atom or a bromine atom, and X ¹ and X ² may be the same or different. R is a group represented by the general formula (1) Same as the case.)

Converting the 4-substituted sulfonyl-1,2-dihalogenobenzene to a 4-substituted sulfonyl-1,2-benzenedithiol represented by the following general formula (7):

[0025]

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(In the formula, R is the same as in the case of the general formula (6).)

Reacting the 4-substituted sulfonyl-1,2-benzenedithiol with a salt of a transition metal and a quaternary ammonium salt or a quaternary phosphonium salt.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION The substituted benzenedithiol metal complex according to the present invention is represented by the following general formula (1).

[0029]

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In the formula, R represents a thiomorpholino group represented by the following formula (2) or a 4-alkylpiperazino group represented by the following formula (3).

[0031]

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[0032]

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R ¹ in the general formula (3) has 1 to 4 carbon atoms.
Alkyl group, specifically, a methyl group, an ethyl group,
Propyl group, iso-propyl group, n-butyl group, te
An rt-butyl group and a sec-butyl group can be exemplified.

In the general formula (1), M represents a transition metal. Here, the transition metal is not particularly limited, and examples thereof include copper, cobalt, and nickel.

Further, in the general formula (1), A ⁺ is
A quaternary ammonium group or a quaternary quaternary phosphonium group is shown. Specific examples of the quaternary ammonium group include a tetra-n-butylammonium group, a tetraethylammonium group, a tetraphenylammonium group, a tetrabenzylammonium group, and a trimethylbenzylammonium group. Specific examples of the quaternary phosphonium group include a tetra-n-butylphosphonium group, a tetraethylphosphonium group, a tetraphenylphosphonium group, and a tributylbenzylphosphonium group.

A specific example of the substituted benzenedithiol metal complex represented by the general formula (1) is 4-thiomorpholinosulfonyl- represented by the following general formula (1-a).
Examples thereof include a 1,2-benzenedithiol metal complex and a 4-methylpiperidinosulfonyl-1,2-benzenedithiol metal complex represented by the following general formula (1-b). In the general formulas (1-a) and (1-b), M and A ⁺ are the same as those in the general formula (1).

[0037]

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[0038]

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Next, a preferred method for producing the substituted benzenedithiol metal complex represented by the general formula (1) will be described.

The substituted benzenedithiol metal complex represented by the general formula (1) can be synthesized from 1,2-dihalogenobenzene as a starting material and an intermediate synthesized therefrom. Hereinafter, the manufacturing method will be specifically described for each process.

(Step 1) In this step, 1,2-dihalogenobenzene is reacted with chlorosulfonic acid in the presence of anhydrous sodium sulfate in a solvent to synthesize 3,4-dihalogenobenzenesulfonic acid.

The amount of chlorosulfonic acid used here is
The molar amount is preferably set to 1.5 to 3.0 times the molar amount of 1,2-dihalogenobenzene, and more preferably set to 1.7 to 2.1 times the molar amount. Further, the amount of anhydrous sodium sulfate is from 0.05 to 1,2-dihalogenobenzene.
It is preferably set to 0.15 moles, and 0.07 to
It is more preferable to set the molar ratio to 0.1 times. Further, the solvent used in this reaction is preferably a halogenated hydrocarbon solvent such as chloroform, carbon tetrachloride, and 1,2-ethylene dichloride.

The temperature during the reaction is preferably set in the range of 50 to 100 ° C., more preferably 70 to 85 ° C. The optimum reaction time varies depending on the reaction temperature, but is usually 1 to 4 hours.

(Step 2) Thionyl chloride is reacted with 3,4-dihalogenobenzenesulfonic acid obtained in step 1 to synthesize 3,4-dihalogenobenzenesulfonyl chloride.

The amount of thionyl chloride used here is as follows:
Usually, it is 1.0 to 2.0 times mol, preferably 1.1 to 1.5 times mol with respect to 3,4-dihalogenobenzenesulfonic acid.

In this reaction, a halogenated hydrocarbon solvent such as chloroform, carbon tetrachloride, and 1,2-ethylene dichloride is preferably used as in the case of step 1. Here, when the same solvent as in the case of Step 1 is used,
Since the reaction can be performed continuously, it is advantageous in terms of work efficiency, yield, and the like.

The reaction temperature in this step is 45 to 7
The temperature is preferably set in the range of 0 ° C, and more preferably in the range of 50 to 60 ° C. The optimum reaction time varies depending on the reaction temperature, but is usually 1 to 4 hours.

(Step 3) Reaction of 3,4-dihalogenobenzenesulfonyl chloride obtained in Step 2 with thiomorpholine represented by the following formula (4) or 4-alkylpiperidine represented by the general formula (5) To synthesize a 4-substituted sulfonyl-1,2-dihalogenobenzene.
Note that R ¹ in the general formula (5) is the same as in the case of the general formula (3).

[0049]

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[0050]

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Here, among the metal complexes represented by the general formula (3), R in the general formula (1) includes, for example, the general formula (1-
4-methylpiperidinosulfonyl-1, b)
When producing a 2-benzenedithiol metal complex,
A compound of the general formula (5) wherein R ¹ is a methyl group;
Use methylpiperidine.

The amount of the compound represented by the formula (4) or the general formula (5) used in this reaction is usually 1 to 3,4-dihalogenobenzenesulfonic acid used in the step 2. 5 to 4.0 times mol, preferably 2.0 to 3.0 times.
It is twice the mole.

In this reaction, a halogenated hydrocarbon solvent such as chloroform, carbon tetrachloride, and 1,2-ethylene dichloride is preferably used as in the case of step 2. Here, if the same solvent as in the case of Step 2 is used, the reaction can be performed continuously, which is advantageous in terms of work efficiency, yield, and the like. The reaction temperature is 15 to 40.
C. is preferably set to 20.degree. C., more preferably 20 to 30.degree. Further, the reaction time varies depending on the reaction temperature, and the optimum condition is usually 1 to 3 hours.

The 4-substituted sulfonyl-1,2-dihalogenobenzene obtained in this step is represented by the following general formula (6). In the general formula (6), X ¹ and X ² represent a chlorine atom or a bromine atom, and X ¹ and X ² may be the same or different. R is the same as in the general formula (1).

[0055]

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(Step 4) The halogen group of the 4-substituted sulfonyl-1,2-dihalogenobenzene obtained in Step 3 is substituted with a mercapto group, and the 4-substituted compound represented by the following general formula (7) is obtained.
A substituted sulfonyl-1,2-benzenedithiol is synthesized. That is, in this step, the 4-substituted sulfonyl-1,2
-Dihalogenobenzene is substituted with 4-substituted sulfonyl-1,2-
Convert to benzenedithiol. Note that R in the general formula (7) is the same as in the general formula (1).

[0057]

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Here, the substitution of a halogen group with a mercapto group can be carried out, for example, according to the method described in JP-A-6-25151 or JP-A-5-117225. Specifically, when the 4-substituted sulfonyl-1,2-dihalogenobenzene obtained in Step 3 is reacted with sodium bisulfide using iron powder and sulfur powder as catalysts, the halogen group is replaced with a mercapto group. Thus, an iron complex is formed in the system, and the target 4-substituted sulfonyl-1,2-benzenedithiol is obtained by decomposing the iron complex using zinc oxide.

The amount of sodium hydrosulfide used here is usually 1.5 to 4.0 times mol, preferably 1.8 to 2.0 times mol of 4-substituted sulfonyl-1,2-dihalogenobenzene. It is 5 times mol. The amount of iron powder used as a catalyst is usually 0.4 to 2.0 times mol, preferably 0.5 to 1.0 times mol of 4-substituted sulfonyl-1,2-dihalogenobenzene. is there. Further, the amount of sulfur powder used as a catalyst is usually 1.0 to 20.0% by weight, preferably 1.0 to 5.0% by weight of the 4-substituted sulfonyl-1,2-dihalogenobenzene. .

The reaction temperature in this step is 60 to 1
The temperature is preferably set to 40 ° C, and more preferably to 70 to 110 ° C.

(Step 5) A method of reacting the 4-substituted sulfonyl-1,2-benzenedithiol obtained in Step 4 with a transition metal salt and a quaternary ammonium salt or a quaternary phosphonium salt in a lower alcohol; Alternatively, a lower alcohol is added to the N, N-dimethylformamide solution of the 4-substituted sulfonyl-1,2-benzenedithioliron complex obtained in step 4, and a transition metal salt and a quaternary ammonium salt or a quaternary phosphonium salt are added. To obtain a substituted benzenedithiol metal complex represented by the general formula (1).

The lower alcohol used here includes, for example, methanol, ethanol, isopropanol, tert-butanol and the like.
Among them, it is preferable to use methanol from the viewpoint of economy.

As the transition metal salt, a transition metal (M) salt contained in the general formula (1) of the target substituted benzenedithiol metal complex is used. Specific examples of the transition metal salt include copper (II) chloride, cobalt chloride, nickel (II) chloride, copper (II) bromide, cobalt bromide,
Examples thereof include halides of transition metals such as cobalt iodide and nickel iodide, nitrates such as copper nitrate and cobalt nitrate, sulfates such as copper sulfate and cobalt sulfate, and acetates such as copper acetate and cobalt acetate. Preferred as transition metal salts are halides, particularly chlorides, in terms of economy, reactivity and the like.

The amount of the transition metal used is preferably set to 0.3 to 10 times the mol of the 4-substituted sulfonyl-1,2-benzenedithiol. When the amount is less than 0.3 times mol, the yield is low, and conversely, even if it exceeds 10 times mol, the yield is not improved and it is uneconomical.

Further, a quaternary ammonium salt or a quaternary ammonium salt
As the quaternary phosphonium salt, a salt of a quaternary ammonium group or a quaternary phosphonium group (A ⁺ ) contained in the general formula (1) of the target substituted benzenedithiol metal complex is used. Specifically, examples of the quaternary ammonium salts include tetra-n-butylammonium salts such as tetra-n-butylammonium bromide and tetra-n-butylammonium chloride, and tetraethylammonium salts such as tetraethylammonium bromide and tetraethylammonium chloride. , Tetraphenylammonium salts such as tetraphenylammonium bromide and tetraphenylammonium chloride, tetrabenzylammonium salts such as tetrabenzylammonium bromide and tetrabenzylammonium chloride, and trimethylbenzylammonium salts such as trimethylbenzylammonium bromide and trimethylbenzylammonium chloride. Examples can be given.

The quaternary phosphonium salts include tetra-n-butylphosphonium bromide, tetra-n-
Tetra-n-butylphosphonium salts such as butylphosphonium chloride, tetraethylphosphonium salts such as tetraethylphosphonium bromide and tetraethylphosphonium chloride, tetraphenylphosphonium salts such as tetraphenylphosphonium bromide and tetraphenylphosphonium chloride, tetrabenzylphosphonium bromide, tetrabenzylphosphonium Examples thereof include tetrabenzylphosphonium salts such as chloride, and trimethylbenzylphosphonium salts such as trimethylbenzylphosphonium bromide and trimethylbenzylphosphonium chloride.

Among these, preferred are quaternary such as tetra-n-butylammonium bromide, tetra-n-butylammonium chloride, tetraethylammonium bromide and tetraethylammonium chloride in view of economy and reactivity. It is an ammonium salt.

The amount of the quaternary ammonium salt or quaternary phosphonium salt used is determined by the amount of the 4-substituted sulfonyl-
The molar amount is preferably set to 0.3 to 1.0 times the molar amount of 1,2-benzenedithiol, and more preferably set to 0.4 to 0.9 times the molar amount. When the molar ratio is less than 0.3 times, the yield is low. On the contrary, when the molar ratio exceeds 1.0 times, the yield is not improved and it is uneconomic.

The reaction in this step is preferably carried out in the presence of an alkoxide, since the yield can be increased. Examples of the alkoxide that can be used here include sodium methylate, sodium ethylate, potassium tert-butylate and the like, and it is preferable to use sodium methylate from the viewpoint of economy.

When such an alkoxide is used, the amount of the alkoxide used is preferably set to 1.5 to 10 times the molar amount of the 4-substituted sulfonyl-1,2-benzenedithiol, and is preferably 2.0 to 3. It is more preferable to set the molar amount to 0 times. When the molar ratio is less than 1.5 times, the yield hardly increases,
Conversely, the use of more than 10 moles is uneconomical because the yield is not improved.

The reaction temperature in this step is preferably set at 15 to 40 ° C., and more preferably 25 to 35 ° C. The reaction time varies depending on the reaction temperature, and the optimum condition is usually 1 to 10 hours.

The substituted benzenedithiol metal complex of the present invention obtained through the above-mentioned steps is useful as a dye stabilizer. For this reason, when the substituted benzenedithiol metal complex of the present invention is mixed with an indolenine-based cyanine dye used as an optical information recording medium, the recording layer hardly causes reproduction deterioration due to repeated irradiation of reproduction light and light deterioration under storage in a bright room. An optical recording disk provided with

Further, since the substituted benzenedithiol metal complex of the present invention itself can function as an optical information recording medium material, a recording layer for an optical recording disk can be formed by itself.

When forming a recording layer for an optical recording disk using the substituted benzenedithiol metal complex of the present invention, the recording layer alone or a mixture thereof with an indolenine-based cyanine dye is dissolved in a solvent such as alcohol. The solution is dissolved to prepare a coating solution, and this coating solution is applied to the resin substrate of the optical recording disk.

[0075]

Next, the present invention will be described in detail with reference to examples.

[0076]

Example 1 A 300 ml four-necked flask equipped with a stirrer, a condenser and a thermometer was prepared.
90 g of ethylene dichloride and chlorosulfonic acid 7
1.5 g (0.61 mol) was added, and 1,2-dichlorobenzene 53.degree.
0 g (0.36 mol) was added dropwise and reacted at 75 ° C. for 2 hours.

Next, the obtained reaction product solution containing 3,4-dichlorobenzenesulfonic acid was cooled to 50 ° C., and 47.6 g (0.40 mol) of thionyl chloride was added dropwise to 50-55.
The reaction was carried out at 2 ° C. for 2 hours. After the reaction solution was cooled to room temperature, it was dropped into 360 g of water and stirred at 0 to 10 ° C for 0.5 hour.

The obtained reaction product liquid was separated, and the organic layer obtained by removing the aqueous layer was replaced with 210 g of thiomorpholine.
The mixture was dropped into a mixture of 4 g (0.76 mol) and 240 g of 1,2-ethylene dichloride, and reacted at room temperature for 1 hour. 185 g of water was further added thereto, the mixture was separated, and the aqueous layer was removed. Then, the solvent was distilled off under reduced pressure to obtain 106.8 g of 4-thiomorpholinosulfonyl-1,2-dichlorobenzene. The yield was 95% based on 1,2-dichlorobenzene.

The obtained 4-thiomorpholinosulfonyl-
62.4 g (0.2 mol) of 1,2-dichlorobenzene
183 g of N, N-dimethylformamide and 33.6 g (0.42 mol) of 70% sodium hydrosulfide were added to
The reaction was performed at 5 ° C. for 3 hours.

5.9 g (0.11 mol) of iron powder was added to this solution.
And 6.7 g (0.21 mol) of sulfur powder were added.
The reaction was carried out at ９５95 ° C. for 6 hours.

The reaction solution was mixed with 1080 g of methanol at room temperature.
Was added, 77.2 g of a 28% sodium methylate-methanol solution (0.4 mol as sodium methylate) was added, and the mixture was stirred for 1 hour.
I) 23.8 g (0.1 mol) of hexahydrate was added and reacted at room temperature for 3 hours.

Further, 32.2 g (0.1 mol) of tetrabutylammonium bromide was added to the reaction solution and reacted at room temperature for 2 hours.

The obtained reaction solution was concentrated and purified by silica gel column chromatography. The fraction is concentrated and the desired green 4-thiomorpholinosulfonyl-
Solid of 1,2-benzenedithiol nickel complex73.
0 g was obtained. The yield is 4-thiomorpholinosulfonyl-
It was 80% based on 1,2-dichlorobenzene. The obtained 4-thiomorpholinosulfonyl-1,2-
The structural formula of the benzenedithiol nickel complex is as follows.

[0084]

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The obtained 4-thiomorpholinosulfonyl-
The analytical values and physical properties of the 1,2-benzenedithiol nickel complex are as follows.

[0086]

[Table 1]

[0087]

Example 2 The nickel chloride (I) used in Example 1 was used.
I) The same operation as in Example 1 was performed, except that 17.1 g (0.1 mol) of cupric chloride dihydrate was used instead of 23.8 g (0.1 mol) of hexahydrate. Thus, 77.9 g of the desired dark green 4-thiomorpholinosulfonyl-1,2-benzenedithiol copper complex was obtained. The yield is 8 based on 4-thiomorpholinosulfonyl-1,2-dichlorobenzene.
5%. The structural formula of the obtained 4-tomorpholinosulfonyl-1,2-benzenedithiol copper complex is as follows.

[0088]

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The obtained 4-thiomorpholinosulfonyl-
The analytical values and physical properties of the 1,2-benzenedithiol copper complex are as follows.

[0090]

[Table 2]

[0091]

Example 3 Instead of 53.0 g (0.36 mol) of 1,2-dichlorobenzene used in Example 1, 1,2
-The same operation as in Example 1 was performed except that 84.9 g (0.36 mol) of dibromobenzene was used, and 73.0 g of a target green 4-thiomorpholinosulfonyl-1,2-benzenedithiol nickel complex was obtained. I got The yield was 80% based on 4-thiomorpholinosulfonyl-1,2-dichlorobenzene.

[0092]

Example 4 Instead of 53.0 g (0.36 mol) of 1,2-dichlorobenzene used in Example 2, 1,2
The same operation as in Example 2 was carried out except that 84.9 g (0.36 mol) of dibromobenzene was used, and the desired dark green 4-thiomorpholinosulfonyl-1,2-benzenedithiol copper complex was used. 9 g were obtained. The yield was 85% based on 4-thiomorpholinosulfonyl-1,2-dichlorobenzene.

[0093]

Example 5 Thiomorpholine 7 used in Example 1
The same operation as in Example 1 was carried out, except that 75.3 g (0.76 mol) of 4-methylpiperidine was used instead of 8.4 g (0.76 mol), to obtain the desired green 4-methylpiperidine. 65.4 g of nosulfonyl-1,2-benzenedithiol nickel complex was obtained. The yield is 72 based on 4-methylpiperidinosulfonyl-1,2-dichlorobenzene.
%Met. The structural formula of the obtained 4-methylpiperidinosulfonyl-1,2-benzenedithiolnickel complex is as follows.

[0094]

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The analytical values and physical properties of the obtained 4-methylpiperidinosulfonyl-1,2-benzenedithiolnickel complex are as follows.

[0096]

[Table 3]

[0097]

Example 6 The nickel chloride (I) used in Example 5 was used.
I) The same operation as in Example 5 was performed, except that 17.1 g (0.1 mol) of cupric chloride dihydrate was used instead of 23.8 g (0.1 mol) of hexahydrate. Thus, 75.5 g of the desired dark green 4-methylpiperidinosulfonyl-1,2-benzenedithiol copper complex was obtained. The yield was 83% based on 4-methylpiperidinosulfonyl-1,2-dichlorobenzene. The structural formula of the obtained 4-methylpiperidinosulfonyl-1,2-benzenedithiol copper complex is as follows.

[0098]

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The analytical values and physical properties of the obtained 4-methylpiperidinosulfonyl-1,2-benzenedithiol copper complex are as follows.

[0100]

[Table 4]

[0101]

Example 7 Instead of 53.0 g (0.36 mol) of 1,2-dichlorobenzene used in Example 5, 1,2
The same operation as in Example 5 was carried out except that 84.9 g (0.36 mol) of dibromobenzene was used, and the desired green 4-methylpiperidinosulfonyl-1,2-benzenedithiol nickel complex 66 was obtained. 0.5 g was obtained. The yield is 4-
It was 74% based on methylpiperidinosulfonyl-1,2-dichlorobenzene.

[0102]

Example 8 Instead of 53.0 g (0.36 mol) of 1,2-dichlorobenzene used in Example 6, 1,2
The same operation as in Example 6 was carried out except that 84.9 g (0.36 mol) of dibromobenzene was used, and the intended dark green 4-methylpiperidinosulfonyl-1,2-benzenedithiol copper complex was obtained. 79.1 g were obtained. The yield was 87% based on 4-methylpiperidinosulfonyl-1,2-dichlorobenzene.

[0103]

According to the present invention, it is possible to provide a substituted benzenedithiol metal complex which can function not only as a singlet oxygen quencher but also as an optical information recording medium itself.

Further, according to the production method of the present invention, a substituted benzenedithiol metal complex which can function not only as a singlet oxygen quencher but also as an optical information recording medium itself can be produced.

Continued on front page F term (reference) 4H048 AA01 AA02 AB76 AB92 AC61 AC90 BD70 VA20 VA32 VA40 VA42 VA56 VB10 4H050 AA01 AA02 AB76 AB92 WB14 WB15 WB16 WB21

Claims (12)

[Claims] 1. A substituted benzenedithiol metal complex represented by the following general formula (1). Embedded image (Wherein R is Or (R ¹ represents an alkyl group having 1 to 4 carbon atoms), M represents a transition metal, and A ⁺ represents a quaternary ammonium group or a quaternary phosphonium group. ) 2. The substituted benzenedithiol metal complex according to claim 1, wherein the transition metal is copper, cobalt or nickel. 3. The method according to claim 1, wherein the quaternary ammonium group is tetra-
The substituted benzenedithiol metal complex according to claim 1, which is one of an n-butylammonium group, a tetraethylammonium group, a tetraphenylammonium group, a tetrabenzylammonium group, and a trimethylbenzylammonium group. 4. The method according to claim 1, wherein the quaternary phosphonium group is tetra-
The substituted benzenedithiol metal complex according to claim 1, which is one of an n-butylphosphonium group, a tetraethylphosphonium group, a tetraphenylphosphonium group, and a tributylbenzylphosphonium group. 5. A 4-thiomorpholinosulfonyl-1,2-benzenedithiol metal complex represented by the following general formula (1-a). Embedded image (In the formula, M represents a transition metal, and A ⁺ represents a quaternary ammonium group or a quaternary phosphonium group, respectively.) 6. A 4-methylpiperidinosulfonyl-1,2-benzenedithiol metal complex represented by the following general formula (1-b). Embedded image (In the formula, M represents a transition metal, and A ⁺ represents a quaternary ammonium group or a quaternary phosphonium group, respectively.) 7. The reaction of 3,4-dihalogenobenzenesulfonyl chloride with thiomorpholine represented by the following formula (4) and one of 4-alkylpiperidines represented by the general formula (5): Synthesizing a 4-substituted sulfonyl-1,2-dihalogenobenzene represented by the general formula (6); Embedded image (R ¹ represents an alkyl group having 1 to 4 carbon atoms) (Wherein X ¹ and X ² represent a chlorine atom or a bromine atom;
¹ and X ² may be the same or different, and R is Or (R ¹ represents an alkyl group having 1 to 4 carbon atoms). ) The 4-substituted sulfonyl-1,2-dihalogenobenzene is converted to a 4-substituted sulfonyl- represented by the following general formula (7).
Converting to 1,2-benzenedithiol; (Wherein, R is the same as in the case of the general formula (6).) The 4-substituted sulfonyl-1,2-benzenedithiol is a transition metal salt and a quaternary ammonium salt or a quaternary phosphonium salt. And a method for producing a substituted benzenedithiol metal complex represented by the following general formula (1). Embedded image (In the formula, R is the same as that in the general formula (6), M represents a transition metal, and A ⁺ represents a quaternary ammonium group or a quaternary phosphonium group, respectively.) 8. In the step of converting the 4-substituted sulfonyl-1,2-dihalogenobenzene to the 4-substituted sulfonyl-1,2-benzenedithiol, the 4-substituted sulfonyl-1,2-benzenedithiol is treated with iron powder and sulfur powder as catalysts. The method for producing a substituted benzenedithiol metal complex according to claim 7, wherein the sulfonyl-1,2-dihalogenobenzene is reacted with sodium hydrosulfide. 9. The method for producing a substituted benzenedithiol metal complex according to claim 7, wherein the transition metal salt is a transition metal salt of one of copper, cobalt and nickel. 10. The quaternary ammonium salt is one of a tetra-n-butylammonium salt, a tetraethylammonium salt, a tetraphenylammonium salt, a tetrabenzylammonium salt and a trimethylbenzylammonium salt. A method for producing the substituted benzenedithiol metal complex as described above. 11. The substituted benzenedithiol according to claim 7, wherein the quaternary phosphonium salt is one of a tetra-n-butylphosphonium salt, a tetraethylphosphonium salt, a tetraphenylphosphonium salt, and a tributylbenzylphosphonium salt. A method for producing a metal complex. 12. The reaction of the 4-substituted sulfonyl-1,2-benzenedithiol with a salt of the transition metal and the quaternary ammonium salt or the quaternary phosphonium salt in the presence of an alkoxide. 8. The method for producing the substituted benzenedithiol metal complex according to 7.