JPH0615550B2 - Novel 4-tert-butyl-1,2-benzenedithiol metal complex and process for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel compound, that is, 4-tert-butylbenzenedithiol metal complex represented by the structural formula of the following formula (I) and a method for producing the same.

(M in the formula is copper, cobalt, platinum, iron, nickel or palladium.
Radium, A Represents a quaternary ammonium group. ) Dithiol-metal complexes such as bis (1,2-dithiof)
Enolate) nickel tetra-n-butylammonium,
Bis (4,5-dimethyl-1,2-dithiophenole
G) copper tetra-n-butylammonium, bis (1,2,
3,4-tetrachloro-5,6-dithiophenolate)
Ortho such as cobalt tetra-n-butylammonium
The benzenedithiol metal complex is in the ultraviolet, visible, and near infrared regions.
It is known to strongly absorb the light of.

(JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, Vol. 88, pp. 43-50 and 4870-4875, 1.
966) Because of this physical property, the ortho-benzenedithiol metal complex is a useful compound used as an optical information recording medium. (JP-A-57-11090, JP-A-58-1756)
93) Therefore, the 4-tert-butylbenzenedithiol metal complex of the present invention is a substance useful as an optical information recording medium, and is a novel compound which has not been described in any conventionally known document.

(Means for Solving Problems) As a result of intensive investigations by the present inventors, a method for industrially producing a 4-tert-butyl-1,2-benzenedithiol metal complex represented by the following formula (I) was obtained. 4-tert-butyl-1,2-benzenedithiol represented by the following formula (II) (this substance is also a novel chemical substance disclosed by the present inventors and has been filed as Japanese Patent Application No. 62-11928). .) With alkali metal alkoxides, copper, cobalt, platinum, iron, nickel or palladium salts and the fourth.
The inventors have found that the target product can be obtained in good yield by reacting a primary ammonium salt in a lower alcohol, and have reached the present invention.

(M in the formula is copper, cobalt, platinum, iron, nickel or palladium.
Radium, A Represents a quaternary ammonium group. )That is, the gist of the present invention is to provide novel 4-tert-butyl.
-1,2-benzenedithiol metal complexes and their
To provide a manufacturing method.

4-tert-butyl-1,2 used as one of the raw materials
-Benzenedithiol is described in Japanese Patent Application No. 62-11928.
It is advantageous to manufacture according to the number.

That is, 4-tert-butylbenzenethiol or di (4-tert-butylphenyl) disulfide and sulfur monochloride in the presence of iodine or a Lewis acid solvent,
It can be produced by reacting in a solvent and then reducing with at least one kind of metal particles or metal powder selected from zinc, tin and iron.

The amount of sulfur monochloride used is 0.5 to 2.0 times mol, preferably 0.55 times, of 4-tert-butylbenzenethiol.
~ 1.5 times the molar amount.

When di (4-tert-butylphenyl) disulfide is used for one of the raw materials, it is 1 to 4 times the molar amount of the raw material,
Preferably, 1.1 to 3.0 times mol of sulfur monochloride is used.

Examples of Lewis acid catalysts used include zinc chloride, ferric chloride, aluminum chloride, stannic chloride, boron trifluoride, antimony trichloride, antimony pentachloride, and the like. Among them, zinc chloride gives good results. can get.

The amount of these Lewis acid catalysts used is 0.05 to 2 times mol, preferably 4-tert-butylbenzenethiol.
The molar ratio is 0.1 to 1 times, and is 0.1 to 4 times, preferably 0.2 to 2 times the mol of di (4-tert-butylphenyl) disulfide.

When iodine is used, it is 0.1 to 4 times mol, preferably 0.2 to 2 times, with respect to 4-tert-butylbenzenethiol and di (4-tert-butylphenyl) disulfide.
It is twice the mole.

As the solvent used in the reaction, chloroform, carbon tetrachloride, 1,1,2-trichloroethane, 1,1,2,2-
Halogenated hydrocarbon solvents such as tetrachloroethane, monochlorobenzene, 0-dichlorobenzene, 1,2,4-trichlorobenzene are suitable.

The reaction can be carried out while maintaining the temperature within the range of room temperature to 140 ° C., but preferably when iodine is used
40 ° C., 60 to 100 when Lewis acid catalyst is used
The temperature is ° C.

The optimum reaction time varies depending on the amount of catalyst added and the reaction temperature, but is usually 12 to 72 hours. By reducing the reaction product, 4-tert-butyl-1,2-
Although benzenedithiol can be obtained, the amount of metal particles or metal powder used in the reduction reaction is 1 to 10 times mol, preferably 3 to 7 times mol, of 4- (tert-butylbenzenethiol), di (4 -Tert-butylphenyl)
2 to 13 times by mole, preferably 4 to
It is 11 times the mole. An acid is added in order to keep the reaction solution acidic during the reduction, and as the type of acid, one selected from acetic acid, hydrochloric acid and sulfuric acid may be used. Examples of the metal particles or metal powder used in the reduction include zinc, tin, iron and the like. The reduction reaction temperature is kept below room temperature at the time of addition of metal particles or powder and addition of acid, and then 40-80.
It may be held at ℃. The reaction time is usually 0.5 to 3
It's time.

The thus obtained 4-tert-butyl-1,2-benzenedithiol was added with alkoxide, copper, cobalt, platinum,
By reacting a salt of iron, nickel or palladium, and a quaternary ammonium salt in a lower alcohol,
The desired product, 4-tert-butyl-1,2-benzenedithiol metal complex, can be obtained.

Examples of the alkoxide used in the present invention include sodium methylate, sodium ethylate, and potassium tert-butyrate. Among them, sodium methylate is economically advantageous.

The amount of alkoxide used is 4-tert-butyl-1,
It is 1.5 to 10 times mol, preferably 2.0 to 2.5 times mol, relative to 2-benzenedithiol.

Further, as the salt of copper, cobalt, platinum, iron, nickel or palladium used in the present invention, cupric chloride, cobalt chloride, nickel chloride, ferric chloride, potassium dichloroplatinate, palladium chloride, bromide. Cupric, cobalt bromide, cobalt iodide, transition metal halides such as nickel iodide, copper nitrate, nitrates such as cobalt nitrate, copper sulfate,
Examples thereof include sulfates such as cobalt sulfate, and acetates such as copper acetate and cobalt acetate.

The amount of the salt of copper, cobalt, platinum, iron, nickel or palladium used is 0.4 to 1.0 times the mole of 4-tert-butyl-1,2-benzenedithiol. When the amount is less than this amount, the yield is low, and the yield is not improved even if the amount is added more than this amount, which is uneconomical.

As the quaternary ammonium salt used in the present invention, tetra-n-butylammonium bromide, tetra-n-butyl chloride, tetraethylammonium bromide, tetraethylammonium chloride, tetraphenylammonium bromide, tetraphenylammonium chloride, tetrabenzylammonium bromide, Tetrabenzylammonium chloride, trimethylbenzylammonium bromide, trimethylammonium chloride and the like can be mentioned.

The amount of these quaternary ammonium salts used is 4-tert.
Usually 0 for butyl-1,2-benzenedithiol.
It is about 4 to 1.0 times the molar amount.

As the solvent used in this reaction, lower alcohols such as methanol, ethanol, isopropanol and tert-butyl alcohol are preferable. Good results are obtained when the reaction is carried out by stirring at room temperature for 15 minutes to 5 hours.

(Example) Hereinafter, the present invention will be specifically described with reference to examples.

Production Example 1 To 340 g of chloroform, 50 g of di (4-tert-butylphenyl) disulfide, 8.5 g of iodine and 45 g of sulfur monochloride were added, reacted at room temperature for 24 hours, added with 64 g of zinc while cooling, and further added with 240 g of concentrated hydrochloric acid. 60 ℃
And reacted for 1 hour.

The reaction product is filtered and extracted with chloroform. Chloroform is distilled off and distilled under reduced pressure to give a boiling point of 125 ° C (4 mmH
g), 41 g of 4-tert-butyl-1,2-benzenedithiol were obtained. Purity is 99.3%, yield is 68%
Met.

Example 1 To 5.0 g (0.025 mol) of 4-tert-butyl-1,2-benzenedithiol obtained in Preparation Example 1 was added 64 g of a 4.7% sodium methylate-methanol solution, and the mixture was stirred and cupric chloride was added thereto. -A solution of 2.2 g (0.013 mol) of dihydrate dissolved in 31 g of methanol was added, followed by 4.4 g of tetra-n-butylammonium bromide.
A solution prepared by dissolving (0.013 mol) in 19 g of methanol was added, and the mixture was stirred at room temperature for 1 hour in an air atmosphere.

The reaction solution was filtered, and methylene chloride-ethanol (1:
The solution of 5) was recrystallized twice and dried to obtain 5.9 g of a green solid. The yield was 68%.

The analytical and physical properties of this complex were as follows.

Elemental analysis value Melting point 169.5 to 171.0 ℃ UV / Visible absorption spectrum (solvent: methylene chloride) Maximum absorption wavelength 323nm 398nm 645nm Molar absorption coefficient 10200 29800 460 Infrared absorption spectrum (KBr, cm-1) 2960,2872,1536,1456,1378,1278 1246,1152,1124,862,806,736 686,604 Example 2 Cupric chloride dihydrate used in Example 1 2.2 g
Example 1 except that 3.1 g (0.013 mol) of cobalt chloride hexahydrate was used instead of (0.013 mol).
The same operation was performed.

The reaction solution was filtered, and methylene chloride-ethanol (1:
The solution of 5) was recrystallized twice, filtered and dried to obtain 5.8 g of a blue solid. The yield was 66%.

The analytical and physical properties of this complex are as follows.

Elemental analysis value Melting point 167.5-168.5 ° C UV / visible spectrum (solvent: methylene chloride) Maximum absorption wavelength 317nm 361nm 666nm Molar absorption coefficient 15100 15900 13200 Infrared absorption spectrum (KBr, cm-1) 2960,2872,1454,1378,1272,1246 1154 , 1110,878,810,686,608 Example 3 Under a nitrogen atmosphere, 55 g of 5% sodium ethylate-ethanol solution was added to 5.0 g (0.025 mol) of 4-tert-butyl-1,2-benzenedithiol and stirred,
A solution prepared by dissolving 5.3 g (0.011 mol) of potassium dichloroplatinate in 31 g of ethanol was added and stirred for 1 hour.
Sodium borohydride (1.5 g, 0.04 mol) was added, and the mixture was vigorously stirred for 1 hour, and a solution prepared by dissolving tetra-n-butylammonium bromide (4.4 g, 0.013 mol) in ethanol (20 g) was added. Stir for hours.
The reaction solution was filtered, recrystallized twice with an ethanol-pyridine solution, and dried to obtain 4.7 g of a green solid. The yield was 45%.

Elemental analysis value Melting point 178.5 to 179.5 ° C Near infrared absorption spectrum (solvent: methylene chloride) Maximum absorption wavelength 920 nm Molar absorption coefficient 18000 Infrared absorption spectrum (KBr, cm-1) 2960,2872,1565,1450,1372,12780 1245,1152, 1134,872,780,736 686,605 Example 4 4-tert-Butyl-1,2-benzenedithiol 5.
4.7 g sodium methylate-into 0 g (0.025 mol)
Add 64 g of methanol solution and stir to mix nickel chloride-6.
A solution prepared by dissolving 3.1 g (0.013 mol) of the hydrate in 31 g of methanol was added, and further a solution prepared by dissolving 4.4 g (0.013 mol) of tetra-n-butylammonium bromide in 19 g of methanol was added. The mixture was stirred at room temperature under an air atmosphere for 1 hour.

The reaction solution was filtered, and methylene chloride-ethanol (1:
The solution of 5) was recrystallized twice, filtered and dried to obtain 5.5 g of a blue solid. The yield was 63%.

The analytical and physical properties of this complex are as follows.

Elemental analysis value Melting point 169-170 ℃ Ultraviolet / visible / near infrared spectrum (solvent: methylene chloride) Maximum absorption wavelength 313nm 360nm 925nm Molar absorption coefficient 29860 12000 13080 Infrared absorption spectrum (KBr, cm-1) 2964,2872,1576,1480, 1376,1294 1242,1092,874,806,606 (Effect of the invention) The 4-tert-butyl-1,2-benzenedithiol metal complex of the present invention is useful as an optical information recording medium,
By the method of the present invention, a novel optical information recording medium can be industrially manufactured at low cost.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C07F 15/04 7537-4H 15/06 7537-4H // B41M 5/26 C09K 3/00 104 8517 -4H (72) Inventor Takeshi Morishita, 1 at 346 Miyanishi, Harima-cho, Kako-gun, Hyogo Iron Works Co., Ltd. (72) Inventor Akio Nakatsuka 1 at 346, Miyanishi, Harima-cho, Kako-gun, Hyogo Steel Chemical Industry Research Institute Co., Ltd. (56) References JP-A-63-165392 (JP, A)

Claims (7)

[Claims] 1. The following formula (I)(M in the formula is copper, cobalt, platinum, iron, nickel or palladium.
Radium, A Represents a quaternary ammonium group. ) A novel 4-tert-butyl-1,2-be represented by
Benzenedithiol metal complex. 2. After reacting 4-tert-butylbenzenethiol or di (4-tert-butylphenyl) disulfide with sulfur monochloride in the presence of iodine or a Lewis acid catalyst in a solvent, zinc, tin, A novel 4-tert-butyl-1,2-benzenedithiol represented by the following formula (II) and an alkali metal alkoxide, copper, cobalt, obtained by reduction with at least one metal selected from iron, 4-tert-butyl-characterized in that a salt of platinum, iron, nickel or palladium and a quaternary ammonium salt are reacted in a solvent with stirring.
Process for producing 1,2-benzenedithiol metal complex. 3. The method according to claim (2), wherein the Lewis acid catalyst is zinc chloride. 4. A salt of copper, cobalt, platinum, iron, nickel or palladium is a halide.
The method described. 5. The method according to claim 2, wherein the salt of copper, cobalt, platinum, iron, nickel or palladium is a sulfate. 6. The method according to claim 2, wherein the salt of copper, cobalt, platinum, iron, nickel or palladium is a nitrate. 7. The method according to claim 2, wherein the salt of copper, cobalt, platinum, iron, nickel or palladium is an acetate salt.