JPH01163189A - Novel complex compound - Google Patents

Abstract

NEW MATERIAL:A compound expressed by the formula [R1 and R2 represent F, Cl or Br; M represents Ni, Pd or Pt; A represent counter cation (onium); n is 1 or 2]. EXAMPLE:(Dithio-p-fluorobenzyl)-1,2-(dicyano-ethylenethiolato)Ni(II)te tra-n- butylammonium salt. USE:An optical recording medium. PREPARATION:A benzoin or a benzyl derivative is reacted with phosphorus pentasulfide, then hydrolyzed and a transition metal compound such as nickel chloride, etc., is added thereto to initially afford a bis-(dithiobenzyl derivative) metal complex. On the other hand, sodium-cis-1,2-dicyano-1,2-ethylene dithiolate is synthesized and reacted with nickel chloride, etc., and a quaternary ammonium, etc., is added thereto to form a bis-(cis-1,2-dicyano-1,2-ethylene-dithiolate) metal complex onium salt. Then both the former and the latter are refluxed in a solvent to subject ligand-interchange reaction.

Description

[Detailed Description of the Invention] [Technical Field] The present invention relates to a novel complex compound useful for optical recording media of optical disk devices. There has been a proposal to generate thermal deformation with a beam irradiation light and perform reproduction and reading using the difference in reflected light from the recording paper and the undeformed portion (for example, Japanese Patent Application Laid-Open No. 51-13
5886, JP-A-57-11090, JP-A-57-70
503 etc.).

This material has adjustable melting point and decomposition point, low thermal conductivity, and can form a recording film layer by coating, which improves productivity.
This method is expected to reduce costs. However, the current disadvantage is that organic dyes fade when exposed to natural light or reproduced laser beams, and their long-term stability is not sufficient.
Further, the solvent used in film formation by the coating method is limited to halogenated hydrocarbons, etc., and there have been various practical problems in relation to the resin material used as the substrate.

[Objective 1] The object of the present invention is to provide a novel transition metal complex compound for use in optical recording media that does not have the above-mentioned problems.

[Structure] The present inventor has been conducting research on new compounds that selectively absorb near-infrared light and are useful for optical information recording media with excellent stability. It was discovered that a compound is compatible with these requirements, leading to the present invention.

That is, the present invention provides the following general formula in which R1
, R2 is selected from the group consisting of FSCl, Br, and M is N
i, Pd5Pt, A represents a counter cation (onium), and n represents 1 or 2.

Preferred specific examples of the complex compound of the present invention represented by the above general formula include 1, (sothio-P-fluorobenzyl)-(1
,2-zineanoethylenethiolate) Ni(n) anion 2, (dithio-m-fluorobenzyl) 1.
2-dicyanoethylene thiolate)Ni(II) anion 3, (dithio-P-chlorobenzyl)-(1,
2-dicyanoethylene thiolate)Ni(n) anion 4, (dithio-0-chlorobenzyl)-(1,
2-dicyanoethylene thiolate)N1(n) anion 5, (dithio-P-bromobenzyl)-(1,
2-dicyanoethylenethiolet))Ni(If) anion 6, (dithio-m-bromobenzyl)-(1,
2-dicyanoethylene thiolate)N1(II) anion 7, (di-2,4-dichlorobenzyl)be1,2
-dicyanoethylene thiolate)N1(II) Anion 8, (dithio-3,4-dichlorobenzyl)-(1,2
-Zineγnoethylenethiolet))Ni1) Anion The examples of M or Ni have been described above, but as M, Pd
5Pt and the like are also included.

As the counter cation A of the above complex anion, N11Il (C2H5)4; tetraethyl-ammonium cation N8(n C4H9)4; tetra-n-butyl-ammonium cation ditri-n-butyl-am cation, N" ( CH3) 3 (CL6H33);
Trimethyl-〇-hexadecane ammonium cation, P” (n-C4H9)4; Tetra-n-butyl-phosphonium cation, PΦ (C2H5)(C6H12)3; Ethyl-tri-n-hexyl-phosphonium cation, P” (Ca Hay)4; tetra n-octyl-phosphonium, etc. can be used in combination.

First, the method for producing the complex represented by the general formula is 5chrau
zcr ctal JAC887, 1483C65) (According to this, after reacting each benzoin derivative or benzyl derivative with phosphorus pentasulfide, hydrolysis and addition of a transition metal compound such as nickel chloride, bis-
(Dithiobenzyl derivative) A metal complex can be obtained.

Separately Inorganic 5 synthesis 10.
Sodium-cis-1 as described in 8 ('67)
, 2-dicyano-1,2-ethylene dithiolate, reacted with a transition metal compound such as nickel chloride, and added quaternary ammonium or phosphonium to this reaction solution to synthesize bis-(cis- 1,2-dicyano-1,2-ethylene dithiolate) metal complex onium salt is removed.

Next, bis-(dithiobenzyl derivative) metal complex and bis-
The novel complex of the present invention can be obtained by refluxing (cis-1,2-dicyano-1,2-ethylenedithiolate) metal complex onium salt in a selected solvent and carrying out a ligand exchange reaction.

Example 1 (dithio-P-fluorobenzyl + 1.2 (dicyanoethylene 1,000 ole)) Synthesis of Ni (II) tetrabutylammonium salt (compound of specific example 1), 1-1. Bis(dithio-P-fluorobenzyl+N1(
Synthesis of p,p'-difluorobenzoin 4.62 parts and phosphorus pentasulfide 5. 100 parts of dioxane was added to -80 parts, heated under reflux, and reacted for 4 hours. The reaction solution gradually turns yellow.

After the reaction is complete, insoluble matter is filtered off, and a solution obtained by dissolving 2.25 parts of nickel chloride hexahydrate in 30 parts of water is added to the filtrate, giving it a brownish-black color.

Next, reflux is continued in a hot water bath to carry out a hydrolysis reaction. As the reaction progresses, black needle-like crystals begin to precipitate. After reacting for 3 hours, the mixture was cooled and the black needle crystals were filtered off.

2.8 for recrystallization from toluene-ethylene dichloride mixed solvent
6 parts of black needle-like crystals are obtained.

1111), 288℃ Elemental analysis value 1-2
Synthesis of Ni(II) tetra-n-butylammonium (dithiolate) 5.6 parts of sodium-cls-1,2-dicyano-1,2-ethylene dithiolate was dissolved in water-methanol (1:I
V) V) Dissolved in 80 parts of nickel chloride hexahydrate 3.6
When a solution of 1 part dissolved in 20 parts of water is added, a dark reddish brown color appears. Then tetra-n-butylammonium bromide 1
A solution of 0.3 part dissolved in 20 parts of water-methanol (1:lV/V) is added, and the mixture is stirred at room temperature for 1 hour. The precipitated orange-red crystals are filtered and recrystallized from an acetone-butanol mixed solvent. Yield 11.2 parts, Ilp, 141-14
2°C (literature n+p, 143-144°C).

1-3 Synthesis of (dithio-P-fluorobenzylthi 1.2 + dicyanoethylene thiolate) Ni(n) tetra-n-butylammonium salt, 0.38 part of the complex obtained in 1-1, and 1-2 0.54 part of the obtained complex was dissolved in an acetone-toluene mixed solvent (1:IV/
V) Add to 50 parts and reflux for 6 hours.

After the reaction, the solvent was distilled off and the crude product obtained was mixed with methanol.
Recrystallization from an acetone mixed solvent (3:IV/V) yields 0.62 part of dark brown cubic crystals.

mp, 126-127℃, λwax 890r+m
(CI12 ClCl12C1).

Example 2 Synthesis of (dithio-P-probenzyl+1,2+dicyanoethylene thiolate) Ni(■) tetra-n-butylammonium salt (compound of specific example 5) 2-1 Bischild dithio P-promobenzylthi N1 (I
Synthesis of I) 50 parts of dioxane was added to 2.80 parts of p,p'-dibromobenzoin and 2.45 parts of phosphorus trisulfide, and the mixture was heated under reflux and reacted for 6 hours. The reaction solution turns yellow. After the reaction is completed, the insoluble matter is filtered off, and a solution of 0.90 parts of nickel chloride aqueous salt dissolved in 10 parts of water is added to the filtrate, giving it a black edge color.

The hot water bath raw reflux is continued to carry out the hydrolysis reaction.

As the reaction progresses, black crystals begin to precipitate. After reacting for 2 hours, the reaction mixture was cooled and the crystals were filtered off to obtain 1.25 parts of black-green crystalline powder. ip, 314°C 2-2 (dithio-P-bromobenzyl + 1.2 dicyanoethylene thiolate)Ni (n) Synthesis of tetra-n-butylammonium salt, 0.55 parts of the complex obtained in 2-1 and 1 Complex 0 obtained in -2
．． 41 parts are refluxed for 6 hours with 50 parts of ethylene dichloride. After the reaction is completed, the solvent is distilled off, and the resulting crude product is extracted with hot methanol and allowed to cool to obtain dark brown crystals. Recrystallization from a methanol-acetone mixed solvent (3: IV/V) yields 0.27 parts of dark brown cubic solid crystals. mp, 1
81.5-183℃, λmax 885nm (CI
12ClClI2CI).

Example 3 Synthesis of (dithio-3,4-dichlorobenzyl+1,2+dicyanoethylene thiolate) Ni(II) tetra-n-butylammonium salt (compound of Example 8) 3-1 bis(dithio-3,4 -dichlorobenzyl +N
1 (Synthesis of I) 2.58 parts of 4-dichlorobenzyl and 26 parts of phosphorus pentasulfide
50 parts of dioxane was added to 28 parts, heated under reflux, and reacted for 12 hours. The reaction solution turns yellow-orange. After the reaction is complete, insoluble matter is filtered off, and a solution of 0.90 parts of nickel chloride hexahydrate dissolved in 10 parts of water is added to the filtrate, giving it a brownish-black color.

Subsequently, reflux is continued in a hot water bath to carry out a hydrolysis reaction.

No crystals were precipitated even after 3 hours of reaction, and green-black columnar crystals were precipitated after several days of cooling. The crystals are separated by filtration and recrystallized from a methanol-acetone mixed solvent (3:IV/V) to obtain 0.72 parts of black columnar crystals. B, 309
°C (decomposition) Elemental analysis value 3-2 (dithio-3,4-dichlorobenzyl) 1.2
+dicyanoethylene thiolate N1(II) tetra-
Synthesis of n-butylammonium salt, 0.30 parts of the complex obtained in 3-1 and 0.3 parts of the complex obtained in 1-2
One part is refluxed for 6 hours with 40 parts of ethylene dichloride. After the reaction was completed, the crude product obtained by distilling off the solvent was extracted with hot methanol, a small amount of the extract was added to the extract, the mixture was shaken, the precipitated black precipitate was separated by filtration, and the filtrate was concentrated and left to cool. Obtain black massive crystals. Methanol-acetone (3:IV/
Recrystallization from V) yields 0.18 part of black massive crystals. +
np, 139-140℃, λrAax 880nn+(
0112CIC112CI).

Elemental analysis values Example 4 (dithio-P-fluorobenzyl + 1.2 + dicyanoethylene thiolate) Ni (II) ) Synthesis of monohexyl-ethylphosphonium salt (phosphonium salt of the compound of Example 1), 4- 1 bis+1,2-dicyano-1,2-ethylene dithiolate) Ni (I
I) Synthesis 1-2 of tri-hexyl-ethylphosphonium salt using sodium-cis-1,2-dicyano-
Reddish brown crystals were obtained from 4.7 parts of 1,2-ethylene dithiolate, 3.0 parts of nickel chloride hexahydrate, and 98 parts of tono-n-hexyl-ethylphosphonium bromide,
Recrystallize from methanol to obtain 5.4 parts of the desired product. l
l1p, 77-78°C0 4-2 (dithio-P-fluorobenzyl 1.2-4 dicyanoethylene thiolate Ni (II) Synthesis of tri-hexyl-ethylphosphonium salt, obtained in 1-1 0.62 parts of the complex and 0°7 of the complex obtained in 4-1
8 parts are refluxed for 1 hour with 50 parts of ethylene dichloride. After the reaction was completed, the crude product obtained by distilling off the solvent was extracted with hot methanol, a small amount of dilution was added to the extract, the mixture was stirred at room temperature, the solid black precipitate was filtered off, and the filtrate was concentrated and allowed to cool. The precipitated dark brown crystals are filtered to obtain 0.42 parts of the desired product. mp, 99-101℃, λraax885r+m
(C112CIC112CI).

Elemental analysis value [Reference example: A 2,2'-dichloroethane solution of cocyanin dye (Nippon Kanko Shiki Co., Ltd. NK-2421) was prepared, and a weight ratio of 1
(dithio-P-fluorhensyl+(l,2-dianoethylenethiolate)nickeltetra-n-butylammonium) of Compound Example 1 was dissolved at 5%.This solution was coated on a glass substrate and dried for 11 days. A recording layer having a thickness of GOO was formed by this process to produce a recording medium.

This recording medium was irradiated with light of 54,000 lux using a 500 watt tungsten lamp, and then the rate of decrease in the absorption peak of the dye was measured. These results were compared to those using the same dye but with no nickel complex added and those with no nickel complex added, respectively.
Bis(1,2,4)-trichloro-5,9-dithioferrate nickel(n)tetra-n-butylammonium (formula below) is added, and the rate of decrease is relative to ■. was 0.20 and 0.83 for ■. Furthermore, when we confirmed the stability against reproduction light for the same recording medium, we found that it was 7.5 times more stable than the one in (2) above, and 1. - Re-kegged more than 8 times.

[Effect] As explained above, the maximum absorption wavelength of the complex of the present invention is 800 nm.
r + m or more, it is excellent as a −heavyt oxygen inchar and has improved solubility in solvents,
When applied to optical information recording media, it is possible to improve storage stability, simplify the production process, and reduce costs.

Furthermore, the complex of the present invention is a useful compound that can be used not only for optical information media but also for infrared photosensitive material filters, selective light absorption or heat ray blocking materials, antioxidants, and the like.

[Brief explanation of the drawing]

FIG. 1 is an infrared absorption spectrum diagram of the compound of Example 1,
Figure 2 is the same spectrum diagram of the compound of Example 2, Figure 3 is the same spectrum diagram of the compound of Example 3, and Figure 4 is the same spectrum diagram of the compound of Example 4.
The same spectrum diagram.

Claims (1)

[Claims] A complex compound represented by the following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the formula, R_1 and R_2 are selected from the group consisting of F, Cl, and Br, and M is Ni, Pd, selected from the group consisting of Pt, A represents a countercation (onium), and n represents 1 or 2.