JPH0445160A - New methine dye - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (Y is cyclopentane or atom group necessary for forming cyclohexane ring; Z1 to Z4 are H, halogen, alkyl, nitro, cyano, acyl or sulfo, etc., or may form benzene ring by binding of Z1 with Z2 and Z3 with Z4; R is alkyl). EXAMPLE:A compound expressed by formula II. USE:Useful for an optical recording material. PREPARATION:A compound expressed by formula III (X<-> is an acid anion such as methyl sulfuric acid; (n) is 1 or 2) is subjected to condensation reaction together with 3,4-dihydroxy-3-cyclobutene-1,2-dione expressed by formula IV in a solvent such as butanol and in the presence of an organic base such as pyridine at 100-150 deg.C for 0.5-5hr.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel methine dye. % of methine dyes useful in various optical recording materials.

[Conventional technology]

SQUA IJ IJum dye exhibits photoconductivity, and is used as a carrier-generating substance for electrophotographic photoreceptors (%
05536), laser light absorbing material for laser-written liquid crystal display (% 1974-197485),
Or recording material for optical discs (% closed 1984-4622)
No. 1, JP-A-58217758 and JP-A-59-12
No. 9954 and other publications).

[Problem that the invention seeks to solve]

However, conventionally known squarylium dyes are not necessarily satisfactory in terms of sensitivity, residual potential, or stability during repeated use, and the selection range of carrier transport substances is also limited. It does not fully satisfy the wide range of demands of

Furthermore, in recent years, Ar laser He-Ne has been used as a light source for photoreceptors.
Gas lasers such as lasers and semiconductor lasers are beginning to be used. These lasers are characterized by their ability to produce 0N101" F in time series, and are particularly promising as light sources for copiers with image processing functions, including intelligent copiers, and printers for computer output.

An object of the present invention is to provide a novel squarylium dye useful as an electrophotographic photoreceptor exhibiting excellent electrophotographic properties. A further object of the present invention is to provide a novel squarylium dye useful as a photoreceptor for electrophotographic printers, recording materials for optical disks, and the like.

[Failure to solve the problem]

As a result of intensive research aimed at achieving the above-mentioned improvements, the present inventors discovered a squarylium compound represented by the following general formula CI), realized that the object could be achieved, and completed the present invention. .

That is, the gist of the present invention is a methine dye represented by general formula [I].

General formula [I] In the formula, Yld represents an atomic group necessary to form a cyclopentane or cyclohexane ring, and Zl, Z2, Z5 and Z4 may be the same or different, and each represents a hydrogen atom, Represents a halogen atom, an alkyl group, an alkoxy group, a nitro group, a cyano group, a carboxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfo group, a trifluoromethyl group, an alkynodi or an arylsulfonyl group, and Zl, Z2, Z3 and They may be connected to each other at Z4 to form a benzene ring. R represents an alkyl group.

The novel methine dye of the present invention has a structure represented by the above general formula CD, and the details are as shown below.

That is, Y represents an atomic group necessary to form a sochlorobentane or cyclohexane ring, and specifically, a tetramethylene or pentamethylene group forms a 5- or 6-membered ring with the carbon atom at the 3-position of the 3H-indole ring. It is something. The halogen atom in Zl, Z2, Z3, and Z4 is fluorine.

Chlorine, bromine, iodine, etc. are chlorine, bromine, iodine atoms, etc., alkyl groups include methyl, ethyl, propyl, methyl, pentyl, etc. having 5 or less carbon atoms, and alkoxy groups include methoxy, ethkyne, propoxy, butoxy, pentyl oxyne, etc. having 5 or less carbon atoms, alkoxy Carbonyl groups include methoxycarbonyl, etquincarbonyl, propoxycarbonyl, butquincarbonyl, pentyloxycarbonyl, etc. having 5 or less carbon atoms, acyl groups include acetyl, propionyl, benzoyl, etc., and carbamoyl groups include carbamoyl, N Examples of the alkyl or arylsulfonyl group include methylcarbamoyl, N-ethylcarbamoyl, N,N-diethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl, etc., and methylsulfonyl, ethylsulfonyl, benzenesulfonyl, etc. R is an unsubstituted alkyl group or a substituted alkyl group having 18 or less carbon atoms such as methyl, ethyl, propinopeptyl, pentyl, octyl, delen, dodecyl, hexadenol, octadecyl (substituents include, for example, carboxyne group, sulfo group, cyano group) , hydroxy group, alkoxy group having 8 or less carbon atoms, such as methoxy/, ethoxy, propoxy, benzyloxo, phenethyloxy L; alkoxycarbonyl group having 5 or less carbon atoms, such as methquine carbonyl, ethquine carbonyl,
phenoxycarbonyl, benzyloxycarbonyl, etc.
Aryl group having 10 or less carbon atoms, such as phenyl, chlorophenyl, tolyl, etc. Aryloxy group having 10 or less carbon atoms, such as phenoxy, tolyloxy group, 8 carbon atoms
The following acyloxy groups, for example, acetyloxy, propionyloxy, etc., acyl groups having 8 or less carbon atoms, for example,
Acetyl, propionyl, benzoyl, mesyl, etc., carbamoyl groups, e.g. carbamoyl, N,N-dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl, etc., sulfamoyl groups, e.g. eva, sulfamoyl, N,N-dimethylsulfamoyl, morpholino sulfonyl, piperidinosulfonyl, etc.).

The novel methine dye represented by the general formula [ID is, for example,
The following general formula [In the formula 100, Y, Z1 to Z4 and R have the same meaning as explained in Ichifunezo CI]. In addition, X- represents an acid anion such as methyl sulfate, ethyl sulfate, benzenesulfonic acid, toluenesulfone, chlorine, bromine, iodine, perchlorate ion, etc., and n represents 1 or 2). and 3,4-dihydroxy-3-ene-1,2-dione represented by the following structural formula are condensed in the presence of an organic base such as pyridine in a solvent such as butanol, hexanol or cyclohexanol. You can get it. The reaction temperature is preferably 100 to 150°C
The reaction time is preferably 0.5 to 5 hours.

The novel methine dye of the present invention can be used as a carrier-generating material for electrophotographic photoreceptors, a laser light absorbing material for laser-written liquid crystal displays, a recording material for optical disks, etc., and can also be used for silver halide photographic light-sensitive materials. filter dye,
Effective as a sensitizing dye.

Specific examples of the methi/dye represented by the general formula [ID] of the present invention are shown below, but the present invention is not limited thereto.

Dye (A) Dye CB) Dye (C) Dye (D) Dye (E) Dye (F) Dye (G) 03H 8o, H Dye (H) Dye (L) Dye CM) Dye (N) Dye (0) Dye (P) Dye (Q) Dye (R) OOH OOH Dye (S) Next, synthesis examples of methine dyes according to the present invention will be explained in detail with reference to the following examples.

Example 1 Synthesis of dye (I); 18.69% of 1-naphthylhydrazine and 16.3'f of acetylcyclohexane were mixed, 1.2- of acetic acid was added thereto, and the mixture was heated to a bath temperature of 90 to 95°C for 1 hour. .

Next, acetic acid 70.0rnJ! was added and heated under reflux for 7 hours.

Thereafter, the acetic acid was distilled off under reduced pressure, and the residue was chromatographed with benzene/ethyl acetate (5:1). Add n-hexane to crystallize, number of houses, mp after drying, 69.0-73.
15.52 grey-white crude crystals at 0° C. were obtained.

3H-indole derivative obtained above 12.0? and ethyl iodide40. Put Of into a sealed tube and bath temperature 95-100℃
The mixture was heated for 17 hours. After adding ethyl ether and stirring well, the crystals were separated. After washing with acetone and drying, 10.7 f of a grayish white powder with m and p of 189.0 to 189.5°C was obtained.

3H-indolium derivatives 2.02 and 3.4 obtained above
-dihydroxy-3-cyclobutene-1,2 dione 0.
3? 25.0-n-butanol and 1.51n-pyridine
t was added, and the mixture was heated under reflux for 1 hour. After cooling to room temperature, the precipitated crystals were collected. After washing with methanol, it was recrystallized from pyridine. After washing with methanol and drying, mp, 278.5℃
A dark purple crystalline powder of 1.22% (decomposition) was obtained. The maximum absorption value of the methylene chloride solution was 686 nm.

Example 2 Synthesis of dye (K); φ metachlorophenylhydrazine hydrochloride 20. ! M-acetylcyclohexane20. Of methanol 80.0
- and 40.0 - of triethylamine were added, and after mixing well, 3.0 - of acetic acid was added and the mixture was heated under reflux for 1 hour. After evaporating the solvent under reduced pressure, 60°C of acetic acid was added to the residue, and the mixture was heated under reflux for 6 hours. After acetic acid was distilled off under reduced pressure, b, p
, 17.6 of a colorless fraction with an angle of 160.0 to 170.0° was obtained. This product was converted into picrate using picric acid, recrystallized with benzene, and then made alkaline to produce 6-chloro-3
5.82 H-indole derivatives were obtained. On the other hand, the furnace solution from benzene recrystallization was concentrated under reduced pressure, and the residue was made alkaline to obtain 4-chloro-3H-indole derivative 8.32.

4-chloro-3H-indole derivative obtained above 2.3
Mix r and 2.02 ethyl paratoluenesulfonate,
It was heated to a bath temperature of 150.0 to 155.0°C for 4 hours. After cooling, crush the solidified material and wash with ethyl ether.
,2-dione 0.6? , nheptatool 50.0m/,
Pyridine 3.0- was added, and the mixture was heated under reflux for 1 hour. The solvent was distilled off under reduced pressure, washed with water, and then recrystallized with methanol. After drying
, p, 260.0°C (decomposed) copper-colored crystalline powder 1.3
I got 2. Maximum absorption value of methylene chloride solution is 661
It was nm.

Example 3 Synthesis of dye (Q); parachlorophenylhydrazine hydrochloride 25. Oy, acetylcyclohexane 24.3t VC methanol 100.
After adding 0m and triethylamine 35.4F and mixing well, add acetic acid 3.0TnI! was added and heated under reflux for 1 hour. After distilling off the solvent under reduced pressure, the residue was diluted with acetic acid 7.
0.0- was added and heated under reflux for 5 hours.

After removing acetic acid under reduced pressure, distillation is performed under reduced pressure, b, p, 157. Q
Pale yellow fraction 1 distilled at ~160.0℃1535■H7
8.27 was obtained. m, p, were 91.0-91.5°C.

5-chloro-3H-indole derivative obtained above 4.7
9 and para-toluenesulfonic acid-n-octyl ether 5
．． 71 and heated to 150.0 to 155.0°C for 4 hours. After cooling and washing with ethyl ether, 3.
4-dihydroxy-3-cyclofty7-1.2-dione 1.11, n-butanol 100°0-, pyridine 6.
0- was added thereto, and the mixture was heated under reflux for 1 hour. After the solvent was distilled off under reduced pressure, the residue was recrystallized from ethanol.

After drying, a golden green crystalline powder of m, p, 210.0° (decomposed) was obtained. The maximum absorption value of the methylene chloride solution was 653 nm.

Example 4 The methine dye shown below was also synthesized in a manner similar to that shown in Example 1.2. The maximum absorption value of the methylene chloride solution for the obtained dye (λC1;j;)C12nm)
Table 1 shows the color tone, shape, m, and p of the crystals.

Table-1 * Added trace amount of triethylamine

Claims (1)

[Claims] 1. A methine dye represented by the following general formula [I]. General formula [I] (In the formula, Y represents an atomic group necessary to form a cyclopentane or cyclohexane ring, and Z_1, Z_2, Z_
3 and Z_4 may be the same or different, and each represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a nitro group, a cyano group, a carboxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, or a sulfo group. ,
It represents a trifluoromethyl group or a sulfone group, and Z_1 and Z_2, Z_3 and Z_4 may be connected to each other to form a benzene ring. R represents an alkyl group. )