JPS5941363A - Pyrylium dye, thiopyrylium dye and its preparation - Google Patents

Abstract

NEW MATERIAL:The (thio)pyrylium dye of formula I or II (X is O or S; R is methyl or ethyl; Z<-> is anion). EXAMPLE:The compound of formula III. USE:Applicable to the electrophotographic photosensitive coating film of an electrophotographic printer using a semiconductor laser, a coating film of optical disk writable and readable by a semiconductor laser, an infrared cut filter, etc. PROCESS:The objective dye can be prepared by reacting the (thio)pyrylium salt of formula IV or V (e.g. 4-methyl-2,6-diphenylpyrylium perchlorate) with 4-formyl- 4'-N,N'-dialkylaminostilbene of formula VI preferably at a molar ratio of 1:1- 2 in a solvent such as acetic anhydride at 50 deg.C- the boiling point of the solvent for 3min-2hr.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel biryllium dyes, thiopyrylium dyes, and methods for producing the same.

The dye according to the present invention has the following general formula (1) and general formula (2).
).

(In the formula, X represents an oxygen atom or a sulfur atom, R represents a methyl group or an ethyl group, and 2θ represents an anion.) Pyrylium salt or thiopyrylium salt represented by 4) (in the formula, X represents an oxygen atom or a sulfur atom, and ze represents an anion such as perchlorate, fluoroborate, sulfoacetate, etc.) and the following general formula ( 5), which can be easily obtained by reacting 4-7 orbarium 4'-N,N-dialkylaminostilbene (wherein R represents a methyl group or an ethyl group) in a solvent. I can do it.

A wide range of organic solvents can be used as the solvent, but in particular alcohols such as ethanol, nitriles such as acetonitrile, ketones such as methyl ethyl keto 7, nitro compounds such as nitrobenzene, and halogenated hydrocarbons such as tetrachloroethane. Acid anhydrides such as acetic anhydride are preferable. Furthermore, bases can be added to promote the reaction. Specific examples include bases such as piperidine, trietherabane, hexylazine, pyridine, and quinoline.

The proportion of the original compound in the reaction system is 4-4-2 as shown in the general formula (5) per mole of the bi-IJ salt or the thiopyrylium salt shown in the general formula (3) or the general formula (4).
From 0.5 to 10 mol, preferably from 1 to 2 mol, of forzuru-4'-N,N-dialkylazunosalben is used.

The reaction temperature ranges from around 50° C. to the reflux temperature of the solvent or base. The reaction time is 1 minute to 10 hours, preferably 5 minutes to 2 hours.

The biryllium dye or thiopyrylium dye according to the present invention has absorption from around 60OIIIll to around 900m, and can be used as an electrophotographic photosensitive coating for electrophotographic printing/printing using a semiconductor laser, and can be written and reproduced by a semiconductor laser. It is expected that it will be applied to optical disc coatings and infrared cut filters.

Next, a preliminary example for producing the biryllium dye or thiopyrylium dye of the present invention will be shown.

Example 1 Manufacturing method of biryllium dye (dye AI).

4-Methyl-2,6-siphenylbyrylium perchlorate 4°O2,4-formyl-4' in a Mitsuro flask
-N,N-Dimethylazunostilbene 6.02 and acetic anhydride 60+FJ are charged, heated and stirred, and reacted at 160°C for 5 minutes. After cooling, the precipitated crystals were separated and added with 50% glacial acetic acid.
After washing with 50 m/m of methanol and drying, dye 5.52 was obtained.

Yield: 82.2%, temperature point: 209-211°C, solution absorption temperature: λmax 739 nm (dichloromethane solution)! = 1.45X105 Infrared absorption spectrum: 1640, 1580, 152
0,1494°1170,1 (195(cIn-1
) Elemental analysis: c35H3oczNo5 total'! A-Eclipse Analytical candy o 72.46 72.37 H5,225,3O N 2.42 2.39 Example 2 Preparation of thiopyrylium dye (dye A2) 4-Methyl-2,6-diphenylthiopyrylium in a Mituro flask Barchlorate 1.2M', 4-Formyru 4'-N, N
-0.93 t of dietylaminostilbene and 1115 t of anhydrous vinegar were charged, heated and stirred, and reacted at 100 to 120°C for 5 minutes.

After cooling, the precipitated crystals were separated and mixed with 5-5 g of glacial acetic acid and 1-1 methanol.
0#+7! After sequential washing and drying, dye 1.1f was obtained.

Yield: 53.4% Decomposition point: 205-206°C Solution absorption spectrum: λmax”” 784 nmε-
1,23x10” (dichloromethane solution) Infrared absorption spectrum: 1638.1605,1510
．． 1485°117[), 1145.1105.107
0(cIn-1) Elemental analysis: 057J40t) JO48 calculated value Analysis value C71,1971,14 H'5.50 5.61 N 2.24 2.18 S 5.14 5.10 Example 6 Thiopyrylium dye (dye Black 6) Production method In a Mitsuro flask, add 2.0f% 2-methyl-4,6-diphenylthiopyrylium barchlorate 4-foyl-4'-N,N-
Diethylaminosuti 4. (Prepared Reuben 0.15F and acetic anhydride ACJme and heated and stirred to 125-13
The reaction was carried out at 0°C for 5 minutes. After cooling the slag, 40 ml of isopropyl ether was added, and the precipitate was sequentially read with 20 ml of P-based isozolobyl ether and 20 ml of 2-methyl alcohol, and dried after PP to obtain a dye of 1.44 F.

Yield: 42% Decomposition point: 221-224°C Solution absorption spectrum: Nax” 768 nmg=8
．． 5X10' (dichloromethane solution) Infrared absorption spectrum: 1615, 1600, 1500
．． 1475゜1270.1105 (Kushi-1) Elemental analysis: 057H540tNO4S calculated value Analysis value 0 71.19 71.02 H5,505,67 N 2.24 2.09 8 5.14 5.16

[Brief explanation of the drawing]

Figures 1, 2, and 5 are explanatory diagrams showing dye A1, Dye A2, and Dye A3 in dichloromethane solution) and infrared absorption. fP burushi Kano suitable length (nm) i length (nm) Figure 3 t (nm)

Claims (1)

[Claims] 1) A biryllium dye or thiopyrylium dye represented by the following general formula (1) or general formula (2). (In the formula, X represents an oxygen atom or a sulfur atom, R represents a methyl group or an ethyl group, and zo represents an anion.) 2) A biryllium salt represented by the following general formula (3) or general formula (41) or Thiopyrylium salt 6H5 (in the formula, X represents an oxygen atom or a sulfur atom and represents a zeFi anion) and 4-forzuru 4 represented by the following general formula (5)
A biryllium dye represented by the following general formula (1) or general formula (2), characterized in that it is reacted with '-N,N-dialkyl agunostilbene (in the formula, R represents a methyl group or an ethyl group); or Teopi IJ Method for producing IJum dye. (In the formula, X represents an oxygen atom or a sulfur atom, R represents a methyl group or an ethyl group, and zo represents an anion.)