JPS63312364A - Phthalocyanine compound - Google Patents

Abstract

NEW MATERIAL:A compound of formula M-Pc-(ORf)n (M is metal, metal oxide, metal halide or H; Pc is phthalocyanine nucleus, ORf is fluorine-substituted alkoxy; m is 1-8). USE:Coloring matter for use in optical recording media. (Having absorption in the near-infrared region; highly soluble). PREPARATION:4-Nitrophthalonitrile and a fluoroalcohol are made to react in an aprotic polar solvent in the presence of potassium carbonate to form 4-(fluoroalkoxy) phthalonitrile. This product is then allowed to react, in the presence of an ammonium molybdate catalyst or in the absence of any catalyst, with various metal halides and urea at 180-200 deg.C.

Description

Detailed Description of the Invention (1) Background of the Invention (Technical Field) The present invention relates to a novel phthalocyanine compound, particularly a highly soluble phthalocyanine compound having absorption in the near-infrared region.

(Prior art and its problems) Phthalocyanine compounds are stable against light, heat, temperature, etc., and have excellent robustness. In particular, metal phthalocyanines are widely used as various dyes and pigments due to their high stability and strong color tone, and because metal ions exist in a large n-electron conjugated system, they are used for electrical conduction, photoelectric grooves, and energy conversion. It is attracting attention as a material for electrodes, catalysts, etc., and as a polymer material for films and thin films with advanced functions by blending with polymers.
Various studies are being conducted.

One of the uses of these phthalocyanine compounds is as a light absorber.

For example, they are used as dyes for optical recording media by coating them on plastic substrates, but the solubility of phthalocyanine dyes is generally very poor, making it difficult to create optical recording media by coating. Canadian Journal of Chemistry (Volume 63) for the purpose of improving the solubility of phthalocyanine dyes.

623-631, 1985), the central metal into which a bulky alkyl group or alkoxy group is introduced is Cu,
Co.

Examples of Zn phthalocyanine have been reported, but although improved solubility in halogenated hydrocarbons was observed, solubility in other solvents was insufficient.

It is known that vanadyl phthalocyanine is advantageous as a phthalocyanine for optical recording media because it has absorption on the long wavelength side, but VO (vanadyl ) was synthesized, and it was found that the solubility was worse than that of the metal phthalocyanine mentioned above. Therefore, with the above method, it is difficult to obtain a dye that can be applied directly to a plastic substrate such as injection molded polycarbonate or injection molded polymethyl methacrylate, which are readily available but have poor solvent resistance.

II. OBJECTS OF THE INVENTION An object of the present invention is to provide a phthalocyanine compound having absorption in the near-infrared region and having good solubility.

III Disclosure of the invention Such objects are achieved by the invention described below.

That is, the present invention is a phthalocyanine compound characterized by having a fluorine-containing substituent.

The phthalocyanine compound of the present invention has good absorption in the near-infrared region, is chemically stable, and can be used in various solvents, such as ketone solvents such as acetone, methyl cellosolve solvents, and alcohol-based solvents such as octafluoropentyl alcohol. Because it dissolves well in solvents and aromatic solvents such as benzene,
It is useful as a dye for coatable optical recording media.

IV Specific composition of all inventions Hereinafter, a specific configuration of the present invention will be explained in detail.

The present invention is based on the following formula (I) M-Pc-(ORf)n (I) (where M represents a metal, a metal oxide, a metal chloride, or hydrogen, Pc represents a phthalocyanine nucleus, and OR
f represents a fluorine-substituted alkoxy group, and n represents an integer of 1 to 8).

The above phthalocyanine Pc is represented by the following formula (II).

Specific examples of the above M include Pb, Cu, Co,
Ni, Mn.

Examples include metals such as Mg, metal oxides such as VO, metal chlorides such as AlCl, and Hx 2 (two atomic hydrogen), but VO, Mn, Pb, etc. are preferable due to the position of absorption wavelength. In addition, the substituent ORf is selected from linear or branched alkoxy groups substituted with one or more fluorine, but OCH3 (C
F2) Those represented by the general formula mZ (m is an integer of 1 to 5, 2 is a hydrogen atom or a fluorine atom) are desirable. The number n of substituents ORf is an integer of 1 to 8 per phthalocyanine nucleus. The substitution position of the substituent ORf is 1 to 1 in formula (II)
16. Among the 16 substitution positions of the phthalocyanine nucleus, hydrogen atoms are bonded to the remaining substitution positions where ORf is not substituted, but some or all of these positions are bonded to other substituents, such as alkyl groups or alkoxy groups. Alternatively, it may be substituted with a halogen atom such as chlorine.

Examples of specific compounds of the present invention are shown below.

(1) Tetra-(2,2,3,3,4,4,5,5-octafluoropentyloxy)-vanadyl phthalocyanine (2) Tetra-(2,2,3,3-tetrafluoropropoxy)-vanadyl Phthalocyanine (3) tetra-(2,2,2-trifluoroethoxy)
-vanadyl phthalocyanine (4) tetra-(2,2,3,3,4,4,5,5-octafluoropentyloxy)-copper phthalocyanine (5) tetra-(2,2,3,3-tetrafluoropropoxy) )-Phthalocyanine The phthalocyanine compound of the present invention is described in Canadian Journal of Chemistry (Volume 63).

623-631, 1985). That is, 4-nitrophthalonitrile and a fluoroalcohol are reacted in an aprotic polar solvent in the presence of potassium carbonate to form 4-nitrophthalonitrile.
Make (fluoroalkoxy)phthalonitrile. The thus obtained fluorine-containing phthalonitrile is reacted with various metal chlorides and urea at 180-200°C in the presence of an ammonium molybdate catalyst or in the absence of a catalyst, thereby producing a fluorine-containing alkoxy-substituted metal. Phthalocyanine can be synthesized. Furthermore, fluorine-containing alkoxy metal phthalocyanine or fluorine-containing alkoxy metal-free phthalocyanine can also be synthesized by reacting fluorine-containing phthalonitrile with an organic base such as DBU in alcohol in the presence or absence of a metal salt. .

N02Phn-+RfOPhn→(RfO)4Pc-M
(III) (IV) (V) ■Specific Examples of the Invention Hereinafter, specific examples of the present invention will be shown and the present invention will be explained in further detail.

First, as a reference example, 2, 2, 3, 3, 4, 4, 5.
An example of the synthesis of 5-octafluoropentyloxyphthalonitrile is shown.

Reference Example 4-Nitrophthalonitrile (III) 2.40g (1
4.4 mmol).

2.2,3,3,4,4,5,5; 8.70 g (37.5 mmol) of octafluoropentyl alcohol and 6.0 g of potassium carbonate in a nitrogen atmosphere with 20 m of dry DMF
1 at 70°C for 9 hours.

(Potassium carbonate was charged every 3 hours in 3 batches of 2.0 g.) After the reaction was completed, the reaction solution was stirred at room temperature (25°C).
), pour 200ml of water and extract with ether (20ml).
0ml x 2 times). The ether extraction layer is magnesilla sulfate.

After drying with a vacuum pump overnight, the ether was distilled off, and the mixture was further dried with a vacuum pump.

Yield 4.51g (12.6mmol)' [Yield 87
．． 6%] Melting point 42.5-44.0°C IR (KBr) 2250.2240.1610.157
5.1495.1310°1260, 1180.116
0.1135.1120.980.895°81565
5cm-1 NMRδ(CDC1a) 4.58[2H,t,,J
=12.5Hzl, 6.07[LH.

t, t, , J = 51.5Hz, 5.5Hz], 7.
33[II-(,d,,J=8.0Hz], 7.38
[LH,s,].

7.83 [LH, d,, J = 8.0Hz first order,
An example of synthesis of a fluorine-containing substituted phthalocyanine compound is shown.

Example 1 Compound (IV) (ORf=OCH2(CF2)4H)
2.15g (6.0mmol), vanadium trichloride 0
．． 38g (2.4mmol), 7.0g of urea from 190~
The mixture was heated to 2208C and reacted in a molten state for 1 hour. After the reaction was completed, the mixture was cooled to room temperature, and then water and chloroform were added to dissolve the product. The separated chloroform layer was dried overnight by adding magnesium sulfate. 1.66 g of the solid obtained by distilling off the solvent was separated and purified using a silica gel column using toluene as an eluent to obtain 1.18 g of a dark green solid.
(0.79 mmol) was obtained.

Yield 52.7% λmax () luene) = 695 nm (log e = 5.
20) MASS (FD) 1500 (M+1) Example 2 Compound (M (ORf=OCH2(CF2)2H) 1
．． 55g (6.0mmo1), vanadium trichloride 0.3
Using 8 g (2.4 mmol) and 7.0 g of urea, 1.07 g of a crude product was obtained in the same manner as in Example 1. This was separated and purified using a silica gel column using toluene-ethyl acetate as an eluent, and 0.86 g (0.78 mmo
l) was obtained.

Yield 52.0% λmaX (chloroform) = 695 nm (log ε = 5
．． 16) MASS (FD) 1l100(+1)IR
(KBr) 605.1505.1485.1460
．． 1400, 1340° 1290, 1240.1200
．． 1110.1090.1000゜950, 880.8
30.750.690cm 1 Example 3 Compound (IV) (OR(=OCR20F3) 1.3
6g (6.0mmol).

A crude product 1.1 was prepared in the same manner as in Example 1 using 0.38 g (2.4 mmol) of vanadium trichloride and 7.0 g of urea.
8g was obtained.

This was purified by column in the same manner as in Example 2, and the black-green solid 0.
72g (0.74mmol) was obtained.

Yield 49.4% λmax (chloroform) = 695 nm (log ε = 5
．． 08) MASS (FD) 972 (M+1) Example 4 Compound (IV) (ORf=OCH2(CF2)4H)
1.08g (3.0mmo1), cupric chloride 0.16
The reaction was carried out in the same manner as in Example 1 using 3.5 g of urea and 10 mg of ammonium molybdate. The product was eluted with acetone and purified with a silica gel column to give 0.68 g (0.45 mmol) of a dark blue solid.
I got it.

Yield 60.0% MASS (FD) 1496 (M+1) Example 5 Compound (IV) (ORf= 0CH2(CF2)2H
) 1.03g (4.0mmol), DBU 1.54
g (4.0 mmol) in 10 ml of dry ethanol.
The reaction was carried out under reflux for an hour. After distilling off the ethanol from the reaction solution,
Purified in the same manner as in Example 4 to obtain 0.55 g of dark blue solid (0
, 53 mmol) was obtained.

Yield: 53.1% MASS (FD) 11035 (+1) As a comparative example, a synthesis example of a neopentyloxyphthalocyanine compound is shown.

Comparative Example 1 Compound (IV) (4-neopentyloxyphthalonitrile) 1.29 g (6.0 mmol), vanadium trichloride 0.38 g (2.4 mmol), and urea 7.0 g were used in the same manner as in Example 1. Transfer the crude product to a silica gel column using toluene.

Separation and purification using ethyl acetate as an eluent resulted in a black solid of 0.3
1 g (0.34 mmol) was obtained.

Yield 22.8% Comparative Example 2 Using 0.86 g (4.0 mmol) of compound (IV) (4-neopentyloxyphthalonitrile), Example 5
In the same manner as above, the crude product was separated and purified using a silica gel column using toluene as the eluent to obtain 0.43 g of black solid (0.
, 43 mmol) was obtained.

Yield: 43.0% VI Overall Invention Specific Effects In order to demonstrate the excellent solubility of the phthalocyanine compounds of the present invention, the solubility of the compounds of Examples in diisobutyl ketone is shown as an example. (Table 1) Solubility was determined by adding a predetermined amount of diisobutyl ketone to a predetermined amount of the phthalocyanine compound, dissolving it by heating, allowing it to cool, and visually observing whether the phthalocyanine compound was dissolved.

Table 1 Solubility Data The solubility data of the compounds of Comparative Examples 1 and 2 shows that the vanadyl phthalocyanine compound has poor solubility compared to the copper phthalocyanine compound, but the solubility of the compounds of Examples 1 to 3 indicates that the fluorinated substituted It can be seen that the solubility was significantly improved by the introduction of the group. It can also be seen that the solubility of the copper phthalocyanine compound is improved by introducing the fluorine-containing substituent.

Therefore, the phthalocyanine compound of the present invention is useful as a light absorbent for optical recording media, electrophotography, and the like.

Claims (1)

[Claims] The following formula (I) M_-P_c_-(OR_f)_n(I) (wherein M represents a metal, a metal oxide, a metal chloride, or hydrogen, and P_c represents a phthalocyanine nucleus. , O
A phthalocyanine compound characterized in that R_f represents a fluorine-substituted alkoxy group, and n represents an integer of 1 to 8.