JPS63313760A - Fluorine-containing alkoxyphthalonitrile - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (Phn is phthalonitrile; ORf is fluorine-substituted alkoxy; n is 1-4). EXAMPLE:Tetra-(2,2,3,3,4,4,5,5-octanofluoropentyloxy)-phthalonitrile. USE:It is used as a starting substance of phthalocyanine pigments to be coated on an optical recording medium. PREPARATION:For example, the reaction between a nitrophthalocyanine and a fluoroalcohol is carried out in an aprotin polar solvent in the presence of potassium carbonate to give a phthalonitrile substituted with fluoroalkoxy groups. Phn is a phthalonitrile represented by formula II, and it is preferred to use OCH2(CF2)mZ (m is 1-5; Z is H, F) as an ORf.

Description

Detailed Description of the Invention (1) Background of the Invention (Technical Field) The present invention relates to a novel fluorine-containing alkoxyphthalonitrile compound. The phthalonitrile compound of the present invention is useful as a raw material for phthalocyanine and the like either as such or as dicarboxylic acids and derivatives thereof (amides, imides, acid anhydrides) easily obtained by hydrolysis or the like.

(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.In addition, because metal ions exist in a large n-electron conjugated system, metal phthalocyanines are used for electrical conduction, photoconductivity, 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.

These phthalocyanine compounds are produced using phthalonitrile and phthalic acid derivatives as raw materials, but they generally have poor solubility and therefore cannot be coated. Canadian Journal of Chemistry (Vol. 63, 623-63)
1, 1985) reports an example in which phthalocyanine having the above-mentioned substituents and having a central metal of Cu, Co, or Zn was synthesized using phthalonitrile into which a bulky alkyl group or alkoxy group was introduced. However, although the phthalocyanine showed improved solubility in halogenated hydrocarbons, its 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 in various solvents was worse than that of the metal phthalocyanine described 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. Therefore, a phthalocyanine having a substituent that further improves solubility and a phthalonitrile compound as a raw material thereof have been desired.

II. OBJECTS OF THE INVENTION An object of the present invention is to provide a phthalonitrile compound that is a raw material for a phthalocyanine compound with good solubility.

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

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

By converting the phthalonitrile compound of the present invention into phthalocyanine, it has low 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, etc. Since it provides a phthalocyanine compound that dissolves well in cellosolve solvents, alcohol solvents such as octafluoropentyl alcohol, and aromatic solvents such as benzene, it is useful as a raw material for phthalocyanine dyes 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) Phn-(ORf)n (I) (wherein, Phn represents phthalonitrile, ORf represents a fluorine-substituted alkoxy group, and n represents an integer of 1 to 4)
It is a phthalonitrile compound characterized by the following.

The above phthalonitrile Phn is represented by the following formula (II).

The above substituent ORf is selected from linear or branched alkoxy groups substituted with one or more fluorine, but OCH3(CF2)mz(m
is an integer of 1 to 5, and 2 is a hydrogen atom or a fluorine atom). The number n of substituents ORf is an integer of 1 to 4 per phthalonitrile. substituent OR
The substitution position of f is any one of 1 to 4 in formula (II). Among the four substitution positions of phthalonitrile, 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)-phthalonitrile (2) Tetra-(2,2,3,3-tetrafluoropropoxy)-phthalonitrile Oral nitrile (3) tetra-(2,2,2-trifluoroethoxy)
- Phthalonitrile The phthalocyanine compound of the present invention is described, for example, in the Canadian Journal of Chemistry (Volume 63).

623-631, 1985). That is, a fluoroalkoxy-substituted phthalonitrile is obtained by reacting a nitro-substituted phthalonitrile and a fluoroalcohol in an aprotic polar solvent in the presence of potassium carbonate. The thus obtained fluorine-containing phthalonitrile is produced by reacting 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. Can be converted to phthalocyanine. Furthermore, fluorine-containing phthalonitrile can be converted into a fluorine-containing alkoxymetal phthalocyanine or a fluorine-containing alkoxy metal-free phthalocyanine by reacting it 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.

Example 1 4-nitrophthalonitrile (III) 2.49 g (1
4.4 mmol).

2. 8.70 g (37.5 mmol) of 2,3,3,4,4,5.5-octafluoropentyl alcohol and 6.0 g of potassium carbonate were mixed in 20 m of dry DMF under nitrogen atmosphere.
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 extracted layer was dried over magnesium sulfate overnight, the ether was distilled off, and the layer was further dried using a vacuum pump.

Yield 4.51g (12.6mmol) [Yield 87
．． 6%1 Melting point 42.5-44.0°C IR (KBr) 2250.2240.1610.1
575.1495.1310゜1260, 1180.1
160.1135.1120.980°895, 815
．． 655cm-1 NMRδ(CDC1a) 4.58[2H,t,,J
=12.5Hz], 6.07[IH,t,t,,
J=51.5Hz, 5.5Hz].

7.33 [IH, d,, J=8.0Hz], 7.38
[IH,s, ], 7.83[LH,d,, J = 8
．． 0 Hz] Example 2 4-nitrophthalonitrile (III) 2.49 g (1
4.4 mmol).

2.2,3.3-Tetrafluoropropyl alcohol 4
．． 95g (37.5mmol), potassium carbonate 6.0g
3.49 g (13,5
mmol) [yield 93.9%].

Melting point 72.0-73.0°C IR (KBr) 2240.1605.1570.1
495.1305.1260゜1150, 1105.9
80.895cm-1NMRδ (CDC13) 4.
47[2H,t,t,,J=12.0Hz.

0.7Hzl, 5.97[IH,t,t,, J=5
2, () Hz, 4, 0 Hz].

7.22 [IH, d,, J = 8.0 Hzl.

7.32[LH,s] 7.73[LH,d,.

J = 8.0 Hz] Example 3 4-nitrophthalonitrile (III) 2.49 g (1
4.4 mmol).

2.2.2-Trifluoroethanol 3.75 g (37
, 5 mmol) and 6.0 g of potassium carbonate, 3.08 g (13.6 mmol) [
A yield of 94.6% was obtained.

Melting point 76.0-77.0°C IR (KBr) 2245.1610.1585.1
495.1320°1255cm-1 NMRδ (CD013) 4.46[2H,q,,J
=7.7HzHz].

7.23 [IH, d,, J = 8.6 Hzl.

7.30 [IH, s, ] 7.73 [IH, d,.

J=8.6Hz] Next, as a reference example, an example of conversion to a fluorine-containing substituted phthalocyanine compound will be shown.

Reference Example 1 Compound (IV) (ORf=OCR2(CF2)4H)
2.15g (6.0mmo1), vanadium trichloride 0
．． 38g (2.4mmol), 7.0g of urea from 190~
The mixture was heated to 220'C 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 ε = 5.
20) MASS (FD) 1500 (M+1) VI All inventions Specific effects The phthalocyanidianine compound obtained from the phthalonitrile of the present invention can be used in various solvents, such as ketone solvents such as acetone, methyl cellosolve solvents, and octafluoropentyl alcohol. The phthalonitrile compound of the present invention is useful as a raw material for a phthalocyanine dye for coatable optical recording media because it is well soluble in alcoholic solvents such as , aromatic solvents such as benzene, and the like.

Claims (1)

[Claims] The following formula (I) Phn-(OR_f)n(I) (wherein, Phn represents phthalonitrile, OR_f represents a fluorine-substituted alkoxy group, and n represents an integer from 1 to 4) A phthalonitrile compound characterized by: