JP3270695B2 - Method for producing vanadyl naphthalocyanine compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a vanadyl naphthalocyanine compound, and more particularly, to a vanadyl naphthalocyanine compound useful as a near-infrared absorbing agent, an information recording material, an organic photoconductor, a dye, etc., in a high yield and a high yield. It relates to a method of producing with purity.

[0002]

2. Description of the Related Art As a method for producing a naphthalocyanine compound, the Wyler method is well known. In the Wyler method, a 2,3-naphthalenedicarboxylic acid compound or an anhydride thereof and a metal or a metal derivative are melt-reacted in urea in the presence of a catalyst such as ammonium molybdate.
At this time, as a reaction solvent, for example, trichlorobenzene,
Methods using nitrobenzene, chloronaphthalene, polyethylene glycol, quinoline, benzonitrile and the like are also known. However, this method has a disadvantage that the yield and purity of the obtained naphthalocyanine compound are low.

[0003] Many naphthalocyanine compounds have low solubility in organic solvents, and such compounds are difficult to purify with a solvent. In particular, when the melt reaction is performed in urea, it is difficult to isolate the naphthalocyanine compound after the reaction because the compound solidifies.

Japanese Patent Application Laid-Open No. 63-159386 discloses that
A method for producing a naphthalocyanine compound by reacting a 2,3-naphthalenedicarboxylic acid derivative, a metal halide or oxide, and urea in a quinoline or chloronaphthalene solvent has been proposed. However, the naphthalocyanine compound obtained by this method still has a low yield and purity.

Japanese Unexamined Patent Publication (Kokai) No. 63-154767 discloses an aluminum naphthalocyanine or the like by reacting 2,3-naphthalenedicarboxylic acid or / and its anhydride, a metal or / and its compound and urea in the presence of a catalyst. A method using 1,3-dimethyl-2-imidazolidinone has been proposed for producing the naphthalocyanine compound.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to produce a vanadyl naphthalocyanine compound with high yield, high purity, economically and simply using a highly economical raw material.

[0007]

As a result of various studies to solve the above problems, the present inventors have found that 2,3-naphthalenedicarboxylic acid derivatives, vanadium compounds and urea can be used to prepare 1,3-dimethyl-2. -Imidazolidinone (hereinafter D)
MI) as a reaction solvent,
It has been found that a vanadyl naphthalocyanine compound can be produced with high yield and high purity in the absence of a catalyst.

That is, the present invention relates to a method for producing a vanadyl naphthalosinin compound represented by the following general formula (I):
Reacting at least one kind of a 2,3-naphthalenedicarboxylic acid derivative selected from compounds represented by the following general formulas (II) to (VI), a vanadium compound, and urea with DMI in the absence of a catalyst: The present invention relates to a method for producing a vanadyl naphthalocyanine compound represented by the general formula (I).

[0009]

Embedded image (Wherein, R is each independently an alkyl group, an alkoxy group, an alkylthio group, an arylthio group, a dialkylamino group,
It represents a nitro group, anilino group, methylanilino group, N-phenyl-N-methylamino group, and n represents an integer of 0 to 6. )

[0010]

Embedded image (In the formula, R and n are the same as those in the general formula (I).)

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION As a raw material used in the production method of the present invention, a 2,3-naphthalenedicarboxylic acid derivative represented by the following general formula (II): 2,3-naphthalenedicarboxylic acid compound represented by (III), 2,3-naphthalenedicarboxylic acid imide compound represented by the following general formula (IV), 2,3-naphthalenedicarboxylic acid imide compound represented by the following general formula (V)
Examples include naphthalenedicarboxylic acid diamide compounds and 2,3-naphthalenedinitrile compounds represented by the following general formula (VI).

[0012]

Embedded image (Wherein, R represents an alkyl group, an alkoxy group, an alkylthio group, an arylthio group, a dialkylamino group, a nitro group,
Anilino group, methylanilino group, N-phenyl-N-methylamino group is shown, and n shows the integer of 0-6. )

Particularly, the 2,3-naphthalenedicarboxylic acid derivative represented by the above general formula (II) or (III) is preferable from the viewpoint of economy. Also, from the viewpoint of availability, n is 0 to 2
Are preferred.

[0014] In the 2,3-naphthalene dicarboxylic acid derivatives of the general formula (II) ~ (VI), by carrying out the reaction with two or more substituents R _n are different, the general formula (I) In vanadyl naphthalocyanine compounds, 1
A compound in which different types of substituents are mixed in the molecule can be produced.

As the 2,3-naphthalenedicarboxylic acid derivative, two or more of the compounds represented by formulas (II) to (VI) may be used simultaneously.

In the above formulas (II) to (VI), when R is an alkyl group, it is preferably a straight-chain or branched alkyl group having 1 to 15 carbon atoms, and preferably a straight-chain or branched alkyl group having 1 to 8 carbon atoms. Is particularly preferred. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl,
Isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, n-hexyl group, isohexyl group, n-heptyl group, isoheptyl group, sec-heptyl group, n-octyl Group, tert-octyl group, 2-ethylhexyl group, n-dodecyl group and the like.

When R is an alkoxy group, the total number of carbon atoms is 1
~ 15 linear, branched or cyclic alkoxy groups are preferred,
Particularly, a linear, branched or cyclic alkoxy group having 1 to 8 carbon atoms is preferred. Examples are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isopentyloxy, n
-Hexyloxy group, cyclohexyloxy group, n-heptyloxy group, isoheptyloxy group, sec-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, methoxyethoxy group, methoxypropoxy group, methoxybutoxy group, Ethoxyethoxy group, ethoxypropoxy group, ethoxybutoxy group, n-propoxyethoxy group, isopropoxyethoxy group, (2-methoxyethoxy) methoxy group, (2-ethoxyethoxy)
Methoxy group, 2- (2-methoxyethoxy) ethoxy group, 2- (1-methoxyethoxy) ethoxy group, 2-
(2-ethoxyethoxy) ethoxy group, 2- (propoxyethoxy) ethoxy group, 3- (2-methoxyethoxy) propoxy group, 3- (2-ethoxyethoxy) propoxy group, 2-methylthioethoxy group, 2-ethylthio An ethoxy group, a 2-dimethylaminoethoxy group and the like can be mentioned.

When R is an alkylthio group, a straight-chain, branched or cyclic alkylthio group having a total of 1 to 15 carbon atoms is preferred, and a straight-chain, branched or cyclic alkylthio group having a total of 1 to 8 carbon atoms is particularly preferred. Examples include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, sec-butylthio, tert-butylthio, n-pentylthio, isopentylthio, n
-Hexylthio group, cyclohexylthio group, n-octylthio group and the like.

When R is an arylthio group, examples thereof include a phenylthio group, a p-methylphenylthio group, a p-tert-butylphenylthio group and a naphthylthio group.

When R is a dialkylamino group, the alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, particularly preferably a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Examples include dimethylamino, diethylamino, di-n-propylamino, diisopropylamino, di-n-butylamino, diisobutylamino, di-n-pentylamino, di-n-hexylamino, -N-heptylamino group, di-n-octylamino group, N-ethyl-N-methylamino group, N
-Isopropyl-N-ethylamino group, N-sec-butyl-N-ethylamino group, N-isopentyl-N-ethylamino group, N-cyclohexyl-N-methylamino group, N-sec-heptyl-N-ethyl Amino group, N-
(2-ethylhexyl) -N-butylamino group and the like.

Other specific examples of preferred R include nitro, anilino, methylanilino, N-phenyl-N-methylamino and the like.

In the present invention, DMI is used as a solvent. DM
I is used in an amount of 1 to 10 with respect to the 2,3-naphthalenedicarboxylic acid derivative represented by the general formulas (II) to (VI).
The weight is 0 times, preferably 2 to 50 times the weight.

The vanadium compound used in the present invention is V
Cl ₃ , VOCl ₃ , (CH ₃ COCH = C (CH ₃ ) O) ₂
VO (vanadyl (II) acetylacetonate) is preferred.

The amount of the vanadium compound used is 0.2 to 0.6 times, preferably 0.1 to 2.0 times the molar amount of the 2,3-naphthalenedicarboxylic acid derivative represented by the above general formulas (II) to (VI).
It is 25 to 0.4 times mol.

The amount of urea used in the present invention is 1 to 100 times, preferably 1 to 100 times the weight of the 2,3-naphthalenedicarboxylic acid derivative represented by the above general formulas (II) to (VI).
５０50 times the weight.

The reaction temperature is 80 to 300 ° C., preferably 1 to
00-250 ° C. When the reaction temperature is lower than 80 ° C., the reaction rate is extremely slow. When the reaction temperature is higher than 300 ° C., decomposition of the formed vanadyl naphthalocyanine compound is accelerated.

The reaction time is 1 to 25 hours, preferably 2 to 1 hour.
5 hours.

After the reaction, the reaction product is cooled and filtered at 50 to 150 ° C. as it is, or methanol, ethanol, isopropyl alcohol, dimethylformamide,
After diluting and dispersing with a solvent such as dimethylacetamide, dimethylsulfoxide, or N-methylpyrrolidone, the resultant is collected by filtration and, if necessary, further washed with the above diluting solvent to obtain a desired vanadyl naphthalocyanine compound.

Although the vanadyl naphthalocyanine compound obtained by the production method of the present invention has a sufficient purity, it is soluble in an organic solvent by a sublimation method or an organic solvent in a field where higher purity is required depending on the use. The vanadyl naphthalocyanine compound may be further purified by recrystallization or column chromatography.

According to the production method of the present invention, since there is no need to use an expensive catalyst, the production cost is reduced, and the operation of removing the catalyst from the product by filtration is not required.

The obtained vanadyl naphthalocyanine compound has a sufficient purity and a high yield for applications such as near-infrared absorption filters, heat-shielding films, protective glasses, information recording materials, and organic photoconductors. The production method of the present invention is a very useful production method.

[0032]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to the examples.

Example 1 Synthesis of vanadyl naphthalocyanine 2,3-naphthalenedicarboxylic anhydride 6 under a nitrogen stream
g, 7.2 g of urea, 20 g of DMI and 1.3 g of vanadium oxychloride were stirred at 210 to 215 ° C. for 10 hours. The mixture was cooled to 100 ° C. and filtered, and the collected matter was sufficiently washed with methanol and dried to obtain 4.6 g of a dark green powder. It was confirmed to be the target substance from the following analysis results. In this example and the following examples, metal was confirmed by the atomic absorption method.

[0034]

[Table 1] The thus obtained compound in a concentrated sulfuric acid solution was 929 n
m shows the maximum absorption (the visible-near infrared absorption spectrum is shown in FIG. 1), and the gram extinction coefficient is 1.1 × 10 ⁵ ml /
g. cm.

Example 2 Synthesis of vanadyl naphthalocyanine 2,3-naphthalenedicarboxylic anhydride 6 under a nitrogen stream
g, urea 13.7 g, DMI 30 g and vanadium oxychloride 1.73 g were stirred at 185 to 190 ° C. for 5 hours. The mixture was cooled to 100 ° C., filtered, and the collected matter was sufficiently washed with methanol and dried to obtain 4.7 g of a dark green powder. It was confirmed to be the target substance from the following analysis results.

[0036]

[Table 2] The thus obtained compound in a concentrated sulfuric acid solution was 929 n
m shows a maximum absorption, and the gram extinction coefficient is 1.0 × 10 ⁵
ml / g. cm.

Example 3 Synthesis of vanadyl naphthalocyanine In the same manner as in Example 1 except that 6 g of 2,3-naphthalenedicarboxylic acid imide was used instead of 6 g of 2,3-naphthalenedicarboxylic anhydride in Example 1. This gave 5.0 g of a dark green powder. It was confirmed to be the target substance from the following analysis results.

[0038]

[Table 3] The thus obtained compound in a concentrated sulfuric acid solution was 929 n
m shows a maximum absorption, and the gram extinction coefficient is 1.0 × 10 ⁵
ml / g. cm.

Example 4 Synthesis of tetra-tert-pentylvanadyl naphthalocyanine Instead of 6 g of 2,3-naphthalenedicarboxylic anhydride in Example 1, 7-tert-pentyl-2,3-naphthalenedicarboxylic anhydride was used. 6.0 g of dark green powder was obtained in the same manner as in Example 1 except that 8.1 g was used. It was confirmed to be the target substance from the following analysis results.

[0040]

[Table 4] The toluene solution of the compound thus obtained was 808.
It shows a maximum absorption in nm and a gram extinction coefficient of 1.9 × 10
⁵ ml / g. cm.

Comparative Example 1 Synthesis of Aluminum Naphthalocyanine A pale green powder was obtained by performing the same operation as in Example 1 except that 1 g of anhydrous aluminum chloride was used instead of 1.3 g of vanadium oxychloride in Example 1. 2 g were obtained. The DMF solution of the compound thus obtained is 775 nm
Showed a maximum absorption, but the gram extinction coefficient was 4.8 × 10
² ml / g. cm, and it was confirmed that it contained only a trace amount of the target substance.

Comparative Example 2 Synthesis of Copper Naphthalocyanine Example 1 was repeated except that 0.74 g of copper (I) chloride was used instead of 1.3 g of vanadium oxychloride in Example 1.
The same operation as described above was performed to obtain 3.3 g of a pale orange powder. The DMF solution of the compound thus obtained is 400 nm or more.
It showed no maximum absorption in the range of 1100 nm, and it was confirmed that the desired product was not obtained.

Comparative Example 3 Synthesis of Zinc Naphthalocyanine A green powder was prepared in the same manner as in Example 1 except that 1.2 g of zinc sulfate was used instead of 1.3 g of vanadium oxychloride in Example 1. 2 g were obtained. The DMF solution of the compound thus obtained showed a maximum absorption at 760 nm (the visible-near infrared absorption spectrum is shown in FIG. 2), but the gram extinction coefficient was 2.2 × 10 ³ ml / g. cm, and it was confirmed that it contained only a trace amount of the target substance.

Comparative Example 4 Synthesis of titanyl naphthalocyanine Light green color was obtained in the same manner as in Example 1, except that 1.3 g of vanadium oxychloride in Example 1 was replaced with 2.6 g of titanium n-butoxide. 2.7 g of a powder were obtained. The DMF solution of the compound thus obtained is
Does not show a maximum absorption in the range of 400 nm to 1100 nm,
It was confirmed that the desired product was not obtained.

Comparative Example 5 Synthesis of Vanadyl Naphthalocyanine Quinoline 20 was used instead of DMI 20 g in Example 1.
g of dark green powder except that g was used.
2 g were obtained.

The concentrated sulfuric acid solution of the compound thus obtained shows a maximum absorption at 929 nm and a gram extinction coefficient of 2.6 × 10 ⁴ ml / g. cm. The yields of the products obtained in the respective Examples and Comparative Examples and the gram extinction coefficients in the solutions are summarized in Table 1 below.

[0047]

[Table 5]

As shown in Table 1, a vanadium compound was used as a metal compound (that is, only when a vanadyl naphthalocyanine compound was produced), and D was used as a solvent.
Only when MI was used, the target product was obtained in high purity and high yield in the absence of a catalyst.

[0049]

According to the method of the present invention, a vanadyl naphthalocyanine compound can be produced with high yield, high purity, economically and simply.

[Brief description of the drawings]

FIG. 1 is a visible-near infrared absorption spectrum of a concentrated sulfuric acid solution of a naphthalocyanine compound obtained in Example 1.

FIG. 2 is a visible-near infrared absorption spectrum of a DMF solution of a naphthalocyanine compound obtained in Comparative Example 3.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yojiro Kumagai 1-43, Yugecho Minami, Yao-shi, Osaka Yamamoto Kasei Co., Ltd. (72) Inventor Matsu ▲ saki ▼ 1190 No. Mitsui Toatsu Chemical Co., Ltd. (72) Ryu Oi 1190 No. Mitsui Toatsu Chemical Co., Ltd., Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture (56) References JP-A-9-48926 (JP, A) JP-A-8-311359 (JP, A) JP-A-63-159386 (JP, A) JP-A-63-154767 (JP, A) JP-A-61-215663 (JP, A) JP-A-60-23451 (JP, A) JP-A-1-287175 (JP, A) JP-A-61-186384 (JP, A) JP-A-63-113076 (JP, A) JP-A-8-2255752 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C09B 47/04 CA (ST N)

Claims (4)

(57) [Claims] 1. A method for producing a vanadyl naphthalosinin compound represented by the following general formula (I), wherein at least one kind of 2,3-naphthalenedicarboxylic acid selected from the compounds represented by the following general formulas (II) to (VI): The acid derivative, vanadium compound, and urea were converted to 1,3 in the absence of a catalyst.
A method for producing a vanadyl naphthalocyanine compound represented by the general formula (I), wherein the reaction is carried out using dimethyl-2-imidazolidinone. Embedded image (Wherein, R is each independently an alkyl group, an alkoxy group, an alkylthio group, an arylthio group, a dialkylamino group,
It represents a nitro group, anilino group, methylanilino group, N-phenyl-N-methylamino group, and n represents an integer of 0 to 6. ) (In the formula, R and n are the same as those in the general formula (I).) 2. The method for producing a vanadyl naphthalocyanine compound according to claim 1, wherein the reaction is carried out in a hydrogen stream. 3. The method according to claim 1, wherein the vanadium compound is VCl ₃ or VOC.
l ₃ , (CH ₃ COCH = C (CH ₃ ) O) ₂ VO;
A method for producing a vanadyl naphthalocyanine compound according to claim 1 or 2. 4. The method according to claim 1, wherein the 2,3-naphthalenedicarboxylic acid derivative is at least one selected from the general formulas (II) and (III):
The method for producing a vanadyl naphthalocyanine compound according to any one of claims 1 to 3, which is a seed.