JPS61186386A - Phythalocyanin compound and its preparation - Google Patents

Abstract

NEW MATERIAL:A compound that is composed of monolithium phthalocyanin and 1,8-diazabicyclo[5.4.0]undecene-7: appearance; reddish violet crystals, chemical formula; LiH(C32H16N8).(C9H16N2), elementary analyses; C 73%, H 4.94%, N 20.9%, Li 1.03%. USE:Intermediate for preparation of non-metallic phthalocyanin. It decomposes readily in a dilute mineral acid to give non-metallic phthalocyanin of high purity in high yield. PREPARATION:The reaction of phthalonitrile with metallic lithium is carried out in the presence of 1,8-diaza-bicyclo[5.4.0]undecene-7 (DBU) in a solvent preferably in ethanol at 65-195 deg.C. It is preferred that more than 0.1mol of DBU and metallic lithium, respectively, and more than 200ml of the solvent are used.

Description

Detailed Description of the Invention <Industrial Application Field> The present invention relates to a novel phthalocyanine compound and a method for producing the same.
This relates to a novel phthalocyanine compound which is a higher-order compound consisting of monolithium phthalocyanine and 1,8-diaza-bicyclo[5°4.0]undecene-7, which is thought to be represented by CsJ+JJ (C9HIJ rich g). This compound is metal-free phthalocyanine (hereinafter referred to as HgPc).
It is an important intermediate for manufacturing (sometimes abbreviated as).

Phthalocyanine compounds have characteristics such as high coloring power, excellent heat resistance, and light resistance, and are therefore widely used as pigments in the color material industry. In addition, since phthalocyanine compounds have semiconducting properties and photoconductivity, a lot of research has been done on them in recent years, and they are being used as electrophotographic photoreceptors or photoreceptors for semiconductor laser printers, and their importance is increasing. It is increasing every year. Among them, metal-free phthalocyanine has a unique hue with a strong yellowish blue color as a pigment, and has excellent photoconductivity as an electronic material, making it extremely valuable industrially. It is a high quality material.

<Prior art> Conventionally, as a method for producing metal-free phthalocyanine, for example, phthalonitrile and alcoholade or a strong organic base, that is,
1゜8-Diaza-bicyclo(5,4,0]undecene-
A method of synthesizing the compound by reacting with compounds such as No. 7 is known (Japanese Unexamined Patent Publication No. 105962/1982). However, with this method, the yield was only 63% in 14 hours of reaction.
It stays at a low value of %.

In addition, "Phthalocyanine Compounds J" (ACS sonagraph Ilh) by Moser and Thomas.
157. Re1nhold Publ-ishin
G Corp, New York (1963)), metal-free phthalocyanines can be produced by acid-treating phthalocyanines that can be demetallized with acids such as sulfuric acid, such as dilithium phthalocyanine, disodium phthalocyanine, and magnesium phthalocyanine. This method does not provide a very high yield of the original metal phthalocyanine, and since concentrated sulfuric acid is used for its decomposition, the phthalocyanine decomposes, etc., making it difficult to obtain a highly purified product.

As described above, the conventional techniques have the problems of low yields and difficulty in obtaining highly purified products.

<Problems to be solved by the invention> As described above, the conventional technology is unsatisfactory as an industrial production method, such as requiring a long time to produce metal-free phthalocyanine and having low yield and purity of the target product. It was something. Furthermore, low purity is a fatal drawback in the field of electronic materials, and there is a serious problem in that it is difficult to obtain desired electrical and electronic properties.

<Means for Solving the Problems> In order to eliminate such inconveniences in the prior art, the present inventors conducted intensive studies and discovered a novel phthalocyanine compound that is different from any of the conventionally known phthalocyanine compounds. The present invention was achieved by discovering that this new phthalocyanine compound can be easily decomposed into metal-free phthalocyanine, and that the yield and purity of metal-free phthalocyanine can be significantly improved.

That is, the first invention consists of monolithium phthalocyanine (hereinafter sometimes abbreviated as LtHPc) and 1,8-diaza-bicyclo(5,4,0]undecene-7 (hereinafter D
(sometimes abbreviated as BU) is a higher-order compound consisting of
Regarding the phthalocyanine compound (hereinafter sometimes abbreviated as the compound of the present invention) that can be represented by the following chemical formula (% formula %), the second invention provides a method for producing the compound of the present invention, comprising: A) phthalonitrile and metallic lithium or lithium. B) metal-free phthalocyanine and metallic lithium or lithium alcoholate, or LiHPc and DBU.
It is characterized in that the reaction is carried out in a solvent in the presence of.

The invention of the wood brush 2 will be described in more detail as follows.

゛That is, for 1 mole of phthalonitrile, DBU is 0.
．． 1 mole or more, metallic lithium or lithium compound is 0.
Using 1 mol or more and 200 ml or more of solvent, 65 to 19
The reaction is typically carried out for 30 minutes to 24 hours at a temperature of 5°C. Or, for 1 mol of metal-free phthalocyanine, 0.5 mol or more of metallic lithium or lithium alcolade, 0.5 mol or more of DBU, and 800 mj of solvent! The DBU
Using 0.5 mol or more of the solvent and 800 ml or more of the solvent, the reaction is usually carried out at a temperature of room temperature to 200° C. for 30 minutes to 10 hours.

As the solvent used in the reaction, organic compounds that grow hydroxyl groups are suitable, primary and secondary alcohols are preferred, and alcohols with carbon numbers greater than or equal to ethanol are particularly preferred; examples include Eva, ethanol, n-propanol, 130-
Examples include propatool, n-butanol, 1so-butanol, 5ec-butanol, n-pentanol, and ethylene glycol monoalkyl ethers such as 2-methoxyethanol and 2-ethoxyethanol.

As lithium compounds, lithium mineral acid salts, organic acid salts, alcolades, etc. are used, and examples thereof include:
These include lithium chloride, lithium bromide, lithium iodide, lithium acetate, and lithium ethylate.

Although there are no particular restrictions on the reaction method, in a reaction using phthalonitrile as a raw material, after heating a mixed system of phthalonitrile and lithium or a lithium compound and a solvent to a predetermined temperature, DBU is added in portions. This is a preferred method for increasing the purity of the compound of the present invention.

The compound of the present invention obtained in this way is a reddish-purple crystal, and is stable in water and organic solvents, but is unstable in dilute mineral acid aqueous solutions, easily decomposes, and is quantitatively ineffective. Becomes metal phthalocyanine.

As shown in Example 1 below, the compound of the present invention is L
Not only is it different from both iHPc and DBU, but it is also different from a mixture of the two, and it is recognized as a higher-order compound consisting of both, and it is recognized that it can be expressed as a single compound with the chemical formula of LiH(CstH+hNm) ・(C9H+Jm).

The compound of the present invention is easily decomposed to produce LPc by adding a dilute mineral acid aqueous solution in an alcohol solvent. Therefore, the compound of the present invention is useful as an intermediate for producing H, Pc, and in producing H, Pc, a decomposition reaction can also be carried out in the reaction completed solution for producing the compound of the present invention. However, in order to obtain H and Pc with high purity, it is preferable to isolate and purify the compound of the present invention once and then decompose it.

Furthermore, as shown in the Examples below, using n-butanol as a solvent, HtPc could be obtained in a high yield of 82% in a short reaction time of 6 hours below the boiling point, and the obtained HtPc
, Pc can be obtained with higher purity than with conventional production methods.

<Effects of the Invention> The compound of the present invention can be produced in high yield by a simple method as described above, and then it can be easily quantitatively decomposed into metal-free phthalocyanine. Furthermore, the obtained metal-free phthalocyanine can be obtained with higher purity than that obtained by conventional synthesis methods, and has good properties as a pigment or a raw material for electronic materials.

Therefore, the compound of the present invention is extremely useful as an intermediate for producing high-purity metal-free phthalocyanine in high yield.

<Examples, etc.> The present invention will be explained in more detail below using Examples, Comparative Examples, and Reference Examples, but the scope of the present invention is not limited thereby.

Example 1 512.6 g of phthalonitrile, 50.8 g of lithium chloride, and 2j1 of 2-methoxyethanol were added to a 31-piece glass tube flask equipped with a stirrer, a dropping funnel, a reflux condenser, a thermometer, and a nitrogen gas inlet tube. The mixture was charged and heated on an oil bath under a nitrogen atmosphere and maintained at reflux temperature. When the reflux temperature was reached, DBU was started to be added dropwise from the dropping funnel, and 608.6 g was added over a period of 2 hours. Further under reflux,
The reaction was carried out for 6 hours.

Immediately after the reaction, filtration was performed to obtain reddish-purple crystals, which were washed with 2-methoxyethanol II1, then with 411 parts of water, and then with 17 parts of acetone, and dried to give reddish-purple crystals 54.
7.6 g was obtained.

Elemental analysis value LiH (C3J+Js)/CCqH+hN
t) as CHN Li Calculated value (%) 73.2 4.95 20.8
1.03 Actual value (%)? 3.0 4.94
20.9 1.03I R(KBr)am-'(±
33-9.740. 752.1060.1330.1
486.1645, etc. NMR (deuterated pyridine) δ value 0.5-0.8 (8H, CHz) H-1.3 (2H, and H port 1.8-2.1 (6H, N -CH* )8.0~8
．． 2(8H, \CH, benzene ring-H)〆9.7-9.9 (8H,"CH, benzene ring-H) and the X-ray diffraction pattern of this product is as shown in the figure.

Furthermore, 0.5 g of this crystal was accurately weighed, added to 30 ml of 0.1N HCl aqueous solution, and stirred at room temperature for 30 minutes, and excess hydrochloric acid was removed by 0.5 g. After titration with I N NaOH aqueous solution, 2 in the crystals
It contained an equivalent amount of base.

In addition, as a result of thermogravimetric analysis, the decomposition point was 334℃, and the temperature was 22.6℃.
wt% decreased. This value is LiH(C3J+Js)
'(CJtJt) to C41l14N! (D B U
) is consistent with the decrease. In addition, DBU is a liquid at room temperature and vaporizes at about 250°C under normal pressure.
In the case of a mixture of U and LiHPc, weight loss due to vaporization of DBU will occur before this decomposition point is reached. Therefore, the fact that the decomposition point is 334°C means that this crystal is not a mixture of monolithium phthalocyanine and DBU.
It is clear that it is a single compound.

From the above, the reddish-purple crystal has the chemical formula LiH(C3J
+Js)・(CJ+,,Nz) It is a phthalocyanine compound consisting of monolithium phthalocyanine and []BU (hereinafter abbreviated as LiHPc-DBtl).
.

Reference Example 1 LiHPc-DBUS and OOg obtained in Example 1 were placed in a four-eye flask, 100 ml of a 5% HCI aqueous solution was added, and the mixture was stirred at room temperature for 30 minutes.

Filter the crystals, add 100ml of water and then 100ml of acetone.
After washing and drying in step 1, reddish-purple microcrystals 3.73
I got g. What was obtained from this X-ray diffraction and infrared absorption spectrum measurement was metal-free phthalocyanine ()It
Furthermore, as a result of purity analysis, H2
It contained 98.6% Pc. Therefore, the yield of H, Pc from Example 1 was 78.3 molχ, and Comparative Example 1
It is possible to obtain HtPc with a higher yield and higher purity than that of the conventional method.

Reference Example 2 In the same manner as in Reference Example 1, a decomposition reaction of 5.00 g of LiHPc/DBU was carried out 5 times. The amounts of thPc obtained were 3.71 g, 3, 73 g, 3.73 g, and 3, respectively.
．． 70 g and 3.74 g, and decomposition is proceeding almost quantitatively.

Example 2 In a 100 mf four-eye flask similar to Example 1, 6.41 g of phthalonitrile, 1.06 g of lithium chloride, and the
36 ml of each alcohol shown in the table was charged, heated on an oil bath under a nitrogen gas atmosphere, and maintained at reflux temperature. Addition of DBtJ was started from the dropping funnel when the reflux temperature was reached, and 7.61 g was added over 30 minutes. Further under reflux,
The reaction was carried out for 6 hours.

Immediately after the reaction, filtration was performed to obtain crystals of LiHPc-DBU, which were mixed with 100 mJ of methanol and then 1% hydrochloric acid (1%).
00m1, water 100mj! , and 100mJ of acetone!
By washing with water and drying, crystals of LiHPc 811 were obtained.

Next, for reference, LiHPc-DB was prepared in the same manner as Reference Example 1.
U was decomposed to obtain HzPc. These results are the first
Shown in the table.

Table 1 Example 3 The reaction was carried out in the same manner as in Example 2 except that 2-methoxyethanol was used as the alcohol. However, the reaction times were 3 hours, 6 hours, and 12 hours. LiH at this time
The amount of Pc-DBU obtained was 6.72 g and 6.8 g, respectively.
The yields as HtPc were 73.4%, 74.8%, and 68.4%, respectively. In other words, the reaction rate of LiHPc-Dull is 2-
Under refluxing of methoxyethanol, the reaction is fast and is almost completed in about 3 hours.

Example 4 A reaction was carried out in the same manner as in Example 2 except that 2-methoxyethanol was used as the alcohol, and LiHPc/DBIJ
was synthesized (using a 200ml Yotsuro flask)
. After the reaction was completed, the mixture was cooled to room temperature, 110 ml of 5% hydrochloric acid was added, and the mixture was stirred at room temperature for 3 hours. By filtering this, washing and drying in the same manner as in Example 2, HtPc5.01
g (purity 95.1%) was obtained (yield 74.3%).

Comparative Example 1 512.6 g of phthalonitrile and 2.2 g of 2-methoxyethanol were placed in a 3i glass flask equipped with a stirrer, a dropping funnel, a reflux condenser, a thermometer, and a nitrogen gas inlet tube.
1 was charged, heated on an oil bath under a nitrogen gas atmosphere, and maintained at reflux temperature. When the reflux temperature was reached, DBU was started dropping from the dropping funnel, and it took 2 hours to reach 608.6
g was added. After further reaction under reflux for 14 hours, red-purple crystals were obtained by cooling to room temperature and filtering.
Add this to 1j of 2-methoxyethanol! , then water 41,
It was further washed with 11 acetone and dried to obtain 359.3 g of reddish-purple microcrystals. What was obtained from this X-ray diffraction and infrared absorption spectrum measurement was β-〇, Pc
Met. Furthermore, as a result of purity analysis, H and Pc were 92.5%.
It contained. Therefore, H for phthalonitrile Pc
The yield is 64.8%.

[Brief explanation of the drawing]

The drawing shows an X-ray diffraction pattern of a crystal obtained in an example of the present invention.

Claims (1)

[Claims] 1. A higher order compound consisting of monolithium phthalocyanine and 1,8-diaza-bicyclo[5,4,0]undecene-7, which has the following chemical formula LiH(C_3_2H_1_6N_8)・(C_9H_
1_6N_2) A phthalocyanine compound that can be represented by: 2.A) Phthalonitrile and metallic lithium or lithium compound are combined into 1,8-diaza-bicyclo[5,4,0
[B) Metal-free phthalocyanine and metallic lithium or lithium alcoholate, or monolithium phthalocyanine, 1,8-diaza-bicyclo[5,4,0] monolithium phthalocyanine and 1,8-, characterized by reacting in a solvent in the presence of undecene-7.
A higher order compound consisting of diaza-bicyclo[5,4,0]undecene-7, with the following chemical formula LiH(C_3_2H_1_6N_8)・(C_9H_
1_6N_2) Method for producing a phthalocyanine compound that can be represented by