JP2523640B2 - Phthalocyanine compound - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel phthalocyanine compound having absorption in the near infrared region and excellent solubility.

(Prior Art and Problems Thereof) In recent years, a semiconductor laser has been used as a light source in the fields of optical recording, electrophotography, and the like, so that there is an increasing demand for development of a dye having absorption in the near infrared region. Above all, many studies have been conducted on phthalocyanine compounds having excellent stability. However, most of them are insoluble in a solvent, and in order to practically form a dye into a thin film, vapor deposition or dispersion in a resin and some steps are required. A phthalocyanine compound having a solubility that is practically advantageous has recently been disclosed. For example, there is 3,6-octaalkoxy phthalocyanine (JP-A-61-223056), but it has problems that absorption in the near infrared region is insufficient and that raw materials for production are expensive. Also,
Thioether substituent-introduced phthalocyanines have been disclosed (JP-A-60-209583 and JP-A-61-152685), which have sufficient absorption in the near infrared region due to the substituent effect. However, these phthalocyanines have a synthetic yield of 20-
It is about 30% and there is a problem in manufacturing efficiency. Further, the introduced amount of the substituent is 5 to 16 on average per phthalocyanine molecule, and therefore, it is a mixture of substantially different introduced ratios, or even if it is not, it is asymmetrically substituted. It is considered that the stacking (stacking) of phthalocyanine molecules, which is considered important in application, is insufficient. At the same time, including symmetrical substitutions such as 8-substitution or 16-substitution type, as the introduction amount of the substituent increases, that is, as the molecular weight of the compound increases, the weight per weight, that is, the film thickness when used as a thin film, for example. The extinction coefficient per unit decreases.

(Problems to be Solved by the Present Invention) The present invention has been made in view of the above circumstances of the prior art. Therefore, it is an object of the present invention to provide a novel substituted phthalocyanine compound which can be efficiently produced, has absorption in the near infrared region, has excellent solubility, and has a substituent in a symmetrical position in the smallest possible amount.

(Means and Actions for Solving Problems) The present inventors have completed the present invention by finding that tetrakisalkylthiometal phthalocyanine achieves the above object. That is, the invention has the general formula (I) (In the formula (I), X and Y directly linked to four benzene rings.
Are each SR (R represents a linear alkyl group having 1 to 20 carbon atoms), the other is H, and M is an axial coordination selected from the group consisting of an oxygen atom and a halogen atom. Represents a trivalent or higher valent metal having offspring. ) Relating to a phthalocyanine compound.

The phthalocyanine of the present invention is optimally obtained by heat-condensing 4-alkylthiophthalonitrile with the metal salt or metal oxide by a known method.
In addition, 4-alkylthiophthalonitrile as a raw material is optimally prepared by reacting 4-nitrophthalonitrile with an alkylthiol in an aprotic polar solvent using an inorganic base or an organic base such as a tertiary amine compound as a catalyst. can get. It is known that the nitro group of 4-nitrophthalonitrile is easily replaced by various nucleophiles,
By this method, 4-aryloxyphthalonitrile, 4
-Arylthiophthalonitrile and phthalocyanines condensed with these (Macromolecules 1984 17 1614-162
4) Alternatively, 4-alkoxyphthalonitrile and a phthalocyanine obtained by condensing the 4-alkoxyphthalonitrile (JP-A-61-207365) are reported. It has been found that -alkylthiophthalonitrile can be obtained. That is, the phthalocyanine of the present invention is easily synthesized, for example, by the reaction represented by the formula (II) shown below.

(In the formula (II), X and Y directly connected to four benzene rings.
Are each SR (R represents a linear alkyl group having 1 to 20 carbon atoms), the other is H, and M is an axial coordination selected from the group consisting of an oxygen atom and a halogen atom. Represents a trivalent or higher valent metal having offspring. ) According to this method, the synthesis yield of the first step in formula (II) is almost
About 90%, the second-stage synthetic yield is about 50-85%, and the total yield is about 45-75%, and it is possible to manufacture with considerably high efficiency. The phthalocyanine compound of the present invention is tetrahydrofuran, chloroform, dichloromethane, benzene,
It is soluble in a solvent such as toluene, and its solubility is about 1 to 10% by weight, although it varies depending on the chain length of the substituted alkyl group and the type of central metal. Therefore, a purified product can be obtained by an ordinary method such as column chromatography.

The alkylthio group of the phthalocyanine compound of the present invention has the effect of lengthening the absorption wavelength, and therefore the central metal is a trivalent or higher valent metal having an axial ligand selected from the group consisting of oxygen atoms and halogen atoms. Any of them may be used, but TiO, VO, Al, Cl, InCl, SiCl _{2 and the} like are preferable in order to have sufficient absorption in the near infrared region.

Further, since the phthalocyanine of the present invention has several X-ray diffraction peaks in a powder state, it can be seen that there is stacking (stacking) of molecules with each other. This is because the number of substitutions and the substitution position of the alkylthio group are symmetrical. It is thought to be because. Further, since the X-ray diffraction peak was retained in the thin film obtained by once dissolving it in the solvent and then coating and drying it, it was found that this laminated layer was stable even in a practically used form.

(Effects of the Invention) The phthalocyanine compound of the present invention has absorption in the near infrared region and excellent solubility, and thus can be effectively applied to fields of application such as optical recording and electrophotographic technology.

(Example) As a reference example, a synthetic example of 4-alkylthiophthalonitrile (hereinafter abbreviated as CnSPN, where Cn represents a linear alkyl group having carbon number n) is shown below.

Reference Example 1 4-Nitrophthalonitrile 10.4 g, ethyl mercaptan 5.0 g, N, N-dimethylformamide (DMF) 15 ml at room temperature at room temperature 1.8-diazabicyclo [5,4,0] -7-undecene (DBU) After dropping 9.1 g (heat was generated by dropping), 6
After reacting at 0 ° C. for 5 hours, the reaction product was concentrated, the residue was dissolved in chloroform, and a slightly yellow crystal precipitated by adding a hydrochloric acid aqueous solution was separately dried to obtain the desired product, 2-ethyl. 10.4 g of thiophthalonitrile (C ₂ SPN) was obtained (yield 92%).

 The analytical values of the target substance are shown below.

Elemental analysis (wt%, calculated value in Katsuko): C 63.76 (63.80) H 4.25 (4.28) N 14.86 (14.88) S 16.98 (17.03) mp (° C): 134.1 Reference Example 2 4-nitrophthalonitrile 10.4 g, n -DBU9.1g was added dropwise to a mixed solution of butanethiol 6.5g and DMF15ml at room temperature (heat was generated by the addition), and the mixture was reacted at 75 ° C for 4 hours, then the reaction product was concentrated and the residue was converted to chloroform. After dissolution, washing with an aqueous solution of hydrochloric acid, an aqueous solution of sodium carbonate, and pure water in this order, the chloroform layer was concentrated and the resulting crude product was recrystallized from methanol to give 4-butylthiophthalonitrile (C ₄ SPN) 11.6 g was obtained (yield 89%).

 The analytical values of the target substance are shown below.

Elemental analysis (wt%, calculated value in Katsuko): C 66.91 (66.64) H 5.68 (5.59) N 12.81 (12.95) S 14.93 (14.82) mp (℃): 60.7 Reference Example 3 n-butanethiol 6.5 g instead of 6.5 g , N-octanethiol, which is the target product recrystallized and purified from methanol by the same operation as in Reference Example 2 except that 10.5 g of 4-octanethiol was used
14.5 g of octylthiophthalonitrile (C ₈ SPN) was obtained (yield 89%).

 The analytical values of the target substance are shown below.

Elemental analysis (wt%, calculated value in Katsuko): C 70.06 (70.55) H 7.37 (7.40) N 10.07 (10.28) S 11.79 (11.77) mp (° C): 47.8 Synthesis example of tetrakisalkylthiometal phthalocyanine as an example below Indicates.

Example 1 A mixture of 4-C ₂ SPN 1.88 g obtained in Reference Example 1, vanadium trichloride VCl ₃ 0.55 g, DBU 3.04 g, and N, N-dimethylaminoethanol 10 ml was refluxed for 4 hours under a nitrogen atmosphere. The resulting dark green product was added to 10% hydrochloric acid aqueous solution to cause precipitation separation, and the crude product obtained by washing this with pure water and methanol was subjected to chloroform-methanol (97/3 v / By using (v%) as a developing solution (Rf = 0.87), the target tetrakisethylthiometal phthalocyanine (central metal and axial ligand)
VO) 1.06 g was obtained (yield 51%).

 The analytical values of the target substance are shown below.

Elemental analysis (wt%, calculated in Katsuko): C 58.54 (58.59) H 3.72 (3.93) N 13.56 (13.67) S 15.57 (15.64) V 5.97 (6.21) Visible absorption spectrum λmax: 900nm (coating film) 718nm (chloroform) Solution) Solubility: 1 in chloroform, terrahydrofuran, benzene, etc.
~ 10wt% dissolution X-ray diffraction pattern Bragg angle 2θ: 5.4 ° 8.5 ° 26.0 ° (coating film) The infrared spectrum of the target product is shown in FIG.

Example 2 Obtained by reacting a mixture of 4-C ₂ SPN 1.88 g obtained in Reference Example 1, InCl ₃ 3 indium chloride 0.77 g, and 1-chloronaphthalene 10 ml under a nitrogen atmosphere at 200 ° C. for 4 hours. The dark green product is precipitated and separated by adding to ethanol, and then washed with 3% ethanol hydrochloric acid-water-methanol solution, and then Soxhlet extraction to remove impurities with acetone, whereby the target tetrakisethylthiometal phthalocyanine (center 1.59 g of metal and axial ligand InCl) was obtained (yield 70%).

 The analytical values of the following target products are shown.

Elemental analysis (wt%, calculation value in Katsuko): C 52.89 (53.19) H 3.17 (3.57) N 11.44 (12.40) S 13.22 (14.20) Cl 5.50 (3.92) In 11.63 (12.71) Visible absorption spectrum λmax: 740nm (coating) Membrane) 717 nm (chloroform solution) Solubility: 1 in chloroform, terrahydrofuran, benzene, etc.
~ 10wt% dissolution X-ray diffraction pattern Bragg angle 2θ: 5.5 ° 14 ° 26.0 ° (coating film) The infrared spectrum of the target product is shown in FIG.

Example 3 The reaction product was separated and reacted in the same manner as in Example 1 except that 2.16 g of 4-C ₄ SPN obtained in Reference Example 2 was used, and chloroform was used as a developing solution for column purification (Rf = 0.85). 1.53 g of tetrakisbutylthiometal phthalocyanine (central metal and axial ligand VO) was obtained (yield 66%). The analytical values of the target substance are shown below.

Elemental analysis (wt%, calculated value in Katsuko): C 61.36 (61.85) H 5.18 (5.19) N 11.67 (12.02) S 13.35 (13.76) V 5.33 (5.46) Visible absorption spectrum λmax: 850nm (coating film) 719nm (chloroform) Solution) Solubility: 1-5 wt% dissolution in chloroform, terrahydrofuran, etc. X-ray diffraction pattern Bragging angle 2θ: 6.3 ° 6.9 ° 8.0 ° Approx. 25 ° (coating film) The infrared spectrum of the target product is shown in Fig. 3. .

Example 4 Obtained by reacting a mixture of 4.25 g of 4-C ₄ SPN obtained in Reference Example 2, 0.96 g of TiCl ₄ 4 titanium chloride and 10 ml of 1-chloronaphthalene at 210 ° C. for 3 hours under a nitrogen atmosphere. The resulting dark green product was precipitated and separated by adding to ethanol, further thoroughly washed with ethanol, refluxed in 100 ml of 1% aqueous ammonia-methanol solution, titanylated, separated, and washed with water and methanol. The crude product thus obtained was purified by column using chloroform-ethyl acetate (90/10 v / v%) as a developing solution (Rf = 0.90).
2.32 g of the target product, tetrakisbutylthiometal phthalocyanine (central metal and axial ligand TiO) was obtained (yield 67
%).

 The analytical values of the target substance are shown below.

Elemental analysis (wt%, calculated in Katsuko): C 62.27 (62.05) H 4.92 (5.21) N 11.92 (12.06) S 13.67 (13.81) Ti 5.06 (5.15) Visible absorption spectrum λmax: 750nm (coating film) 720nm (chloroform) Solution) Solubility: 1 in chloroform, terrahydrofuran, benzene, etc.
˜10 wt% dissolution X-ray diffraction pattern Bragging angle 2θ: 4.5 ° About 25 ° (coating film) Example 5 The same as Example 2 except that 4.16 g of 4-C ₄ SPN obtained in Reference Example 2 was used. Tetrakisbutyl thiometal phthalocyanine (central metal and axial ligand InCl) 2.15
g was obtained (yield 85%).

 The analytical values of the target substance are shown below.

Elemental analysis (wt%, calculated in Katsuko): C 55.85 (56.77) H 4.34 (4.76) N 10.61 (11.03) S 12.43 (12.63) Cl 4.04 (3.49) In 11.08 (11.31) Visible absorption spectrum λmax: 740nm (coating) Membrane) 717 nm (chloroform solution) Solubility: 1 in chloroform, terrahydrofuran, benzene, etc.
˜10 wt% dissolution X-ray diffraction pattern Bragging angle 2θ: 5.0 ° 25.2 ° (coating film) Example 6 Reaction separation was performed in the same manner as in Example 1 except that 2.72 g of 4-C ₄ SPN obtained in Reference Example 3 was used. Then, column purification using chloroform as a developing solution (Rf = 0.95) gave 1.67 g of the target product tetrakisoctylthiometal phthalocyanine (central metal and axial ligand VO) (yield 58%).

 The analytical values of the target substance are shown below.

Elemental analysis (wt%, analysis value in Katsuko): C 67.29 (66.46) H 7.08 (6.97) N 9.81 (9.69) S 11.18 (11.09) V 4.32 (4.40) Visible absorption spectrum λmax: 830 nm (coating film) 720 nm (chloroform) Solution) Solubility: 1 in chloroform, terrahydrofuran, benzene, etc.
~ 10% dissolution X-ray diffraction pattern Bragging angle 2θ: 4.0 ° (coating film)

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum of the tetrakisethylthiometal phthalocyanine (central metal and axial ligand VO) obtained in Example 1. FIG. 2 is an infrared absorption spectrum of the tetrakisethylthiometal phthalocyanine (central metal and axial ligand InCl) obtained in Example 2. FIG. 3 is an infrared absorption spectrum of the tetrakisbutylthiometal phthalocyanine (central metal and axial ligand VO) obtained in Example 3.

Front page continuation (72) Inventor Sadanori Sano No. 5-8 Nishimitabicho, Suita City Central Research Institute, Nippon Catalysis Chemical Co., Ltd. (56) Reference JP-A-63-37991 (JP, A) JP-A-61- 198242 (JP, A) West German patent publication 2531823 (DE, A)

Claims (1)

(57) [Claims] 1. A general formula (I) [Formula (I) Formula, X and Y directly linked to four benzene rings
Is an SR (R is a straight-chain alkyl group having 1 to 20 carbon atoms) in one side, H is the other side, and M is an axial ligand selected from the group consisting of an oxygen atom and a halogen atom. Represents a metal having a valence of 3 or more. ] The phthalocyanine compound represented by these.