JP5169064B2 - Soluble porphyrin derivative - Google Patents

Description

  The present invention relates to a soluble porphyrin derivative suitable for a wet film forming method and a method for producing the same.

  Porphyrin is a macrocyclic compound and its derivatives in which four pyrrol rings are alternately bonded to four methine groups at the α position, and there are a plurality of strong peaks in the visible region, and the Q band ( Qband), a compound having a characteristic peak called a soret band in the vicinity of 400 nm. Such porphyrins can coordinate with a metal at the center and have a large π-electron conjugated system, so that they can be used as electron carriers and have sharp absorption peaks in a specific wavelength region. Attempts have been made to apply to various uses such as electronic materials, optical materials, medical materials and display materials.

  Thus, porphyrin is expected to be applied to a wide range of industrial fields as a functional material in the future. However, there is a problem that the rigid skeleton easily aggregates and the solvent solubility is poor. For example, tetraphenylporphyrin (hereinafter sometimes abbreviated as “TPP”) is useful as a phosphorescent guest molecule in an organic EL device, but has a very low solvent solubility, and therefore forms a film in an organic EL device. However, it had to be formed by a vapor phase film forming method such as vacuum deposition. In general, the wet film-forming method applied to the substrate using a solvent does not require a large-scale vapor deposition apparatus as compared with the vacuum vapor deposition method, can be expected to simplify the manufacturing process steps, and has high material utilization efficiency. There is an advantage that the cost is low and the area of the base material can be increased. Therefore, if the solvent solubility of the porphyrin derivative is improved, there is an advantage that various functional films can be formed by a wet film forming method. Even when a film is not formed, if the solubility of various solvents is improved, it can be applied to applications such as catalysts that function in a solvent.

  As an application of a porphyrin derivative, Patent Document 1 discloses a field effect transistor using an organic semiconductor layer containing an organic semiconductor made of a porphyrin compound having a specific structure. The porphyrin compound disclosed here forms a film by a wet film formation method, but has a special structure in which a bicyclo compound is bonded to a pyrrole ring.

JP 2006-245559 A

  The present invention has been made to solve the above problems, and an object of the present invention is to provide a soluble porphyrin derivative capable of forming a highly stable film by a wet film forming method and a method for producing the same. It is in.

The soluble porphyrin derivative according to the present invention is represented by the following formula (2).

(In Formula (2), each R is independently a substituted or unsubstituted alkyl group having 3 or more carbon atoms.)

Porphyrin derivative of the present invention, as represented by the above following formula (2), because they have a specific substituent R at a specific position, unlike the conventional solvent solubility was very low TPP, solvent solubility In addition, a highly stable film can be formed by a wet film forming method, and the thermal stability is high.
Porphyrin derivatives is coordinated platinum as represented above following formula (2) is, d orbitals between platinum adjacent by [pi-[pi stacking in the porphyrin ring plane can be formed a d-d bonds, Compared to porphyrin derivatives not coordinated with platinum, further improvement in conductivity can be expected.

In soluble porphyrin derivatives according to the present invention, before following formula (2), the substituents R is, when the number of carbon atoms is 7 or more alkyl groups, among others, solubility in a solvent as a readily soluble in n- hexane A high and highly stable amorphous film can be formed. Therefore, in such a case, it is suitable for an application where an amorphous film such as an organic EL is required.

The soluble porphyrin derivative according to the present invention has a high solvent solubility and can form a highly stable film by a wet film forming method, unlike TPP having a very low solvent solubility. Moreover, the soluble porphyrin derivative according to the present invention has higher thermal stability than TPP. Furthermore, the soluble porphyrin derivative according to the present invention can form a crystalline film or an amorphous film by adjusting the carbon number and branching degree of the substituent R, and can be appropriately applied according to the application field. It is.
In addition, among the soluble porphyrin derivatives according to the present invention, the porphyrin derivative coordinated with platinum can form a dd bond between the d orbitals of platinum by π-π stacking in the plane of the porphyrin ring. A further improvement in conductivity can be expected as compared with the case where it is not.
Moreover, according to the manufacturing method which concerns on this invention, the said soluble porphyrin derivative can be obtained easily.

Below, the soluble porphyrin derivative of this invention and its manufacturing method are demonstrated in detail in order.
The first soluble porphyrin derivative according to the present invention is represented by the following general formula (1).

(In Formula (1), each R is independently a substituted or unsubstituted alkyl group having 3 or more carbon atoms.)

  Moreover, the 2nd soluble porphyrin derivative which concerns on this invention is represented by following formula (2).

(In Formula (2), each R is independently a substituted or unsubstituted alkyl group having 3 or more carbon atoms.)

The porphyrin derivative according to the present invention has a specific substituent R at a specific position as represented by the above formula (1) and the above formula (2). In contrast, solvent solubility is high. Therefore, it is possible to form a highly stable film in which aggregation or the like hardly occurs by a wet film forming method. In addition, the porphyrin derivative according to the present invention has higher thermal stability than conventional TPP.
Among them, in the porphyrin derivative in which platinum is coordinated as represented by the above formula (2), adjacent d orbitals of platinum can form a dd bond by π-π stacking in the porphyrin ring plane. In addition, further improvement in conductivity can be expected compared to porphyrin derivatives not coordinated with platinum.

In formula (1), each R is independently a substituted or unsubstituted alkyl group having 3 or more carbon atoms. The alkyl group may contain a cyclic structure in addition to a straight chain or branched chain.
Examples of the unsubstituted alkyl group having 3 or more carbon atoms include an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, and an n-nonyl group. , N-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, etc., straight chain alkyl groups. In addition, an i-propyl group, a sec-butyl group, in which one or more hydrogen atoms other than the terminal of these linear alkyl groups are substituted with an alkyl group such as a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, tert-butyl group, 1-methylbutyl group, 2-methylbutyl group, 1-ethylpropyl group, 2-ethylpropyl group, 1,2-dimethylpropyl, 1,3-dimethylpropyl, 2,3-dimethylpropyl, 1, 1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 4,4-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 1,4- Dimethylbutyl group, 2,3-dimethylbutyl group, 2,4-dimethylbutyl group, 3,4-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 3-ethylbutyl group Group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylpentyl group, 2,2-dimethylpentyl group, 3,3-dimethylpentyl group Group, 4,4-dimethylpentyl group, 5,5-dimethylpentyl group, 1,2-dimethylpentyl group, 1,3-dimethylpentyl group, 1,4-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,4-dimethylpentyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 4-ethylpentyl group, 1-methylhexyl group, 2-methylhexyl Group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1,1-diethylpropyl group, 2,2-diethylpropyl group, 3,3 -Diethylpropyl group, 1,2-diethylpropyl group, 2,3-diethylpropyl group, 1,1-dimethylhexyl group, 2,2-dimethylhexyl group, 3,3-dimethylhexyl group, 4,4-dimethyl Hexyl group, 5,5-dimethylhexyl group, 6,6-dimethylhexyl group, 1,2-dimethylhexyl group, 1,3-dimethylhexyl group, 1,4-dimethylhexyl group, 1,5-dimethylhexyl group 1,6-dimethylhexyl group, 2,3-dimethylhexyl group, 2,4-dimethylhexyl group, 2,5-dimethylhexyl group, 3,4-dimethylhexyl group, 3,5-dimethylhexyl group, 3 , 6-dimethylhexyl group, 4,5-dimethylhexyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl , It can be exemplified 5- ethylhexyl group, a branched alkyl group such as 6-methyl heptyl group. Further, it may be an alkyl group containing a cyclic structure such as cyclohexylmethyl or cyclohexylethyl. Examples of the alkyl group having 3 or more substituted carbon atoms include those in which one or more hydrogen atoms of the alkyl group exemplified above are substituted with a substituent that does not excessively inhibit the effects of the present invention. . For example, one or more hydrogen atoms of an alkyl group are halogen atoms, substituted or unsubstituted aromatic groups, trifluoromethyl groups, cyano groups, nitro groups, alkoxy groups, aryloxy groups, alkylthio groups, dialkylamino groups, and the like. A substituted one can be exemplified.

  Further, the plurality of substituents R present in the soluble porphyrin derivative represented by the above formula (1) or formula (2) according to the present invention may be all the same or different from each other. From the viewpoint of the synthesis of the porphyrin derivative, it is preferable that the plurality of substituents R are all the same.

  By appropriately selecting the substituent R, various properties such as the solubility of the porphyrin derivative according to the present invention in the solvent, the crystallinity / non-crystallinity (amorphous) of the film, and the thermal characteristics such as the thermal decomposition temperature are adjusted. be able to. Therefore, the substituent R can be appropriately selected depending on the field to which the porphyrin derivative of the present invention is applied.

For example, when the substituent R is a linear alkyl group having 3 to 6 carbon atoms, a crystalline film can be easily obtained. Therefore, the substituent R is suitably used for applications requiring a crystalline film such as an organic transistor. It is done.
In addition, when the substituent R is a linear alkyl group having 7 or more carbon atoms, an amorphous film can be easily obtained. For example, an application that requires an amorphous film such as an organic EL element or an organic solar battery. Is preferably used.
Further, when the substituent R is a linear alkyl group, π-π stacking is likely to occur, and in the case of the above formula (2), the bonding between platinum is facilitated.
In addition, when the substituent R is a branched alkyl group, for example, when the substituent R is a 2-ethylhexyl group having 8 carbon atoms, the intermediate between the straight-chain alkyl group having 6 carbon atoms and the straight-chain alkyl group having 7 carbon atoms is used. Thus, it is possible to obtain intermediate characteristics of a linear alkyl group.
Further, when the substituent R is an alkyl group containing a cyclic structure, for example, when the substituent R is a cyclohexylmethyl group having 7 carbon atoms, the Tg or melting point is higher than when the same carbon number is an n-heptyl group having 7 carbon atoms. The heat resistance tends to be improved as compared with a substituent having the same number of carbon atoms, such as an increase of

The carbon number of the substituent R in the soluble porphyrin derivative of the present invention is 3 or more. However, if the carbon number of R is too large, the packing density of the porphyrin derivative in the film is relatively reduced due to the excluded volume effect when the film is formed into a film. It tends to be low, and physical properties such as charge transportability may be inferior. On the other hand, if the carbon number of R is too large, the amorphousness becomes high and purification by recrystallization tends to be difficult. From such a point, the number of carbon atoms of the substituent R is preferably 10 or less.
Especially, when carbon number of all the substituents R in Formula (1) or Formula (2) is 7 or 8, and it is a linear or branched alkyl group, so that it dissolves easily in n-hexane, In addition to the characteristics that the solvent solubility is improved, the disadvantages when the carbon number is too large are less likely to be a problem, which is preferable from the viewpoint of good balance.

  Moreover, the soluble porphyrin derivative according to the present invention has a higher thermal decomposition temperature and higher thermal stability than conventional tetraphenylporphyrin. Thermophysical properties such as the thermal decomposition temperature vary depending on the choice of substituent R in formula (1) or formula (2). Since the soluble porphyrin derivative according to the present invention has a higher thermal decomposition temperature than conventional tetraphenylporphyrins, it can be applied to devices that can be heated at the time of use. In addition, the soluble porphyrin derivative according to the present invention exhibits a glass transition temperature that is not found in conventional tetraphenylporphyrins, and may be amorphous. When the soluble porphyrin derivative according to the present invention is amorphous, there is a merit that a uniform film can be formed by a wet film forming method.

  The method for producing a soluble porphyrin derivative represented by the following formula (1) according to the present invention includes a step of reacting an aldehyde represented by the following formula (3) with pyrrole using trifluoroacetic acid as a catalyst. .

(In Formula (3), each R is independently an alkyl group having 3 or more carbon atoms.)

(In Formula (1), each R is independently an alkyl group having 3 or more carbon atoms.)

  According to the present invention, a soluble porphyrin derivative represented by the following formula (1) can be synthesized with high yield by having the above-described steps. According to the production method of the present invention, the soluble porphyrin derivative represented by the above formula (1) can be easily obtained.

In addition, when propionic acid generally used as an acid catalyst was used for the aldehyde represented by the above formula (3) and pyrrole, the cyclization reaction to porphyrin did not proceed at all. The aldehyde represented by the above formula (3) is presumed to have an increased pKa because an ether substituent is introduced. In addition, when BF ₃ .Et ₂ O, which is a Lewis acid, was used, the reaction progressed and the purification was repeated to obtain the desired product, but the yield was as low as 1%. The reason for this low yield is that when Lewis acid is used, the reaction rate is fast, so it is expected that the polymer reaction is likely to be prioritized over the cyclization reaction. It was considered necessary to select a catalyst.
On the other hand, when trifluoroacetic acid is used as in the production method of the present invention, a cyclization reaction of aldehyde and pyrrole represented by the above formula (3) to porphyrin can be obtained with a yield of about 20%. I found out that

The manufacturing method according to the present invention can be carried out, for example, as follows.
First, 3,5-dihydroxybenzyl alcohol (1 equivalent) and potassium carbonate (2.5 equivalents) in dimethylformamide in the presence of alkyl bromide (2.5-4 equivalents) in a nitrogen or argon atmosphere Stir at 90 ° C. After extraction with chloroform-water, the organic layer was washed twice with water, washed with a saturated aqueous sodium thiosulfate solution, dried over anhydrous magnesium sulfate, filtered and concentrated, and the residue obtained was concentrated on silica gel column chromatography ( For example, 3,5-bisalkoxybenzyl alcohol is obtained by purification with a chromatographic tube: inner diameter 4 cm, length 25 cm, developing solvent: hexane → chloroform.

  A mixture of 3,5-bisalkoxybenzyl alcohol (1 equivalent) and manganese (IV) oxide (4 equivalents) was stirred in chloroform in the presence of anhydrous magnesium sulfate under nitrogen or argon at room temperature for several days. . The residue obtained by concentrating the filtrate after filtration was subjected to silica gel column chromatography (for example, chromatographic tube: inner diameter 4 cm, length 25 cm, developing solvent: chloroform-hexane (volume ratio is 3: 2 or 4: 1)). By separation and purification, 3,5-bis (alkoxy) benzaldehyde is obtained.

A mixture of pyrrole (1 equivalent) and 3,5-bis (alkoxy) benzaldehyde (1 equivalent) was stirred in chloroform (about 0.01 M) at room temperature. This solution was bubbled with argon for 1 hour. Subsequently, trifluoroacetic acid (1.0 to 1.5 equivalents) was added and stirred overnight at room temperature. To this solution, 2,3-dichloro-5,6-dicyanobenzoquinone (1 equivalent) was added and stirred for another 5 hours. Triethylamine (1.5 equivalents) is added and after hydrolysis, the solution is concentrated to give a residue. The resulting residue is passed through silica gel using chloroform as a developing solvent to obtain 5,10,15,20-tetrakis [3,5-bis (alkoxy) phenyl] porphyrin. If necessary, it is further purified by silica gel column chromatography (developing solvent: chloroform-hexane (volume ratio is 3: 2 or 1: 1)) and the like.
The reaction time may be appropriately adjusted and is not particularly limited.

Since the soluble porphyrin derivative according to the present invention has good solvent solubility, it is possible to form a film by a wet film forming method.
In the case of forming a film by a wet film forming method, first, a coating solution containing a soluble porphyrin derivative, a solvent, and other components as required is prepared.
The organic solvent is not particularly limited as long as it dissolves a soluble porphyrin derivative and is appropriately selected depending on the application. For example, when used in electronics, a solvent that does not contain water is preferable and a non-aqueous solvent is preferable from the viewpoint of consistently forming in an inert atmosphere. Non-aqueous solvents include, for example, benzene, toluene, xylene isomers and mixtures thereof, mesitylene, tetralin, p-cymene, cumene, ethylbenzene, diethylbenzene, butylbenzene, chlorobenzene, dichlorobenzene and isomers thereof. Aromatic solvents including mixtures, anisole, phenetol, butylphenyl ether, tetrahydrofuran, 2-butanone, 1,4-dioxane, diethyl ether, diisopropyl ether, diphenyl ether Ether solvents such as dibenzyl ether, diglyme, etc., chloro solvents such as dichloromethane, 1,1-dichloroethane, 1,2-dichloroethane, trichloroethylene, tetrachloroethylene, chloroform, carbon tetrachloride, 1-chloronaphthalene Medium, and cyclohexanone. In addition, the soluble porphyrin derivative according to the present invention can use a non-polar alkane-based solvent such as n-hexane, cyclohexane, and n-pentane as a solvent depending on the selection of the substituent R. As a solvent used, two or more kinds of mixed solvents may be used.
As a coating method for forming a film containing a porphyrin derivative using the above coating solution, a spin coating method, a casting method, a dipping method, a bar coating method, a blade coating method, -The coat method, the gravure coat method, the flexographic printing method, the spray coat method, the ink jet method and the like.

  Since the soluble porphyrin derivative according to the present invention can be dissolved in n-hexane or the like in which the organic compound is relatively hardly soluble, according to the soluble porphyrin derivative according to the present invention, a multilayer film composed of the organic compound is formed by a wet film formation method. Can be formed. For example, if the organic compound in the lower layer is dissolved in an organic solvent such as chloroform but not in n-hexane, the lower layer is formed by a wet film formation method in a chloroform solution, and then a soluble porphyrin derivative is formed on the layer. Even if a coating film is formed by a wet film forming method using the n-hexane solution, the lower layer is not dissolved and mixed by n-hexane.

Since the soluble porphyrin derivative according to the present invention has a large π electron conjugated system, it can be used as an electron carrier and can be widely applied to the electronics field. For example, the organic semiconductor is suitably used for an organic transistor, an organic solar cell, and the like. Further, it is suitably used as an organic layer of an organic light emitting device such as an organic EL element.
Furthermore, since the soluble porphyrin derivative according to the present invention has a sharp absorption peak in a specific wavelength region, etc., in addition to the dye, a photocatalyst utilizing an excited state generated by light absorption, photoradical generation, photovoltaic power Widely applicable to various uses such as electronic materials, optical materials, medical materials, display materials, etc.

  In the following examples, all reagents were obtained using commercially available products. The pyrrole was distilled under reduced pressure and stored under an argon atmosphere. Other reagents were used in the reaction without purification. As silica gel column chromatography at the time of purification, Merca silica gel 60, chromatographic tube: inner diameter 4 cm, length 25 cm was used.

Example 1
A soluble porphyrin derivative (5,10,15,20-tetrakis [3,5-bis (cyclohexylmethyloxy) phenyl] porphyrin) represented by the above formula (1) was produced according to the following scheme.

(1) Synthesis of 3,5-bis (cyclohexylmethyloxy) benzyl alcohol 3,5-dihydroxybenzyl alcohol (6.040 g, 43.100 mmol) and potassium carbonate (14.575 g, 0.105 mol) were added to dimethylformamide (DMF). The mixture was stirred at 90 ° C. in a nitrogen or argon atmosphere in the presence of cyclohexylmethyl bromide (14.8 ml, 0.107 mol) in 40 ml. After extraction with chloroform-water, the organic layer was washed twice with water, washed with a saturated aqueous sodium thiosulfate solution, dried over anhydrous magnesium sulfate, filtered and concentrated, and the residue obtained was concentrated on silica gel column chromatography ( The target product (3,5-bis (cyclohexylmethyloxy) benzyl alcohol, R in formula [A] is cyclohexylmethyl) (solid, 4.450 g, yield) 31.1%).

When ¹ HNMR and ¹³ CNMR of the obtained compound were measured, the following data was obtained.
¹ H NMR (400 MHz, CDCl ₃ , TMS): δ (ppm) 1.00−1.10 (m, 4H, CH ₂ ), 1.15−1.36 (m, 6H, CH ₂ ), 1.69−1.88 (m, 12H, CH ₂ + CH), 6.69 (t, J = 2.0 Hz, 1H, arom.H), 6.98 (d, J = 2.0 Hz, 2H, arom.H), 9.89 (s, 1H, CHO).
¹³ C NMR (100.4 MHz, CDCl ₃ ): δ (ppm) 25.73, 26.45, 29.82, 37.57 (aliphatic), 73.84 (ether), 107.52, 107.98, 138.23, 160.89 (aromatic), 192.18 (aldehyde).

(2) Synthesis of 3,5-bis (cyclohexylmethyloxy) benzaldehyde 3,5-bis (cyclohexylmethyloxy) benzyl alcohol (4.436 g, 13.342 mmol) and manganese (IV) oxide (4.082 g, 46.954 mol) The mixture was stirred in 45 ml of chloroform in the presence of anhydrous magnesium sulfate under nitrogen or argon at room temperature for several days. The residue obtained by concentrating the filtrate after filtration was separated and purified by silica gel column chromatography (developing solvent: chloroform-hexane (3: 2 v / v)) to obtain the target compound (3,5-bis (cyclohexyl). Methyloxy) benzaldehyde, R of formula [B] was cyclohexylmethyl) (solid, 3.576 g, yield 81.1%).

When ¹ HNMR and ¹³ CNMR of the obtained compound were measured, the following data was obtained.
¹ H NMR (400 MHz, CDCl ₃ , TMS): δ (ppm) 1.00−1.10 (m, 4H, CH ₂ ), 1.15−1.36 (m, 6H, CH ₂ ), 1.69−1.88 (m, 12H, CH ₂ + CH), 6.69 (t, J = 2.0 Hz, 1H, arom.H), 6.98 (d, J = 2.0 Hz, 2H, arom.H), 9.89 (s, 1H, CHO).
¹³ C NMR (100.4 MHz, CDCl ₃ ): δ (ppm) 25.73, 26.45, 29.82, 37.57 (aliphatic), 73.84 (ether), 107.52, 107.98, 138.23, 160.89 (aromatic), 192.18 (aldehyde).

(3) Synthesis of 5,10,15,20-tetrakis [3,5-bis (cyclohexylmethyloxy) phenyl] porphyrin Pyrrol (0.55 ml) and 3,5-bis (cyclohexylmethyloxy) benzaldehyde (2.547) g, 7.707 mmol) was stirred in chloroform (700 ml) at room temperature. This solution was bubbled with argon for 1 hour. Subsequently, trifluoroacetic acid (0.86 ml) was added, and the mixture was stirred overnight at room temperature. To this solution was added 2,3-dichloro-5,6-dicyanobenzoquinone (1.801 g, 7.934 mmol), and the mixture was further stirred for 5 hours. After hydrolysis by adding triethylamine (1.7 ml), the solution was concentrated, and the resulting residue was passed through silica gel using chloroform as a developing solvent. Further purification was performed by silica gel column chromatography (developing solvent: chloroform). Finally, by recrystallization from dichloromethane-methanol, the target compound (5,10,15,20-tetrakis [3,5-bis (cyclohexylmethyloxy) phenyl] porphyrin, R of formula [C] (Cyclohexylmethyl) (red purple powder, 0.390 g, yield 13.4%) was obtained.

When ¹ HNMR and MALDI-TOF-MS of the obtained compound were measured, the following data was obtained.
¹ H NMR (400 MHz, CDCl ₃ , TMS): δ (ppm) −2.86 (s, 2H, NH), 1.04-1.36 (m, 40H, CH ₂ ), 1.68−1.93 (m, 48H, CH ₂ + CH), 3.91 (d, J = 6.0 Hz, 16H, ArOCH ₂ ), 6.87 (t, J = 2.2 Hz, 4H, arom.H), 7.36 (d, J = 2.0 Hz, 8H, arom.H), 8.95 (s, 8H, pyrrole H).
MALDI-TOF-MS (no matrix): m / z = 1512.50 (M ⁺ )

(Example 2)
According to the same scheme as in Example 1, 5,10,15,20-tetrakis [3,5-bis (2-ethylhexyloxy) phenyl] porphyrin was produced.

(1) Synthesis of 3,5-bis (2-ethylhexyloxy) benzyl alcohol 3,5-dihydroxybenzyl alcohol (5.000 g, 35.679 mmol) and potassium carbonate (12.328 g, 89.200 mol) were added to dimethylformamide. The mixture was stirred at 90 ° C. in a nitrogen or argon atmosphere in the presence of 2-ethylhexyl bromide (15.5 ml, 89.889 mmol) in 30 ml of (DMF). After extraction with chloroform-water, the organic layer was washed twice with water, washed with a saturated aqueous sodium thiosulfate solution, dried over anhydrous magnesium sulfate, filtered and concentrated, and the residue obtained was concentrated on silica gel column chromatography ( The target product (3,5-bis (2-ethylhexyloxy) benzyl alcohol, R in formula [A] is 2-ethylhexyl) (oil, 8.017 g) Yield 61.6%).

When ¹ HNMR and ¹³ CNMR of the obtained compound were measured, the following data was obtained.
¹ H NMR (400 MHz, CDCl ₃ , TMS): δ (ppm) 0.905 (t, J = 7.0 Hz, 6H, CH ₃ ), 0.93 (t, J = 7.4 Hz, 6H, CH ₃ ), 1.30−1.54 (m, 19H, CH ₃ + CH ₂ ), 1.67−1.76 (m, 2H, CH), 3.83−3.89 (m, 4H, ArOCH ₂ ), 4.36 (q, J = 7.2 Hz, 2H, CH ₂ O) , 6.64 (t, J = 2.2 Hz, 1H, arom.H), 7.16 (d, J = 2.8 Hz, 2H, arom.H)
¹³ C NMR (100.4 MHz, CDCl ₃ ): δ (ppm) 11.10, 14.05, 14.33, 23.03, 23.89, 29.09, 30.55, 39.41 (aliphatic), 61.03, 70.76 (ether), 106.34, 107.59, 132.19, 160.39, 166.57 (aromatic).

(2) Synthesis of 3,5-bis (2-ethylhexyloxy) benzaldehyde 3,5-bis (2-ethylhexyloxy) benzyl alcohol (5.208 g, 14.285 mmol) and manganese (IV) oxide (5.208 g) , 14.285 mol) was stirred in 30 ml of chloroform in the presence of anhydrous magnesium sulfate under nitrogen or argon at room temperature for several days. The residue obtained by concentrating the filtrate after filtration was separated and purified by silica gel column chromatography (developing solvent: chloroform-hexane (1: 1 v / v)) to obtain the target compound (3,5-bis (2 -Ethylhexyloxy) benzaldehyde, R of formula [B] was 2-ethylhexyl) (oil, 4.720 g, yield 91.1%).

When ¹ HNMR and ¹³ CNMR of the obtained compound were measured, the following data was obtained.
¹ H NMR (400 MHz, CDCl ₃ , TMS): δ (ppm) 0.91 (t, J = 6.8 Hz, 6H, CH ₃ ), 0.93 (t, J = 7.2 Hz, 6H, CH ₃ ), 1.30−1.545 (m, 16H, CH ₂ ), 1.69−1.78 (m, 2H, CH), 3.845 (m, 4H, ArOCH ₂ ), 6.71 (t, J = 2.2 Hz, 1H, arom.H), 6.99 (d, J = 2.4 Hz, 2H, arom.H), 9.90 (s, 1H, CHO).
¹³ C NMR (100.4 MHz, CDCl ₃ ): δ (ppm) 11.08, 14.06, 23.01, 23.83, 29.04, 30.48, 39.32 (aliphatic), 70.83 (ether), 107.51, 107.99, 138.25, 160.97 (aromatic), 192.16 ( aldehyde).

(3) Synthesis of 5,10,15,20-tetrakis [3,5-bis (2-ethylhexyloxy) phenyl] porphyrin Pyrrol (0.40 ml) and 3,5-bis (2-ethylhexyloxy) ) A mixture of benzaldehyde (2.020 g, 5.572 mmol) was stirred in chloroform (450 ml) at room temperature. This solution was bubbled with argon for 1 hour. Subsequently, trifluoroacetic acid (0.62 ml) was added, and the mixture was stirred overnight at room temperature. To this solution was added 2,3-dichloro-5,6-dicyanobenzoquinone (1.894 g, 8.343 mmol), and the mixture was further stirred for 5 hours. After hydrolysis by adding triethylamine (1.4 ml), the solution was concentrated, and the resulting residue was passed through silica gel using chloroform as a developing solvent. Further purification was performed by silica gel column chromatography (developing solvent: chloroform-hexane (1: 1 v / v)). Finally, by solidifying under reduced pressure, the target compound (5,10,15,20-tetrakis [3,5-bis (2-ethylhexyloxy) phenyl] porphyrin, R in formula [C] is 2- Ethylhexyl) (red purple viscous solid, 0.477 g, yield 20.9%) was obtained.

When ¹ HNMR and MALDI-TOF-MS of the obtained compound were measured, the following data was obtained.
¹ H NMR (400 MHz, CDCl ₃ , TMS): δ (ppm) −2.82 (s, 2H, NH), 0.88 (t, J = 6.8 Hz, 24H, CH ₃ ), 0.95 (t, J = 7.6 Hz , 24H, CH ₃ ), 1.26−1.62 (m, 64H, CH ₂ ), 1.77−1.83 (m, 8H, CH), 4.00 (d, J = 6.0 Hz, 16H, ArOCH ₂ ), 6.89 (t, J = 2.2 Hz, 4H, arom.H), 7.37 (d, J = 2.0 Hz, 8H, arom.H), 8.97 (s, 8H, pyrrole H).
MALDI-TOF-MS (no matrix): m / z = 1640.574 (M ⁺ )

(Example 3)
According to the same scheme as in Example 1, 5,10,15,20-tetrakis [3,5-bis (octyloxy) phenyl] porphyrin was produced.

(1) Synthesis of 3,5-bis (octyloxy) benzyl alcohol 3,5-dihydroxybenzyl alcohol (7.017 g, 50.072 mmol) and potassium carbonate (17.221 g, 0.125 mol) were added to 65 ml of dimethylformamide (DMF). In the presence of n-octyl bromide (22.0 ml, 0.126 mol), the mixture was stirred at 90 ° C. in a nitrogen or argon atmosphere. After extraction with chloroform-water, the organic layer was washed twice with water, washed with a saturated aqueous sodium thiosulfate solution, dried over anhydrous magnesium sulfate, filtered and concentrated, and the residue obtained was concentrated on silica gel column chromatography ( The target product (3,5-bis (octyloxy) benzyl alcohol, R in formula [A] is n-octyl) (oil, 14.150 g, yield 77.5) was purified by developing solvent: hexane → chloroform. %).

When ¹ HNMR and ¹³ CNMR of the obtained compound were measured, the following data was obtained.
¹ H NMR (400 MHz, CDCl ₃ , TMS): δ (ppm) 0.89 (t, J = 7.2 Hz, 6H, CH ₃ ), 1.24−1.36 (m, 16H, CH ₂ ), 1.40−1.475 (m, 4H, CH ₂ ), 1.64 (t, J = 6.2 Hz, 1H, OH), 1.73−1.80 (m, 4H, CH ₂ ), 3.93 (t, J = 6.6 Hz, 4H, ArOCH ₂ ), 4.62 (d , J = 6.4 Hz, 2H, CH ₂ O), 6.38 (t, J = 2.2 Hz, 1H, arom.H), 6.50 (d, J = 2.4 Hz, 2H, arom.H)
¹³ C NMR (100.4 MHz, CDCl ₃ ): δ (ppm) 14.08, 22.64, 26.04, 29.23, 29.25, 29.33, 31.80 (aliphatic), 65.48, 68.08 (ether), 100.55, 105.05, 143.17, 160.54 (aromatic).

(2) Synthesis of 3,5-bis (octyloxy) benzaldehyde A mixture of 3,5-bis (octyloxy) benzyl alcohol (7.159 g, 19.637 mmol) and manganese (IV) oxide (7.002 g, 80.541 mol) was mixed with chloroform. The mixture was stirred in 45 ml in the presence of anhydrous magnesium sulfate under nitrogen or argon for several days at room temperature. The residue obtained by concentrating the filtrate after filtration was separated and purified by silica gel column chromatography (developing solvent: chloroform-hexane (3: 2 v / v)) to obtain the target compound (3,5-bis (octyloxy). Benzaldehyde, R in formula [B] is n-octyl) (oil, 5.521 g, yield 77.5%).

When ¹ HNMR and ¹³ CNMR of the obtained compound were measured, the following data was obtained.
¹ H NMR (400 MHz, CDCl ₃ , TMS): δ (ppm) 0.89 (t, J = 6.8 Hz, 6H, CH ₃ ), 1.26−1.39 (m, 16H, CH ₂ ), 1.435−1.49 (m, 4H, CH ₂ ), 1.75−1.82 (m, 4H, CH ₂ ), 3.98 (t, J = 6.6 Hz, 4H, ArOCH ₂ ), 6.695 (t, J = 2.6 Hz, 1H, arom.H), 6.98 (d, J = 2.4 Hz, 2H, arom.H), 9.89 (s, 1H, CHO).
¹³ C NMR (100.4 MHz, CDCl ₃ ): δ (ppm) 14.08, 22.64, 25.99, 29.12, 29.21, 29.30, 31.79 (aliphatic), 68.44 (ether), 107.59, 108.02, 138.30, 160.76 (aromatic), 192.10 ( aldehyde).

(3) Synthesis of 5,10,15,20-tetrakis [3,5-bis (octyloxy) phenyl] porphyrin Pyrrol (0.40 ml) and 3,5-bis (octyloxy) benzaldehyde (1.997 g, 5.508 mmol ) Was stirred in chloroform (450 ml) at room temperature. This solution was bubbled with argon for 1 hour. Subsequently, trifluoroacetic acid (0.62 ml) was added, and the mixture was stirred overnight at room temperature. To this solution was added 2,3-dichloro-5,6-dicyanobenzoquinone (1.991 g, 8.771 mmol), and the mixture was further stirred for 5 hours. Triethylamine (1.3 ml) was added and the solution was concentrated after hydrolysis. The residue obtained using chloroform as a developing solvent was passed through silica gel. Further silica gel column chromatography (developing solvent: chloroform-hexane (3: 2 v / v )). Finally, by solidifying under reduced pressure, the target compound (5,10,15,20-tetrakis [3,5-bis (octyloxy) phenyl] porphyrin, R in formula [C] is n-octyl) (red A purple viscous solid, 0.490 g, yield 21.7%) was obtained.

When ¹ HNMR and MALDI-TOF-MS of the obtained compound were measured, the following data was obtained.
¹ H NMR (400 MHz, CDCl ₃ , TMS): δ (ppm) −2.84 (s, 2H, NH), 0.85 (t, J = 6.8 Hz, 24H, CH ₃ ), 1.265−1.375 (m, 64H, CH ₂ ), 1.45−1.505 (m, 16H, CH ₂ ), 1.82-1−1.89 (m, 16H, CH ₂ ), 4.11 (t, J = 6.6 Hz, 16H, ArOCH ₂ ), 6.88 (t, J = 2.2 Hz, 4H, arom.H), 7.36 (d, J = 2.0 Hz, 8H, arom.H), 8.93 (s, 8H, pyrrole H).
MALDI-TOF-MS (no matrix): m / z = 1640.272 (M ⁺ )

Example 4
According to the same scheme as in Example 1, 5,10,15,20-tetrakis [3,5-bis (heptyloxy) phenyl] porphyrin was produced.

(1) Synthesis of 3,5-bis (heptyloxy) benzyl alcohol 3,5-dihydroxybenzyl alcohol (6.017 g, 42.936 mmol) and potassium carbonate (114.906 g, 0.108 mol) were added to 60 ml of dimethylformamide (DMF). In the presence of n-heptyl bromide (20.5 ml, 0.130 mol), the mixture was stirred at 90 ° C. in a nitrogen or argon atmosphere. After extraction with chloroform-water, the organic layer was washed twice with water, washed with a saturated aqueous sodium thiosulfate solution, dried over anhydrous magnesium sulfate, filtered and concentrated, and the residue obtained was concentrated on silica gel column chromatography ( The target product (3,5-bis (heptyloxy) benzyl alcohol, R in formula [A] is n-heptyl) (oil, 9.308 g, yield 64.4) was purified by developing solvent: hexane → chloroform. %).

When ¹ HNMR and ¹³ CNMR of the obtained compound were measured, the following data was obtained.
¹ H NMR (400 MHz, CDCl ₃ , TMS): δ (ppm) 0.89 (t, J = 7.0 Hz, 6H, CH ₃ ), 1.26−1.47 (m, 16H, CH ₂ ), 1.685 (t, J = 6.0 Hz, 1H, OH), 1.73-1.80 (m, 4H, CH ₂ ), 3.93 (t, J = 6.6 Hz, 4H, ArOCH ₂ ), 4.61 (d, J = 6.0 Hz, 2H, CH ₂ O) , 6.37 (t, J = 2.2 Hz, 1H, arom.H), 6.495 (d, J = 2.4 Hz, 2H, arom.H)
¹³ C NMR (100.4 MHz, CDCl ₃ ): δ (ppm) 14.05, 22.59, 26.00, 29.03, 29.25, 31.77 (aliphatic), 65.46, 68.07 (ether), 100.59, 105.07, 143.19, 160.55 (aromatic).

(2) Synthesis of 3,5-bis (heptyloxy) benzaldehyde A mixture of 3,5-bis (heptyloxy) benzyl alcohol (9.308 g, 27.660 mmol) and manganese (IV) oxide (9.726 g, 0.112 mol) in chloroform The mixture was stirred in 60 ml in the presence of anhydrous magnesium sulfate under nitrogen or argon at room temperature for several days. The residue obtained by concentrating the filtrate after filtration was separated and purified by silica gel column chromatography (developing solvent: chloroform-hexane (3: 2 v / v)) to obtain the target compound (3,5-bis (heptyloxy). Benzaldehyde, R of formula [B] is n-heptyl) (oil, 7.127 g, yield 77.0%).

When ¹ HNMR and ¹³ CNMR of the obtained compound were measured, the following data was obtained.
¹ H NMR (400 MHz, CDCl ₃ , TMS): δ (ppm) 0.90 (t, J = 7.2 Hz, 6H, CH ₃ ), 1.285−1.49 (m, 16H, CH ₂ ), 1.75−1.82 (m, 4H, CH ₂ ), 3.98 (t, J = 6.4 Hz, 4H, ArOCH ₂ ), 6.69 (t, J = 2.2 Hz, 1H, arom.H), 6.98 (d, J = 2.4 Hz, 2H, arom. H), 9.89 (s, 1H, CHO).
¹³ C NMR (100.4 MHz, CDCl ₃ ): δ (ppm) 14.05, 22.58, 25.95, 29.00, 29.12, 31.75 (aliphatic), 68.44 (ether), 107.60, 108.04, 138.32, 160.77 (aromatic), 192.06 (aldehyde) .

(3) Synthesis of 5,10,15,20-tetrakis [3,5-bis (heptyloxy) phenyl] porphyrin Pyrrol (0.40 ml) and 3,5-bis (heptyloxy) benzaldehyde (1.638 g, 4.897 mmol) ) Was stirred in chloroform (450 ml) at room temperature. This solution was bubbled with argon for 1 hour. Subsequently, trifluoroacetic acid (0.54 ml) was added, and the mixture was stirred overnight at room temperature. To this solution was added 2,3-dichloro-5,6-dicyanobenzoquinone (1.098 g, 4.837 mmol), and the mixture was further stirred for 5 hours. After hydrolysis by adding triethylamine (1.1 ml), the solution was concentrated, and the resulting residue was passed through silica gel using chloroform as a developing solvent. Further purification was performed by silica gel column chromatography (developing solvent: chloroform-hexane (1: 1 v / v)). Finally, by recrystallization from dichloromethane-methanol, the target compound (5,10,15,20-tetrakis [3,5-bis (heptyloxy) phenyl] porphyrin, R in the formula [C] is n- (Heptyl) (red purple powder, 0.228 g, yield 12.2%).

When ¹ HNMR and MALDI-TOF-MS of the obtained compound were measured, the following data was obtained.
¹ H NMR (400 MHz, CDCl ₃ , TMS): δ (ppm) −2.84 (s, 2H, NH), 0.865 (t, J = 6.8 Hz, 24H, CH ₃ ), 1.25−1.40 (m, 48H, CH ₂ ), 1.45−1.53 (m, 16H, CH ₂ ), 1.82-1−1.89 (m, 16H, CH ₂ ), 4.11 (t, J = 6.6 Hz, 16H, ArOCH ₂ ), 6.88 (t, J = 2.2 Hz, 4H, arom.H), 7.36 (d, J = 2.4 Hz, 8H, arom.H), 8.93 (s, 8H, pyrrole H).
MALDI-TOF-MS (no matrix): m / z = 1526.570 (M ⁺ )

(Example 5)
According to the same scheme as in Example 1, 5,10,15,20-tetrakis [3,5-bis (hexyloxy) phenyl] porphyrin was produced.

(1) Synthesis of 3,5-bis (hexyloxy) benzyl alcohol 3,5-dihydroxybenzyl alcohol (7.004 g, 49.979 mmol) and potassium carbonate (17.266 g, 0.125 mol) were added to 60 ml of dimethylformamide (DMF). In the presence of n-hexyl bromide (18.0 ml, 0.128 mol), the mixture was stirred at 90 ° C. in a nitrogen or argon atmosphere. After extraction with chloroform-water, the organic layer was washed twice with water, washed with a saturated aqueous sodium thiosulfate solution, dried over anhydrous magnesium sulfate, filtered and concentrated, and the residue obtained was concentrated on silica gel column chromatography ( The target product (3,5-bis (heptyloxy) benzyl alcohol, R in formula [A] is n-hexyl) (oil, 10.455 g, yield 67.8) was purified by developing solvent: hexane → chloroform. %).

When ¹ HNMR and ¹³ CNMR of the obtained compound were measured, the following data was obtained.
¹ H NMR (400 MHz, CDCl ₃ , TMS): δ (ppm) 0.90 (t, J = 7.2 Hz, 6H, CH ₃ ), 1.31-1.35 (m, 8H, CH ₂ ), 1.41-1.48 (m, 4H, CH ₂ ), 1.71 (t, J = 6.0 Hz, 1H, OH), 1.73−1.80 (m, 4H, CH ₂ ), 3.93 (t, J = 6.6 Hz, 4H, ArOCH ₂ ), 4.61 (d , J = 6.0 Hz, 2H, CH ₂ O), 6.375 (t, J = 2.6 Hz, 1H, arom.H), 6.50 (d, J = 2.4 Hz, 2H, arom.H)
¹³ C NMR (100.4 MHz, CDCl ₃ ): δ (ppm) 14.01, 22.59, 25.70, 29.21, 31.56 (aliphatic), 65.45, 68.06 (ether), 100.55, 105.05, 143.18, 160.53 (aromatic).

(2) Synthesis of 3,5-bis (hexyloxy) benzaldehyde A mixture of 3,5-bis (hexyloxy) benzyl alcohol (10.437 g, 33.836 mmol) and manganese (IV) oxide (13.314 g, 0.153 mol) was mixed with chloroform. The mixture was stirred in 60 ml in the presence of anhydrous magnesium sulfate under nitrogen or argon at room temperature for several days. The residue obtained by concentrating the filtrate after filtration was separated and purified by silica gel column chromatography (developing solvent: chloroform-hexane (3: 2 v / v)) to obtain the target compound (3,5-bis (hexyloxy). Benzaldehyde, R in formula [B] is n-hexyl) (oil, 9.420 g, yield 90.9%).

When ¹ HNMR and ¹³ CNMR of the obtained compound were measured, the following data was obtained.
¹ H NMR (400 MHz, CDCl ₃ , TMS): δ (ppm) 0.91 (t, J = 7.0 Hz, 6H, CH ₃ ), 1.32−1.365 (m, 8H, CH ₂ ), 1.42−1.50 (m, 4H, CH ₂ ), 1.75−1.82 (m, 4H, CH ₂ ), 3.99 (t, J = 6.6 Hz, 4H, ArOCH ₂ ), 6.70 (t, J = 2.4 Hz, 1H, arom.H), 6.98 (d, J = 2.4 Hz, 2H, arom.H), 9.89 (s, 1H, CHO).
¹³ C NMR (100.4 MHz, CDCl ₃ ): δ (ppm) 13.99, 22.57, 25.66, 29.08, 31.52 (aliphatic), 68.44 (ether), 107.59, 108.03, 138.32, 160.76 (aromatic), 192.07 (aldehyde).

(3) Synthesis of 5,10,15,20-tetrakis [3,5-bis (hexyloxy) phenyl] porphyrin Pyrrol (0.35 ml) and 3,5-bis (hexyloxy) benzaldehyde (1.515 g, 4.911 mmol ) Was stirred in chloroform (450 ml) at room temperature. This solution was bubbled with argon for 1 hour. Subsequently, trifluoroacetic acid (0.54 ml) was added, and the mixture was stirred overnight at room temperature. To this solution was added 2,3-dichloro-5,6-dicyanobenzoquinone (1.143 g, 5.035 mmol), and the mixture was further stirred for 5 hours. After hydrolysis by adding triethylamine (1.2 ml), the solution was concentrated, and the resulting residue was passed through silica gel using chloroform as a developing solvent. The product was further purified by silica gel column chromatography (developing solvent: chloroform-hexane (3: 2 v / v)). Finally, by recrystallization from dichloromethane-methanol, the target compound (5,10,15,20-tetrakis [3,5-bis (hexyloxy) phenyl] porphyrin, R of formula [C] is n- (Hexyl) (red purple powder, 0.351 g, yield 20.1%).

When ¹ HNMR and MALDI-TOF-MS of the obtained compound were measured, the following data was obtained.
¹ H NMR (400 MHz, CDCl ₃ , TMS): δ (ppm) −2.84 (s, 2H, NH), 0.88 (t, J = 7.2 Hz, 24H, CH ₃ ), 1.29−1.38 (m, 32H, CH ₂ ), 1.46−1.52 (m, 16H, CH ₂ ), 1.82-1-1.89 (m, 16H, CH ₂ ), 4.11 (t, J = 6.6 Hz, 16H, ArOCH ₂ ), 6.88 (t, J = 2.6 Hz, 4H, arom.H), 7.37 (d, J = 2.0 Hz, 8H, arom.H), 8.94 (s, 8H, pyrrole H).
MALDI-TOF-MS (no matrix): m / z = 1526.570 (M ⁺ )

(Example 6)
According to the same scheme as in Example 1, 5,10,15,20-tetrakis [3,5-bis (pentyloxy) phenyl] porphyrin was produced.

(1) Synthesis of 3,5-bis (pentyloxy) benzyl alcohol 3,5-dihydroxybenzyl alcohol (7.016 g, 50.065 mmol) and potassium carbonate (17.277 g, 0.125 mol) were added to 60 ml of dimethylformamide (DMF). The mixture was stirred at 90 ° C. in a nitrogen or argon atmosphere in the presence of n-pentyl bromide (18.5 ml, 0.149 mol). After extraction with chloroform-water, the organic layer was washed twice with water, washed with a saturated aqueous sodium thiosulfate solution, dried over anhydrous magnesium sulfate, filtered and concentrated, and the residue obtained was concentrated on silica gel column chromatography ( The target product (3,5-bis (pentyloxy) benzyl alcohol, R in formula [A] is n-pentyl) (oil, 9.880 g, yield 70.4) %).

When ¹ HNMR and ¹³ CNMR of the obtained compound were measured, the following data was obtained.
¹ H NMR (400 MHz, CDCl ₃ , TMS): δ (ppm) 0.93 (t, J = 7.0 Hz, 6H, CH ₃ ), 1.33-1.47 (m, 8H, CH ₂ ), 1.66 (t, J = 6.0 Hz, 1H, OH), 1.74−1.81 (m, 4H, CH ₂ ), 3.93 (t, J = 6.6 Hz, 4H, ArOCH ₂ ), 4.61 (d, J = 5.6 Hz, 2H, CH ₂ O) , 6.38 (t, J = 2.4 Hz, 1H, arom.H), 6.50 (d, J = 2.0 Hz, 2H, arom.H)
¹³ C NMR (100.4 MHz, CDCl ₃ ): δ (ppm) 13.99, 22.43, 28.20, 28.945 (aliphatic), 65.47, 68.06 (ether), 100.59, 105.08, 143.19, 160.555 (aromatic).

(2) Synthesis of 3,5-bis (pentyloxy) benzaldehyde A mixture of 3,5-bis (pentyloxy) benzyl alcohol (9.873 g, 35.209 mmol) and manganese (IV) oxide (12.304 g, 0.142 mol) was mixed with chloroform. The mixture was stirred in 60 ml in the presence of anhydrous magnesium sulfate under nitrogen or argon at room temperature for several days. The residue obtained by concentrating the filtrate after filtration was separated and purified by silica gel column chromatography (developing solvent: chloroform-hexane (3: 2 v / v)) to obtain the target compound (3,5-bis (pentyloxy) Benzaldehyde, R of formula [B] was n-pentyl) (oil, 8.012 g, yield 81.7%) was obtained.

When ¹ HNMR and ¹³ CNMR of the obtained compound were measured, the following data was obtained.
¹ H NMR (400 MHz, CDCl ₃ , TMS): δ (ppm) 0.94 (t, J = 7.2 Hz, 6H, CH ₃ ), 1.34−1.48 (m, 8H, CH ₂ ), 1.76−1.83 (m, 4H, CH ₂ ), 3.99 (t, J = 6.6 Hz, 4H, ArOCH ₂ ), 6.70 (t, J = 2.4 Hz, 1H, arom.H), 6.98 (d, J = 2.4 Hz, 2H, arom. H), 9.89 (s, 1H, CHO).
¹³ C NMR (100.4 MHz, CDCl ₃ ): δ (ppm) 13.97, 22.40, 28.14, 28.81 (aliphatic), 68.43 (ether), 107.60, 108.04, 138.325, 160.77 (aromatic), 192.06 (aldehyde).

(3) Synthesis of 5,10,15,20-tetrakis [3,5-bis (pentyloxy) phenyl] porphyrin Pyrrol (0.40 ml) and 3,5-bis (pentyloxy) benzaldehyde (1.534 g, 5.510 mmol) ) Was stirred in chloroform (500 ml) at room temperature. This solution was bubbled with argon for 1 hour. Subsequently, trifluoroacetic acid (0.60 ml) was added, and the mixture was stirred overnight at room temperature. To this solution was added 2,3-dichloro-5,6-dicyanobenzoquinone (1.280 g, 5.639 mmol), and the mixture was further stirred for 5 hours. After hydrolysis by adding triethylamine (1.2 ml), the solution was concentrated, and the resulting residue was passed through silica gel using chloroform as a developing solvent. The product was further purified by silica gel column chromatography (developing solvent: chloroform-hexane (3: 2 v / v)). Finally, by recrystallization from dichloromethane-methanol, the target compound (5,10,15,20-tetrakis [3,5-bis (pentyloxy) phenyl] porphyrin, R of formula [C] is n- Pentyl) (red purple crystals, 0.334 g, yield 18.6%).

When ¹ HNMR and MALDI-TOF-MS of the obtained compound were measured, the following data was obtained.
¹ H NMR (400 MHz, CDCl ₃ , TMS): δ (ppm) −2.83 (s, 2H, NH), 0.93 (t, J = 7.4 Hz, 24H, CH ₃ ), 1.35−1.53 (m, 32H, CH ₂ ), 1.84−1.91 (m, 16H, CH ₂ ), 4.12 (t, J = 6.6 Hz, 16H, ArOCH ₂ ), 6.89 (t, J = 2.6 Hz, 4H, arom.H), 7.37 (d , J = 2.4 Hz, 8H, arom.H), 8.94 (s, 8H, pyrrole H).
MALDI-TOF-MS (no matrix): m / z = 1303.791 (M ⁺ )

(Example 7)
According to the same scheme as in Example 1, 5,10,15,20-tetrakis [3,5-dibutoxyphenyl] porphyrin was produced.

(1) Synthesis of 3,5-dibutoxybenzyl alcohol 3,5-dihydroxybenzyl alcohol (7.008 g, 50.007 mmol) and potassium carbonate (17.288 g, 0.125 mol) in 60 ml of dimethylformamide (DMF) The mixture was stirred at 90 ° C. in a nitrogen or argon atmosphere in the presence of n-butyl bromide (14.0 ml, 0.131 mol). After extraction with chloroform-water, the organic layer was washed twice with water, washed with a saturated aqueous sodium thiosulfate solution, dried over anhydrous magnesium sulfate, filtered and concentrated, and the residue obtained was concentrated on silica gel column chromatography ( The target product (3,5-dibutoxybenzyl alcohol, R of formula [A] is n-butyl) (oil, 5.268 g, yield 41.7%) by purifying with developing solvent: hexane → chloroform Got.

When ¹ HNMR and ¹³ CNMR of the obtained compound were measured, the following data was obtained.
¹ H NMR (400 MHz, CDCl ₃ , TMS): δ (ppm) 0.90 (t, J = 7.2 Hz, 6H, CH ₃ ), 1.31-1.35 (m, 8H, CH ₂ ), 1.41-1.48 (m, 4H, CH ₂ ), 1.71 (t, J = 6.0 Hz, 1H, OH), 1.73−1.80 (m, 4H, CH ₂ ), 3.93 (t, J = 6.6 Hz, 4H, ArOCH ₂ ), 4.61 (d , J = 6.0 Hz, 2H, CH ₂ O), 6.375 (t, J = 2.6 Hz, 1H, arom.H), 6.50 (d, J = 2.4 Hz, 2H, arom.H)
¹³ C NMR (100.4 MHz, CDCl ₃ ): δ (ppm) 14.01, 22.59, 25.70, 29.21, 31.56 (aliphatic), 65.45, 68.06 (ether), 100.55, 105.05, 143.18, 160.53 (aromatic).

(2) Synthesis of 3,5-dibutoxybenzaldehyde A mixture of 3,5-dibutoxybenzyl alcohol (5.268 g, 20.875 mmol) and manganese (IV) oxide (7.259 g, 83.502 mmol) was anhydrous in 50 ml of chloroform. The mixture was stirred for several days at room temperature under nitrogen or argon in the presence of magnesium sulfate. The residue obtained by concentrating the filtrate after filtration was separated and purified by silica gel column chromatography (developing solvent: chloroform-hexane (3: 2 v / v)) to obtain the target compound (3,5-dibutoxybenzaldehyde. , R in formula [B] was n-butyl) (oil, 4.405 g, yield 84.3%).

When ¹ HNMR and ¹³ CNMR of the obtained compound were measured, the following data was obtained.
¹ H NMR (400 MHz, CDCl ₃ , TMS): δ (ppm) 0.98 (t, J = 7.4 Hz, 6H, CH ₃ ), 1.45−1.54 (m, 4H, CH ₂ ), 3.995 (t, J = 6.4 Hz, 4H, ArOCH ₂ ), 6.70 (t, J = 2.2 Hz, 1H, arom.H), 6.98 (d, J = 2.4 Hz, 2H, arom.H), 9.89 (s, 1H, CHO).
¹³ C NMR (100.4 MHz, CDCl ₃ ): δ (ppm) 13.775, 19.18, 31.15 (aliphatic), 68.115 (ether), 107.59, 108.03, 138.32, 160.77 (aromatic), 192.05 (aldehyde).

(3) Synthesis of 5,10,15,20-tetrakis [3,5-dibutoxyphenyl] porphyrin of pyrrole (0.40 ml) and 3,5-bis (butyroxy) benzaldehyde (1.260 g, 5.033 mmol) The mixture was stirred in chloroform (500 ml) at room temperature. This solution was bubbled with argon for 1 hour. Subsequently, trifluoroacetic acid (0.56 ml) was added, and the mixture was stirred overnight at room temperature. To this solution was added 2,3-dichloro-5,6-dicyanobenzoquinone (1.153 g, 5.079 mmol), and the mixture was further stirred for 5 hours. After hydrolysis by adding triethylamine (1.2 ml), the solution was concentrated, and the resulting residue was passed through silica gel using chloroform as a developing solvent. Subsequently, the target compound (5,10,15,20-tetrakis [3,5-dibutoxyphenyl] porphyrin, R in the formula [C] is n-butyl) by recrystallization from dichloromethane-methanol. (Red purple crystals, 0.319 g, 21.3% yield) was obtained.

When ¹ HNMR and MALDI-TOF-MS of the obtained compound were measured, the following data was obtained.
¹ H NMR (400 MHz, CDCl ₃ , TMS): δ (ppm) −2.84 (s, 2H, NH), 0.98 (t, J = 7.4 Hz, 24H, CH ₃ ), 1.49−1.58 (m, 16H, CH ₂ ), 1.81-1.88 (m, 16H, CH ₂ ), 4.12 (t, J = 6.6 Hz, 16H, ArOCH ₂ ), 6.88 (t, J = 2.2 Hz, 4H, arom.H), 7.37 (d , J = 2.4 Hz, 8H, arom.H), 8.94 (s, 8H, pyrrole H).
MALDI-TOF-MS (no matrix): m / z = 1189.258 (M ⁺ )

(Example 8)
According to the same scheme as in Example 1, 5,10,15,20-tetrakis [3,5-bis (propoxy) phenyl] porphyrin was produced.

(1) Synthesis of 3,5-bis (propoxy) benzyl alcohol 3,5-dihydroxybenzyl alcohol (7.023 g, 50.115 mmol) and potassium carbonate (17.305 g, 0.125 mol) were added to 60 ml of dimethylformamide (DMF). In the presence of n-propyl bromide (18.5 ml, 0.111 mol), the mixture was stirred at 90 ° C. in a nitrogen or argon atmosphere. After extraction with chloroform-water, the organic layer was washed twice with water, washed with a saturated aqueous sodium thiosulfate solution, dried over anhydrous magnesium sulfate, filtered and concentrated, and the residue obtained was concentrated on silica gel column chromatography ( The target product (3,5-bis (propoxy) pentyl alcohol, R in formula [A] is n-propyl) (solid, 4.903 g, yield 43.6) %).

When ¹ HNMR and ¹³ CNMR of the obtained compound were measured, the following data was obtained.
¹ H NMR (400 MHz, CDCl ₃ , TMS): δ (ppm) 1.02 (t, J = 7.4 Hz, 6H, CH ₃ ), 1.74 (t, J = 6.2 Hz, 1H, OH), 1.75−1.84 ( m, 4H, CH ₂ ), 3.90 (t, J = 6.6 Hz, 4H, ArOCH ₂ ), 4.61 (d, J = 6.0 Hz, 2H, CH ₂ O), 6.38 (t, J = 2.4 Hz, 1H, arom.H), 6.50 (d, J = 2.0 Hz, 2H, arom.H)
¹³ C NMR (100.4 MHz, CDCl ₃ ): δ (ppm) 10.49, 22.55 (aliphatic), 65.42, 69.56 (ether), 100.57, 105.07, 143.19, 160.51 (aromatic).

(2) Synthesis of 3,5-bis (propoxy) benzaldehyde A mixture of 3,5-bis (propoxy) benzyl alcohol (4.888 g, 21.792 mmol) and manganese (IV) oxide (7.703 g, 88.604 mmol) was mixed with chloroform. The mixture was stirred in 50 ml in the presence of anhydrous magnesium sulfate under nitrogen or argon at room temperature for several days. After filtration, the residue obtained by concentrating the filtrate is separated and purified by silica gel column chromatography (developing solvent: chloroform-hexane (3: 2 v / v)) to obtain the target compound (3,5-bis (propoxy) Benzaldehyde, R of formula [B] was n-propyl) (oil, 4.201 g, yield 86.7%) was obtained.

When ¹ HNMR and ¹³ CNMR of the obtained compound were measured, the following data was obtained.
¹ H NMR (400 MHz, CDCl ₃ , TMS): δ (ppm) 1.04 (t, J = 7.2 Hz, 6H, CH ₃ ), 1.78−1.865 (m, 4H, CH ₂ ), 3.96 (t, J = 6.6 Hz, 4H, ArOCH ₂ ), 6.71 (t, J = 2.2 Hz, 1H, arom.H), 6.99 (d, J = 2.0 Hz, 2H, arom.H), 9.89 (s, 1H, CHO).
¹³ C NMR (100.4 MHz, CDCl ₃ ): δ (ppm) 10.44, 22.45 (aliphatic), 69.91 (ether), 107.60, 108.04, 138.32, 160.75 (aromatic), 192.05 (aldehyde).

(3) Synthesis of 5,10,15,20-tetrakis [3,5-bis (propoxy) phenyl] porphyrin Pyrrol (0.40 ml) and 3,5-bis (propoxy) benzaldehyde (1.108 g, 4.985 mmol) ) Was stirred in chloroform (500 ml) at room temperature. This solution was bubbled with argon for 1 hour. Subsequently, trifluoroacetic acid (0.56 ml) was added, and the mixture was stirred overnight at room temperature. To this solution was added 2,3-dichloro-5,6-dicyanobenzoquinone (1.139 g, 5.017 mmol), and the mixture was further stirred for 5 hours. After hydrolysis by adding triethylamine (1.1 ml), the solution was concentrated, and the resulting residue was passed through silica gel using chloroform as a developing solvent. Further purification was performed by silica gel column chromatography (developing solvent: chloroform). Finally, by recrystallization from dichloromethane-methanol, the target compound (5,10,15,20-tetrakis [3,5-bis (propoxy) phenyl] porphyrin, R in the formula [C] is n- Propyl) (red purple crystals, 0.208 g, yield 15.5%).

When ¹ HNMR and MALDI-TOF-MS of the obtained compound were measured, the following data was obtained.
¹ H NMR (400 MHz, CDCl ₃ , TMS): δ (ppm) −2.835 (s, 2H, NH), 1.07 (t, J = 7.2 Hz, 24H, CH ₃ ), 1.84−1.93 (m, 16H, CH ₂ ), 4.08 (t, J = 6.6 Hz, 16H, ArOCH ₂ ), 6.89 (t, J = 2.2 Hz, 4H, arom.H), 7.37 (d, J = 2.0 Hz, 8H, arom.H) , 8.94 (s, 8H, pyrrole H).
MALDI-TOF-MS (no matrix): m / z = 1077.691 (M ⁺ )

Example 9
According to the following scheme, a soluble porphyrin derivative represented by the above formula (2) (5,10,15,20-tetrakis [3,5-bis (cyclohexylmethyloxy) phenyl] porphyrin platinum (II)) was produced. .

  A mixture of 5,10,15,20-tetrakis [3,5-bis (cyclohexylmethyloxy) phenyl] porphyrin (0.152 g, 100.521 μmol) and platinum (II) chloride (0.131 g, 0.492 mmol) was added to nitrogen or argon. Under an atmosphere, the mixture was refluxed for 9 hours in 30 ml of benzonitrile. After cooling, benzonitrile was distilled off, and the resulting residue was purified by silica gel column chromatography (developing solvent: chloroform), followed by recrystallization from dichloromethane-methanol to obtain the desired product (5, 10, 15, 20-tetrakis [3,5-bis (cyclohexylmethyloxy) phenyl] porphyrin platinum (II), R in formula [D] was cyclohexylmethyl) (orange powder, 0.155 g, yield 90.4%).

When ¹ HNMR, ¹³ CNMR, and MALDI-TOF-MS of the obtained compound were measured, the following data was obtained.
¹ H NMR (400 MHz, CDCl ₃ , TMS): δ (ppm) 1.03-1.35 (m, 40H, CH ₂ ), 1.665-1.92 (m, 48H, CH ₂ + CH), 3.89 (d, J = 5.6 Hz, 16H, ArOCH ₂ ), 6.85 (t, J = 2.0 Hz, 4H, arom. H), 7.29 (d, J = 2.4 Hz, 8H, arom. H), 8.85 (s, 8H, pyrrole H).
¹³ C NMR (100.4 MHz, CDCl ₃ ): δ (ppm) 25.815, 26.52, 29.95, 37.81 (aliphatic), 73.81 (ether), 101.24, 113.54, 122.14, 130.63, 140.60, 143.05, 158.62 (aromatic).
MALDI-TOF-MS (no matrix): m / z = 1705.42 (M ⁺ )

(Example 10)
In the same manner as in Example 9, the soluble porphyrin derivative represented by the above formula (2) (5,10,15,20-tetrakis [3,5-bis (2-ethylhexyloxy) phenyl] porphyrin platinum (II) ) Was manufactured.

  A mixture of 5,10,15,20-tetrakis [3,5-bis (2-ethylhexyloxy) phenyl] porphyrin (0.160 g, 97.533 μmol) and platinum (II) chloride (0.123 g, 0.462 mmol) was added to nitrogen. Alternatively, the mixture was heated to reflux for 9 hours in 30 ml of benzonitrile under an argon atmosphere. After cooling, benzonitrile was distilled off, and the resulting residue was purified by silica gel column chromatography (developing solvent: chloroform), followed by recrystallization from dichloromethane-methanol to obtain the desired product (5, 10, 15, 20-tetrakis [3,5-bis (2-ethylhexyloxy) phenyl] porphyrin platinum (II), R in formula [D] was 2-ethylhexyl) (orange solid, 0.156 g, yield 87.2%) was obtained. .

When ¹ HNMR, ¹³ CNMR, and MALDI-TOF-MS of the obtained compound were measured, the following data was obtained.
¹ H NMR (400 MHz, CDCl ₃ , TMS): δ (ppm) 0.88 (t, J = 6.8 Hz, 24H, CH ₃ ), 0.94 (t, J = 7.6 Hz, 24H, CH ₃ ), 1.25−1.60 (m, 64H, CH ₂ ), 1.76−1.82 (m, 8H, CH), 3.975 (d, J = 6.0 Hz, 16H, ArOCH ₂ ), 6.86 (t, J = 2.2 Hz, 4H, arom.H) 7.30 (d, J = 2.0 Hz, 8H, arom. H), 8.87 (s, 8H, pyrrole H).
¹³ C NMR (100.4 MHz, CDCl ₃ ): δ (ppm) 11.15, 14.06, 23.04, 23.93, 29.11, 30.58, 39.52 (aliphatic), 70.92 (ether), 101.295, 113.55, 122.175, 130.64, 140.62, 143.04, 158.70 (aromatic).
MALDI-TOF-MS (no matrix): m / z = 1833.392 (M ⁺ )

(Example 11)
In the same manner as in Example 9, a soluble porphyrin derivative (5,10,15,20-tetrakis [3,5-bis (octyloxy) phenyl] porphyrin platinum (II)) represented by the above formula (2) was produced. .

  A mixture of 5,10,15,20-tetrakis [3,5-bis (octyloxy) phenyl] porphyrin (0.153 g, 93.266 μmol) and platinum (II) chloride (0.136 g, 0.511 mmol) under nitrogen or argon atmosphere The mixture was heated to reflux in 30 ml of benzonitrile for 9 hours. After cooling, benzonitrile was distilled off, and the resulting residue was purified by silica gel column chromatography (developing solvent: chloroform) to obtain the desired product (5,10,15,20-tetrakis [3,5-bis (octyloxy). ) Phenyl] porphyrin platinum (II), R in formula [D] is n-octyl) (orange solid, 0.168 g, yield 98.2%).

When ¹ HNMR, ¹³ CNMR, and MALDI-TOF-MS of the obtained compound were measured, the following data was obtained.
¹ H NMR (400 MHz, CDCl ₃ , TMS): δ (ppm) 0.85 (t, J = 6.8 Hz, 24H, CH ₃ ), 1.22-1.39 (m, 64H, CH ₂ ), 1.43-1.54 (m, 16H, CH ₂ ), 1.81-1.88 (m, 16H, CH ₂ ), 4.09 (t, J = 6.6 Hz, 16H, ArOCH ₂ ), 6.86 (t, J = 2.2 Hz, 4H, arom.H), 7.29 (d, J = 2.4 Hz, 8H, arom. H), 8.84 (s, 8H, pyrrole H).
¹³ C NMR (100.4 MHz, CDCl ₃ ): δ (ppm) 14.06, 22.64, 26.11, 29.235, 29.39, 29.72, 31.81 (aliphatic), 68.42 (ether), 101.325, 113.65, 122.13, 130.65, 140.64, 143.11, 158.50 (aromatic).
MALDI-TOF-MS (no matrix): m / z = 1833.903 (M ⁺ )

(Example 12)
In the same manner as in Example 9, a soluble porphyrin derivative (5,10,15,20-tetrakis [3,5-bis (heptyloxy) phenyl] porphyrin platinum (II)) represented by the above formula (2) was produced. .

  A mixture of 5,10,15,20-tetrakis [3,5-bis (heptyloxy) phenyl] porphyrin (0.152 g, 99.460 μmol) and platinum (II) chloride (0.122 g, 0.459 mmol) under nitrogen or argon atmosphere The mixture was heated to reflux in 30 ml of benzonitrile for 9 hours. After cooling, benzonitrile was distilled off, and the resulting residue was purified by silica gel column chromatography (developing solvent: chloroform), followed by recrystallization from dichloromethane-methanol to obtain the desired product (5, 10, 15, 20-tetrakis [3,5-bis (heptyloxy) phenyl] porphyrin platinum (II), R in formula [D] was n-heptyl) (orange solid, 0.154 g, yield 90.0%) was obtained.

When ¹ HNMR, ¹³ CNMR, and MALDI-TOF-MS of the obtained compound were measured, the following data was obtained.
¹ H NMR (400 MHz, CDCl ₃ , TMS): δ (ppm) 0.86 (t, J = 6.8 Hz, 24H, CH ₃ ), 1.26−1.51 (m, 48H, CH ₂ ), 1.81-1.88 (m, 16H, CH ₂ ), 4.09 (t, J = 6.6 Hz, 16H, ArOCH ₂ ), 6.86 (t, J = 2.2 Hz, 4H, arom.H), 7.295 (d, J = 2.4 Hz, 8H, arom. H), 8.84 (s, 8H, pyrrole H).
¹³ C NMR (100.4 MHz, CDCl ₃ ): δ (ppm) 14.05, 22.58, 26.05, 29.08, 29.37, 31.77 (aliphatic), 68.39 (ether), 101.30, 113.63, 122.11, 130.63, 140.62, 143.09, 158.48 (aromatic ).
MALDI-TOF-MS (no matrix): m / z = 1722.270 (M ⁺ )

(Example 13)
In the same manner as in Example 9, a soluble porphyrin derivative (5,10,15,20-tetrakis [3,5-bis (hexyloxy) phenyl] porphyrin platinum (II)) represented by the above formula (2) was produced. .

  A mixture of 5,10,15,20-tetrakis [3,5-bis (hexyloxy) phenyl] porphyrin (0.152 g, 99.460 μmol) and platinum (II) chloride (0.122 g, 0.459 mmol) under nitrogen or argon atmosphere The mixture was heated to reflux in 30 ml of benzonitrile for 9 hours. After cooling, benzonitrile was distilled off, and the resulting residue was purified by silica gel column chromatography (developing solvent: chloroform), followed by recrystallization from dichloromethane-methanol to obtain the desired product (5, 10, 15, 20-tetrakis [3,5-bis (hexyloxy) phenyl] porphyrin platinum (II), R in formula [D] was n-hexyl) (orange solid, 0.154 g, yield 90.0%) was obtained.

When ¹ HNMR, ¹³ CNMR, and MALDI-TOF-MS of the obtained compound were measured, the following data was obtained.
¹ H NMR (400 MHz, CDCl ₃ , TMS): δ (ppm) 0.86 (t, J = 6.8 Hz, 24H, CH ₃ ), 1.26−1.51 (m, 48H, CH ₂ ), 1.81-1.88 (m, 16H, CH ₂ ), 4.09 (t, J = 6.6 Hz, 16H, ArOCH ₂ ), 6.86 (t, J = 2.2 Hz, 4H, arom.H), 7.295 (d, J = 2.4 Hz, 8H, arom. H), 8.84 (s, 8H, pyrrole H).
¹³ C NMR (100.4 MHz, CDCl ₃ ): δ (ppm) 14.05, 22.58, 26.05, 29.08, 29.37, 31.77 (aliphatic), 68.39 (ether), 101.30, 113.63, 122.11, 130.63, 140.62, 143.09, 158.48 (aromatic ).
MALDI-TOF-MS (no matrix): m / z = 1722.270 (M ⁺ )

(Example 14)
In the same manner as in Example 9, a soluble porphyrin derivative (5,10,15,20-tetrakis [3,5-bis (pentyloxy) phenyl] porphyrin platinum (II)) represented by the above formula (2) was produced. .

  A mixture of 5,10,15,20-tetrakis [3,5-bis (pentyloxy) phenyl] porphyrin (0.147 g, 112.746 μmol) and platinum (II) chloride (0.153 g, 0.575 mmol) under a nitrogen or argon atmosphere. The mixture was heated to reflux in 30 ml of benzonitrile for 9 hours. After cooling, benzonitrile was distilled off, and the resulting residue was purified by silica gel column chromatography (developing solvent: chloroform), followed by recrystallization from dichloromethane-methanol to obtain the desired product (5, 10, 15, 20-tetrakis [3,5-bis (pentyloxy) phenyl] porphyrin platinum (II), R in formula [D] was n-pentyl) (orange crystals, 0.144 g, yield 85.4%).

When ¹ HNMR, ¹³ CNMR, and MALDI-TOF-MS of the obtained compound were measured, the following data was obtained.
¹ H NMR (400 MHz, CDCl ₃ , TMS): δ (ppm) 0.92 (t, J = 7.4 Hz, 24H, CH ₃ ), 1.34−1.51 (m, 32H, CH ₂ ), 1.82-1−1.89 (m, 16H, CH ₂ ), 4.095 (t, J = 6.8 Hz, 16H, ArOCH ₂ ), 6.86 (t, J = 2.2 Hz, 4H, arom.H), 7.30 (d, J = 2.4 Hz, 8H, arom. H), 8.845 (s, 8H, pyrrole H).
¹³ C NMR (100.4 MHz, CDCl ₃ ): δ (ppm) 14.00, 22.48, 28.25, 29.05 (aliphatic), 68.37 (ether), 101.28, 113.635, 122.105, 130.63, 140.61, 143.09, 158.47 (aromatic).
MALDI-TOF-MS (no matrix): m / z = 1496.645 (M ⁺ )

(Example 15)
In the same manner as in Example 9, a soluble porphyrin derivative (5,10,15,20-tetrakis [3,5-bis (butoxy) phenyl] porphyrin platinum (II)) represented by the above formula (2) was produced. .

  A mixture of 5,10,15,20-tetrakis [3,5-bis (butoxy) phenyl] porphyrin (0.159 g, 133.433 μmol) and platinum (II) chloride (0.176 g, 0.662 mmol) under a nitrogen or argon atmosphere. The mixture was heated to reflux in 30 ml of benzonitrile for 9 hours. After cooling, benzonitrile was distilled off, and the resulting residue was purified by silica gel column chromatography (developing solvent: chloroform), followed by recrystallization from dichloromethane-methanol to obtain the desired product (5, 10, 15, 20-tetrakis [3,5-bis (butoxy) phenyl] porphyrin platinum (II), R in formula [D] was n-butyl) (orange crystals, 0.157 g, yield 85.0%).

When ¹ HNMR, ¹³ CNMR, and MALDI-TOF-MS of the obtained compound were measured, the following data was obtained.
¹ H NMR (400 MHz, CDCl ₃ , TMS): δ (ppm) 0.98 (t, J = 7.6 Hz, 24H, CH ₃ ), 1.475−1.57 (m, 16H, CH ₂ ), 4.12 (t, J = 6.6 Hz, 16H, ArOCH ₂ ), 6.86 (t, J = 2.4 Hz, 4H, arom.H), 7.30 (d, J = 2.8 Hz, 8H, arom.H), 8.85 (s, 8H, pyrrole H) .
¹³ C NMR (100.4 MHz, CDCl ₃ ): δ (ppm) 13.88, 19.29, 31.42 (aliphatic), 68.07 (ether), 101.28, 113.63, 122.105, 130.63, 140.61, 143.09, 158.48 (aromatic).
MALDI-TOF-MS (no matrix): m / z = 1384.197 (M ⁺ )

(Example 16)
In the same manner as in Example 9, a soluble porphyrin derivative (5,10,15,20-tetrakis [3,5-bis (propoxy) phenyl] porphyrin platinum (II)) represented by the above formula (2) was produced. .

  A mixture of 5,10,15,20-tetrakis [3,5-bis (propoxy) phenyl] porphyrin (0.151 g, 139.894 μmol) and platinum (II) chloride (0.189 g, 0.711 mmol) under nitrogen or argon atmosphere The mixture was heated to reflux in 30 ml of benzonitrile for 9 hours. After cooling, benzonitrile was distilled off, and the resulting residue was purified by silica gel column chromatography (developing solvent: chloroform), followed by recrystallization from dichloromethane-methanol to obtain the desired product (5, 10, 15, 20-tetrakis [3,5-bis (propoxy) phenyl] porphyrin platinum (II), R in formula [D] was n-propyl) (orange crystals, 0.141 g, yield 79.2%).

When ¹ HNMR, ¹³ CNMR, and MALDI-TOF-MS of the obtained compound were measured, the following data was obtained.
¹ H NMR (400 MHz, CDCl ₃ , TMS): δ (ppm) 1.06 (t, J = 7.2 Hz, 24H, CH ₃ ), 1.83−1.92 (m, 16H, CH ₂ ), 4.065 (t, J = 6.6 Hz, 16H, ArOCH ₂ ), 6.87 (t, J = 2.2 Hz, 4H, arom.H), 7.30 (d, J = 2.4 Hz, 8H, arom.H), 8.85 (s, 8H, pyrrole H) .
¹³ C NMR (100.4 MHz, CDCl ₃ ): δ (ppm) 10.56, 22.68 (aliphatic), 69.86 (ether), 101.33, 113.64, 122.11, 130.63, 140.62, 143.10, 158.47 (aromatic).
MALDI-TOF-MS (no matrix): m / z = 1273.003 (M ⁺ )

The following evaluation was performed about the porphyrin derivative obtained above. As Comparative Example 1, tetraphenylporphyrin (OR substituent is hydrogen) was used, and as Comparative Example 2, tetraphenylporphyrin platinum (II) (OR substituent was hydrogen) was evaluated in the same manner as in Example. It was.
(1) Thermophysical property evaluation Differential thermal and thermogravimetric simultaneous measurement (TG-DTA) is performed at 10 ° C. in a nitrogen atmosphere using a TG / DTA simultaneous measurement device (product name: DTG-60A, manufactured by Shimadzu Corporation). At a rate of temperature increase of / min, a weight loss temperature of 2% was defined as the thermal decomposition temperature. The differential scanning calorimetry (DSC) is measured using a differential scanning calorimeter (DSC204, manufactured by NETZSCH) at a heating / cooling rate of 5 ° C./min in an argon atmosphere, melting temperature (Tm), crystal The conversion temperature (Tc) and glass transition point (Tg) were measured. Table 1 shows the results.

  From the results in Table 1, it was suggested that the thermophysical properties do not depend on the central metal but on the type of substituent. Furthermore, when R is all 2-ethylhexyl, since R is an intermediate value between all n-hexyl and R are all n-heptyl, the thermophysical properties are longer in the R chain (2- In the case of ethylhexyl, it was suggested that it depends on the hexyl moiety.

(2) Absorption spectrum measurement About the porphyrin derivative, the chloroform solution and the absorption spectrum in the form of a film were measured.
(I) porphyrin derivative of Examples 1 to 16 of the absorption spectrum measured concentration of the chloroform solution is ^{1.0 × 10 -6 mol / dm 3} , and the chloroform solution of porphyrin derivatives of Comparative Examples 1 and 2, (product name: The absorption spectrum was measured using UV-2550 (manufactured by Shimadzu Corporation) under the conditions of air and room temperature.
(Ii) Measurement of absorption spectrum of film A 10 mg / 1 ml chloroform solution of the porphyrin derivatives of Examples 1 to 16 was prepared, spin-coated on quartz at 2000 rpm / 10 sec, and a film comprising the porphyrin derivatives of Examples 1 to 16 Was formed by a wet film formation method (thickness 40-60 nm). On the other hand, the porphyrin derivatives of Comparative Examples 1 and 2 could not be dissolved in chloroform at a high concentration (10 mg / 1 ml) for forming a coating film, and a film could not be formed by a wet film formation method. .
About the film | membrane consisting of the porphyrin derivative of Examples 1-16, the absorption spectrum was measured on the conditions of air | atmosphere and room temperature using (Product name: UV-2550, Shimadzu Corporation Corp.).

  In FIG. 1, the result of the absorption spectrum of the porphyrin derivative of Examples 1-8 and the chloroform solution of TPP is shown. FIG. 2 shows the results of absorption spectra of the porphyrin derivatives of Examples 9 to 16 and the TPP chloroform solution coordinated with Pt. Moreover, the result of the absorption spectrum of the film | membrane which consists of a porphyrin derivative of Examples 1-8 is shown in FIG. In FIG. 4, the result of the absorption spectrum of the film | membrane which consists of a porphyrin derivative of Examples 9-16 is shown. 3 and 4 are normalized so that the maximum absorbance is 1. FIG.

From the results of FIG. 1, it was revealed that the porphyrin derivatives of Examples 1 to 8 change the Soret-band due to the introduction of substituents when the absorption spectrum is measured with the molecule diluted. In particular, the cyclohexylmethyloxy derivative showed a specific spectrum as compared with other compounds.
On the other hand, from the results of FIG. 2, the porphyrin derivatives of Examples 9 to 16 in which platinum is integrated in the porphyrin derivatives of Examples 1 to 8, respectively, even if the absorption spectrum is measured in a dilute state, Soret- The peak of the band became one, no change due to the introduction of substituents was observed, and the spectrum was the same as that of TPP. It is presumed that the porphyrin structure is fixed by the integration of platinum.

  In addition, from the results of FIG. 3, when the spectra of the porphyrin derivatives of Examples 1 to 8 are measured in a film state, the Soret-band is integrated into one, and the Q-band is split or has a new peak. It became clear to show. In the case of a membrane, it is suggested that part (face to edge) and / or all (face to face) overlap of porphyrin derivatives occurs.

  2 and 4, when the porphyrin derivatives of Examples 9 to 16 are in the form of a film, both Soret-band and Q-band are observed to have a long wavelength shift of several nanometers. In a molecule having a linear structure as a group, a new absorption is observed around 590 nm. This suggests the formation of dd bonds of platinum between molecules in addition to the overlap of part (face to edge) and / or the whole (face to face) of porphyrin derivatives. This suggests further improvement in conductivity as compared with the case without the above.

It is a figure which shows the absorption spectrum of the porphyrin derivative of Examples 1-8, and the chloroform solution of TPP. It is a figure which shows the absorption spectrum of the chloroform solution of the porphyrin derivative of Examples 9-16 and TPP which Pt coordinated. It is a figure which shows the absorption spectrum of the film | membrane consisting of the porphyrin derivative of Examples 1-8. It is a figure which shows the absorption spectrum of the film | membrane consisting of the porphyrin derivative of Examples 9-16.

Claims (2)

A soluble porphyrin derivative represented by the following formula (2).
(In Formula (2), each R is independently a substituted or unsubstituted alkyl group having 3 or more carbon atoms.) The soluble porphyrin derivative according to claim 1 , wherein, in the formula (2), R is a substituted or unsubstituted alkyl group having 7 or more carbon atoms.