WO2008016085A9 - Isoindoles, compounds prepared from the same, and processes for production of both - Google Patents

Abstract

The invention provides a process for the production of isoindoles represented by the general formula (2) by a simple means of reducing phthalonitriles represented by the general formula (1). Isoindole polymers, π-conjugated cyclic compounds (particularly porphyrins) and porphyrin complexes which are useful as organic semiconductors can be prepared from the isoindoles obtained by the process. Further, the invention also provides a process for producing isoindole polymers directly by using not isoindoles but phthalonitriles as the starting compound.

Description

Isoindoles, compounds obtained therefrom, and methods for producing them

The present invention relates to a novel process for producing isoindoles and novel isoindoles. Furthermore, the present invention provides novel compounds obtained from isoindoles, specifically isoindole multimers (including polymers), isoindole derivatives (1-position substitution), π conjugated cyclic compounds (especially porphyrins) and porphyrin complexes, and the like It relates to a manufacturing method.

Isoindoles are used as pigment materials such as porphyrins, and are polymerized to form organic thin film transistors, organic solar cells, organic EL, electrophotographic photosensitive members, photorefractive materials, secondary batteries, capacitors, antistatic agents, It is expected to use for an electrochromic material etc.

Since porphyrins obtained from pyrroles (including isoindoles) are relatively easy to obtain despite having a very large π electron system, nonlinear optical materials, photoelectric conversion element dopants, photoconductive carrier generating materials, It has been actively studied as an optical recording material. In these porphyrins and the like, tuning of the absorption wavelength and the fluorescence emission wavelength is an important issue that affects the performance as a dye.

Expand the π electron system rather than using an electron donating group or electron withdrawing group as an auxiliary chromophore for longer wavelength and higher efficiency (increased absorption coefficient ε) of absorption and emission wavelengths Is effective. Examples of porphyrins in which the π electron system is expanded include tetrabenzoporphyrins described below.

As described above, JP-A-2004 of JP-A-2004 of Japan uses tetrabenzoporphyrin or its copper complex in which π electron system is expanded with high planarity as a material of an organic electronic device, especially an organic semiconductor. -6750 or JP-A-2005-93990.

If it is possible to synthesize halogen-containing tetrabenzoporphyrin, particularly fluorine-containing tetrabenzoporphyrin, it may be useful as an organic electronic device, particularly an n-type organic field effect transistor (OFET) or a conductive material. However, due to its high planarity, tetrabenzoporphyrin has low solubility in organic solvents and can not be used as a starting material for synthesis of halogen-containing tetrabenzoporphyrin. Although JP-A-2004-6750 or JP-A-2005-93990 mentioned above mentions fluorine-containing tetrabenzoporphyrin or its copper complex, it is not currently manufactured, and the method of manufacturing them is unknown. is there.

DE Remy et al., Tetrahedron Lett, 1983, 24, p. 1451-1454, has the following formula: 4,5,6,7-tetrafluoro-2H-isoindole (A), formaldehyde and zinc acetate II) is reacted, 2 ¹ 2 2 ² 2 ³ 2 ⁴ 2 7 ¹ 7 ² 7 ³ 7 ⁴ 12 ¹ 12 ² 12 ³ 12 ⁴ 17 ¹ 17 ² 17 It is reported that a zinc (II) complex (B) of ³ , 17, ⁴ -hexadecafluoro-21H, 23H-tetrabenzoporphyrin (hereinafter abbreviated as "hexadecafluorotetrabenzoporphyrin") is synthesized.

D. E. Remy et al. Report that the above complex (B) was synthesized only by the results of ultraviolet-visible absorption spectroscopy and mass spectrometry, but the zinc (II) complex which is said to be synthesized ( B) can not measure NMR and is not isolated as a substance. D. E. Remy et al. Postulates that paramagnetic impurities are present in that the NMR could not be measured. However, despite the fact that the starting material is a zinc (II) salt and an organic starting material, a paramagnetic species (such as a zinc (I) complex or an organic radical) is formed that is sufficiently stable to prevent NMR measurements. Is hard to think. D. E. Remy et al. Overlooked, but as the reason why the NMR of the above complex (B) could not be measured, it is considered that an isoindole oligomer was formed by a thermal polymerization reaction. Although the molecular weight of the complex (B) is 861.81, the mass analysis of the paper of D. E. Remy et al. Gives an actual measurement value of 877 which is far from the theoretical value. It is not considered that the above-mentioned complex (B) of high purity is obtained in the paper of E. Remy et al.

Furthermore, in the article of D. E. Remy et al., The complex (B) is not purified and is not isolated as a substance. (I) In the synthesis method of the paper of D. E. Remy et al., The complex (B) itself is not sufficiently synthesized by the influence of thermal polymerization etc., and (II) the synthesis method Even if the complex (B) itself is synthesized in, it is considered that its purification is difficult. This is because tetrabenzoporphyrin and complexes thereof have high planarity and low solubility, which makes purification difficult.

The article by D. E. Remy et al. Reports that the yield is low in the absence of metal and it is important that metal ions participate in the reaction (No. 1453 of the article by D. E. Remy et al. Page 6 to line 11, especially line 11). As described in the paper by D. E. Remy et al., In general, in the case of porphyrin synthesis, when a metal ion is present in the reaction system, the metal ion acts as a central nucleus, so that a porphyrin ring is likely to be formed. There is also a theory.

Also, in the paper of D. E. Remy et al., It is reported that if nickel (II) acetate or copper (II) acetate is used instead of zinc (II) acetate, only a trace amount of the desired product is detected. (Refer to D. E. Remy et al., Page 1453, line 12 to line 18, particularly line 15 to line 16). Thus, in the synthesis reaction of D. E. Remy et al., The presence of zinc (II) acetate is essential.

Halogen-containing tetrabenzoporphyrins are expected to be applied to organic electronic devices and the like. However, as an example of the preparation of halogen-containing tetrabenzoporphyrins, the paper of D. E. Remy et al. Reports the synthesis of hexadecafluorotetrabenzoporphyrin zinc complex, but the substance has not been isolated, and also NMR It can not be said that the manufacturing method is not sufficiently established because it can not be measured.

Also, in the synthesis method of D. E. Remy et al., The presence of zinc (II) acetate is essential, and it is reported that a zinc porphyrin complex can be obtained as a product, not a metal free porphyrin. However, since tetrabenzoporphyrin and its complex are difficult to purify, it is desirable that metal-free porphyrin can be produced with high purity. If high purity metal-free porphyrins are obtained, metal porphyrin complexes other than zinc as reported in the article of D. E. Remy et al. Can also be produced with high purity, and the metal-free porphyrins themselves or so obtained as such Various complexes can be effectively utilized as organic device materials.

Multimers (in particular, polymers) obtained from isoindoles are known to have superior properties as compared to other conductive polymers, and have been actively studied until now (for example, JP-A-S62) JP-A-S63-223031, JP-A-S63-307604, JP-A-H02-263824, JP-A-H02-263825, JP-A-H03-166225, etc.).

In JP-A-S62-270621, polyisoindoles are described to be more stable than polyacetylene and to be less de-doped than polythiophene. Therefore, isoindole multimers are expected to be applied to a wide range of applications such as organic thin film transistors, organic solar cells, organic EL, electrophotographic photosensitive members, photorefractive materials, secondary batteries, capacitors, antistatic agents, electrochromic materials, etc. There is.

As a method for producing this isoindole multimer, oxidative polymerization of isoindoles (or isoindolines of its reductant) has been known (for example, JP-A-S62-270621 and JP-A-S63-). 223031, etc.). However, isoindoles, which are starting materials for isoindole multimers, are unstable and difficult to handle. Furthermore, isoindoles themselves were not readily available until now. The conventionally known method for producing isoindoles is composed of a multistep reaction process, and isoindoles can not be easily produced.

For example, in J. Borstein, D. E. Remy, and J. E. Shields, "SYNTHESIS AND REACTIONS OF 4, 5, 6, 7-TETRAFLUOROISOINDOLE", Tetrahedron Lett., 1974, pp. 4247-4250, As shown, tetrafluorobenzine is first formed, for example, by reaction of pentafluorobenzene with n-butyllithium, and then by Diels-Alder reaction of this with N-benzylpyrrole to form N-benzyl-7-aza-tetrafluoro. It is disclosed to produce 4,5,6,7-tetrafluoro-2H-isoindole by forming benzonorbornadiene and further subjecting it to hydrogenation and thermal decomposition.

Also, P. S. Anderson, M. E. Christry, E. L. Engelhardt, G. F. Lundell and G. S.
In Ponticello, "N-Trimethlysillpyrroles as Diense in the Syntehsis of 1,4-Dihydronaphthalen-1, 4-imines and Isoindoles (1)", J. Heterocyclic Chem., 1977, 14, pp. 213-218, As shown, first react tetrafluorobenzine formed by the above method with N-trimethylsilylpyrrole, and then quench with water to give tetrafluoro-1,4-dihydronaphthalene-1,4-imine It is disclosed to form 4,5,6,7-tetrafluoro-2H-isoindole by forming it and reacting it with N'-α-chlorobenzylidene-N ² -phenylhydrazine.

The first object of the present invention is to provide a novel production method by which isoindoles which have hitherto been difficult to produce can be easily obtained. The present invention also provides novel isoindoles, isoindole polymers, and methods of making the polymers.

The production method of the present invention which has achieved the first object is characterized in that a phthalonitrile represented by the following formula (1) (hereinafter sometimes abbreviated as "phthalonitrile (1)") is reduced. It is a manufacturing method of iso indole shown in the following formula (2) (hereinafter sometimes abbreviated as “iso indole (2)”).

In the above formulas (1) and (2), X represents a halogen atom, Y is R ¹ , OR ² or SR ³ (wherein R ¹ , R ² and R ³ are each independently alkyl, Represents an aryl or alkylaryl group, and, provided that m + n ≦ 4, m represents an integer of 1 to 4; n represents an integer of 0 to 3;

In the present invention, it is preferable to reduce phthalonitrile (1) with a hydride reducing reagent, and it is more preferable to use a hydride reducing reagent such that 2 to 6 moles of hydride are contained per 1 mole of phthalonitrile (1). . Furthermore, it is recommended to mix the reaction mixture with the protonic acid or the alkali after the phthalonitrile (1) and the hydride reducing reagent are mixed and the reduction reaction is carried out. Preferred hydride reduction reagents are aluminum hydrides or complexes thereof, or boron hydrides or complexes thereof.

In the present invention, reduction of phthalonitrile (1) by catalytic hydrogenation is also a preferred embodiment. Here, "reducing phthalonitrile (1) by catalytic hydrogenation method" means reducing phthalonitrile (1) by contact with hydrogen gas in the presence of a catalyst.

The present invention is a novel isoindole represented by the following formula (2) (excluding 4,5,6,7-tetrafluoro-2H-isoindole), or a novel N-substituted represented by the following formula (3) An isoindole is provided (except that in which X is a fluorine atom and m = 4, hereinafter may be abbreviated as “N-substituted isoindole (3)”) (wherein X, Y, m and n have the same meaning as described above, and R ⁴ represents an alkyl, aryl, alkylaryl or acyl group).

The present invention further comprises a repeating unit represented by the following formula (4) or (5) by oxidative polymerization of isoindole (2) or N-substituted isoindole (3) produced by the above production method. A method for producing a polymer, and a polymer itself having a repeating unit represented by the following formula (4) or (5) (except that in which X is a fluorine atom and m = 4, each of Also provided are indole (4) ′ ′, sometimes abbreviated as “polyisoindole (5)” (wherein X, Y, R ⁴ , m and n are as defined above). In the present invention, “oxidative polymerization” means chemical oxidative polymerization with an oxidizing agent or electrolytic oxidative polymerization by electrically oxidizing a monomer in a solvent in the presence of an electrolyte.

The second object of the present invention, unlike the synthesis method of D. E. Remy et al., Is to produce a π-conjugated cyclic compound (especially halogen-containing tetrabenzoporphyrin) with high purity without using metal salt or metalloid salt. Provide the technology to Another object of the present invention is to provide a method capable of producing not only zinc ions but also metal porphyrin complexes having various metal ions as central nuclei.

The production method of the present invention capable of achieving the second object is characterized in that the 1-substituted form of isoindole represented by the following formula (6) from the halogen-containing isoindole represented by the following formula (2) (hereinafter referred to as isoindole Production of a π-conjugated cyclic compound (hereinafter sometimes abbreviated as “π-conjugated cyclic compound (7)”) represented by the following formula (7) via the 1-substituted compound may be abbreviated as “intermediate” It is characterized by

In the above formulae, X represents a halogen atom.
Y represents R ¹ , OR ² or SR ³ (wherein R ¹ , R ² and R ³ each independently represent an alkyl, aryl or alkylaryl group), provided that m + n ≦ 4 And m represents an integer of 1 to 4 and n represents an integer of 0 to 3.
Z represents OH or NR ⁵ R ⁶ (wherein, R ⁵ and R ⁶ each independently represent a C _1-4 alkyl group).
A represents N or NH, j represents an integer of 1 to 5, k represents an integer of 0 or 1, and a double line consisting of a solid line and a dotted line represents a single bond or a double bond, The cyclic compound represented by the formula (7) forms a π-conjugated system at the doublet.

In the present invention, “C _ab ” means that the carbon number is a or more and b or less, and “π conjugated system” means that two or more double bonds are mutually single single bonds. "P-conjugated cyclic compound where k = 0" means a compound in which isoindole rings at both ends of (C) _k in formula (7) are directly bonded to each other. Do.

Among the above-mentioned production methods of the present invention, it is preferable to produce a halogen-containing tetrabenzoporphyrin represented by the following formula (7a) (hereinafter sometimes abbreviated as “porphyrin (7a)”) (in the following formula, X , Y, m, n and Z have the same meaning as described above).

In the present invention, the above 1-substituted isoindole is hydroxymethylated-2H-isoindole represented by the following formula (6c) or aminomethylated-2H-isoindole represented by the following formula (6d).

The hydroxymethylated-2H-isoindole represented by the above formula (6c) forms a first intermediate represented by the following formula (6b) by formylation of (I) isoindole (2), Then, a second intermediate represented by the following formula (6a) is formed by reducing this intermediate (6b) or by aminomethylenating (II) isoindole (2), and this intermediate The compound is preferably produced by hydrolyzing (6a) to form a first intermediate represented by the following formula (6b) and then reducing the intermediate (6b) (in the formula, X , Y, m, n and Z have the same meanings as described above, and R ⁷ and R ⁸ each independently represent a C _1-4 alkyl group).

More preferably, hydroxymethylated-2H-isoindole represented by the above formula (6c) is reacted with isoindole (2) and dialkylformamide in the presence of a phosphoryl halide to obtain a compound represented by the above formula (6b) The first intermediate shown or the second intermediate of formula (6a) above can be formed and prepared from these intermediates. The hydroxymethylated-2H-isoindole (6c) thus obtained is at least one aliphatic monocarboxylic acid selected from acetic acid, propionic acid and butyric acid, and / or ZnCl ₂ , BF ₃ and BF ₃ It is preferable to produce porphyrin (7a) by cyclodehydration in the presence of at least one Lewis acid selected from O (C ₂ H ₅ ) ₂ and then reacting with an oxidizing agent.

By aminomethylating isoindole (2), aminomethylated-2H-isoindole represented by the above formula (6d) can be produced. As a preferred method of producing porphyrin (7a) via this aminomethylated-2H-isoindole (6d), isoindole (2), formaldehyde, and dialkylamine are reacted in the presence of (I) acid (II) isoindole (2) is reacted with methylenedialkylammonium halide and then reacted with an oxidizing agent.

In the method for producing halogen-containing tetrabenzoporphyrin of the present invention, isoindole (2) is preferably represented by the following formula (2a), and 4,5,6,7-tetrafluoro-2H-isoindole More preferably, it is 4,5,6,7-tetrachloro-2H-isoindole.

In the above formulae, X ¹ and X ⁴ each independently represent F or Cl, and X ² and X ³ each independently represent H, F or Cl.

The present invention also provides aminomethylenated-1H-isoindole, formyl-2H-isoindole and hydroxymethylated-2H-isoindole represented by the following formulas (6a) to (6c). These compounds are useful for producing π-conjugated cyclic compounds (especially halogen-containing tetrabenzoporphyrins) as described above. Moreover, these compounds can be used not only in the production of porphyrins, but also in the production of polymer materials such as polyisoindolenine vinylene (wherein X, Y, m, n, R ⁷ and R ⁸ are Same meaning as above).

The present invention relates to a π-conjugated cyclic compound (7) (particularly porphyrin (7a)), and a halogen-containing tetrabenzoporphyrin complex represented by the following formula (8) (hereinafter sometimes abbreviated as "porphyrin complex (8)") (In the following formulas, X and Y have the same meanings as described above, and M represents a metal or metalloid ion).

Porphyrin complex (8) can be produced by mixing porphyrin (7a) and a salt containing metal or metalloid ion M.

In the method for producing halogen-containing tetrabenzoporphyrin of the present invention, porphyrin (7a) is produced by cyclizing the 1-substituted form of isoindole represented by the above-mentioned formula (6). Once cyclization of the variant (6) is carried out, formation of a halogen-containing tetrabenzoporphyrinogen (a reduced form of porphyrin, hereinafter sometimes abbreviated as "porphyrinogen (11)") represented by the following formula (11) is once formed It is thought that. Then, porphyrin (7a) can be obtained by causing an oxidant (such as quinones or oxygen in the air) to act on this porphyrinogen (11). Therefore, during the above halogen-containing tetrabenzoporphyrin preparation process, that is, the step after cyclization and before oxidation of the 1-position substitution (6) of isoindole (that is, the step considered to be formed by porphyrinogen (11)) The porphyrin complex (8) can also be produced by adding a salt containing a metal or metalloid ion M and subsequent oxidation. That is, porphyrin complex (8) can be produced by mixing porphyrinogen (11) and a salt containing metal or metalloid ion M and then causing an oxidant to act [in the following formula, X , Y, m and n have the same meaning as described above].

As a method for producing porphyrin complex (8) by mixing porphyrinogen (11) with a salt containing metal or metalloid ion M and then reacting with an oxidizing agent, preferably,
(I) By reacting isoindole (2) with dialkylformamide in the presence of a phosphoryl halide to form an intermediate represented by the above formula (6b), and reducing this intermediate (6b) , Forming an intermediate represented by the above formula (6c), which is an acid (preferably at least one aliphatic monocarboxylic acid selected from acetic acid, propionic acid and butyric acid, and / or / or After mixing with ZnCl ₂ , BF ₃ and at least one Lewis acid selected from BF ₃ · O (C ₂ H ₅ ) ₂ and then with metal or metalloid ion containing salts M, the oxidizing agent is How to work,
(II) reacting isoindole (2) with dialkylformamide in the presence of a phosphoryl halide to form an intermediate represented by the above formula (6a) and hydrolyzing this intermediate (6a) Thus, an intermediate represented by the above formula (6b) is formed, and the intermediate (6b) is reduced to form an intermediate represented by the above formula (6c). Acid (preferably at least one aliphatic monocarboxylic acid selected from acetic acid, propionic acid and butyric acid, and / or at least one selected from ZnCl ₂ , BF ₃ and BF ₃ · O (C ₂ H ₅ ) ₂ Mixing with a seed (Lewis acid) and then mixing with a metal or metalloid ion containing salt M, followed by the action of an oxidizing agent,
After the reaction of isoindole (2), formaldehyde and dialkylamine in the presence of (III) acid, and then mixing the reaction mixture with the metal or metalloid metal salt M, the oxidant acts How to
(IV) A method in which isoindole (2) is reacted with methylenedialkylammonium halide, and then the reaction mixture is mixed with a salt containing metal or metalloid ion M, and then the oxidizing agent is allowed to act.

A third object of the present invention is to provide a method for producing isoindole multimers using phthalonitriles, which are easier to handle and obtain than isoindoles, as a starting material.

The present invention, which has achieved the third object, is a repeating unit represented by the following formula (2) characterized by catalytically hydrogenating a phthalonitrile represented by the following formula (9) in the presence of an acid. A method of producing a multimer having In the present invention, "catalytic hydrogenation" has the same meaning as described above, and "multimer" means "having two or more repeating units".

In the above formulae, D represents a halogen atom, R ¹ , OR ² or SR ³ (wherein R ¹ , R ² and R ³ each independently represent an alkyl, aryl or alkylaryl group), p represents an integer of 0 to 4;

In the method for producing an isoindole multimer according to the present invention, at least one selected from the group consisting of (I) acetic acid, trifluoroacetic acid, phosphoric acid, hydrochloric acid, nitric acid and sulfuric acid is used as the acid, (II) palladium It is a preferred embodiment to use at least one selected from the group consisting of a catalyst, a rhodium catalyst, a platinum catalyst and a nickel catalyst as a catalyst for catalytic hydrogenation.

Moreover, as a preferred embodiment of the method for producing an isoindole multimer of the present invention, a method for producing a multimer having a repeating unit represented by the following formula (4) using a phthalonitrile represented by the following formula (1) (In the following formulas, X, Y, m and n have the same meaning as described above).

In the following, a phthalonitrile represented by the above formula (9) is referred to as “phthalonitrile (9)” and an isoindole multimer having a repeating unit represented by the above formula (10) (or (4)) It may be abbreviated as isoindole multimer (10) (or (4)).

The present invention will first be described with respect to a method for producing isoindoles.
According to the production method of the present invention, isoindole (2) can be produced by a simple reaction step of reducing phthalonitrile (1) (preferably by reduction using a hydride reducing reagent or reduction by catalytic hydrogenation method) It is characterized by Therefore, first, reduction with a hydride reducing reagent will be described.

In a preferred embodiment of the present invention in which 4,5,6,7-tetrafluoro-2H-isoindole is produced by reducing tetrafluorophthalonitrile with hydrogenated diisobutylaluminum, the reaction as shown by the following formula: It is estimated that the mechanism proceeds. In addition, it is presumed that the same reaction mechanism proceeds in the catalytic hydrogenation method. However, the invention is not limited to such an estimation:

If the amount of hydride reduction reagent is too small, the yield of the desired product isoindole (2) decreases. On the other hand, when the amount of the hydride reducing reagent is too large, there is a possibility that a side reaction may occur in which the halogen of phthalonitrile (1) is substituted by hydride. Therefore, the hydride reducing agent is preferably 2 to 6 moles, more preferably 2.5 to 5 moles, still more preferably 2.7 to 4.5 moles of hydride per 1 mole of phthalonitrile (1). It is recommended to use. As understood from the above-described presumed reaction mechanism, the optimum amount of the hydride reducing reagent is such that 3 moles of hydride will be contained with respect to 1 mole of phthalonitrile (1).

After the reduction reaction of phthalonitrile (1) with the hydride reducing reagent, the hydride reducing reagent is quenched with water. At this time, it is preferable to use an acid (preferably a protic acid) or an alkali together with water. This is because the yield of isoindole (2) is improved.

The following can be presumed as the reason why the yield is improved by using a protonic acid or an alkali. However, the present invention is not limited to this assumption: As shown in the above-described presumed reaction mechanism, after reduction reaction, residue of hydride reducing reagent (for example, aluminum or boron) remains attached to nitrogen of isoindole (2) It is considered to be in the state of If this residue is added, it may be considered that the subsequent purification such as silica gel column chromatography does not work well. Therefore, it is considered that the purification yield is improved by promoting the elimination of the residue by adding a protonic acid or alkali. It is surprising that the yield of isoindole (2) is also improved by mixing a strong base such as NaOH. This is because phthalonitrile (1) which is the starting material is mixed with NaOH or the like to release the halogen bonded to carbon. However, as a result of investigations by the present inventors, it has been found that mixing of the reaction mixture with NaOH or the like does not release the halogen, and the purification yield of isoindole (2) is improved.

When quenching with water after the reduction reaction, it is possible not to use an acid or an alkali, or to use an extremely small amount of acid or alkali relative to the hydride reduction reagent. However, from the viewpoint of yield, it is recommended to use an acid, preferably a protonic acid, in an amount that preferably makes the reaction system neutral to acidic. Specifically, it is recommended to use a protonic acid in an amount such that proton (H ⁺ ) is preferably at least 1 mol, more preferably at least 1.5 mol, per 1 mol of hydride reducing reagent. . However, since protonic acid may also adversely affect the subsequent processing steps, particularly the purification step, when an excess of protonic acid is used, it is preferable to neutralize the remaining protonic acid with a base. Therefore, in consideration of the subsequent treatment steps, the amount of proton (H ⁺ ) is preferably 4 mol or less, more preferably 3 mol or less, with respect to 1 mol of the hydride reducing reagent.

Likewise, from the viewpoint of yield, it is recommended to mix the reaction mixture and the alkali after the reduction reaction. The amount of alkali used is preferably 1 mol or more (more preferably 2 mol or more), preferably 5 mol or less (more preferably 3 mol or less) per 1 mol of hydride reducing reagent. When an excess of alkali is used, it may be neutralized before the next purification step, if necessary.

In the production method of the present invention, as shown above, it is presumed that isoindole (2) is produced by the reduction reaction of the portion of the cyano group, and the halogen X and the substituent Y in the above formula are produced. Is considered not to significantly affect this reduction reaction. Therefore, in the present invention, it is considered that phthalonitrile (1) having all kinds of halogen X and substituent Y can be used. However, since it is considered that the target substance isoindole (2) is stabilized by the presence of a halogen atom, from the viewpoint of the stability of isoindole (2), the halogen atom in phthalonitrile (1) It is recommended that the number of X is 1 or more (ie, m ≧ 1), preferably 2 or more, more preferably 3 or more, and still more preferably 4. As phthalonitrile (1), for example, those commercially available from Aldrich, Synquest, Azmax Co., Ltd. or Central Pharmaceutical Co., Ltd., or those which can be synthesized by known methods can be used.

X in the above formula represents a halogen atom, preferably a fluorine, chlorine or bromine atom, more preferably a fluorine or chlorine atom, still more preferably a fluorine atom. As X, multiple types of halogen atoms may be present simultaneously. R ¹ , R ² and R ³ in the above formulas are each independently preferably a C _1-20 alkyl group, more preferably a C _1-10 alkyl group, still more preferably a C _1-5 alkyl group; preferably C _6-20 aryl group, more preferably C _6-12 aryl group; or preferably C _7-20 alkyl aryl group, more preferably C _7-15 alkyl aryl group, still more preferably C _7-10 alkyl aryl group . R ¹ , R ² and R ³ may contain a halogen atom on their carbon skeleton. When any one of R ¹ , OR ² and SR ³ exists as a substituent Y, the plurality of R ¹ , R ² and R ³ may be different substituents (for example, an alkyl group and an aryl group) good.

As the phthalonitrile (1), first, those having n = 0, that is, halogen-containing phthalonitriles having only a halogen atom X as a substituent can be mentioned. Halogen-containing phthalonitriles are commercially available from, for example, Aldrich. Also, non-commercially available halogen-containing phthalonitriles can also be produced from commercially available halogen-containing phthalonitriles by a conventionally known halogen substitution reaction.

For example, JP-A-2002-332254 uses a fluorine atom of fluorine-containing isophthalonitrile using a brominating agent (eg, sodium bromide, potassium bromide and lithium bromide, preferably sodium bromide and potassium bromide) Thus, a technique of substitution with a bromine atom is disclosed. Also By J. M. Birchell, R. N. Haszeldlne, and J. O. Morley, "Polyfluoroarenes. Part XI. Reactions of Tetrafluorophthalonitriles with Nucleophilic Reagents",
J. Chem. Soc. (C), 1970, p. 456- 462 discloses a technique for substituting a fluorine atom of tetrafluoroisophthalonitrile with a chlorine atom using LiCl.

Specific examples of halogen-containing phthalonitriles include 4-fluorophthalonitrile, tetrafluorophthalonitrile, 4,5-dichlorophthalonitrile, tetrachlorophthalonitrile, 4-chloro-3,5,6-trifluorophthalonitrile, etc. Be Among these, tetrafluorophthalonitrile is preferable from the viewpoint of availability and the like.

Phthalonitriles (1) having an R ¹ group as substituent Y can be prepared by a coupling reaction well known in the synthetic chemistry field using halogen-containing phthalonitriles. For example, phthalonitrile (1) having an R ¹ group is specifically subjected to a coupling reaction of a halogen-containing phthalonitrile with a Grignard reagent in the presence of a nickel or palladium catalyst, and specifically the halogen atom of the halogen-containing phthalonitrile It can be obtained by substitution with an alkyl, aryl or alkylaryl group from a Grignard reagent. This coupling reaction is well known in the synthetic chemistry field as Kumada-Tamao coupling. The phthalonitrile (1) having an R ¹ group can also be obtained by conducting a coupling reaction of a halogen-containing phthalonitrile with an organic boron compound in the presence of a palladium catalyst. This coupling reaction is also well known in the synthetic chemistry field as Suzuki-Miyaura coupling.

Phthalonitriles (1) having an OR ² group or an SR ³ group as a substituent Y are halogens of halogen-containing phthalonitriles by a conventionally known method, for example, a method as described in JP-A-2002-302477. It can be produced by replacing the atom with HOR ² and / or HSR ³ . The halogen-containing phthalonitrile used in this aromatic nucleophilic substitution reaction is preferably fluorine-containing and / or chlorine-containing phthalonitrile, more preferably fluorine-containing phthalonitrile, still more preferably tetra-methane, from the viewpoint of reactivity to the halogen substitution reaction. It is fluorophthalonitrile. Also, the nucleophilic substitution reaction of the halogen-containing phthalonitrile preferentially proceeds at the 4- and 5-positions of the phthalonitrile. Therefore, from the viewpoint of easy availability, as the phthalonitrile (1) having an OR ² group or an SR ³ group, the following formula (1a) or (1d), in particular, the following formula (1b) or (1c), or Phthalonitriles shown by 1e) or (1f) are preferred.

In the above formulas (1a) to (1f), Y ¹ and Y ² each independently represent OR ² or SR ³ , and R ² and R ³ are each independently preferably, preferably a C _1-20 alkyl group Preferably a C _1-10 alkyl group, more preferably a C _1-5 alkyl group; preferably a C _6-20 aryl group, more preferably a C _6-12 aryl group; or preferably a C _7-20 alkyl aryl group, Preferably, it represents a C _7-15 alkylaryl group, more preferably a C _7-10 alkylaryl group. R ² and R ³ may also contain a halogen atom on their carbon skeleton. R ² and R ³ in the above formula (1e) or (1f) may be the same or different, but are preferably the same from the viewpoint of easiness of production.

As the hydride reduction reagent, metal or metalloid hydrides or their complexes can be used. Examples of metal hydrides and the like include the following.

Aluminum hydrides such as alkylalanes, dialkylalanes, alkoxyalanes and dialkoxyalanes.

_{LiAlH 4, LiAlH 3 R, LiAlH} 2 R 2, LiAlHR 3, NaAlH 4, NaAlH 3 R, NaAlH 2 R 2, NaAlHR 3, NaAlH 2 (OCH 2 CH 2 OCH 3) 2, Al 2 H 3 (OCH 2 CH ₂ OCH ₃ ) ₃ , R ₃ N—AlH ₃ , complexes of aluminum hydride such as Et ₂ O—AlH ₃ (wherein R represents an alkyl, aryl or alkoxy group).

Boro hydrides such as diborane (B ₂ H ₆ ), alkyl boranes, dialkyl boranes, alkoxy boranes, dialkoxy boranes and the like.

_{NaBH 4, NaBH 3 R, NaBH} 2 R 2, NaBHR 3, NaBH 3 CN, NaBH 3 N (CH 3) 2, NaBH 3 (NH (t-Bu)), NaBH 3 S 3, NaBH 2 (SCH 2 CH _{2 S), LiBH 4, LiBH} 3 R, LiBH 2 R 2, LiBHR 3, H 3 N-BH 3, RH 2 N-BH 3, R 2 HN-BH 3, R 3 N-BH 3, THF-BH ₃ , complexes of boron hydrides such as pyridine-BH ₃ , R ₂ HP-BH ₃ , R ₃ P-BH ₃ , KBHR ₃ (wherein R represents an alkyl, aryl or alkoxy group).

Silicon hydrides such as Cl ₂ SiH ₂ , Cl ₃ SiH, R ₂ SiH ₂ , R ₃ SiH, ((CH ₃ ) ₃ Si) ₃ SiH, polymethylhydrosilane, wherein R is alkyl, aryl, benzyl or alkoxy Represents a group).

Tin hydrides such as R ₂ SnH ₂ , R ₃ SnH, Ph ₂ SnH ₂ , Ph ₃ SnH, (n-Bu) ₂ SnH ₂ , triethyltin hydride, trimethyltin hydride and the like (wherein R is alkyl, aryl Or an alkoxy group).

Among the above, from the viewpoint of reactivity, aluminum hydride or a complex thereof or boron hydride or a complex thereof is preferable, and hydrogenated diisobutylaluminum and a BH ₃ complex are more preferable. As the hydride reducing reagent, only one type can be used alone, or two or more types can be used in combination.

The hydride reducing reagent may be used in combination with a Lewis acid. It is believed that the addition of the Lewis acid accelerates the reduction reaction, especially when using silicon hydride or tin hydride. In the present invention, only one Lewis acid can be used alone, or two or more Lewis acids can be used in combination.

The Lewis acid is not particularly limited. For example, AlCl ₃ , AlBr ₃ , TiCl ₄ , SnCl ₂ , SnCl ₄ , SnCl ₄ , FeCl ₃ , BF ₃ , BF ₃ .O (C ₂ H ₅ ) ₂ , trispentafluorophenyl boron, Listed are halogen compounds of NbF ₅ , TaF ₅ , PF ₅ , AsF ₅ , SbF ₅ etc. Periodic Table Group IIIB, IVA, IVB, VA or VB elements, their complexes or alkoxide compounds Be

The reduction reaction in the method of the present invention is usually carried out using a solvent. The solvent is not particularly limited, but those which can dissolve phthalonitrile (1) which is a starting material are preferable. As solvents, for example, chlorohydrocarbons such as chloroform and methylene chloride; aromatic hydrocarbons such as benzene, toluene and xylene; ethers such as THF, dioxane, cyclopentyl methyl ether, diisopropyl ether and diethyl ether; dimethylformamide, Amides such as dimethylacetamide; and sulfolanes such as sulfolane, 3-methylsulfolane, 2,4-dimethylsulfolane and the like can be mentioned. The solvents can be used alone or in combination of two or more. When a solvent is used, the concentration of phthalonitrile (1) is preferably about 0.01 to 1 M, more preferably about 0.05 to 0.5 M.

In the reduction reaction using a hydride reducing reagent, in order to suppress decomposition of the reducing reagent, it is preferable to carry out under an inert gas atmosphere such as nitrogen or argon. In addition, the solution of hydride reduction reagent may be added slowly while cooling the solution of phthalonitriles, or the solution of phthalonitriles may be added slowly while cooling the solution of the hydride reduction reagent. The temperature of the reduction reaction is also influenced by the solvent used, but is preferably 0 ° C. or more, more preferably 20 ° C. or more, preferably 150 ° C. or less, more preferably 120 ° C. or less. The time of the reduction reaction is preferably 30 minutes or more, more preferably 1 hour or more, still more preferably 2 hours or more, preferably 48 hours or less, more preferably 24 hours or less.

In order to improve the yield of the desired product isoindole (2), it is preferable to mix the reaction mixture with a protonic acid or alkali after the reduction reaction using a hydride reducing reagent.

First, the case of using a protonic acid will be described. There is no particular limitation on the protic acid, and organic or inorganic protic acids can be used. In the present invention, only one protonic acid can be used alone, or two or more protonic acids can be used in combination. The reaction mixture after the reduction reaction and the protonic acid are preferably at a temperature of about -30 ° C to 30 ° C, more preferably at a temperature of about -10 ° C to 10 ° C, and even more preferably under cooling in an ice bath or the like (about 0 ° C). It is recommended to mix in.

Examples of inorganic protonic acids include hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, sulfuric acid; phosphoric acids such as orthophosphoric acid and pyrophosphoric acid; perhalogen acids such as perchloric acid; phosphomolybdic acid, silicomolybdic acid, Examples thereof include heteropolyacids such as phosphotungstic acid, silicotungstic acid, lintungstomolybdic acid, and phosphovanadomolybdic acid.

Examples of organic protic acids include arylsulfonic acids such as benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, etc .; methanesulfonic acid, trifluoromethanesulfonic acid, trichloromethanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, t- Alkyl sulfonic acids such as butyl sulfonic acid; formic acid, acetic acid, propionic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, trifluoroacetic acid, pentafluoropropionic acid, n-butyric acid, isobutyric acid, pivalic acid, valeric acid, caproic acid, Saturated aliphatic carboxylic acids such as caprylic acid, capric acid, lauric acid, myristic acid, cyclohexane carboxylic acid; acrylic acid, methacrylic acid, propiolic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, oleic acid, etc. Unsaturation of Aliphatic carboxylic acid; benzoic acid, phthalic acid, isophthalic acid, and aromatic carboxylic acids such as terephthalic acid.

Next, the case of using an alkali will be described. It is recommended to mix the reaction mixture and the alkali after the reduction reaction, preferably at a temperature of about -30 ° C to about 30 ° C, more preferably about -10 ° C to about 10 ° C. The alkali is preferably an alkali metal or alkaline earth metal hydroxide, carbonate, monocarboxylate (such as acetate), dicarboxylate (such as oxalate), organic amine and the like. Among these, alkali metal hydroxides (in particular, LiOH, NaOH, KOH) which are strong bases are preferable. From the viewpoint of cost, NaOH is more preferable. Further, as the organic amine, ethanolamine and methylamine which can form a complex with boron or the like to promote elimination of the hydride reducing reagent residue are more preferable. One of these alkalis may be used alone, or two or more thereof may be used in combination.

After the reduction reaction with a hydride reducing reagent, it is recommended to purify the desired product isoindole (2) from the reaction mixture by a conventional treatment process. For example, when an excess of protonic acid or alkali is used, it is recommended to carry out a neutralization step, a washing step with water or saline, a concentration step and a purification step. In the present invention, the purification means is not particularly limited, and means generally used in the technical field such as silica gel column chromatography, alumina column chromatography, sublimation purification, recrystallization and the like can be used.

In the present invention, isoindole (2) can also be produced by reducing phthalonitrile (1) by catalytic hydrogenation. As the catalyst used for the catalytic hydrogenation reaction, conventional metal catalysts known in the art can be used. The metal catalyst is used in such an amount that the central metal of the catalyst is preferably 0.01 to 30 mol%, more preferably 0.1 to 20 mol%, still more preferably 1 to 10 mol% with respect to phthalonitrile (1). It is recommended to use

Examples of the metal catalyst include homogeneous catalysts constituted by coordinating phosphine or the like to ruthenium or rhodium. However, in view of reactivity, easiness of recovery after reaction and regeneration treatment, it is preferable to use a heterogeneous catalyst in the present invention. Among heterogeneous catalysts, in order to increase the surface area and improve the catalytic activity, a catalyst in which fine metal powder is supported on a carrier is preferable. Examples of heterogeneous catalysts include metals such as nickel, Raney nickel, copper-chromium oxide, ruthenium, palladium, rhodium, platinum or oxides or hydroxides thereof (including those in powder form) such as activated carbon, alumina, diatomaceous earth, etc. And those supported on the carrier of Among these, a catalyst in which palladium is supported on activated carbon is more preferable because it exhibits excellent catalytic activity.

When a heterogeneous catalyst is used, a step of activating the catalyst by mixing it with a protic acid in a hydrogen atmosphere prior to the catalytic hydrogenation reaction may be adopted as needed. Although the objective isoindole (2) can be obtained without using a protic acid, it is recommended to use a protic acid in order to improve the yield. The protonic acid described above can be used as the protonic acid used for activation. Among these, trifluoroacetic acid, hydrochloric acid, nitric acid and sulfuric acid are preferable. More or less amount of protonic acid relative to phthalonitrile (1) generates a large amount of impurities and reduces the yield. Therefore, the amount of proton (H ⁺ ) is preferably 0.6 to 1.6 mol, more preferably 0.8 to 1.2 mol, still more preferably 0.9 to 1 mol of phthalonitrile (1) as a raw material. It is recommended to use the protic acid to be 1.1 mole, most preferably 1 mole. The activation temperature is usually from room temperature to about 50 ° C., and the activation time is preferably 10 minutes or more, more preferably 30 minutes or more, still more preferably 1 hour or more, preferably 5 hours or less. More preferably, it is 3 hours or less, still more preferably 2 hours or less.

The reduction by catalytic hydrogenation is usually carried out using a solvent. The solvent is not particularly limited, but those which can dissolve the above-mentioned phthalonitrile (1) which is a starting material are preferable. As solvents, for example, aromatic hydrocarbons such as benzene, toluene, xylene and the like; ethers such as THF, dioxane, cyclopentyl methyl ether, diisopropyl ether, diethyl ether and the like; alcohols such as methanol, ethanol, propanol and the like; methyl acetate, ethyl acetate , Esters such as propyl acetate and butyl acetate; amides such as dimethylformamide, dimethylacetamide; sulfolanes such as sulfolane, 3-methylsulfolane, 2,4-dimethylsulfolane; and formic acid, acetic acid, propionic acid, trifluoroacetic acid Etc. can be mentioned. In the catalytic hydrogenation method, mixed solvents of amides or acetic acids and water can also be used. The solvents can be used alone or in combination of two or more. When a solvent is used, the concentration of phthalonitrile (1) is preferably about 0.01 to 1 M, more preferably about 0.05 to 0.5 M.

The temperature of the catalytic hydrogenation is also affected by the solvent used, but is preferably 0 ° C. or more, more preferably 20 ° C. or more, preferably 150 ° C. or less, more preferably 120 ° C. or less. The time of the reduction reaction is preferably 30 minutes or more, more preferably 1 hour or more, still more preferably 2 hours or more, preferably 72 hours or less, more preferably 48 hours or less. It is preferred to use hydrogen under pressure to promote catalytic hydrogenation. The hydrogen pressure is preferably 1.1 atmospheres or more, more preferably 1.5 atmospheres or more, and further preferably 2 atmospheres or more. However, the hydrogen pressure is preferably 5 atm or less, more preferably 3 atm or less, due to the restriction of equipment and the like.

Hydrogen gas can be constantly supplied to the reaction system to carry out a catalytic hydrogenation reaction. Alternatively, after hydrogen gas is supplied to a constant pressure, the reaction system is sealed to carry out a catalytic hydrogenation reaction, and after the pressure in the system decreases as the reaction proceeds, hydrogen gas can be supplied again. It is desirable to depressurize the reaction system prior to the hydrogen gas supply. In addition, in order to cause a large amount of hydrogen atoms to be adsorbed to the catalyst, it is a preferred embodiment to repeat the pressure reduction and the supply of hydrogen gas a plurality of times.

The novel isoindole represented by the above formula (2) other than 4,5,6,7-tetrafluoro-2H-isoindole can be produced by the production method of the present invention described above. Thus, the present invention also provides such a novel isoindole (2). Furthermore, the present invention also provides novel N-substituted isoindoles (3) obtained from isoindole (2) (except those in which X is a fluorine atom and m = 4). The novel isoindole (2) or N-substituted isoindole (3) of the present invention can be used as a raw material for polyisoindole or dyes. Moreover, isoindole (2) can be further used as a raw material of porphyrin.

R ⁴ in the above formula (3) (and formula (5)) is preferably a C _1-10 alkyl group, more preferably a C _1-5 alkyl group (eg methyl group, ethyl group, n-propyl group, n -Butyl group, n-pentyl group etc.); preferably C _6-20 aryl group, more preferably C _6-12 aryl group (eg phenyl group, tolyl group etc.); preferably C _7-15 alkyl aryl group, more preferably Preferably, a C _7-10 alkyl aryl group (eg, a benzyl group etc.); or preferably a C _2-10 acyl group, more preferably a C _2-5 acyl group (eg, an acetyl group, a benzoyl group, a t-butoxycarbonyl group etc.) It is.

There is no particular limitation on the method for obtaining N-substituted isoindole (3) from isoindole (2), and various known methods for obtaining a substituted amine from an amine can be used. Below, some examples are shown.

R ⁴ is an alkyl group or an alkyl aryl by reacting isoindole (2) with halogenated alkyl or halogenated alkyl aryl (wherein a halogen is bonded to a carbon atom of the alkyl moiety) in the presence of a base The group N-substituted isoindole (3) can be prepared. As the base, a strong base (eg, n-butyllithium, alkali metal hydride (eg, NaH, KH), etc.) is preferable. This alkylation reaction is carried out, for example, usually at about -100 ° C to 100 ° C, preferably at about -80 ° C to 70 ° C. The halogenated alkyl is preferably one having about 1 to 10 carbon atoms (preferably about 1 to 5 carbon atoms), more preferably a primary alkyl halide, still more preferably a primary alkyl iodide (eg methyl iodide) Ethyl iodide, n-propyl iodide, n-butyl iodide, n-pentyl iodide and the like). The halogenated alkylaryl is preferably one having about 7 to 15 carbon atoms (preferably about 7 to 10 carbon atoms), and more preferably a halogenated alkyl aryl iodide (eg, benzyl iodide).

N-substituted isoindoles (3) in which R ⁴ is an aryl group can be produced, for example, by the well-known personal name reaction Buchwald-Hartwig cross coupling reaction. Specifically, N-substituted isoindole (3) wherein R ⁴ is an aryl group is produced by reacting isoindole (2) with a halogenated aryl or aryl triflate in the presence of a Pd catalyst and a strong base it can. As a Pd catalyst, phosphine ligands (eg, 2,2'-bis (diphenylphosphino) -1,1-binaphthyl, 2,2'-bis (diphenylphosphino) biphenyl etc.) or dibenzylidene are generally used. Those containing an acetone ligand or the like are used. As a strong base, lithium bis (trimethylsilyl) amide, NaOt-Bu, K ₂ CO _{3 and the} like are generally used. As a reaction partner with isoindole (2), aryl halides having about 6 to 20 carbon atoms (preferably about 6 to 12 carbon atoms) are preferred, and aryl iodides or bromides (eg iodobenzene, 4-iodotoluene etc.) Is more preferred. The reaction may proceed at a temperature as low as room temperature, but the reaction temperature is generally about 50 to 150.degree.

N-substituted isoindole (3) wherein R ⁴ is an acyl group is an acyl halide having 2 to about 10 carbon atoms (preferably about 2 to 5 carbon atoms), an acid anhydride, a carboxylic acid ester, a carboxylic acid amide, a carbonic acid It can be produced by an acylation reaction using an acid. However, from the viewpoint of reactivity, it is recommended to use an acyl halide (preferably acyl chloride) or an acid anhydride. Specifically, by reacting isoindole (2) with an acyl halide or an acid anhydride (Schotten-Baumann reaction) in a basic aqueous solution (eg NaOH aqueous solution) or a basic organic solution (eg pyridine solution) And N-substituted isoindole (3) wherein R ⁴ is an acyl group. Examples of the reaction partner of isoindole (2) include acetic anhydride, acetyl chloride, benzoyl chloride and the like.

Further, as a specific example of the acyl group of R ⁴ , t-butoxycarbonyl group ((CH ₃ ) CO—C (= O) —) can be mentioned. t-Butoxycarbonyl groups are well known as protecting groups for amino groups, for example di-t-butyl dicarbonate and isoindole (2) in the presence of a base such as pyridine, triethylamine, n-BuLi or NaH Can be introduced by reacting

Polyisoindole (4) obtained by polymerizing isoindole (2) or N-substituted isoindole (3) of the present invention (hereinafter sometimes abbreviated as "isoindole (2) or (3)") Or (5), particularly poly (fluorine-containing isoindole) is particularly useful as a conductive material, more specifically, as an electrode material, display material, electromagnetic wave shielding material and the like in the field of organic thin film transistors and organic solar cells. The polymerization can be carried out by a known method such as electrolytic oxidation polymerization or chemical oxidation polymerization. The polyisoindole (4) or (5) may be optionally doped.

First, chemical oxidative polymerization will be described as a polymerization method. As an oxidizing agent used in chemical oxidative polymerization, for example, oxygen, hydrogen peroxide; tetrachloro-1,2-benzoquinone, tetrachloro-1,4-benzoquinone, 2,3-dichloro-5,6-dicyano-1 Quinones such as 4, 4-benzoquinone; halogens such as iodine, bromine and chlorine; metal chlorides such as iron (III) chloride and copper (II) chloride; metal oxides such as manganese dioxide, lead dioxide and osmium tetraoxide; Nitric acid, oxo acids such as chloric acid; potassium chlorate, sodium hypochlorite, sodium bromate, potassium bromate, potassium permanganate, potassium dichromate, potassium persulfate, sodium persulfate, potassium persulfate, ammonium persulfate, etc. An acid salt is mentioned. Among these oxidizing agents, oxygen, hydrogen peroxide, quinones, halogens and metal chlorides are preferable, and oxygen and metal chlorides are more preferable. The oxidizing agent may be used alone or in combination of two or more. In the oxidation polymerization, if necessary, an acid catalyst (for example, an inorganic acid such as hydrochloric acid, nitric acid or sulfuric acid) or a metal catalyst (for example, an oxide such as lead, manganese or silver), copper (I) chloride, copper (I) chloride-chloride Aluminum or the like may be used. It is recommended to use a catalyst, especially when using oxygen as an oxidant. The amount of the oxidizing agent excluding oxygen is preferably 1 mol or more (more preferably 2 mol or more), preferably 6 mol or less (more preferably 5 mol or less) per 1 mol of isoindoles.

Chemical oxidative polymerization is usually carried out in a solvent. As a solvent for chemical oxidative polymerization, for example, chlorinated hydrocarbons such as chloroform, methylene chloride, carbon tetrachloride, dichloroethane, tetrachloroethane, chlorobenzene and the like; nitrohydrocarbons such as nitromethane, nitroethane, nitrobenzene and the like; N- And amides such as methyl pyrrolidone; and carbon disulfide. The solvents may be used alone or in combination of two or more. The concentration of isoindole (2) or (3) when a solvent is used is preferably about 0.01 to 1 M, more preferably about 0.05 to 0.5 M. Chemical oxidative polymerization is generally carried out at a temperature in the range of about -80 ° C. to 100 ° C. (preferably about -20 ° C. to 60 ° C.) for about 0.1 to 100 hours (preferably 0 °) depending on the solvent used. 5 to 72 hours).

Next, electrolytic oxidation polymerization will be described. In the present invention, the reaction apparatus is not limited, and a reaction apparatus used for producing polypyrrole, polythiophene and the like by electrolytic oxidation polymerization can be used. Examples of the electrolyte include tetraethylammonium bromide, tetraethylammonium chloride, tetraethylammonium fluoride, tetra-n-butylammonium bromide, tetra-n-butylammonium chloride, tetra-n-butylammonium fluoride, tetraethylammonium tetrafluoroborate, and tetraethylammonium tetrafluoroborate. Ammonium salts such as n-butylammonium hexafluorophosphate and tetra-n-butylammonium hexafluoroantimony; phosphonium salts such as tetraphenylphosphonium bromide and tetraphenylphosphonium chloride; lithium salts such as lithium perchlorate and lithium hexafluoroborate; Sulfonates such as potassium benzenesulfonate and sodium toluenesulfonate; sulfuric acid, Acid, an acid such as trifluoroacetic acid. These electrolytes may be used alone or in combination of two or more. The anions of these electrolytes are incorporated into the polymer as a dopant during electrolytic oxidation polymerization.

Solvents for electrolytic oxidation polymerization include, for example, chlorinated hydrocarbons such as methylene chloride; nitriles such as acetonitrile, benzonitrile and propionitrile; cyclic ethers such as dioxane, tetrahydrofuran and propylene carbonate; sulfolane, 3-methylsulfolane And sulfolanes such as 2,4-dimethyl sulfolane; and amides such as dimethylformamide and dimethylacetamide. The solvents may be used alone or in combination of two or more. The concentration of isoindole (2) or (3) when a solvent is used is preferably about 0.01 to 1 M, more preferably about 0.05 to 0.5 M. The electrolytic oxidation polymerization is generally performed at a temperature in the range of about -80 ° C. to about 100 ° C. (preferably about -20 ° C. to about 60 ° C.) for about 0.1 to about 100 hours (preferably 0. 5 to 72 hours). The current density in electrolytic oxidation polymerization is generally about 1.0 to 5.0 mA / cm ² .

By oxidative polymerization as described above, isoindole (2) or (3) can be polymerized to produce a polymer. In the method of the present invention, not only one homopolymer of isoindole (2) or (3) may be used to form a homopolymer, but also two or more of these may be used in combination to form a copolymer. It is also possible to copolymerize isoindole (2) and / or (3) with other monomers (eg pyrrole, thiophene) to form a copolymer. Thus, the polyisoindoles (4) or (5) of the present invention encompass both homopolymers and copolymers. When forming a copolymer using other monomers such as pyrrole, the total content of isoindole (2) and / or (3) in the used monomers (ie, the above formula (4) and / or (5) in the copolymer Is preferably 10% by mass or more.

The weight average molecular weight (value by GPC measurement in terms of styrene) of the polyisoindole (4) or (5) of the present invention is usually about 1,000 to 500,000, preferably about 3,000 to 300,000, Preferably, it is about 5,000 to 100,000.

Next, the present invention will be described with respect to a method for producing a π-conjugated cyclic compound. In the following, among the π-conjugated cyclic compounds (7), a method of producing a representative porphyrin (7a) will be mainly described. The production method of the present invention forms intermediate (6) (1-substituted isoindole) from isoindole (2), and then produces π-conjugated cyclic compound (7) (particularly porphyrin (7a)). It is characterized by On the other hand, when a conventional porphyrin which is not modified with benzene ring is synthesized from pyrrole, a method of producing porphyrin in one step by reacting pyrrole with formaldehyde in the presence of acid (I), or (II 2.) A method for preparing porphyrin in multiple steps by forming 2-substituted form (for example, 2-hydroxymethylpyrrole or 2-dimethylaminomethylpyrrole) as an intermediate from pyrrole once and cyclizing this 2-position substituted form Etc. are known.

However, as a result of investigations by the present inventors, it has been found that even if it is attempted to cyclize (in particular, porphyrinate) isoindole in a one-step reaction like pyrrole, a π-conjugated cyclic compound (especially tetrabenzoporphyrin) is not sufficiently obtained. I found it. The reason why tetrabenzoporphyrin can not be obtained sufficiently is that, unlike pyrrole, isoindole has an easily polymerizable 1H-isoindole structure, and in one-step reaction, not only cyclization but also polymerization occurs. Be done.

Then, as a result of the present inventors continuing investigation further, 1-position substitution of isoindole (hydroxymethyl form as an intermediate, instead of directly producing a π-conjugated cyclic compound in a one-step reaction from halogen-containing isoindole Alternatively, it has been found that a π-conjugated cyclic compound (particularly, halogen-containing tetrabenzoporphyrin) can be produced with good selectivity and yield by a multistep reaction forming an aminomethyl form. The reason why the selectivity and the yield are improved by passing through the intermediate is that, when it is attempted to produce a π-conjugated cyclic compound (especially tetrabenzoporphyrin) directly from isoindole, the isoindole ring is activated to form a non-porphyrin. In the intermediate, it is considered that the 1-position substituent, not the isoindole ring, is activated to smoothly form a π-conjugated cyclic compound. The present invention is not limited to such an estimation mechanism.

Therefore, the method for producing a π-conjugated cyclic compound (in particular, halogen-containing tetrabenzoporphyrin) of the present invention is characterized in that a 1-substituted form of halogen-containing isoindole is once formed as an intermediate.

As a π-conjugated cyclic compound to be produced, porphyrin (7a); corrole represented by the following formula (7b) (in the above formula (7), j = 1, k = 0); saphyrin represented by the following formula (7c) In the formula (7), j = 2, k = 0); and pentaphilin represented by the following formula (7d) (in the above formula (7), j = 2, k = 1) is preferable, and the porphyrin (7a) is More preferable. Hereinafter, π-conjugated cyclic compounds represented by the following formulas (7b) to (7d) are abbreviated as “corrole (7b)”, “saphyrin (7c)” and “pentaphilin (7d)”, respectively.

The present invention also provides the 1-substituted halogen-containing isoindole itself. These 1-substituted compounds not only have the advantage of being useful for the preparation of π-conjugated cyclic compounds (especially halogen-containing tetrabenzoporphyrins) as described above, but also have the advantage of being more stable than unsubstituted halogen-containing isoindoles. Have. Furthermore, these 1-substituted compounds can also be used for the production of compounds other than π-conjugated cyclic compounds, for example, polymers such as polyisoindolenine vinylene. Also in the method for producing halogen-containing tetrabenzoporphyrin of the present invention, a trace amount of polymer or other cyclic compound is formed as a by-product.

The isoindole (2) used in the method for producing the π-conjugated cyclic compound (7) of the present invention can be obtained or produced as described above.

Among isoindoles (2), those represented by the above formula (2a) are preferable from the viewpoint of stability and the like, and 4,5,6,7-tetrafluoroiso-2H-indole or 4,5,6, 6 7-tetrachloro-2H-isoindole is more preferred, and 4,5,6,7-tetrafluoro-2H-isoindole is more preferred.

There is no particular limitation on the method for producing hydroxymethylated-2H-isoindole (6c) or aminomethylated-2H-isoindole (6d) from isoindole (2), and it is known in the field of synthetic organic chemistry Can be used in any way. However, from the viewpoint of ease of reaction, etc., hydroxymethylated-2H-isoindole (6c) is formylated with Vilsmeier and then reduced to give aminomethylated-2H-isoindole (6d) as Mannich reaction. It is preferable to manufacture by this.

First, a preferred method for producing hydroxymethylated-2H-isoindole (6c) is described. Phosphoryl halide POX ⁵ ₃ (wherein, X ⁵ is, F, represents. Cl or Br) in the presence of, isoindole (2) with a dialkyl formamide HCONR ⁷ R ⁸ (wherein, R ⁷ and R ⁸ are In the Vilsmeier reaction in which each is independently represented by a C _1-4 alkyl group, the first intermediate formylation, which is a first intermediate, is caused by differences in reaction conditions, specifically by differences in substrate reactivity or reaction temperature. 2H-isoindole (6b) or a second intermediate aminomethylenated-1H-isoindole (6a) is formed. For example, when 4,5,6,7-tetrafluoro-2H-isoindole is used as isoindole (2), the hydrolysis reaction in Vilsmeier reaction is carried out under reflux to obtain the first intermediate (6b) The reaction is carried out at room temperature to give a second intermediate (6a). When the second intermediate (6a) is obtained, it can be easily converted to the first intermediate (6b) by hydrolysis.

As the phosphoryl halide used for the Vilsmeier reaction, for example, phosphoryl fluoride, phosphoryl chloride or phosphoryl bromide can be mentioned, and among these, phosphoryl chloride is preferable from the viewpoint of reactivity. In addition, sulfonyl chlorides such as p-toluenesulfonyl chloride, methanesulfonyl chloride, trifluoromethane sulfonyl chloride, 2,2,2-trifluoroethane sulfonyl chloride, etc. instead of phosphoryl halide or together with phosphoryl halide, trifluoromethane sulfonic acid Anhydrides, sulfonic acid anhydrides such as methanesulfonic acid anhydride and sulfonic acid anhydride, phosgene, thiophosgene, oxalyl chloride and the like can also be used. Examples of the dialkylformamide include dimethylformamide (DMF), diethylformamide, diisopropylformamide and dibutylformamide, among which DMF (R ⁷ = R ⁸ = CH ₃ ) is preferable. In order to increase the conversion to intermediates (6a) or (6b), it is preferable to use dialkylformamide and phosphoryl halide in an equivalent or more amount with respect to isoindole (2). Specifically, the amount of dialkylformamide and halogenated phosphoryl is preferably 1 mol or more, more preferably 1.1 mol or more, and still more preferably 1.3 mol or more, per 1 mol of isoindole (2). . However, if the amount of dialkylformamide or the like is too much, the cost of raw materials and purification increases. Therefore, the amount of the dialkylformamide and the halogenated phosphoryl is preferably 5 mol or less, more preferably 3 mol or less, still more preferably 2 mol or less, per 1 mol of isoindole (2).

The Vilsmeier reaction for producing intermediates (6a) or (6b) is usually carried out in solution. One of the starting materials, dialkylformamide, in particular DMF, can be used as a solvent substitute. As other solvents, for example, chlorohydrocarbons such as chloroform and methylene chloride; halogenated benzenes such as chlorobenzene; and alkylbenzenes such as toluene and xylene can be used. The solution concentration of isoindole (2) is preferably about 0.01 to 2 M, more preferably about 0.05 to 1 M.

The isols (2), phosphoryl halide, and dialkyl formamide may be mixed to form Vilsmeier reagent ([R ⁷ R ⁸ NCHCHX ⁵ ] ⁽⁺⁾ X ^{5 (−)} ) in the reaction system. Alternatively, the phosphoryl halide and dialkylformamide may be mixed to form the Vilsmeier reagent in advance. When Vilsmeier reagent is formed in advance, isoindole (2) may be added to Vilsmeier reagent, or conversely, Vilsmeier reagent may be added to isoindole (2). In each of the addition and mixing steps, cooling may be performed as necessary in order to suppress heat generation. The temperature of the Vilsmeier reaction is influenced by the solvent used, but is usually 0 ° C. or more, preferably 20 ° C. or more, preferably 140 ° C. or less, more preferably 120 ° C. or less. The time of Vilsmeier reaction is preferably 5 minutes or more, more preferably 10 minutes or more, more preferably 30 minutes or more, preferably 20 hours or less, more preferably 15 hours or less, still more preferably 10 hours or less.

Aminomethylenated-1H-isoindole (6a) can be readily converted to formylated-2H-isoindole (6b) by hydrolysis. This hydrolysis can be carried out simply by mixing aminomethylenated-1H-isoindole (6a) and water, but it is preferable to use an aqueous alkaline solution such as sodium acetate, sodium hydrogencarbonate or sodium hydroxide. When an aqueous alkaline solution is used, the temperature of hydrolysis is usually 0 to 100 ° C., preferably 20 to 80 ° C., and the time is usually 0.5 to 10 hours, preferably 1 to 5 hours.

Hydroxymethylated-2H-isoindole (6c) can be prepared by reducing formylation-2H-isoindole (6b). The reduction of formyl groups (aldehydes) to hydroxymethyl groups (alcohols) is easy and can be done by methods well known in the art of synthetic organic chemistry. Examples of the reducing agent include complexes of boron hydrides such as NaBH ₄ and BH ₃ -THF, and complexes of aluminum hydrides such as LiAlH ₄ and diisobutylaluminum hydride. In addition, it is necessary to suppress the reduction of the isoindole ring and to perform the reduction only under the condition of the formyl group. For example, when using a strong reducing agent such as LiAlH _4, it is sufficient to terminate the reduction reaction in a short time.

After preparing the intermediates (6a), (6b) or (6c), without purifying them, the reaction mixture as it is is used to prepare the following intermediates or π-conjugated cyclic compounds (7) (especially porphyrin (7a)): It can also be used for manufacturing. However, in order to produce highly pure π-conjugated cyclic compound (7), it is recommended to purify one or more of intermediates (6a), (6b) and (6c) and then use it in the next step Be done. As a purification method, for example, silica gel column chromatography, alumina column chromatography, sublimation purification, recrystallization, crystallization and the like can be used.

Hydroxymethylated-2H-isoindole (6c) is more stabilized than the starting material isoindole (2), but is more reactive than the pyrrole used to make regular porphyrins . Therefore, when hydroxymethylated-2H-isoindole (6c) is reacted in the presence of chloroacetic acid or the like usually used to synthesize porphyrin from pyrrole, it is polymerized to form isoindole oligomers and the like. In order to produce π-conjugated cyclic compound (7) (especially porphyrin (7a)) from hydroxymethylated-2H-isoindole (6c) while suppressing the polymerization reaction, dehydration using an acid weaker than chloroacetic acid It is necessary to cyclize. As acids for this, such as acetic acid, aliphatic monocarboxylic acids such as propionic and butyric; succinic acid, glutaric acid, adipic acid, aliphatic dicarboxylic acids such as pimelic acid; and ZnCl _2, BF ₃ and BF ₃ · O Weak Lewis acids such as (C ₂ H ₅ ) ₂ can be used, of which the said aliphatic monocarboxylic acids and the said Lewis acids are preferred. The aliphatic monocarboxylic acid and / or the Lewis acid can be used alone or in combination of two or more.

The above-mentioned dehydrating cyclization may be carried out after isolating hydroxymethylated-2H-isoindole (6c), or after reduction of formylated-2H-isoindole (6b), the reaction mixture is used as it is May be When the isolated hydroxymethylated-2H-isoindole (6c) is used for dehydrating cyclization, the amount of the acid used per mole of hydroxymethylated-2H-isoindole (6c) is 1.5 moles in the Lewis acid. The degree is about 1.5 moles or more in the aliphatic carboxylic acid. The aliphatic carboxylic acid can also be used in excess as a solvent. When the reaction mixture is used for dehydrating cyclization without isolation of the hydroxymethylated-2H-isoindole (6c) obtained with a hydride reducing reagent, said aliphatic carboxylic acid is for quenching of the hydride reducing reagent Can also be used. In this case, the aliphatic carboxylic acid is preferably used in excess.

The reaction temperature of the dehydrocyclization of hydroxymethylated-2H-isoindole (6c) may be appropriately set according to its reactivity, and is, for example, usually 0 ° C. or higher, preferably 20 ° C. or higher, preferably 140 C. or less, more preferably 120 ° C. or less. The reaction time is preferably 0.1 hours or more, more preferably 0.5 hours or more, preferably 96 hours or less, more preferably 72 hours or less.

By the above-described dehydrating cyclization, a reduced form of the π-conjugated cyclic compound (7) (in particular, porphyrinogen (11)) is obtained, and by oxidizing this with an oxidizing agent, the π-conjugated cyclic compound (7) (particularly, porphyrin (7a)) can be produced. When a weak acid of acetic acid or so is used in the cyclodehydration, this weak acid may or may not be neutralized before oxidation of the reduced form of the π-conjugated cyclic compound (7) (especially porphyrinogen (11)). Although good, preferably prior to the oxidation step, it is recommended to neutralize the acid used in the cyclodehydration.

As oxidizing agents for this purpose, oxygen, oxygen-containing gases such as air; p-chloranil (6,3,5,6-tetrachloro-p-benzoquinone), DDQ (6,3-dicyano-5,6-dichloro) Quinones such as -p-benzoquinone) can be used. The oxidizing agents can be used alone or in combination of two or more. The oxidation reaction temperature is, for example, usually 10 ° C. or more, preferably 20 ° C. or more, preferably 100 ° C. or less, more preferably 80 ° C. or less. The reaction time is preferably 30 minutes or more, more preferably 1 hour or more, preferably 48 hours or less, more preferably 24 hours or less.

The reaction for synthesizing π-conjugated cyclic compound (7) (particularly porphyrin (7a)) from hydroxymethylated-2H-isoindole (6c) by dehydration cyclization and oxidation is usually a solution reaction. The aliphatic carboxylic acid can be used as a solvent therefor. Further, as other solvents, for example, chlorinated hydrocarbons such as chloroform and methylene chloride; aromatic hydrocarbons such as benzene, toluene and xylene; ethers such as THF, dioxane, cyclopentyl methyl ether, diisopropyl ether and diethyl ether Alcohols such as methanol, ethanol and propanol; esters such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate; and amides such as dimethylformamide and dimethylacetamide. The solvents can be used alone or in combination of two or more. When a solvent is used, the concentration of the starting material hydroxymethylated-2H-isoindole (6c) is preferably about 1 to 1000 mM, more preferably about 5 to 500 mM.

The π-conjugated cyclic compound (7) (particularly porphyrin (7a)) obtained as described above can be purified by sublimation, recrystallization, crystallization or the like. For example, if it is a porphyrin (7a) having a substituent such as a phenoxy group, it can also be purified by silica gel column chromatography or alumina column chromatography.

Next, a preferred method for producing aminomethylated-2H-isoindole (6d) is described. Aminomethylated-2H-isoindole (6d) is an isoindole (2), formaldehyde, and a dialkylamine NHR ⁵ R ⁶ (wherein R ⁵ and R ⁶ are each independently C) in the presence of an acid _{1 to 4} alkyl group) can be produced by the Mannich reaction. In addition, halogenated methylene dialkyl ammonium H ₂ C = NR ⁵ R ⁶ X ⁶ prepared in advance, wherein R ⁵ and R ⁶ each independently represent a C _1-4 alkyl group, and X ⁶ represents a halogen atom. Mannich reaction may be carried out using is.) And isoindole (2).

First, the case of using formaldehyde and dialkylamine will be described. Examples of the acid used for this Mannich reaction include inorganic acids such as hydrohalic acid (hydrochloric acid, hydrofluoric acid, hydrobromic acid, hydroiodic acid), nitric acid, sulfuric acid; and formic acid, trifluoroacetic acid, trichloroacetic acid, etc. And the like. Among these, hydrochloric acid, hydrobromic acid, sulfuric acid and trifluoroacetic acid are preferable. It is recommended to use a monobasic acid in an amount of preferably 1 to 2 moles, more preferably 1.1 to 1.5 moles, relative to 1 mole of isoindole (2). When a polybasic acid is used, the recommended amount to be used is an amount obtained by multiplying the above amount of monobasic acid by the valence number of polybasic acid. Further, examples of the dialkylamine include dimethylamine, diethylamine, diisopropylamine and dibutylamine. Among these, dimethylamine (R ⁵ = R ⁶ = CH ₃ ) is preferable from the viewpoint of reactivity and the like. It is recommended to use dialkylamine and formaldehyde, preferably in an amount of 1 to 2 moles, more preferably 1.1 to 1.5 moles, each with respect to 1 mole of isoindole (2).

Next, the case of using a methylenedialkylammonium halide is described. The methylenedialkylammonium halide can be prepared from formaldehyde and a dialkylamine, or for example methylenedimethylammonium halide can be obtained from Aldrich. As the methylene dialkyl dialkyl halide, methylene dimethyl dimethyl halide is preferable, and methylene dimethyl ammonium iodide and methylene dimethyl ammonium chloride are more preferable. The amount of methylenedialkylammonium halide is preferably 1 to 2.5 mol, more preferably 1.05 to 2 mol, still more preferably 1.1 to 1.5 mol, per 1 mol of isoindole (2). Recommended for use with

The Mannich reaction is usually performed using a solvent. As solvents, chlorohydrocarbons such as chloroform and methylene chloride; aromatic hydrocarbons such as benzene, toluene and xylene; ethers such as THF, dioxane, cyclopentyl methyl ether, diisopropyl ether and diethyl ether; methanol, ethanol, Alcohols such as propanol; esters such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate; and nitriles such as acetonitrile, propionitrile and benzonitrile can be mentioned. The solvents can be used alone or in combination of two or more. When a solvent is used, the concentration of the starting material isoindole (2) is preferably about 0.01 to 2 M, more preferably about 0.05 to 1 M.

The temperature of the above Mannich reaction is influenced by the solvent used, etc., but is usually 0 ° C. or more, preferably 20 ° C. or more, preferably 120 ° C. or less, more preferably 100 ° C. or less. The reaction time is preferably 1 hour or more, more preferably 2 hours or more, preferably 72 hours or less, more preferably 48 hours or less.

Intermediate (6d), which is a 1-position substitution of isoindole (2), is considered to be more stable than isoindole (2), as with intermediates (6a) to (6c). However, since the intermediate (6d) is more active than the intermediate (6c), it is cyclized as soon as it is formed, thereby reducing the π-conjugated cyclic compound (7) (especially porphyrinogen (11)), The π-conjugated cyclic compound (7) (especially porphyrin (7a)) is then formed. Thus, in the method of the present invention which undergoes the Mannich reaction, the π-conjugated cyclic compound (7) can be produced by causing the oxidizing agent to act after the Mannich reaction. The Mannich reaction and the subsequent oxidation reaction after the cyclization reaction can be carried out in the same manner as described above.

The porphyrins (7a) obtained as described above can be combined with various metal or metalloid ions to form porphyrin complexes (8), as is well known in the field of porphyrin chemistry. Examples of metal or metalloid ions to be bound to the porphyrin complex (8) include Group 2 elements excluding Be and Ra, rare earth elements, Th, U, Group 4 to 12 elements, and Group 13 elements excluding B. Mention may be made of the ions of Group 14 elements excluding C and Group 15 elements excluding N and P. Among these, metal ions are preferable, and Co, Zn, Cu, Ni, Pd, Pt, Fe or Mn ions are more preferable. The porphyrin ligand can be bound to a trivalent or higher metal or metalloid ion, in which case the central metal of the porphyrin complex is bound to a halogen, an alkyl, an alkoxyl group or the like to balance the charge.

In order to form porphyrin complexes (8) of these metals or metalloids, metal salts containing metal or metalloid ions, such as halide salts (in particular chloride salts, bromide salts and iodide salts) or acetates, etc. And porphyrin (7a) may be mixed. It is also possible to add a metal salt containing metal or metalloid ion followed by oxidation after cyclization of intermediate (6c) or (6d) and before oxidation (ie, at the stage of porphyrinogen (11)). , Porphyrin complex (8) can be formed. This complexing reaction is usually carried out in a solvent, and as the solvent therefor, the same one as in the preparation of porphyrin can be used. The temperature for the complexing reaction is preferably 0 ° C. or more, more preferably 10 ° C. or more, preferably 80 ° C. or less, more preferably 60 ° C. or less. The time for the complexation reaction is preferably 1 hour or more, more preferably 2 hours or more, preferably 96 hours or less, more preferably 72 hours or less.

Among the porphyrin (7a) and porphyrin complexes (8) of the present invention, hexadecafluoro-tetrabenzoporphyrin and 2 ^{1, 2} 2, 2 ^3, 2 ^4, 7 ^1, 7 ^2, 7 ^3, 7 ^4, 12 ^1, 12 ² , 12 ³ , 12 ⁴ , 17 ¹ , 17 ² , 17 ³ , 17 ⁴ -hexadecachloro-21H, 23H-tetrabenzoporphyrin and complexes thereof are preferred, and hexadecafluorotetrabenzoporphyrin and complexes thereof are preferred. Since fluorine or chlorine, in particular fluorine, is electron-withdrawing, porphyrins containing a large number of them and complexes thereof are expected to be particularly applicable to materials of n-type organic semiconductors or organic field effect transistors. .

The present invention, which relates to a method for producing isoindole multimer, will now be described in detail. The method for producing an isoindole multimer of the present invention is characterized in that phthalonitriles are used as starting materials, not isoindoles. The phthalonitriles are much more stable and easier to handle than isoindoles. Moreover, phthalonitriles are sold as raw materials, such as a pigment, and are easily available.

As a result of intensive studies by the present inventors, it has been surprisingly found that catalytic hydrogenation of phthalonitriles in the presence of an acid can produce an isoindole multimer. As this reaction mechanism, what is shown by the following chemical formula is presumed. However, the present invention is not limited to this estimation mechanism.

As shown by the above chemical formula, hydrogen is first added to the cyano group of phthalonitrile (9) and then cyclized to form intermediate (a) (1-imino-1H-isoindoles) . An acid (proton in the above chemical formula) is added to the tertiary amine nitrogen of this intermediate (a) to form an intermediate (b). On the other hand, addition of hydrogen to the tertiary amine portion of intermediate (a) forms intermediate (c) (1-iminoisoindolines), and hydrogen is further added to the imino group of intermediate (c). Addition is followed by elimination of the amino group as ammonia to form intermediate (d) (2H-isoindoles). Thus, either acid or hydrogen is added to intermediate (a) to form intermediate (b) or (d), and addition of these results in intermediate (e) (an imino group A dimer having an isoindoline skeleton and an isoindole skeleton is formed. From this intermediate (e), a dimer (f) of 2H-isoindoles is formed by hydrogen addition to the imino group as described above and elimination of the amino group (also a dimer ( f) are also included within the scope of isoindole multimers (10) of the present invention). It is thought that by repeating such a reaction, an isoindole multimer (10) having a repeating number of 2 or more is formed from phthalonitrile (9).

In the production method of the present invention, as shown above, it is presumed that isoindoles are formed in the reaction system by reduction of the cyano group, and then these are added to form an isoindole multimer. Therefore, it is presumed that the substituent D of phthalonitrile (9) does not greatly affect this reaction (particularly, the reduction reaction). Therefore, in the production method of the present invention, all kinds of phthalonitriles (9), more specifically, unsubstituted phthalonitriles (p = 0 in the formula (9)) or phthalonitriles having all kinds of substituents D Can be used.

The phthalonitrile (9) used in the present invention includes phthalonitrile (unsubstituted phthalonitrile) or substituted phthalonitrile having a substituent such as a halogen atom as described above. The substituted phthalonitriles include those having only one type of substituent (for example, a halogen atom) or two or more types of substituents (for example, a halogen and an alkyl group).

The halogen atom of phthalonitrile (9) is preferably a fluorine, chlorine or bromine atom, more preferably a fluorine or chlorine atom, still more preferably a fluorine atom. In phthalonitrile (9), plural kinds of halogen atoms may be present at the same time.

R ¹ , R ² and R ³ in the above formula (9) are each independently preferably a C ₁ to C ₂₀ alkyl group, more preferably a C ₁ to C ₁₀ alkyl group, still more preferably C ₁ to C ₅ Alkyl group; preferably C ₆ -C ₂₀ aryl group, more preferably C ₆ -C ₁₂ aryl group; or preferably C ₇ -C ₂₀ alkyl aryl group, more preferably C ₇ -C ₁₅ alkyl aryl group, more preferably Is a C ₇ -C ₁₀ alkylaryl group. R ¹ , R ² and R ³ may contain a halogen atom on their carbon skeleton. When any one of R ¹ , OR ² and SR ³ exists as a substituent D, the plurality of R ¹ , R ² and R ³ may be different substituents (for example, an alkyl group and an aryl group) good.

Among the above phthalonitriles (9), phthalonitrile (1) having a halogen atom X is preferable. Isoindole multimer (4) produced from phthalonitrile (1) having a halogen atom (in particular, a fluorine atom which is a strong electron-withdrawing group) is expected to be applied to new applications such as n-type semiconductors This is because that. In the above formula (1), the number m of halogen atoms X is preferably 2 or more, more preferably 3 or more, and still more preferably 4. Incidentally halogen atom X in the formula (1), examples of R ^1, R ² and R ³ include those described above.

Phthalonitriles can be obtained or manufactured as described above. As phthalonitriles used in the method for producing an isoindole multimer, phthalides represented by the above-mentioned formula (1a) or (1d), particularly above-mentioned formula (1b) or (1c), or above-mentioned formula (1e) or (1f) Nitriles are preferred.

As an acid used by the manufacturing method of the iso indole multimer of this invention, inorganic or organic protic acid is preferable. Examples of inorganic protonic acids include hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, sulfuric acid; phosphoric acids such as orthophosphoric acid and pyrophosphoric acid; perhalogen acids such as perchloric acid; phosphomolybdic acid, silicomolybdic acid, Examples thereof include heteropolyacids such as phosphotungstic acid, silicotungstic acid, lintungstomolybdic acid, and phosphovanadomolybdic acid.

Examples of organic protic acids include arylsulfonic acids such as benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, etc .; methanesulfonic acid, trifluoromethanesulfonic acid, trichloromethanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, t- Alkyl sulfonic acids such as butyl sulfonic acid; formic acid, acetic acid, propionic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, trifluoroacetic acid, pentafluoropropionic acid, n-butyric acid, isobutyric acid, pivalic acid, valeric acid, caproic acid, Saturated aliphatic carboxylic acids such as caprylic acid, capric acid, lauric acid, myristic acid, cyclohexane carboxylic acid; acrylic acid, methacrylic acid, propiolic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, oleic acid, etc. Unsaturation of Aliphatic carboxylic acid; benzoic acid, phthalic acid, isophthalic acid, and aromatic carboxylic acids such as terephthalic acid.

Among the protic acids, acetic acid, trifluoroacetic acid, phosphoric acid, hydrochloric acid, nitric acid and sulfuric acid are preferable. When using a protic acid as the acid, it is recommended that the amount of proton (H ⁺ ) be equal to or more than the molar amount of phthalonitrile (9) as the starting material. It is because polymerization can be promoted by using an equimolar or more proton. The amount of proton is preferably 1 to 10 moles, more preferably 1.05 to 7 moles, and still more preferably 1.1 to 5 moles relative to 1 mole of phthalonitrile (9).

As catalysts used for catalytic hydrogenation, conventional metal catalysts known in the art can be used. Preferably, the central metal of the catalyst is 0.01 to 30% by mole, more preferably 0.1 to 20% by mole, still more preferably 1 to 10% by mole relative to phthalonitrile (9). It is recommended to use metal catalysts.

Examples of the metal catalyst include homogeneous catalysts constituted by coordinating phosphine or the like to ruthenium or rhodium. However, in view of reactivity, easiness of recovery after reaction and regeneration treatment, it is preferable to use a heterogeneous catalyst in the present invention. Among heterogeneous catalysts, in order to increase the surface area and improve the catalytic activity, a catalyst in which fine metal powder is supported on a carrier is preferable. Heterogeneous catalysts, for example, metals such as nickel, Raney nickel, copper-chromium oxide, ruthenium, palladium, rhodium, platinum and platinum oxide, or fine powders of these metals supported on a support such as activated carbon, alumina, diatomaceous earth It can be mentioned. Among these metal catalysts, palladium catalysts, rhodium catalysts, platinum catalysts and nickel catalysts are preferable, and from the viewpoint of catalytic activity, catalysts in which palladium is supported on activated carbon are more preferable.

When a heterogeneous catalyst is used, a catalyst activation step of mixing the catalyst and the protonic acid under a hydrogen atmosphere before catalytic hydrogenation may be employed as needed. The activation temperature is usually from room temperature to about 50 ° C., and the activation time is preferably 10 minutes or more, more preferably 30 minutes or more, still more preferably 1 hour or more, preferably 5 hours or less. More preferably, it is 3 hours or less, still more preferably 2 hours or less.

The catalytic hydrogenation is usually carried out using a solvent. The solvent is not particularly limited, but those which can dissolve phthalonitrile (9) which is a starting material are preferable. As solvents, for example, aromatic hydrocarbons such as benzene, toluene, xylene and the like; ethers such as THF, dioxane, cyclopentyl methyl ether, diisopropyl ether, diethyl ether and the like; alcohols such as methanol, ethanol, propanol and the like; methyl acetate, ethyl acetate , Esters such as propyl acetate and butyl acetate; amides such as dimethylformamide, dimethylacetamide; sulfolanes such as sulfolane, 3-methylsulfolane, 2,4-dimethylsulfolane; and formic acid, acetic acid, propionic acid, trifluoroacetic acid Etc. can be mentioned. In the catalytic hydrogenation method, mixed solvents of amides or acetic acids and water can also be used. The solvents can be used alone or in combination of two or more. Among these solvents, solvents in which the solubility of the isoindole multimer is high, such as ethyl acetate, propyl acetate, dimethylformamide, dimethylacetamide, sulfolane, 3-methylsulfolane and 2,4-dimethylsulfolane are preferable. When a solvent is used, the concentration of phthalonitrile (9) is preferably about 0.01 to 5 M, more preferably about 0.05 to 1 M.

The temperature of the catalytic hydrogenation is also affected by the solvent used, but is preferably 0 ° C. or more, more preferably 20 ° C. or more, preferably 150 ° C. or less, more preferably 120 ° C. or less. The time of the catalytic hydrogenation reaction is preferably 30 minutes or more, more preferably 1 hour or more, still more preferably 2 hours or more, preferably 48 hours or less, more preferably 24 hours or less. It is preferred to use hydrogen under pressure to promote catalytic hydrogenation. The hydrogen pressure is preferably 1.1 atmospheres or more, more preferably 1.5 atmospheres or more, and further preferably 2 atmospheres or more. However, the hydrogen pressure is preferably 5 atm or less, more preferably 3 atm or less, due to the restriction of equipment and the like.

Catalytic hydrogenation can be carried out by continuously supplying hydrogen gas to the reaction system. Alternatively, after hydrogen gas is supplied to a constant pressure, the reaction system is sealed to carry out catalytic hydrogenation, and after the pressure in the system decreases as the reaction proceeds, hydrogen gas can be supplied again. It is desirable to depressurize the reaction system prior to the hydrogen gas supply. Further, in order to adsorb a large amount of hydrogen to the catalyst, it is a preferable embodiment to repeat the decompression and the supply of hydrogen gas a plurality of times, especially when the catalytic hydrogenation is performed in the presence of a solvent.

The number of repeating units of the isoindole multimer to be produced is 2 or more, preferably 3 or more, more preferably 5 or more. This is because as the number of repeating units of isoindole multimer increases and the molecular weight increases, the mechanical properties as a multimer, particularly as a polymer, improve. However, isoindole multimers having too large a molecular weight are difficult to produce and the handleability of the multimer itself is also reduced. Therefore, the weight average molecular weight (value by GPC measurement in terms of polystyrene) of the isoindole multimer is preferably about 1,000 to 500,000, more preferably about 3,000 to 300,000, and still more preferably 5,000 to 10 It is about 10,000.

After the isoindole multimer is produced by the production method of the present invention, doping may be performed by a known method in order to improve the conductivity of the multimer.

EXAMPLES Hereinafter, the present invention will be more specifically described by way of examples. However, the present invention is not limited by the following examples, and appropriate modifications may be made within the scope which can be adapted to the above-mentioned and the following gist. Of course, implementation is also possible, and all of them are included in the technical scope of the present invention.

The following Examples 1 to 21 are examples of isoindoles (2) and (3) of the present invention, and polyisoindoles (4) and (5). Examples 22 to 34 are examples of the intermediate (6) (= “the 1-position substitution of isoindole”), porphyrin (7a) and porphyrin complex (8) of the present invention. Examples 35 to 38 are examples relating to the isoindole multimer (10) of the present invention.

Example 1: Reduction of tetrafluorophthalonitrile with hydrogenated diisobutylaluminum

In a four-necked reaction vessel equipped with a reflux condenser, a dropping funnel, and a thermometer, 3.0 g (15.0 mmol) of tetrafluorophthalonitrile (manufactured by Nippon Shokubai Co., Ltd.) was added, and after nitrogen substitution, it was dehydrated with a syringe Added 75 ml. While cooling in an ice bath, 61 ml (60.3 mmol) of a 0.99 M solution of diisobutylaluminum hydride (purchased from Kanto Chemical Co., Ltd.) in toluene was slowly added dropwise from the dropping funnel. After completion of the dropwise addition, the mixture was stirred at room temperature overnight, and then quenched by adding 45 ml (90 mmol) of 2 M hydrochloric acid while cooling in an ice bath. The reaction product was extracted with ethyl acetate, neutralized with aqueous sodium bicarbonate solution, washed with saturated brine, and dried over anhydrous sodium sulfate, and the extract was concentrated by an evaporator. The concentrate was purified by silica gel column chromatography (solvent: dichloromethane). The desired product 4,5,6,7-tetrafluoro-2H-isoindole was obtained in 22.6% yield (0.64 g, 3.4 mmol).

Example 2 Reduction of Tetrafluorophthalonitrile with Diisobutylaluminium The reaction was carried out under the same conditions as in Example 1, but only 100 ml of water was added during quenching without using a protonic acid. Shortly after the addition of water, the reaction solution gelled. The solid matter was removed by celite filtration, and purification was performed by the same operation as in Example 1. As a result, the target substance 4,5,6,7-tetrafluoro-2H-isoindole was obtained in a yield of 0.6% (0.017 g) , 0.09 mmol).

Example 3: Reduction of tetrafluorophthalonitrile by hydrogenated diisobutylaluminum In the same manner as in Example 1, except that the concentrate was purified by sublimation, 4,5,6,7-tetrafluoro-2H-isoindole was used. The yield was 9.87% (0.28 g, 1.48 mmol).

Example 4 Reduction of Tetrafluorophthalonitrile with Diisobutylaluminum Hydrogenate 0.2 g (1.06 mmol) of tetrafluorophthalonitrile was added to an eggplant flask and purged with nitrogen, and then 6 ml of dehydrated toluene was added. While cooling in an ice bath, 4.21 ml (4 mmol) of a 0.95 M solution of diisobutylaluminum hydride in toluene was slowly added dropwise, and after returning to room temperature, the mixture was stirred for 23 hours. After that, 15 ml (15 mmol) of 1 M aqueous NaOH solution was slowly added to the reaction mixture. Further, ethyl acetate is added, the gel is filtered through celite, the reaction product is extracted with ethyl acetate, washed several times with pure water, dried over anhydrous sodium sulfate, the solvent is removed under reduced pressure, and the concentrate is The residue was purified by chromatography on silica gel short column (solvent: chloroform). The desired product 4,5,6,7-tetrafluoro-2H-isoindole (skin solid) was obtained in 20.8% yield (39.4 mg, 0.21 mmol).

Example 5: Reduction of 4,5-bis (pentafluorophenoxy) -3,6-difluorophthalonitrile with diisobutylaluminum hydride

The raw material 4,5-bis (pentafluorophenoxy) -3,6-difluorophthalonitrile was first prepared as follows: 20.1 g of tetrafluorophthalonitrile in a 200 ml reaction vessel equipped with a dropping funnel and a thermometer 100.45 mmol), 13.99 g (240.79 mmol) of potassium fluoride and 130 ml of methyl isobutyl ketone were added. After cooling with an ice bath, a solution of 37.0 g (201.02 mmol) of pentafluorophenol dissolved in 70 ml of methyl isobutyl ketone is slowly added from the dropping funnel, and then the reaction is carried out by stirring at room temperature for 2 days The The reaction solution was filtered to remove inorganic salts, washed with water using a separatory funnel, and dried over anhydrous sodium sulfate, and then the reaction solution was concentrated with an evaporator. The concentrate is purified by reprecipitation with a toluene / hexane solvent to give 4,5-bis (pentafluorophenoxy) -3,6-difluorophthalonitrile in a yield of 70.83% (37.4 g, 70.81 mmol). Obtained by).

Next, 1.50 g (2.84 mmol) of 4,5-bis (pentafluorophenoxy) -3,6-difluorophthalonitrile was added to a four-necked reaction vessel equipped with a reflux condenser, a dropping funnel and a thermometer, and nitrogen was added. After substitution, 25.5 ml of dehydrated toluene was added by a syringe. While cooling with an ice bath, 11.5 ml (11.4 mmol) of a toluene solution of 0.99 M hydrogenated diisobutylaluminum (purchased from Kanto Chemical Co., Ltd.) was slowly dropped from the dropping funnel. After completion of the dropwise addition, the reaction was allowed to proceed at 95 ° C. for 4 hours, and allowed to cool to room temperature, followed by quenching by adding 10 ml (20 mmol) of 2 M hydrochloric acid while cooling in an ice bath. The reaction product was extracted with ethyl acetate, neutralized with aqueous sodium bicarbonate solution, washed with saturated brine, and dried over anhydrous sodium sulfate, and the extract was concentrated by an evaporator. The concentrate was purified by silica gel column chromatography (solvent: dichloromethane). The desired product 5,6-bis (pentafluorophenoxy) -4,7-difluoro-2H-isoindole was obtained in a yield of 34.04% (0.50 g, 0.97 mmol).

Spectral data of 5,6-bis (pentafluorophenoxy) -4,7-difluoro-2H-isoindole (1) NMR spectrum (apparatus: JEOL, model: JNM-AL400)
¹ H-NMR (CDCl ₃ ): δ 7.31 (m, 2 H), 9.62 (brs, 1 H)
¹⁹ F-NMR (CDCl ₃ ): δ-143.57 (s, 2F), -157.50 (m, 4F), -162.50 (m, 2F), -163.49 (m, 4F)
(2) Mass spectrum (Device: manufactured by Nippon Denshi, model: JMS-MS 700v)
MS (EI): m / z = 518 (M ⁺ ) (calculated molecular weight: 517)

Example 6: Reduction of 4-pentafluorophenoxy-3,5,6-trifluorophthalonitrile with diisobutylaluminum hydride

After 0.364 g (1 mmol) of 4-pentafluorophenoxy-3,5,6-trifluorophthalonitrile prepared in the same manner as in Example 5 was added to an eggplant flask and purged with nitrogen, 7 ml of dehydrated toluene was added. While cooling in an ice bath, 4.04 ml (4 mmol) of a 0.99 M solution of diisobutylaluminum hydride in toluene was slowly added dropwise, and after returning to room temperature, the mixture was stirred for 24 hours. After that, 16 ml (16 mmol) of 1 M aqueous NaOH solution was slowly added to the reaction mixture. Further, ethyl acetate is added, the gel is filtered through celite, the reaction product is extracted with ethyl acetate, washed several times with pure water, dried over anhydrous sodium sulfate, the solvent is removed under reduced pressure, and the concentrate is The residue was purified by chromatography on silica gel short column (solvent: dichloromethane). The objective 5-pentafluorophenoxy-4,6,7-trifluoro-2H-isoindole (brown solid) was obtained in a yield of 17.5% (61.7 mg, 0.17 mmol).

NMR spectrum of 5-pentafluorophenoxy-4,6,7-trifluoro-2H-isoindole (apparatus: JEOL, model: JNM-AL400)
¹ H-NMR (CDCl ₃ ): δ 7.35 (m, 2 H), 9.57 (brs, 1 H)
¹⁹ F-NMR (CDCl ₃ ): δ-143.22 (s, 1F), 151.45 (m, 1F), -157.15 (m, 2F), -162.22 (m, 1F), -163.02 (m, 1F), 163.31 (m, 2F)

Example 7: Reduction of 4,5-bis (pentafluorothiophenoxy) -3,6-difluorophthalonitrile with diisobutylaluminum hydride

After adding 0.560 g (1 mmol) of 4,5-bis (pentafluorothiophenoxy) -3,6-difluorophthalonitrile prepared by the same method as in Example 5 to an eggplant flask and carrying out nitrogen substitution, 30 ml of dehydrated toluene was added. added. While cooling in an ice bath, 4.04 ml (4 mmol) of a 0.99 M solution of diisobutylaluminum hydride in toluene was slowly added dropwise, and after returning to room temperature, the mixture was stirred for 24 hours. After that, 16 ml (16 mmol) of 1 M aqueous NaOH solution was slowly added to the reaction mixture. Further, ethyl acetate is added, the gel is filtered through celite, the reaction product is extracted with ethyl acetate, washed several times with pure water, dried over anhydrous sodium sulfate, the solvent is removed under reduced pressure, and the concentrate is The residue was purified by chromatography on silica gel short column (solvent: dichloromethane). The desired product 5,6-bis (pentafluorothiophenoxy) -4,7-difluoro-2H-isoindole (green solid) was obtained in a yield of 20.2% (110.7 mg, 0.20 mmol) .

Spectral data of 5,6-bis (pentafluorothiophenoxy) -4,7-difluoro-2H-isoindole (1) NMR spectrum (apparatus: JEOL, model: JNM-AL400)
¹ H-NMR (CDCl ₃ ): δ 7.35 (q, J = 1.5 Hz, 2 H), 9.62 (brs, 1 H)
¹⁹ F-NMR (CDCl ₃ ): δ-109.65 (s, 2F), -134.32 (m, 4F), -153.89 (t, J = 21 Hz, 2F), -161.71 (m. , 4F)
(2) Mass spectrum (Device: manufactured by Nippon Denshi, model: JMS-MS 700v)
MS (EI): m / z = 549 (M ⁺ ) (calculated molecular weight: 548.95)

Example 8: Reduction of 4-chloro-3,5,6-trifluorophthalonitrile with diisobutylaluminum hydride

The starting 4-chloro-3,5,6-trifluorophthalonitrile was first prepared as follows: 1000 g (5 mol) of tetrafluorophthalonitrile, N-methyl-2 in a 5 L reaction vessel equipped with a reflux condenser. 1004 g of pyrrolidone and 2343 g of acetonitrile were charged, the temperature was raised to 75 ° C., 233 g (5.5 mol) of lithium chloride were successively added, and reaction was carried out at this temperature for 7 hours. The reaction solution was concentrated by an evaporator to remove any acetonitrile, and then the concentrate was poured into water, and the precipitate was filtered to obtain a crudely purified product. Subsequently, the crude product is dissolved in methyl isobutyl ketone and washed with water to remove inorganic salts, the aqueous phase and the organic phase are separated, the organic phase is dried over anhydrous sodium sulfate, concentrated by an evaporator and concentrated Under reduced pressure to give 4-chloro-3,5,6-trifluorophthalonitrile in a yield of 40.7% (440.5 g, 2.03 mol).

Next, 1.50 g (6.93 mmol) of 4-chloro-3,5,6-trifluorophthalonitrile is added to a four-necked reaction vessel equipped with a reflux condenser, a dropping funnel and a thermometer, and the system is purged with nitrogen, 7 ml of dehydrated toluene was added by a syringe. While cooling with an ice bath, 28 ml (27.7 mmol) of a toluene solution of 0.99 M hydrogenated diisobutylaluminum (purchased from Kanto Chemical Co., Ltd.) was slowly dropped from the dropping funnel. After completion of the dropwise addition, the reaction was allowed to proceed at 95 ° C. for 4 hours, and allowed to cool to room temperature, followed by quenching by adding 21 ml (42 mmol) of 2 M hydrochloric acid while cooling in an ice bath. The reaction product was extracted with ethyl acetate, neutralized with aqueous sodium bicarbonate solution, washed with saturated brine, and dried over anhydrous sodium sulfate, and the extract was concentrated by an evaporator. The concentrate was purified by silica gel column chromatography (solvent: dichloromethane). The desired product 5-chloro-4,6,7-trifluoro-2H-isoindole was obtained in a yield of 12.64% (0.18 g, 0.88 mmol).

Spectral data of 5-chloro-4,6,7-trifluoro-2H-isoindole (1) NMR spectrum (instrument: JEOL, model: JNM-AL400)
¹ H-NMR (CDCl ₃ ): δ 7.29 (m, 2H), 9.39 (brs, 1H)
¹⁹ F-NMR (CDCl ₃ ): δ -125.66 (dt, J = 20 Hz, 2 Hz, 1 F), -150.76 (dd, J = 16 Hz, 2 Hz, 1 F), -151.58 (ddd, J = 20 Hz, 16 Hz, 2 Hz, 1 F),
(2) Mass spectrum (Device: manufactured by Nippon Denshi, model: JMS-MS 700v)
MS (EI): m / z = 205 (M ⁺ ) (calculated molecular weight: 204.99)

Example 9: Reduction of 4,5-dichloro-3,6-difluorophthalonitrile with diisobutylaluminum hydride

0.233 g (1 mmol) of 4,5-dichloro-3,6-difluorophthalonitrile prepared in the same manner as in Example 8 was added to an eggplant flask and purged with nitrogen, and then 7 ml of dehydrated toluene was added. While cooling in an ice bath, 4.04 ml (4 mmol) of a 0.99 M solution of diisobutylaluminum hydride in toluene was slowly added dropwise, and after returning to room temperature, the mixture was stirred for 24 hours. After that, 16 ml (16 mmol) of 1 M aqueous NaOH solution was slowly added to the reaction mixture. Further, ethyl acetate is added, the gel is filtered through celite, the reaction product is extracted with ethyl acetate, washed several times with pure water, dried over anhydrous sodium sulfate, the solvent is removed under reduced pressure, and the concentrate is The residue was purified by chromatography on silica gel short column (solvent: dichloromethane). The desired product, 5,6-dichloro-4,7-difluoro-2H-isoindole (a pale yellow solid) was obtained in a yield of 27.1% (60.3 mg, 0.27 mmol).

Spectral data of 5,6-dichloro-4,7-difluoro-2H-isoindole (1) NMR spectrum (apparatus: JEOL, model: JNM-AL400)
¹ H-NMR (CDCl ₃ ): δ 7.33 (q, J = 1.5 Hz, 2 H), 9.50 (brs, 1 H)
¹⁹ F-NMR (CDCl ₃ ): δ-122.01 (s, 2F)
(2) Mass spectrum (Device: manufactured by Nippon Denshi, model: JMS-MS 700v)
MS (EI): m / z = 221 (M ⁺ ) (calculated molecular weight: 220.96)

Example 10: Reduction of 4,5-bis (hexylthio) -3,6-difluorophthalonitrile with diisobutylaluminum hydride

After adding 2.0 g (5.04 mmol) of 4,5-bis (hexylthio) -3,6-difluorophthalonitrile prepared by the same method as in Example 5 to an eggplant flask and carrying out nitrogen substitution, 40 ml of dehydrated toluene was added. The While cooling in an ice bath, 20.5 ml (20.30 mmol) of a 0.99 M solution of diisobutylaluminum hydride in toluene was slowly added dropwise, and after returning to room temperature, the mixture was stirred for 16 hours. Then, 20 ml (20 mmol) of 1 M aqueous NaOH solution was slowly added to the reaction mixture. Further, ethyl acetate is added, the gel is filtered through celite, the reaction product is extracted with ethyl acetate, washed several times with pure water, dried over anhydrous sodium sulfate, the solvent is removed under reduced pressure, and the concentrate is The residue was purified by chromatography on silica gel short column (solvent: dichloromethane). The desired product 5,6-bis (hexylthio) -4,7-difluoro-2H-isoindole (yellow liquid) was obtained in a yield of 22.1% (60.429 g, 1.11 mmol).

NMR spectrum of 5,6-bis (hexylthio) -4,7-difluoro-2H-isoindole (apparatus: manufactured by Varian, model: Mercury 2000)
¹ H-NMR (CDCl ₃ ): δ 0.85 (t, 6 H, J = 6.4 Hz), 1.26 to 1.66 (m, 16 H), 2.89 (t, 4 H, J = 7.3 Hz ), 7.32 (m, 2 H), 9.6 (brs, 1 H)
¹⁹ F-NMR (CDCl ₃ , hexafluorobenzene): δ 50.08 (s, 2F)

Example 11: Reduction of tetrafluorophthalonitrile with BH ₃

After replacing the three-necked reaction vessel equipped with a reflux condenser, a dropping funnel and a thermometer with nitrogen, 20 ml (19.8 mmol) of a 0.99 M THF-BH ₃ complex (purchased from Kanto Chemical Co., Ltd.) in THF and 35 ml of THF was added. Separately, a solution of 3.0 g (14.99 mmol) of tetrafluorophthalonitrile dissolved in 10 ml of toluene was prepared, and this solution was slowly dropped into the reaction vessel at room temperature. After completion of the dropwise addition, the mixture was heated to 65 ° C. and reacted for 4 hours. After that, the reaction solution was returned to room temperature again, and while cooling in an ice bath, it was quenched by adding 18 ml (36 mmol) of 2 M hydrochloric acid. The reaction product was extracted with ethyl acetate, washed with distilled water and then with brine and dried over anhydrous sodium sulfate, and the extract was concentrated by an evaporator. The concentrate was purified by silica gel column chromatography (solvent: dichloromethane). The desired product 4,5,6,7-tetrafluoro-2H-isoindole was obtained in a yield of 37% (1.05 g, 5.55 mmol).

Example 12: Reduction of tetrafluorophthalonitrile by catalytic hydrogenation

In a 100 ml three-necked flask, palladium activated carbon supported palladium (purchased from Aldrich, Pd: 10% by mass) 0.75 g (Pd amount: 0.70 mmol), 30 ml of methanol, 1.3 ml of 3 M sulfuric acid 3.9 mmol) were added. Next, after the system is depressurized and the operation of supplying hydrogen (hydrogen substitution) is repeated three times, the catalyst is activated by stirring for 10 minutes at room temperature while being pressurized with a hydrogen balloon (about 1.1 atm) It turned Thereafter, a solution of 1.50 g (7.5 mmol) of tetrafluorophthalonitrile dissolved in 20 ml of toluene was added to an eggplant flask and vigorously stirred at room temperature for 13 hours. The reaction solution is neutralized with aqueous sodium bicarbonate solution, then the Pd catalyst (Pd / C) is removed by celite filtration, extracted with chloroform, washed with distilled water and then with saturated brine, dried over anhydrous sodium sulfate and then extracted The product was concentrated by an evaporator. The concentrate was purified by silica gel column chromatography (solvent: chloroform). The desired product 4,5,6,7-tetrafluoro-2H-isoindole was obtained in 41.6% yield (0.59 g, 3.12 mmol).

Example 13: Reduction of tetrafluorophthalonitrile by catalytic hydrogenation

0.5 g (Pd amount: 0.47 mmol), a catalyst (purchased from Aldrich, Pd: 10% by mass) in which palladium is supported on activated carbon in a 100 ml three-necked flask, 20 ml of ethyl acetate, 0.6 g of trifluoroacetic acid (5.26 mmol) was added. Next, after the system is depressurized and the operation of supplying hydrogen (hydrogen substitution) is repeated three times, the catalyst is stirred for 30 minutes at room temperature under pressure (about 1.1 atm) with a hydrogen balloon. It was activated. Thereafter, a solution of 1.00 g (5 mmol) of tetrafluorophthalonitrile dissolved in 20 ml of ethyl acetate was added to an eggplant flask and vigorously stirred at room temperature for 13 hours. The reaction solution is neutralized with aqueous sodium bicarbonate solution, then the Pd catalyst (Pd / C) is removed by celite filtration, extracted with chloroform, washed with distilled water and then with saturated brine, dried over anhydrous sodium sulfate and then extracted The product was concentrated by an evaporator. The concentrate was purified by silica gel column chromatography (solvent: chloroform). The desired product 4,5,6,7-tetrafluoro-2H-isoindole was obtained in 33.4% yield (0.316 g, 1.67 mmol).

Example 14: Reduction of tetrafluorophthalonitrile by catalytic hydrogenation

In a 100 ml eggplant flask, 1.0 g (Rh amount: 0.49 mmol) of Rh / alumina catalyst (purchased from Aldrich, Rh: 5% by mass) and 20 ml of methanol are added and hydrogen-replaced, and stirred at room temperature for 45 minutes did. Thereafter, 0.28 ml (5 mmol) of acetic acid was added, a solution of 1.0 g (5 mmol) of tetrafluorophthalonitrile dissolved in 20 ml of methanol was added dropwise, and after hydrogen substitution again, the mixture was stirred at room temperature for 65 hours. Thereafter, 4.5 ml of a saturated aqueous solution of sodium hydrogen carbonate was added, followed by filtration through Celite, extraction with ethyl acetate and chloroform, washing with distilled water, and concentration under reduced pressure to obtain 0.96 g of a black purple solid. The product is purified by silica gel column chromatography (solvent: chloroform) to give 4,5,6,7-tetrafluoro-2H-isoindole as a skin-colored solid in a yield of 4.1% (0%). .038 g, 0.20 mmol).

Example 15: Reduction of tetrafluorophthalonitrile by catalytic hydrogenation

In a 1000 ml three-necked flask, 3.77 g (Pd: 7.09 mmol) of palladium hydroxide supported on activated carbon (purchased from Aldrich, Pd: 20% by mass), 300 ml of methanol, and 3 M sulfuric acid 12. 5 ml (37.5 mmol) were added. Next, after the system is depressurized and the operation of supplying hydrogen (hydrogen substitution) is repeated three times, the catalyst is activated by stirring for 10 minutes at room temperature while being pressurized with a hydrogen balloon (about 1.1 atm) It turned Thereafter, a solution of 15 g (75 mmol) of tetrafluorophthalonitrile in a mixed solvent of 200 ml of toluene and 200 ml of ethyl acetate was added to an eggplant flask and stirred at room temperature for 14 hours. The reaction solution is neutralized with aqueous sodium bicarbonate solution, then the Pd catalyst is removed by Celite filtration, extracted with toluene, washed with distilled water and then with saturated brine, and dried over anhydrous sodium sulfate, and the extract is concentrated by an evaporator did. The concentrate was purified by silica gel column chromatography (solvent: chloroform). The desired product 4,5,6,7-tetrafluoro-2H-isoindole was obtained in a 28% yield (3.976 g, 21.02 mmol).

Example 16: Reduction of 4,5-bis (pentafluorophenyl) -3,6-difluorophthalonitrile by catalytic hydrogenation

A catalyst (purchased from Aldrich, Pd: 10% by mass) with palladium supported on activated carbon in a 100 ml three-necked reaction vessel (0.86 g of Pd: 0.81 mmol), 30 ml of methanol, 0.5 ml of 3 M sulfuric acid (1.5 mmol) was added. The system is depressurized and nitrogen supply operation (nitrogen substitution) is repeated three times, and then the pressure reduction and hydrogen supply operation (hydrogen substitution) are repeated three times, and then pressure is applied with a hydrogen balloon (approximately 1 The catalyst was activated by stirring for about 5 minutes at room temperature under a pressure of 1 atm. Thereafter, a solution of 1.50 g (3.02 mmol) of 4,5-bis (pentafluorophenyl) -3,6-difluorophthalonitrile in a mixed solvent of 15 ml of toluene and 30 ml of ethyl acetate is added to the reaction solution, Stir vigorously at room temperature for 15 hours. The reaction solution was neutralized with aqueous sodium bicarbonate solution, extracted with ethyl acetate, washed with distilled water and then with saturated brine, and dried over anhydrous sodium sulfate, and the extract was concentrated by an evaporator. The concentrate was purified by silica gel column chromatography (solvent: chloroform). The desired product 5,6-bis (pentafluorophenyl) -4,7-difluoro-2H-isoindole was obtained in a yield of 49.1% (0.72 g, 1.48 mmol).

Spectral data of 5,6-bis (pentafluorophenyl) -4,7-difluoro-2H-isoindole (1) NMR spectrum (apparatus: JEOL, model: JNM-AL400)
¹ H-NMR ((CD ₃ ) ₂ CO): δ 7.78 (s, 2 H), 12.34 (brs, 1 H)
¹⁹ F-NMR ((CD ₃ ) ₂ CO): δ-115.2179 (s, 2F), -133.78 (d, J = 22 Hz, 4F), -147.68 (t, J = 21 Hz, 2F) ), -156.37 (t, J = 18 Hz, 4 F)
(2) Mass spectrum (Device: manufactured by Nippon Denshi, model: JMS-MS 700V)
MS (EI): m / z = 485 (M ⁺ ) (calculated molecular weight: 485.01)

Example 17 Reduction of 4,5-bis (2,5-dimethylphenoxy) -3,6-difluorophthalonitrile by catalytic hydrogenation

In a 100 ml three-necked flask, a catalyst of palladium supported on activated carbon (purchased from Aldrich, Pd: 10% by mass) 1.00 g (Pd amount: 0.94 mmol), 5 ml of methanol, 1.25 ml of 3 M sulfuric acid 3.75 mmol) were added. After the system has been depressurized and the operation of supplying hydrogen (hydrogen substitution) is repeated three times, the catalyst is activated by stirring for 10 minutes at room temperature while being pressurized (about 1.1 atm) with a hydrogen balloon It turned Thereafter, a solution of 3.00 g (7.42 mmol) of 4,5-bis (2,5-dimethylphenoxy) -3,6-difluorophthalonitrile in 20 ml of ethyl acetate is added to the flask and the solution is allowed to stand at room temperature for 14 hours. Stir vigorously. The reaction solution is neutralized with aqueous sodium bicarbonate solution, then the Pd catalyst is removed by Celite filtration, extracted with toluene, washed with distilled water and then with saturated brine, and dried over anhydrous sodium sulfate, and the extract is concentrated by an evaporator did. The concentrate was purified by silica gel column chromatography (solvent: chloroform). The desired product, 5,6-bis (2,5-dimethylphenoxy) -4,7-difluoro-2H-isoindole was obtained in 21% yield (0.623 g, 1.58 mmol).

NMR spectrum of 5,6-bis (2,5-dimethylphenoxy) -4,7-difluoro-2H-isoindole (Device: manufactured by Varian, model: Mercury 2000)
¹ H-NMR (CDCl ₃ ): δ 1.83 (s, 3 H), 2.16 (s, 3 H), 6.46 (s, 1 H), 6.67 (d, 1 H, J = 7.30 Hz) , 6.93 (d, 1 H, J = 7.30 Hz), 7.35 (m, 2 H), 9.47 (brs, 1 H)
¹⁹ F-NMR (CDCl ₃ , hexafluorobenzene): δ 19.39 (s, 2F)

Example 18: Alkylation of 4,5,6,7-tetrafluoro-2H-isoindole with methyl iodide

In a 10 ml two-necked reaction vessel, 0.096 g (0.507 mmol) of 4,5,6,7-tetrafluoro-2H-isoindole was added, and after replacing with nitrogen, 3.5 ml of dehydrated THF was added and cooled to −78 ° C. did. Thereto, 0.6 ml (0.942 mmol) of a 1.57 M n-butyllithium n-hexane solution was slowly added using a syringe and stirred at -78 ° C. for 30 minutes. Then, 0.2 g (1.409 mmol) of methyl iodide was slowly added to it using a syringe and stirred for 14 hours as it was without cooling. Water was added to terminate the reaction, the reaction product was extracted with ethyl acetate, and the organic phase was washed successively with aqueous sodium bicarbonate solution, water and saturated brine, and then dried over anhydrous sodium sulfate. After removing anhydrous sodium sulfate by filtration, the organic phase was concentrated. The concentrate is purified by silica gel column chromatography (solvent: ethyl acetate) to give the target 4,5,6,7-tetrafluoro-2-methylisoindole in a yield of 58.2% (0.060 g) , 0.295 mmol).

Example 19: Alkylation of 4,5,6,7-tetrafluoro-2H-isoindole with iodination-n-pentyl

In a 10 ml two-necked reaction vessel, 0.49 g (2.59 mmol) of 4,5,6,7-tetrafluoro-2H-isoindole was added, and after nitrogen substitution, 17 ml of dehydrated THF was added and cooled to -78.degree. Thereto, 2 ml (3.14 mmol) of a 1.57 M n-butyllithium n-hexane solution was slowly added using a syringe, and the mixture was stirred at -78 ° C for 30 minutes. Then, 0.67 g (3.38 mmol) of i-n-pentyl iodide was slowly added to it using a syringe, and the solution was stirred for 14 hours without cooling. Water was added to terminate the reaction, the reaction product was extracted with ethyl acetate, and the organic phase was washed successively with aqueous sodium bicarbonate solution, water and saturated brine, and then dried over anhydrous sodium sulfate. After removing anhydrous sodium sulfate by filtration, the organic phase was concentrated. The concentrate is purified by silica gel column chromatography (solvent: ethyl acetate) to give the target 4,5,6,7-tetrafluoro-2-n-pentylisoindole in a yield of 83.6% (0%). .564 g, 2.176 mmol).

Mass spectrum of 4,5,6,7-tetrafluoro-2-n-pentylisoindole (apparatus: JEOL, model: JMS-MS 700v)
MS (EI): m / z = 259 (M ⁺ ) (calculated molecular weight: 259.1)

Example 20: Oxidative polymerization of 4,5,6,7-tetrafluoro-2H-isoindole 0.18 g (0.95 mmol) of 4,5,6,7-tetrafluoro-2H-isoindole is weighed in an eggplant flask. Then, 4.3 g of chloroform was added to this and stirred to prepare an isoindole solution. In a separate container, 0.63 g (3.88 mmol) of iron (III) chloride was weighed, and 3.4 g of water was added to prepare an aqueous iron chloride solution. The aqueous iron chloride solution was slowly added to the previously prepared isoindole solution, and after stirring at room temperature for 48 hours, the reaction solution was poured into a large amount of water. The solution obtained by filtration is washed with dilute hydrochloric acid, water and then chloroform, and then the residue is vacuum-dried to obtain black poly (4,5,6,7-tetrafluoro-2H-isoindole). 0.109 g (converted yield 61.2%) was obtained.

The average molecular weight of the obtained polymer (as measured by GPC in terms of polystyrene) was Mn = 23,400 and Mw = 41,200. The conductivity of the polymer (measured by the two-terminal method) was 4 × 10 ⁻⁶ S / cm ² .

Example 21 Oxidative polymerization of 4,5,6,7-tetrafluoro-2-n-pentylisoindole In an eggplant flask, 0.248 g of 4,5,6,7-tetrafluoro-2-n-pentylisoindole was added. 0.96 mmol) was weighed, and to this, 4.5 g of chloroform was added and stirred to prepare an isoindole solution. In a separate container, 0.62 g (3.82 mmol) of iron (III) chloride was weighed out, and 3.5 g of water was added to prepare an aqueous iron chloride solution. The aqueous iron chloride solution was slowly added to the previously prepared isoindole solution, and after stirring at room temperature for 48 hours, the reaction solution was poured into a large amount of water. The solution obtained by filtration is washed with dilute hydrochloric acid, water and then chloroform, and then the residue is vacuum-dried to obtain black poly (4,5,6,7-tetrafluoro-2-n-pentyl). 0.05 g (converted yield 20.3%) of isoindole was obtained. The average molecular weight of the obtained polymer (measured by GPC in terms of polystyrene) was Mn = 20,400 and Mw = 29,500.

Example 22 Preparation of 2- (N, N-dimethylaminomethylene) -4,5,6,7-tetrafluoro-1H-isoindole (hereinafter abbreviated as "amino methylene compound")

A 50 ml two-necked eggplant flask equipped with a reflux apparatus is purged with nitrogen, 0.21 ml (2.75 mmol) of dimethylformamide is added while cooling with an ice bath, and 0.26 ml (2.75 mmol) of phosphoryl chloride is slowly added thereto. It was added dropwise and stirred for 15 minutes. 2 ml of methylene chloride is added to dissolve the precipitated solid, and a solution of 480 mg (2.54 mmol) of 4,5,6,7-tetrafluoro-2H-isoindole in 2 ml of methylene chloride is slowly added dropwise thereto, and then The ice bath was removed and heated to 55 ° C. and refluxed for 15 minutes. The reaction mixture is then cooled to room temperature, and a solution of 1.25 g of sodium acetate dissolved in 2.5 ml of ion-exchanged water is slowly added, and then the reaction mixture is extracted with diethyl ether, and the extracted organic phase is washed with an aqueous solution of sodium hydrogen carbonate After washing and drying over anhydrous sodium sulfate, concentration under reduced pressure gave a brown solid. This was purified by silica gel chromatography (solvent: chloroform) to obtain 350 mg (1.43 mmol, yield 58.7%) of an aminomethylene compound.

Spectrum data of amino methylene compound (1) NMR spectrum (Device: JEOL, model: JNM-AL400)
¹ H-NMR (CDCl ₃ ): δ 3.39 (s, 3 H), 3.78 (s, 3 H), 7.53 (s, 1 H), 8.09 (s, 1 H)
¹⁹ F-NMR (CDCl ₃ ): δ-166.15 (dd, J = 21, 20 Hz, 1 F), −161.89 (dd, J = 21, 20 Hz, 1 F), −151.46 (dd, J = 21, 20 Hz, 1 F), -148.22 (dd, J = 21, 20 Hz, 1 F)
(2) Mass spectrum (Device: manufactured by Nippon Denshi, model: JMS-MS 700v type)
MS (EI): m / z = 244 (M ⁺ ) (calculated molecular weight: 244.19)

Example 23 Preparation of 1-formyl-4,5,6,7-tetrafluoro-2H-isoindole (hereinafter abbreviated as "formyl form")

A 50 ml two-necked eggplant flask equipped with a reflux apparatus is purged with nitrogen, 0.21 ml (2.75 mmol) of dimethylformamide is added while cooling with an ice bath, and 0.26 ml (2.75 mmol) of phosphoryl chloride is slowly added thereto. It was added dropwise and stirred for 15 minutes. 1.5 ml of methylene chloride was added to the precipitated solid to dissolve the solid, and a solution of 470 mg (2.49 mmol) of 4,5,6,7-tetrafluoro-2H-isoindole in 6 ml of methylene chloride was slowly added to the solid. It was added dropwise and then the ice bath was removed and heated to 55 ° C. and refluxed for 15 minutes. The reaction solution was then cooled to room temperature, and a solution of 1.25 g of sodium acetate dissolved in 2.5 ml of ion-exchanged water was slowly added, followed by refluxing at 55 ° C. for 2 hours and cooling to room temperature. The reaction mixture was then extracted with diethyl ether, and the extracted organic phase was washed with aqueous sodium hydrogen carbonate solution, dried over anhydrous sodium sulfate and concentrated under reduced pressure to give a brown solid. This was purified by silica gel chromatography (solvent: ethyl acetate 30% by volume / hexane 70% by volume) to obtain 70 mg (0.322 mmol, 13.0% yield) of a formyl form.

Spectrum data of formyl form (1) NMR spectrum (apparatus: manufactured by JEOL, model: JNM-AL400)
¹ H-NMR ((CD ₃ ) ₂ CO): δ 8.01 (s, 1 H), 9. 81 (s, 1 H)
¹⁹ F-NMR ((CD ₃ ) ₂ CO)): δ-168.54 (dd, J = 17, 18 Hz, 1 F), −162.64 (dd, J = 17, 18 Hz, 1 F), −149. 20 (dd, J = 20, 18 Hz, 1 F), -146.90 (brs, 1 F)
(2) Mass spectrum (Device: manufactured by Nippon Denshi, model: JMS-MS 700v type)
MS (EI): m / z = 217 (M ⁺ ) (calculated molecular weight: 217.12)

Example 24 Preparation of Formyl Form from Amino Methylene Form

326.7 mg (1.34 mmol) of aminomethylene was added to a 100 ml eggplant flask equipped with a reflux apparatus and purged with nitrogen, and 35 ml of ethanol was added thereto for dissolution, and then 2 ml (2 mmol) of 1 M aqueous NaOH solution was added The mixture was heated at 60.degree. C. for 1.5 hours and cooled to room temperature. The reaction mixture is then extracted with ethyl acetate, ethanol is removed by water, dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain 208.6 mg (0.96 mmol, yield) of formyl as a white solid. 71.7%).

Example 25 Preparation of 1-hydroxymethyl-4,5,6,7-tetrafluoro-2H-isoindole (hereinafter abbreviated as "hydroxymethyl")

108.6 mg (0.5 mmol) of formyl compound is added to a 100 ml eggplant flask and purged with nitrogen, 20 ml of dry THF is added thereto, and 1.1 ml (1.1 mmol) of 1 M diisobutylaluminum hydride solution is stirred at -78 ° C. ) Was added and stirred for another 2 hours. Quench with 1 M HCl still at -78 ° C., return to room temperature and extract the reaction mixture with ethyl acetate, wash with aqueous sodium bicarbonate and water, dry over anhydrous sodium sulfate and then under reduced pressure Concentration gave 103 mg (0.47 mmol, crude yield 94%) of the hydroxymethyl compound as a reddish-purple solid.

Example 26: Preparation of hexadecafluorotetrabenzoporphyrin from hydroxymethyl form

103 mg (crude yield 0.47 mmol) of the hydroxymethyl compound obtained in Example 25 is directly added to a 100 ml eggplant flask and purged with nitrogen, and then 47 ml of ethanol is added and dissolved, and 3 ml (51.8 mmol) of acetic acid is added After stirring, it was stirred at room temperature for 3 days. Then, 3.18 ml (51.8 mmol) of triethylamine is added to the reaction mixture for neutralization, and then 119.3 mg (0.47 mmol) of DDQ (2,3-dicyano-5,6-dichloro-p-benzoquinone) is added. Stir at room temperature overnight. Then, the reaction mixture was suction filtered to obtain 28 mg (crude yield: 0.035 mmol, crude yield: 29.8%) of hexadecafluorotetrabenzoporphyrin as a dark green solid.

Spectral data of hexadecafluorotetrabenzoporphyrin (1) Mass spectrum (apparatus: manufactured by Applied Biosystems, model: Voyager-DE ^TM PRO)
MS (TOF-MS): m / z = 798.80 (M ⁺ ) (calculated molecular weight: 798.03)
(2) Ultraviolet-visible absorption spectrum (apparatus: manufactured by Hitachi High-Technologies, model: U-2800)
λ _max (CHCl ₃ ) = 416, 430, 599, 667, 690 nm

In addition, from TOF-MS measurement, corrole represented by the following formula (actual value: m / z = 785.87, calculated molecular weight: 786.03), saphirin (actual value: m / z = 985.) In a crude product. It was confirmed that 95, calculated molecular weight: 985.04) and pentaphilin (found value: m / z = 997.93, calculated molecular weight: 997.04) were formed.

Example 27 Preparation of hexadecafluorotetrabenzoporphyrin via 1- (N, N-dimethylamino) methyl-4,5,6,7-tetrafluoro-2H-isoindole ("aminomethyl")

After 100 mg (0.529 mmol) of 4,5,6,7-tetrafluoro-2H-isoindole and 102 mg (0.553 mmol) of methylenedimethylammonium iodide were added to a reaction vessel and nitrogen substitution was carried out, 8.41 g of acetonitrile was added. Add and stir at room temperature for 32 hours. After that, 150 mg (661 mmol) of DDQ was added and stirred at room temperature for another 24 hours. Thereafter, 14.2 g of saturated aqueous sodium bicarbonate solution was added to terminate the reaction. The filtrate obtained by filtering the reaction solution was further ultrasonically washed with methanol and then chloroform to obtain 20 mg (0.025 mmol, yield 18.94%) of hexadecafluorotetrabenzoporphyrin.

Example 28: 1- (N, N- dimethylamino) methyl-5,6-bis (pentafluorophenyl) -4,7 undergo difluoro -2H- isoindole ( "aminomethyl body") ² 2, 2 ³ , 7 ² , 7 ³ , 12 ² , 12 ³ , 17 ² , 17 ³ -octakis (pentafluorophenyl)-2 ¹ , 2 ⁴ , 7 ¹ , 7 ⁴ , 12 ¹ , 12 ⁴ , 17 ¹ , 17 ⁴ Of 1-octafluoro-21H, 23H-tetrabenzoporphyrin (hereinafter abbreviated as "octakis (pentafluorophenyl) octafluorotetrabenzoporphyrin")

Into a reaction vessel, 200 mg (0.40 mmol) of 5,6-bis (pentafluorophenyl) -4,7-difluoro-2H-isoindole and 76.3 mg (0.41 mmol) of methylenedimethylammonium iodide were added and nitrogen substitution was carried out After that, 17.7 g of acetonitrile was added and stirred at room temperature for 48 hours. After the reaction, the reaction solution was concentrated using an evaporator, and subsequently, the concentrate was dissolved in chloroform, and the chloroform phase was washed with water, dried over anhydrous sodium sulfate, and concentrated again using an evaporator. The concentrate is purified by silica gel column chromatography (solvent: ethyl acetate 50% by volume / hexane 50% by volume) to obtain 12 mg (0.006 mmol, yield 6.0) of octakis (pentafluorophenyl) octafluorotetrabenzoporphyrin. %) Got.

Spectral data of octakis (pentafluorophenyl) octafluorotetrabenzoporphyrin (1) Mass spectrum (apparatus: manufactured by Applied Biosystems, model: Voyager-DE ^TM PRO)
MS (TOF-MS): m / z = 1984.26 (M ⁺ ) (calculated molecular weight: 1981.98)
(2) Ultraviolet-visible absorption spectrum (apparatus: manufactured by Shimadzu Corporation, model: uv-1650Pc)
λ _max (CHCl ₃ ) = 435, 451, 576, 623, 632 nm

Example 29: Preparation of hexadecafluorotetrabenzoporphyrin zinc complex (hereinafter abbreviated as "porphyrin zinc complex") In a reaction vessel, 300 mg (1.59 mmol) of 4,5,6,7-tetrafluoro-2H-isoindole ) And 300 mg (1.62 mmol) of methylenedimethyliodide were added, and after purging with nitrogen, 69.3 g of methylene chloride was added, and the mixture was stirred at room temperature for 48 hours. After that, the atmosphere was opened from the nitrogen atmosphere to the atmosphere, 256 mg (1.40 mmol) of zinc acetate was added, and the mixture was stirred at the atmosphere and at room temperature for further 48 hours. Oxidation of porphyrinogen is presumed to be mainly performed by stirring under this atmosphere. Thereafter, the reaction solution was transferred to a separatory funnel, washed with water, and concentrated by an evaporator. The concentrate was ultrasonically washed three times with methanol and ethyl acetate to obtain 92 mg (0.107 mmol, yield 26.9%) of a porphyrin zinc complex.

Spectral data of porphyrin zinc complex (1) NMR spectrum (Device: manufactured by VARIAN, model: Mercury 2000)
¹ H-NMR (THF): δ 10.85 (s, 1 H)
¹⁹ F-NMR (THF, standard substance: hexafluorobenzene): δ 7.20 (m, 2F), 18.4 (m, 2F)
(2) Mass spectrum (apparatus: manufactured by Applied Biosystems, model: Voyager-DE ^TM PRO)
MS (TOF-MS): m / z = 860.84 (M ⁺ ) (calculated molecular weight: 859.95)
(3) Ultraviolet-visible absorption spectrum (apparatus: manufactured by Shimadzu Corporation, model: uv-1650Pc)
λ _max (THF) = 407, 432, 623 nm

Example 30 Preparation of Porphyrin Zinc Complex In a reaction vessel, 517 mg (2.734 mmol) of 4,5,6,7-tetrafluoro-2H-isoindole and 528 mg (2.85 mmol) of methylenedimethylammonium iodide are added and then nitrogen is added. After substitution, 41.27 g of acetonitrile was added and stirred at room temperature for 48 hours. Thereafter, 700 mg (3.81 mmol) of zinc acetate was added, and the mixture was stirred at room temperature for another 6 hours, and then 910 mg (4.008 mmol) of DDQ was added and stirred at room temperature for another 24 hours. Thereafter, the reaction solution is poured into 60 g of saturated aqueous sodium bicarbonate solution, the filtrate is collected by filtration, and the filtrate is washed with methanol and then with isopropyl alcohol, and then 50 mg (0.058 mmol, yield 8. 49%).

Example 31: Preparation of hexadecafluorotetrabenzoporphyrin copper complex (hereinafter abbreviated as "porphyrin copper complex") In a reaction vessel, 700 mg (3.70 mmol) of 4,5,6,7-tetrafluoro-2H-isoindole ) And methylenedimethyliodide (700 mg (3.78 mmol)) were added, and after purging with nitrogen, 98.3 g of acetonitrile was added and stirred at room temperature for 48 hours. Then, under nitrogen atmosphere, the atmosphere was opened to the atmosphere, 744 mg (3.73 mmol) of copper acetate monohydrate was added, and the mixture was stirred for 48 hours under the atmosphere and at room temperature. Oxidation of porphyrinogen is presumed to be mainly performed by stirring under this atmosphere. After that, the reaction solution was concentrated by an evaporator, and the concentrate was ultrasonically washed with methanol, ethyl acetate and then THF to obtain 250 mg (0.291 mmol, yield 31.4%) of a porphyrin copper complex.

Spectral data of porphyrin copper complex (1) Mass spectrum (apparatus: manufactured by Applied Biosystems, model: Voyager-DE ^TM PRO)
MS (TOF-MS): m / z = 859.78 (M ⁺ ) (calculated molecular weight: 858.95)
(2) Ultraviolet-visible absorption spectrum (apparatus: manufactured by Shimadzu Corporation, model: uv-1650Pc)
λ _max (THF) = 405, 422, 620 nm

Example 32: Preparation of hexadecafluorotetrabenzoporphyrin nickel complex (hereinafter abbreviated as "porphyrin nickel complex") In a reaction vessel, 100 mg (0.529 mmol) of 4,5,6,7-tetrafluoro-2H-isoindole And after 100 mg (0.54 mmol) of methylenedimethyliodide were added and the atmosphere was replaced with nitrogen, 5.53 g of acetonitrile was added and the mixture was stirred at room temperature for 24 hours. Thereafter, 133 mg (0.534 mmol) of nickel acetate tetrahydrate were added, and the mixture was stirred at room temperature for 22 hours. After that, 124 mg (0.546 mmol) of DDQ was added and stirred at room temperature for 48 hours. Then, while stirring, the reaction solution was poured into 15 ml of 1 M aqueous sodium bicarbonate solution, filtered, and the obtained filtrate was washed with methanol and then with dilute hydrochloric acid. Furthermore, the filtrate was ultrasonically washed sequentially with each solvent of ethyl acetate, methanol and chloroform, and then Soxhlet extraction was performed to obtain 4 mg (0.005 mmol, yield 3.5%) of a porphyrin nickel complex.

Spectrum data of porphyrin nickel complex (1) Mass spectrum (Apparatus: manufactured by Applied Biosystems, Model: Voyager-DE ^TM PRO)
MS (TOF-MS): m / z = 854.69 (M ⁺ ) (calculated molecular weight: 853.95)
(2) Ultraviolet-visible absorption spectrum (apparatus: manufactured by Shimadzu Corporation, model: uv-1650Pc)
λ _max (THF) = 405, 430, 617 nm

Example 33: Preparation of hexadecafluorotetrabenzoporphyrin cobalt complex (hereinafter abbreviated as "porphyrin cobalt complex") In a reaction vessel, 100 mg (0.529 mmol) of 4,5,6,7-tetrafluoro-2H-isoindole And 100 mg (0.54 mmol) of methylenedimethyliodide were added, and the atmosphere was purged with nitrogen, and then 5.54 g of acetonitrile was added and stirred at room temperature for 24 hours. Thereafter, 134 mg (0.538 mmol) of cobalt acetate tetrahydrate was added, and the mixture was stirred at room temperature for 22 hours. Thereafter, 120 mg (0.529 mmol) of DDQ was added and stirred at room temperature for 48 hours. Then, while stirring, the reaction solution was poured into 8 ml of 1 M aqueous sodium bicarbonate and filtered. The obtained filtrate is dissolved in benzonitrile, poured into methanol to precipitate crystals, and filtered again, and the obtained filtrate is ultrasonically washed sequentially with each solvent of ethyl acetate, methanol and chloroform, Soxhlet extraction gave 3 mg (0.004 mmol, yield 2.7%) of a porphyrin cobalt complex.

Spectrum data of porphyrin cobalt complex (1) Mass spectrum (Apparatus: manufactured by Applied Biosystems, Model: Voyager-DE ^TM PRO)
MS (TOF-MS): m / z = 855. 84 (M ⁺ ) (calculated molecular weight: 854. 95)
(2) Ultraviolet-visible absorption spectrum (apparatus: manufactured by Shimadzu Corporation, model: uv-1650Pc)
λ _max (THF) = 421, 433, 447, 614 nm

Example 34: Preparation of octakis (pentafluorophenyl) octafluorotetrabenzoporphyrin zinc complex In a reaction vessel, 200 mg (0.40 mmol) of 5,6-bis (pentafluorophenyl) -4,7-difluoro-2H-isoindole After 76.3 mg (0.41 mmol) of methylenedimethylammonium iodide was added and the atmosphere was replaced with nitrogen, 17.7 g of acetonitrile was added and stirred at room temperature for 48 hours. Then, under nitrogen atmosphere, the atmosphere was opened to atmosphere, 64.7 mg (0.35 mmol) of zinc acetate was added, and the mixture was stirred at atmosphere and at room temperature for further 48 hours. Oxidation of porphyrinogen is presumed to be mainly performed by stirring under this atmosphere. Thereafter, the reaction solution is concentrated by an evaporator, the concentrate is dissolved in chloroform, the chloroform phase is washed with water and dilute hydrochloric acid, dried over anhydrous sodium sulfate, and concentrated again by an evaporator. The concentrate is purified by silica gel chromatography (solvent: ethyl acetate 20% by volume / hexane 80% by volume) to obtain 21 mg (0.010 mmol, yield) of octakis (pentafluorophenyl) octafluorotetrabenzoporphyrin zinc complex. 2%).

Spectral data of octakis (pentafluorophenyl) octafluorotetrabenzoporphyrin zinc complex (1) NMR spectrum (apparatus: JEOL, model: JNM-AL400)
¹ H-NMR (C ₅ D ₅ N): δ 11.97 (s, 1 H)
¹⁹ F-NMR (C ₅ D ₅ N): δ-159.49 (m, 2F), -149.55 (m, 1F), -138.13 (m, 2F), -118.73 (s, 1F)
(2) Mass spectrum (apparatus: manufactured by Applied Biosystems, model: Voyager-DE ^TM PRO)
MS (TOF-MS): m / z = 2047.14 (M ⁺ ) (calculated molecular weight: 2043.9)
(3) Ultraviolet-visible absorption spectrum (apparatus: manufactured by Shimadzu Corporation, model: uv-1650Pc)
λ _max (THF) = 429, 457, 595, 643 nm

Example 35 Preparation of (4,5,6,7-tetrafluoro-2H-isoindole) Multimer A catalyst in which palladium was supported on activated carbon in a 500 ml three-necked flask (purchased from Aldrich, Pd: 10 Mass%) 5.12 g (Pd amount: 4.81 mmol), 200 ml of methanol, 12.5 ml (37.5 mmol) of 3 M sulfuric acid were added. Next, after the system was depressurized and the operation of supplying hydrogen (hydrogen substitution) was repeated three times, the catalyst was activated by stirring at room temperature for 10 minutes while being pressurized with a hydrogen balloon. Thereafter, a solution of 10.0 g (49.98 mmol) of tetrafluorophthalonitrile in 200 ml of toluene was added to the flask and vigorously stirred at room temperature for 17 hours. The reaction solution was neutralized with aqueous sodium bicarbonate solution, and the palladium catalyst was removed by celite filtration. The filtrate was extracted with ethyl acetate, washed with distilled water and then with brine and dried over anhydrous sodium sulfate, and the extract was concentrated by an evaporator. The concentrate is purified by silica gel column chromatography (solvent: ethyl acetate) to obtain 6.19 g (converted yield) of (4,5,6,7-tetrafluoro-2H-isoindole) multimer of interest 65.5%) obtained. The average molecular weight of the obtained multimer (measured by GPC in terms of polystyrene) was Mn = 1,000 and Mw = 1,600.

Example 36 Preparation of (4,7-difluoro-5,6-bis (2,5-dimethylphenoxy) -2H-isoindole) Multimer A catalyst in which palladium was supported on activated carbon in a 100 ml three-necked flask (Purchase from Aldrich, Pd: 10% by mass) 1.01 g (Pd amount: 0.94 mmol), 5.1 g of methanol, and 1.5 ml (4.5 mmol) of 3 M sulfuric acid were added. Next, after the system is depressurized and the operation of supplying hydrogen (hydrogen substitution) is repeated three times, the catalyst is activated by stirring for 10 minutes at room temperature while pressurized with a hydrogen balloon (about 1.1 atm) It turned Thereafter, a solution of 3.00 g (7.42 mmol) of 3,6-difluoro-4,5-bis (2,5-dimethylphenoxy) phthalonitrile dissolved in 15 ml of ethyl acetate is added to the flask and the reaction is continued for 14 hours at room temperature. It stirred. The reaction solution was neutralized with aqueous sodium bicarbonate solution, and the palladium catalyst was removed by celite filtration. The filtrate was extracted with toluene, washed with distilled water and then with saturated brine, and dried over anhydrous sodium sulfate, and the extract was concentrated by an evaporator. The concentrate is purified by silica gel column chromatography (solvent: chloroform) to obtain the desired (4,7-difluoro-5,6-bis (2,5-dimethylphenoxy) -2H-isoindole) multimer. And 1.01 g (converted yield 34.9%) were obtained. The average molecular weight of the obtained multimer (as measured by GPC in terms of polystyrene) was Mn = 1,800 and Mw = 2,100.

Example 37 Preparation of (4,7-difluoro-5,6-bis (pentafluorophenyl) -2H-isoindole) Multimer A catalyst in which palladium was supported on activated carbon in a 20 ml two-necked flask (from Aldrich) 0.3 g (Pd: 0.28 mmol), 3 g of methanol, 0.4 ml (1.2 mmol) of 3 M sulfuric acid were added. Next, after the system is depressurized and the operation of supplying hydrogen (hydrogen substitution) is repeated three times, the catalyst is activated by stirring for 10 minutes at room temperature while pressurized with a hydrogen balloon (about 1.1 atm) It turned Thereafter, a solution of 1.00 g (2.02 mmol) of 3,6-difluoro-4,5-bis (pentafluorophenyl) phthalonitrile dissolved in 5.1 g of ethyl acetate is added to the flask and stirred at room temperature for 14 hours did. The reaction solution was neutralized with aqueous sodium bicarbonate solution, and the palladium catalyst was removed by celite filtration. The filtrate was extracted with toluene, washed with distilled water and then with saturated brine, and dried over anhydrous sodium sulfate, and the extract was concentrated by an evaporator. The concentrate is purified by silica gel column chromatography (solvent: chloroform) to obtain the desired (4,7-difluoro-5,6-bis (pentafluorophenyl) -2H-isoindole) multimer, 0. 34 g (converted yield 43.1%) were obtained. The average molecular weight of the obtained multimer (as measured by GPC in terms of polystyrene) was Mn = 1,300 and Mw = 1,500.

Example 38 Preparation of (5,6-dichloro-2H-isoindole) Multimer A catalyst in which palladium was supported on activated carbon in a 200 ml three-necked flask (purchased from Aldrich, Pd: 10% by mass). 00 g (Pd amount: 0.94 mmol), 5 g of methanol and 4.1 ml (12.3 mmol) of 3 M sulfuric acid were added. Next, after the system is depressurized and the operation of supplying hydrogen (hydrogen substitution) is repeated three times, the catalyst is activated by stirring for 10 minutes at room temperature while pressurized with a hydrogen balloon (about 1.1 atm) It turned Thereafter, a solution of 3.00 g (15.23 mmol) of 4,5-dichlorophthalonitrile in 90 ml of ethyl acetate was added to the flask and stirred at room temperature for 14 hours. The reaction solution was neutralized with sodium bicarbonate aqueous solution and then washed with ethyl acetate while removing the palladium catalyst by celite filtration. The filtrate was washed with distilled water and then saturated brine, dried over anhydrous sodium sulfate and concentrated by an evaporator. After adding methanol to this concentrate and vigorously stirring, low molecular weight substances are removed by filtration to obtain 0.76 g of a target (5,6-dichloro-2H-isoindole) polymer (conversion yield 25) .3%) obtained. The average molecular weight of the obtained multimer (as measured by GPC in terms of polystyrene) was Mn = 5,900 and Mw = 6,900.

The method for producing isoindoles of the present invention has fewer reaction steps and can produce isoindoles more inexpensively than conventional methods. The production method of the present invention can use various phthalonitriles because the reaction process is simple, and thereby various novel isoindoles can be manufactured. These novel isoindoles are expected to be used as constituent materials for organic thin film transistors, organic solar cells and the like as pigment materials or by polymerizing.

The process for producing the π-conjugated cyclic compound (7) of the present invention is characterized in that the π-conjugated cyclic compound (7) (particularly porphyrin (7a)) is produced from isoindole (2) via the intermediate (6). I assume. By passing through this intermediate (6), particularly the halogen-containing tetrabenzoporphyrin can be selectively produced in high purity. Moreover, according to the production method of the present invention, halogen-containing tetrabenzoporphyrin can be produced without using a metal salt.

The π-conjugated cyclic compounds (7) of the present invention (preferably porphyrin (7a), corrole (7b), saphyrin (7b) and pentaphyrin (7d); more preferably porphyrin (7a)) have various uses, such as organic Electronic devices, particularly organic conductive materials, organic semiconductor materials, n-type organic field effect transistors (OFETs), solar cell materials, photoconductive elements, non-linear optical materials, photoelectric conversion element dopants, photoconductive carrier generating materials, optical recording materials And catalysts and the like. Furthermore, the porphyrin complex (8) of the present invention can be applied to the same application. The compounds represented by the above formulas (6a) to (6c) can be applied not only to the production of the π-conjugated cyclic compound (7) but also to the production of polymer materials such as polyisoindolenine vinylene.

The method for producing an isoindole multimer of the present invention can produce an isoindole multimer by using phthalonitriles which are more stable and easier to obtain than isoindoles as a starting material. The isoindole multimer obtained by the production method of the present invention is useful as a conductive material, more specifically, as an electrode material, a display material, an electromagnetic wave shielding material and the like in the field of organic thin film transistors and organic solar cells.

Claims (30)

1. A process for producing isoindole represented by the following formula (2), which comprises reducing phthalonitrile represented by the following formula (1).
   

   

   
   [Wherein, X represents a halogen atom, Y represents R ¹ , OR ² or SR ³ , wherein R ¹ , R ² and R ³ each independently represent an alkyl, aryl or alkylaryl group] And m represents an integer of 1 to 4 and n represents an integer of 0 to 3, provided that m + n ≦ 4. ]
2. The process according to claim 1, wherein the phthalonitrile represented by the above formula (1) is reduced by a hydride reducing reagent.
3. The production method according to claim 2, wherein the hydride reducing reagent is used such that the amount of hydride is 2 to 6 moles relative to 1 mole of phthalonitrile represented by the above formula (1).
4. The production method according to claim 2, wherein the phthalonitrile represented by the above formula (1) and the hydride reducing reagent are mixed, reduction reaction is performed, and then the reaction mixture and the protonic acid are mixed.
5. The production method according to claim 2, wherein the phthalonitrile represented by the above formula (1) and the hydride reducing reagent are mixed, the reduction reaction is carried out, and then the reaction mixture and the alkali are mixed.
6. The method according to claim 2, wherein the hydride reducing reagent is aluminum hydride or a complex thereof, or boron hydride or a complex thereof.
7. The production method according to claim 1, wherein the phthalonitrile represented by the above formula (1) is reduced by catalytic hydrogenation.
8. Isoindole represented by the following formula (2) (excluding 4,5,6,7-tetrafluoro-2H-isoindole).
   

   

   
   [Wherein, X represents a halogen atom, Y represents R ¹ , OR ² or SR ³ , wherein R ¹ , R ² and R ³ each independently represent an alkyl, aryl or alkylaryl group] And m represents an integer of 1 to 4 and n represents an integer of 0 to 3, provided that m + n ≦ 4. ]
9. N-substituted isoindole represented by the following formula (3) (excluding those in which X is a fluorine atom and m = 4).
   

   

   
   [Wherein, X represents a halogen atom, Y represents R ¹ , OR ² or SR ³ , wherein R ¹ , R ² and R ³ each independently represent an alkyl, aryl or alkylaryl group] And R ⁴ represents an alkyl, aryl, alkylaryl or acyl group, and m represents an integer of 1 to 4 and n represents an integer of 0 to 3, provided that m + n ≦ 4. . ]
10. A polymer having a repeating unit represented by the following formula (4) (excluding those in which X is a fluorine atom and m = 4).
    

    

    
    [Wherein, X represents a halogen atom, Y represents R ¹ , OR ² or SR ³ , wherein R ¹ , R ² and R ³ each independently represent an alkyl, aryl or alkylaryl group] And m represents an integer of 1 to 4 and n represents an integer of 0 to 3, provided that m + n ≦ 4. ]
11. A polymer having a repeating unit represented by the following formula (5) (excluding those in which X is a fluorine atom and m = 4).
    

    

    
    [Wherein, X represents a halogen atom, Y represents R ¹ , OR ² or SR ³ , wherein R ¹ , R ² and R ³ each independently represent an alkyl, aryl or alkylaryl group] And R ⁴ represents an alkyl, aryl, alkylaryl or acyl group, and m represents an integer of 1 to 4 and n represents an integer of 0 to 3, provided that m + n ≦ 4. . ]
12. A method for producing a π-conjugated cyclic compound represented by the following formula (7) from a halogen-containing isoindole represented by the following formula (2) via a 1-position substitution of isoindole represented by the following formula (6).
    

    

    
    [Wherein, X represents a halogen atom.
    Y represents R ¹ , OR ² or SR ³ (wherein R ¹ , R ² and R ³ each independently represent an alkyl, aryl or alkylaryl group), provided that m + n ≦ 4 And m represents an integer of 1 to 4 and n represents an integer of 0 to 3.
    Z represents OH or NR ⁵ R ⁶ (wherein, R ⁵ and R ⁶ each independently represent a C _1-4 alkyl group).
    A represents N or NH, j represents an integer of 1 to 5, k represents an integer of 0 or 1, and a double line consisting of a solid line and a dotted line represents a single bond or a double bond, The cyclic compound represented by the formula (7) forms a π-conjugated system at the doublet. ]
13. The halogen-containing tetrabenzoporphyrin represented by the following formula (7a) is produced from the halogen-containing isoindole represented by the following formula (2) through the 1-position substitution of isoindole represented by the following formula (6): The manufacturing method as described in 12.
    

    

    
    [Wherein, X represents a halogen atom, and Y represents R ¹ , OR ² or SR ³ , wherein R ¹ , R ² and R ³ each independently represent an alkyl, aryl or alkylaryl group. And m is an integer of 1 to 4 and n is an integer of 0 to 3, provided that m + n ≦ 4.
    Z represents OH or NR ⁵ R ⁶ (wherein, R ⁵ and R ⁶ each independently represent a C _1-4 alkyl group). ]
14. The first intermediate represented by the following formula (6b) is formed by formylation of the halogen-containing isoindole represented by the above formula (2), and then the above intermediate (6b) is reduced to form the first intermediate The production method according to claim 13, which forms hydroxymethylated-2H-isoindole represented by the following formula (6c) as a 1-position substitution of isoindole.
    

    

    
    [Wherein, X represents a halogen atom, and Y represents R ¹ , OR ² or SR ³ , wherein R ¹ , R ² and R ³ each independently represent an alkyl, aryl or alkylaryl group. And m is an integer of 1 to 4 and n is an integer of 0 to 3, provided that m + n ≦ 4. ]
15. The halogen-containing isoindole represented by the above formula (2) is reacted with dialkylformamide in the presence of a phosphoryl halide to form a first intermediate represented by the above formula (6b). Manufacturing method described.
16. By aminomethylenation of the halogen-containing isoindole represented by the above formula (2) to form a second intermediate represented by the following formula (6a), and then hydrolyzing this intermediate (6a) The method according to claim 14, wherein the first intermediate represented by the above formula (6b) is formed.
    

    

    
    [Wherein, X represents a halogen atom, and Y represents R ¹ , OR ² or SR ³ , wherein R ¹ , R ² and R ³ each independently represent an alkyl, aryl or alkylaryl group. And m represents an integer of 1 to 4, n represents an integer of 0 to 3, and R ⁷ and R ⁸ each independently represent a C _1-4 alkyl group, provided that m + n ≦ 4. Represents ]
17. The halogen-containing isoindole represented by the above formula (2) is reacted with a dialkylformamide in the presence of a phosphoryl halide to form a second intermediate represented by the above formula (6a) Manufacturing method described.
18. Acetic acid, at least one aliphatic monocarboxylic acid, and / or ZnCl _2, BF ₃ and _{BF 3 · O (C 2 H} 5) at least one Lewis acid selected from ₂ selected from propionic acid and butyric acid Is produced by dehydrating the hydroxymethylated-2H-isoindole represented by the above formula (6c) in the presence of (6c) and then reacting with an oxidizing agent to produce the halogen-containing tetrabenzoporphyrin represented by the above formula (7) The manufacturing method according to claim 14.
19. The aminomethylated -2H-isoindole represented by the following formula (6d) is formed as a 1-substituent of the above isoindole by aminomethylating the halogen-containing isoindole represented by the above formula (2). The manufacturing method as described in 13.
    

    

    
    [Wherein, X represents a halogen atom, and Y represents R ¹ , OR ² or SR ³ , wherein R ¹ , R ² and R ³ each independently represent an alkyl, aryl or alkylaryl group. And m is an integer of 1 to 4, n is an integer of 0 to 3, and R ⁵ and R ⁶ are each independently a C _1-4 alkyl group, provided that m + n ≦ 4. Represents ]
20. In the presence of an acid, the halogen-containing isoindole represented by the above formula (2), formaldehyde, and a dialkylamine are reacted, and then the oxidizing agent is allowed to act to obtain the halogen-containing tetratetra represented by the above formula (7). The method according to claim 19, wherein benzoporphyrin is produced.
21. A halogen-containing tetrabenzoporphyrin represented by the above formula (7) is produced by reacting a halogen-containing isoindole represented by the above formula (2) with a methylenedialkylammonium halide and then reacting with an oxidizing agent. Item 19. The method according to Item 19.
22. Aminomethylenated-1H-isoindole represented by the following formula (6a):
    

    

    
    [Wherein, X represents a halogen atom, and Y represents R ¹ , OR ² or SR ³ , wherein R ¹ , R ² and R ³ each independently represent an alkyl, aryl or alkylaryl group. And m represents an integer of 1 to 4, n represents an integer of 0 to 3, and R ⁷ and R ⁸ each independently represent a C _1-4 alkyl group, provided that m + n ≦ 4. Represents ]
23. Formylated 2H-isoindole represented by the following formula (6b).
    
    [Wherein, X represents a halogen atom, and Y represents R ¹ , OR ² or SR ³ , wherein R ¹ , R ² and R ³ each independently represent an alkyl, aryl or alkylaryl group. And m is an integer of 1 to 4 and n is an integer of 0 to 3, provided that m + n ≦ 4. ]
24. Hydroxymethylated-2H-isoindole represented by the following formula (6c):
    

    

    
    [Wherein, X represents a halogen atom, and Y represents R ¹ , OR ² or SR ³ , wherein R ¹ , R ² and R ³ each independently represent an alkyl, aryl or alkylaryl group. And m is an integer of 1 to 4 and n is an integer of 0 to 3, provided that m + n ≦ 4. ]
25. The pi-conjugated cyclic compound shown by following formula (7).
    

    

    
    [Wherein, X represents a halogen atom.
    Y represents R ¹ , OR ² or SR ³ (wherein R ¹ , R ² and R ³ each independently represent an alkyl, aryl or alkylaryl group), provided that m + n ≦ 4 And m represents an integer of 1 to 4 and n represents an integer of 0 to 3.
    A represents N or NH, j represents an integer of 1 to 5, k represents an integer of 0 or 1, and a double line consisting of a solid line and a dotted line represents a single bond or a double bond, The cyclic compound represented by the formula (7) forms a π-conjugated system at the doublet. ]
26. The π-conjugated cyclic compound according to claim 25, which is a halogen-containing tetrabenzoporphyrin represented by the following formula (7a).
    

    

    
    [Wherein, X represents a halogen atom, and Y represents R ¹ , OR ² or SR ³ , wherein R ¹ , R ² and R ³ each independently represent an alkyl, aryl or alkylaryl group. And m is an integer of 1 to 4 and n is an integer of 0 to 3, provided that m + n ≦ 4. ]
27. The halogen-containing tetrabenzoporphyrin complex shown by following formula (8).
    

    

    
    [Wherein, X represents a halogen atom, and Y represents R ¹ , OR ² or SR ³ , wherein R ¹ , R ² and R ³ each independently represent an alkyl, aryl or alkylaryl group. And m represents an integer of 1 to 4, n represents an integer of 0 to 3, and M represents a metal or metalloid ion, provided that m + n ≦ 4. ]
28. A process for producing a multimer having a repeating unit represented by the following formula (10), which comprises catalytic hydrogenation of a phthalonitrile represented by the following formula (9) in the presence of an acid.
    

    

    
    [Wherein, D represents a halogen atom, R ¹ , OR ² or SR ³ (wherein R ¹ , R ² and R ³ each independently represent an alkyl, aryl or alkylaryl group), and p represents an integer of 0 to 4; ]
29. The method according to claim 28, wherein at least one selected from the group consisting of acetic acid, trifluoroacetic acid, phosphoric acid, hydrochloric acid, nitric acid and sulfuric acid is used as the acid.
30. The production method according to claim 28, wherein at least one member selected from the group consisting of a palladium catalyst, a rhodium catalyst, a platinum catalyst and a nickel catalyst is used as a catalyst for catalytic hydrogenation.