WO2008016085A1

WO2008016085A1 - Isoindoles, compounds prepared from the same, and processes for production of both

Info

Publication number: WO2008016085A1
Application number: PCT/JP2007/065080
Authority: WO
Inventors: Hidemitsu Uno; Go Masuda; Toshiya Iida
Original assignee: Nippon Shokubai Co., Ltd.
Priority date: 2006-08-02
Filing date: 2007-08-01
Publication date: 2008-02-07
Also published as: WO2008016085A9

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

Specification

Isoindoles, compounds obtained therefrom and process for producing them

Technical field

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

Background art

[0002] Isoindoles are used as pigment materials for porphyrins and the like, and are polymerized to obtain organic thin film transistors, organic solar cells, organic EL, electrophotographic photosensitive members, photorefractive materials, secondary batteries, capacitors, and charging. It is expected to be used for inhibitors, electrochromic materials, 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, photoconductivity It has been actively studied as a caustic material, an optical recording material, etc. In these porphyrins and the like, the tuning of the absorption wavelength and the fluorescence emission wavelength is an important issue that affects the performance as a dye.

[0004] For longer wavelength and higher efficiency of absorption and emission wavelengths (increase of absorption coefficient ε), π electron system is more preferable than using electron donating group or electron withdrawing group as an auxiliary dye. It is effective to extend the Examples of porphyrins having an expanded π electron system include tetrabenzoporphyrins described below.

[Formula 1]

As described above, it is possible to use tetrabenzoporphyrin or its copper complex with high planarity and expanded π electron system as a material of an organic electronic device, in particular, an organic semiconductor. — Α — 2004 — 6750 or JP — Α — 2005 — 93990.

If it is possible to synthesize a halogen-containing tetrabenzo-porphyrin, in particular a fluorine-containing tetrabenzo-porphyrin, it may be useful as an organic electronic device, particularly an η-type organic field effect transistor (OFE) or a conductive material. . Because of its high planarity, tetrabenzo porphyrin can not be used as a starting material for halogen-containing tetrabenzo porphyrin synthesis which is low in solubility in organic solvents. In JP-A-2004-6750 or JP-A-2005-93990 described above, the fluorine-containing tetrabenzo-porphyrin or its copper complex is not produced to be effective, and methods for producing them are also mentioned. Is unknown.

[0008] DE Remy et al., Tetrahedron Lett, 1983, 24, p. 1451-1454, has a formula of 4, 5, 6, 7, 7-tetrafluoro-2H-isoindole (A), formaldehyde, etc. as shown by the following formula. And acetic acid (iKil) are reacted with each other to give 2 ¹ , 2 ² , 2 ³ , 2 ⁴ , 7 ¹ , 7 ² , 7 ³ , 7 ⁴ , 12 ¹ , 12 ² , 12 ³ , 12 ⁴ , 1 7 ¹ , 17 ² , 17 ³ , 17 ^4- Hexadecafluoro-capped 21H, 23H-tetrabenzoporphyrin (hereinafter abbreviated as "hexadecaphoric fluorotetrabenzo porphyrin") zinc (II) complex (B) It is reported that it was synthesized.

[Chem. 2]

[0010] The article of DE Remy et al. Reports that the above complex (B) is synthesized only by the results of UV-visible absorption spectroscopy and mass spectrometry, but the zinc (II) complex which is supposed to be synthesized (B) ) Can not be measured by NMR and has not been isolated as a substance. According to the paper of DE Remy et al., The fact that NMR could not be measured is presumed to be due to the presence of paramagnetic impurities. However, despite the fact that the starting material is a zinc (II) salt and organic starting material, a paramagnetic species (such as a zinc (I) complex or an organic radical) is formed that is stable enough to prevent NMR measurements. It is hard to think. As the reason why DE Remy et al. Could not measure the NMR of the complex (B), it may be considered that an isoindole oligomer was formed by a thermal polymerization reaction. Moreover, although the molecular weight of the above complex (B) is 861.81, the mass analysis of the article of DE Remy et al. Gives an actual measurement value of 877, which is far from the theoretical value, and the article of DE Remy et al. The above complex (B) of high purity is obtained in / !, is not considered! /.

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 article of DE Remy et al., The complex (B) itself is not sufficiently synthesized under the influence of thermal polymerization and the like, and (II) the complex is not Even if (B) itself is synthesized, its purification may be difficult. This is because tetrabenzoporphyrin and its complexes have high planarity and low solubility, making purification difficult.

[0012] The article of DE Remy et al. Reports that it is important that metal ions with a low yield participate in the reaction in the absence of metal (DE Remy et al., P. 1453). Lines 6 to 11, especially line 11). As described in the article of DE Remy et al., It is generally accepted that 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.

[0013] Also, in the paper of DE Remy et al., It is reported that when nickel (II) acetate or copper (II) acetate is used in place of zinc (II) acetate, the target product is detected only in trace amounts. (Refer to page 1253 line 12 to line 18, especially line 15 to line 16 of the article of DE Remy et al.). Thus, in the synthesis reaction of DE Remy et al., The presence of zinc (II) acetate is essential. [0014] 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 work of DE Remy et al. Reports the synthesis of hexadefluorotetrabenzoborophyllin zinc complexes The substance has not been isolated, and It is impossible to measure NMR, etc., and its manufacturing method is well established!

[0015] Further, in the synthesis method of the article of D. E. Remy et al., It is reported that the presence of zinc (II) acetate is essential, and a zinc porphyrin complex which is not metal porphyrin can be obtained as a product. Since tetrabenzoporphyrin and its complex are difficult to purify, it is desirable to be able to produce metal free porphyrins with high purity. If high purity metal-free porphyrins are obtained, metal porphyrin complexes other than zinc as reported in the article of DE Remy et al. Can also be produced with high purity, and the metal-free porphyrins thus obtained or themselves can be obtained. Various complexes can be effectively utilized as organic device materials.

[0016] Multimers (in particular, polymers) obtained from isoindoles are known to have superior properties as compared to other conductive polymers, and have been extensively studied (eg, JP-A-S62-270621, JP-A-S63-223031, JP-A-S63-307604, JP-A-H02-263824, JP-A-H02-263825, JP-A-H03-166225 etc.).

[0017] JP-A-S62-270621 describes that polyisoindole is more stable than polyacetylene and is more difficult to dedope than polithiophen. Therefore, isoindole polymers are used in 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, electochromic materials, etc. Application is expected!

[0018] As a method for producing this isoindole multimer, oxidative polymerization of isoindoles (or isoindolines of a reductant thereof) has hitherto been known (eg, 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, the isoindoles themselves were not readily available. The conventionally known process for producing isoindoles comprises a multistep reaction process, and isoindoles can be easily produced. It was because I could not do it.

For example, in J. Borstein, DE Remy, and JE Shields, "SYNTHESIS AND REACTION S OF 4, 5, 6, 7-TETRAFLUOROISOINDOLE", Tetrahedron Lett., 1974, pp. 4247-4250, First, tetrafluorobenzene is formed by the reaction of pentafluorobenzene with n-butyllithium and the like, and then this is reacted with N-benzylpyridine to form N-benzyl 7-azatetra. It is disclosed that 4,5,6,7-tetrafluoro-2H-isoindole is produced by forming fluorobenzonorbornagene and further subjecting it to hydrogenation and thermal decomposition.

[Formula 3]

[0021] Also P. S. Anderson, M. E. Christry, E. Engelhardt, G. F. Lundell and G. S.

Ponticello, "Among ririmethlylylpyrroles as Diense in the Syntehsis of 1,4-Dihydorona phthalen-l, 4-imines and Isoindoles (1)", J. Heterocyclic Chem., 19 ", 14, pp. 213-218, As shown by the following formula, first, tetrafluorene benzene formed by the above-mentioned method and the like are reacted with N-trimethylsilylpyrrole, and then it is entangled with water to give tetraphenyl oleo-l, 4-dihydronaphthalene l, 4-imine. formation and further which the N 'alpha-click Rorobe Njiriden New ² - by reacting phenylalanine hydrazine, 4, 5, 6, it is disclosed to produce a 7-Tetorafuruo port 2Η- isoindole /! .

[Formula 4]

CeH ₅ NHN = CC ₆ H ₅

Ci

Disclosure of the invention

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 isindoles, isoindole polymers, and methods of making the polymers.

The production method of the present invention, which has achieved the first object, is characterized by reducing phthalonitrile (hereinafter sometimes referred to as “lid opening”) represented by the following formula (1), It is a method for producing indole (hereinafter referred to as “isoindole (2)” for short) having the following formula (2).

[Chem. 5]

In the above formulas (1) and (2), X represents a halogen atom, and Y is

OR ² or SR ³ (wherein R ² and R ³ each independently represent an alkyl, aryl or alkyl aryl group), and m is 1 to 1 provided that m + n≤ 4 Represents an integer of 4; n represents an integer of 0 to 3;

[0027] In the present invention, it is preferable to reduce phthalonitrile (1) with a hydride reducing reagent, and it is preferable to use a hydride reducing reagent so as to be 1 to 6 hydrides per mole of phthalonitrile (1). preferable. Furthermore, phthalonitrile (1) and hydride reduction reagent are mixed, It is recommended to mix the reaction mixture with a protonic acid or alkali after the reaction. Preferred hydride reducing agents 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 provides a novel isoindole represented by the following formula (2) (excluding 4,5,6,7-tetrafluorinated 2H-isoindole) or a novel N represented by the following formula (3) — Provides a substituted isindole (wherein X is a fluorine atom and m = 4 and may be abbreviated as “N-substituted isoindole (3)” hereinafter) (in the following formula, X, Y, m and η are as defined above, and R ⁴ represents an alkyl, aryl, alkylaryl or acyl group).

[Formula 6]

The present invention is further represented by the following formula (4) or (5) by oxidative polymerization of isoindole (2) or 置換 -substituted isoindole (3) produced by the above production method. A method of producing a polymer having a repeating unit, and the polymer itself having a repeating unit represented by the following formula (4) or (5) (except for those in which X is a fluorine atom and m = 4, respectively) Are also provided as “polyisoindole (4)”, “polyisoindole (5)” (wherein X, Y, R ⁴ , m and n are as defined above). Is). 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 electrolytic substance.

[Formula 7]

(4) (5)

[0033] A second object of the present invention is that, unlike the synthesis method of DE Remy et al., Pi-conjugated cyclic compounds (especially halogen-containing tetrabenzoporphyrin) with high purity without using metal salts or metalloid salts. To provide the technology to manufacture. The present invention also provides a method capable of producing a metal porphyrin complex having various metal ions as core nuclei which are made only by zinc ions.

[0034] The production method of the present invention which has achieved the second object is a compound comprising a 1-substituted form of isoindole represented by the following formula (6) from a halogen-containing isoindole represented by the following formula (2) (hereinafter referred to as The 1-position substitution of isoindole is sometimes abbreviated as "intermediate", and then the π-conjugated cyclic compound represented by the following formula (7) (hereinafter abbreviated as "兀 conjugated cyclic compound (7)" Are characterized by manufacturing.

[Formula 8]

In the above formulae, X represents a halogen atom.

The wolf is

OR ² or SR ³ (wherein, R ² and R ³ each independently represent an alkyl, aryl or alkylaryl group), provided that m + n 条件 4, m is 1 Represents an integer of -4, and n represents an integer of 0-3.

Z represents OH or NR ⁵ R ⁶ (wherein R ⁵ and R ⁶ each independently represent a C alkyl group)

1-4

The Represents.

A represents N or NH, j represents an integer of from! To 5, k represents an integer of 0 or 1, A double line consisting of a solid line and a dotted line represents a single bond or a double bond, and the cyclic compound represented by the formula (7) forms a 71 conjugated system at the double line part.

In the present invention, “/” and “C” mean that the carbon number is a or more and b or less, “π ab

“Conjugated system” means a structure in which two or more double bonds are linked to each other via only one single bond, and “k-zero π-conjugated cyclic compound” means a structure in formula (7). (I) at both ends of (C)

k

It means a compound in which n and dole rings are directly bonded to each other.

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

[Chem. 9]

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

[Formula 10]

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, the intermediate (6b) is reduced or (II) isoindole (2) aminomethylenated to form a second intermediate represented by the following formula (6a). By hydrolyzing the intermediate 1⁄2 a), a first intermediate represented by the following formula 1⁄2 b) is formed: Is preferably prepared by reducing this intermediate (6b) by the following! /, Wherein X, Y, m, n, and Z have the same meaning as described above, R ⁷ and R ⁸ are independently C al

1-4 represents a kill group).

[Formula 11]

More preferably, the hydroxymethylated 2H isoindole represented by the above formula (6c) is reacted with isoindole (2) and a dialkylformamide in the presence of a phosphoryl halide to obtain the above formula (6b) Embedded image or a second intermediate represented by the above-mentioned formula (6a) can be formed from these intermediates. The thus obtained hydroxymethylated 2H isoindole (6c) is selected from acetic acid, propionic acid and butyric acid, at least one aliphatic monocarboxylic acid selected from these, and / or ZnCl, BF.

23 and BF-O (C H) power Dehydrative cyclization in the presence of at least one Lewis acid selected

3 2 5 2

It is preferable to produce porphyrin (7a) by reacting it with an oxidizing agent.

Yes

Aminomethylated 2H-isoindole represented by the above formula (6d) can be produced by aminomethylating isoindole (2). As a preferred method of producing porphyrin (7a) via this aminomethylated 2H-isoindole (6d), isoindole (2), formaldehyde and dialkylamine in the presence of (I) acid The reaction may be followed by reaction with an oxidizing agent, or the reaction of (II) isoindole (2) with a halogenated methylene dialkyl ammonium and then with an oxidizing agent.

In the method for producing the halogen-containing tetrabenzo-porphyrin of the present invention, isoindole ( 2) Force S, which is preferably a compound represented by the following formula (2a): 4, 5, 6, 7 tetrafluoro-2H isoindole or 4, 5, 6, 7 tetrachloro-mono-2H isoindole Is more preferred.

[Formula 12]

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

The present invention also provides aminomethylenated 1H isoindenoles, forminoleated 2H-isoindoles and hydroxymethylated 2H-isoindoles represented by the following formulas (6a) to (6c). These compounds are useful for producing .zeta. Conjugated cyclic compounds (especially halogen-containing tetrabenzoporphyrins) as described above. Also, these compounds can be used for the production of polymer materials such as polyisoindolenine vinylene which can be made only by the production of porphyrins (wherein X, Y, m, n, R ⁷ and R ⁸ are Same meaning as above).

[Formula 13]

(6a) (6b) (6c)

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

[Formula 14]

The borophyrin complex (8) can be produced by mixing the porphyrin (7a) with the metal or metal salt containing the metalloid ion M.

[0054] In the method for producing halogen-containing tetrabenzoporphyrin of the present invention, 1S isoindole producing porphyrin (7a) by cyclizing the 1-position-substituted isoindole represented by the above formula (6). Cyclization of the 1-position substitution product (6) of a compound of the formula (11), a halogen-containing tetrabenzophorphylinogen (a reduced form of porphyrin, hereinafter referred to as "borophyrinogen (11)") represented by the following formula (11) S) is considered to form. Then, an oxidant (such as quinones or oxygen in the air) is allowed to act on this porphyrinogen (11) to obtain porphyrin (7a). Therefore, during the halogen-containing tetrabenzoborophyrin preparation method described above, ie, the step after cyclization and before oxidation of the 1-substituted compound (6) of isoindole (ie, the step considered to be formed by porphyrinogen (11) The porphyrin complex (8) can also be produced by adding a salt containing metal or metalloid metal M and then performing 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 η are as defined above].

[Formula 15]

[0056] After mixing borophylinogen (11) with a metal or metalloid ion-containing salt, The method for producing porphyrin complex (8) by reacting an oxidizing agent is preferably

(I) In the presence of a phosphoryl halide, isoindole (2) is reacted with a dialkylformamide to form an intermediate represented by the above formula 1⁄2b), and the intermediate (6b) is reduced by Forming an intermediate represented by the above formula 1⁄2c), the intermediate 1⁄2c) is an acid (preferably at least one aliphatic monocarboxylic acid selected from acetic acid, propionic acid and butyric acid, and / or ZnCl, BF And BF-0 (CH 2) power, mixed with at least one selected Lewis acid), and then mixed with a metal or metalloid ion containing salt M, and then the oxidizing agent is allowed to act,

(II) In the presence of phosphoryl halide, isoindole (2) is reacted with dialkyl formamide to form an intermediate represented by the above formula (6a), and this intermediate (6a) is hydrolyzed The intermediate (6b) is reduced to form an intermediate represented by the above formula (c), and the intermediate (c) is converted to an acid (c) At least one aliphatic monocarboxylic acid, preferably selected from acetic acid, propionic acid and butyric acid, and / or ZnCl, BF and BF-0 (CH 2) power, at least selected

(1) mixing with one type of Lewis acid, and then mixing with a metal or metalloid ion containing salt M, and then causing an oxidizing agent to act;

After reacting isoindole (2), formaldehyde and dialkylamine in the presence of an acid (III), and then mixing the reaction mixture with the metal or metalloid ion containing salt M, the oxidizing agent is added. How to work,

(IV) A method of reacting isoindole (2) with a methylenedialkylammonium halide, then mixing the reaction mixture with a salt containing metal or metalloid ion M, and then acting an oxidizing agent.

Can be mentioned.

[0057] A third object of the present invention is to provide a method for producing isoindole multimers using phthalonitriles, which is easier to handle and obtain than isoindoles, as a starting material.

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

[Formula 16]

In the above formulae, D is a halogen atom, R ¹ , OIT or SR ³ (wherein, R ² and R ^{3 each} independently represent an alkyl, aryl or alkylaryl group. And p represents an integer of 0 to 4.

In the method for producing an isoindole multimer of 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) It is a preferred embodiment to use at least one member selected from the group consisting of a palladium catalyst, a rhodium catalyst, a platinum catalyst and a Nickenore catalyst as a catalyst for catalytic hydrogenation.

Further, as a preferred embodiment of the method for producing an isoindole multimer of the present invention, a phthalonitrile represented by the following formula (1) is used to produce a multimer having a repeating unit represented by the following formula (4) (In the following formulas, X, Y, m and η have the same meanings as described above).

[Formula 17]

(14)

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

BEST MODE FOR CARRYING OUT THE INVENTION First, the method for producing isoindoles will be described from the present invention.

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, the reduction by the hydride reducing reagent will be described.

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

[Formula 18]

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 to be substituted by the halogen power S hydride of phthalonitrile (1) may occur. Therefore, the hydride reducing reagent is used so that 1 to 2 moles, more preferably 2.5 to 5 moles, and even more preferably 2. 7 to 4.5 moles of hydridoca per mole of phthalonitrile (1). It is recommended to do. As understood from the above-described presumed reaction mechanism, the optimum amount of hydride reducing reagent is 1 mol of phthalonitrile (1),

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

The following can be estimated 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-mentioned presumed reaction mechanism, after reduction reaction, residue (eg, aluminum or boron) of hydride reducing reagent is added to nitrogen of isoindole (2). It is thought that it is in the state as it is. If this residue remains added, subsequent purification such as silica gel column chromatography may not be successful. Therefore, it is considered that the purification yield can be 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 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. As a result of investigations by the present inventors, it was found that mixing of the reaction mixture with NaOH or the like did not release the halogen, and the purification yield of isoindole (2) was improved.

In the course of reduction reaction with water, it is possible not to use an acid or an alkali, or to use an excessive amount of an acid or an alkali relative to a hydride reducing reagent. However, from the point of view of yield, it is recommended to use an acid, preferably a protonic acid, in an amount that preferably makes the reaction system neutral or acidic. Specifically, it is recommended to use a protonic acid in an amount such that the proton (H +) is preferably 1 mol or more, more preferably 1.5 mol or more, per 1 mol of hydride reduction reagent. Ru. 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 moles or less, more preferably 3 moles or less, per hydride reducing reagent.

Similarly, 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 mole or more, preferably 2 moles or more, preferably 5 moles or less, preferably 3 moles or less, per 1 mole of hydride reducing reagent. If an excess of alkali is used, it may be neutralized prior to the next purification step, if necessary. In the production method of the present invention, it is presumed that isoindole (2) is produced by the reduction reaction of the part of the cyano group as described above, and the halogen X in the above formula is And, the substituent Y is considered not to greatly 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 the target substance isoindole (2) is considered to be stabilized by the presence of a halogen atom, from the viewpoint of the stability of isoindole (2), the halogen in phthalonitrile (1) is It is recommended that the number of atoms X is 1 or more (ie, m l l), preferably 2 or more, more preferably 3 or more, and still more preferably 4. As the phthalonitrile (1), for example, those commercially available from Aldrich, Synquest, Azamax Co., Central Chemical Co., Ltd., etc., or those which can be synthesized by known methods can be used.

[0074] 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, two or more kinds of halogen atoms may exist simultaneously. In the above formula

R ² and R ³ are each independently preferably a C alkyl group, more preferably a C alkyl group, and still more preferably

1-20 1-20

Or C alkyl group; preferably C aryl group, more preferably C aryl group;

1-5 6-20 6-12 is preferably C alkylaryl group, more preferably C alkylaryl group, further

7-20 7-15

Preferably it is C alkyl aryl group. R ¹ , R ² and R ³ are on their carbon skeleton

7-10

It may contain a halogen atom. When any one of R ¹ , OR ² and SR ³ is present as a substituent Y,

R ² and R ³ may be different substituents (eg, an amino group and an amino group)! / ァ.

As the phthalonitrile (1), first, one having n = 0, ie, a halogen-containing phthalonitrile having only a halogen atom X as a substituent can be mentioned. Halogen-containing phthalonitriles are commercially available from Aldrich など and others. In addition, non-commercially available halogen-containing phthalonitriles can be produced from commercially available halogen-containing phthalonitriles by a conventionally known halogen substitution reaction.

For example, in JP-A-2002-332254, a fluorine atom of fluorine-containing isophthalonitrile is used as a brominating agent (eg, sodium bromide, potassium bromide and lithium bromide, preferably sodium bromide). It is disclosed that substitution with bromine atom is carried out using lithium and potassium bromide). By JM Birchell, RN Haszeialne, and JO Morley, Polyfluoroarenes s. Part XI.Reactions of Tetrafluorophthalonitrile with Nucleophil Reagents,

J. Chem. Soc. (C), 1970, p. 456-462 discloses a technique of substituting fluorine atoms of tetrafluoroisophthalonitrile with chlorine atoms using LiCl.

Specific examples of the halogen-containing phthalonitrile include 4 fluorophthalonitrile, tetrafluoro phthalonitrile, 4, 5-dichloro phthalonitrile, tetrachloro phthalonitrile, 4 chloro-3, 5, 6 trifluoro phthalonitrile, etc. Be Among these, tetrafluorophthalonitrile is preferable from the viewpoint of availability and the like.

Phthalonitriles (1) having an R ¹ group as a substituent Y can be produced 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. 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 Ichitamao 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 the Suzuki-Miyaura coupling.

Phthalonitrile (1) having an OR ² group or an SR ³ group as a substituent Y is a halogen-containing compound according to a conventionally known method, for example, a method as described in JP-A-2002-302477. It can be produced S by replacing the halogen atom of phthalonitrile with HOR ² and / or HSR ³ . From the viewpoint of the reactivity to the substitution reaction of halogen, the halogen-containing phthalonitrile to be used for this aromatic nucleophilic substitution reaction is preferably a fluorine-containing and / or chlorine-containing phthalonitrile, more preferably a fluorine-containing phthalonitrile, still more preferably Tetrafluorophthalonitrile. 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 availability, O As phthalonitrile (1) having an R ² group or an SR ³ group, the following formula (la) or (Id), in particular, the following formula (lb) or (lc), there is a following formula (le) or Phthalonitrile represented by (If) is preferred.

[Formula 19]

In the above formulas (la) to (; If), Y ¹ and Y ² each independently represent OR ² or SR ³ , and R ² and R ³ are each independently preferably a C alkyl group, More preferably, C alkyl

1-20 alkyl group, more preferably C alkyl group; preferably C aryl group, more preferably C alkyl group

1-5 6-20 6-1 aryl group; or preferably C alkylaryl group, more preferably C alkyl

2 7-20 7-15 represents a phenyl group, more preferably a C alkylaryl group. Also, R ² and R ³

7-10

The carbon skeleton of the above may contain a nitrogen atom or a halogen atom. In the above formula (le) or (If)

R ² and R ³ may be the same or different, but are preferably the same from the viewpoint of ease of production! / ,.

[0082] As a hydride reducing agent, it is possible to use metal or metalloid hydrides or their complexes S. Examples of metal hydrides and the like include the following.

[0083] Alminium hydrides such as alkylsilanes, dialkylalans, alkoxyalans, dialkoxysilanes and the like.

LiAlH, LiAlH R, LiAlH R, LiAlHR, NaAlH, NaAlH R, NaAlH R, Na

A1 HR, NaAlH (OCH 2 CH 2 OCH 2), Al 2 H (OCH 2 CH 2 OCH 2) 3, R N — A1 H,

Complexes of aluminum hydrides such as Et 2 O-AIH, where R represents an alkyl, aryl or alkoxy group. Boron hydrides such as diborane (BH 2), alkyl boranes, dialkyl boranes, alkoxy boranes, dialkoxy boranes, and the like.

NaBH, NaBH R, NaBH R, NaBHR, NaBH CN, NaBH N (CH 2) 2, NaB

H (NH (t-Bu)) NaBH S, NaBH (SCH CH S), LiBH, LiBH R, LiBH R

,

, Complex of boron hydride such as LiBHR, HN-BH, RH N-BH, RHN-BH, RN-BH, THF-BH, pyridin-BH, R HP-BH, RP-BH, KBHR During ~

R represents an alkyl, aryl or alkoxy group. ).

CI Hydrides such as CI SiH, CI SiH, R SiH, R SiH, ((CH 3) Si) SiH, polymethylhydrosilane (wherein R represents an alkyl, aryl, benzyl or alkoxy group)

Tin hydrides such as R SnH, R SnH, Ph SnH, Ph SnH, (n-Bu) SnH, triethyl nodecyl hydride, trimethyl tin hydride (wherein R represents an alkyl, aryl or alkoxy group) ).

Among the above, from the viewpoint of reactivity, aluminum hydride or a complex thereof, or hydrogenated diisobutylaluminum preferred by boron hydride or a complex thereof, and a BH 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.

[0090] The hydride reducing reagent may be used in combination with a Lewis acid. The addition of a Lewis acid is considered to accelerate the progress of the reduction reaction, especially when using a kehyd 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, A1C1, AlBr, TiCl, SnCl, SnCl,

FeCl ,: BF ,: BF '0 (C 2 H 5), trispentafluorophenylboron, NbF, TaF, P

Periodic table group IIIB, IVA, IVB, VA or V such as F, AsF, SbF, etc.

Examples thereof include halogen compounds of Group B elements, and complexes or alkoxide compounds thereof.

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 a solvent, for example, chloroforms such as chloroform, methylene chloride and the like; chlorinated hydrocarbons; benzene, Aromatic hydrocarbons such as noren and xylene; Ethers such as THF, dioxane, cyclopentyl methyl ether, diisopropyl ether and jetyl ether; Amides such as dimethyl formamide and dimethylacetamide; and sulfolane, 3-methylsulfolane Sulfolanes such as 2,4 dimethyl sulfolane 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 1M, more preferably about 0.05 to 0.5M.

[0093] 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! /. Alternatively, the solution of the hydride reducing reagent may be added slowly while cooling the solution of the phthalonitriles, or it may be good even if the solution of phthalonitriles is added slowly while the solution of the hydride reducing reagent is cooled. Yes. The temperature of the reduction reaction is also influenced by the solvent used, 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 protic acid or an 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 type of protonic acid can be used alone, or two or more types of protonic acids can be used in combination. The reaction mixture after 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; more preferably at a temperature of about 10 ° C, more preferably under cooling in an ice bath or the like. Mixing at about 0 ° C is recommended.

As the inorganic protic acid, for example, hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, sulfuric acid; phosphoric acid such as orthophosphoric acid, pyrophosphoric acid; perhalogenated acid such as perchloric acid; phosphomolybdic acid, Examples thereof include heteropolyacids such as keyl molybdic acid, phosphotungstic acid, calybdic tungstic acid, lintan-dust molybdic acid, and livanadomolybdic acid. Examples of organic protic acids include arylsulfonic acids such as benzenesulfonic acid, p-toluenesulfonic acid and naphthalenesulfonic acid; methanesulfonic acid, trifluoromethanesulfonic acid, trichloromethanesulfonic acid, ethanesulfonic acid Alkylsulfonic acids such as propanesulfonic acid and t-butynosulfonic acid; formic acid, acetic acid, propionic acid, vicinal acetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, trifluoroacetic acid, pentafluoropropionic acid, n-butyric acid, isobutyric acid Saturated aliphatic carboxylic acids such as, vivalic acid, valeric acid, caproic acid, purilic acid, purilic acid, lauric acid, myristic acid, cyclohexanecarboxylic acid, etc .; acrylic acid, methacrylic acid, propiolic acid, crotonic acid, Maleic acid, fumaric acid, citraconic acid, mesaconic acid, oleic acid Unsaturated aliphatic carboxylic acid; benzoic acid, phthalic acid, isophthalic acid, and aromatic carboxylic acids such as terephthalic Le acid.

Next, the case of using an alkali will be described. After the reduction reaction, it is recommended that the reaction mixture and the alkali be mixed at a temperature of about -30 ° C to about 30 ° C, more preferably about -10 ° C to about 10 ° C. As the alkali, preferably, hydroxides of alkali metals or alkaline earth metals, carbonates, monocarboxylates (such as acetates), dicarboxylates (such as sulfates), organic amines and the like can be mentioned. 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 and the like to promote the elimination of the hydride reducing reagent residue are more preferable. One of these alkalis may be used alone, or two or more of these alkalis may be used in combination.

After the reduction reaction with a hydride reducing reagent, it is recommended to purify the object 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 means for purification 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 central metal of the catalyst is preferably such that the central metal of the catalyst is 0.0 to! 30 to 30%, more preferably to 0 to 20 mol%, still more preferably to! 10 mol% relative to the phthalonitrile (1). It is recommended to use metal catalysts in quantities.

[0101] Examples of the metal catalyst include homogeneous catalysts in which ruthenium, rhodium or the like is coordinated with phosphine or the like. However, in view of reactivity and ease of recovery after reaction and regeneration treatment, it is preferable to use a heterogeneous catalyst in the present invention. Among the heterogeneous catalysts, in order to increase the surface area and improve the catalytic activity, a catalyst having a fine metal powder 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 And those supported on a carrier such as 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 protonic acid in a hydrogen atmosphere prior to the catalytic hydrogenation reaction may be employed as necessary. It is recommended to use a protonic acid in order to improve the yield of the target isoindole (2) which can be obtained without using a protonic acid. As the protonic acid used for activation, it is possible to use the above-mentioned protonic acid S. Among these, trifluoroacetic acid, hydrochloric acid, nitric acid and sulfuric acid are preferred. More or less amount of protonic acid relative to phthalonitrile (1) produces many impurities and lowers the yield. Therefore, the proton (H +) power is preferably 0.6 to 1.6 mono-, more preferably 0.8 to 1.2 mono-, more preferably 0.9 to 1 mol of phthalonitrile (1) as a raw material. · It is recommended to use protic acid to be 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, more preferably 2 hours or less.

In the case of reduction by catalytic hydrogenation, it 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 a solvent, for example, aromatic hydrocarbons such as benzene, toluene, xylene, etc .; THF, di- Ethers such as xanthene, cyclopentinolemethinolee tenole, diisopropinolee tenolee, getinoleate tenole; alcohols such as methanol, ethanol, propanol, etc .; esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate; Amides such as dimethylformamide and dimethylacetoamide; sulfolanes such as sulfolane, 3-methylsulfolane and 2, 4-dimethyl sulfolane; and carboxylic acids such as formic acid, acetic acid, propionic acid and trifluoroacetic acid . In the catalytic hydrogenation method, mixed solvents of amides or acetic acid 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 0.1 to 1 M, more preferably about 0.05 to 0.5 M.

The temperature of the catalytic hydrogenation is also influenced by the solvent used, preferably 0 ° C. or more, more preferably 20 ° C. or more, preferably 150 ° C. or less, more preferably 120 ° C. or less It is. 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 still more 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 reduce the pressure of the reaction system before supplying hydrogen gas. In addition, in order to cause a large amount of hydrogen atoms to be adsorbed to the catalyst, it is a preferable embodiment that the pressure reduction and the supply of hydrogen gas are repeated several times.

According to the production method of the present invention described above, the novel isoindole represented by the above formula (2) other than 4,5,6,7-tetrafluoro-2H-isoindole can be produced. 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) (excluding those in which X is a fluorine atom and m = 4). Novel isoindole (2) or N of the present invention The substituted isoindole (3) can be used as a raw material such as polyisoindole or dye. In addition, 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 alkyl group, more preferably C

1-10 1-alkyl group (for example, methyl group, ethyl group, n propyl group, n butyl group, n pliers

Five

Group C), preferably C-aryl group, more preferably C-aryl group (eg.

6-20 6-12

Group, tolyl group, etc.); preferably C alkylaryl group, more preferably C alkyl

7-15 7-10 aryl group (such as benzyl group); or preferably C-acyl, more preferably

2-10

C asyl group (eg, acetyl group, benZyl group, t butoxycarbonyl group, etc.)

2-5

There are no particular limitations on the method of obtaining N-substituted isoindole (3) from isoindole (2). Various known methods can be used to obtain a substituted amine from phenylalanine. Below are some examples.

[0109] By reacting isoindole (2) with a halogenated alkyl or halogenated alkyl aryl (wherein a carbon atom is bonded to a carbon atom of an alkyl moiety! /,) In the presence of a base N-substituted isoindole (3) wherein R ⁴ is an alkyl group or an alkylaryl group. As the base, a strong base (eg, n-butyllithium, alkali metal hydride (eg, NaH, KH) and the like) is preferable. This alkylation reaction is carried out, for example, usually at about -100 ° C to about 100 ° C, preferably at about -80 ° C to 70 ° C. As the halogenated alkyl, one having 1 to about 10 carbon atoms (preferably about 1 to 5 carbon atoms) is preferable, primary alkyl halide is more preferable, and primary alkyl iodide is more preferable. (For example, methyl iodide, methyl iodide, methyl n propione, methyl n butyl, methyl n pentayl and the like). The halogenated alkylaryl is preferably one having about 7 to 15 (preferably 7 to 10) carbon atoms, and more preferably a halogenated iodohalide (such as benzyl iodide). .

[0110] The N-substituted isoindole (3) in which R ⁴ is a aryl group can be produced, for example, by the well-known personal reaction Buchwald-Hartwig cross coupling reaction. Specifically, isoindole (2) and halogenated aryl or aryl in the presence of Pd catalyst and a strong base By reacting with triflate, N-substituted isoindole (3) in which R ⁴ is a aryl group can be produced. As the Pd catalyst, generally, phosphine ligands (for example, 2,2′-bis (diphenylphosphino) one-1,1-binaphthyl, 2,2,1-bis (diphenylphosphino) biphenyl etc.) or Those containing dibenzylideneacetone ligands and the like are used. As a strong base, in general, lithium bis (trimethylsilyl) amide, NaO-t-Bu, K 2 CO, etc.

2 3 etc. are used. As a reaction partner with isoindole (2), halogenated aryl having about 6 to 20 (preferably about 6 to 12) carbon atoms is preferable, and iodide or aryl bromide (eg, benzene benzene, 4-toluene toluene, etc.) Is more preferred. The reaction may proceed at a temperature as low as room temperature. The reaction temperature is generally about 50 to 150 ° C.

The N-substituted isoindole (3) in which R ⁴ is an acyl group is one having a carbon number of 2 to 10 (preferably about 2 to 5) halogenated acid, acid anhydride, carboxylic acid ester, carbonic acid. It can be produced by asylation reaction using acid amide and carboxylic acid. However, from the viewpoint of reactivity, it is recommended to use oxo-, fluoro-halogenated (preferably chloro-acyl) or acid anhydride. Specifically, by reacting isoindole (2) with a halogenated halide or an acid anhydride in a basic aqueous solution (for example, aqueous NaOH solution) or a basic organic solution (for example, a pyridine solution) (Schotten— (Baumann reaction), N-substituted isoindole (3) in which R ⁴ is an asyl group can be produced. Examples of the reaction partner of isoindole (2) include acetic anhydride, acetyl chloride, benzyl chloride and the like.

Further, as a specific example of the asyl group of R ⁴ , t — butoxycarbonyl group ((CH 2) CO— C (=

3

o) One) can be mentioned. The t-butoxycarbonyl group is well known as a protecting group for the amino group, for example di-t-butyl dicarbonate and isoindole (2) in the presence of a base such as pyridine, triethylamine, n-BuU or NaH. The ability to induce by reacting with the power S.

The isoindole (2) or N-substituted isoindole (3) of the present invention (hereinafter “isoindole”

Polyisoindole (4) or (5) obtained by polymerizing (2) or (3) “abbreviated by the force S)), particularly poly (fluorinated isoindole), is more preferably used as a conductive material. Specifically, electrode materials, display materials, electromagnetic waves in the fields of organic thin film transistors and organic solar cells It is useful as a shielding material etc. The polymerization can be carried out by known methods such as electrolytic oxidation polymerization and chemical oxidation polymerization. For polyisoindole (4) or (5), if necessary, add a layer.

First, chemical oxidative polymerization will be described as the polymerization method. Examples of the oxidizing agent used in the chemical oxidative polymerization include oxygen, hydrogen peroxide; tetrachloro-1,2-benzoquinone, tetrachloro-1,4-benzoquinone, 2,3-dichloro-5,6-dicyano-1,4 Quinones such as benzoquinone; halogens such as iodine, bromine and chlorine; metal chlorides such as iron chloride (111) 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, sodium persulfate, potassium persulfate, ammonium persulfate, etc. Can be mentioned. Among these oxidizing agents, oxygen, hydrogen peroxide, quinones, halogens, metal chlorides are preferred, and oxygen and metal chlorides are preferred. 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 chloride (I) -Aluminum chloride 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, preferably 2 mol or more), preferably 6 mol or less, 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 oxidation polymerization, for example, chlorohydrocarbons such as chloroform, methylene chloride, carbon tetrachloride, dichloroethane, tetrachloroethane, and benzene, etc .; nitromethane, nitroetane, nitrobenzene, etc. Examples include nitro hydrocarbons, amides such as N-methyl pyrrolidone, and carbon disulfide. The solvents may be used alone or in combination of two or more. When a solvent is used, the concentration of isoindole (2) or (3) is preferably about 0.01 to 1M, more preferably about 0.05 to 0.5M. Chemical oxidation polymerization is generally carried out at a temperature in the range of about −80 ° C. to about 100 ° C. (preferably about −20 ° C. to 60 ° C.), generally 0 .; It is carried out for about 100 hours (preferably about 0.5 to 72 hours). Next, electrolytic oxidation polymerization will be described. In the present invention, there is no limitation on the reaction apparatus, and it is possible to use the reaction apparatus used in the production of polypyrrole, polythiophen, etc. by electrolytic oxidation polymerization. Examples of the electrolyte include tetraethyl ammonium bromide, tetraethyl ammonium chloride, tetra ethyl ammonium fluoride, tetra n-butyl ammonium ammonium bromide, tetra n-butyl ammonium chloride, tetra n-butyl ammonium ammonium and the like. Ammonium salts such as um fluoride, tetraethylammonium tetrafluoroborate, tetra-n-butyl ammonium hexafluorophosphate, tetra-n-butyl ammonium hexahydrate, and the like; tetraphenylphosphonium; Phosphonium salts such as nimb bromide and tetraphenylphosphonium chloride; lithium salts such as lithium persulfate and lithium hexafluoroborate; sulfonates such as potassium benzenesulfonate and sodium toluenesulfonate; sulfuric acid , Examples include acids such as hydrochloric acid and 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.

As a solvent for electrolytic oxidation polymerization, for example, chlorinated hydrocarbons such as methylene chloride; acetates such as acetonitrile, nitriles such as benzonitrile and propiodiitol; cyclic ethers such as cyclohexane, tetrahydrofuran and propylene carbonate Sulfolanes such as sulfolane, 3-methylsulfolane and 2, 4-dimethylsulfolane; 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 1M, more preferably about 0.05 to 0.5M. Electrolytic oxidation polymerization is generally carried out at a temperature in the range of about -80 ° C. to about 100 ° C. (preferably about -20 ° C. to 60 ° C.), generally 0.;! To-depending on the solvent used. It is performed for about 100 hours (preferably about 0.5 to 72 hours). The current density at the time of electrolytic oxidation polymerization is generally about 1. 0 to 5. OmA / cm ² .

By oxidative polymerization as described above, a polymer can be produced by polymerizing isoindole (2) or (3). In the method of the present invention, it is possible to form a copolymer by combining two or more of them by using only one of isoindole (2) or (3) to form a homopolymer. It is also possible to copolymerize isoindole (2) and / or (3) with other monomers (eg, pyrrole, thiophen) to form a copolymer. So the book The inventive polyisoindoles (4) or (5) encompass both homopolymers and copolymers. When other monomers such as pyrrole are used to form a copolymer, the total content of isoindole (2) and / or (3) in the used monomer (ie, the above formula (4) and / or (5) in the copolymer The total content of) is preferably 10% by mass or more.

[0119] The weight average molecular weight (in straight line according to 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 30,000 to 300,000. It is about 300,000, more preferably about 5,000 to about 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 co-functional cyclic compounds (7), the method for producing a representative porphyrin (7a) will be mainly described. According to the production method of the present invention, intermediate (6) (1-position substitution of isoindole) is once formed from isoindole (2), and 71 conjugated cyclic compound (7) (especially porphyrin (7a)) is produced therefrom. It is characterized by On the other hand, when normal porphyrins not modified with benzene ring are synthesized from pyrrole, pyrrole is reacted with formaldehyde in the presence of acid (I) to produce porphyrin in one step, or II) From pyrrole, once form a 2-substituted form (for example, 2-hydroxymethylpyrrole or 2-dimethylaminomethylbirole) as an intermediate, and cyclize this 2-position-substituted form to form porphyrin in multiple steps Methods of manufacturing and the like are known.

However, as a result of investigations by the present inventors, even when isoindole is cyclized (especially, porphyrinated) in a one-step reaction like pyrrole, a 兀 conjugated cyclic compound (especially, tetrabenzopolophylline) is sufficiently obtained. I found it impossible. The reason why tetrabenzoporphyrin is not obtained sufficiently is that, unlike pyrrole, isoindole has a 1H-isoindole structure that is easy to polymerize, and in a one-step reaction, not only a cyclization reaction but also a polymerization reaction occurs. It is guessed.

[Formula 20]

2H

The

Therefore, as a result of the present inventors continuing investigation further, one step from halogen-containing isoindole Rather than directly producing a 兀 conjugated cyclic compound by a reaction, the multi-step reaction which forms a 1-substituted form of isoindole (hydroxymethyl form or an aminomethyl form) as an intermediate, It has been found that halogen tetrabenzoporphyrin can be produced with good selectivity and yield. The reason why the selectivity and 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, Although polymers other than porphyrin are formed, 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 tetrabenzoborophyrin) of the present invention is characterized in that the 1-position substitution product of halogen-containing isoindole is once formed as an intermediate.

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

[Formula 21]

(7b) Saphyrin {7c) Penylphilin {7cn} The present invention also provides the 1-substituted form of halogen-containing isoindole itself. These 1-substituted compounds have the advantage of being useful for the preparation of な -conjugated cyclic compounds (especially halogen-containing tetrabenzoporphyrins) as described above, and are substituted by unsubstituted halogen-containing isoindoles. It has the advantage of being more stable. 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), from the viewpoint of stability etc., those represented by the above formula (2a) are preferable, and 4,5,6,7 tetrafluoroiso- 1 2H indole or 4,5 Further preferred is 4,5,6,7 tetrafluorinated 1H isoindole, which 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 known in the field of organic synthesis chemistry. Can be used in any way. In view of the ease of reaction and the like, hydroxymethylated-2H isoindole (6c) is formylated by Vilsmeier reaction and then reduced to give aminomethylated-2H isoindole (6 d) as Mannich. Preferred to manufacture by reaction! /.

First, a preferred method for producing hydroxymethylated 2H-isoindole (6c) will be described. In the presence of a halogenated phosphoryl POX ⁵ (wherein X ⁵ represents F, C and C represents Br),

3

In Vilsmeier reaction in which soindole (2) is reacted with dialkylformamide HCONR ⁷ R ⁸ (wherein R ⁷ and R ⁸ each independently represent a C alkyl group), the reaction conditions are different.

1-4

In particular, the first intermediate formylated 2H-isoindole (6b) or the second intermediate aminomethylenated 1H-isoindole (specifically, depending on the reactivity of the substrate or the difference in reaction temperature). 6a) is formed. For example, when using 4, 5, 6, 7 tetrafluoro-2H-isoindole as isoindole (2), the hydrolysis reaction in Vilsmeier reaction is carried out under reflux to obtain a first intermediate (6b), The reaction is carried out at room temperature to obtain the second intermediate (a). 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 Vilsmeier reaction, for example, phosphoryl fluoride, chloride Among them, phosphoryl chloride is preferred from the viewpoint of the reactivity S, which includes phosphoryl or phosphoryl bromide. Also, instead of phosphoryl halide, or together with phosphoryl halide, p-toluenesulfoxide, methanesulfoxide, trifluoromethanesulfoxide, trifluoromethanesulfoxide, 2, 2, 2-trifluoroethanesulfoyl chloride, etc. Sulfonic acid anhydrides such as sulfonyl chloride, trifluoromethanesulfonic acid anhydride, methanesulfonic acid anhydride, sulfonic acid anhydride, etc., phosgene, thiophosgene, oxalyl chloride, etc. can be used. As the dinolequinolefonolemamide, for example, dimethylformamide (DMF), jetylformamide, diisopropylformamide, dibutylformamide and the like. Among these, DMF (R ⁷ = R ⁸ = CH 2) is preferable. Intermediate (6a) or

In order to increase the conversion to (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 diaminol formamide and the amount of phosphoryl halide are each 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). is there. If too much of the amount of dialkylformamide, etc. is used, the cost of raw materials and purification will increase. Therefore, the amount of the dialkylformamide and the non-phosphorylated phosphoryl is preferably 5 mol or less, more preferably 3 mol or less, still more preferably 2 mol or less, with respect to 1 mol of isoindole (2).

[0133] 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, methylene chloride and the like; halogenated benzenes such as benzene and the like; and alkylbenzenes such as toluene and xylene can be used. The solution concentration of isoindole (2) is preferably (about 0. 0 !! to about 2 M, and more preferably (0 to 0.5 to 1 M).

[0134] It is also possible to form Vilsmeier reagent ([R ⁷ R ⁸ N = CHX ⁵ ] ( ⁺ ) X ⁵ (in the reaction system by mixing isoindole (2), phosphoryl halide and dialkyl formamide). The Vilsmeier reagent may be formed in advance by mixing the phosphoryl halide and the dialkylformamide, or if the Vilsmeier reagent is to be formed in advance, either isostere (2) is added to the Vilsmeier reagent. Good, conversely add Vilsmeier reagent to isoindole (2) It is good. In each addition and mixing process, cooling may be performed as necessary to suppress heat generation. The temperature of the Vilsmeier reaction is also influenced by the solvent used, etc. The temperature 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) is hydrolyzed to formylated 2H

It can be easily converted to isoindole (6b). This hydrolysis can be carried out simply by mixing aminomethylen-1H-isoindole (6a) with water. Preferably, an aqueous alkaline solution such as sodium acetate, sodium hydrogencarbonate or sodium hydroxide is used. . When an alkaline aqueous 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 5 hours; 10 hours, preferably 5 hours to 5 hours. .

Hydroxymethylation by reducing formyl 2H isoindole (6b)

2H-isoindole (6c) can be produced. The reduction to formyl group (aldehyde) power, hydroxymethyl group (alcohol) is easy and can be done in a manner known in the field of synthetic organic chemistry. As a reducing agent, for example, boros such as NaBH, BH -THF, etc.

4 3

Aluminum hydrogen such as complex hydride, LiAlH, diisobutylaluminum hydride

Four

And the like. In addition, it is necessary to suppress the reduction of the isoindole ring and to carry out the reduction under the conditions of only the formyl group. For example, using a strong reducing agent such as LiAlH

Four

In this case, the reduction reaction may be completed in a short time.

After the intermediates (6a), (6b) or (6c) are produced, without purification of these, the following intermediate or 中間 conjugated cyclic compound (7) (especially porphyrin (7a) may be used as it is in the reaction mixture. )) Can also be used. However, in order to produce a high purity π-conjugated cyclic compound (7), one or more of intermediates (6a), (6b) and (6c) may be purified and then used in the next step. Recommended. 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 a starting material isoindole (2 The more stabilized force is more reactive than the pyrroles used to make regular porphyrins. Therefore, when hydroxymethylated 2H-isoindole (6c) is reacted in the presence of crotonic acetic acid or the like usually used to synthesize porphyrin from pyrrole, it is polymerized to form an isoindole oligomer or the like. In order to produce a π-conjugated cyclic compound (7) (especially porphyrin (7a)) from hydroxymethylated 2H isoindole (6c) while suppressing the polymerization reaction, dehydration is carried out using an acid weaker than croque acetic acid. It is necessary to cyclize. Acids for this purpose, for example aliphatic monocarboxylic acids such as acetic acid, propionic acid and dairy acid; aliphatic dicarboxylic acids such as succinic acid, dartalic acid, adipic acid, pimelic acid; and ZnCl, BF and BF-0 (CH And the like. Among these, the above-mentioned aliphatic monocarboxylic acids and the above-mentioned 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 acid used relative to 1 mole of hydroxymethylated 2H isoindole (6c) is about 1.5 moles in the Lewis acid. The aliphatic carboxylic acid is about 1.5 moles or more. Also, the aliphatic carboxylic acid can be used in excess as a solvent. When the reaction mixture is used for dehydrating cyclization without isolating the hydroxymethylated-2H-isoindole (6c) obtained using a hydride reducing reagent, said aliphatic carboxylic acid is used for the hydrogenation reducing reagent reagent. Can also be used. In this case, the aliphatic carboxylic acid is preferably used in excess!

The reaction temperature of the dehydrating cyclization of the hydroxymethylated 2H isoindole (6c) may be appropriately set according to the reactivity, and is, for example, usually 0 ° C. or higher, preferably 20 ° C. or higher. Preferably it is 140 degrees C or less, More preferably, it is 120 degrees 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.

As a result of the above-mentioned dehydration and cyclization, a reduced form of the π-conjugated cyclic compound (7) (especially porphyrinogen ( 11) is obtained, and by oxidizing this with an oxidizing agent, it is possible to produce S a conjugated cyclic compound (7) (especially porphyrin (7a)). 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 product of the π-conjugated cyclic compound (7) (especially porphyrinogen (11)). Although it is preferable, it is recommended to neutralize the acid used in the cyclodehydration, preferably before the oxidation step.

As oxidizing agents for this purpose, oxygen, oxygen-containing gas such as air; and ρ chloranil (6,3,5,6-tetrachloro-benzoquinone), DDQ (6,3-dicyano 5,6-dichloro) Quinones such as ρ 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 dehydrating 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, chlorohydrocarbons such as chloroform, methylene chloride and the like; aromatic hydrocarbons such as benzene, toluene and xylene; THF, dioxane, cyclopentyl methyl ether, diisopropyl ether, jetyl ether Ethers such as methanol; 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 dimethylacetoamide. The solvent 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! M to about 100 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 aminomethylation-2H-isoindole (6d) will be described. Aminomethylated 2H-isoindole (6d) is an isoindole (2), a formaldehyde and a dialkylamine NHR ⁵ R ⁶ (wherein R ⁵ and R ⁶ are each independently C) in the presence of an acid. It can be produced by the Mannich reaction using an alkyl group. In addition,

1-4

Halogenated methylenedialkyl ammonium ammonium HC = NR ⁵ R ⁶ X ⁶ (wherein, R ⁵ and R ⁶ each independently represent a C alkyl group, and X ⁶ represents a halogen atom), and iso.

1-4

It is good to carry out the Mannich reaction using indonesore (2)! / ヽ.

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 ·! To 1.5 moles per mole of isoindole (2). When a polybasic acid is used, the recommended amount to be used is the above amount of monobasic acid multiplied by the valence of polybasic acid. Further, as a dialkylamine, for example, a power such as dimethylamine, diethylamine, diisopropylamine and dibutylamine and the like, among them, from the viewpoint of reactivity and the like, dimethylamine (R ⁵ = R ⁶ CHCH 2) is preferable. Gial

3

It is recommended to use quiramine and formaldehyde in an amount of preferably 1 to 2 moles, more preferably 1 ·! To 1.5 moles per 1 mole of isoindole (2), respectively.

Next, the case of using a halogenated methylene dialkyl ammonium will be described. Can be prepared, for example, and can also be obtained from Waldrich, Inc., as a methylated dimethyldimethyl ammonium. Halo and methylene chloride dimethyl ammonium are more preferred as halogenated methylene dialkyl ammoniums! The halogenated methylenedialkyl ammonium is preferably;! To 2.5 mol, more preferably 1 · 0.5 to 2 mol, still more preferably 1 · ·! To 1 · 5 mol per 1 mol of isoindole (2). It is recommended to use in the amount of [0148] The Mannich reaction is usually performed using a solvent. As solvents, chlorohydrocarbons such as chloroform, methylene chloride and the like; aromatic hydrocarbons such as benzene, toluene, xylene and the like; ethers such as THF, dioxane, cyclopentyl methyl ether, diisopropyl ether, gethyl ether and the like; methanol And alcohols such as ethanol and propanol; esters such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate; and nitriles such as acetonitrile, propionitrile, benzonitrile and the like. 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 05 to 1 M.

The temperature of the above Mannich reaction is also influenced by the solvent used, etc. The temperature is usually 0 ° C. or more, preferably 20 ° C. or more, preferably 120 ° C. or less, more preferably 100 ° C. or less is there. 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.

[0150] Intermediate (6d), which is a 1-substituted form of isoindole (2), is considered to be more stable than isoindole (2), similarly to intermediates (6a) to (6c). However, since the intermediate (6d) is active as compared to the intermediate (6c), it is cyclized as soon as it is formed, and the reduced form of the 兀 conjugated cyclic compound (7) (especially morphylinogen (11)), The π-conjugated cyclic compound (7) (especially porphyrin (7a)) is then formed. Therefore, in the method of the present invention through the Mannich reaction, the 上記 conjugated cyclic compound (7) can be produced by the action of an oxidizing agent after the above Mannich reaction. The Mannich reaction and the subsequent oxidation reaction after the cyclization reaction are carried out in the same manner as described above.

[0151] The porphyrin (7a) obtained as described above is well known in the field of porphyrin chemistry! /, And is bound to various metal or metalloid ions to form porphyrin complexes (8). Ability to form S Can. 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. It is possible to list S ions of Group 14 elements excluding C and Group 15 elements excluding N and P. Among these, Co, Zn, Cu, Ni, Pd, Pt, Fe or Mn ion is preferred, of which metal ion is preferred. The porphyrin ligand is a trivalent or higher gold The metal or metalloid ion can be bound, in which case the central metal of the borophyrin complex is bound to a halogen, an alkyl, an alkoxyl group, etc. to charge balance.

[0152] In order to form porphyrin complexes (8) of these metals or metalloids, metal salts containing metal or metalloid ions, such as halide salts (especially chloride salts, bromide salts and iodide salts) Or acetate and the like, and porphyrin (7a) may be mixed. In addition, after the metal compound containing metal or metalloid ion is added after the cyclization of intermediate (6c) or (6d) and before the oxidation (ie, the step of porphyrinogen (11)), In addition, 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.

[0153] porphyrin (7a) and Borufuirin Kisadekafuruo Rotetora base emission zone porphyrins and 2 ¹ also into the complex (8) of the present invention, 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- Hexadecachloroone 21 H, 23 H-Tetrabenzo porphyrin and its complexes are preferred. Rotetrabenzo porphyrins and their complexes 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. is there.

Next, the present invention relating to a method for producing isoindole multimer will be described in detail. The method for producing an isoindole multimer according to the present invention is characterized in that phthalonitriles are used instead of isoindoles as a starting material. The phthalonitriles are much more stable and easier to handle than isoindoles. In addition, phthalonitriles are sold as raw materials for pigments and the like 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, one shown by the following chemical formula is presumed. However, the present invention Not limited to this inference mechanism.

[Chem. 22]

As shown by the above chemical formula, hydrogen is first added to the cyano group of phthalonitrile (9), and then cyclization is carried out to give intermediate (a) (1-imino-1H-isoindole). It is formed. 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, hydrogen is added to the tertiary amine moiety of intermediate (a) to form intermediate (c) (1-iminoisoindolines), and hydrogen is added to the imino group of intermediate (c). Is added, and then the amino group is eliminated as ammonia to form an intermediate (d) (2H-isoindoles). Thus, either acid or hydrogen is added to intermediate (a) to form intermediate (b) or (d), and addition of these forms intermediate (e) (imino A dimer having an isoindoline skeleton having a group and an isoindole skeleton is formed. From this intermediate (e), hydrogenation to the amino group and elimination of the amino group as described above form the dimer (f) of 2H-isoindoles (still 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).

According to the production method of the present invention, it is presumed that isoindoles are formed in the reaction system by reduction of the cyano group as described above, and then these are added to form an isoindole multimer. Be done. 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 (in formula (9)) It is possible to use phthalonitriles with p = 0) or any kind of substituent D.

The phthalonitrile (9) used in the present invention includes phthalonitrile (unsubstituted phthalonitrile) or substituted phthalonitriles having a substituent such as a halogen atom as described above. The substituted phthalonitriles include those having only one type of substituent (for example, nophorogen atom) or two or more types of substituents (for example, norogen 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. Plural kinds of halogen atoms may be present simultaneously in phthalonitrile (9).

Above Formula (9) Alkyl

A group, more preferably a c-c alkyl group, still more preferably a c-c alkyl group;

1 10 1 5

Is a c to c aryl group, more preferably c to c aryl group; or preferably c to c

6 20 6 12 7 20 キノレアリーよりより, more preferably c C C キノノレァさらに more preferably C 〜

7 15 7

C is an alkyl aryl group. R ¹ , R ² and R ³ are halogen atoms on their carbon skeleton

Ten

You may contain a child. When any one of R ¹ , OR ² and SR ³ exists as a substituent D,

R ² and R ³ may be different substituents (eg, an alkyl group and an amino group).

Among the above phthalonitriles (9), phthalonitriles (1) having a halogen atom X are preferable. Isoindole multimers (4) produced from phthalonil (1) having a halogen atom (in particular, a fluorine atom which is a strong electron-withdrawing group) are 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. As examples of the halogen atom X, R ¹ , R ² and R ^{3 in} the above formula (1), those mentioned above can be mentioned.

[0163] The phthalonitriles can be obtained or manufactured as described above. As phthalonitriles used in the method for producing an isoindonolene multimer, the above-mentioned formula (la) or (Id), in particular, the above-mentioned formula (lb) or (lc), there is! /, The above-mentioned formula (le) or ( Phthalonitrile represented by If) is preferred.

As the acid used in the method for producing an isoindole multimer of the present invention, an inorganic or organic propionic acid is preferable. As the inorganic protonic acid, for example, hydrochloric acid, hydrobromic acid, hydrogen iodide Acid, nitric acid, sulfuric acid; phosphoric acid such as orthophosphoric acid, pyrophosphoric acid, etc .; perhalogenated acid such as perchloric acid; phosphomolybdic acid, phosphomolybdic acid, phosphotungstic acid, citric acid tungstic acid, phosphorous acid molybdic acid And heteropolyacids such as nadomolybdic acid.

Examples of organic protic acids include arylsulfonic acids such as benzenesulfonic acid, p-toluenesulfonic acid and naphthalenesulfonic acid; methanesulfonic acid, trifluoromethanesulfonic acid, trichloromethanesulfonic acid, ethanesulfonic acid Alkylsulfonic acids such as propanesulfonic acid and t-butynosulfonic acid; formic acid, acetic acid, propionic acid, vicinal acetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, trifluoroacetic acid, pentafluoropropionic acid, n-butyric acid, isobutyric acid Saturated aliphatic carboxylic acids such as, vivalic acid, valeric acid, caproic acid, purilic acid, purilic acid, lauric acid, myristic acid, cyclohexanecarboxylic acid, etc .; acrylic acid, methacrylic acid, propiolic acid, crotonic acid, Maleic acid, fumaric acid, citraconic acid, mesaconic acid, oleic acid Unsaturated aliphatic carboxylic acid; benzoic acid, phthalic acid, isophthalic acid, and aromatic carboxylic acids such as terephthalic Le acid.

Among the protic acids, acetic acid, trifluoroacetic acid, phosphoric acid, hydrochloric acid, nitric acid and sulfuric acid are preferable. When a protonic acid is used as the acid, it is recommended that the proton (H ⁺ ) strength S be equal to or greater 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 mono, more preferably 1. 05 to 7 mono, and still more preferably 1 .; to 5 mono, per 1 mol of phthalonitrile (9).

[0167] As a catalyst used for catalytic hydrogenation, any conventional metal catalyst known in the technical field can be used. 0. central metal force of the catalyst preferably the phthalonitrile (9) 0;! ~ 30 Monore ^_0/0, more preferably 0.1;! ~ 20 Monore ^_0/0, more preferably;! ~ 10 Monore ⁰ It is recommended to use a metal catalyst in an amount such that / ₀ .

[0168] Examples of the metal catalyst include homogeneous catalysts in which phosphine or the like is coordinated to ruthenium or rhodium. However, in view of reactivity and ease of recovery after reaction and regeneration treatment, it is preferable to use a heterogeneous catalyst in the present invention. Among the heterogeneous catalysts, in order to increase the surface area and improve the catalytic activity, a catalyst having a fine metal powder supported on a carrier is preferable. Heterogeneous catalysts such as nickel, Raney nickel, copper-black oxide And metals such as ruthenium, palladium, rhodium, platinum and platinum oxide or fine powders of these metals supported on a carrier such as activated carbon, alumina and diatomaceous earth. Among these metal catalysts, from the viewpoint of catalyst activity preferred by palladium catalyst, rhodium catalyst, platinum catalyst and nickel catalyst, a catalyst in which palladium is supported on activated carbon is more preferable.

When a heterogeneous catalyst is used, a catalyst activation step of mixing the catalyst and the protonic acid in a hydrogen atmosphere before catalytic hydrogenation may be employed as necessary. The activation temperature is usually about room temperature to 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. The following time is more preferably 3 hours or less, still more preferably 2 hours or less.

[0170] The catalytic hydrogenation is usually performed using a solvent. The solvent is not particularly limited, but those which can dissolve phthalonitrile (9) which is a starting material are preferable. As a solvent, for example, aromatic hydrocarbons such as benzene, toluene, xylene, etc .; Ethers such as THF, dioxane, cyclopentyl methyl ether, diisopropyl ether, jetyl ether; alcohols such as methanol, ethanol, propanol, etc .; acetic acid Esters such as methyl, ethyl acetate, propyl acetate and butyl acetate; Amides such as dimethylformamide, dimethylacetoamide; sulfolanes such as sulfolane, 3-methylsulfolane and 2, 4-dimethylsulfolane; and formic acid, acetic acid It is possible to mention S, carboxylic acids such as propionic acid and trifluoroacetic acid. 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 having high solubility of isoindole multimer, such as ethyl acetate, propyl acetate, dimethylformamide, dimethyl formamide, dimethylacetoamide, sulfolane, 3-methyl sulfolane and 2, 4-dimethyl sulfolane are preferable. When a solvent is used, the concentration of phthalonitrile (9) is preferably about 0.0;! To about 5 M, and more preferably about 0.5 to about 1 M.

[0171] The temperature of the catalytic hydrogenation is also influenced by the solvent used, preferably 0 ° C or more, more preferably 20 ° C or more, preferably 150 ° C or less, more preferably 120 ° C or less It is. The time of the catalytic hydrogenation reaction is preferably 30 minutes or more, more preferably 1 hour or more. Preferably, it is 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 still more 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.

[0172] Catalytic hydrogenation can be carried out by constantly 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 reduce the pressure of the reaction system before supplying hydrogen gas. Further, in order to adsorb a large amount of hydrogen to the catalyst, it is preferable to repeat the pressure reduction and the supply of hydrogen gas a plurality of times, particularly in the case of carrying out the catalytic hydrogenation 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 the isoindole multimer increases and the molecular weight thereof increases, the mechanical properties as a multimer, particularly as a polymer, improve. However, isoindole multimers having too large a molecular weight are difficult to manufacture and the handling / gender 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 30,000 to 300,000, and still more preferably 5,00 to 500; It is about 100,000.

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

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 may be appropriately modified within the scope which can conform to the above-mentioned purpose. It is of course possible to carry out further additions, and all of them are included in the technical scope of the present invention.

Example

[0176] 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 intermediates (6) of the present invention (= “1-substituted form of isoindole”), porphyrin (7a) and porphyrin complex (8) It is an example regarding. Examples 35 to 38 relate to the isoindole multimer (10) of the present invention.

Example 1: Reduction of tetrafluorophthalonitrile with hydrogenated diisobutylaluminum

[Formula 23]

In a four-necked reaction vessel equipped with a reflux condenser, a dropping funnel, and a thermometer, 3.0 g (15. O mmol) of tetrafluorophthalonitrile (manufactured by Nippon Shokubai Co., Ltd.) was added, and after replacing with nitrogen, using a syringe 75 ml of dehydrated toluene were added. While cooling in an ice bath, 61 ml (60.3 mmol) of a solution of 0.93 M diisobutylaluminum hydride (Kanto Kagaku Co., Ltd. also purchased) Tonlene solution was slowly dropped from the dropping funnel. After completion of the dropwise addition, the mixture was stirred at room temperature overnight, and then 45 ml (90 mmol) of 2 M hydrochloric acid was added while cooling in an ice bath to carry out the addition. The reaction product is extracted with ethyl acetate, neutralized with aqueous sodium bicarbonate solution, washed with saturated brine, dried over anhydrous sodium sulfate, and the extract is concentrated by an evaporator. The concentrate was purified by silica gel chromatography (solvent: dichloromethane). The target compound 4, 5, 6, 7-tetrahydrofuran 2H-isoindonol was obtained in a yield of 22.6% (0.64 g, 3.4 mmol).

Example 2 Reduction of Tetrafluorophthalonitrile with Diisobutylaluminum Hydride The reaction was carried out under the same conditions as in Example 1, but only 1 OO ml of water was added without using a protonic acid at the time of Taenchi. The reaction solution gelled shortly after the addition of water. The solid matter was removed by filtration through Celite, and purification was carried out in the same manner as in Example 1. As a result, it was found that the objective substance 4,5,6,7-tetrafluoro-2H-isoindole was obtained in a yield of 0.6% (0. Obtained at 017 g, 0.09 mmol).

Example 3 Reduction of Tetrafluorophthalonitrile by Diisobutylaluminium Hydrogenation was carried out in the same manner as in Example 1, except that the concentrate was purified by sublimation, and 4,5,6,7-tetraphenol 4 The iso indinol was obtained with astringent 9. 87% (0.28 g, 1. 48 mmol).

Example 4 Reduction of Tetrafluorophthalonitrile with Diisobutylaluminum Hydride Tetrafluorophthalonitrile 0 · 0.2 g (l. 06 mmol) was added to an eggplant flask and nitrogen substitution was carried out 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 a silica gel short column (solvent: chloroform). The desired 4,5,6,7-tetrafluorinated 2H isoindole (skin-colored solid) was obtained in a yield of 20.8% (39.4 mg, 0.21 mmol).

Example 5: Reduction of 4, 5 bis (pentafluorophenoxy) 3, 6 difluorophthalonitrile by hydrogenated diisobutylaluminum

[Formula 24]

[0185] First, the raw material 4, 5 bis (pentafluorophenoxy) 3, 6 difluorophthalonitrile was prepared as follows: in a 200 ml reaction vessel equipped with a dropping funnel and a thermometer Nole 20. 1 g (100. 45 mmol), potassium hydroxide 13. 99 g (240. 79 mmol), 130 ml of methyl isobutyl ketone were added. After cooling by an ice bath, from the dropping port,

During Ms. Pingko's Pentafune gift Lofennore 37. 0g (201. 0

The reaction was carried out by slowly adding a solution in which 2 mmol) was dissolved, and then stirring at room temperature for 2 days. 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 by an evaporator. The concentrate is subjected to reprecipitation purification with toluene / hexane solvent to give 4,5-bis (pentafluorophenoxy) 3,6 diphenole open mouth phthalonitrile in a yield of 70. 83% (37.4 g, 37.4 g, 70. 81 mmol) was obtained

Then, in a four-necked reaction vessel equipped with a reflux condenser, a dropping funnel and a thermometer, 4, 5-bis (pentafluorophenoxy) 3, 6 difluorophthalonitrile 1.50 g (2.84 mmol) The reaction mixture was purged with nitrogen, and then 25.5 ml of dehydrated toluene was added by a syringe. Cooling in an ice bath While stirring, 0.95 M (1.14 mmol) of a toluene solution of 0.93M diisobutylaluminum hydride (Kanto Chemical Co., Ltd. Power Purchase) was slowly dropped from the dropping funnel. After completion of the dropwise addition, the mixture was reacted at 95 ° C. for 4 hours, allowed to cool to room temperature, and then cooled with an ice bath while adding 10 ml (20 mmol) of 2 M hydrochloric acid to perform quenching. The reaction product was extracted with ethyl acetate, neutralized with aqueous sodium bicarbonate solution, washed with saturated brine, 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-diphenolic acid 2H isoindonolene was obtained in a yield of 34.04% (0.50 g, 0.97 mmol).

[0187] Spectrum data of 5, 6 bis (pentafluorophenoxy) 4, 7 difluorinated 1 2H iso indonolole

(1) NMR spectrum (Device: JEOL, model: JNM-AL400)

'H-NMR CCDCI): 6 7. 31 (m, 2 H), 9. 62 (brs, 1 H)

¹⁹ F-NMR (CDC 1): δ—143. 57 (s 2 F) 157. 50 (m, 4 F),-162. 50 (m, 2 F),-163. 49 (m, 4 F)

(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 pentafluorophenoxide 3, 5 6 trifluorophthalonitrile with hydrogenated diisobutylaluminum

[Formula 25]

Four pentafluorophenoxides 3,5,6-trifnurorophthalonitrile 0 · 364 g (l mmol) prepared in the same manner as in Example 5 were 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. Then, slowly add 16 ml (16 mmol) of 1 M aqueous NaOH solution to the reaction mixture. And added. 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 concentrated The silica gel

It was purified by (solvent: dichloromethane). The desired product, 5 pentafluorophenyloxy 4,6,7 trifnoleo 2H — isoindole (brown solid), was obtained in a yield of 17 · 5% (61.7 mg 0.17 mmol).

[0191] NMR spectrum of 5 pentafluorophenoxy 4, 6, 7 trifluorinated 2H isoindole (apparatus: JEOL, model: JNM-AL400)

'H-NMR CCDCI): 6 7. 35 (m 2 H) 9. 57 (brs 1 H)

¹⁹ F-NMR (CDC1) δ-143. 22 (s IF) 151. 45 (m IF) 157 15. 15 (m 2 F),-162. 22 (m 1 F),-163. 02 (m 1 F), 163 . 31 (m 2 F)

Example 7 Reduction of 4, 5-Bis (pentafluorothioffenoxy) 3,6-difluorophthalonitryl with Hydrogenated Diisobutylaluminum

[Equation 26]

[0194] 4,5-Bis (pentafluorothioff enoxy) manufactured by the same method as in Example 5 3,

6 0.60 g (1 mmol) of difuranoleophthalonitrile was added to an eggplant flask and purged with nitrogen, and then 30 ml of dehydrated toluene was added. While cooling in an ice bath, 0.40 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 target 5, 6-bis (pentafluorothioff enoxy) 4,

7 Difluoro-2H-isoindole (green solid) was obtained in a yield of 20 · 2% (110. 7 mg 0 · 20 mmol).

[0195] 5, 6 bis (pentafluorothioff enoxy) 4, 7 difluorinated 2H iso ind One nore's nocturnal data

(1) NMR spectrum (Device: JEOL, model: JNM-AL400)

'H-NMR CCDCI): 6 7. 35 (q J = 1. 5 Hz 2 H) 9. 62 (brs 1 H)

¹⁹ F-NMR (CDC 1) δ-109. 65 (s 2 F) 134. 32 (m 4 F) 153. 89 (t J = 21 Hz 2 F),-161. 71 (m 4 F)

(2) Mass spectrum (Device Nippon Electronics, 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 Hydrogenated Diisobutylanoleum

[0197] [Formula 27]

[0198] First, 4 chloro 3, 5, 6 trifluorophthalonitrile as a raw material was produced as follows: 1004 g of tetrafluorophthalonitrile 100 g (5 mol) N methinole 2 pyrrolidone in a 5 L reaction vessel equipped with a reflux condenser. After 2343 g of cetonitrile was charged and the temperature was raised to 75 ° G, 233 g (5.5 mol) of lithium chloride was successively added, and the mixture was reacted 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 isopropyl 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 and concentrated by an evaporator. The concentrate was distilled under reduced pressure to obtain 4chloro-3,5,6 trifino reophthalonitrinole in a yield of 40.7% (440. 5 g 2.03 mol).

Then, in a four-necked reaction vessel equipped with a reflux condenser, a dropping funnel, and a thermometer, 1.5 g (6.93 mmol) of 4-chloro-π-3,5,6-triphenole-π-π-eutrileole was dissolved in After purging 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 0.93 M hydrogenated diisobutylaluminum (Kanto Chemical Co., Ltd. also purchased) was slowly dropped from the dropping funnel. After completion of the addition, the reaction was carried out at 95 ° C for 4 hours After cooling to room temperature, 21 ml (42 mmol) of 2 M hydrochloric acid was added to the mixture while cooling in an ice bath. The reaction product is extracted with ethyl acetate, neutralized with aqueous sodium bicarbonate solution, washed with saturated brine, dried over anhydrous sodium sulfate, and the extract is concentrated by an evaporator.

It was purified by (solvent: dichloromethane). The target 5-chloro-4-, 6, 7-trifluoro-2-H-isoindole was obtained in a yield of 12 · 64% (0.18 g, 0.88 mmol).

[0200] 5-Black mouth 4, 6, 7-Trifluor 2H-Spectrum data of isoindole

(1) NMR spectrum (Device: JEOL, model: JNM-AL400)

'H-NMR CCDCI): 6 7. 29 (m, 2 H), 9. 39 (brs, 1 H)

¹⁹ F-NMR (CDC1): δ-125. 66 (dt, J = 20 Hz, 2 Hz, IF),-150. 76 (dd,

J = 16 Hz, 2 Hz, IF),-151. 58 (ddd, J = 20 Hz, 16 Hz, 2 Hz, IF),

(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 by Hydrogenated Diisobutylanhydride

[Formula 28]

[0203] 0.233 g (1 mmol) of 4,5-dichloro-3,6-difluorophthalonitrile produced 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. Then, 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 Was purified by chromatography on silica gel gel short column (solvent: dichloromethane). The objective 5, 6-dichloro-4, 7-difluoro-2H- isoindole (a pale yellow solid) , Yield 27.1% (60.3 mg, 0.27 mmol).

[0204] Spectral data of 5, 6 dichloro-4, 7 difluoro-2H- isoindole

(1) NMR spectrum (Device: JEOL, model: JNM-AL400)

'H-NMR CCDCI): 6 7. 33 (q, J = 1.5 Hz, 2 H), 9. 50 (brs, 1 H)

¹⁹ F-NMR (CDC 1): 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: Hydrogenation of 4, 5 bis (hexylthio) 3, 6 difluorophthalonitrile: Reduction with diisobutylaluminum

[Chem. 29]

[0207] 4,0 bis (hexylthio) 3,6 difluoro phthalonitrile 2 · 0 g (5.04 mmol) prepared in the same manner as in Example 5 was added to an eggplant flask and purged with nitrogen, and then dehydrated in toluene. Added 40 ml. 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. Thereafter, 20 ml (20 mmol) of a 1 M aqueous solution of NaOH was added to the reaction mixture as it was stirred. 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. 1 mmol).

[0208] NMR spectrum of 5, 6 bis (hexylthio) 4, 7 difluoro-2H- isoindole (apparatus: Varian, model: Mercury 2000)

'H-NMR CCDCI): δ 0.85 (t, 6 H, J = 6. 4 Hz), 1. 26 to 1. 66 (m, 16 H), 2

89 (t, 4H, J = 7. 3 Hz), 7. 32 (m, 2 H), 9. 6 (brs, 1 H)

¹⁹ F-NMR (CDC1, Hexafluorobenzene): δ 50. 08 (s, 2F) [0209] Example 11: Reduction of tetrafluorophthalonitrile with BH

[Chemical formula 30]

After replacing the three-necked reaction vessel equipped with a reflux condenser, a dropping funnel and a thermometer with nitrogen, 20 ml of a THF solution of 0.0. 99 M THF-BH complex (purchased from Kanto Chemical Co., Ltd.) (19.

8111111101) Add 1 ^ 1? 351111. Separately, a solution in which 3 g (14. 99 mmol) of tetrafluorophthalonitrile was 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 allowed to react for 4 hours. After that, the reaction solution was returned to room temperature again, and while cooling in an ice bath, 18 ml (36 mmol) of 2 M hydrochloric acid was added to carry out heating. The reaction product was extracted with ethyl acetate, washed with distilled water and then with saturated brine, and dried over anhydrous sodium sulfate, and the extract was concentrated using an evaporator. The concentrate was purified by silica gel column chromatography (solvent: dichloromethane). The objective 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 Method

[Formula 31]

Three-necked flask 100 ml, catalyst supported palladium on activated carbon (購人from Aldrich, Pd: 10 mass ^_0/0) 0. 75g (Pd weight: 0. 70 mmol), Metanonore 30 ml, stone 3M) 1.3 ml (3.9 mmol) of f _L acid were added. Next, the system is depressurized and then hydrogen is supplied repeatedly (hydrogen substitution) three times, and then the catalyst is stirred for 10 minutes at room temperature with the hydrogen balloon pressurized (about 1.1 atm). It was activated. 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 sodium bicarbonate aqueous solution and filtered through celite to obtain Pd The solvent (Pd / C) was removed, extracted with chloroform, washed with distilled water and then with saturated brine, and dried over anhydrous sodium sulfate, and then the extract was concentrated by an evaporator. The concentrate was purified by silica gel column chromatography (solvent: chloroform). The target compound 4,5,6,7-tetra-fluoro-phenol 2H-isoindonol was obtained in a yield of 41.6% (0. 59 g, 3.12 mmol).

Example 13 Reduction of Tetrafluorophthalonitrile by Catalytic Hydrogenation Method

[Formula 32]

[0217] A three neck flask of 100 ml, (購人from Aldrich, Pd: 10 mass ^_0/0) catalyst supported palladium on activated carbon 0. 5 g (Pd content: 0. 47 mmol), acetic acid Echinore 20 ml, Trifnorrhea 0.6 g (5.26 mmol) of oral acetic acid was added. Next, the system is depressurized and the hydrogen supply operation (hydrogen substitution) is repeated three times, and then the catalyst is stirred at room temperature for 30 minutes under pressure (about 1.1 atm) with a hydrogen balloon. Was activated. Thereafter, a solution of 1.00 g (5 mmol) of tetrafluorophthalonitrile 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, extraction is carried out with a crocodile form, washed with distilled water and then with saturated brine, and dried over anhydrous sodium sulfate. After extraction, the extract was concentrated by an evaporator. The concentrate was purified by silica gel column chromatography (solvent: chloroform). The desired 4,5,6,7-tetrafluoro-2H-isoindole is obtained in a yield of 33.4% (0.3 l og, 1.67 mmol).

Example 14 Reduction of Tetrafluorophthalonitrile by Catalytic Hydrogenation Method

[Formula 33]

[0220] Rh / alumina catalyst (purchased from Aldrich, Rh: 5 mass) in a 100 ml eggplant flask %) 1. Og (Rh amount: 0.49 mmol) and 20 ml of methanol were added, and the mixture was purged with hydrogen and stirred at room temperature for 45 minutes. Thereafter, 0.28 ml (5 mmol) of acetic acid was added, a solution of 1.0 g (5 mmol) of tetrafluorophthaloyl in 20 ml of methanol was added dropwise, and after replacing with hydrogen 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: croform) to obtain 4,5,6,7-tetra-fluoro-ne-ro-ro 2H iso-indonole as the skin-colored solid in a yield of 4.1%. Obtained with (0. 038 g, 0.20 mmol).

Example 15 Reduction of Tetrafluorophthalonitrile by Catalytic Hydrogenation Method

[Formula 34]

[0223] A three neck flask of 1000 ml, catalyst supported palladium hydroxide on activated carbon (購人from Aldo rich Inc., Pd: 20 mass ^_0/0) 3. 77g (Pd weight: 7. 09mmol), Metanonore 300 ml, 12.5 ml (37.5 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 stirred at room temperature for 10 minutes while being pressurized with a hydrogen balloon (about 1.1 atm). It was activated. Thereafter, a solution of 15 g (75 mmol) of tetrafluorophthalonitrile dissolved 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 sodium bicarbonate aqueous solution, then the Pd catalyst is removed by Celite filtration, the mixture is extracted with toluene, washed with distilled water and then with saturated brine and dried over anhydrous sodium sulfate, and the extract is evaporated. Concentrated by The concentrate was purified by silica gel column chromatography (solvent: chloroform). The desired 4,5,6,7 tetrafluoro-2H-isoindole was obtained in 28% yield (3.976 g, 21.02 mmol).

Example 16: Reduction of 4, 5 bis (pentafluorophenyl) 3, 6 difluorophthalonitrile by catalytic hydrogenation [0225]

[0226] A three neck reaction vessel 100 ml, catalyst supported palladium on activated carbon (購人from Aldrich, Pd: 10 mass ^_0/0) 0.86g (Pd amount: 0.81 mmol), sulfuric acid Metanonore 30 ml 3M 0.5 ml (1.5 mmol) was added. After 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 1.1 Under atmospheric pressure, the catalyst was activated by stirring for about 5 minutes at room temperature. After that, a solution of 4,5-bis (pentafluorophenyl) 3, 6 difluorophthalonitrile 1.50 g (3.02 mmol) dissolved in a mixed solvent of 15 ml of toluene and 30 ml of ethyl acetate is added to the reaction solution to obtain a room temperature. The solution was vigorously stirred for 15 hours. The reaction solution was neutralized with aqueous sodium bicarbonate solution, extracted with ethyl acetate, washed with distilled water and then saturated brine, 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 5,6-bis (pentafluorophenyl) -1,7-difluoro-2-H isoindole was obtained in a yield of 49. 1% (0.72 g 1.48 mmol).

[0227] Of 5, 6 bis (pentafluorophenyl) 4, 7 difluoro-2H- isoindole

(1) NMR spectrum (Device: JEOL, model: JNM-AL400)

NMR ((CD) CO) δ 7.78 (s 2H) 12.34 (brs 1H)

¹⁹ F-NMR ((CD) CO) δ-115.2179 (s 2 F) 133. 78 (d J = 22 Hz 4

F), -147.68 (t J = 21 Hz 2 F)-156. 37 (t J = 18 Hz 4 F)

(2) Mass spectrum (apparatus: manufactured by Nippon Denshi, model: JMS-MS 700V)

MS (EI): m / z = 485 (M ⁺ ) (calculated molecular weight: 485 · 01)

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

[Formula 36]

[0230] A three neck flask of 100 ml, the catalyst obtained by supporting palladium on activated carbon (購人from Aldrich, Pd: 10 mass ^_0/0) 1. ^00g (Pd weight: 0. 94 mmol), Metanonore 5 ml, 3M Stone) f _L acid 1. 25 ml (3. 75 mmol) was added. The system is decompressed and then hydrogen is supplied (hydrogen substitution) three times, and then pressurized with a hydrogen balloon (about 1.1 atm) and stirred for 10 minutes at room temperature to catalyze the catalyst. It was activated. After that, a solution of 4,5 bis (2,5 dimethylphenoxy) -3,6 difluorophthalonitrile 3 · 00 g (7.42 mmol) dissolved in 20 ml of ethyl acetate was added to the flask and vigorously stirred at room temperature for 14 hours. . The reaction solution is neutralized with sodium bicarbonate aqueous solution, then the Pd catalyst is removed by Celite filtration, the mixture is extracted with toluene, washed with distilled water and then with saturated brine and dried over anhydrous sodium sulfate, and the extract is evaporated. Concentrated by The concentrate was purified by silica gel column chromatography (solvent: chloroform). 5, 6-bis (2, 5-dimethyl-phenoxyethanol) 4, 7 Ziff Honoré old row 2H Isoindonore of the object, Osamukushi ^{_{21 0/0 (0. 623g,}} 1. 58mmol) was obtained in.

[0231] NMR spectrum of 5, 6 bis (2, 5 dimethyl phenoxy) 4, 7 difluoro-2H- iso indonole (Device: manufactured by Varian, model: Mercury 2000)

'H-NMR CCDCI): 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 (CDC1, Hexafluorobenzene): δ 19. 39 (s, 2F)

Example 18: Alkylation of 4, 5, 6, 7 Tetrafluoro-2H isoindole with Methyl Iodide

[Formula 37]

[0234] 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 nitrogen substitution, 3.5 ml of dehydrated THF was added and It cooled to ° C. Thereto, 0.6 ml (0.42 mmol) of a 1.5 M solution of n-butyllithium in hexane was slowly added using a syringe and stirred at 78 ° C. for 30 minutes. Then, 0.2 g (l. 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 4,5,6,7 tetrafluoro-2-methylisoindole as a target substance at a yield of 58.2% (0.060 g, 0 (29.95 mmol).

Example 19: Alkylation of 4, 5, 6, 7 Tetrafluoro-2H-isoindole with n-Pentyl Iodide

[Formula 38]

[0237] In a 10 ml two-necked reaction vessel, 4, 5, 6 and 7 tetrafluoro-2H-isoindole 0.49 g

After adding (2.59 mmol) and purging with nitrogen, 17 ml of dehydrated THF was added and the mixture was cooled to −78 ° C. Thereto, 2 ml (3.14 mmol) of a 1.5 M solution of n-butyllithium in hexane was slowly added using a syringe and stirred at 78 ° C. for 30 minutes. Then, after slowly adding n-pentyl iodide 0.67 g (3.38 mmol) into it using a syringe, it was stirred without cooling for 14 hours. The reaction was terminated by the addition of water, 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 obtain 4,5,6,7 tetrafluoro-2-n-pentylisoindole as a target substance in a yield of 83.6% (0. 564 g, 2. 176 mmol) were obtained. [0238] Mass spectrum of 4, 5, 6, 7 tetrafluoro-2 n-pentyl isoindole (apparatus: manufactured by JEOL, model: JMS-MS 700v)

MS (EI): m / z = 259 (M ⁺ ) (calculated molecular weight: 259 · 1)

Example 20: Oxidation polymerization of 4,5,6,7 tetrafluoro-2H isoindole

4,5,6 7 Tetrafluro 2H isoindole 0.18g (0. 95m mol) was weighed in an eggplant flask, and 4.3g of cromoform was added to this, and the mixture was stirred to prepare an isoindole solution. . In a separate container, 0.63 g (3. 88 mmol) of iron chloride (111) was weighed out, and 3.4 g of water was added to prepare an aqueous iron chloride solution. The aqueous solution of iron chloride was slowly added to the previously prepared isoindole solution and stirred at room temperature for 48 hours, and then 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 dried under vacuum to obtain black poly (4,5,6,7 tetrafluoro-2H isoindole). 0.19 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 Mw = 41, 200. The conductivity of the polymer (measured by the two-terminal method) was ^{^{4 X 10- 6 S / cm 2}} .

Example 21: Oxidation weight of 4,5,6,7 tetrafluoro-2 n pentylisoindole In an eggplant flask, 4,5,6 7 tetrafluoro-2-n pentylisoindole 0 · 248 g (0. 96 mmol) ) Was added thereto, and 4 g of croform was added thereto and the mixture was stirred to prepare an isoindo solution. In a separate container, 0.62 g (3.82 mmol) of iron chloride (111) was weighed out, and 3.5 g of water was added to prepare an aqueous iron chloride solution. This aqueous solution of iron chloride was slowly added to the previously prepared isoindole solution and stirred at room temperature for 48 hours, and then the reaction solution was poured into a large amount of water. The residue obtained by filtering this solution is washed with dilute hydrochloric acid, water and then chloroform, and then vacuum dried to obtain black poly (4,5,6,7 tetrafluoro-2-n). This obtained penty isoindole 0 · 05 g (converted yield 20 · 3%). The average molecular weight of the obtained polymer (measured by GPC in terms of polystyrene) was Mn = 20,400 Mw = 29,500.

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

[Formula 39]

[0244] A 50 ml two-necked eggplant flask equipped with a reflux apparatus is purged with nitrogen, and 0.21 ml (2.75 mmol) of dimethinolefonolemamide is removed while cooling with an ice bath, and 0.26 ml (2. 75 mmol) of sodium phophorinole is added thereto. ) Was slowly added dropwise and stirred for 15 minutes. 2 ml of methylene chloride was added and the precipitated solid was dissolved, and a solution of 480 mg (2.54 mmol) of 2,4,5,7-tetra-fluoro-methyl 2-H iso indonolole was dissolved in 2 ml of methylene chloride slowly. Add dropwise and then remove the ice bath and heat to 55 ° C. and reflux 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 water, and the extracted organic phase is washed with aqueous sodium hydrogen carbonate solution. Wash, dry over anhydrous sodium sulfate and concentrate under reduced pressure to give a brown solid. This was purified by silica gel chromatography (solvent: croform) to obtain 350 mg (1.43 mmol, yield 58.7%) of an aminomethylene compound.

[Selected data of amino methylene body]

(1) NMR spectrum (Device: JEOL, model: JNM-AL400)

'H-NMR CCDCI): 63. 39 (s, 3 H), 3. 78 (s, 3 H), 7.53 (s, 1 H), 8.09 (s

, 1H)

¹⁹ F-NMR (CDC1): δ -166.15 (dd, J = 21, 20 Hz, IF), -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, IF)

(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: 1 Preparation of formyl 4,5,6,7 tetrafluoro-2H isoindole (hereinafter abbreviated as “formyl form”) [Formula 40]

[0248] A 50 ml two-necked eggplant flask equipped with a reflux apparatus is purged with nitrogen, and while cooling with an ice bath, dimethinolefonolemamide 0.21 ml (2. 75 mmol) is caro-free, and there is 0.26 ml sodium chloride 2. 75 mmol) was slowly added dropwise and stirred for 15 minutes. To the precipitated solid, 1.5 ml of methylene chloride is added to dissolve the solid, and a solution of 47 mg (2. 49 mmol) of 4,5,6,7-tetrafluorinated 2H-isoindole in 6 ml of methylene chloride is dissolved therein. It was slowly dropped, then the ice bath was removed and heated to 55 ° C. and refluxed for 15 minutes. Next, the solution was 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, and then refluxed at 55 ° C. for 2 hours and cooled to room temperature. The reaction mixture was then extracted with jetyl 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. The resultant was purified by silica gel chromatography (solvent: ethyl acetate 30% by volume / hexane 70% by volume) to obtain 70 mg (0.322 mmol, yield 13.0%) of the monolemino compound.

[0249] Spectral data of formyl form

(1) NMR spectrum (Device: JEOL, model: JNM-AL400)

'H-NMRC CCD) CO): δ 8. 01 (s, 1 H), 9. 81 (s, 1 H)

¹⁹ F-NMR ((CD) CO)): δ-168. 54 (dd, J = 17, 18 Hz, 1 F),-162. 64 (dd, J = 17, 18 Hz, IF),-149. 20 ( dd, J = 20, 18 Hz, IF),-146. 90 (brs, 1 F)

MS (EI): m / z = 217 (M ⁺ ) (calculated molecular weight: 217 · 12)

Example 24 Production of Formyl Form from Amino Methylene Form

[Formula 41]

An aminomethylene compound 326.7 mg (l. 34 mmo 1) was added to a 100 ml eggplant flask equipped with a reflux apparatus for nitrogen substitution, and 35 ml of ethanol was added thereto for dissolution, and then 2 ml of a 1 M aqueous solution of NaO H Add (2 mmol) and heat at 60 ° C. for 1.5 h and cool to room temperature. The reaction mixture is then extracted with ethyl acetate, ethanol is removed with water, dried over anhydrous sodium sulfate and concentrated under reduced pressure to give the formyl form 208. 6 mg (0.96 mmol) as a white solid. , Yield 71.7%).

Example 25: Preparation of 1-hydroxymethyl mono, 4, 5, 6, 7 tetrafluoro-2H isoindole (hereinafter abbreviated as “hydroxymethyl form”)

[Formula 42]

[0255] Formyl compound 108. 6 mg (0.5 mmol) is added to a 100 ml eggplant flask and purged with nitrogen, and 20 ml of dry THF is added to this, and 1 M hydrogenated diisobutylammium solution 1 · 1 ml while stirring at 78 ° C. (l. lmmol) was added and stirred for a further 2 hours. After adding 1 M HC1 at 78 ° C, adding it to room temperature and returning to room temperature, the reaction mixture is extracted with ethyl acetate, washed with aqueous sodium hydrogen carbonate solution and water, dried over anhydrous sodium sulfate and then reduced pressure. The reaction mixture was concentrated with to give 103 mg (0.47 mmol, crude yield 94%) of a hydroxymethyl compound as a reddish purple solid.

[0256] Example 26: Preparation of Hexade Force Fluorotetrabenzoporphyrin from Hydroxymethyl Form

[Formula 43]

[0258] 103 mg (crude yield 0.47 mmol) of the hydroxymethyl compound obtained in Example 25 was used as it was.

The reaction mixture was added to a 100 ml eggplant flask and purged with nitrogen, and then 47 ml of ethanol was added for dissolution, and 3 ml (51.8 mmol) of acetic acid was added, followed by stirring at room temperature for 3 days. The reaction mixture is then neutralized by adding 3.18 ml (51. 8 mmol) of trietinoleamine, and then adding DDQ (2,3 disiano-5,6 dichloro-p benzoquinone) 119 · 3 mg (0.47 mmol). Stir at room temperature. Then, the reaction mixture was filtered by suction to obtain 28 mg (crude yield: 0.035 mmol, crude yield: 29.8%) of hexecafluorotetrabenzoporphyrin as a dark green solid.

[0259] Spectral data of Hexede force fluorotetrabenzo porphyrin

(1) Mass spectrum (apparatus: Applied 'Biosystems, model: Voyager-DETM PRO)

MS (TOF-MS): m / z = 798. 80 (M ⁺ ) (calculated molecular weight: 798 · 03)

(2) UV-visible absorption spectrum (Apparatus: manufactured by Hitachi High-Technologies, model: U-2800

)

λ (CHC1) = 416, 430, 599, 667, 690 belly

max 3

From TOF-MS measurement, in the crude product, corrole represented by the following formula (measured value: m / z = 785. 87, calculated molecular weight: 786. 03), safilin (measured value: m / z) = 985. 95, calculated molecular weight: 985. 04) and pentaphenyl (found value: m / z = 997. 93, calculated molecular weight: 997. 04) were confirmed to be formed.

[Formula 44]

Safilin ・ Pentaphy 'Lin

Example 27 1- (N, N-dimethylamino) methyl-4,5,6-7 tetrafluoro-2H

Preparation of Hexadede Fluorotetrabenzoborofluorine via Isoindole ("Aminomethyl")

[Formula 45]

[0264] A reactor vessel was charged with nitrogen by adding 100 mg (0. 529 mmol) of 2,4,5,7-tetra-fluoro-methyl 2H isoindonole and 102 mg (0.553 mmol) of methylenedimethylioamide ammonium iodide. After that, 8.41 g of acetylonitrile was added and stirred at room temperature for 32 hours. After that, 150 mg (661 mmol) of DD Q 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 filtration of the reaction solution is subjected to ultrasonic cleaning with methanol and then with chloroform to form 20 mg (0.025 mmol, yield 18. 94%) of hexadefluorotetrabenzoponorophylline. I got Example 28: 2 ² , 2 ³ , 7 ² , via 1- (N, N- 5, 6-bis (Pentafunole s s s s s if-2 nore) 4, 7

7 ³ , 12 ² , 12 ³ , 17 ² , 17 ³ -Pheninore) 2 ¹ , 2 ⁴ , 7 ¹ , 7 ⁴ , 12 ¹

)Manufacturing of

[Formula 46]

[0267] After adding 5,6 bis (pentafluorophenyl) 4,7- difurooleo 2Η-um 76.3 mg (0.41 mmol) to a reaction vessel and carrying out nitrogen substitution, 17.7 g of acetonitrile is removed. The mixture was 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, then dehydrated with 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 give 12 mg of kactakis (pentafluorophenynore) kectafluoro tetrabenzoporphyrin. (0. 006 mmol, yield 6 · 0%) was obtained.

[0268]

Turtle data

(1) Mass spectrum (apparatus: Applied 'Biosystems, model: Voyager-DE PRO)

MS (TOF-MS): m / z = 1984. 26 (M ⁺ ) (calculated molecular weight: 1981. 98)

(2) UV-visible absorption spectrum (apparatus: manufactured by Shimadzu Corporation, model: uv-1650Pc) λ (CHC1) = 435, 451, 576, 623, 632 belly

max 3

Example 29 Preparation of Hexade Force Fluorotetrabenzo Porphyrin Zinc Complex (hereinafter abbreviated as “borophyrin zinc complex”)

After adding 300 mg (l.59 mmol) of 2,5,7,7-tetrafnourose to a reaction vessel and 300 mg (l.59 mmol) of iodochloromethane, and 300 mg (l.62 mmol) of methylenedimethyliomide iodide, the reaction vessel was purged with nitrogen, 69.3 g of methylene chloride was added and stirred at room temperature for 48 hours. Then, under nitrogen atmosphere, the atmosphere was opened to the atmosphere, 256 mg (l. 40 mmol) of zinc acetate was added, and the mixture was stirred for a further 48 hours under the atmosphere and at room temperature. Oxidation of borophylinogen 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 with an evaporator. The concentrate was sonicated 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) — NMR (THF): δ 10. 85 (s, 1H)

¹⁹ F—NMR (THF, standard substance: hexafluorobenzene): δ 7. 20 (m, 2F), 18. 4 (m, 2F)

(2) Mass spectrum (apparatus: Applied 'Biosystems, model: Voyager-DETM PRO)

MS (TOF-MS): m / z = 860. 84 (M ⁺ ) (calculated molecular weight: 859 · 95)

(3) UV-visible absorption spectrum (apparatus: manufactured by Shimadzu Corporation, model: uv-1650Pc) λ (THF) = 407, 432, 623 應

max

Example 30 Preparation of Porphyrin-Zinc Complex

After adding 517 mg (2. 734 mmol) of methyl 2,5,7,7-tetrafnolose and 278 mg (2. 734 mmol) of iodochloromethane, and 528 mg (2.85 mmol) of methylenedimethyliomide iodide, the reaction vessel was purged with nitrogen, 41. 27 g of acetonitrile were added and stirred at room temperature for 48 hours. Thereafter, 700 mg (3.81 mmol) of zinc acetate was added and stirred at room temperature for further 6 hours, and then 0 mg (4.008 mmol) of DDQ 91 was added and stirred at room temperature for further 24 hours. After that, the reaction liquid The solution is poured into 60 g of aqueous sodium bicarbonate solution, the filtrate is recovered by filtration, and the filtrate is washed with methanol and then isopropyl alcohol, and then 50 mg (0.508 mmol, yield 8. 49%) of a porphyrin zinc complex is obtained by Soxhlet extraction. Obtained.

Example 31 Preparation of Hexade-Fluoro Fluorotetrabenzoborophyllin Copper Complex (hereinafter abbreviated as “Porphyrin-Copper Complex”)

After adding nitrogen gas to the reaction vessel after adding 700 mg (3.70 mmol) of 4,5,6,7-tetrafnolose and 2 mg of isoindodonole and 700 mg (3.78 mmol) of methylenedimethyliomide iodide, 98.3 g of acetonitrile were added and stirred at room temperature for 48 hours. Then, under nitrogen atmosphere, the system was opened to the atmosphere, 744 mg (3.73 mmol) of copper acetate monohydrate was added, and the mixture was stirred at room temperature and for 48 hours. Oxidation of borophylinogen is presumed to be mainly performed by stirring under this atmosphere. Thereafter, 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 (0.21 mmol of a porphyrin copper complex, yield 31.4%).

[0273] Spectral data of borophyrin copper complex

(1) Mass spectrum (apparatus: Applied 'Biosystems, model: Voyager-DETM PRO)

MS (TOF-MS): m / z = 859. 78 (M ⁺ ) (calculated molecular weight: 858. 95)

(2) Ultraviolet-visible absorption spectrum (apparatus: manufactured by Shimadzu, model: uv-1650Pc) λ (THF) = 405, 422, 620 應

max

Example 32 Preparation of Hexade Force Fluorotetrabenzo Porphyrin Nickel Complex (hereinafter abbreviated as “borophyrin nickel complex”)

Reaction vessel After adding 100 mg (0.55 mmol) of 2,5,7,7-tetrafnourace compound and 0.5 mg (0.53 mmol) of methyl iodide and 100 mg (0.54 mmol) of methylenedimethyliomide iodide after nitrogen substitution, 5.53 g of acetonitrile were added and 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 were 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, and filtered, and the obtained filtrate was washed with methanol and then with dilute hydrochloric acid. In addition, the filtrate is cetyl acetate, methanol, croform. After ultrasonic cleaning in order with each solvent of the above, Soxhlet extraction was carried out to obtain 4 mg (0.0005 mmol, yield 3.5%) of a porphyrin nickele complex.

[0275] Spectrum data of porphyrin nickel complex

(1) Mass spectrum (apparatus: Applied 'Biosystems, model: Voyager-DETM PRO)

MS (TOF-MS): m / z = 854. 69 (M ⁺ ) (calculated molecular weight: 853 · 95)

(2) UV-visible absorption spectrum (apparatus: manufactured by Shimadzu Corporation, model: uv-1650Pc) λ (THF) = 405, 430, 617 應

max

Example 33 Preparation of Hexade Force Fluorotetrabenzo Porphyrin Cobalt Complex (hereinafter abbreviated as “borophyrin cobalt complex”)

Reaction vessel After adding 100 mg (0.55 mmol) of 2,5,7,7-tetrafnourace compound and 0.5 mg (0.53 mmol) of methyl iodide and 100 mg (0.54 mmol) of methylenedimethyliomide iodide after nitrogen substitution, 5.54 g of acetonitrile were added and stirred at room temperature for 24 hours. Thereafter, 134 mg (0.538 mmol) of cobalt acetate tetrahydrate were added and stirred at room temperature for 22 hours. After that, 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 was dissolved in benzonitrile, poured into methanol to precipitate crystals, and filtered again, and the obtained filtrate was ultrasonically washed in order with solvents such as ethyl acetate, methanol and chloroform. After that, Soxhlet extraction was carried out to obtain 3 mg (0.04 mmol, yield 2.7%) of a porphyrin cobalt complex.

[0277] Spectral data of porphyrin cobalt complex

(1) Mass spectrum (apparatus: Applied 'Biosystems, model: Voyager-DETM PRO)

MS (TOF-MS): m / z = 855. 84 (M ⁺ ) (calculated molecular weight: 854 · 95)

(2) UV-visible absorption spectrum (apparatus: manufactured by Shimadzu, model: uv-1650Pc) λ (THF) = 421, 433, 447, 614

max

[0278] Example 34: Preparation of kactakis (pentafluorophenyl) kactafluorotetrabenzopolzinc phosphorus zinc complex After adding 200 mg (0.40 mmol) of 5, 6 bis (pentafluorophenyl) 4, 7 difluoro-2H iso indonole and 76. 3 mg (0.4 1 Then, 17.7 g of acetonitrile was prepared and stirred at room temperature for 48 hours. Then, under nitrogen atmosphere, the system was opened to the atmosphere, 64. 7 mg (0.35 mmol) of zinc acetate was added, and the mixture was stirred for a further 48 hours under the atmosphere and at room temperature. It is estimated that the oxidation of borophyrinogen is mainly performed by stirring under this atmosphere. Thereafter, the reaction solution is concentrated by an evaporator, and the concentrate is subsequently dissolved in chloroform, and the chloroform phase is washed with water and dilute hydrochloric acid, then dehydrated with anhydrous sodium sulfate, and again concentrated by an evaporator. Concentrated. The concentrate was purified by silica gel chromatography purified by (solvent acetic Echiru 20 vol% / hexane 80 volume ^_0/0), Okutakisu (pentafluorophenyl We sulfonyl) O Kuta Full O b tetra downy emission zone porphyrin zinc complex 21 mg (0. OlO mmol, yield 10.2%) were obtained.

[0279] Spectrum data of kactakis (pentafluorophenyl) kactafluorotetrabenzo-zinc complex

(1) NMR spectrum (Device: JEOL, model: JNM-AL400)

'H-NMRCC D N): δ 11. 97 (s, 1 H)

¹⁹ F-NMR (CDN): δ— 159. 49 (m, 2F), 1 149. 55 (m, 1 F), 1 138. 13 (m, 2 F),-118. 73 (s, IF)

(2) Mass spectrum (apparatus: Applied 'Biosystems, model: Voyager-DETM PRO)

MS (TOF-MS): m / z = 2047. 14 (M ⁺ ) (calculated molecular weight: 2043 · 9)

(3) Ultraviolet-visible absorption spectrum (apparatus: manufactured by Shimadzu, model: uv-1650Pc) λ (THF) = 429, 457, 595, 643 應

Example 35: Preparation of (4,5,6,7 tetrafluoro-2H isoindole) multimer

Three-necked flask 500 ml, catalyst supported palladium on activated carbon (購人from Aldrich, Pd: 10 mass ^_0/0) 5. 12g (Pd weight: 4. 81 mmol), Metanonore 200 ml, stone 3M) f _L acid 12.5 ml (37.5 mmol) was added. Next, the system is depressurized and then hydrogen is supplied. Operation (hydrogen substitution) is repeated three times, and then pressurized with a hydrogen balloon for 10 minutes at room temperature. Stirring was performed to activate the catalyst. Thereafter, a solution of 10.0 g (49.98 mmol) of tetrafluorophthalonitrile dissolved in 200 ml of toluene was added to the flask and stirred vigorously 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 saturated brine, and dried over anhydrous sodium sulfate, and the extract was concentrated by an evaporator. The concentrated product is purified by silica gel column chromatography (solvent: ethyl acetate) to obtain the desired product (4,5,6,7 tetrafluoro-2H-isoindole) multimer 6.19 g (converted yield) 65.5%) obtained. The average molecular weight of the obtained multimer (as determined 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

Three-necked flask 100 ml, (購人from Aldrich, Pd: 10 mass ^_0/0) catalyst the palladium was supported on activated carbon 1. 01G (Pd weight: 0. 94 mmol), Metanonore 5. lg, of 3M Stone) f _L acid 1.5 ml (4.5 mmol) was added. The system is then decompressed and then hydrogen is supplied repeatedly (hydrogen substitution) three times, and then pressurized with a hydrogen balloon (about 1.1 atm) and stirred for 10 minutes at room temperature to catalyze the catalyst. It was activated. Thereafter, a solution of 3,00 difluoro-4,5-bis (2,5 dimethylphenoxy) phthalonitrile 3 · 00 g (7.42 mmol) in 15 ml of ethyl acetate is added to the flask and the solution is allowed to stand at room temperature for 14 hours. It stirred. The reaction solution was neutralized with sodium bicarbonate water, 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 then the extract was concentrated by an evaporator. The concentrate was purified by silica gel column chromatography grayed roughy (solvent: Black port Holm) to give the desired product (4, 7-Jifuruoro - 5, 6-bi scan ^(2, 5-dimethyl-phenoxyethanol) Single 2H- isoindole ) The multimer was obtained as 1 · O lg (converted yield 34.9%). 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-Difuranoleo 5,6 Bis (pentafuroreorophenole) 2H Isoindole) Multimer

Catalyst with palladium supported on activated carbon in a 20 ml two-necked flask (from Aldrich) 購人, Pd: 10 mass ^_0/0) 0. 3g (Pd weight: 0. 28 mmol), Metanonore 3g, was added 3M stones) f _L acid 0. 4ml (1. 2mmol). Next, after the system is depressurized and the operation of supplying hydrogen (hydrogen replacement) is repeated three times, the catalyst is stirred at room temperature for 10 minutes while pressurized with a hydrogen balloon (about 1.1 atm). It was activated. Then, a solution of 1,00 g (2.02 mmol) of 3,6-difluoro-4,5-bis (pentafluorophenyl) phthalonitrile in solution in 5. 5 g of ethyl acetate was added to the flask and stirred at room temperature for 14 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 toluene, washed with distilled water and then with saturated brine, and dried over anhydrous sodium sulfate, and then the extract was concentrated by an evaporator. The concentrate is purified by silica gel column chromatography (solvent: croform) to obtain 0.34 g of the objective (4,7-difluoro-5,6-bis (pentafluorophenyl) 2H isoindole) multimer. It was obtained (converted yield 43.1%). 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

Three-necked flask 200 ml, (purchased from Aldrich, Pd: 10 mass ^_0/0) catalyst supported palladium on activated carbon 1. 200 g (Pd content: 0. 94 mmol), methanol 5g, sulfuric acid 3M 4. lml (12.3 mmol) was added. Next, after the system is depressurized and the hydrogen supply operation (hydrogen substitution) is repeated three times, the catalyst is stirred for 10 minutes at room temperature while pressurized with a hydrogen balloon (about 1.1 atm). It was activated. 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 with 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, and the target (5, 6 dichloro-2H-isoindole) multimer is obtained as 0.71 g (converted yield 25) . 3%) obtained. The average molecular weight (measured by GPC in terms of polystyrene) of the obtained multimer was Mn = 5,900 and Mw = 6,900.

Industrial applicability [0284] The method for producing isoindoles of the present invention can produce isoindoles more inexpensively because the number of reaction steps is smaller than in the conventional method. 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 of organic thin film transistors, organic solar cells and the like as coloring materials or by polymerizing.

The method for producing a conjugated cyclic compound (7) of the present invention is to produce a conjugated cyclic compound (7) (particularly, porphyrin (7a)) from an isoindole (2) via an intermediate (6). It is characterized by In particular, halogen-containing tetrabenzoporphyrin can be selectively produced in high purity through the intermediate (6). Further, according to the production method of the present invention, halogen-containing tetrabenzoporphyrin can be produced without using a metal salt.

The π-conjugated cyclic compound (7) (preferably porphyrin (7a), corrole (7b), saphirin (7b) and pentaphyrin (7d); more preferably porphyrin (7a)) of the present invention is not limited. Applications: For example, organic electronic devices, especially 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 carriers It can be applied to generating materials, optical recording materials, and catalysts. 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 to the production of polymer materials such as polyisoindolenine vinylene which can be obtained only by the production of the π-conjugated cyclic compound (7).

[0287] The method for producing an isoindole multimer of the present invention is to produce an isoindole multimer by using phthalonitriles that are more stable than isoindoles and easily available as a starting material. S can. 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

The scope of the claims

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, and γ is

ΟΙΤ or SR ³ (wherein, R ² and R ³ each independently represent an alkyl, aryl or alkylaryl group)

, M + n≤4, m represents an integer of 1 to 4, n represents an integer of 0 to 3, and o]

[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 process according to claim 2, wherein the hydride reducing reagent is used so as to be 1 to 6 hydrides per 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) is mixed with a hydride reducing reagent, reduction reaction is performed, and then the reaction mixture and 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, reduction reaction is performed, and then the reaction mixture and alkali are mixed.

[6] The production method according to claim 2, wherein the hydride reduction reagent is aluminum hydride or a complex thereof, or boron hydride or a complex thereof.

7. The 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).

[Formula 2]

[Wherein, X represents a halogen atom, and Y is

OR ² or SR ³ (wherein R ² and R ³ each independently represent an alkyl, aryl or alkylaryl group), provided that m + n≤4, m is 1 Represents an integer of 4 to 4; n represents an integer of 0 to 3; o

[9] N-substituted isoindole represented by the following formula (3) (excluding those in which X is a fluorine atom and m = 4).

[Chemical 3]

X " ¹ヽ.

I] N-R (3)

[Wherein, X represents a halogen atom, and Y is

OR ² or SR ³ (wherein, 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 is an integer of 1 to 4 and n is 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).

[Formula 4]

[Wherein, X represents a halogen atom, and Y is

And m or SR ³ (wherein, R ² and R ³ each independently represent an alkyl, aryl or alkylaryl group), and m is 1 to 1 provided that m + n 、 4 Represents an integer of 4, n represents an integer of 0 to 3

. ]

A polymer having a repeating unit represented by the following formula (5) (excluding those in which X is a fluorine atom and m = 4).

[Chem. 5]

[Wherein, X represents a halogen atom, and Y is

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) through a 1-position substitution of isoindole shown by the following formula (6).

[Chemical 6]

[Wherein, X represents a halogen atom.

The wolf is

1-4

The Represents.

A represents N or NH, j represents an integer of from! 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 71 conjugated system at the doublet. ]

From halogen-containing isoindole represented by the following formula (2), isoin represented by the following formula (6) The production method according to claim 12, wherein a halogen-containing tetrabenzovolphenyline represented by the following formula (7a) is produced via 1-position substitution of dole.

[Chem. 7]

[Wherein, X represents a halogen atom, and γ is

And SR or SR ³ (wherein R ² and R ³ each independently represent an alkyl, aryl or alkylaryl group), and m is 1 to 4 provided that _m + n≤4; And n represents an integer of 0 to 3.

1-4

The Represents. ]

By formylation of the halogen-containing isoindole represented by the formula (2), a first intermediate represented by the following formula b) is formed, and then the intermediate (6b) is reduced to form the first intermediate. The production method according to claim 13, wherein the hydroxymethylated 2H isoindole represented by the following formula (6c) is formed as the 1-position substitution of isoindole.

[Formula 8]

[Wherein, X represents a halogen atom, and γ is

And SR or SR ³ (wherein R ² and R ³ each independently represent an alkyl, aryl or alkylaryl group), and m is 1 to 4 provided that _m + n≤4; And n represents an integer of 0 to 3. ]

The first intermediate represented by the above formula (6b) is formed by reacting the halogen-containing isoindole represented by the above formula (2) with a dialkylformamide in the presence of a phosphoryl halide. The manufacturing method according to claim 14.

By aminomethylenation of the halogen-containing isoindole represented by the above formula (2), a second intermediate represented by the following formula (6a) is formed, and then this intermediate (6a) is hydrolyzed. The method according to claim 14, which forms a first intermediate represented by the above formula 1⁄2 b).

[Chem. 9]

[Wherein, X represents a halogen atom, and Y is

And SR or SR ³ (wherein R ² and R ³ each independently represent an alkyl, aryl or alkylaryl group), and m is 1 to 4 provided that m + n≤4; And n represents an integer of 0 to 3, and R ⁷ and R ⁸ each independently represent a C alkyl group. ]

1-4

[17] A 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), The manufacturing method according to claim 16.

[18] At least one aliphatic monocarboxylic acid selected from acetic acid, propionic acid and butyric acid, and / or at least one selected from ZnCl, BF and BF-0 (C H) power, etc.

2 3 3 2 5 2

Of the hydroxymethylated 2H isoindole represented by the above formula (6c) in the presence of a Lewis acid of the above, followed by the action of an oxidizing agent to obtain a halogen-containing tetrabenzo porphyrin represented by the above formula (7) The manufacturing method according to claim 14, which is manufactured.

[19] The aminomethylated 2H-isoindole represented by the following formula (6d) is formed as a 1-substituent of the above isoindole by amino-methylating the halogen-containing isoindole represented by the above formula (2): Item 13. The production method according to Item 13.

[Chemical 10]

[Wherein, X represents a halogen atom, and Y is

OR ² or SR ³ (wherein, R ² and R ³ each independently represent an alkyl, aryl or alkylaryl group), and m is 1 to 1 provided that m + n1〜4; N represents an integer of 0 to 3; and R ⁵ and R ⁶ each independently represent a C alkyl group. ]

1-4

[20] In the presence of an acid, the halogen-containing isoindole represented by the above formula (2), formaldehyde and dialkylamine are reacted with each other, and then the oxidizing agent is allowed to react with the above formula (7). The production method according to claim 19, wherein the indicated halogen-containing tetrabenzoporphyrin is produced.

[21] A halogen-containing tetrabenzo compound represented by the above formula (7) is reacted by reacting the halogen-containing isoindole represented by the above formula (2) with a methylene chloride dialkyl halide and then causing an oxidizing agent to act. The method according to claim 19, wherein the porphyrin is produced.

[22] Aminomethylenated 1H-isoindole represented by the following formula (6a).

[Formula 11]

[Wherein, X represents a halogen atom, and γ is

And SR or SR ³ (wherein R ² and each independently represent an alkyl, aryl or alkylaryl group), and m is an integer of 1 to 4 provided that m + n≤4 N represents an integer of 0 to 3, and R ⁷ and R ⁸ each independently represent a C alkyl group. ]

1-4

Formylated 2H isoindole represented by the following formula (6b).

[Formula 12]

[Wherein, X represents a halogen atom, and γ is

And SR or SR ³ (wherein R ² and R ³ each independently represent an alkyl, aryl or alkylaryl group), and m is 1 to 4 provided that m + n≤4; And n represents an integer of 0 to 3. ]

[24] Hydroxymethylated 2H isoindonolene represented by the following formula (6c).

[Chem. 13]

[Wherein, X represents a halogen atom, and Y is

OR ² or SR ³ (wherein, R ² and R ³ each independently represent an alkyl, aryl or alkylaryl group), and m is 1 to 1 provided that m + n1〜4; N represents an integer of 4; n represents an integer of 0 to 3; ]

The _pi- conjugated cyclic compound shown by following formula (7).

[Formula 14]

[Wherein, X represents a halogen atom.

The wolf is

[26] The 兀 conjugated cyclic compound according to claim 25, which is a halogen-containing tetrabenzo porphyrin represented by the following formula (7a).

[Formula 15]

[Wherein, X represents a halogen atom, and Y is

[27] A halogen-containing tetrabenzophorphirin complex represented by the following formula (8).

[Chem. 16]

[Wherein, X represents a halogen atom, Υ is

OR ² or SR ³ (wherein, R ² and R ³ each independently represent an alkyl, aryl or alkylaryl group), and m is 1 to 1 provided that m + n1〜4; Represents an integer of 4, n represents an integer of 0 to 3, and M represents a metal or metalloid ion. ]

[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.

[Chemical formula 17]

(9) (10) [Wherein, D represents a halogen atom, R ¹ , OR ² or SR ³ (wherein,

R ² and R ³ each independently represent an alkyl, aryl or alkylaryl group. And p represents an integer of 0-4. ]

[29] The production 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 nickel catalyst, a rhodium catalyst, a platinum catalyst and a nickel catalyst is used as a catalyst for catalytic hydrogenation.