JP5057632B2 - Method for producing porphyrin compound - Google Patents

Description

The present invention relates to a method for efficiently producing a porphyrin compound.

  Porphyrin compounds exhibit semiconductor properties such as electrical conduction and photovoltaic power in the crystalline state, and therefore can be applied to electrical and optical functional elements such as transistors, light-emitting diodes and solar cells, and are particularly suitable for organic transistors. be able to.

  Various studies have been made on the method for producing a porphyrin compound, for example, a method for synthesizing porphyrinogen with pyrrole and aldehyde and oxidizing it to convert it into porphyrin, or tetramerization of 2-hydroxymethylpyrrole. A production method is known that cyclizes to porphyrinogen and oxidizes it to convert it to porphyrin.

  Among these, as the latter method, Non-Patent Documents 1 and 2 include 2-hydroxymethyl produced by reducing a pyrrole-2-carboxylic acid ethyl ester derivative with lithium aluminum hydride when synthesizing a tetrabicycloporphyrin compound. -A method of cyclizing a pyrrole derivative by acid treatment and oxidizing it to synthesize tetrabicyclobenzoporphyrin has been reported.

However, when the inventors tried to synthesize 0.5 g or more of a compound by scaling up by the method described herein, it was found that the yield was greatly reduced.
J. et al. Chem. Soc. Perkin Trans. 1, 3161 (1997) Heterocycles 52, 399 (2000)

  As described above, when a large amount of a porphyrin compound is synthesized by tetramerization of 2-hydroxymethylpyrroles, a high yield synthesis method has been demanded.

  In view of the above, as a result of various investigations, the yield of the porphyrin compound to be produced is dramatically improved by allowing oxygen to sufficiently act in the reaction system in the acid treatment of 2-hydroxymethylpyrroles. The present invention was found.

（式中、Ｒ ¹ 〜Ｒ ⁸ はそれぞれ独立して下記の有機基群から選ばれる１価の有機基を示し、互いに結合して環状構造を形成してもよい。）
有機基群： 水素原子；フッ素原子、塩素原子、臭素原子等のハロゲン原子；ニトロ基；ニトロソ基；シアノ基；イソシアノ基；シアナト基；イソシアナト基；チオシアナト基；イソチオシアナト基；メルカプト基；ヒドロキシ基；ホルミル基；スルホン酸基；カルボキシル基；置換されていても良いアルキル基；置換されていても良いシクロアルキル基；置換されていても良いアルケニル基；置換されていても良いシクロアルケニル基；置換されていても良いアリール基；置換されていても良い複素環基；置換されていても良いアルコキシ基；置換されていても良いアルケニルオキシ基；置換されていても良いアリールオキシ基；置換されていても良いアルキルチオ基；−ＣＯＱ ³ で表されるアシル基；−ＯＣＯＱ ³ で表されるアシルオキシ基；−ＮＱ ⁴ Ｑ ⁵ で表されるアミノ基；−ＣＯＯＱ ³ で表されるカルボン酸エステル基；−ＣＯＮＱ ⁶ Ｑ ⁷ で表されるカルバモイル基；−ＳＯＱ ³ で表されるスルフィニル基；−ＳＯ ₂ Ｑ ³ で表されるスルホニル基；−ＳＯ ₃ Ｑ ³ スルホン酸エステル基；−ＳＯ ₂ ＮＱ ⁶ Ｑ ⁷ で表されるスルファモイル基 That is, the gist of the present invention is to generate porphyrinogens by acid treatment of 2-hydroxymethylpyrroles represented by the following general formula (1), and further oxidize the porphyrinogens to obtain a porphyrin compound. In the method for producing a porphyrin compound for synthesizing the compound, a method for producing a porphyrin compound is characterized in that oxygen is sufficiently allowed to act in the reaction system in the acid treatment of 2-hydroxymethylpyrroles.

(Wherein R ^{1 to} R ⁸ each independently represents a monovalent organic group selected from the following organic group group, and may be bonded to each other to form a cyclic structure.)
Organic group: hydrogen atom; halogen atom such as fluorine atom, chlorine atom, bromine atom; nitro group; nitroso group; cyano group; isocyano group; cyanato group; isocyanato group; thiocyanato group; isothiocyanato group; mercapto group; Formyl group; sulfonic acid group; carboxyl group; optionally substituted alkyl group; optionally substituted cycloalkyl group; optionally substituted alkenyl group; optionally substituted cycloalkenyl group; Aryl group which may be substituted; heterocyclic group which may be substituted; alkoxy group which may be substituted; alkenyloxy group which may be substituted; aryloxy group which may be substituted; acyloxy represented by -OCOQ ^3; acyl group represented by -COQ ^3; which may alkylthio ; Sulfinyl group represented by -SOQ ^3;; carboxylic acid represented by -COOQ ³ ester group;; -NQ ⁴ Q ⁵ group represented by -CONQ ⁶ carbamoyl group represented by Q ⁷ -SO ₂ A sulfonyl group represented by Q ³ ; a —SO ₃ Q ³ sulfonate group; a sulfamoyl group represented by —SO ₂ NQ ⁶ Q ⁷

  A method for efficiently synthesizing a porphyrin compound in large quantities by tetramerization of 2-hydroxymethylpyrroles is provided.

Hereinafter, embodiments of the present invention will be described in detail.
In the production of a porphyrin compound by acid treatment of 2-hydroxymethylpyrroles and then oxidation of porphyrinogens as represented by the following reaction formula, the present invention reacts with acid treatment of 2-hydroxymethylpyrroles. It is characterized by allowing oxygen to sufficiently act in the system.

In the formula, Q ¹ and Q ² each independently represent a monovalent organic group, and Q ¹ and Q ² may be bonded to each other to form a ring structure.

The monovalent organic group of Q ¹ and Q ² is not particularly limited as long as it is a group that does not adversely influence the reaction, and specifically, a hydrogen atom; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom; Nitro group; nitroso group; cyano group; isocyano group; cyanato group; isocyanato group; thiocyanato group; isothiocyanato group; mercapto group; hydroxy group; formyl group; sulfonic acid group; carboxyl group; Cycloalkyl group which may be substituted; alkenyl group which may be substituted; cycloalkenyl group which may be substituted; aryl group which may be substituted; heterocyclic group which may be substituted; An optionally substituted alkoxy group; an optionally substituted alkenyloxy group; an optionally substituted aryloxy group; a substituted Amino group represented by -NQ ⁴ Q ^5;; acyloxy group represented by -OCOQ ^3; acyl group represented by -COQ ^3; alkylthio group can have -COO
A carboxylic acid ester group represented by Q ³ ; a carbamoyl group represented by —CONQ ⁶ Q ⁷ ;
A sulfinyl group represented by OQ ³ ; a sulfonyl group represented by —SO ₂ Q ³ ; a —SO ₃ Q ³ sulfonate group; and a sulfamoyl group represented by —SO ₂ NQ ⁶ Q ⁷ . Among these, an optionally substituted alkyl group; an optionally substituted cycloalkyl group; an optionally substituted alkenyl group; an optionally substituted cycloalkenyl group; an optionally substituted aryl group; An optionally substituted heterocyclic group; an optionally substituted alkoxy group; an optionally substituted alkenyloxy group; an optionally substituted aryloxy group; an optionally substituted alkylthio group; represented by -CONQ ⁶ Q ^7; carboxylic acid ester group represented by -COOQ ^3; amino group represented by -NQ ⁴ Q ^5; acyloxy group represented by -OCOQ ^3; acyl group represented by ³ A carbamoyl group represented by —SOQ ³ ; a sulfonyl group represented by —SO ₂ Q ³ ; a —SO ₃ Q ³ sulfonate group; a —SO ₂ NQ ⁶ Q ^The sulfamoyl group represented by ⁷ has 18 or less carbon atoms, preferably 1
2 or less are mentioned.

  Examples of the alkyl group include linear or branched alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, and n-heptyl group. .

  Examples of the cycloalkyl group include cyclic alkyl groups such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and an adamantyl group.

  Examples of the alkenyl group include linear or branched alkenyl groups such as a vinyl group, a propenyl group, and a hexenyl group.

  Examples of the cycloalkenyl group include cyclic alkenyl groups such as a cyclopentenyl group and a cyclohexenyl group.

  Examples of the aryl group include a phenyl group and a naphthyl group.

  Examples of the heterocyclic group include heterocyclic groups having 1 to 3 hetero atoms such as 2-thienyl group, 2-pyridyl group, 4-piperidyl group, and morpholino group.

  Examples of the alkoxy group include linear or branched alkoxy groups such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, and a tert-butoxy group.

  Examples of the alkenyloxy group include linear or branched alkenyloxy groups such as a propenyloxy group, a butenyloxy group, and a pentenyloxy group.

  Examples of the aryloxy group include a phenoxy group and a naphthyloxy group.

  Examples of the alkylthio group include linear or branched alkylthio groups such as a methylthio group, an ethylthio group, an n-propylthio group, an n-butylthio group, a sec-butylthio group, and a tert-butylthio group.

Examples of Q ³ in the acyl group, acyloxy group, carboxylic acid ester group, sulfinyl group, sulfonyl group, and sulfonic acid ester group include an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group. .

The Q ⁴ and Q ⁵ in the amino group, each independently, a hydrogen atom, a hydroxyl group, a hydrocarbon group, a heterocyclic group, an acyl group represented by -COQ ^3, carboxylic acid ester represented by -COOQ ³ And a sulfonyl group represented by —SO ₂ Q ³ .

Examples of Q ⁶ and Q ⁷ in the carbamoyl group or sulfamoyl group independently include a hydrogen atom, a hydrocarbon group, or a heterocyclic group.

The alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group, heterocyclic group, alkoxy group, alkenyloxy group, aryloxy group, alkylthio group and hydrocarbon group are optional as long as they do not adversely affect the reaction. Specific examples thereof include groups described as specific examples of Q ¹ and Q ² described above.

In addition, Q ¹ and Q ² may be integrated with each other to form a propylene group, a butylene group, or the like, each of which may or may be an aliphatic hydrocarbon group that forms a condensed ring with a pyrrole ring. The condensed ring may be an aromatic carbocyclic ring such as a benzene ring or a naphthalene ring, and further may be substituted with a heteroatom to form a heterocyclic group such as a pyrrole ring or a pyridine ring. An aliphatic carbocycle.

As Q ¹ and Q ² , Q ¹ and Q ² are preferably combined to form the following general formula:

It is preferable that the group represented by these is formed. In the formula, R ^{1 to} R ⁸ are each independently a monovalent organic group similar to Q ¹ and Q ^2, and are bonded to each other to form a cyclic structure as described for Q ¹ and Q ^2. You may do it. When forming a cyclic structure, it is preferable that R ^{1 to} R ⁸ bonded to adjacent carbons preferably form a set to form a cyclic structure. R ^{1 to} R ⁸ are preferably a hydrogen atom.
(Method for producing porphyrinogens)
In the present invention, porphyrinogens are produced by acid treatment of 2-hydroxymethylpyrroles.

  The 2-hydroxymethylpyrroles are not particularly limited as long as they are synthesized according to a known method. For example, it can be produced by reducing pyrrole-2-carboxylic acid esters with a reducing agent such as lithium aluminum hydride.

  The present invention is characterized in that oxygen treatment is sufficiently performed in the reaction system to perform acid treatment of 2-hydroxymethylpyrroles.

Although there is no particular limitation on causing oxygen to sufficiently act in the reaction system, for example, bubbling oxygen or a gas containing oxygen in the reaction system; increasing the surface area of the reaction system and increasing the contact area with oxygen ( Use a reaction vessel in which the value obtained by dividing the cross-sectional area with respect to volume V of the reaction liquid by volume V is 0.5 cm ⁻¹ or more, etc.); Or increase the amount of oxygen taken from the surface by increasing the pressure of the reaction system; substances and oxygen that generate oxygen gas in the reaction system Examples thereof include a method in which a substance that adsorbs gas coexists in the system. Of these, a method of bubbling oxygen or a gas containing oxygen in the reaction system; stirring the reaction system vigorously or stirring; or increasing the pressure of the reaction system, more preferably oxygen or A gas containing oxygen is bubbled; or the reaction system is vigorously stirred or stirred.

  The method for bubbling oxygen or a gas containing oxygen into the reaction system is not particularly limited. For example, an inert tube such as glass is put into the reaction system, and bubbling is performed by blowing oxygen or a gas containing oxygen from there. Can be mentioned. There may be a plurality of air inlets. Further, fine bubbles may be used for bubbling. Although depending on the size of the reaction system, the flow rate of oxygen is preferably 5 mL / min or more, more preferably 50 mL / min or more, and particularly preferably 100 mL / min or more with respect to 1 L of the reaction system. Moreover, 10 L / min or less is preferable, More preferably, it is 5 L / min or less, Most preferably, it is 1 L / min or less.

When stirring the reaction system, the reaction vessel has a baffle plate or a stirring blade that can efficiently stir (anchor blade, inclined paddle blade, flat paddle blade, fiddler blade, Max blend blade (Sumitomo Heavy Industries, Ltd.) Company), Full Zone Wing (Shineko Pantech Co., Ltd.) Helical Ribbon Wing, Bull Margin Wing, Supermix Wing (manufactured by Satake Chemical Machinery), A310 Wing (made by LIGHTTNIN), A320 Wing (made by LIGHTTNIN), Intermig Wing (ecart) Etc.) can be used.

  When the reaction system is set to a high pressure, it is preferably 1.1 atm or higher, more preferably oxygen or a gas containing oxygen such as air pressurized to 2 atm or higher.

In the present invention, when oxygen is sufficiently allowed to act in the reaction system and the acid treatment of 2-hydroxymethylpyrroles is performed, oxygen may be allowed to act on the reaction system before the acid treatment or during the acid treatment. Alternatively, oxygen may be allowed to act on the reaction system. Preferably, in the method of reacting the oxygen acid treatment line cormorants reaction system, more preferably, by the action of oxygen prior to the reaction system to carry out the acid treatment, the oxygen further subsequently in the reaction system even during acid treatment It is a method of acting.

  In addition, as a method of acid treatment, oxygen may sufficiently act on a solution containing acid, and then 2-hydroxymethylpyrroles may be added; oxygen may sufficiently act on a solution containing 2-hydroxymethylpyrroles. Then, an acid may be added; after oxygen has sufficiently acted on the solvent, 2-hydroxymethylpyrroles and an acid may be added. Among these, the method in which oxygen sufficiently acts on a solution containing an acid and then adding 2-hydroxymethylpyrroles is preferable.

  The time for which oxygen is allowed to act is optimal if the raw materials 2-hydroxymethylpyrroles and porphyrinogens are monitored by chromatography, etc., and it is confirmed that the raw materials are sufficiently lost and porphyrinogen is produced. However, it is generally 1 minute or longer and within 3 days, preferably 5 minutes or longer and within 2 days, more preferably 10 minutes or longer and within 1 day.

  The acid used for the acid treatment of 2-hydroxymethylpyrroles may be appropriately selected from those that do not adversely affect the reaction. Specific examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, halogenated hydrogen; acetic acid Aliphatic or aromatic carboxylic acids such as oxalic acid, trifluoroacetic acid, benzoic acid and phthalic acid; aliphatic or aromatic sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid and p-toluenesulfonic acid . Of these, aromatic sulfonic acids are preferable, and p-toluenesulfonic acid is particularly preferable.

  The amount of acid used is desirably adjusted to an amount that allows the reaction to proceed smoothly, but generally 0.1 mol or more, and preferably 0.2 mol or more is used with respect to 1 mol of hydroxymethylpyrroles. When the amount is less than 0.1 mol, the amount of porphyrinogen produced is reduced.

  In addition, the reaction temperature for the acid treatment is usually preferably -20 ° C or higher and 80 ° C or lower. When the temperature is lower than 20 ° C., the reaction does not proceed and the amount of bicycloporphyrinogens is reduced. When the temperature is higher than 60 ° C., a side reaction occurs, and as a result, the amount of bicycloporphyrinogens is reduced.

  In the acid treatment step of 2-hydroxymethylpyrroles, it is desirable to set the reaction time by monitoring the reaction progress and confirming that 2-hydroxymethylpyrroles disappear and porphyrinogens are produced. . The reaction is usually performed for 30 minutes or longer, preferably 1 hour or longer. If the reaction is too slow, the side reaction proceeds and the yield decreases, so it is desirable to set the reaction conditions such as the amount of acid added and the temperature so that the reaction is completed within 12 hours.

The reaction solvent dissolves 2-hydroxymethylpyrroles and may be appropriately selected from those that do not adversely affect the acid treatment. Specific examples thereof include chloroform, methylene chloride, dichloroethane, trichloroethane, and trichloroethylene. Halogenated hydrocarbons; aromatic hydrocarbons such as toluene, benzene, xylene and chlorobenzene; ketones such as acetone, methyl ethyl ketone, cyclopentanone and cyclohexanone; esters such as ethyl acetate, butyl acetate and methyl lactate; pyridine And nitrogen-containing organic solvents such as quinoline; ethers such as ethyl ether, tetrahydrofuran and dioxane; and solvents of amides such as dimethylformamide and dimethylacetamide.

Preferred are halogenated hydrocarbons, aromatic hydrocarbons, ketones, ethers and amides, and more preferred are halogenated hydrocarbons, aromatic hydrocarbons, ethers and amides.
(Method for producing porphyrin compound)
In the present invention, porphyrinogens obtained by the aforementioned method are oxidized to obtain a porphyrin compound. The oxidation step may be performed according to a known method. For example, in the acid treatment step described above, when the raw material 2-hydroxymethylpyrroles disappear and porphyrinogens are sufficiently formed, an oxidizing agent is added to convert the porphyrinogens into a porphyrin compound.

  Examples of the oxidizing agent include organic oxidizing agents such as chloranil, dichlorodicyanobenzoquinone, N-2,4,6-trinitrophenyl-N ′, N′-phenyldihydrazine, inorganic oxidizing agents such as manganese dioxide and selenium dioxide, Can also be used to blow an oxidizing gas such as oxygen. Of these, chloranil and dichlorodicyanobenzoquinone are preferable.

  The amount of the oxidizing agent is desirably adjusted by monitoring the progress of the reaction with LC or the like, but 0.3 to 3 times equivalent of 2-hydroxymethylpyrrole used as a raw material is used. Preferably it is 0.3 times equivalent-1 time equivalent.

  The oxidation reaction is usually carried out at room temperature, but it is also possible to carry out the reaction at a high or low temperature in order to control the side reaction rate. The desired reaction temperature is -20 ° C to 80 ° C. When the temperature is lower than 20 ° C., the reaction does not proceed and the amount of the porphyrin compound generated is reduced. When the temperature is higher than 80 ° C., a side reaction occurs, and as a result, the amount of the porphyrin compound generated decreases.

  The reaction time required for the oxidation may be determined while monitoring the progress of the reaction, but is usually 30 minutes or longer. If the oxidation reaction is carried out for too long, the yield may decrease due to side reactions. Therefore, it is desirable to adjust the amount of the oxidizing agent and the reaction temperature so that the reaction is completed within 12 hours.

  The obtained porphyrin compound can be purified as necessary. As a specific purification method, the target product is taken out by concentrating the reaction solvent or adding a poor solvent. In order to further increase the purity, it can be purified to a desired purity using chromatography, recrystallization, reprecipitation or the like.

In the method for producing a porphyrin compound in the present invention, 0.5 g or more, preferably 0.8 g or more, more preferably 1 g or more of a porphyrin compound can be produced efficiently. The yield from 2-hydroxymethylpyrroles to the porphyrin compound is 20% or more, more preferably 30% or more.
(Application of porphyrin compounds)
Since the porphyrin compound obtained above exhibits semiconductor properties such as electrical conduction and photovoltaic power in the crystalline state, it can be applied to electrical and optical functional elements such as transistors, light emitting diodes, solar cells, etc. It can be used suitably.

  Specific examples of preferred porphyrin compounds used for the above-mentioned applications include those shown by the following formula. That is, at the time of coating, the structure with poor planarity exists in the porphyrin compound, so that it has high solubility and film forming property, while it is converted into a structure with high planarity by heating after film formation. The film has semiconductor characteristics.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
(Example)
Under a nitrogen atmosphere, lithium aluminum hydride (4.92 g, 127 mmol) was suspended in tetrahydrofuran (THF, 172 ml). After cooling to 0 ° C., a solution of ethyl 4,7-dihydro-4,7-ethano-2H-isoindole-1-carboxylate (6.93 g, 31.9 mmol) in THF (172 ml) was added dropwise. Thereafter, the temperature was raised to 10 ° C., and the whole was stirred for about 3 hours. It was confirmed by HPLC that 4,7-dihydro-4,7-ethano-2H-isoindole was produced, and the reaction solution was added to a saturated aqueous ammonium chloride solution to stop the reaction. Thereafter, extraction was performed with chloroform (manufactured by Wako Pure Chemical Industries, Ltd., using amylene as a stabilizer), and the extracted chloroform solution was concentrated. Separately, a chloroform suspension (700 ml) of p-toluenesulfonic acid (739 mg, 4.28 mmol) (manufactured by Wako Pure Chemical Industries, Ltd., using amylene as a stabilizer) was prepared, and compressed air was added while stirring. Bubbling was performed at 500 mL / min for about 10 minutes. The oxygen flow rate was 100 mL / min. To this acidic solution, the previously concentrated solution was added dropwise at room temperature while continuing stirring and bubbling. It was confirmed by HPLC that cyclic tetramerization of 4,7-dihydro-4,7-ethano-2H-isoindole proceeded and bicycloporphyrinogen was produced. 50 ml was reserved for another experiment. After stirring for about 3 hours from the start of dropping, the mixture was left overnight. Chloranil (775 mg, 3.15 mmol) was added at room temperature, and as confirmed by HPLC, porphyrinogen remained. Further, chloranil (237 mg, 0.96 mmol) was added at room temperature. Furthermore, when the progress of the reaction was confirmed by HPLC, porphyrinogen had completely disappeared, so the reaction was stopped by pouring into water, and the organic layer was separated. The extract was washed with an aqueous sodium hydrogen carbonate solution (twice) and dried over anhydrous sodium sulfate. Concentration under reduced pressure, purification by silica gel column chromatography using chloroform as a developing solvent, and further purification by reprecipitation using a chloroform-methanol mixed solvent gave the desired bicycloporphyrin derivative (1.14 g). By repeating the same purification from the fraction containing impurities, a total of 1.75 g of bicycloporphyrin derivative was obtained. The yield was 35%. When converted in consideration of the amount removed for another reaction, the yield was 38%.
(Comparative example)
Under a nitrogen atmosphere, lithium aluminum hydride (2.58 g, 68.0 mmol) was suspended in tetrahydrofuran (THF, 92 ml). After cooling to 0 ° C., a solution of ethyl 4,7-dihydro-4,7-ethano-2H-isoindole-1-carboxylate (4.00 g, 18.4 mmol) in THF (184 ml) was added dropwise. Thereafter, the temperature was raised to 10 ° C., and the whole was stirred for about 3 hours. Ethyl acetate (appropriate amount) was added to stop the reaction, and the reaction solution was added to a saturated aqueous ammonium chloride solution. Extraction was performed with chloroform (3 times each of 750 ml), and the extracted chloroform solution was divided into 5 parts, and further chloroform was added to make 1000 ml each. To this, 1.58 g (9.2 mmol) of paratoluenesulfonic acid was added. After stirring for 24 hours, chloranil (0.47 g, 1.9 mmol) was added to each at room temperature, and the mixture was further stirred for 24 hours. The reaction was stopped by pouring into water, and the organic layer was separated. It was washed with an aqueous sodium hydrogen carbonate solution and dried over anhydrous sodium sulfate. The solution was concentrated under reduced pressure and purified by silica gel column chromatography using chloroform as a developing solvent, but only 19 mg of a bicycloporphyrin compound was obtained. The yield was 0.7%.

Claims (8)

Porphyrin compound production method for synthesizing a porphyrin compound by generating porphyrinogens by acid treatment of 2-hydroxymethylpyrroles represented by the following general formula (1), and further oxidizing the porphyrinogens In claim 2, a method for producing a porphyrin compound, wherein oxygen is sufficiently allowed to act in the reaction system for acid treatment of 2-hydroxymethylpyrroles.

(Wherein R ^{1 to} R ⁸ each independently represents a monovalent organic group selected from the following organic group group, and may be bonded to each other to form a cyclic structure.)
Organic group: hydrogen atom; halogen atom such as fluorine atom, chlorine atom, bromine atom; nitro group; nitroso group; cyano group; isocyano group; cyanato group; isocyanato group; thiocyanato group; isothiocyanato group; mercapto group; Formyl group; sulfonic acid group; carboxyl group; optionally substituted alkyl group; optionally substituted cycloalkyl group; optionally substituted alkenyl group; optionally substituted cycloalkenyl group; Aryl group which may be substituted; heterocyclic group which may be substituted; alkoxy group which may be substituted; alkenyloxy group which may be substituted; aryloxy group which may be substituted; acyloxy represented by -OCOQ ^3; acyl group represented by -COQ ^3; which may alkylthio ; Sulfinyl group represented by -SOQ ^3;; carboxylic acid represented by -COOQ ³ ester group;; -NQ ⁴ Q ⁵ group represented by -CONQ ⁶ carbamoyl group represented by Q ⁷ -SO ₂ A sulfonyl group represented by Q ³ ; a —SO ₃ Q ³ sulfonate group; a sulfamoyl group represented by —SO ₂ NQ ⁶ Q ⁷ It is characterized by bubbling oxygen-containing gas in the reaction system for acid treatment.
The manufacturing method of the porphyrin compound of Claim 1. The method for producing a porphyrin compound according to claim 1 or 2, wherein the reaction system is stirred for the acid treatment. In performing an acid treatment, the oxygen flow rate supplied in a reaction system shall be 5 mL / more or less and 10 L / min or less with respect to 1 L of reaction systems, It is any one of Claims 1-3 characterized by the above-mentioned. A method for producing a porphyrin compound. In the acid treatment, the acid used is inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, halogenated hydrogen; aliphatic or aromatic carboxylic acid such as acetic acid, oxalic acid, trifluoroacetic acid, benzoic acid, phthalic acid; methanesulfone The porphyrin compound according to any one of claims 1 to 4, comprising at least one of aliphatic or aromatic sulfonic acids such as acid, trifluoromethanesulfonic acid, and p-toluenesulfonic acid. Production method. 6. The production of a porphyrin compound according to any one of claims 1 to 5, wherein the amount of acid used for the acid treatment is 0.1 mol or more per mol of hydroxymethylpyrroles. Method. The method for producing a porphyrin compound according to any one of claims 1 to 6, wherein the reaction temperature is -20 ° C or higher and 80 ° C or lower in performing the acid treatment. The method for producing a porphyrin compound according to any one of claims 1 to 7, wherein the reaction time is 30 minutes or more and 12 hours or less in the acid treatment.