JP2007112748A - Chlorine-substituted porphyrin compound and method for producing chlorine-substituted porphyrin compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new chlorine-substituted porphyrin compound usable as dyes, semiconductors or intermediates therefor. <P>SOLUTION: The chlorine-substituted porphyrin compound has a structure represented by general formula (I). The method for producing the chlorine-substituted porphyrin compound comprises at least a step of chlorinating the meso-positions of a porphyrin compound using N-chlorosuccinimide. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention can efficiently chlorinate meso-positions of novel chlorine-substituted porphyrin compounds and porphyrin compounds that can be used as dyes, semiconductors, or intermediates for synthesizing them, and is also safer The present invention relates to a method for producing an excellent chlorine-substituted porphyrin compound.

  A compound having a porphyrin skeleton (hereinafter, collectively referred to as “porphyrin compound” as appropriate) is a pigment that is contained in hemoglobin, enzyme, chlorophyll, and the like and exhibits various functions in vivo. A strong absorber is shown in the near-ultraviolet to visible light and near-infrared regions, and studies have been made on photocatalysts, photoradical generation, photovoltaic power, photocurrent, phototherapy, etc. using excited states generated by light absorption. Large π-electron conjugated systems are also known to exhibit semiconductor properties in the solid state, and their application to transistors has also been demonstrated.

  However, most of the conventionally known porphyrin compounds have a benzene ring at their meso position and have a limited molecular structure. Since a compound having such a structure cannot have a planar structure, it was not expected to be used for a semiconductor that requires particularly good planarity.

  Accordingly, a porphyrin compound having a novel structure is demanded. Among them, a chlorine-substituted porphyrin compound obtained by chlorinating a part of the porphyrin compound is expected to be used as a dye or a semiconductor, By further substituting the atom with another group (for example, fluorine atom or bromine atom), the use as an intermediate for synthesizing another porphyrin compound useful as a dye or semiconductor is expected.

  Conventionally, as a method of chlorinating the meso-position of a porphyrin compound, a method of allowing hydrogen peroxide-hydrochloric acid to act is known (see, for example, Patent Document 1). Hydrogen peroxide oxidizes —C═C—. However, it was not a widely available method.

Bonnett, R .; Gale, I. A. D., Stephenson, G. F. J. Chem. Soc. C, 1966, pp. 1600-1604

  From the above background, a method capable of efficiently chlorinating a specific part of a porphyrin compound and having excellent safety, and a chlorine-substituted porphyrin compound having a novel structure obtained thereby have been demanded. .

  The present invention has been made in view of the above-described background, and the object thereof is to provide a novel chlorine-substituted porphyrin compound that can be used as a dye, a semiconductor, or an intermediate in the synthesis thereof, And it is providing the manufacturing method of the chlorine substituted porphyrin compound which can chlorinate the meso position of a porphyrin compound efficiently and was excellent in safety | security.

  As a result of intensive studies, the present inventors have found that by using N-chlorosuccinimide, the meso position of the porphyrin compound can be efficiently and safely chlorinated. Moreover, it was found that by using this technique, a chlorine-substituted porphyrin compound having a novel structure can be obtained, and the above problems can be effectively solved, and the present invention has been completed.

（上記一般式（Ｉ）において、Ｑ¹〜Ｑ⁴は各々独立に、水素原子又は塩素原子を表わすが、Ｑ¹〜Ｑ⁴のうち少なくとも一つは塩素原子であり、Ｒ¹〜Ｒ⁸は各々独立に、水素原子又は任意の置換基を表わすが、Ｒ¹とＲ²、Ｒ³とＲ⁴、Ｒ⁵とＲ⁶、及び、Ｒ⁷とＲ⁸の組み合せのうちの少なくとも１組は互いに結合して、置換基を有していてもよい環を形成しており、Ｍは、金属原子又は２個の水素原子を表わす。） That is, the gist of the present invention resides in a chlorine-substituted porphyrin compound represented by the following general formula (I) (claim 1).

(In the general formula (I), Q ^{1 to} Q ⁴ each independently represents a hydrogen atom or a chlorine atom, but at least one of Q ^{1 to} Q ⁴ is a chlorine atom, and R ^{1 to} R ⁸ are Each independently represents a hydrogen atom or an optional substituent, and at least one of the combinations of R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , and R ⁷ and R ⁸ is And bonded to form an optionally substituted ring, and M represents a metal atom or two hydrogen atoms.)

  Another gist of the present invention resides in a method for producing a chlorine-substituted porphyrin compound, characterized by having at least a step of chlorinating the meso position of the porphyrin compound using N-chlorosuccinimide (claim). 2).

  Here, the chlorine-substituted porphyrin compound obtained by chlorination is preferably a chlorine-substituted porphyrin compound represented by the above general formula (I) (Claim 3).

The chlorine-substituted porphyrin compound of the present invention has a novel structure and is expected to be used as a dye, a semiconductor, or an intermediate for synthesizing them.
Further, according to the method for producing a chlorine-substituted porphyrin compound of the present invention, various porphyrin compounds in which the meso position is chlorinated, including the chlorine-substituted porphyrin of the present invention, can be efficiently produced, and safety is ensured. Also excellent.

  Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following description, and various modifications can be made within the scope of the gist of the present invention.

[I. Chlorine-substituted porphyrin compound]
[I-1. Structure of chlorine-substituted porphyrin compound]
The chlorine-substituted porphyrin compound of the present invention is characterized by having a structure represented by the following general formula (I).

In the general formula (I), Q ^{1 to} Q ⁴ each independently represents a hydrogen atom or a chlorine atom. However, at least one of Q ^{1 to} Q ⁴ is a chlorine atom. The number of chlorine atoms is arbitrary as long as it is 1 or more. Even if only one of Q ^{1 to} Q ⁴ is a chlorine atom, two or three are chlorine atoms, all four are It may be a chlorine atom. Further, when two of Q ^{1 to} Q ⁴ are chlorine atoms, there may be two kinds of combinations of positions, 5,10-dichloro form and 5,15-dichloro form, either of which may be used. .

In general formula (I), M represents a metal atom or two hydrogen atoms. The metal atom is a divalent metal such as Zn, Cu, Fe, Ni, or Co, or a trivalent or more such as Fe—X, Al—X, Ti═O, Si (X ¹ ) (X ² ), or the like. And an atomic group in which other metal is bonded to each other (in the above formula, X, X ¹ and X ² represent a monovalent group such as a halogen atom, an alkyl group or an alkoxy group). . Of these, divalent metals such as Cu and Zn are preferable.

In general formula (I), R < ¹ > -R < ⁸ > represents a hydrogen atom or arbitrary substituents each independently. However, at least one of the combinations of R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , and R ⁷ and R ⁸ is bonded to each other to form a ring (hereinafter referred to as “nuclear condensation”). May be referred to as a “ring”. Among them, it is preferable that two pairs at opposite positions form a nuclear condensed ring, and it is particularly preferable that all four sets form a nuclear condensed ring.

  Among porphyrin compounds having a nuclear condensed ring structure, those having a planar structure in which the ring is π-conjugated exhibit a strong absorption band in the visible light region, and thus exhibit excellent properties as a pigment or dye. Moreover, since the porphyrin compound of the ring structure which is not conjugated has high solubility, it can be utilized as a solution dissolved in an appropriate solvent or as a solid dissolved in a polymer. Moreover, the porphyrin compound which has a bicyclo structure can be used as a precursor at the time of manufacturing the porphyrin compound which the ring has conjugated.

  The structure of the nuclear condensed ring is not particularly limited, and may be a saturated ring or an unsaturated ring, may be a hydrocarbon ring or a heterocyclic ring, and more than one ring may be condensed. However, it is preferably a 5- to 6-membered monocycle and a 2-3 condensed ring thereof. If this nucleus condensed ring is too large, the basic skeleton is unexpectedly affected. Therefore, the number of carbon atoms in the nucleus condensed ring is usually preferably 20 or less.

  When the nuclear condensed ring is an aromatic ring such as benzene, naphthalene, anthracene, pyridine, quinoline, etc., the whole compound has planarity, which is preferable because the π-conjugated system is easily spread and suitable for semiconductor materials. Further, it is a bicyclo ring such as bicyclo [2,2,2] octa-2,5-diene or bicyclo [2,2,2] hepta-2,5-diene, or a saturated hydrocarbon ring such as cyclohexene. In this case, the solubility in various solvents and polymers is increased, which is preferable. In particular, it is preferable because it is suitable for uses such as a precursor for forming an organic semiconductor film by a coating process as described later, phototherapy, an additive to a polymer material, and the like. These nuclear condensed rings may further have a substituent described later.

R ^{1 to} R ⁸ other than those forming a nuclear condensed ring each independently represent a hydrogen atom or an arbitrary substituent. When R ^{1 to} R ⁸ are substituents, if the molecular weight is too large, the basic skeleton is unexpectedly affected. Therefore, the molecular weight is usually 1000 or less, preferably 500 or less, and more preferably 200 or less. The lower limit of the molecular weight of the substituent is not particularly limited and is 1 or more.

When R ^{1 to} R ⁸ are substituents, examples thereof include the following.
An optionally substituted straight chain having 1 to 18 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and an n-heptyl group; A branched alkyl group; an optionally substituted cyclic alkyl group having 3 to 18 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and an adamantyl group; a substituted group such as a vinyl group, a propenyl group, and a hexenyl group An optionally substituted linear or branched alkenyl group having 2 to 18 carbon atoms; an optionally substituted cyclic alkenyl group having 3 to 18 carbon atoms such as a cyclopentenyl group and a cyclohexenyl group; a propynyl group and a hexynyl group; An optionally substituted linear or branched alkynyl group having 2 to 18 carbon atoms; 2-thienyl group, 2-pyridyl group, 4-piperidyl group, morpholy An optionally substituted heterocyclic group, such as a phenyl group, a tolyl group, a xylyl group, a mesityl group, etc., an optionally substituted aryl group having 6 to 18 carbon atoms; a benzyl group, a phenethyl group, etc. Optionally substituted aralkyl groups having 7 to 20 carbon atoms; substituted with methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, etc. C1-C18 linear or branched alkoxy group which may be substituted; C3-C18 linear or branched alkenyloxy which may be substituted, such as propenyloxy group, butenyloxy group, pentenyloxy group, etc. Groups; methylthio groups, ethylthio groups, n-propylthio groups, n-butylthio groups, sec-butylthio groups, tert-butylthio groups, etc. It includes good linear or branched alkylthio group having 1 to 18 carbon atoms.

Other specific examples include halogen atoms such as fluorine atom, chlorine atom, bromine atom; nitro group; nitroso group; cyano group; isocyano group; cyanato group; isocyanato group; thiocyanato group; isothiocyanato group; hydroxyamino group; a formyl group; a sulfonic group; a carboxyl group; carbamate represented by -NHCOOR ^13; acylamino group represented by -NHCOR ^12; amino group represented by -NR ¹⁰ R ^11; acyl group represented by -COR ⁹ A carboxylate group represented by —COOR ¹⁴ ; an acyloxy group represented by —OCOR ¹⁵ ; a carbamoyl group represented by —CONR ¹⁶ R ¹⁷ ; a sulfonyl group represented by —SO ₂ R ¹⁸ ; —SO ₂ NR ¹⁹ R sulfamoyl group represented by ^20; Sur represented by -SO ₃ R ²¹ Phosphate ester groups; -NHSO ₂ sulfonamide group represented by R ^22; etc. sulfinyl group represented by -SOR ^23, and the like. Here, R ⁹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁸ , R ²¹ , R ²² , R ²³ are each independently a hydrocarbon group that may be substituted, or may be substituted. R ¹⁰ , R ¹¹ , R ¹⁶ , R ¹⁷ , R ¹⁹ , R ²⁰ each independently represents a hydrogen atom, an optionally substituted hydrocarbon group, or an optionally substituted heterocyclic ring Represents any of the groups.

The hydrocarbon group represented by R ^{9 to} R ²³ represents a linear or branched alkyl group, a cyclic alkyl group, a linear or branched alkenyl group, a cyclic alkenyl group, an aralkyl group, an aryl group, or the like. Among them, a linear or branched alkyl group having 1 to 18 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and an n-heptyl group is preferable. A cyclic alkyl group having 3 to 18 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group and an adamantyl group; a linear or branched alkenyl group having 2 to 18 carbon atoms such as a vinyl group, a propenyl group and a hexenyl group; C3-C18 cyclic alkenyl groups such as pentenyl group and cyclohexenyl group; C7-C20 aralkyl groups such as benzyl group and phenethyl group; C6 such as phenyl group, tolyl group, xylyl group and mesityl group -18 aryl groups and the like. The aryl group portion of these groups may be further substituted with the same substituent as R ^{1 to} R ⁸ described above.

The heterocyclic group represented by R ^{9 to} R ²³ may be a saturated heterocyclic ring such as a 4-piperidyl group, a morpholino group, a 2-morpholinyl group, a piperazyl group, a 2-furyl group, a 2-pyridyl group, An aromatic heterocyclic ring such as a 2-thiazolyl group and a 2-quinolyl group may be used. These may contain a plurality of hetero atoms or may further have a substituent, and the bonding position thereof is not particularly limited. Preferred structures for the heterocyclic ring are a 5- or 6-membered saturated heterocyclic ring, a 5- or 6-membered monocyclic ring and an aromatic heterocyclic ring thereof.

R ^{1 to} R ⁸ may have a linear or branched alkyl group, a cyclic alkyl group, a linear or branched alkenyl group, a cyclic alkenyl group, a linear or branched alkynyl group, a linear or branched alkoxy group, The linear or branched alkylthio group and the alkyl chain portion of the alkyl group represented by R ^{9 to} R ²³ may further have a substituent, and examples of the substituent include the following.

  Alkoxy groups having 1 to 10 carbon atoms such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group; methoxymethoxy group, ethoxymethoxy group, propoxymethoxy Groups, ethoxyethoxy groups, propoxyethoxy groups, methoxybutoxy groups, etc., alkoxyalkoxy groups having 2 to 12 carbon atoms; methoxymethoxymethoxy groups, methoxymethoxyethoxy groups, methoxyethoxymethoxy groups, methoxymethoxyethoxy groups, ethoxyethoxymethoxy groups, etc. An alkoxyalkoxyalkoxy group having 3 to 15 carbon atoms; an aryl group having 6 to 12 carbon atoms such as a phenyl group, a tolyl group, and a xylyl group (which may be further substituted with any substituent); a phenoxy group , Tolyloxy group, xylyloxy Group, an aryloxy group having 6 to 12 carbon atoms such as naphthyloxy group; allyloxy group, an alkenyloxy group having 2 to 12 carbon atoms such as vinyloxy groups.

  Further, as other substituents, heterocyclic groups such as 2-thienyl group, 2-pyridyl group, 4-piperidyl group, morpholino group; cyano group; nitro group; hydroxyl group; amino group; N, N-dimethylamino group An alkylamino group having 1 to 10 carbon atoms such as N, N-diethylamino group; an alkylsulfonylamino group having 1 to 6 carbon atoms such as methylsulfonylamino group, ethylsulfonylamino group and n-propylsulfonylamino group; fluorine atom Halogen atoms such as chlorine atom and bromine atom; C2-C7 alkoxycarbonyl groups such as carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl; methyl Carbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyl group An alkylcarbonyloxy group having 2 to 7 carbon atoms such as a cis group, an isopropylcarbonyloxy group, an n-butylcarbonyloxy group; a methoxycarbonyloxy group, an ethoxycarbonyloxy group, an n-propoxycarbonyloxy group, an isopropoxycarbonyloxy group, Examples thereof include an alkoxycarbonyloxy group having 2 to 7 carbon atoms such as an n-butoxycarbonyloxy group.

  Specific examples of the chlorine-substituted porphyrin compound of the present invention include compounds having the following structure. However, the following compounds are merely examples, and the chlorine-substituted porphyrin compound of the present invention is not limited to the following examples.

[I-2. Characteristics and applications of chlorine-substituted porphyrin compounds]
The chlorine-substituted porphyrin compound of the present invention has a novel structure in which it has a nuclear condensed ring structure and its meso position is substituted with at least one chlorine atom. And it is anticipated that it has an optical function, an electrical function, a chemical function, etc. according to the structure. Therefore, various uses such as uses as dyes and semiconductors and intermediates for synthesizing them are expected.

  For example, the chlorine-substituted porphyrin compound of the present invention has an absorption band in the near-infrared to visible to near-ultraviolet light wavelength region, and therefore can be used as a dye. Specifically, the chlorine-substituted porphyrin compound of the present invention exhibits a weaker Q band in the visible light region in addition to the strong Soret band near 400 nm that is characteristic of porphyrin. In particular, when it has a structure in which a π-conjugated system is condensed, such as a benzene ring or a naphthalene ring, the absorption band corresponding to this Q band has a characteristic that it shows strong absorption in the visible to near infrared region. Therefore, if this characteristic as a dye is used, it can be applied to dyes for dyeing, recording such as ink jet and thermal transfer, storage of optical disks, optical filters such as displays, and the like.

  Further, when the chlorine-substituted porphyrin compound of the present invention has a π-conjugated structure with high planarity, it can be used as an organic semiconductor. An organic semiconductor is a material capable of transporting electric charges, and exhibits various functions by controlling the carrier density in the semiconductor by doping impurities or an applied electric field. For example, a rectifier element, a transistor, etc. are mentioned as an example.

  Further, the chlorine-substituted porphyrin compound of the present invention can be used as an optical functional material by utilizing its strong light absorption band. An example is a device that functions by causing charge separation by absorbed light. Specific examples of such an element include a solar cell and a photoelectric conversion element (photodiode). A solar cell uses an internal electric field generated at a junction with a metal or another semiconductor to cause charge separation by light and take it out to the outside. In addition, the chlorine-substituted porphyrin compound of the present invention utilizes a excited state generated by light absorption to sensitize a radical generator or generate a radical directly from the excited state, thereby generating a photo radical generator. Can also be used.

  In addition, the chlorine-substituted porphyrin compound of the present invention is an intermediate for synthesizing various compounds by introducing a useful substituent at the meso position utilizing the high reactivity of the moiety substituted with a chlorine atom. Can be used as Examples of the substituent that can be introduced include a fluorine atom. The fluorination reaction often requires special reagents and equipment, and it is usually difficult to perform fluorination by directly substituting a hydrogen atom, but the chlorine-substituted porphyrin compound of the present invention substituted with a chlorine atom Can be used to easily obtain a fluorinated product using a reaction in which a chlorine atom is replaced with a fluorine atom. As a method for converting a chlorine atom into a fluorine atom, for example, the method described in Comprehensive Organic Transformations, 2nd Edition, R. C. Larock, Weiley, 1999, pp.671-672 can be used. As a specific application, by fluorination of an organic semiconductor, it can be used to control its HOMO (highest occupied molecular orbital) level-LUMO (lowest unoccupied molecular orbital) level, By adjusting and changing the semiconductor characteristics, it is possible to improve the injection characteristics from the electrodes, improve the stability against oxidation, and further manufacture an n-type semiconductor.

  Further, in the case where the chlorine-substituted porphyrin compound of the present invention has a structure having high solubility, a method of use such as conversion to a less soluble dye or semiconductor after forming a film by a coating process can be considered.

[II. Method for producing chlorine-substituted porphyrin compound]
The method for synthesizing the chlorine-substituted porphyrin compound of the present invention is arbitrary, but a preferred example is porphyrin using N-chlorosuccinimide (hereinafter sometimes abbreviated as “NCS”). A method having at least a step of chlorinating the meso-position of the compound (hereinafter abbreviated as “NCS chlorination step” as appropriate) And a manufacturing method of Hereinafter, although the manufacturing method of this invention is demonstrated, the method for synthesize | combining the chlorine substituted porphyrin compound of this invention is not limited to this manufacturing method of this invention.

  For example, when 5-monochlorobicycloporphyrin is produced by chlorinating one of the meso positions of bicycloporphyrin with NCS, the reaction process is represented by the following reaction formula.

  According to the production method of the present invention, the production object is a chlorine-substituted porphyrin compound having one or more nuclear condensed rings represented by the general formula (I) (that is, the chlorine-substituted porphyrin compound of the present invention). It is not limited. That is, various chlorine-substituted porphyrin compounds in which one or more meso positions are substituted with chlorine can be produced by the production method of the present invention regardless of the presence or absence of a nuclear condensed ring. Therefore, unless otherwise specified, the following description will be made assuming that the chlorine-substituted porphyrin compound to be produced is not limited to the chlorine-substituted porphyrin compound of the present invention (that is, the presence or absence of a nuclear condensed ring is not particularly limited).

  Further, the production method of the present invention is not particularly limited as long as it has at least the above-described NCS chlorination step, and may be carried out with arbitrary modifications such as adding other steps. Is possible. In the following description, the NCS chlorination process, which is a feature of the production method of the present invention, will be described first, followed by the addition of other processes and modified examples.

[II-1. NCS chlorination process]
As described above, the NCS chlorination step is a step of chlorinating the meso position of a porphyrin compound as a raw material (hereinafter referred to as “raw porphyrin compound” as appropriate) with NCS. The structure of the raw material porphyrin compound is not particularly limited, and may be appropriately selected according to the structure of the chlorine-substituted porphyrin compound to be manufactured.

For example, when synthesizing the chlorine-substituted porphyrin compound represented by the above general formula (I) (that is, the chlorine-substituted porphyrin compound of the present invention), all of Q ^{1 to} Q ⁴ in the general formula (I) are hydrogen atoms. What is necessary is just to use the porphyrin compound which is these as a raw material porphyrin compound.

  Moreover, when synthesizing a chlorine-substituted porphyrin compound having no nuclear condensed ring, for example, a porphyrin compound represented by the following general formula (II) can be used as a raw material porphyrin compound.

In the general formula (II), M is the same as M in the general formula (I).
R ¹ ′ to R ⁸ ′ each independently represents a hydrogen atom or an arbitrary substituent. Examples of optional substituents, same substituents described above for R ¹ to R ⁸ in the general formula (I).

  By adjusting the amount of NCS used, the number of chlorine substitutions in the target chlorine-substituted porphyrin compound can be controlled. For example, if 1 mol equivalent of NCS is used per 1 mol of raw material porphyrin compound, a monochlorine-substituted porphyrin compound is mainly obtained, and if 2 mol equivalent of NCS is used, it is mainly a dichlorine substituted porphyrin compound. When about 3 molar equivalents of NCS are used, trichlorinated porphyrin compounds are mainly obtained, and when about 4 molar equivalents of NCS are used, mainly tetrachlorinated porphyrin compounds are obtained. .

  The chlorination reaction is usually carried out by dissolving a raw material porphyrin compound in a solvent and contacting the raw material porphyrin compound with NCS in this solution. The timing for adding NCS to the reaction system is not particularly limited. NCS may be added and mixed together with the raw material porphyrin compound in the solvent, or the raw material porphyrin compound may be dissolved in the solvent, and then NCS may be added to the resulting solution and mixed.

  The solvent is not particularly limited as long as the raw material porphyrin compound can be dissolved, but halogenated hydrocarbons such as chloroform, methylene chloride, dichloroethane, trichloroethane, and trichloroethylene; hexane, heptane, octane, isooctane, Aliphatic hydrocarbons such as nonane and decane; aromatic hydrocarbons such as toluene, benzene, xylene and chlorobenzene; lower alcohols such as methanol, ethanol, propanol and butanol; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, etc. Ketones; Esters such as ethyl acetate, butyl acetate and methyl lactate; Nitrogen-containing organic solvents such as pyridine and quinoline; Ethers such as ethyl ether, tetrahydrofuran and dioxane; Dimethylformamide and di An amide such as chill acetamide and the like. Among these, halogenated hydrocarbons are preferable from the viewpoint of excellent solubility. Any one of these solvents may be used alone, or two or more thereof may be used in any composition and combination.

The conditions during the chlorination reaction are not particularly limited, but are generally as follows.
The reaction temperature is usually room temperature or higher, preferably 50 ° C. or higher. If the reaction temperature is too low, the reaction rate may be slow. On the other hand, the upper limit of the reaction temperature may be appropriately selected according to conditions such as the boiling point of the solvent used and the stability of the raw material porphyrin compound, but is usually 100 ° C. or lower, preferably 80 ° C. or lower.

  The reaction pressure is usually normal pressure, but can be carried out under various pressure conditions. Specifically, the pressure reduction side can be carried out usually in the range of 0.1 atm or more due to the vapor pressure of the solvent, and the high pressure side can usually be carried out in the range of 10 atm or less due to problems with the apparatus.

  Although the reaction time varies depending on conditions such as reaction temperature and reaction pressure, it is usually 1 hour or longer, preferably 8 hours or longer, and usually 100 hours or shorter, preferably 72 hours or shorter.

  During the chlorination reaction, the reaction is carried out while monitoring the progress of the reaction by various analytical methods such as various types of chromatography and nuclear magnetic resonance (hereinafter abbreviated as “NMR” where appropriate). By carrying out, an appropriate reaction time can be determined.

  After completion of the chlorination reaction, the desired product can be obtained by purifying the obtained product using techniques such as recrystallization, reprecipitation, column chromatography, sublimation, etc., to obtain the desired chlorine-substituted porphyrin compound. Can do. In particular, when the obtained chlorine-substituted porphyrin compound is used for applications such as semiconductors sensitive to impurities, a high-purity chlorine-substituted porphyrin compound is required. Specifically, it is preferable to carry out purification until the metal impurities contained in the product are usually 100 ppm or less, particularly 10 ppm or less.

[II-2. Deethylene removal reaction process]
In the case of producing a chlorine-substituted porphyrin compound having a structure in which an aromatic ring is condensed (for example, chlorine-substituted tetrabenzoporphyrin), the corresponding chlorine-substituted bicycloporphyrin compound is synthesized by the above-mentioned NCS chlorination step, and is then used as a precursor. It is also possible to obtain the target chlorine-substituted porphyrin compound by further carrying out a deethylene reaction as a body.

  For example, when 5-monochlorotetrabenzoporphyrin is produced by carrying out a deethylenation reaction using 5-monochlorobicycloporphyrin as a precursor, the reaction process is represented by the following reaction formula.

  The method for the deethylene reaction is not particularly limited, and may be performed using a known method. As an example, a chlorine-substituted bicycloporphyrin compound as a precursor is usually 100 ° C. or higher, preferably 150 ° C. or higher, and usually 400 ° C. or lower under vacuum conditions of 10 Pa or less or in an inert atmosphere such as argon gas. The method of deethylenating by heating to a high temperature of preferably 300 ° C. or less, usually for 1 minute or more, preferably 3 minutes or more, and usually for 24 hours or less, preferably 12 hours or less. .

  In general, porphyrin compounds having a structure in which aromatic rings are condensed often have low solubility in a solvent. In this case, this method of synthesizing a highly soluble chlorine-substituted bicycloporphyrin compound first and then deethylating it as a precursor is easy to synthesize and purify the precursor, and also to deethylenate the reaction. Is convenient for obtaining a high-purity chlorine-substituted porphyrin compound from the point that it proceeds almost quantitatively.

[II-3. Metal salt contact process]
When producing a chlorine-substituted porphyrin metal complex, a porphyrin metal complex may be used as a raw material porphyrin compound and chlorinated by the NCS chlorination step described above. It can also be produced by chlorinating it by the NCS chlorination step described above and then contacting the resulting metal-free chlorine-substituted porphyrin compound with a metal salt.

  As an example of the latter method, when 5-monochlorobicycloporphyrin metal complex is produced by contacting 5-monochlorobicycloporphyrin with a metal salt, the reaction process is represented by the following reaction formula. In the following reaction formula, M represents an arbitrary metal atom, and X represents an atom or an atomic group that forms a salt with M.

  In this case, as the metal salt, a salt of a target metal element that is easily dissolved in the solvent used in the NCS chlorination reaction (for example, a metal acetate or the like) may be selected. The amount of metal salt used varies depending on the type of metal salt used and the like, but usually about 1 molar equivalent or an excess amount of metal salt is used per 1 mol of the metal-free chlorine-substituted porphyrin compound. There is no particular limitation on the contact method between the metal-free chlorine-substituted porphyrin compound and the metal salt. After synthesizing a metal-free chlorine-substituted porphyrin compound by the NCS chlorination process described above, a metal salt may be added directly to the reaction solution and mixed. To obtain a highly pure metal salt, a metal-free body is used. It is preferred to introduce the metal after removal and purification.

[II-4. Others]
According to the production method of the present invention described above, a chlorine-substituted porphyrin compound can be produced in a more efficient and safer manner than conventional methods by chlorinating the meso position of the porphyrin compound using NCS. Can do.

  In the above description, it is assumed that a chlorine-free porphyrin compound is used as a raw material for the NCS chlorination process. However, a porphyrin compound in which a part of the meso position is substituted with chlorine (from one chlorine substitution to three chlorine substitutions). It is also possible to produce a porphyrin compound (dichlorine substituted to tetrachlorine substituted porphyrin compound) having a larger number of chlorine substitutions by subjecting the chlorine substituted porphyrin compound) to the NCS chlorination step and further performing chlorine substitution. .

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example, this invention is not limited to a following example, unless the summary is exceeded.

[Example 1: Monochlorobicycloporphyrin zinc complex]
Under light shielding and argon atmosphere, 0.062 g (0.10 mmol) of bicycloporphyrin was dissolved in 15 ml of chloroform. To this was added 0.014 g (0.11 mmol) of N-chlorosuccinimide (NCS), and the mixture was stirred under reflux for 3 days. After completion of the reaction, the reaction mixture was washed successively with saturated aqueous sodium hydrogen carbonate, water, and saturated brine (once each) and concentrated. The reaction mixture was dissolved in 10 ml of a mixed solvent of chloroform and methanol (volume ratio of chloroform: methanol: 9: 1), and then 0.439 g (2.0 mmol) of zinc acetate dihydrate was added. Stir for 2 hours. After completion of the reaction, the reaction solution was washed in turn with water and saturated saline (each once), concentrated, purified by silica gel column chromatography (mobile phase: chloroform), and dried to obtain monochlorobicycloporphyrin. The zinc complex was obtained as a reddish purple powder (yield 31 mg, yield 43%, raw material recovery 27 mg).

  The obtained product was measured for mass spectrum (hereinafter abbreviated as “MS” where appropriate) and NMR spectrum. The results are shown in FIGS. 1 and 2, respectively. From these results, it can be seen that the product is a monochlorobicycloporphyrin zinc complex having a structure represented by the following chemical formula.

[Example 2: Dichlorobicycloporphyrin zinc complex]
Under light shielding and argon atmosphere, 0.062 g (0.10 mmol) of bicycloporphyrin was dissolved in 15 ml of chloroform. To this, 0.028 g (0.22 mmol) of N-chlorosuccinimide (NCS) was added and stirred for 3 days under reflux. After completion of the reaction, the reaction mixture was washed successively with saturated aqueous sodium hydrogen carbonate, water, and saturated brine (once each) and concentrated. The reaction mixture was dissolved in 10 ml of a mixed solvent of chloroform and methanol (volume ratio of chloroform: methanol 9: 1), and 0.439 g (2.0 mmol) of zinc acetate dihydrate was added. Stir for 2 hours. After completion of the reaction, the reaction solution was washed successively with water and saturated brine (each once), concentrated, and then roughly purified by silica gel column chromatography (mobile phase: chloroform) to obtain a crude product. This was further purified by GPC and dried to obtain a dichlorobicycloporphyrin zinc complex (a mixture of two types of 5,10-disubstituted and 5,15-disubstituted) as a reddish purple powder (yield) 24 mg, yield 32%, monochloro body by-product amount 11 mg, raw material recovery amount 17 mg).

  The resulting product was measured for MS and NMR spectra. The results are shown in FIGS. 3 and 4, respectively. From these results, it can be seen that the main product is a dichlorobicycloporphyrin zinc complex having a structure represented by the following chemical formula (a mixture of two types of 5,10-disubstituted and 5,15-disubstituted).

[Example 3: Tetrachlorobicycloporphyrin]
Under light shielding and argon atmosphere, 0.062 g (0.10 mmol) of bicycloporphyrin was dissolved in 15 ml of chloroform. N-chlorosuccinimide (NCS) 0.056g (0.44mmol) was added to this, and it stirred under recirculation | reflux for 3 days. After completion of the reaction, the reaction mixture was washed successively with saturated aqueous sodium hydrogen carbonate, water, and saturated brine (once each) and concentrated. This was purified by silica gel column chromatography (mobile phase: chloroform) to obtain tetrachlorobicycloporphyrin (yield 53 mg, yield 70%).

  The obtained product was measured for NMR spectrum, MS and absorption spectrum. The results are shown in FIGS. 5, 6 and 7, respectively. From these results, it is understood that the main product is tetrachlorobicycloporphyrin having a structure represented by the following chemical formula. In the absorption spectrum of FIG. 7, since a strong absorption band is seen in the visible light region, it can be seen that the obtained tetrachlorobicycloporphyrin is promising as a dye material.

[Example 4: Tetrachlorotetrabenzoporphyrin]
About 2 mg of the porphyrin compound (tetrachlorobicycloporphyrin) powder obtained in Example 5 was heated at 200 ° C. for 10 minutes under a vacuum reduced pressure by a vacuum pump to convert the structure, and the structure represented by the following chemical formula: Tetrachlorotetrabenzoporphyrin was obtained (yield 2 mg, yield 100%). The product structure was confirmed by measuring NMR spectrum, TOF-MS, and UV spectrum.

  The absorption spectrum was measured about the obtained tetrachlorotetrabenzoporphyrin. The measurement results are shown in FIG. Since a strong and sharp absorption band is observed at 494 nm, this tetrachlorotetrabenzoporphyrin is expected to be used as a filter material that cuts off light in this wavelength band.

[Example 5: Tetrachlorobicycloporphyrin zinc complex]
Under light shielding and argon atmosphere, 0.062 g (0.10 mmol) of bicycloporphyrin was dissolved in 15 ml of chloroform. N-chlorosuccinimide (NCS) 0.056g (0.44mmol) was added to this, and it stirred under recirculation | reflux for 3 days. After completion of the reaction, the reaction mixture was washed successively with saturated aqueous sodium hydrogen carbonate, water, and saturated brine (once each) and concentrated. The reaction mixture was dissolved in 10 ml of a mixed solvent of chloroform and methanol (volume ratio of chloroform: methanol 9: 1), and 0.439 g (2.0 mmol) of zinc acetate dihydrate was added. Stir for 2 hours. After completion of the reaction, the reaction solution is washed successively with water and saturated saline (once each), concentrated, and purified by silica gel column chromatography (mobile phase: chloroform) to obtain a structure represented by the following chemical formula. Of tetrachlorobicycloporphyrin zinc complex was obtained (yield 58 mg, yield 70%).

  The absorption spectrum was measured about the obtained compound. The measurement results are shown in FIG. Since a strong and sharp absorption band is observed at 442 nm, the obtained tetrachlorobicycloporphyrin zinc complex is expected to be used as a filter material for cutting light in this wavelength band.

[Example 6: Tetrachlorotetrabenzoporphyrin zinc complex]
By converting about 2 mg of the powder of the porphyrin compound (tetrachlorobicycloporphyrin zinc complex) obtained in Example 5 by heating at 200 ° C. for 10 minutes under vacuum reduced pressure by a vacuum pump, the tetrachlorotetrabenzoporphyrin zinc complex is converted. Got. The product structure was confirmed by measuring NMR spectrum, TOF-MS, and UV spectrum.

  The absorption spectrum of the resulting tetrachlorotetrabenzoporphyrin zinc complex was measured. The measurement results are shown in FIG. Since a strong and sharp absorption band is observed at 479 nm, this tetrachlorotetrabenzoporphyrin zinc complex is expected to be used as a filter material for cutting light in this wavelength band.

[Example 7: Mono- and di-chlorooctaethylporphyrin]
Under light shielding and argon atmosphere, 0.114 g (0.20 mmol) of octaethylporphyrin (manufactured by Aldrich) was dissolved in chloroform. To this, 0.028 g (0.22 mmol) of N-chlorosuccinimide was added, and the mixture was refluxed and stirred for 3 days. After completion of the reaction, the reaction mixture was washed successively with saturated aqueous sodium hydrogen carbonate, water, and saturated brine (one time each), and concentrated. This was purified by silica gel column chromatography (chloroform: hexane = 9: 1) to give 0.068 g (yield 56%) of 5-chlorooctaethylporphyrin having a structure represented by the following chemical formula and 5,15-dichloroocta 0.012 g (yield 11%) of ethyl porphyrin was obtained.

  Furthermore, except that the amount of NCS was doubled, 0.024 g of 5-chlorooctaethylporphyrin (yield 20%) and 5,15-dichlorooctaethylporphyrin 0. 060 g (yield 46%) was obtained.

  The obtained mono- and di-chlorooctaethylporphyrin were measured for NMR spectrum, absorption spectrum and MS. The NMR spectrum, absorption spectrum, and MS measurement results of monochlorooctaethylporphyrin are shown in FIGS. Moreover, the NMR spectrum, absorption spectrum, and MS measurement result of dichlorooctaethylporphyrin are shown in FIGS.

[Example 8: Organic FET]
Using the porphyrin compound (tetrachlorobicycloporphyrin) obtained in Example 3, an N-type silicon (Si) substrate on which an oxide film having a thickness of 300 nm is formed (Sb dope, resistivity 0.02 Ω · cm or less, Sumitomo Gold electrodes (source and drain electrodes) having a gap with a length (L) of 10 μm and a width (W) of 500 μm were formed on the metal industry). Further, chromium was deposited on an exposed Si portion by scraping an oxide film at a position different from that of this electrode, and this portion was used as a gate electrode for applying a voltage to the silicon substrate.

  7 mg of the porphyrin compound obtained in Example 3 was dissolved in 1 mL of chloroform, and this was spin-coated on the above-mentioned substrate to obtain a good film. Then, the semiconductor film was produced on the board | substrate with which the electrode was formed by heat-processing for 5 minutes at 180 degreeC.

As a result of evaluating the electric characteristics of the FET (field effect transistor) element thus obtained using a semiconductor parameter analyzer 4155C manufactured by Agilent, the FET characteristics were shown, and the saturation mobility was 2.3 × 10 ⁻⁶ cm ² / V · s.

Since the chlorine-substituted porphyrin compound of the present invention has excellent optical functions, electrical functions, chemical functions, etc., it is suitably used in various applications such as applications as dyes and semiconductors, and applications as intermediates thereof. Can be used.
Further, according to the method for producing a chlorine-substituted porphyrin compound of the present invention, various chlorine-substituted porphyrin compounds including the chlorine-substituted porphyrin compound of the present invention can be efficiently produced, so that a porphyrin serving as a dye, a semiconductor, or an intermediate thereof It can be used suitably in the use which manufactures a compound.

2 is an MS of monochlorobicycloporphyrin zinc complex obtained in Example 1. 2 is an NMR spectrum of the monochlorobicycloporphyrin zinc complex obtained in Example 1. 2 is an MS of the dichlorobicycloporphyrin zinc complex obtained in Example 2. 2 is an NMR spectrum of the dichlorobicycloporphyrin zinc complex obtained in Example 2. 4 is an MS of tetrachlorobicycloporphyrin obtained in Example 3. 3 is an NMR spectrum of tetrachlorobicycloporphyrin obtained in Example 3. 4 is an absorption spectrum of tetrachlorobicycloporphyrin obtained in Example 3. 4 is an absorption spectrum of tetrachlorotetrabenzoporphyrin obtained in Example 4. 6 is an absorption spectrum of a tetrachlorobicycloporphyrin zinc complex obtained in Example 5. 4 is an absorption spectrum of a tetrachlorotetrabenzoporphyrin zinc complex obtained in Example 6. 2 is an NMR spectrum of monochlorooctaethylporphyrin obtained in Example 7. 4 is an absorption spectrum of monochlorooctaethylporphyrin obtained in Example 7. It is the monochlorooctaethyl porphyrin MS obtained in Example 7. 2 is an NMR spectrum of dichlorooctaethylporphyrin obtained in Example 7. 4 is an absorption spectrum of dichlorooctaethylporphyrin obtained in Example 7. 4 is an MS of dichlorooctaethylporphyrin obtained in Example 7.

Claims (3)

A chlorine-substituted porphyrin compound represented by the following general formula (I):

(In the above general formula (I),
Q ^{1 to} Q ⁴ each independently represents a hydrogen atom or a chlorine atom, and at least one of Q ^{1 to} Q ⁴ is a chlorine atom,
R ^{1 to} R ⁸ each independently represents a hydrogen atom or an arbitrary substituent, and among the combinations of R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , and R ⁷ and R ⁸ At least one pair of the above is bonded to each other to form an optionally substituted ring,
M represents a metal atom or two hydrogen atoms. ) A method for producing a chlorine-substituted porphyrin compound, comprising at least a step of chlorinating a meso position of a porphyrin compound using N-chlorosuccinimide. The method for producing a chlorine-substituted porphyrin compound according to claim 2, wherein the chlorine-substituted porphyrin compound obtained by chlorination is the chlorine-substituted porphyrin compound according to claim 1.

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