JP4841935B2 - Method for producing iodonium salt - Google Patents

Description

  The present invention relates to a novel method for producing an iodonium salt that is useful as a radical polymerization initiator, an acid generator, and a cationic polymerization initiator.

Conventionally, as a negative photosensitive lithographic printing plate, a PS plate having a configuration in which an oleophilic photosensitive resin composition is provided on a hydrophilic support is widely used, and the plate making method is usually through a lithographic film. After the mask exposure, the desired printing plate was obtained by dissolving and removing the non-image area with alkaline water or the like.
In recent years, digitization technology that electronically processes, stores, and outputs image information using a computer or the like has become widespread, and even in the plate making method of a lithographic printing plate, using laser light, without a lithographic film, A CTP technique for directly producing a printing plate is established, and a chemically amplified negative CTP printing plate that generates an acid by light or heat by exposure and causes the crosslinking reaction by using the acid as a catalyst (see, for example, Patent Document 1). ), Or negative CTP printing plates (see, for example, Patent Document 2) in which radicals are generated by heat or light and the radicals are used as a catalyst have been developed.
In recent years, in the development of the semiconductor field, the light source of the irradiation apparatus used for fine processing, especially lithography, has become shorter and shorter with the increase in the density of semiconductor elements. 2. Description of the Related Art Chemically amplified resist compositions that contain an acid generator in a product, generate an acid from the acid generator by exposure, and form an image with the acid have come to be used generally. As acid generators used in chemically amplified resist compositions, sulfonium salts, iodonium salts, diazodisulfone compounds and the like have been studied.
These onium salts useful as acid generators, such as sulfonium salts, iodonium salts, and diazonium salts, are also used as cationic polymerization initiators.

As described above, onium salts such as iodonium salts, diazonium salts, and sulfonium salts are widely used as acid generators for CTP, radical generators, and acid generators for resist compositions. Among these, as acid generators and radical generators, iodonium salts excellent in the balance between stability and reactivity, particularly diaryl iodonium salts, are preferred and have recently been attracting attention. The known methods are concerned with safety, such as using peracetic acid, using nitric acid or sulfuric acid in excess, or using a large amount as a solvent. In such a production method, although many synthesis examples such as alkyl-substituted diaryl iodonium salts are seen, the present inventors have focused on a synthesis method relating to electron donating iodonium salts and bis (alkoxyphenyl) iodonium salts. Have not been studied much, and as such a technique, a method using lead organostannate and dicyanoiodonium (see, for example, Non-Patent Document 1), acetic acid, acetic anhydride, sulfuric acid and sodium periodate are used. Only the method to be used (for example, see Non-Patent Document 2) is known. In addition, in the case of a synthesis reaction using peracetic acid, there was a problem in that during the synthesis of the intermediate iodoaryl diacetate, the purity of the diaryliodonium salt was reduced due to heat generation during the peracetic acid reaction and side reactions accompanying the heat generation. . In addition, the current situation is that little is known about a method for producing an iodonium salt having an electron-donating group in addition to a bis (alkoxyphenyl) iodonium salt.
Japanese Patent Laid-Open No. 7-20629 JP 2001-343742 A Tetrahedron Letter, (1992) P1419-1422. J. et al. A. C. S. (1953), P2705

  An object of the present invention made in consideration of the above problems is to provide a diaryl iodonium salt useful as an acid generator and a radical generator, which can be produced stably and in a high yield. It is providing the manufacturing method of an iodonium salt.

As a result of intensive studies, the present inventor has found that in a method for producing an iodonium salt in which a peracid is allowed to act on an iodoaryl compound, the compound represented by the following general formula (I) or general formula (II) is an amino acid in the molecule. By using a compound having a group and a carboxylic acid, it was possible to suppress side reactions and heat generation, and it was found that a high-purity diaryliodonium salt could be produced, and the present invention was completed.
That is, in the method for producing a diaryl iodonium salt of the present invention, a compound represented by the following general formula (I) or general formula (II) is mixed with an iodoaryl compound and a peracid, and then an aromatic compound is added. it shall be the features a.

In general formula (I), R ¹ and R ² each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a hydrogen atom. R ¹ and R ² may be bonded to each other to form a ring. X represents a divalent linking group.
In the general formula (II), Y represents a 4- to 14-membered ring structure containing N, and the carboxylic acid group shown here is directly or directly on the carbon atom or nitrogen atom constituting the ring structure of Y. It is linked via any linking group. R ³ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a hydrogen atom.

More specifically, the iodoaryl compound is allowed to act with a peracid in a solvent containing the compound represented by the general formula (I) or the general formula (II), and then an aromatic compound is added. Or it is preferable to add the salt.
In addition, by using a compound having an electron-donating substituent as the starting aromatic compound, a symmetric or asymmetrical diaryliodonium salt compound having an electron-donating group at an arbitrary position can be obtained.

  ADVANTAGE OF THE INVENTION According to this invention, the highly purified diaryliodonium salt useful as an acid generator and a radical generator can be manufactured stably and with a high yield. In addition, according to the production method of the present invention, it is possible to easily produce a symmetric or asymmetric diaryliodonium salt, a diaryliodonium salt having an electron donating group, and the like by selecting a raw material. .

Hereinafter, the present invention will be described in detail.
In the production method of the present invention, first, (1) a compound represented by the above general formula (I) or general formula (II) (hereinafter referred to as “ compound having an amino group and a carboxylic acid group in the molecule ” as appropriate) . ) , An iodoaryl compound and a peracid to allow the peracid to act on the iodoaryl compound to obtain an iodoaryl diacetate as an intermediate, and then (2) adding an aromatic compound, A diaryl iodonium salt compound is obtained by coupling an iodoaryl diacetate and an aromatic compound.
Therefore, a symmetric or asymmetric diaryl iodonium salt compound can be obtained by appropriately selecting an iodoaryl compound as a raw material and an aromatic compound to be coupled.
Further, in the present invention, (1) in the step of reacting the iodoaryl compound with a peracid, the compound having an amino group and a carboxylic acid group is allowed to coexist in the molecule to react the iodoaryl compound with the peracid. It is possible to suppress the side reaction and heat generation of this, and it is possible to produce a high-purity diaryliodonium salt.
In addition, it is also possible to introduce a desired anion into the diaryliodonium salt by adding an acid or a salt thereof during or after the coupling reaction of the diaryliodonium salt of the present invention.

< Compound represented by general formula (I) or general formula (II) (compound having an amino group and a carboxylic acid group in the molecule ) >
Compounds in the molecule used in the present invention having an amino group and a carboxylic acid is a compound represented by the following general formula (I) or Formula (II).

In general formula (I), R ¹ and R ² each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a hydrogen atom, and R ¹ and R ² are bonded to each other to form a ring. It may be formed.
Further, when R ^1, R ² is a functional group other than a hydrogen atom, respectively, it is possible to introduce a substituent having 1 or more functional groups shown below. Substitutable functional groups include alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, aryl groups, alkoxy groups, aryloxy groups, halogen atoms, hydroxyl groups, amide groups, sulfo groups, haloalkyl groups, amino groups, A thiol group, a carboxyl group, an alkoxycarbonyl group, a urethane group, a urea group, a thioalkoxy group, an alkylcarbonyl group, an arylcarbonyl group, and a nitro group.
R ¹ and R ² are preferably a hydrogen atom, an alkyl group, or a cyclic structure in which R ¹ and R ² are linked from the viewpoint of the effect of stabilizing the reaction.
X represents a divalent linking group. More specifically, X is an alkylene group such as methylene group or ethylene group, an aliphatic cyclic compound such as vinyl group, cycloalkyl group or cycloalkenyl group, an aromatic group such as phenylene group or naphthyl group, or oxyalkylene. Groups, heterocyclic groups such as furan and benzofuran groups, thienyl groups, cyclic compounds having heteroatoms such as tetrahydrofuran and tetrahydrothiophene, and linked cyclic compounds such as biphenyl. These can be substituted with the above-described substituents. It is. From the viewpoint of suppressing side reactions during the reaction, an alkylene group and an aliphatic cyclic compound are preferable.

In formula (II), Y represents a 4- to 14-membered ring structure containing N. The ring structure may be aromatic or non-aromatic, and may have a condensed ring structure. Moreover, carbon, nitrogen, oxygen, and sulfur can be contained as a ring constituent atom. Further, the ring structure may be further linked to or condensed with another ring structure. Preferred ring structures include pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, triazine ring, quinoline ring, benzoquinoline ring, acridine ring, isoquinoline ring, quinazoline ring, phenazine ring, phenanthrene ring, piperidine ring, pyrrolidine ring, piperazine A ring, a morpholine ring, a thiomorpholine ring, and the like.
Here, at least on the ring structure of Y, or when Y is connected to or condensed with another ring structure, at least one carboxylic acid group is present in any of them. The carboxylic acid may be directly connected to the ring or may be connected by a divalent linking group. Divalent linking groups for linking carboxylic acid groups to the ring structure include alkylene groups such as methylene groups and ethylene groups, aliphatic cyclic compounds such as vinyl groups, cycloalkyl groups and cycloalkenyl groups, phenylene groups and naphthyl groups. An aromatic group such as a group, a heterocyclic group such as a furan group, a benzofuran group, and a thienyl group, a cyclic compound having a hetero atom such as tetrahydrofuran and tetrahydrothiophene, and a linked cyclic compound such as biphenyl.
R ³ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a hydrogen atom, and when the cyclic compound containing Y is a pyridine ring, R ³ does not exist. R ³ is preferably a hydrogen atom or an alkyl group.
Y and the ring structure connected to or condensed with Y can be substituted with a substituent having the functional group shown below. Substitutable functional groups include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, aryloxy groups, halogen atoms, hydroxyl groups, amide groups, sulfo groups, haloalkyl groups, amino groups, thiol groups, carboxyl groups, alkoxycarbonyls. Group, urethane group, urea group, thioalkoxy group, alkylcarbonyl group, arylcarbonyl group and nitro group.
Specific examples of the compound having an amino group and a carboxylic acid group in the molecule that can be suitably used in the present invention are listed below, but the present invention is not limited thereto.

A preferable addition amount of the compound having an amino group and a carboxylic acid group in the molecule in the production method of the present invention is 0.001 mol% or more, preferably 0.01% with respect to the iodoaryl compound as a starting material. The range is from mol% to 1000 mol%, more preferably from 0.05 mol% to 100 mol%.
The mechanism of heat generation by introducing the compound according to the present invention into the system and the suppression of the generation of by-products associated therewith is not clear. However, when the peracid is reacted with the iodoaryl compound, the peracid is decomposed. By trapping the excessive radicals accompanying the compound, side reactions can be suppressed and heat generation can be suppressed. For this reason, the promotion of side reactions caused by heat generation is also suppressed, thereby further increasing the purity. It is thought that it leads to improvement.

<Iodoaryl compound>
In the present invention, an iodoaryl compound that can be used as a starting material when producing a diaryliodonium salt includes iodobenzene; an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom. , Iodobenzene substituted with 1 to 5 substituents selected from a hydroxyl group, an amide group, a sulfo group, a haloalkyl group, and an amino group. When the iodobenzene having the substituent has a plurality of substituents, the substituents may be the same or different from each other.
Further, as other iodoaryl compounds, compounds such as iodonaphthalene, iodoanthracene, iodophenanthrene, and derivatives thereof, specifically, compounds in which the above-described substituents are introduced into these compounds can be used. Examples of such compounds.

<Peracid>
As the peracid that can be used in the present invention, any peracid having an —O—O— bond can be used. However, peracetic acid, perbenzoic acid, performic acid, monoperphthalic acid, permaleic acid, peroxanic acid, peroxyacid, Examples thereof include succinic acid, perglutaric acid, peradipic acid, pertrifluoroacetic acid, perchloroacetic acid, and hydrogen peroxide.
From the viewpoint of availability and handling, hydrogen peroxide water and peracetic acid are preferable.
In the present invention, first, the iodoaryl compound and peracid are mixed to produce an intermediate iodoaryl diacetate. From the viewpoint of reactivity and safety, the amount of peracid added is iodoaryl. 10 mol%-10000 mol% are preferable with respect to a compound, and it is more preferable that it is about 100 mol%-1000 mol%.

<Solvent>
The solvent that can be suitably used in the present invention can be used without particular limitation as long as it can dissolve the aryliodo compound and peracid, but is preferably a liquid that can be mixed with carboxylic acid. Examples of the solvent that can be suitably used in the present invention include dichloromethane, dichloroethane, chloroform, acetonitrile, acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, dimethylacetamide, N-methylpyrrolidone, diethyl ether, tetrahydrofuran, 1,2- Dimethoxyethane, diisopropyl ether, butyl methyl ether, sec-butyl methyl ether, butyl ethyl ether, t-butyl methyl ether, 2-methoxyethyl ether, diethylene glycol diethyl ether, diethoxymethane, 2-methyltetrahydrofuran, 2,5-dimethyl Tetrahydrofuran, 2,2,5,5, -tetramethyltetrahydrofuran, tetrahydropyran, 3-methyltetrahydropyran, di Hexane, ethyl acetate, butyl acetate, acetic acid, propionic acid, acetic anhydride, toluene, anisole and xylene.
Preferably, a combination of acetic acid is preferable when peracetic acid is used, and a combination of acetic anhydride is preferable when hydrogen peroxide water is used.

The reaction temperature when the iodoaryl compound and peracid are reacted in the presence of a compound having an amino group and a carboxylic acid group in the molecule may be not less than the melting point of the solvent used. In view of the above, it is preferably in the range of −20 ° C. to 200 ° C., more preferably in the range of 10 ° C. to 60 ° C., and the reaction time is preferably (0 hours) to 200 hours after completion of the reaction agent mixing, more preferably the reaction agent. After mixing is completed (0 hour) to 50 hours.
In the production method of the present invention, first, after a compound having an amino group and a carboxylic acid group in the molecule, an aryl iodonium compound, and a peracid are mixed and reacted to produce iodoaryl diacetate. The intermediate is coupled with an aromatic compound to obtain the desired diaryliodonium salt.

<Aromatic compounds>
Since the aromatic compound that can be used in the present invention is used for iodonium chlorination, it can be used as long as it has at least one hydrogen atom on the aromatic group, more specifically, aromatic. Substitutable aromatic benzene, naphthalene, anthracene, phenanthrene and other aromatic hydrocarbons having one hydrogen atom on the group, or substitutable indole, thiazole, tetrazole, thiophene, benzophenone, benzothiophene, pyridine, pyrimidine, triazine, etc. An aromatic compound having a hetero atom can be mentioned. Here, the functional groups that can be substituted include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, aryloxy groups, halogen atoms, hydroxyl groups, amide groups, sulfo groups, haloalkyl groups, amino groups, thiol groups, carboxyls. Group, an alkoxycarbonyl group, a urethane group, a urea group, a thioalkoxy group, an alkylcarbonyl group, an arylcarbonyl group, and a nitro group, and may be substituted by 1 to 5 by these substituents. When the aromatic compound has a plurality of substituents, these substituents may be the same or different from each other.
Among these, a benzene compound having a substituent is preferable from the viewpoint of stability and production suitability of the coupling body, and an aromatic compound substituted with an alkoxy group is particularly preferable from the viewpoint of stability.

As such an aromatic compound, it is preferable to use a compound into which an electron-donating substituent is introduced from the viewpoint of improving characteristics as a radical initiator and an acid generator of the resulting diaryl iodonium salt. That is, by introducing an electron donating group into the iodonium salt, decomposition of the iodonium salt with water or anion, or decomposition over time due to nucleophilic species is suppressed, discoloration over time associated with decomposition, dark polymerization, etc. Is believed to be suppressed.
The electron donating group that can be introduced into the aromatic compound is preferably an alkyl group, an alkoxy group, an amino group, a urea group, an alkoxyalkyl group, an acyloxyamino group, a cycloalkyl group, or an allyl group. A substituent such as an alkyl group, an alkenyl group, an aryl group, a hydroxyl group, an alkoxy group, a thiol group, a thioalkoxy group, an amino group, or a halogen atom may be included as long as the electron donating property is not lost.
Among these, particularly preferable electron donating groups include an alkyl group and an alkoxy group, and the most preferable substituent is an alkoxy group.
Preferable specific examples of the electron donating group include an alkyl group having 1 to 20 carbon atoms, such as a methyl group, an n-butyl group, a t-butyl group, an n-octyl group, and a dodecyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a butoxy group, a heteroxy group, an octyloxy group, a dodecyloxy group, and a cyclohexyl group.

When the aromatic compound has a plurality of electron donating groups, they may be the same or different from each other.
As the number of electron-donating groups substituted, the resulting diaryl iodonium salt preferably has 2 or more electron-donating groups, more preferably 3 or more, and most preferably 4 substituted.
The electron donating group introduced into the aromatic compound is introduced into the aryl group of the iodonium salt that is the target substance, and preferred substitution positions include the para position and the ortho position. One or more electron-donating groups may be introduced into both of the two aryl groups in the iodonium salt, or two or more electron-donating groups may be introduced into only one of them.
If the standard as a physical property value in introducing the electron donating group is given, it is preferable that the sum of Hammett values of substituents (electron donating groups introduced into the aryl group) is −0.27 or less, -0.54 or less is more preferable, and -0.84 or less is most preferable.
The Hammett value represents the degree of electron withdrawing of the substituent in the diaryliodonium salt obtained by the production method of the present invention. As the Hammett value in the present invention, the Chemical Society of Japan, Chemical Handbook, Basic II ( 1984, published by Maruzen Co., Ltd.). Note that the Hammett value is usually calculated with the substitution position at the m-th and p-th values, but as an electronic effect, the o-th value may be calculated as the same value as the p-th value.

  The addition amount of the aromatic compound is preferably 50 mol% or more with respect to the iodoaryl compound from the viewpoint of production suitability and yield, more preferably 100 to 1000 mol%, and more preferably 100 to 500 mol%. Most preferably, it is mol%.

<Acid>
In the method of the present invention, an iodoaryl compound is allowed to react with a peracid in a solvent containing a compound having an amino group and a carboxylic acid group in the molecule, and then an acid or a salt thereof is added together with the aromatic compound. be able to.
Examples of the acid that can be used in this step include alkylsulfonic acid, arylsulfonic acid, phosphoric acid, phosphate ester having at least one acid group, sulfinic acid, sulfuric acid, monosulfate ester, nitric acid, hydrogen halide, periodate Examples include acids, perchloric acid, tetrafluoroboric acid, hexafluorophosphoric acid, halogen-substituted carboxylic acids, hexafluoroantimony, and salts thereof. Examples of other acids include organoboron compounds such as tetraarylborate, phosphorus compounds, and silyl compounds.

As preferred acids that can be used in the present invention, arylsulfonic acid such as para-toluenesulfonic acid, perfluoroalkanesulfonic acid such as trifluoromethanesulfonic acid, nonafluorobutanesulfonic acid, etc., from the viewpoint of reactivity and iodonium salt removability , Tetrafluoroboric acid, hexafluorophosphoric acid and the like.
The addition amount of the acid is preferably 100 mol% or more with respect to the iodoaryl compound from the viewpoint of production suitability, more preferably 100 to 1000 mol%, and preferably 100 to 200 mol%. Most preferred.

  In this step, when the intermediate and the aromatic compound are subjected to a coupling reaction, it is possible to react by adding a solvent so that the reaction can be easily controlled. The solvent that can be added is preferably a solvent that can be mixed with the solvent used in the reaction of the iodoaryl compound and peracid, and is dichloromethane, dichloroethane, chloroform, acetonitrile, acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, dimethyl. Acetamide, N-methylpyrrolidone, diethyl ether, tetrahydrofuran, 1,2-dimethoxyethane, diisopropyl ether, butyl methyl ether, sec-butyl methyl ether, butyl ethyl ether, t-butyl methyl ether, 2-methoxyethyl ether, diethylene glycol diethyl Ether, diethoxymethane, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, 2,2,5,5, -tetramethyltetrahydro Orchids, tetrahydropyran, 3-methyltetrahydropyran, dioxane, ethyl acetate, butyl acetate, acetic acid, propionic acid, acetic anhydride, toluene, anisole and xylene. From the viewpoint of suppressing side reactions, non-aromatic solvents are preferable, and among them, acetonitrile is preferable from the viewpoint of handling and taking out products after the reaction.

  The reaction temperature for obtaining the desired diaryliodonium salt by coupling an aromatic compound to this intermediate may be at least the melting point of the solvent to be used, but from the viewpoint of reactivity-safety, preferably -78. The reaction time is preferably immediately after mixing (0 hour) to 100 hours, more preferably from (0 hour) to 48 hours from the viewpoint of productivity. It is a range.

The iodonium salt obtained by the method of the present invention can be converted to a desired salt structure by performing salt exchange by the method described in WO02 / 081439. By this method, the counter anion can be suitably converted to PF ₆ ⁻ , CIO ₄ ⁻ , BF ₄ ^{− and the} like.
Specific examples of iodonium salts (diaryl iodonium salts) that can be obtained by the production method of the present invention and subsequent known salt exchange formulations are given below, but the compounds obtained by the production method of the present invention are limited to the following iodonium salts. I don't mean.

  According to the production method of the present invention, a diaryliodonium salt useful as an acid generator and a radical generator, in particular, an electron-donating diaryliodonium salt that has not been studied in the past can be produced in a high yield. And it has the advantage of being excellent in manufacturing stability. Moreover, since side reactions are effectively suppressed, a diaryliodonium salt having an arbitrary structure can be easily produced by selecting raw materials.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.
<Example 1>
6.62 g of octyloxyiodobenzene (iodoaryl compound) is dissolved in 20 ml of acetic acid and stirred. The temperature is maintained at 30 ° C., and 0.25 g of picolinic acid (a compound having an amino group and a carboxylic acid group in the molecule) is added thereto and stirred at room temperature for 10 minutes. Adjust the temperature to 30 ° C, slowly add 8.0 g of 38-39% peracetic acid / acetic acid solution over 1 hour, stir at 30 ° C-35 ° C for 6 hours, leave at room temperature for 12 hours, add 30 ml of acetonitrile dropwise. Cool to ice so that the internal temperature becomes 5 ° C. or less, add 3.20 g of 1,3,5-trimethoxybenzene (aromatic compound), and dissolve 3.62 g of paratoluenesulfonic acid in 50 ml of acetonitrile. And dropped. Thereafter, the mixture was stirred at 5 ° C. or lower for 2 hours, then poured into 500 ml of ice water, extracted with 500 ml of dichloromethane, and the aqueous layer was further extracted with 200 ml of dichloromethane. The organic layer is washed with an aqueous solution in which 75.6 g of sodium sulfite is dissolved in 500 ml of water, and the organic layer is further washed twice with 300 ml of water. The organic layer was concentrated until the amount of the solvent became 1/10, 100 ml of ethyl acetate was added, the mixture was concentrated again, and allowed to stand to leave 7.05 g of the following iodonium salt [Exemplary Compound (I-36)] : 53%). The HPLC purity was 98.7%.

The structure of the obtained diaryl iodonium salt was confirmed by NMR.
NMR 400 MHz CDCl ₃ 0.879 (m, 3H); 1.275-1.299 (m, 8H); 1.350-1.420 (m, 2H); 1.777 (m, 2H); 321 (s, 3H); 3.853 (s, 3H); 3.880 (s, 3H); 3.900 (q, 2H); 6.146 (s, 2H); 6.780 (d, 2H) , J = 8.8); 7.093 (d, 2H, J = 8.0); 7.701 (d, 2H, J = 8.0); 7.785 (d, 2H, J = 8. 8)

<Comparative Example 1>
In Example 1, when the reaction was carried out without adding picolinic acid which is a compound having an amino group and a carboxylic acid group in the molecule, 6.10 g of the same iodonium salt as in Example 1 was obtained (yield: 46 %). The HPLC purity was 90.7%.

<Example 2>
In Example 1, 4-octyloxyiodobenzene was changed to 4-butoxyiodobenzene, 1,3,5-trimethoxybenzene was changed to butoxyiodobenzene, and picolinic acid was changed to 1.51 g of N-phenylglycine. When the sulfonic acid was changed to nonafluorobutanesulfonic acid, the following iodonium salt [the above exemplified compound (I-33)] was obtained in a yield of 65%. The HPLC purity was 97.8%.

NMR 400 MHz CDCl ₃ 0.956 (t, 6H, J = 7.6); 1.659 (m, 4H); 1.756 (m, 4H); 3.941 (t, 4H, J = 6.8) ); 6.890 (d, 4H, J = 5.2); 7.879 (d, 4H, J = 5.2)

<Comparative example 2>
In Example 2, the reaction was carried out without adding N-phenylglycine, which is a compound having an amino group and a carboxylic acid group in the molecule, and the same iodonium salt as in Example 2 was obtained in a yield of 53%. Obtained. The HPLC purity was 89.9%.

<Example 3>
In Example 1, when the reaction was carried out by changing 4-octyloxyiodobenzene to iodobenzene and picolinic acid to 0.12 g of proline, the following iodonium salt [Exemplary Compound (I-26)] was obtained in a yield of 61. %. The HPLC purity was 98.4%.

NMR 400 MHz CDCl ₃ 2.327 (s, 3H); 3.873 (s, 9H); 6.712 (s, 2H); 7.108 (d, 2H, J = 8.0); 7.313 ( m, 2H); 7.460 (t, 1H, J = 7.6); 7.727 (d, 2H, J = 8.0); 7.870 (m, 2H)
<Comparative Example 3>
When the reaction was carried out without adding proline which is a compound having an amino group and a carboxylic acid group in the molecule in Example 3, the same iodonium salt as in Example 3 was obtained in a yield of 57%. The HPLC purity was 91.1%.

<Example 4>
In Example 1, when 4-octyloxyiodobenzene was changed to 4-butoxyiodobenzene and picolinic acid was changed to 0.20 g of glycine and the reaction was carried out, the following iodonium salt [the above exemplified compound (I-34)] was obtained. The yield was 68%. The HPLC purity was 99.0%.

NMR 400 MHz CDCl ₃ 0.950 (t, 3H, J = 7.2); 1.450 (m, 2H); 1.727 (m, 2H); 2.315 (s, 3H); 3.846 ( 3.887 (s, 6H); 3.898 (m, 2H); 6.151 (s, 2H); 6.778 (d, 2H, J = 8.8); 7.077 (D, 2H, J = 8.0); 7.669 (d, 2H, J = 8.0); 7.766 (d, 2H, J = 8.8)

<Comparative example 4>
In Example 4, 8-quinaldic acid, which is a compound having an amino group and a carboxylic acid group in the molecule, was added to 0.34 g of 1-naphthalenecarboxylic acid, a compound having a carboxylic acid group in the molecule and having no amino group. The reaction was carried out and the same iodonium salt as in Example 4 was obtained in a yield of 59%. The HPLC purity was 90.2%.

<Example 5>
Keep 20 ml of acetic anhydride at 30 ° C., add 5 g of 30% hydrogen peroxide solution dropwise, and stir at 30 ° C. to 35 ° C. for 5 hours. Here, picolinic acid (compound having an amino group and a carboxylic acid group in the molecule) 0 .25 g is added, the temperature is adjusted to 10 ° C., and 6.62 g of octyloxyiodobenzene (iodoaryl compound) is added dropwise. After stirring at 10-15 ° C. for 6 hours, left at room temperature for 12 hours, 30 ml of acetonitrile was added dropwise, and the mixture was cooled with ice so that the internal temperature was 5 ° C. or less, and 1,3,5-trimethoxybenzene (aromatic compound) 3.20 g was added, and 3.62 g of paratoluenesulfonic acid was dissolved in 50 ml of acetonitrile and added dropwise. Thereafter, the mixture was stirred at 5 ° C. or lower for 2 hours, then poured into 500 ml of ice water, extracted with 500 ml of dichloromethane, and the aqueous layer was further extracted with 200 ml of dichloromethane. The organic layer is washed with an aqueous solution in which 75.6 g of sodium sulfite is dissolved in 500 ml of water, and the organic layer is further washed twice with 300 ml of water. The organic layer is concentrated until the amount of the solvent becomes 1/10, 100 ml of ethyl acetate is added, the solution is concentrated again, and left to stand to give the same iodonium salt as in Example 1 [the exemplified compound (I-36)]. Obtained in 7.25 g (yield: 55%). The HPLC purity was 98.5%.
<Comparative Example 5>
In Example 5, the reaction was carried out without adding picolinic acid. It was 6.85 g (yield 52%) and HPLC purity 89.6%.

  As is clear from the above examples, the production method of the present invention shows that the desired diaryliodonium salt can be obtained with high purity and high yield. Moreover, in contrast with Examples 1-5 and Comparative Examples 1-5, which differed only in that the compounds each having an amino group and a carboxylic acid group were not used, this compound was reacted with an iodoaryl compound and a peracid. It was confirmed that the coexistence improves the purity and yield of the obtained target substance.

<Example 6>
6.62 g of octyloxyiodobenzene (iodoaryl compound) is dissolved in 20 ml of acetic acid and stirred. The temperature is maintained at 30 ° C., and 0.25 g of picolinic acid (a compound having an amino group and a carboxylic acid group in the molecule) is added thereto and stirred at room temperature for 10 minutes. Adjust the temperature to 30 ° C, slowly add 8.0g of 38-39% peracetic acid / acetic acid solution over 1 hour, stir at 30 ° C-35 ° C for 6 hours, then leave at room temperature for 12 hours, internal temperature is 25 ° C Then, 3.20 g of 1,3,5-trimethoxybenzene, which is an aromatic compound, was slowly added, and further 3.62 g of paratoluenesulfonic acid was slowly added. Thereafter, the mixture was stirred at 20 ° C. or lower for 2 hours, then poured into 500 ml of ice water, extracted with 500 ml of dichloromethane, and the aqueous layer was further extracted with 200 ml of dichloromethane. The organic layer is washed with an aqueous solution in which 75.6 g of sodium sulfite is dissolved in 500 ml of water, and the organic layer is further washed twice with 300 ml of water. The organic layer was concentrated until the amount of the solvent became 1/10, 100 ml of ethyl acetate was added, the mixture was concentrated again, and allowed to stand. The same iodonium salt as obtained in Example 1 above [the exemplified compound (I- 36)] was obtained (yield: 52%). The HPLC purity was 98.5%.

<Example 7>
The reaction was carried out in the same manner as in Example 5 except that picolinic acid was changed to 8-quinolinic acid, and the same iodonium salt [the above exemplified compound (I-36)] was obtained.
The yield was 7.20 g (55%), and the purity was 98.6%.
<Example 8>
6.62 g of octyloxyiodobenzene (iodoaryl compound) is dissolved in 20 ml of acetic acid and stirred. The temperature is maintained at 20 ° C., and 0.25 g of picolinic acid (a compound having an amino group and a carboxylic acid group in the molecule) is added thereto and stirred at room temperature for 10 minutes. The temperature was adjusted to 20 ° C., 6.90 g of mCPBA (3-chloroperoxybenzoic acid) was slowly added, stirred at 25 ° C. to 30 ° C. for 6 hours, allowed to stand at room temperature for 12 hours, and 30 ml of acetonitrile was added dropwise. Cool to ice so that the internal temperature is 5 ° C. or less, add 3.20 g of 1,3,5-trimethoxybenzene (aromatic compound), and dissolve 3.62 g of paratoluenesulfonic acid in 50 ml of acetonitrile. It was dripped. Thereafter, the mixture was stirred at 5 ° C. or lower for 2 hours, then poured into 500 ml of ice water, extracted with 500 ml of dichloromethane, and the aqueous layer was further extracted with 200 ml of dichloromethane. The organic layer is washed with an aqueous solution in which 75.6 g of sodium sulfite is dissolved in 500 ml of water, and the organic layer is further washed twice with 300 ml of water. The organic layer is concentrated until the amount of the solvent becomes 1/10, 100 ml of ethyl acetate is added, the mixture is concentrated again, and left to stand to give the same iodonium salt as in Example 1 [the exemplified compound (I-36)]. Obtained in 7.00 g (yield: 52%). The HPLC purity was 98.1%.

  Thus, it can be seen that the excellent effect of the present invention can be obtained even when a compound having an amino group and a carboxylic acid group in the molecule to be used or peracid is changed.

Claims (3)

A method for producing a diaryliodonium salt, comprising mixing a compound represented by the following general formula (I) or general formula (II), an iodoaryl compound and a peracid, and then adding an aromatic compound.

In general formula (I), R ¹ and R ² each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a hydrogen atom. R ¹ and R ² may be bonded to each other to form a ring. X represents a divalent linking group.
In the general formula (II), Y represents a 4- to 14-membered ring structure containing N, and the carboxylic acid group shown here is directly or directly on the carbon atom or nitrogen atom constituting the ring structure of Y. It is linked via any linking group. R ³ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a hydrogen atom. In the solvent containing the compound represented by the general formula (I) or the general formula (II), after reacting the iodoaryl compound with a peracid, an aromatic compound is added, and further an acid or a salt thereof is added. The method for producing a diaryl iodonium salt according to claim 1 . The production method according to claim 1 or 2, wherein the aromatic compound is a compound having an electron-donating substituent.