JP2009035526A - Production method of iodine compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for efficiently manufacturing an iodine compound in a high yield that is useful as a raw material of an electroconductive polymer or a raw material of functional coloring matter such as organic EL coloring matter or the like. <P>SOLUTION: An amino compound having a 2-amino-o-terphenylene skeleton, nitrite salts, an acid and an iodizing agent are caused to react, where the nitrite salts are added in the presence of the iodizing agent, to thereby provide the iodine compound having a 2-iodo-o-terphenylene skeleton with high selectivity in a high yield, while reducing the amount of a compound having a triphenylene skeleton as a by-product. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing an iodine compound useful as a raw material for a conductive polymer or a functional dye such as an organic EL dye.

  In recent years, functional materials such as conductive polymers and organic EL dyes have been actively developed. These functional materials include those having a polyphenylene structure in which phenyl groups are connected and those having a polyphenylene vinylene skeleton in which phenyl groups and vinyl groups are alternately polymerized, and it is also possible to use a doping agent such as an alkali metal. There is interest as a conductive polymer material. In addition, conjugated polymers having a structure in which phenyl groups are linked have been found in dyes used in organic EL, which have been actively studied in recent years. The construction of the polyphenylene skeleton usually employs the Woolman reaction in which aryl iodide is heated and coupled with copper powder. Since the structure of the conjugated polymer to be produced is also determined depending on the structure of the aryl iodide to be used, the method for obtaining the aryl iodide as a raw material is a very important step.

  Iodine compounds can be obtained by a synthesis method by halogen-iodine exchange reaction with a halogen compound such as a chlorine compound or a bromine compound, a synthesis method by addition reaction of iodine to a double bond, diazotization of an amino compound, potassium iodide, etc. Among them, a synthesis method of reacting with an iodinating agent is particularly suitable for diazotization of an amino compound and reaction with an iodinating agent such as potassium iodide, such as yield, operability, and regioselectivity. From the point of view, it is the most efficient method. The usual iodination method via diazotization involves reacting an amino compound with a nitrite such as sodium nitrite in an acidic aqueous solution, followed by a diazotization reaction and then reacting with an iodinating agent such as potassium iodide. Is implemented.

  On the other hand, an iodine compound having a 2-iodo-o-terphenylene skeleton can be given as one of iodine compounds useful as a raw material for conductive polymers and functional dyes such as organic EL dyes. The iodine compound is obtained by reacting the corresponding amine with sodium nitrite in an aqueous hydrochloric acid solution to diazotize it and treating with excess potassium iodide. The yield is 19%. It was very low (for example, refer nonpatent literature 1). As a cause of this, it has been confirmed that triphenylene having three phenyl groups bonded in the ortho position is generated as a by-product (hereinafter referred to as a cyclized product that is not iodinated and has an aromatic ring bonded thereto). Has been. This reaction is considered to proceed as shown by the following formula since a cyclized product is formed.

  As described above, when a large amount of cyclized product is produced, not only the yield is reduced, but also purification of the target iodine compound becomes difficult, so the above method has room for improvement. Such a problem has not been confirmed when 2-amino 1,1′-biphenyl, which is one less phenyl group than 2-iodo-o-terphenylene, is used as a raw material. %, The target 2-iodine-1,1′-biphenyl is obtained (for example, see Non-Patent Document 2).

  That is, the present situation is that a method for obtaining 2-iodo-o-terphenylene in high yield via diazotization has not been established.

Chem. Pharm. Bull. 28, 1980, pages 1468-1476. Tetrahedron, 60, 2004, pages 145-158

  As described above, a method for obtaining an iodine compound having a 2-iodo-o-terphenylene skeleton in a high yield has not been established. Further, in order to obtain the iodine compound in a high yield, it is necessary to reduce the amount of the compound having a triphenylene skeleton that is by-produced during the reaction. Therefore, an object of the present invention is to provide a method for efficiently producing an iodine compound useful as a raw material for a conductive polymer or a functional dye such as an organic EL dye in a high yield.

  The present inventors have intensively studied to solve the above problems. As a result, when reacting an amino compound having a 2-amino-o-terphenylene skeleton, a nitrite, an acid, and an iodinating agent, by adding the nitrite in the presence of an iodinating agent, The amount of the compound having a triphenylene skeleton, which is a product, is reduced, and an iodine compound having a 2-iodo-o-terphenylene skeleton is obtained with high selectivity and high yield, thereby completing the present invention. It was.

  That is, the present invention provides the following formula (1):

(In the formula, A, B, and C are each independently a group that forms an aromatic ring with two carbon atoms to which the group is bonded.)
By reacting an amino compound, a nitrite, an acid, and an iodinating agent represented by the following formula (2):

{In formula, A, B, and C are synonymous with said Formula (1). }
A method for producing an iodine compound, comprising adding a nitrite to a solution containing an amino compound, an acid, and an iodinating agent.

  In addition, according to the second aspect of the present invention, 1 to 5 nitrites are added to a solution containing 2 to 10 mol of an acid and 1 to 20 mol of an iodinating agent with respect to 1 mol of an amino compound represented by the formula (1). It is a manufacturing method of the iodine compound characterized by adding mol.

  Furthermore, a third aspect of the present invention is the method for producing an iodine compound according to the above invention, wherein after adding nitrites, an acid, an iodinating agent, and nitrites are further added.

  According to a fourth aspect of the present invention, in the third aspect of the present invention, the total amount of the acid used is more than 2 moles and 20 moles or less, and the total amount of the iodinating agent is 1 mole relative to 1 mole of the amino compound represented by formula (1) And 30 mol or less, and the total amount of nitrites is more than 1 mol and 10 mol or less.

  According to the production method of the present invention, the generation of a cyclized product to which an aromatic ring is bonded is reduced, the selectivity of the starting amino compound as the target iodine compound can be increased, and the purification of the iodine compound is facilitated. Become. Furthermore, according to the production method of the present invention, the reaction rate of the amino compound can be increased, and the yield of the iodine compound can be increased efficiently.

  Therefore, the production method of the present invention obtains iodine compounds that are useful as raw materials for conductive polymers and functional dyes such as organic EL dyes in high yield (high selectivity and high amino compound reaction rate). This is a very useful method in industrial practice.

In the production method of the present invention, when reacting an amino compound having a 2-amino-o-terphenylene skeleton, a nitrite, an acid, and an iodinating agent, the nitrite is added in the presence of the iodinating agent. By adding, the amount of the compound having a triphenylene skeleton as a by-product can be reduced, and an iodine compound having a 2-iodo-o-terphenylene skeleton can be obtained with high selectivity and high yield. Hereinafter, the reactants, reaction conditions, reaction procedures, products and the like used in the production method of the present invention will be described in detail.
The amino compound used in the method of the present invention is represented by the following formula (1).

(In the above formula, A, B and C are each independently a group which forms an aromatic ring with two carbon atoms to which the group is bonded.)
In the present invention, A, B, and C are divalent groups that form an aromatic ring together with two carbon atoms to which the group is bonded (hereinafter this aromatic ring is simply formed by A. , B may be an aromatic ring, or C may be an aromatic ring. Examples of the aromatic ring formed by these A, B, and C include benzene, naphthalene, anthracene, phenanthrene, and pyrene. Among these, benzene and naphthalene are particularly preferable from the viewpoint of the usefulness of the obtained iodine compound. Preferably there is.

  The production method of the present invention is a method in which an amino compound having a specific structure represented by the formula (1) is iodinated. That is, in the present invention, the bonding position of each of the aromatic rings formed by A, B, and C, the bonding position of the amino group in the aromatic ring formed by A are the positions shown in Formula (1), and C is The present invention is applied to an amino compound having a structure in which one carbon atom to be bonded is bonded to a hydrogen atom. Therefore, the aromatic ring formed by A, B, and C may have a substituent in order to obtain a more useful iodine compound. Amino compounds including those having this substituent are represented by the following formula (3).

(In the formula, A, B, and C are each independently a group that forms an aromatic ring with the carbon atom to which the group is bonded, and R ¹ , R ² , and R ³ are each independently an alkyl group, an alkoxy group, An aryl group, an allyl group, a vinyl group, a thienyl group, a furyl group, a fluorine atom, or a halogen atom such as a chlorine atom, which may be the same or different and may form a ring, and m, n and o are each independently an integer of 0 to 10.)
R ¹ , R ² and R ³ are each independently an alkyl group, an alkoxy group, an aryl group, an allyl group, a vinyl group, a thienyl group, a furyl group, a fluorine atom, a halogen atom of a chlorine atom, and are the same May be different from each other and may form a ring.

In the above formula ^(3), the alkyl group of R ^1, R 2, ^{R 3,} include alkyl groups having 1 to 12 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl Group, undecyl group, dodecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group and the like. Among these, in view of the usefulness of the obtained iodine compound, a methyl group, An ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a pentyl group, a hexyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group are preferable, and a methyl group and an ethyl group are particularly preferable. preferable.

  Moreover, as an alkoxy group, a C1-C12 alkoxy group is mentioned. Specifically, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, t-butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group , Nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group, methylenedioxy group, ethylenedioxy group, propylenedioxy group, benzyloxy, and the like. From the point of usefulness, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, pentyloxy group, hexyloxy group, methylenedioxy group, propylenedioxy group, benzyl Oxy groups are preferred, especially methoxy groups, ethoxy groups, and methylenedioxy groups Benzyloxy group is preferred.

  Examples of the aryl group include a phenyl group, a naphthyl group, an anthranyl group, a pyrenyl group, and a petacenyl group. Of these, a phenyl group, a naphthyl group, and an anthranyl group are preferable, and a phenyl group is particularly preferable from the viewpoint of the usefulness of the obtained iodine compound.

  M, n, and o in the formula (3) each independently represent an integer of 0 to 10, and any of the effects of the present invention can be sufficiently exerted. 5, particularly preferably 0 to 3. As a matter of course, when m, n, and o are 0, it indicates that there is no substituent.

  Specific examples of suitable compounds among the compounds represented by the formula (3) include the following, but are not limited thereto.

  As the nitrites used in the present invention, nitrites used in the diazotization reaction can be used without limitation, but sodium nitrite and potassium nitrite are used because they are easily available and have good reactivity. It is preferred to use. The nitrites can be used alone or as an aqueous solution, but are preferably used in an aqueous solution from the viewpoint of handling. An organic solvent that does not affect the reaction can be added to the aqueous solution.

  As the iodinating agent used in the present invention, an iodinating agent usually used for iodination of a diazo compound can be used without limitation, but since it is easily available and has good reactivity, iodine, lithium iodide, Examples thereof include sodium iodide and potassium iodide. The iodinating agent can be used alone or as an aqueous solution, but it is preferable to use it in an aqueous solution from the viewpoint of handling. An organic solvent that does not affect the reaction can also be added to the aqueous solution.

  The acid used in the present invention is not particularly limited, but it is relatively easy to obtain, is miscible with water, and the reaction proceeds efficiently, so that hydrogen chloride (hydrochloric acid), bromide is used. Hydrogen (hydrobromic acid) and sulfuric acid are preferred. The acid can be used alone or as an aqueous solution, but is preferably used in an aqueous solution from the viewpoint of handling. An organic solvent that does not affect the reaction can be added to the aqueous solution. In addition, although the usage-amount of this acid is explained in full detail below, in order to advance reaction, it is preferable to use the quantity which a reaction system will be on acidic conditions (pH is less than 7), and is represented by Formula (1). It is preferable to use 2 mol or more per 1 mol of the amino compound.

  Next, the order of addition of the reactants (amino compound, iodinating agent, acid, nitrites) used in the present invention and the amount added will be described.

  Usually, as shown in Non-Patent Documents 1 and 2, when an iodine compound is produced through diazotization using an amino compound as a raw material, the amino compound is reacted with nitrites under acidic conditions, The compound is converted to a diazo compound and then reacted with an iodinating agent.

  However, when the conventional order of addition described above is applied to the amino compound represented by the formula (1) used in the present invention, it is considered that the corresponding diazo compound is decomposed, resulting in a cyclization reaction, and triphenylene. A by-product having a skeleton (cyclized product) is produced in a large amount. This is a problem peculiar to the amino compound represented by the formula (1).

  In the present invention, by carrying out the reaction by adding nitrites in the presence of the amino compound, acid, and iodinating agent, it is possible to significantly reduce the by-product of the cyclized product. The selectivity of the iodine compound can be increased. By adding the reactants in this order, the iodine compound is generated faster than the cyclized product is by-produced, so it is considered that the selectivity of the iodine compound can be increased.

  In the present invention, the order of adding the amino compound, the acid, and the iodinating agent is not particularly limited, and these components may be added simultaneously or sequentially from a certain component. Among these, in order to efficiently produce an ammonium salt of an amino compound as an intermediate, it is preferable to add an amino compound, an acid, and an iodinating agent in this order. The present invention is characterized in that nitrites are added to a solution containing these amino compound, acid, and iodinating agent.

  In the present invention, considering the reaction rate, the selectivity of the iodine compound represented by the formula (2), etc., the reactant is 2 mol or more of acid and 1 mol or more of iodinating agent with respect to 1 mol of amino compound. It is preferable to add 1 mol or more of nitrites to the solution. The upper limit of the amount of acid, iodinating agent, and nitrites is not particularly limited, but the ease of purification of iodine compounds, high selectivity, and further, the iodine obtained is described in detail below. In order to increase the yield of the compound efficiently, it is preferable that the acid is 10 mol or less, the iodinating agent is 20 mol or less, and the nitrites are 5 mol or less with respect to 1 mol of the amino compound. It is preferable that the amount is 5 mol or less, the iodinating agent is 10 mol or less, and the nitrites are 2 mol or less. Even when such an amount of the reactant is used, the solution to which nitrites are added is preferably acidic.

  Further, in the present invention, by adding nitrites to a solution containing an amino compound, an acid, and an iodinating agent, the cyclized product is reduced and the ratio of becoming an iodine compound is increased (the selectivity is increased). In addition, the reaction rate of the amino compound can be increased by adding an acid, an iodinating agent, and nitrites. Hereinafter, a reaction including adding a nitrite to a solution containing an amino compound, an acid, and an iodinating agent is a first reaction. After the first reaction, an acid, an iodinating agent, and a nitrite are further added. In some cases, the reaction is performed by adding a kind to the second reaction. As described above, this first reaction is preferably performed under acidic conditions, and this second reaction is also preferably performed under acidic conditions. The acid, iodinating agent, and nitrites added in the second reaction can also be handled as an aqueous solution as described above.

  In the present invention, the reason why the reaction rate of the amino compound is increased by the second reaction is not clear, but is estimated as follows. That is, in the addition order of the reactants in the first reaction, it is considered that the iodinating agent is easily consumed by the acid and nitrite, and in the second reaction, the iodinating agent consumed in the second reaction, other acids, By adding nitrite, it is considered that the reaction rate of the amino compound can be made very high. Therefore, it is considered that by performing the second reaction after the first reaction, the remaining amino compound reacts again and the yield of the iodine compound can be increased. In this second reaction, the acid, iodinating agent, and nitrites can be added in several portions.

  Thus, when an acid, an iodinating agent, and nitrites are added to increase the reaction rate of the amino compound, the reactants before adding the acid, iodinating agent, and nitrites, Each reactant in one reaction is particularly preferably 1 to 5 mol of nitrite added to a solution containing 2 to 10 mol of acid and 1 to 20 mol of iodinating agent with respect to 1 mol of amino compound, In particular, it is preferable to add 1 to 2 mol of nitrites to a solution containing 2 to 5 mol of acid and 1 to 10 mol of iodinating agent. In the first reaction, by performing the reaction within the above range, the selectivity of the iodine compound can be efficiently increased with a small amount of the reactant. Then, after the first reaction is performed within the above range, the second reaction is performed, whereby the reaction rate of the amino compound can be increased while maintaining the high selectivity of the iodine compound. The rate can be made higher. In addition, by performing the first reaction within the above range, the order in which the acid, the iodinating agent, and nitrites are added when performing the second reaction is not limited as in the first reaction. The reason for this is not clear, but the iodinating agent is not completely consumed in the first reaction, and it is estimated that the iodinating agent remains in the reaction system. Yes. However, in order to further improve the reaction rate, the order of addition in the second reaction is preferably added in the order of acid, nitrite, and then iodinating agent.

  In the present invention, in the first reaction, the selectivity of the iodine compound is increased with as little reactant as possible. Further, in the second reaction, an acid, an iodinating agent, and nitrites are added, thereby The reaction rate can be further increased. Therefore, the amount of acid, iodinating agent, and nitrites used in the second reaction may be an amount that can sufficiently increase the reaction rate of the amino compound. In particular, considering the reaction rate, iodine compound yield, ease of purification, economics, etc., the first reaction is carried out in the above range, and the use of acids, iodinating agents, and nitrites in the second reaction The total amount of acid used is more than 2 mol and less than 20 mol, the total amount of iodinating agent is more than 1 mol and less than 30 mol, and the total amount of nitrites is 1 with respect to 1 mol of amino compound initially charged. It is preferable to adjust so that it may exceed 10 mol or less, and in particular, the total amount of acid used is 4 to 20 mol, the total amount of iodinating agent is 2 to 30 mol, and the total amount of nitrites is 2 to 10 mol. It is preferable to adjust so that it may become mol. The total amount is the total amount of the acid, iodinating agent, and nitrites used in the first reaction and the second reaction. Increasing the yield of iodine compounds while reducing the amount of acid, iodinating agent, and nitrites used by adjusting the amounts of acid, iodinating agent, and nitrites used in the second reaction to the above ranges be able to.

  The reaction of the present invention is carried out by mixing the above reactants (amino compound, iodinating agent, acid, nitrite) in a solution, but the reaction is carried out in a mixed solution of water and an organic solvent. It is preferable from the viewpoint of efficiency. The water here includes water in an aqueous solution of nitrites, water in an aqueous solution of an iodinating agent, and water in an aqueous solution of an acid. As the organic solvent to be used, an organic solvent that does not inhibit the reaction can be used. Specific examples include ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, nitriles such as acetonitrile, ethers such as diethyl ether, tetrahydrofuran and dioxane, esters such as methyl acetate and ethyl acetate, formic acid and acetic acid. Carboxylic acids can be mentioned. Of these, acetone, acetonitrile, and tetrahydrofuran are particularly preferable, and acetone and acetonitrile are particularly preferable because they are well mixed with water and the target iodine compound is obtained with high selectivity.

  In the present invention, when the reaction product is reacted in a mixed solution of water and an organic solvent, if the amount of water used is too much, the post-treatment becomes troublesome, and if too little, the progress of the reaction becomes slow. It is preferable that it is 1-100 mass parts with respect to 1 mass part of amino compounds to perform, especially 5-50 mass parts. Further, if the amount of the organic solvent used is too large, the post-treatment becomes troublesome, and if it is too small, the progress of the reaction slows, so that 1 to 100 parts by weight, particularly 5 to 50 parts per 1 part by weight of the amino compound to be used. It is preferable that it is a mass part. In addition, it is preferable to implement reaction with water and the amount of organic solvents of the said range for both said 1st reaction and 2nd reaction.

  In the present invention, if the temperature is too low, the reaction rate becomes extremely slow, and if it is too high, by-products are increased, so that the temperature is -30 to 50 ° C, particularly -20 to 30 ° C, It is preferable to carry out at −10 to 25 ° C. Both the first reaction and the second reaction are preferably carried out at this reaction temperature.

  The reaction time may be appropriately determined while confirming the degree of progress of the reaction according to other reaction conditions, but a sufficient yield of iodine compound can usually be obtained within 24 hours. When performing 1st reaction and 2nd reaction, the time which put both reaction together should just be the said range.

  The iodine compound thus obtained has a structure represented by the following formula (2).

{In formula, A, B, and C are synonymous with said Formula (1). }
Moreover, when an amino compound is shown by the said Formula (3), the iodine compound obtained has a structure shown by following formula (4).

{In the formula, A, B, C, R ¹ , R ² , R ³ , m, n, and o are as defined in the formula (3). }
The structure of the compound represented by the above formula (4) corresponds to the structure of the amino compound used as a raw material. Therefore, specific examples of suitable compounds include the following.

  The iodine compound obtained by such a method can be separated from the reaction solution by, for example, the following method. That is, an extraction solvent is added to the reaction liquid after completion of the reaction, and the aqueous layer is separated by liquid separation operation. Thereafter, a reducing agent such as an aqueous sodium thiosulfate solution is dropped to reduce iodine present in the organic layer. The organic layer is washed with water to neutral, and then concentrated under reduced pressure, whereby a crude iodine compound can be separated. The purity of the crude product thus obtained can be confirmed by high performance liquid chromatography (hereinafter referred to as HPLC) analysis, and usually has an HPLC purity of 60% or more (here HPLC purity refers to each of the solvents excluding the solvent). It is an area percentage where the total peak area value is 100, and the HPLC purity shown below also has the same meaning), and contains the target iodine compound.

  The crude product thus obtained is a known method such as adsorption treatment or crystallization (recrystallization) with an adsorbent such as silica gel, alumina, activated carbon, vacuum distillation, steam distillation, sublimation purification, column chromatography, Further refinement can be achieved by purification.

  The iodine compound obtained by the method of the present invention has a structure in which phenyl groups are connected, and exhibits excellent performance as a raw material for conductive polymers and functional dyes such as organic EL dyes. Can do. In addition, it has a skeleton in which phenyl groups are linked at the o-position, and the steric structure is significantly different from compounds linked at the p-position and m-position, which are relatively easy to synthesize. It has the potential to be fully demonstrated. For example, a polymer in which phenyl groups are linked at the o-position is expected to be able to form a column shape depending on the steric effect of the substituent, and is different from a polymer in which conjugated systems are simply linked on a plane. Expected to show performance.

  The iodine compound obtained by the method of the present invention can be widely used not only as a raw material for conductive polymers and organic EL dyes but also as a raw material for heat-resistant polymers and dyes for recording materials.

  Examples of the present invention will be described below, but the present invention is not limited thereto.

Example 1
In a 1000 ml four-necked flask, 9.80 g (0.040 mol) of 2-amino-o-terphenylene as an amino compound, 153 g of acetonitrile as a solvent, and 39.2 g of water were stirred, stirred at 15 ° C., and 6% 80.3 g (0.132 mol) of hydrochloric acid was added dropwise. After cooling the reaction solution to 2 ° C., 66.4 g (0.20 mol) of 50% aqueous potassium iodide solution was added dropwise. Thereto, 14.5 g (0.042 mol) of a 20% aqueous sodium nitrite solution was added dropwise at 5 ° C. or less (first reaction). As a result of HPLC analysis after stirring at 2 ° C. for 3 hours, the starting amino compound was 38%, the diazonium salt was 2%, the target iodine compound was 57%, and the by-product triphenylene (diazonium salt was denitrogenated). In the following, even in different skeletons, 3% of by-products generated in the same reaction were referred to as cyclized products). As an additional portion, 80.3 g (0.132 mol) of 6% hydrochloric acid was added, then 14.5 g (0.042 mol) of 20% aqueous sodium nitrite solution was added, and 66.4 g (50% aqueous potassium iodide solution was added). 0.20 mol) and stirring at 5 ° C. for 2 hours (second reaction), the starting amino compound disappeared, the diazonium salt was 0.6%, the target iodine compound was 86%, The product cyclized product was 5.4%, and other impurities of unknown structure were generated 8%. 160 g of toluene was added to the reaction solution as an extraction solvent, and a liquid separation operation was performed to separate the aqueous layer. The organic layer (toluene layer) was washed twice with 320 g of 10% aqueous sodium thiosulfate solution and four times with 160 g of 20% brine, neutralized to pH, and concentrated under reduced pressure to obtain 12 g of orange oil. . The obtained orange oil was purified by silica gel column chromatography using chloroform as a developing solvent, and converted into 2-iodo-o-terphenylene as 11.1 g of a white solid (yield: 78%, HPLC purity). : 99%). Analysis value is
HPLC-mass spectrum (APCI ⁺ ): m / z 356 (M ⁺ )
Elemental _analysis: C _{18 H} 13 _{I 1} Calculated: C; 60.69, H; 3.68
Found: C; 60.84, H; 3.79
Met.
Example 2
In Example 1, when adding the reactant, the same operation was carried out except that 20% sodium nitrite, 6% hydrochloric acid and 50% potassium iodide were used in this order. After purification by column chromatography, 10.9 g of a white solid (yield: 77%, HPLC purity: 99%) was obtained. The mass spectrum of the obtained white solid was the same as in Example 1.

Example 3
The same operation as in Example 1 was carried out except that the solvent was changed to acetone. After purification by column chromatography, 10.6 g of a white solid (yield: 74%, HPLC purity: 99%) was obtained. The mass spectrum of the obtained white solid was the same as in Example 1.

Example 4
In a 2000 ml four-necked flask, 11.8 g (0.040 mol) of 2-amino-1- (2-biphenyl) naphthalene as an amino compound, 185 g of acetonitrile and 47.2 g of water as a solvent, and stirred at 15 ° C. Thereafter, 80.3 g (0.132 mol) of 6% hydrochloric acid was added dropwise. After cooling the reaction solution to 2 ° C., 66.4 g (0.20 mol) of 50% aqueous potassium iodide solution was added dropwise. Thereto, 14.5 g (0.042 mol) of a 20% aqueous sodium nitrite solution was added dropwise at 5 ° C. or lower. After stirring at 2 ° C for 3 hours, HPLC analysis revealed that the starting amino compound was 41%, the diazonium salt was 1%, the target iodine compound was 56%, and the cyclized product by-product was 2%. Was. As an additional portion, 80.3 g (0.132 mol) of 6% hydrochloric acid was added, then 14.5 g (0.042 mol) of 20% aqueous sodium nitrite solution was added, and 66.4 g (50% aqueous potassium iodide solution was added). 0.20 mol) and stirring at 5 ° C. for 2 hours, the starting amino compound disappeared, the diazonium salt was 0.2%, the target iodine compound was 87%, and the ring was a by-product. 6.2% of chemicals and 6.6% of other impurities with unknown structure were produced. To the reaction solution was added 185 g of toluene as an extraction solvent, and a liquid separation operation was performed to separate the aqueous layer. The organic layer (toluene layer) was washed twice with 320 g of 10% aqueous sodium thiosulfate solution and four times with 160 g of 20% brine, neutralized to pH, and concentrated under reduced pressure to obtain 13 g of orange oil. . The obtained orange oil was purified by silica gel column chromatography using chloroform as a developing solvent to obtain 10.5 g of a white solid (yield: 65) as 2-iodo-1- (2-biphenyl) naphthalene. %, HPLC purity 98%). Analysis value is
HPLC-mass spectrum (APCI ⁺ ): m / z 406 (M ⁺ )
Elemental analysis value: As C ₂₂ H ₁₅ I ₁ Calculation value: C; 65.04, H; 3.72
Found: C; 65.41, H; 3.88
Met.

Example 5
In a 2000 ml four-necked flask, 17.3 g (0.040 mol) of 2-amino-4-benzyloxy-6-methoxy-1- (2-biphenyl) naphthalene as an amino compound, 300 g of acetonitrile as a solvent, and water were added. After adding 70 g and stirring at 15 ° C., 80.3 g (0.132 mol) of 6% hydrochloric acid was added dropwise. After cooling the reaction solution to 2 ° C., 66.4 g (0.20 mol) of 50% aqueous potassium iodide solution was added dropwise. Thereto, 14.5 g (0.042 mol) of a 20% aqueous sodium nitrite solution was added dropwise at 5 ° C. or lower. After stirring for 3 hours at 2 ° C., HPLC analysis revealed that the starting amino compound was 45%, the diazonium salt was 2%, the target iodine compound was 47%, and the by-product cyclized product was 6%. Was. As an additional portion, 80.3 g (0.132 mol) of 6% hydrochloric acid was added, then 14.5 g (0.042 mol) of 20% aqueous sodium nitrite solution was added, and 66.4 g (50% aqueous potassium iodide solution was added). 0.20 mol) and stirring at 5 ° C. for 2 hours, the starting amino compound disappeared, the diazonium salt was 0.5%, the target iodine compound was 86%, and the ring was a by-product. 8.5% of chemicals and 5% of other impurities with unknown structure were produced. 300 g of toluene was added to the reaction solution as an extraction solvent, and a liquid separation operation was performed to separate the aqueous layer. The organic layer (toluene layer) was washed 3 times with 320 g of 10% aqueous sodium thiosulfate solution and 4 times with 200 g of 20% brine, neutralized to pH, and concentrated under reduced pressure to obtain 20 g of orange oil. . The obtained orange oil was purified by silica gel column chromatography using chloroform as a developing solvent to obtain 2-iodo-4-benzyloxy-6-methoxy-1- (2-biphenyl) naphthalene as 16. 6 g of a white solid (yield: 77%, HPLC purity 98%) was obtained. Analysis value is
HPLC-mass spectrum (APCI ^<+> ): m / z 542 (M ^<+> )
¹ H-NMR spectrum (in _{CDCl 3): δ3.9ppm (s,} 3H, CH 3 of _{OCH 3), δ5.2ppm (m,} 2H, OCH 2 Ph of _CH 2), _δ6.9~7.5ppm ( m, 18H, H of aryl moiety)
Met.

Examples 6-7
In Example 5, the same operation was performed except that the amounts of 6% hydrochloric acid, 20% sodium nitrite aqueous solution and 50% potassium iodide aqueous solution were changed to the amounts shown in Table 1. The results are shown in Table 1. In addition, the usage-amount in Table 1 is the quantity with respect to the amino compound used as a raw material.

Example 8
In a 2000 ml four-necked flask, 18.5 g (0.040 mol) of 2-amino-4-benzyloxy-6,7-dimethoxy-1- (2-biphenyl) naphthalene as an amino compound and 480 g of acetonitrile as a solvent, 74 g of water was added and stirred at 15 ° C., and then 80.3 g (0.132 mol) of 6% hydrochloric acid was added dropwise. After cooling the reaction solution to 2 ° C., 66.4 g (0.20 mol) of 50% aqueous potassium iodide solution was added dropwise. Thereto, 14.5 g (0.042 mol) of a 20% aqueous sodium nitrite solution was added dropwise at 5 ° C. or lower. After stirring at 2 ° C. for 3 hours, HPLC analysis revealed 48% of the starting amino compound, 2% of the diazonium salt, 48% of the target iodine compound, and 2% of the cyclized product as a by-product. Was. As an additional portion, 80.3 g (0.132 mol) of 6% hydrochloric acid was added, then 14.5 g (0.042 mol) of 20% aqueous sodium nitrite solution was added, and 66.4 g (50% aqueous potassium iodide solution was added). 0.20 mol) and stirring at 5 ° C. for 2 hours, the starting amino compound disappeared, the diazonium salt was 3.2%, the target iodine compound was 85%, and the ring as a by-product. 4.7% of chemicals and 7.1% of impurities with unknown structure were produced. Furthermore, after adding 80.3 g (0.132 mol) of 6% hydrochloric acid, 14.5 g (0.042 mol) of 20% sodium nitrite aqueous solution was added, and 50% potassium iodide aqueous solution was added 66. When 4 g (0.20 mol) was added and stirred at 5 ° C. for 2 hours, the diazonium salt was 0.3%, the target iodine compound was 87%, the by-product cyclized product was 4.5%, In addition, 8.2% of impurities with unknown structure were generated. To the reaction solution, 480 g of toluene was added as an extraction solvent, and a liquid separation operation was performed to separate the aqueous layer. The organic layer (toluene layer) was washed 3 times with 320 g of 10% aqueous sodium thiosulfate solution and 5 times with 300 g of 20% brine, neutralized to pH, and concentrated under reduced pressure to obtain 19 g of orange oil. . The obtained orange oil was purified by silica gel column chromatography using chloroform as a developing solvent to give 2-iodo-4-benzyloxy-6,7-dimethoxy-1- (2-biphenyl) naphthalene. 17.1 g of a white solid (yield: 75%, HPLC purity 98%) was obtained. Analysis value is
HPLC-mass spectrum (APCI ⁺ ): m / z 572 (M ⁺ )
¹ H-NMR spectrum (during _{CDCl 3): δ3.6ppm (s,} 3H, CH 3 of _{OCH 3), δ3.8ppm (s,} 3H, CH 3 of _{OCH 3), δ5.3ppm (m,} 2H, OCH _CH 2) a _{2 Ph, δ6.9~7.5ppm (m, 17H} , aryl sites H)
Met.

Comparative Example 1
In a 2000 ml four-necked flask, 17.3 g (0.040 mol) of 2-amino-4-benzyloxy-6-methoxy-1- (2-biphenyl) naphthalene as an amino compound, 300 g of acetonitrile as a solvent, and water were added. After adding 70 g and stirring at 15 ° C., 80.3 g (0.132 mol) of 6% hydrochloric acid was added dropwise. After cooling the reaction solution to 2 ° C., 14.5 g (0.042 mol) of 20% aqueous sodium nitrite solution was stirred at 2 ° C. for 30 minutes, and 66.4 g (0.20 mol) of 50% aqueous potassium iodide solution was added dropwise. As a result of performing HPLC analysis after stirring at 2 ° C. for 3 hours, the starting amino compound disappeared, the diazonium salt was 3%, the target iodine compound was 47%, and the cyclized product as a byproduct was 44%. %, And other impurities of unknown structure were generated at 6%. 300 g of toluene was added to the reaction solution as an extraction solvent, and a liquid separation operation was performed to separate the aqueous layer. The organic layer (toluene layer) was washed twice with 320 g of 10% aqueous sodium thiosulfate solution and four times with 200 g of 20% brine, neutralized to pH, and concentrated under reduced pressure to obtain 20 g of orange oil. . The obtained orange oil was purified by silica gel column chromatography using chloroform as a developing solvent to give 2-iodo-4-benzyloxy-6-methoxy-1- (2-biphenyl) naphthalene. 6 g of a white solid (yield: 26%, HPLC purity 85%) was obtained. The diazo compound was decomposed and a large amount of cyclized product was formed as a by-product, so it seems that the yield decreased.

Comparative Example 2
The same operation as in Comparative Example 1 was performed except that the reaction was performed at -15 ° C. After column chromatography purification, 8.2 g of white solid (yield 38%, HPLC purity 89%) was obtained. In order to suppress the decomposition of the diazo compound, the temperature was lowered, but a great effect was not obtained.

Claims (4)

Following formula (1)

(In the formula, A, B, and C are each independently a group that forms an aromatic ring with two carbon atoms to which the group is bonded.)
By reacting an amino compound, a nitrite, an acid, and an iodinating agent represented by the following formula (2):

{In formula, A, B, and C are synonymous with said Formula (1). }
A method for producing an iodine compound, comprising adding a nitrite to a solution containing an amino compound, an acid, and an iodinating agent.   The nitrite is added in an amount of 1 to 5 mol to a solution containing 2 to 10 mol of an acid and 1 to 20 mol of an iodinating agent with respect to 1 mol of an amino compound represented by the formula (1). 2. A method for producing an iodine compound according to 1.   The method for producing an iodine compound according to claim 1 or 2, further comprising adding an acid, an iodinating agent, and nitrites after adding the nitrites.   The total amount of acid used is more than 2 mol and less than 20 mol, the total amount of iodinating agent is more than 1 mol and less than 30 mol, and the total amount of nitrites is 1 mol of the amino compound represented by formula (1). It is more than 1 mol and 10 mol or less, The manufacturing method of the iodine compound of Claim 3 characterized by the above-mentioned.