JP5797539B2 - Method for producing three-coordinate hypervalent iodine compound - Google Patents

Description

  The present invention relates to a method for producing a tri-coordinate hypervalent iodine compound, and more particularly to a tri-coordinate supervalent iodine compound that is excellent in production safety and economy, and that can obtain a tri-coordinate hypervalent iodine compound in a high yield. The present invention relates to a method for producing a valent iodine compound.

  Since hypervalent iodine compounds are less toxic than heavy metal oxidants, they are expected to expand their use as clean and environmentally friendly oxidants instead of heavy metal oxidants. Tri-coordinate hypervalent iodine compounds have a trivalent oxidation state of iodine and generally have the general formula (3)

(In the formula (3), A ′ is an aromatic group which may contain a substituent, a chain aliphatic group which may contain a substituent, a cyclic aliphatic group which may contain a substituent, A non-aromatic heterocyclic group which may contain a substituent, or a group which is a combination thereof, and the ligand L represents a group such as an acyloxy group or an aryloxy group. It is a valence iodine compound.

  As a general method for producing a tricoordinate hypervalent iodine compound, there is a one-step reaction in which an organic peroxide is reacted with an organic iodine compound. For example, regarding a method for producing (diacetoxyiodo) aryls, A method of causing peracetic acid to act on iodobenzene as shown in the following reaction formula (4) (for example, see Non-patent Document 1) has been reported. As an improved method, there is a method in which an organic peroxide is produced from an organic or inorganic peroxide in a reaction system, and this is reacted with an organic iodine compound. For example, as shown in the following reaction formula (5) , Sodium perborate tetrahydrate (for example, see Non-Patent Document 2), sodium periodate (for example, Non-Patent Document 3), sodium percarbonate (SPC) (for example, non- Patent Document 4), m-chloroperbenzoic acid (mCPBA) (for example, see Non-Patent Document 5), potassium persulfate (for example, see Non-Patent Document 6), urea peroxide (UHP) (for example, Non-Patent Document) 7) and the like, and a method for producing (diacetoxyiodo) aryls by the action of an oxidizing agent is reported.

（式（５）中、Arは置換基を含んでいてもよい芳香族基を示す。）

(In the formula (5), Ar represents an aromatic group which may contain a substituent.)

  However, any of these production methods uses an organic peroxide such as peracetic acid, or is generated in a reaction system and reacted with an organic iodine compound. Organic peroxides have a particularly high explosion risk and are difficult to handle and transport. In general, organic peroxide is an expensive reagent. For this reason, a cheaper and safer method is expected as a method for producing a tricoordinate hypervalent compound.

  On the other hand, as another method for producing a tricoordinate hypervalent iodine compound, a method using a chlorine-based oxidizing agent that is cheaper and easier to handle than an organic peroxide is known. In this production method, dichloroiodo compounds are produced and isolated by reaction of iodobenzene and chlorine (see, for example, Non-Patent Document 8) as shown in the following reaction formula (6). Subsequently, a tricoordinate hypervalent iodine compound is produced by a ligand exchange reaction by reaction with a salt as shown in the following reaction formula (7). Specifically, a method in which mercury acetate is allowed to act (for example, see Non-Patent Document 9), a method in which mercury oxide is allowed to act on (dichloroiodo) aryls in acetic acid (for example, see Non-Patent Document 10), (dichloroiodo) ) A method in which lead acetate is allowed to act on aryls in acetic acid (for example, see Non-Patent Document 11) has been reported.

(In the formula (7), Ar represents an aromatic group which may contain a substituent.)

  However, dichloroiodo compounds as intermediates are known to decompose during storage (see, for example, Non-Patent Document 8), and it is dangerous to store for a long time. The hypervalent iodine compound production method is a two-stage reaction in which a raw material dichloroiodo compound used for a ligand exchange reaction is separately prepared and isolated.

J. G. Sharefkin, H. Saltzman, "IODOSOBENZENE DIACETATE", Organic Syntheses, Coll. Vol. 5, 660 (1973). A. McKillop, D. Kemp, "Further Functional Group Oxidations Using Sodium Perborate", Tetrahedron, 45, 3299 (1989). P. Kazmierczak, L. Skulski, L. Kraszkiewicz, "Syntheses of (Diacetoxyiodo) arenes or Iodylarenes from Iodoarenes, with Sodium Periodate as the Oxidant", Molecules, 6, 881 (2001). A. Zielinska, L. Skulski, "Easy Preparation of (Diacetoxyiodo) arenes from Iodoarenes with Sodium Percarbonate as the Oxidant", Molecules, 7, 806 (2002). H. Tohma, A. Maruyama, A. Maeda, T. Maegawa, T. Dohi, M. Shiro, T. Morita, Y. Kita, "Preparation and Reactivity of 1,3,5,7-Tetrakis [4- ( diacetoxyiodo) phenyl] adamantane, a Recyclable Hypervalent Iodine (III) Reagent ", Angewandte Chemie International Edition, 43, 3595 (2004). M.-D. Hossain, T. Kitamura, "Alternative, Easy Preparation of (Diacetoxyiodo) arenes from Iodoarenes Using Potassium Peroxodisulfate as the Oxidant", Synthesis, 1932 (2005). T.-K. Page, T. Wirth, "Simple Direct Synthesis of [Bis (trifluoroacetoxy) iodo] arenes", Synthesis, 3153 (2006). H. J. Lucas and E. R. Kennedy, "IODOBENZENE DICHLORIDE", Organic Syntheses, Coll. Vol. 3, 482 (1955). M. Ochiai, Y. Takaoka, Y. Masaki, "Synthesis of Chiral Hypervalent Organoiodinanes, Iodo (III) binaphthyls, and Evidence for Pseudorotation on Iodine", Journal of the American Chemical Society, 112, 5677 (1990). R. T. Taylor, T. A. Stevenson, "Mercury Mediated Synthesis of Bis (carboxy) iodobenzenes", Tetrahedron Letters, 29, 2033 (1988). R. Neu, "Zur Kenntnis der Aryljodidchloride (I. Mitteil.)", Berichte der Deutschen Chemischen Gesellschaft, 72B, 1505 (1939).

  In the above-described method for producing a tricoordinate hypervalent iodine compound, in the one-step method using an organic peroxide, the danger and the economic efficiency of the organic peroxide are problems, and dichloroiodo compounds In the method in which the ligand exchange reaction is carried out after the production and isolation of the compound, problems are found in the instability of dichloroiodo compounds and the efficiency of being a two-step reaction. Thus, a safe, inexpensive and efficient method for producing a tricoordinate hypervalent iodine compound is desired.

  Therefore, the present invention has been devised in view of the above-described problems, and its object is to produce a non-tricoordinate hypervalent iodine compound from an I-valent organic iodine compound. To provide a method for producing a tricoordinate hypervalent iodine compound in an efficient one-pot process using an inexpensive chlorine-based oxidizing agent without isolating dichloroiodo compounds as an intermediate in an aqueous solvent. is there.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor found that any one of an organic anion, a metal cation, an optionally substituted ammonium cation, or an optionally substituted polyammonium cation. In the presence of an organic salt consisting of a cation of general formula (1)

  (In the formula (1), A is an aromatic group which may contain a substituent, a chain aliphatic group which may contain a substituent, a cyclic aliphatic group which may contain a substituent, A non-aromatic heterocyclic group that may contain a group, or a group that is a combination thereof, and n is an integer of 1 or more) and a chlorine-based oxidizing agent. By general formula (2)

(In the formula (2), A represents an aromatic group which may contain a substituent, a chain aliphatic group which may contain a substituent, a cyclic aliphatic group which may contain a substituent, a substituted group. A non-aromatic heterocyclic group which may contain a group, or a group which is a combination thereof, R ¹ and R ² may be the same or different, or may be bonded to each other; ¹ and R ² may each contain an acyl group which may contain a substituent, an aromatic group which may contain a substituent, a chain aliphatic group which may contain a substituent, or a substituent. A good cyclic aliphatic group, a non-aromatic heterocyclic group which may contain a substituent, or a combination thereof, and n is an integer of 1 or more.) It was newly found out that a monovalent iodine compound is produced in one pot.

  That is, in the present invention, in order to produce the tricoordinate hypervalent iodine compound represented by the general formula (2) in a non-aqueous solvent, the chlorine of the organic iodine compound represented by the general formula (1) Coordination by oxidation reaction by a system oxidant and coexistence of an organic salt comprising an organic anion and any one of a metal cation, an optionally substituted ammonium cation, or an optionally substituted polyammonium cation The whole process of the child exchange reaction is performed in one pot.

The process according to claim 1 three-coordinate hypervalent iodine compounds described, and anions of carboxylic acids, metal cations, under carboxylate coexisting consisting of any one of the cations of an ammonium cation which may be substituted, In the non-aqueous solvent, the general formula (1)

  (In the formula (1), A is an aromatic group which may contain a substituent, a chain aliphatic group which may contain a substituent, a cyclic aliphatic group which may contain a substituent, A non-aromatic heterocyclic group which may contain a group, or a group which is a combination thereof, and n is an integer of 1 or more.) Formula (2)

(In the formula (2), A represents an aromatic group which may contain a substituent, a chain aliphatic group which may contain a substituent, a cyclic aliphatic group which may contain a substituent, a substituted group. A non-aromatic heterocyclic group that may contain a group, or a group that is a combination thereof, R ¹ and R ² may be the same or different from each other, or may be bonded to each other; R ¹ and R ² each contain an acyl group which may contain a substituent, an aromatic group which may contain a substituent, a chain aliphatic group which may contain a substituent, or a substituent. A cyclic aliphatic group which may be substituted, a non-aromatic heterocyclic group which may contain a substituent, or a combination thereof, wherein n is an integer of 1 or more. The valent iodine compound is produced in one pot.

The method for producing a tricoordinate hypervalent iodine compound according to claim 2 is the method according to claim ¹ , wherein R ¹ and R ^{2 in} formula (2) are the same or different from each other, or R ¹ and R ² may be bonded to each other, and each of R ¹ and R ² is an acyl group which may contain a substituent.

In the method for producing a tricoordinate hypervalent iodine compound according to claim 3 , in the invention according to claim 1 or 2 , A in formula (1) and formula (2) may contain a substituent. It is an aromatic group.

The method for producing a tricoordinate hypervalent iodine compound according to claim 4 is the method according to claim 1 or 2 , wherein A may contain a substituent in formulas (1) and (2). A saturated chain aliphatic group or an unsaturated cyclic aliphatic group which may contain a substituent.

  According to the present invention, the oxidation process of the organic iodine compound by the chlorine-based oxidant and the ligand exchange reaction process of the dichloroiodo compound by the organic salt are performed in one pot without separately performing.

  Therefore, the process of isolating and purifying the dichloroiodo compound can be omitted, and the yield can be improved and the production efficiency can be improved as compared with the reaction performed in two steps. In addition, it is known that dichloroiodo compounds decompose during storage (see, for example, Non-Patent Document 8), but in the present invention in which dichloroiodo compounds are not isolated, purified, or stored, this decomposition is performed. Loss can be avoided.

  Furthermore, in the ligand exchange reaction step in the two-step reaction in which the dichloroiodo compound is once isolated, since the dichloroiodo compound is present in the solution at a high concentration, the regeneration of the organic iodine compound by the decomposition of the dichloroiodo compound is easy. Occurs and is dangerous and reduces the yield and purity of the final product. On the other hand, in the method for producing a tricoordinate hypervalent iodine compound according to the present invention, when an oxidation reaction with a chlorine-based oxidant proceeds, an organic salt that is a ligand exchange reaction agent already exists. The dichloroiodo compound is not present at a high concentration in the reaction solution, and the tricoordinate hypervalent iodine compound as the final product is produced. Even if the decomposition reaction of the dichloroiodide compound in the solution proceeds, the present invention is a one-pot reaction, and the oxidation reaction with the chlorine-based oxidant is simultaneously performed. Therefore, the organic iodine compound as the decomposition product is oxidized again. It undergoes a reaction and is finally converted to a tricoordinate hypervalent iodine compound. Therefore, in the method for producing a tricoordinate hypervalent iodine compound according to the present invention characterized by a one-pot process, the yield and purity of the tricoordinate hypervalent iodine compound can be improved. In addition, it is possible to construct a safe process in which a degradable dichloroiodo compound is not present at a high concentration.

  In addition, according to the present invention, a chlorine-based oxidant composed of chlorine, a hypochlorous acid-based oxidant, or the like is used as an oxidant. Conventionally, organic peroxide-based oxidizing agents such as peracetic acid used in a method for producing a tri-coordinate hypervalent iodine compound in one pot are known as substances having a particularly high explosion risk. Not only use but also transport and storage must be done with particular care. Also, organic peroxide oxidants are expensive and difficult to obtain. On the other hand, the chlorinated oxidant used in the present invention is a very inexpensive oxidant. In addition, since it is widely used industrially, it can be easily obtained, and there are many knowledges on safe use, and there is an advantage that the use environment of a chlorine-based oxidizing agent can be easily constructed.

  Furthermore, although a non-aqueous solvent is used in the present invention, the final product is selected by selecting a combination of a non-aqueous solvent and a cation constituting an organic salt and lowering the solubility of a chloride salt as a by-product of the reaction. It becomes possible to improve the yield and purity of the product.

It is a typical simple flowchart in the manufacturing method of the tricoordinate hypervalent iodine compound to which this invention is applied.

  Hereinafter, as an embodiment of the present invention, a method for producing a tricoordinate hypervalent iodine compound will be described in detail.

  In the method for producing a tricoordinate hypervalent iodine compound to which the present invention is applied, any one of an organic anion and a metal cation, an optionally substituted ammonium cation, or an optionally substituted polyammonium cation As a starting material in a non-aqueous solvent in the presence of an organic salt consisting of

  (In the formula (1), A is an aromatic group which may contain a substituent, a chain aliphatic group which may contain a substituent, a cyclic aliphatic group which may contain a substituent, A non-aromatic heterocyclic group which may contain a group, or a group which is a combination thereof, and n is an integer of 1 or more), and an organic iodine compound represented by the general formula (2)

(In the formula (2), A represents an aromatic group which may contain a substituent, a chain aliphatic group which may contain a substituent, a cyclic aliphatic group which may contain a substituent, a substituted group. A non-aromatic heterocyclic group which may contain a group, or a group which is a combination thereof, R ¹ and R ² may be the same or different, or may be bonded to each other; ¹ and R ² may each contain an acyl group which may contain a substituent, an aromatic group which may contain a substituent, a chain aliphatic group which may contain a substituent, or a substituent. A good cyclic aliphatic group, a non-aromatic heterocyclic group which may contain a substituent, or a combination thereof, and n is an integer of 1 or more.) A method for producing a monovalent iodine compound is provided.

  FIG. 1 is a typical simplified flow chart in a method for producing a tricoordinate hypervalent iodine compound to which the present invention is applied.

In the present invention, as shown in FIG. 1, in S11, the organic iodine compound is dissolved in a non-aqueous solvent, and an organic anion, a metal cation, an optionally substituted ammonium cation, or an optionally substituted polyammonium. An organic salt composed of any one of the cations is mixed, and an oxidation reaction and a ligand substitution reaction are performed by adding a chlorine-based oxidizing agent in S12. In the subsequent S13, ripening may be performed, and as a result, the tricoordinate hypervalent iodine compound as the final product is produced in one pot. In addition, the addition order of each reagent is not limited to the order shown above and the order shown in FIG. Further, the chlorine-based oxidant may be added or generated in the reaction system using another oxidant or the like. The organic anion in the organic salt is the ligand —OR ¹ , —OR ² on iodine in the tricoordinate hypervalent iodine compound of the final product represented by the general formula (2).

  In order to produce this tricoordinate hypervalent iodine compound in the conventional method, a high-risk and expensive organic peroxide-based oxidant is used, or unstable dichloroiodine from the organic iodine compound once. Two-step reactions have been used in which compounds are prepared and isolated followed by a ligand exchange reaction with an organic salt. However, an inexpensive and safe method for producing a tricoordinate hypervalent iodine compound has not yet been achieved.

（式（８）中、Aは置換基を含んでいてもよい芳香族基、置換基を含んでいてもよい鎖式脂肪族基、置換基を含んでいてもよい環式脂肪族基、置換基を含んでいてもよい非芳香族複素環基、又はこれらの組合せである基であり、nは1以上の整数である。）で示される不安定なジクロロヨード化合物を単離することなく、しかも爆発危険性を有し高価な有機過酸化物系酸化剤ではなく、安価で且つ取扱いに関する知見の多い塩素系酸化剤を使用した三配位超原子価ヨウ素化合物の製造法を提供するものである。本発明では、前述の有機塩を共存させることで、塩素系酸化剤による酸化反応と同時に配位子交換反応が進行し、最終生成物である三配位超原子価ヨウ素化合物が生成する、いわゆるワンポットによる製造方法を特徴としている。 Therefore, in the present invention, the general formula (8)

(In the formula (8), A represents an aromatic group which may contain a substituent, a chain aliphatic group which may contain a substituent, a cyclic aliphatic group which may contain a substituent, a substituted group. A non-aromatic heterocyclic group which may contain a group, or a group which is a combination thereof, and n is an integer of 1 or more.) In addition, it provides a method for producing a tricoordinate hypervalent iodine compound using a chlorine-based oxidant that is not an expensive organic peroxide-based oxidant and is inexpensive and has a lot of knowledge about handling. is there. In the present invention, by the coexistence of the organic salt described above, the ligand exchange reaction proceeds simultaneously with the oxidation reaction by the chlorine-based oxidant, and the so-called tricoordinate hypervalent iodine compound is generated, which is the so-called final product. It features a one-pot manufacturing method.

  Hereinafter, the raw materials, additives, and reaction conditions used in the method for producing a tricoordinate hypervalent iodine compound to which the present invention is applied will be described in detail.

  General formula (1)

  (In the formula (1), A is an aromatic group which may contain a substituent, a chain aliphatic group which may contain a substituent, a cyclic aliphatic group which may contain a substituent, A non-aromatic heterocyclic group that may contain a group, or a group that is a combination thereof, and n is an integer of 1 or more.) Aromatic compound which may contain, a chain aliphatic compound which may contain a substituent, a cyclic aliphatic compound which may contain a substituent, a non-aromatic heterocyclic ring which may contain a substituent In a compound selected from the group consisting of a compound or a compound formed by combining these, one or more hydrogen atoms are substituted with iodine atoms.

  More specifically, the aromatic compound in the organic iodine compound represented by the general formula (1) is, for example, benzene, biphenyl, terphenyl, naphthalene, binaphthyl, azulene, anthracene, phenanthrene, tetracene, chrysene, helicene, fullerene. , Furan, thiophene, pyrrole, pyrazole, imidazole, isoxazole, thiazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, benzofuran, indole, thianaphthene, benzimidazole, benzoxazole, benzothiazole, benzotriazole, purine, quinoline, Examples thereof include isoquinoline, quinoxaline, dibenzothiophene, acridine, phenanthroline, carbazole, thianthrene, phenoxathiin and the like.

  Examples of the chain aliphatic compound in the organic iodine compound represented by the general formula (1) include methane, ethane, ethene, ethyne, propane, propene, propyne, butane, butene, butyne, butadiene, butadiyne, pentane, pentene, Examples include pentyne, pentadiene, pentadiyne, hexane, hexene, hexyne, hexadiene, hexadiyne, hexatriene, hexatriin and the like.

  Examples of the cycloaliphatic compound in the organic iodine compound represented by the general formula (1) include cyclopropane, cyclobutane, cyclopentane, cyclohexane, adamantane, norbornane, norbornene, and the like.

  Examples of the non-aromatic heterocyclic compound in the organic iodine compound represented by the general formula (1) include pyrrolidine, pyrroline, imidazolidine, imidazoline, pyrazolidine, pyrazoline, piperidine, piperazine, tetrahydrofuran, pyran, morpholine and the like.

  In the organic iodine compound represented by the general formula (1), an aromatic compound which may contain a substituent, a chain aliphatic compound which may contain a substituent, and a ring which may contain a substituent Examples of the compound formed by combining a formula aliphatic compound or a non-aromatic heterocyclic compound which may contain a substituent include, for example, fluorene, chroman, isochroman, xanthene, indoline, isoindoline, dihydroanthracene, thioxanthene, imino And dibenzyl.

  Furthermore, in the organic iodine compound represented by the general formula (1), the substituent that the aromatic compound, the chain aliphatic compound, the cyclic aliphatic compound, and the non-aromatic heterocyclic compound may include, for example, Alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, cycloalkynyl group, aryl group, heteroaryl group, heterocyclyl group, nitrile group, formyl group, acyl group, alkoxycarbonyl group, carboxyl group, amino group, Examples thereof include an alkylamino group, a nitro group, a hydroxyl group, an alkoxy group, an aryloxy group, an acyloxy group, a halogen group, and a sulfone group.

  The chlorine-based oxidant is, for example, chlorine or a hypochlorous acid-based oxidant. Hypochlorous acid oxidizing agents include sodium hypochlorite, calcium hypochlorite (bleaching powder), and the like. This chlorinated oxidant has a track record of being widely used industrially and has the advantage of being inexpensive.

  Specifically, the organic anion is an aromatic compound which may contain a substituent, a chain aliphatic compound which may contain a substituent, a cyclic aliphatic compound which may contain a substituent, a substituted In the compound selected from the group consisting of a non-aromatic heterocyclic compound which may contain a group, or a compound formed by combining these, a carboxyl group of a compound in which one or more hydrogen atoms are each substituted with a carboxyl group or a hydroxyl group, and An anion obtained by removing a proton from a hydroxyl group or any one thereof.

More specifically, (-OR ¹ in the general formula ^(2), -OR 2) organic anion and aromatic compounds in, for example, benzene, biphenyl, terphenyl, naphthalene, binaphthyl, azulene, anthracene, phenanthrene, tetracene, Chrysene, helicene, fullerene, furan, thiophene, pyrrole, pyrazole, imidazole, isoxazole, thiazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, benzofuran, indole, thianaphthene, benzimidazole, benzoxazole, benzothiazole, benzotriazole , Purine, quinoline, isoquinoline, quinoxaline, dibenzothiophene, acridine, phenanthroline, carbazole, thianthrene, phenoxathiin, etc. It is below.

(-OR ¹ in the general formula ^(2), -OR 2) organic anions as the chain aliphatic compound in, for example, methane, ethane, ethene, ethyne, propane, propene, propyne, butane, butene, butyne, butadiene, Examples include butadiyne, pentane, pentene, pentyne, pentadiene, pentadiyne, hexane, hexene, hexyne, hexadiene, hexadiyne, hexatriene, hexatriin and the like.

Examples of the cycloaliphatic compound in the organic anion (—OR ¹ , —OR ² in the general formula (2)) include cyclopropane, cyclobutane, cyclopentane, cyclohexane, adamantane, norbornane, norbornene, and the like.

Examples of the non-aromatic heterocyclic compound in the organic anion (—OR ¹ , —OR ² in the general formula (2)) include pyrrolidine, pyrroline, imidazolidine, imidazoline, pyrazolidine, pyrazoline, piperidine, piperazine, tetrahydrofuran, pyran, Examples include morpholine.

Further, (-OR ¹ in the general formula ^(2), -OR 2) organic anion in, an aromatic compound may contain a substituent, a good chain aliphatic also contain substituent compounds, a substituent Examples of the compound formed by combining a cycloaliphatic compound which may be contained or a non-aromatic heterocyclic compound which may contain a substituent include, for example, fluorene, chroman, isochroman, xanthene, indoline, isoindoline, dihydro Anthracene, thioxanthene, iminodibenzyl and the like can be mentioned.

Further, in the organic anion (—OR ¹ , —OR ² in the general formula (2)), an aromatic compound, a chain aliphatic compound, a cyclic aliphatic compound, or a non-aromatic heterocyclic compound may be included. Group is, for example, alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, cycloalkynyl group, aryl group, heteroaryl group, heterocyclyl group, nitrile group, formyl group, acyl group, alkoxycarbonyl group, Examples thereof include a carboxyl group, an amino group, an alkylamino group, a nitro group, a hydroxyl group, an alkoxy group, an aryloxy group, an acyloxy group, a halogen group, and a sulfone group.

Examples of the metal cation in the organic salt include Li ⁺ , Na ⁺ , K ⁺ , Mg ²⁺ and Ca ²⁺ .

  Specific examples of the non-aqueous solvent include dichloromethane, chloroform, carbon tetrachloride, dichloroethane, acetone, acetonitrile, ethyl acetate, benzene, toluene, methanol, ethanol, n-propanol, isopropanol, diethyl ether, tetrahydrofuran, dioxane and the like. Thus, by using a solvent having a lower solubility of the chloride salt that is a by-product of the reaction, it is possible to improve the yield and purity of the tricoordinate hypervalent iodine compound that is the final product.

  In addition to the raw materials and additives described above, for example, a conjugate acid of an organic anion constituting an organic salt may be added.

  The chlorine-based oxidizing agent may be added to the reaction solution itself, or may be generated in the reaction system using an oxidizing agent other than the chlorine-based oxidizing agent. Regarding the addition of the chlorine-based oxidant, it is added in an amount of 1 to 30 times mol, preferably about 1 to 10 times mol to the organic iodine compound, and gradually added over 0 to 300 minutes, preferably over 30 to 60 minutes. To do. The reaction solution temperature at the time of addition of the chlorine-based oxidant is −30 to 100 ° C., preferably 10 to 50 ° C.

  The organic salt is added in an amount of about 2 to 100 times mol, preferably about 2 to 5 times mol for the organic iodine compound. This organic salt is desirably added at the beginning of the reaction, but is not limited thereto.

  Moreover, when adding the conjugate acid of the organic anion which comprises organic salt, the addition amount is 0-10 times mole with respect to an organic iodine compound, Preferably it is 1-3 times mole. The conjugate acid is desirably added at the initial stage of the reaction, but is not limited thereto.

  After actually mixing all these reagents, it may be aged at -30 to 100 ° C, preferably 10 to 50 ° C, or may be carried out for 0 to 100 hours, preferably 1 to 5 hours.

  According to the present invention composed of the processes as described above, the oxidation process of the organic iodine compound by the chlorine-based oxidant and the ligand exchange reaction process of the dichloroiodo compound by the organic salt can be carried out in one pot. It is possible to produce tricoordinate hypervalent iodine compounds. The one-pot process eliminates the process of isolating and purifying unstable dichloroiodo compounds, so that the yield can be improved or the production efficiency can be improved, and the dichloroiodo compound can be decomposed during storage. Loss due to can be avoided.

  Furthermore, since the organic salt coexists at the time of the oxidation reaction with the chlorine-based oxidant, the decomposable dichloroiodo compound does not exist in a high concentration in the reaction solution, and the final product is generated. Even if the decomposition reaction of the dichloroiodo compound proceeds in the reaction solution, the organic iodine compound, which is the decomposition product, is again subjected to the oxidation reaction by the chlorinated oxidant, and as a result, the final product, which is more than three-coordinated. The yield and purity of the valence iodine compound can be improved. Moreover, it is a safe process in that a degradable dichloroiodo compound is not present at a high concentration.

  In addition, the chlorine-based oxidizer used in the present invention is very cheap and easily available as compared with the organic peroxide-based oxidizer used in the conventional method, and there are many knowledges on safe use. It is possible to easily construct a manufacturing process.

(Diacetoxyiodo) benzene (DAIB) Iodobenzene 2.04 g (10.0 mmol), 1.20 g (20 mmol) of acetic acid, 4.10 g (50 mmol) of sodium acetate, and 6.4 ml of dichloromethane were added, and the mixture was stirred at room temperature for about 5 minutes. Here, chlorine gas generated by dropwise addition of 30% hydrogen peroxide to 13.75 g (132.0 mmol) of concentrated hydrochloric acid was aerated over 30 minutes. Then, after further stirring at room temperature for 1 hour, the reaction solution was washed with water. Sodium acetate and acetic acid were added to the dichloromethane layer and stirred, followed by washing with water. After this operation was further performed twice, the dichloromethane layer was dried with magnesium sulfate in the presence of sodium acetate. Magnesium sulfate and sodium acetate were removed by filtration, and then dichloromethane was distilled off, followed by drying at 50 ° C. under reduced pressure for 3 hours to obtain 3.111 g of DAIB (yield 96.6%).

¹ H-NMR (CDCl ₃ , 400 MHz) d 8.07 (d, 2H), 7.58 (t, 1H), 7.48 (t, 2H), 1.99 (s, 6H).

Add (dibenzoyloxyiodo) benzene (DBIB) iodobenzene 2.04 g (10.0 mmol), benzoic acid 2.44 g (20 mmol), sodium benzoate 7.21 g (50 mmol), dichloromethane 25 ml, and at room temperature for about 5 minutes Stir. Here, chlorine gas generated by dropwise addition of 30% hydrogen peroxide to 13.75 g (132.0 mmol) of concentrated hydrochloric acid was aerated over 30 minutes.

Thereafter, when the mixture was further stirred at room temperature for 1 hour, it was confirmed by ¹ H-NMR that DBIB was produced at a reaction rate of 85.9%.

¹ H-NMR (CDCl ₃ , 400 MHz) d 8.22 (d, 2H), 7.91 (d, 4H), 7.61 (t, 1H), 7.53 (t, 2H), 7.48 (t, 2H), 7.35 (t, 4H).

Add (diadipoyloxyiodo) benzene (DAzIB) iodobenzene 2.04 g (10.0 mmol), adipic acid 1.46 g (10 mmol), disodium adipate 4.75 g (25 mmol), dichloromethane 19 ml, and add 5 ml at room temperature. Stir for about a minute. Chlorine gas generated by dropwise addition of 30% hydrogen peroxide to 13.75 g (132.0 mmol) of concentrated hydrochloric acid was aerated over 30 minutes. Thereafter, the mixture was further stirred at room temperature for 1 hour, and it was confirmed by ¹ H-NMR that DAzIB was produced at a reaction rate of 27.1%.

¹ H-NMR (CDCl ₃ , 400 MHz) d 8.06 (br, 2H), 7.56 (br, 1H), 7.46 (br, 2H), 2.24 (br, 4H), 1.52 (br, 4H).

Add para (diacetoxyiodo) toluene (PDAITol) paraiodotoluene 2.18 g (10.0 mmol), acetic acid 1.20 g (20 mmol), sodium acetate 4.10 g (50 mmol), dichloromethane 6.4 ml and stir at room temperature for about 5 minutes. did. Chlorine gas generated by dropwise addition of 30% hydrogen peroxide to 13.75 g (132.0 mmol) of concentrated hydrochloric acid was aerated over 30 minutes. Then, after further stirring at room temperature for 1 hour, the reaction solution was washed with water. Sodium acetate and acetic acid were added to the dichloromethane layer and stirred, followed by washing with water. After this operation was further performed twice, the dichloromethane layer was dried with magnesium sulfate in the presence of sodium acetate. Magnesium sulfate and sodium acetate were removed by filtration, and then dichloromethane was distilled off, followed by drying at 50 ° C. under reduced pressure for 3 hours to obtain 3.245 g of PDAITol (yield 96.5%).

¹ H-NMR (CDCl ₃ , 400 MHz) d 7.93 (d, 2H), 7.25 (d, 2H), 2.40 (s, 3H), 1.96 (s, 6H).

Para (diacetoxyiodo) chlorobenzene (PCDAIB) 1.19 g (5.0 mmol ) of parachloroiodobenzene, 0.6 g (10 mmol) of acetic acid, 2.05 g (25 mmol) of sodium acetate, and 3.2 ml of dichloromethane are added, and at room temperature for about 5 minutes. Stir. Chlorine gas generated by adding 30% hydrogen peroxide dropwise to 6.88 g (66.0 mmol) of concentrated hydrochloric acid was aerated over 30 minutes. Then, after further stirring at room temperature for 1 hour, the reaction solution was washed with water. Sodium acetate and acetic acid were added to the dichloromethane layer and stirred, followed by washing with water. After this operation was further performed twice, the dichloromethane layer was dried with magnesium sulfate in the presence of sodium acetate. Magnesium sulfate and sodium acetate were removed by filtration, and then dichloromethane was distilled off, followed by drying at 50 ° C. under reduced pressure for 3 hours to obtain 1.547 g (yield 86.8%) of PCDAIB.

¹ H-NMR (CDCl ₃ , 400 MHz) d 7.97 (d, 2H), 7.40 (d, 2H), 1.95 (s, 6H).

Add meta (diacetoxyiodo) nitrobenzene (MDAINB) metaiodonitrobenzene 2.49 g (10.0 mmol), acetic acid 1.20 g (20 mmol), sodium acetate 4.10 g (50 mmol), dichloromethane 6.4 ml and stir at room temperature for about 5 minutes. . Chlorine gas generated by adding 30% hydrogen peroxide dropwise to 13.75 g (132.0 mmol) of concentrated hydrochloric acid was aerated over 30 minutes. Then, after further stirring at room temperature for 1 hour, the reaction solution was washed with water. Sodium acetate and acetic acid were added to the dichloromethane layer and stirred, followed by washing with water. After this operation was further performed twice, the dichloromethane layer was dried with magnesium sulfate in the presence of sodium acetate. Magnesium sulfate and sodium acetate were removed by filtration, and then dichloromethane was distilled off, followed by drying at 50 ° C. under reduced pressure for 3 hours to obtain 3.40 g of MDAINB (yield 92.6%).

¹ H-NMR (CDCl ₃ , 400 MHz) d 8.92 (s, 1H), 8.42 (d, 1H), 8.37 (d, 1H), 7.70 (t, 1H), 2.04 (s, 6H).

4,4′-bis (diacetoxyiodo) biphenyl (BDAIBP) 4,4′- diiodobiphenyl 2.03 g (5.0 mmol), acetic acid 18.0 g (300 mmol), acetic anhydride 5.10 g (50 mmol), sodium acetate 4.10 g (50 mmol) was added, and the mixture was stirred at room temperature for about 5 minutes. Chlorine gas generated by dropwise addition of 30% hydrogen peroxide to 13.75 g (132.0 mmol) of concentrated hydrochloric acid was aerated over 30 minutes. Then, after further stirring for 1 hour at room temperature, water was added to collect the precipitated crystals. The obtained crystals were suspended in acetic acid in the presence of sodium acetate and stirred for a while, and water was added to collect the precipitated crystals. This operation was further performed twice, followed by drying in the presence of phosphorus pentoxide under reduced pressure at 50 ° C. for 3 hours and further at room temperature for 15 hours to obtain 2.91 g of BDAIBP (yield 90.7%).

¹ H-NMR (CDCl ₃ , 400 MHz) d 8.17 (d, 4H), 7.64 (d, 4H), 2.00 (s, 12H).

1,4-bis (diacetoxyiodo) benzene (BDAIB) 1,4-diiodobenzene 1.65 g (5.0 mmol), acetic acid 18.0 g (300 mmol), acetic anhydride 5.10 g (50 mmol), sodium acetate 4.10 g ( 50 mmol) was added and stirred at room temperature for about 5 minutes. Chlorine gas generated by dropwise addition of 30% hydrogen peroxide to 13.75 g (132.0 mmol) of concentrated hydrochloric acid was aerated over 30 minutes. Then, after further stirring for 1 hour at room temperature, water was added to collect the precipitated crystals. The obtained crystals were suspended in acetic acid in the presence of sodium acetate and stirred for a while, and water was added to collect the precipitated crystals. This operation was further performed twice, followed by drying in the presence of phosphorus pentoxide under reduced pressure at 50 ° C. for 3 hours and further at room temperature for 15 hours to obtain 1.74 g of BDAIB (yield 61.5%).

¹ H-NMR (CD ₃ OD, 400 MHz) d 11.60 (s, 4H), 2.03 (m, 12H).

Claims (4)

And anions of carboxylic acids, metal cations, carboxylate presence consisting of any one of the cations of an ammonium cation which may be substituted, in a non-aqueous solvent, the general formula (1)

(In the formula (1), A is an aromatic group which may contain a substituent, a chain aliphatic group which may contain a substituent, a cyclic aliphatic group which may contain a substituent, A non-aromatic heterocyclic group which may contain a group, or a group which is a combination thereof, and n is an integer of 1 or more.) Formula (2)

(In the formula (2), A represents an aromatic group which may contain a substituent, a chain aliphatic group which may contain a substituent, a cyclic aliphatic group which may contain a substituent, a substituted group. A non-aromatic heterocyclic group that may contain a group, or a group that is a combination thereof, R ¹ and R ² may be the same or different from each other, or may be bonded to each other; R ¹ and R ² each contain an acyl group which may contain a substituent, an aromatic group which may contain a substituent, a chain aliphatic group which may contain a substituent, or a substituent. A cyclic aliphatic group which may be substituted, a non-aromatic heterocyclic group which may contain a substituent, or a combination thereof, wherein n is an integer of 1 or more. A method for producing a tricoordinate hypervalent iodine compound, comprising producing a valence iodine compound in one pot. R ¹ and R ² in the formula (2) may be the same or different from each other, or may be bonded to each other, and R ¹ and R ² may each be an acyl group that may contain a substituent. A method for producing a tricoordinate hypervalent iodine compound according to claim 1. Production method of the formula (1) and (2), A is three-coordinate hypervalent iodine compound according to claim 1 or 2 Ru aromatic group Der also contain substituents. Equation (1) and (2), A may also contain substituent unsaturated chain aliphatic group, or contain a substituent which is also be unsaturated cycloaliphatic radical claim 1 or 3. A method for producing a tricoordinate hypervalent iodine compound according to 2.

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