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Method of producing iodizing agent, and method of producing aromatic iodine compound

外国特許コード F110005641
整理番号 RX08P13WO
掲載日 2011年9月9日
出願国 アメリカ合衆国
出願番号 53027408
公報番号 20100105969
公報番号 8383868
出願日 平成20年3月7日(2008.3.7)
公報発行日 平成22年4月29日(2010.4.29)
公報発行日 平成25年2月26日(2013.2.26)
国際出願番号 JP2008054184
国際公開番号 WO2008111521
国際出願日 平成20年3月7日(2008.3.7)
国際公開日 平成20年9月18日(2008.9.18)
優先権データ
  • 特願2007-061067 (2007.3.9) JP
  • 特願2007-061068 (2007.3.9) JP
  • 2008JP054184 (2008.3.7) WO
発明の名称 (英語) Method of producing iodizing agent, and method of producing aromatic iodine compound
発明の概要(英語) A method of the present invention, for producing an iodizing agent, includes the step of electrolyzing iodine molecules in a solution by using an acid as a supporting electrolyte.
This realizes (i) a method of producing an iodine cation suitable for use as an iodizing agent that does not require a sophisticated separation operation after iodizing reaction is completed, and (ii) an electrolyte used in the method.
Further, a method of the present invention, for producing an aromatic iodine compound, includes the step of causing an iodizing agent, and an aromatic compound whose nucleus has one or more substituent groups and two or more hydrogen atoms, to react with each other under the presence of a certain ether compound.
This realizes such a method of producing an aromatic iodine compound that position selectivity in iodizing reaction of an aromatic compound is improved.
従来技術、競合技術の概要(英語) BACKGROUND ART
There has been demand in a wide variety of fields for an aromatic iodine compound in which an iodine atom is bound to a nucleus of an aromatic compound, as an intermediate used for various organic synthesis.
In order to produce such an aromatic iodine compound, a method of using an iodine cation has been known.
In the method, the iodine cation generated by electrolysis is used as an iodizing agent (see Patent Literature 1 and Non Patent Literatures 1 through 3).
The iodine cation is a significantly-effective iodizing agent having high reactivity.
For example, Non Patent Literatures 1 and 2 disclose a method of producing an iodine cation by electrolyzing iodine molecules by using metal salt as a supporting electrolyte in an organic solvent (acetonitrile).
Further, Non Patent Literatures 1 and 2 disclose that the iodine cation thus obtained was caused to react with various aromatic compounds.
Furthermore, Non Patent Literature 3 discloses a method of producing an iodine cation by using quaternary ammonium salt as a supporting electrolyte.
Meanwhile, in such iodizing reaction, a binding position of an iodine atom is determined in accordance with a sort of a substituent group bound to an aromatic compound.
That is, the iodine atom is meta oriented, or ortho-para oriented.
Here, "meta oriented" means a property that the iodine atom is bound to an aromatic compound in a meta-position with respect to a substituent group, and "ortho-para oriented" means a property that the iodine atom is bound to an aromatic compound in either an ortho-position or a para-position, with respect to a substituent group.
In a case where the iodine atom is ortho-para oriented, a product in which iodine is bound in the ortho-position, and another product in which iodine is bound in the para-position, are mixed together in a resultant product of the reaction.
In the iodizing reaction in which iodine is ortho-para oriented as described above, in some cases, the product in which iodine is bound in the ortho-position, and the product in which the iodine is bound in the para-position are obtained at a ratio of substantially 1:1.
However, in recent years, there has been demand for an improvement in selectivity (hereinafter, referred to as "position selectivity" in some cases) of a binding position of an iodine atom in such iodizing reaction.
Patent Literature 1 and Non Patent Literature 4 disclose a production method whose purpose is an improvement in selectivity of the binding position of iodine.
Specifically, Patent Literature 1 describes that if iodine molecules are subjected to electrolytic oxidation with the use of a carbon electrode, and then toluene is iodized, a compound in which iodine is bound in the para-position can be obtained more in amount than a compound in which iodine is bound in the ortho-position.
Further, Non Patent Literature 4 describes that toluene was iodized in a solution containing methyl ester orthoformate having three ester bonds, so that the product in which iodine is bound in the ortho-position, and the product in which iodine is bound in the para-position, were obtained at a ratio of 3:7.

CITATION LIST
Patent Literature 1
Specification of EP Patent No. 0376858 B (Publication Date: Jul. 4, 1990)
Non Patent Literature 1
L. L. Miller, E. P. Kujawa, C. B. Cambell, "Iodation with electrolytically generated iodine (I)" J. Am. Chem. Soc., 92, 2821, (1970)
Non Patent Literature 2
L. L. Miller, B. F. Watkins, "Scope and mechanism of aromatic iodination with electrolytically generated iodine (I)" J. Am. Chem. Soc., 98, 1515, (1976)
Non Patent Literature 3
R. Lines, V. D. Parker, "Electrophilic aromatic substitution by positive iodine species.
Iodation of deactivated aromatic compounds" Acta Chem.
Scand., B34, p 47, (1980)
Non Patent Literature 4
T. Shono, Y. Matsumura, S. Katoh, K. Ikeda, T. Kamada, "Aromatic iodination by positive iodine active species generated by anodic oxidation in orthoformate" Tetrahedron Letters, 30, 1649, (1989)

特許請求の範囲(英語) [claim1]
1. A method of producing an iodizing agent, comprising the step of electrolyzing iodine molecules in a solution by using an acid as a supporting electrolyte, wherein: the supporting electrolyte contains the acid only;
the acid is at least one selected from the group consisting of: sulphonic acids and phosphoric acids;
the sulphonic acids are represented by the following General Formula (1):
R1SO3H (1)
(where: R1 is one selected from the group consisting of a hydroxyl group, a C1-6 alkyl group, a phenyl group, and a naphthyl group; in the alkyl group, a hydrogen atom may be substituted with a fluorine atom; the phenyl group and the naphthyl group may have a substituent group); and
the phosphoric acids are represented by the following General Formula (2):
(where: R2 and R3 are identically or differently a hydrogen atom, a C1-10 alkyl group, or a phenyl group; and the phenyl group may have a substituent group).
[claim2]
2. The method of producing an iodizing agent, according to claim 1, wherein: the solution contains an organic solvent.
[claim3]
3. The method of producing an iodizing agent, according to claim 2, wherein: the organic solvent is at least one selected from the group consisting of aliphatic nitrile, alcohol, a chlorinated solvent, aliphatic amide, cyclic ether, and nitromethane.
[claim4]
4. A method of producing an iodizing agent according to claim 1, wherein the acid has a concentration of not less than 0.01 mol/L but not more than 19.0 mol/L.
  • 発明者/出願人(英語)
  • YOSHIDA JUNICHI
  • SUGA SEIJI
  • KATAOKA KAZUHIDE
  • MIDORIKAWA KOJI
  • HAGIWARA YUJI
  • NIPPOH CHEMICALS
  • JAPAN SCIENCE AND TECHNOLOGY AGENCY
国際特許分類(IPC)
米国特許分類/主・副
  • 570/217
  • 205/619
  • 570/201
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