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1994 Fiscal Year Final Research Report Summary

Development of A Novel Non-Acid Methodology for Aromatic Nitratio

Research Project

Project/Area Number 05554023
Research Category

Grant-in-Aid for Developmental Scientific Research (B)

Allocation TypeSingle-year Grants
Research Field 物質変換
Research InstitutionKYOTO UNIVERSITY

Principal Investigator

SUZUKI Hitomi  Kyoto University, Chemistry Department Professor, 理学部, 教授 (50025342)

Co-Investigator(Kenkyū-buntansha) TOMARU Junichiro  Nihon Kayaku Co.Ltd.Chemist Research chemist, 化学品研究所, 研究員
MAEDA Koichi  Nissan Chemical Industries Ltd.Central Research Institute Chief Research, 中央研究所, 主任研究員
TAMURA Rui  Ehime University Associate Department of General Professor Education, 教養部, 助教授 (60207256)
Project Period (FY) 1993 – 1994
KeywordsNitration / Aromatics / Nitrogen dioxide / Ozone / Cation radical / Reaction mechanism
Research Abstract

A novel non-acid methodology for the preparative nitration of aromatic compounds with the lower oxides of nitrogen using a combination of ozonized air and some third substance as the promoter has been developed. The reaction, referred to as the kyodai-nitration, is now subject to industrially based research as the promising pollution-free and energy-saving substitute for the century-old, yet currently ongoing commercial process based on the use of nitric acid-sulfuric acid.
Aromatic compounds sudjected to the present novel type of nitration include benzene and alkyl derivatives ; halogenobenzenes ; Aromatic carbonyl compounds, acetals, acylals and anthraguinones ; benzoic acid, its salts, ester, acid chloride, nitrile and amide ; nitrobenzene and alkyl derivatives ; anilides and phenolic esters ; pyridiue and alkyl derivatives ; naphthalene and derivatives ; benzyl cvanide and trifluoromethylbenzene.
For this novel type of aromatic nitration, we have proposed a mechanism in which the reaction proceeds a dual mode depending on the oxidation potential of aromatic substrate ; nitrogen dioxide reacts with ozone to give nitrogen trioxide, which oxidizes aromatic substrate to form cation radical as an intermediate to ring substitution. In the absence of an appropriate oxidizable substrate, nitorgen trioxide is trapped by another molecule of nitrogen dioxide to form dinitrogen pentaoxide, which is a powerful nitrating agent in the presence of acid catalyst.
Although in some respect complimentary to the existing methodology, the kyodai-nitration is highly promising to provide a solution to one of the nowadays problem which the chemical industry is facing.

  • Research Products

    (16 results)

All Other

All Publications (16 results)

  • [Publications] Hitimi Suzuki: "Ozone-mediated Nitration of Aromatic Ketones and Related Compounds with Nitrogen Dioxide" J. Chem. Soc., Perkin TRans. 1,. 903-908 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Hitomi Suzuki: "Ozone-mediated Nitration of Chloro- and Bromo-benzenes and Some of the Methyl Derivatives with Nitrogen Dioxide. A Novel Non-acid Methodology for the Sele-.." J. Chem. Soc., Perkin Trans. 2. 479-484 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Hitomi Suzuki: "Ozone-mediated Reaction of Aromatic Acetals and Acylal with Nitrogen Dioxide: A Novel Methodology for the Nuclear Nitration of Acid-Sensitive Aromatic Com-..." J. Chem. Soc., Perkin Trans. 1. 1367-1369 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Hitomi Suzuki: "Ozone-mediated Nitration of Benzoic Acid, its Alkaline and Alkaline-Earth Salts, Ester, Acid Chloride, Nitrile and Amide with Nitrogen Dioxide" J. Chem. Soc., Perkin Trans. 1. 2413-2416 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Hitomi Suzuki: "Ozone-mediated Reaction of Polychlorobenzenes and Some Related Halogeno Compounds with Nitrogen Dioxide. A Novel Non-acid Methodology for the Selective Mono-..." Synthesis. 841-845 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Hitomi Suzuki: "Unusual Isomer Distribution of Dinitrobenzenes and Nitrophenols Formed as Side Products during the Ozone-mediated Nitration of Benzene with Nitrogen Dioxide" J. Chem. Soc., Perkin Trans. 1. 41-45 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Hitomi Suzuki, Takashi Murashima: "Ozone-mediated Nitration of Aromatic Ketones and Related Compounds with Nitrogen Dioxide" J.Chem.Soc., Perkin Trans.1. 903-908 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Hitomi Suzuki, Tadashi Mori: "Ozone-mediated Nitration of Chloro- and Bromo- benzenes and Some of the Methyl Derivatives with Nitrogen Dioxide.High Ortho-Directing Trends of the Chlorine and Bromine Substituents" J.Chem.Soc., Perkin Trans.2. 479-484 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Hitomi Suzuki, Tadashi Mori, Kohichi Maeda: "Ozone-mediated Reaction of Polychlorobenznes and Related Halogeno Compounds with Nitrogen Dioxids.A Novel Non-acid Methodology for the Selective Mononitration of Moderately Deactivated Aromatic Systems" Synthesis. 841-845 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Hitomi Suzuki, Shuji Yonezawa, Tadashi Mori, Kohichi Maeda: "Ozone-mediated Reaction of Aroamtic Acetals and Acylal with Nitrogen Dioxide.A Novel Methodology for the Nuclear Nitration of Acid-Sensitive Aromatic Compounds under Neutral Conditions" J.Chem.Soc., Perkin Trans.1. 1367-1369 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Hitomi Suzuki, Junichiro Tomaru, Tadashi Murashima: "Ozone-mediated Nitration of Benzoic Acid, its Alkaline and Alkaline-Earth Salts, Ester, Acid Chloride, Nitrile and Amide with Nitrogen Dioxide" J.Chem.Soc., Perkin Trans.1. 2413-2416 (1944)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Hitomi Suzuki, Takashi Murashima, Tadashi Mori: "Ozone-mediated Nitration of Arenes with Nitrogen Dioxide : Chauge-Over of the Orientiug Influences of Alkyl, Alkoxyl and Halogen Substituent Groups from Meta to Ortho-Para Dominance" J.Chem.Soc., Chem.Commun.1443-1444 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Hitomi Suzuki, Tadashi Mori: "Unusual Isomer Distribution of Dinitrobenzenes and Nitrophenols Formed as Side Products during the Ozone-mediated Nitration of Benzene with Nitrogen Dioxide. Further Evidence for the Alternative Mechanism of Electrphilic Nitration of Arenes" J.Chem.Soc., Perkin Trans.2. 41-45 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Hitomi Suzuki, Tadashi Mori: "Nitration of Nonactivated Arenes with a Ternary System NO_2-NO-O_2. Mechanistic Implications with the kyodai-Nitration" J.Chem.Soc., Perkin Trans.1. 291-293 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Hitomi Suzuki, Atsuo Tatsumi, Taro Ishibashi: "Ozone-mediated Reaction of Anilides and Phenyl Esters with Nitrogen Dioxide. Enhanced Ortho Reactivity and Mechanistic Implications" J.Chem.Soc., Perkin Trans.1. 339-343 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Hitomi Suzuki, Shuji Yonezawa, Tadashi Mori: "Aromatic Nitration under Neutral Conditions Using Nitrogen Dioxide and Ozone as the Nitrating Agent. Application to Aromatic Acetals and Acylal" Bull.Chem.Soc.Jpn. 68, in press. (1995)

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 1996-04-15  

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