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CC BY 4.0 · Sustainability & Circularity NOW 2025; 02: a25574354
DOI: 10.1055/a-2557-4354
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Platinum-Catalyzed Regioselective Dehydrogenative Homocoupling of Dimethyl Phthalate for the Direct Synthesis of Sym-BPTT

Soya Ishikawa
1   Pharmaceutical Research Laboratories, Toray Industries, Inc., Tebiro, Kamakura, Kanagawa 248-8555, Japan
,
Katsuhiko Iseki
2   Technology Center, Toray Industries, Inc.,Sonoyama, Otsu, Shiga 520-8558, Japan
,
Haruro Ishitani‡
3   Green and Sustainable Chemistry Social Cooperation Laboratory, Graduate School of Science, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
,
Shū Kobayashi  ‡
3   Green and Sustainable Chemistry Social Cooperation Laboratory, Graduate School of Science, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
4   Department of Chemistry, School of Science, The University of Tokyo,Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
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Abstract

A novel synthesis method for sym-BPTT, an important synthetic intermediate for electronic materials, is reported. This method features a platinum-catalyzed regioselective dehydrogenative homocoupling of dimethyl phthalate. Unlike previous palladium-catalyzed methods, this reaction proceeds with high regioselectivity without requiring any ligands when an appropriate reoxidation system is employed, thus simplifying the purification process. While the yield is currently lower than that of existing methods, this study demonstrates the potential of platinum catalysts for dehydrogenative homocoupling reactions. A preliminary continuous-flow system for this homocoupling reaction was also developed, although the yield was low, and regioselectivity was not well-controlled.

Keywords

Platinum catalyst - Dehydrogenative homocoupling - Continuous-flow synthesis

Supplementary Material

    Supplementary Material for this article is available online at https://doi.org/10.1055/a-2557-4354.
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Publikationsverlauf

Eingereicht: 21. Oktober 2024

Angenommen nach Revision: 10. März 2025

Accepted Manuscript online:
12. März 2025

Artikel online veröffentlicht:
02. April 2025

© 2025. The Author(s). This is an open access article published by Thieme under the terms of the Creative Commons Attribution License, permitting unrestricted use, distribution, and reproduction so long as the original work is properly cited. (https://creativecommons.org/licenses/by/4.0/).

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Bibliographical Record
Soya Ishikawa, Katsuhiko Iseki, Haruro Ishitani, Shū Kobayashi. Platinum-Catalyzed Regioselective Dehydrogenative Homocoupling of Dimethyl Phthalate for the Direct Synthesis of Sym-BPTT. Sustainability & Circularity NOW 2025; 02: a25574354.
DOI: 10.1055/a-2557-4354
 

  • References

  • 5 Ishida T, Aikawa S, Mise Y, Akebi R, Hamasaki A, Honma T, Ohashi H, Tsuji T, Yamamoto Y, Miyasaka M, Yokoyama T, Tokunaga M. ChemSusChem 2015; 8: 695
    Suche in Google Scholar
  • 6 Yang Y, Lan J, You J. Chem. Rev. 2017; 117: 8787 and references therein
    Suche in Google Scholar
    • 7a Zhang X.-W, Shen S.-C, Hidajat K, Kawi S, Yu LE, Simon Ng KY. Catal. Lett. 2004; 96: 1
      Suche in Google Scholar
    • 7b Maphoru MV, Heveling J, Pillai SK. Eur. J. Org. Chem. 2016; 331
    • 7c Maphhoru MV, Pillai SK, Heveling J. J. Catal. 2017; 348: 47
      Suche in Google Scholar
    • 7d Matsumoto K, Yoshida M, Shindo M. Angew. Chem., Int. Ed. 2016; 55: 5272
      Suche in Google Scholar
    • 7e Fujimoto S, Matsumoto K, Iwata T, Shindo M. Tetrahedron Lett. 2017; 58: 973
      Suche in Google Scholar
    • 7f Nabavizadeh SM, Hosseini FN, Park C, Wu G, Abu-Omar MM. Dalton Trans. 2020; 49: 2477
      Suche in Google Scholar
  • 8 We confirmed that contamination amount of Pd in 9.1 mg of Na2PtCl6 was under detection limit. We also tested the reaction using 1.0 mol % of Pd(OAc)2 as a catalyst in the presence of 10 mol % of Cu(OAc)2 without using ligands: this resulted in 2.5% yield with 0.40 of sym/asym regioselectivity
  • 12 A typical procedure for a batch reaction was described using Entry 3 of Table 4, for example: To an autoclave containing a magnetic stirring bar, dimethyl phthalate (6.1 mmol), Na2PtCl4 (0.061 mmol), Cu(OAc)2 (0.61 mmol), and acetic acid (1.0 mL) were added, and the autoclave was heated at 190 °C to start the reaction. After 2 h, the reaction mixture was diluted with EtOAc and filtered through celite. The obtained solution was then concentrated and subjected to analysis by GC-FID
  • 13 Typical procedure for a continuous-flow reaction: A thoroughly mixed composite of Pt/SiO2 (0.4 g, Pt 0.25 mmol) and Celite was packed into a stainless steel column (Φ10 × 100 mm) equipped with a filter and a column head at one end. A double-inlet column head, capable of independently introducing gas and liquid into the reactor, was attached to the other end of the column. Dimethyl phthalate (110 mmol), copper(II) acetate monohydrate (1.6 mmol), and acetic acid (25 mL) were combined and stirred at 90 °C to form a homogeneous substrate solution, and the reservoir temperature was maintained at 90 °C using a plate heater. Toluene was initially fed into the reactor. Subsequently, dry air flow was initiated, and the reactor was heated to 200 °C. The feed was then switched from toluene to the substrate solution, and the outflow was connected to the reservoir to create a recirculation system. This recirculation system was driven for 16 h, and a sample of the solution was taken to be subject to analysis by GC-FID