Efficient Synthesis of 4,8-Dibromo Derivative of Strong Electron-Deficient Benzo[1,2-<i>d</i>:4,5-<i>d</i>’]bis([1,2,3]thiadiazole) and Its S<sub>N</sub>Ar and Cross-Coupling Reactions
An efficient synthesis of hydrolytically and thermally stable 4,8-dibromobenzo[1,2-<i>d</i>:4,5-<i>d</i>’]bis([1,2,3]thiadiazole) by the bromination of its parent heterocycle is reported. The structure of 4,8-dibromobenzo[1,2-<i>d</i>:4,5-<i>d</i>’]bis...
| Main Authors: | , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2022-10-01
|
| Series: | Molecules |
| Subjects: | |
| Online Access: | https://www.mdpi.com/1420-3049/27/21/7372 |
| _version_ | 1797467098120716288 |
|---|---|
| author | Timofey N. Chmovzh Daria A. Alekhina Timofey A. Kudryashev Oleg A. Rakitin |
| author_facet | Timofey N. Chmovzh Daria A. Alekhina Timofey A. Kudryashev Oleg A. Rakitin |
| author_sort | Timofey N. Chmovzh |
| collection | DOAJ |
| description | An efficient synthesis of hydrolytically and thermally stable 4,8-dibromobenzo[1,2-<i>d</i>:4,5-<i>d</i>’]bis([1,2,3]thiadiazole) by the bromination of its parent heterocycle is reported. The structure of 4,8-dibromobenzo[1,2-<i>d</i>:4,5-<i>d</i>’]bis([1,2,3]thiadiazole) was confirmed by X-ray analysis. The conditions for the selective aromatic nucleophilic substitution of one bromine atom in this heterocyclic system by nitrogen nucleophiles are found, whereas thiols formed the bis-derivatives only. Suzuki–Miyaura cross-coupling reactions were found to be an effective method for the selective formation of various mono- and di(het)arylated derivatives of strong electron-deficient benzo[1,2-<i>d</i>:4,5-<i>d</i>’]bis([1,2,3]thiadiazole), and Stille coupling can be employed for the preparation of bis-arylated heterocycles, which can be considered as useful building blocks for the synthesis of DSSCs and OLEDs components. |
| first_indexed | 2024-03-09T18:47:53Z |
| format | Article |
| id | doaj.art-5438ca1d4e6f4428b1821ab8314c540b |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-09T18:47:53Z |
| publishDate | 2022-10-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-5438ca1d4e6f4428b1821ab8314c540b2023-11-24T06:03:08ZengMDPI AGMolecules1420-30492022-10-012721737210.3390/molecules27217372Efficient Synthesis of 4,8-Dibromo Derivative of Strong Electron-Deficient Benzo[1,2-<i>d</i>:4,5-<i>d</i>’]bis([1,2,3]thiadiazole) and Its S<sub>N</sub>Ar and Cross-Coupling ReactionsTimofey N. Chmovzh0Daria A. Alekhina1Timofey A. Kudryashev2Oleg A. Rakitin3N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 119991 Moscow, RussiaN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 119991 Moscow, RussiaN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 119991 Moscow, RussiaN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 119991 Moscow, RussiaAn efficient synthesis of hydrolytically and thermally stable 4,8-dibromobenzo[1,2-<i>d</i>:4,5-<i>d</i>’]bis([1,2,3]thiadiazole) by the bromination of its parent heterocycle is reported. The structure of 4,8-dibromobenzo[1,2-<i>d</i>:4,5-<i>d</i>’]bis([1,2,3]thiadiazole) was confirmed by X-ray analysis. The conditions for the selective aromatic nucleophilic substitution of one bromine atom in this heterocyclic system by nitrogen nucleophiles are found, whereas thiols formed the bis-derivatives only. Suzuki–Miyaura cross-coupling reactions were found to be an effective method for the selective formation of various mono- and di(het)arylated derivatives of strong electron-deficient benzo[1,2-<i>d</i>:4,5-<i>d</i>’]bis([1,2,3]thiadiazole), and Stille coupling can be employed for the preparation of bis-arylated heterocycles, which can be considered as useful building blocks for the synthesis of DSSCs and OLEDs components.https://www.mdpi.com/1420-3049/27/21/7372sulfur–nitrogen heterocyclesbenzo[1,2-<i>d</i>:4,5-<i>d</i>’]bis([1,2,3]thiadiazole)aromatic nucleophilic substitutionSuzuki and Stille cross-coupling reactionsX-ray analysis |
| spellingShingle | Timofey N. Chmovzh Daria A. Alekhina Timofey A. Kudryashev Oleg A. Rakitin Efficient Synthesis of 4,8-Dibromo Derivative of Strong Electron-Deficient Benzo[1,2-<i>d</i>:4,5-<i>d</i>’]bis([1,2,3]thiadiazole) and Its S<sub>N</sub>Ar and Cross-Coupling Reactions Molecules sulfur–nitrogen heterocycles benzo[1,2-<i>d</i>:4,5-<i>d</i>’]bis([1,2,3]thiadiazole) aromatic nucleophilic substitution Suzuki and Stille cross-coupling reactions X-ray analysis |
| title | Efficient Synthesis of 4,8-Dibromo Derivative of Strong Electron-Deficient Benzo[1,2-<i>d</i>:4,5-<i>d</i>’]bis([1,2,3]thiadiazole) and Its S<sub>N</sub>Ar and Cross-Coupling Reactions |
| title_full | Efficient Synthesis of 4,8-Dibromo Derivative of Strong Electron-Deficient Benzo[1,2-<i>d</i>:4,5-<i>d</i>’]bis([1,2,3]thiadiazole) and Its S<sub>N</sub>Ar and Cross-Coupling Reactions |
| title_fullStr | Efficient Synthesis of 4,8-Dibromo Derivative of Strong Electron-Deficient Benzo[1,2-<i>d</i>:4,5-<i>d</i>’]bis([1,2,3]thiadiazole) and Its S<sub>N</sub>Ar and Cross-Coupling Reactions |
| title_full_unstemmed | Efficient Synthesis of 4,8-Dibromo Derivative of Strong Electron-Deficient Benzo[1,2-<i>d</i>:4,5-<i>d</i>’]bis([1,2,3]thiadiazole) and Its S<sub>N</sub>Ar and Cross-Coupling Reactions |
| title_short | Efficient Synthesis of 4,8-Dibromo Derivative of Strong Electron-Deficient Benzo[1,2-<i>d</i>:4,5-<i>d</i>’]bis([1,2,3]thiadiazole) and Its S<sub>N</sub>Ar and Cross-Coupling Reactions |
| title_sort | efficient synthesis of 4 8 dibromo derivative of strong electron deficient benzo 1 2 i d i 4 5 i d i bis 1 2 3 thiadiazole and its s sub n sub ar and cross coupling reactions |
| topic | sulfur–nitrogen heterocycles benzo[1,2-<i>d</i>:4,5-<i>d</i>’]bis([1,2,3]thiadiazole) aromatic nucleophilic substitution Suzuki and Stille cross-coupling reactions X-ray analysis |
| url | https://www.mdpi.com/1420-3049/27/21/7372 |
| work_keys_str_mv | AT timofeynchmovzh efficientsynthesisof48dibromoderivativeofstrongelectrondeficientbenzo12idi45idibis123thiadiazoleanditsssubnsubarandcrosscouplingreactions AT dariaaalekhina efficientsynthesisof48dibromoderivativeofstrongelectrondeficientbenzo12idi45idibis123thiadiazoleanditsssubnsubarandcrosscouplingreactions AT timofeyakudryashev efficientsynthesisof48dibromoderivativeofstrongelectrondeficientbenzo12idi45idibis123thiadiazoleanditsssubnsubarandcrosscouplingreactions AT olegarakitin efficientsynthesisof48dibromoderivativeofstrongelectrondeficientbenzo12idi45idibis123thiadiazoleanditsssubnsubarandcrosscouplingreactions |