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DOI: 10.1055/a-2567-1399
2,8-Dihalogenated Diazocines: Versatile Reactants for Functionalized Photoswitches
This work was supported by the Fonds der Chemischen Industrie (Liebig Fellowship) and the German Research Foundation (DFG; Emmy Noether Programme, 446317932). M.J.N. and V.S. thank the FCI and Avicenna-Studienwerk, respectively, for their Ph.D. scholarships.
Abstract
Diazocine photoswitches possess distinctive structural characteristics and remarkable photochemical properties, leading to their growing application in photopharmacology and smart materials. We report the synthesis of 2,8-pseudo-para-substituted diazocines with two bromo, two iodo, or a combination of both substituents, achieving effective scalability. Besides demonstrating good reactivity in Suzuki cross-coupling reactions, the substituted diazocines predominantly retain their good photochemical properties, rendering them valuable components for said applications.
Key words
photoswitches - diazocines - cross-coupling - gram-scale synthesis - photophysical propertiesSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-2567-1399.
- Supporting Information
Publication History
Received: 25 February 2025
Accepted after revision: 21 March 2025
Accepted Manuscript online:
26 March 2025
Article published online:
12 May 2025
© 2025. The Author(s). This is an open access article published by Thieme under the terms of the Creative Commons Attribution License, permitting copying and reproduction so long as the original work is given appropriate credit. Contents may not be used for commercial purposes or adapted, remixed, transformed or built upon. (https://creativecommons.org/licenses/by/4.0/)
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- 26 2-Bromo-8-iodo-11,12-dihydrodibenzo[c,g][1,2]diazocine (3) A solution of mCPBA (75%, 2.58 g, 11.22 mmol, 2.00 equiv) in glacial HOAc (~0.6 M) was added to a solution of bromo iodo dianiline I (2.34 g, 5.61 mmol, 1.00 equiv) in 1:3 glacial HOAc–CH2Cl2 (60 mL) over 24 hours using a syringe pump. The mixture was then stirred for 18 h at r.t., then neutralized with sat. aq NaHCO3. The organic layer was separated, washed with sat. aq NaHCO3 (25 mL) and sat. aq NaCl (25 mL), dried (MgSO4), and concentrated by rotary evaporation. The residue was purified by column chromatography [silica gel, cyclohexane–EtOAc (100:0 to 70:30 over 15 column volumes)] to give a yellow solid; yield: 1.47 g (63%, 3.56 mmol). Rf = 0.56 (cyclohexane–EtOAc, 8:2). 1H NMR (500 MHz, CD2Cl2): δ = 2.64–2.96 (m, 4 H, H-7, H-8), 6.74 (d, J = 8.3 Hz, 1 H, H-11), 6.78 (d, J = 8.1 Hz, 1 H, H-5), 7.16 (d, J = 1.8, 1 H, H-2), 7.18 (d, J = 2.1 Hz, 1 H, H-14), 7.31 (dd, J = 8.4 Hz, 2.1, 1 H, H-12), 7.39 (dd, J = 8.1, 1.8 Hz, 1 H, H-4). 13C NMR (126 MHz, CD2Cl2): δ = 31.0 (C-7), 31.1 (C-8), 90.9 (C-3), 120.3 (C-13), 120.6 (C-11), 127.2 (C-2), 127.7 (C-6), 129.9 (C-12), 130.2 (C-9), 131.6 (C-15), 132.4 (C-14), 136.1 (C-4), 154.1 (C-10), 156.2 (C-1). HRMS (ESI+ Orbitrap): m/z [M + H]+ calcd for C14H15BrIN2 = 412.9145; found: 412.9138.