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Short Note

2,3-Bis(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenyl)oxirane

Division of Applied Bioscience, Graduate School of Agriculture, Hokkaido University, Kita 9, Nishi 9, Kita-ku, Sapporo 060-8589, Japan
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Author to whom correspondence should be addressed.
Molbank 2014, 2014(1), M816; https://doi.org/10.3390/M816
Submission received: 20 January 2014 / Accepted: 18 February 2014 / Published: 24 February 2014

Abstract

:
The title compound, which has two photoreactive groups in a molecule, was synthesized by the coupling reaction of 3-(4-(bromomethyl)phenyl)-3-(trifluoromethyl)-3H-diazirine in the presence of silver oxide in DMSO.

Graphical Abstract

Diazirine based photoaffinity labeling is a useful chemical biology method to elucidate interactions between low molecular weight bioactive compounds and biomolecules [1]. Photoreactive compound contained two photophores [2,3] is one of the attractive tools for comprehensive analysis of ligand-biomolecule interactions by photoaffinity labeling.
We have synthesized a new two photophores containing compound, 2,3-bis(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenyl)oxirane 2, from 4-[3-(trifluoromethyl)-3H-diazirin-3-yl]benzyl bromide 1 with silver oxide in DMSO [4] without decomposition of diazirinyl ring. 1H- and 13C-NMR chemical shifts for oxirane moiety (3.83 and 62.17 ppm) strongly indicated that the purified compound is trans- isomer [5,6]. The 2,3-trans two-photophores containing oxirane ring is utilized for introduction of 2 to ligand.

Experimental

Synthesis of 2,3-bis(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenyl)oxirane (2)

To a solution of 4-[3-(trifluoromethyl)-3H-diazirin-3-yl]benzyl bromide (1) [7,8] (0.10 g, 0.36 mmol) in anhydrous DMSO (1 mL), silver oxide (0.09 g, 0.39 mmol) was added. The resulting mixture was stirred overnight at room temperature until TLC showed the reaction to be complete. The reaction was filtered by Celite and treated with H2O, which was extracted with diethyl ether. The combined oil layer was dried over MgSO4 and subjected to rotary evaporation to remove the solvent. The crude product was purified by silica gel column chromatography (CH2Cl2/hexane, 1:1) to afford 2 (0.06 g, 41%) as a yellow solid. [α]D −20 (c 0.5, CHCl3). UV(CDCl3) λmax (ε) 250 (2120), 356 (1170). 1H-NMR (270 MHz, CDCl3): δ 7.37 (4H, d, J = 8.1 Hz,), 7.22 (4H, d, J = 8.1 Hz), 3.83 (2H, s). 13C-NMR (68 MHz, CDCl3): δ 138.54, 129.48, 126.91, 126.02, 122.14 (q, 1JCF = 274.7 Hz), 62.17, 28.24 (q, 2JCF = 40.6 Hz). 19F-NMR (470 MHz, CDCl3): δ −65.22. HRMS (FD): m/z calcd for C18H10F6N4O: 412.0759; found: 412.0744.

Supplementary materials

Supplementary File 1Supplementary File 2Supplementary File 3

Acknowledgments

This research was partially supported by the Fugaku Foundation for financial support. Part of this work was performed under the Cooperative Research Program of “Network Joint Research Center for Materials and Devices”.

Conflicts of Interest

The authors declare no conflict of interest.

References and Notes

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Scheme 1. Synthesis of 2,3-bis(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenyl)oxirane (2).
Scheme 1. Synthesis of 2,3-bis(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenyl)oxirane (2).
Molbank 2014 m816 sch001

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MDPI and ACS Style

Wang, L.; Yoshida, T.; Okamoto, M.; Sakihama, Y.; Hashidoko, Y.; Hashimoto, M. 2,3-Bis(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenyl)oxirane. Molbank 2014, 2014, M816. https://doi.org/10.3390/M816

AMA Style

Wang L, Yoshida T, Okamoto M, Sakihama Y, Hashidoko Y, Hashimoto M. 2,3-Bis(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenyl)oxirane. Molbank. 2014; 2014(1):M816. https://doi.org/10.3390/M816

Chicago/Turabian Style

Wang, Lei, Takuma Yoshida, Masashi Okamoto, Yasuko Sakihama, Yasuyuki Hashidoko, and Makoto Hashimoto. 2014. "2,3-Bis(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenyl)oxirane" Molbank 2014, no. 1: M816. https://doi.org/10.3390/M816

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