A Simple Method for the Preparation of 2,4,6-trichloroborazine and Evaluation of 1H-NMR Spectra

Norozi, Aria; Mesbah, Abdul Wahid; Iravani, Effat

doi:10.30492/ijcce.2021.526064.4605

A Simple Method for the Preparation of 2,4,6-trichloroborazine and Evaluation of 1H-NMR Spectra

Document Type : Research Article

Authors

¹ Chemistry and Chemical Engineering Research Center of Iran, Tehran, I.R. IRAN

² Nuclear Science and Technology Research Institute, Tehran, I.R. IRAN

10.30492/ijcce.2021.526064.4605

Abstract

The compound 2,3,6-trichloroborazine (TCB) is known as a valuable precursor to prepare boron nitride and various derivatives of borazine. Difficulties in the preparation of TCB via conventional methods on the one hand, and its importance for material science, on the other hand, were our motivations to modify Brown’s method for TCB synthesis. So far, all reports on the synthesis procedure of TCB are based on the use of gaseous BCl₃ with NH₄Cl powder at 110-130 °C in chlorobenzene requiring complicated low-temperature equipment such as a cold finger condenser, and dry ice-acetone reflux condenser to retain BCl₃ gas in the reaction flask. According to our study, using BCl₃ solution in n-hexane was more convenient than using gaseous BCl₃. The reaction of BCl₃ solution with NH₄Cl was carried out without loss of BCl₃. Furthermore, the reduction in the reflux temperature from 130 °C in some previous studies to 86 °C in our study, was a valuable advantage, leading to the release of the coordinated BCl₃ from the adduct complex [CH₃CN·BCl₃] gradually and the prevention of thermal decomposition of TCB, unwanted polymerization reactions and the formation of undesirable products, resulting in the increased reaction yield. TCB was fully characterized by ATR-FTIR, ¹¹B-, ¹⁴N-, and ¹H-NMR spectroscopic methods. ¹H-NMR spectra of TCB were performed for the first time at various temperatures to elucidate the quadrupole effect of nitrogen, leading to the observation of the proton resonance splitting of the ¹⁴N-H bond by coupling with the ¹⁴N quadrupole nucleus. The broad peak observed at room temperature was clearly split into a triplet at 100 °C due to the long T_qNand fast molecular motion of TCB molecules. The ¹⁴N-NMR spectrum was also shown for the first time as a broad signal at δ = –271.3 ppm (h_1/2 = 186 Hz).

Keywords

Main Subjects

Inorganic Chemistry

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