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3 protocols using 4 aminobenzonitrile

1

Analytical Comparison of Mass Spectrometry Techniques

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For our investigation, we used the same compounds as for Paper-LTPI28 (link) and in a comparison between Paper-LTPI, ESI and APCI27 (link): 3-aminophenol, 2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 2-methoxyaniline (o-anisidine), 3-methoxyaniline (m-anisidine), 4-methoxyaniline (p-anisidine), 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 3-methylaniline (m-toluidine), 3-aminoaniline (m-phenylenediamine), 4-aminoaniline (p-phenylenediamine), 2-aminobenzonitrile, 3-aminobenzonitrile and 4-aminobenzonitrile from Sigma Aldrich (Taufkirchen, Germany); 2-methylaniline (o-toluidine), 4-methylaniline (p-toluidine) from Fluka (Buchs, Switzerland) and aniline from Acros (Geel, Belgium). Acetonitrile (ACN, LC–MS grade) was from VWR (Dresden, Germany) and water (LC–MS grade) from BIOSOLVE (Valkenswaard, Netherlands). 2-aminoaniline (o-phenylenediamine), 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-aminophenol, 4-aminophenol, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, sulfanilic acid and 4-chloroaniline were kindly provided by Prof. em. S. Berger (University of Leipzig, Germany).
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2

Synthesis of Triazine-Based Compounds

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Phloroglucinol was obtained from Sigma-Aldrich and used for the synthesis of 1,3,5-triformylPhloroglucinol (TFP).27 (link) 4-Aminobenzonitrile and trifluoromethanesulfonic acid were purchased from Sigma-Aldrich and used for the synthesis of 1,3,5-tris-(4-aminophenyl)-triazine (TAPT).19 (link) Anhydrous N,N-dimethylformamide, hexamine, trifluoroacetic acid and hydrochloric acid were obtained from Merck, India, and all were used without further purification.
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3

Synthesis of Aryl Diazonium Salts

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Aryl diazonium salt D-NO 2 was prepared by the method published previously by our group. 35 2 g of 4-nitroaniline (≥99%, Sigma-Aldrich) and 10 mL of acetonitrile (≥99.9%, Sigma-Aldrich) were sequentially added to 12 mL of tetrafluoroboric acid (48% in H 2 O, Sigma-Aldrich). Then the mixed solution was transferred to an ice water bath and cooled down to 2 °C under continuous stirring. Afterwards, 2 mL of tert-butyl nitrite (90%, Sigma-Aldrich) was added to the reaction solution drop by drop. The solution was incubated for 30 min under stirring. After 3 times washes by diethyl ether (≥99.7%, Sigma-Aldrich), the resulting diazonium salt D-NO 2 was dissolved in acetone (≥99.9%, Sigma-Aldrich) and kept at room tempera-ture for drying. For the preparation of D-CCH and D-CN, 4-ethynylaniline (97%, Sigma-Aldrich) and 4-aminobenzonitrile (98%, Sigma-Aldrich) were used as corresponding precursors based on the same protocol.
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