Potassium tetraphenylborate

General procedure: To the reaction vessel, 50 mL of THF was added to 3.3 g (17 mmol) of the potassium salt of p-tolyl trifluoroborate obtained in Production Example 1. Under stirring at 0 C., 55 mL (55 mmol) of phenylmagnesium bromide THF solution (1.0 mol / L) prepared from bromobenzene by a conventional method was added dropwise over 1 hour.After completion of the dropwise addition, the reaction was further carried out at room temperature for 1 hour. After filtration of the reaction solution, the filtrate was added to 100 mL of a saturated potassium carbonate aqueous solution and extraction was performed with 200 mL of ethyl acetate. The organic layer (ethyl acetate) was distilled off to obtain a light brown solid. Recrystallization with methanol-ether gave 5.8 g of a white solid. The yield based on the theoretical yield calculated from the potassium salt of p-tolyl trifluoroborate used in the reaction was 97%. From 1 H-NMR, it was confirmed that this white solid was triphenyl (p-tolyl) borate potassium salt. The purity calculated by high performance liquid chromatography (hereinafter referred to as HPLC) under the following conditions was 99%.To a 10 mL round-bottom flask containing N1-(2, 3-bis(diisopropylamino)cycloprop-2-en-1-ylidene)-N8, N8-dimethylnaphthalene-1, 8-diamine hydrochloride (Janus) (1aCl, 70 mg, 0.15 mmol) backfilled with N2(g) was added DCM (3 mL). To the resulting mixture was added potassium hexafluoro borate (108 mg, 0.30 mmol) as a solid in a single portion, and the reaction was allowed to stir for 24 h at room temperature. The crude product was diluted with 10 mL dH2O and extracted three times with 10 mL of dichloromethane. The combined organic extracts were dried over MgSO4 and concentrated under reduced pressure. The purified compound could be acquired by flash column chromatography (11% methanol in DCM) to afford 1dBPh4 as an off-white solid in 88% yield (101.2 mg, 0.14 mmol). m.p. = 184 oC - 189 oC. 1H NMR (300 MHz, CDCl3): delta = (ppm) 13.998 (s, 1H), 7.76-7.50 (m, 1H), 7.59-7.52 (m, 12H), 7.45-7.44 (m, 8H), 7.06-6.90 (m, 5H), 3.92-3.87 (m, 4H), 2.76 (s, 6H), 1.33-1.31 (d, J = 6.90 Hz, 24H). 13C {1H} NMR (75.5 MHz, CDCl3): delta (ppm) = 149.6, 137.4, 136.3, 136.2, 127.3, 127.1, 125.4, 125.4, 125.3, 125.1, 124.1, 121.5, 119.8, 118.5, 112.5, 110.1, 51.3, 46.4, 22.1. 11B {1H} NMR (96.3 MHz, CDCl3) delta (ppm) = -6.51 (s).To a 25 mL round-bottom flask containing N1, N1, N2, N2-tetraisopropyl-3-(naphthalen-1-ylimino)cycloprop-1-ene-1, 2-diamine hydrochloride (2aCl, 225 mg, 0.55 mmol) backfilled with N2(g) was added DCM (10 mL). To the resulting mixture was added potassium tetrafluoro borate (280 mg, 0.71 mmol) as a solid in a single portion, and the reaction was allowed to stir for 24 h at room temperature. The crude product was diluted with 10 mL dH2O and extracted three times with 10 mL of dichloromethane. The combined organic extracts were dried over MgSO4 and concentrated under reduced pressure. The purified compound could be acquired by flash column chromatography (11% methanol in DCM) to afford 2bBPh4 as an off-white solid in 86% yield (330.1 mg, 0.47 mmol). m.p. = 181 C - 182 C. 1H NMR (300 MHz, CDCl3): delta = 7.97-7.94 (m, 1H), 7.89-7.87 (m, 1H), 7.69-7.66 (m, 1H), 7.60 - 7.57 (m, 2H), 7.45 - 7.37 (m, 9H), 7.04 - 7.00 (m, 9H), 6.90-6.85 (m, 4H), 6.25 (s, 1H), 3.46 - 3.37 (m, 4H), 1.06 - 1.03 (d, J = 6.90 Hz, 24H). 1H NMR (300 MHz, CDCl3/D2O): delta = 7.97-7.94 (m, 1H), 7.90-7.87 (m, 1H), 7.70-7.67 (m, 1H), 7.60 - 7.57 (m, 2H), 7.46 - 7.39 (m, 9H), 7.04 - 6.99 (m, 9H), 6.89-6.84 (m, 4H), 3.47 - 3.38 (m, 4H), 1.07 - 1.05 (d, J = 6.90 Hz, 24H). 13C {1H} NMR (75.5 MHz, CDCl3): delta = 136.3, 134.3, 133.1, 129.9, 129.0, 127.9, 127.2, 125.7, 125.6, 125.5, 125.4, 121.6, 121.3, 115.2, 113.7, 50.9, 21.9. 11B {1H} NMR (96.3 MHz, CDCl3) delta (ppm) = -6.51 (s).

Molecular Weight:358.3
Hydrogen Bond Acceptor Count:1
Exact Mass:358.1295123
Monoisotopic Mass:358.1295123
Heavy Atom Count:26
Complexity:308
Covalently-Bonded Unit Count:2
Compound Is Canonicalized:Yes