ꢂꢁꢁꢁ
Z. Guan et al.: 2-Ethyl-1-phenylindazolium hexafluorophosphateꢀ
ꢀ87
1033, 977, 840, 748, 698, 609, 490 cm–1. – MS ((+)-ESI): m/z 1.0 Hz, 1H, Ar-H), 6.76 (ddd, Jꢀ=ꢀ7.7, 7.4, 1.0 Hz, 1H, Ar-H),
(%)ꢀ=ꢀ255.0 (100) [M+H]+. – HRMS ((+)-ESI): m/zꢀ=ꢀ255.0958 3.71 (dq, Jꢀ=ꢀ5.4, 7.3 Hz, 2H, CH2-H), 1.23 (t, Jꢀ=ꢀ7.3 Hz, 3H,
(calcd. 255.0956 for [C15H15N2S]+).
CH3-H) ppm. – 13C NMR (CDCl3 + TMS): δꢀ=ꢀ198.0, 142.1,
141.7, 130.7, 130.4, 129.4, 126.9, 121.9, 119.7, 119.4, 117.1, 40.9,
13.2 ppm. – IR (ATR): νꢀ=ꢀ3166, 3036, 3014, 2978, 2929,
1588, 1505, 1463, 1418, 1372, 1307, 1251, 1210, 1150, 1088,
1023, 967, 742, 696, 486 cm–1. – MS ((+)-ESI): m/zꢀ=ꢀ279.0
3.2 2-Ethyl-1-phenyl-indazol-3-one (8)
A solution of 0.2 mmol of the indazolium salt 5 [26] and [M+Na+]. – HRMS ((+)-ESI): m/zꢀ=ꢀ257.1110 (calcd. 257.1112
0.4 mmol of silver(I) oxide in 5 mL of dichloromethane was for [C15H17N2S]+).
stirred for 24 h at 40ꢀ°C. After evaporation of the solvent
in vacuo, the crude reaction product was purified by flash
column chromatography (silica gel; dichloromethane) 3.6 p-Tolyl-N-ethyl-2-(phenylamino)benzi-
and dried in vacuo. Yield: 43 mg (90 %) of a colorless solid;
midothioate (11)
m.p.: 80–82ꢀ°C. – 1H NMR ([D6]DMSO): δꢀ=ꢀ7.78 (ddd, Jꢀ=ꢀ7.6 ,
0.9, 0.8 Hz, 1H, Ar-H), 7.58–7.53 (m, 3H, Ar-H), 7.46–7.38 (m, A solution of 0.5 mmol of indazolium salt 5 [26], 0.5 mmol
3H, Ar-H), 7.24 (ddd, Jꢀ=ꢀ7.6, 7.0, 0.8 Hz, 1H, Ar-H), 7.14 (d, of 4-methylbenzenethiol and 0.6 mmol of potassium
Jꢀ=ꢀ8.4 Hz, 1H, Ar-H), 3.70 (q, Jꢀ=ꢀ7.1 Hz, 2H, CH2-H), 1.04 (t, t-butoxide in 20 mL of toluene was stirred for 2 h at 60ꢀ°C.
Jꢀ=ꢀ7.1 Hz, 3H, CH3-H) ppm. – 13C NMR ([D6]DMSO): δꢀ=ꢀ162.6, After evaporation of the solvent in vacuo, the crude reac-
149.3, 140.3, 132.7, 130.0, 128.0, 124.8, 123.2, 122.7, 117.5, tion product was purified by flash column chromatog-
112.0, 37.3, 12.9 ppm. – IR (ATR): νꢀ=ꢀ2915, 2848, 1472, 1462, raphy (petroleum ether-ethyl acetateꢀ=ꢀ5:1) and dried
1
1021, 958, 887, 843, 718, 557, 492, 473 cm–1. – MS (70 eV): in vacuo. Yield: 150 mg of a yellow oil (87 %). – H NMR
m/zꢀ=ꢀ238.2 [M]+. – HRMS ((+)-ESI): m/zꢀ=ꢀ239.1183 (calcd. (CDCl3 + TMS): δꢀ=ꢀ9.11 (s, 1H, PhNH-H), 7.56 (dd, Jꢀ=ꢀ7.9, 1 . 5
239.1184 for [C15H15N2O]+).
Hz, 1H, Ar-H), 7.30–7.25 (m, 3H, Ar-H), 7.10–7.07 (m, 4H,
Ar-H), 7.03 (ddd, Jꢀ=ꢀ8.0, 7.0, 1.5 Hz, 1H, Ar-H), 6.97–6.92
(m, 3H, Ar-H), 6.61 (ddd, Jꢀ=ꢀ7.9, 7.0, 1.2 Hz, 1H, Ar-H), 3.80
(q, Jꢀ=ꢀ7.3 Hz, 2H, CH2-H), 2.24 (s, 3H, PhMe-H), 1.41 (t,
Jꢀ=ꢀ7.3 Hz, 3H, CH2CH3-H) ppm. – 13C NMR (CDCl3 + TMS):
δꢀ=ꢀ161.1, 142.8, 142.4, 137.3, 132.1, 132.0, 129.8, 129.7, 129.4,
129.3, 124.0, 121.4, 119.1, 118.6, 115.9, 49.3, 21.1, 16.0 ppm.
3.3 N-Ethyl-2-(phenylamino)benzamide (9)
and N-ethyl-2-(phenylamino)benzthio-
amide (10)
A solution of 1 mmol of the indazolium salt 5 [26], 1 mmol – IR (ATR): νꢀ=ꢀ3019, 2967, 2929, 2867, 1588, 1510, 1449,
of sodium hydrogensulfide hydrate, and 1.2 mmol of 1313, 1197, 1017, 926, 804, 745, 694, 491 cm–1. – MS ((+)-
potassium t-butoxide in 20 mL of toluene was stirred ESI): m/zꢀ=ꢀ347.2. – HRMS ((+)-ESI): m/zꢀ=ꢀ347.1583 (calcd.
for 3 h at reflux temperature. After evaporation of the 347.1582 for [C22H23N2S]+).
solvent in vacuo, the crude reaction product was purified
by flash column chromatography (petroleum ether-ethyl
acetateꢀ=ꢀ5:1) and dried in vacuo.
3.7 Phenyl-N-ethyl-2-(phenylamino)benzi-
midate (12)
3.4 N-Ethyl-2-(phenylamino)benzamide (9)
A solution of 0.5 mmol of the indazolium salt 5 [26],
0.6 mmol of phenol and 0.6 mmol of potassium t-butox-
Yield: 137 mg (57 %), all spectroscopic data are identically ide in 20 mL of toluene was stirred for 2 h at 60ꢀ°C. After
with the literature values [33].
evaporation of the solvent in vacuo, the crude reaction
product was purified by flash column chromatography
(petroleum ether-ethyl acetateꢀ=ꢀ3:1) and dried in vacuo.
Yield: 80 mg of a colorless solid (51 %); m.p.: 68–70ꢀ°C.
3.5 N-Ethyl-2-(phenylamino)benzothio-
amide (10)
1
– H NMR (CDCl3 + TMS): δꢀ=ꢀ11.10 (s, 1H, PhNH-H), 7.57 (dd,
Jꢀ=ꢀ8.1, 1.5 Hz, 1H, Ar-H), 7.39 (dd, Jꢀ=ꢀ8.5, 1.0 Hz, 1H, Ar-H),
Yield: 26 mg of a yellow solid (10 %); m.p.: 107–109ꢀ°C. 7.36–7.32 (m, 2H, Ar-H), 7.29–7.25 (m, 4H, Ar-H), 7.19 (ddd,
1
ref. [37]: 116ꢀ°C. – H NMR (CDCl3 + TMS): δꢀ=ꢀ8.23 (s, Jꢀ=ꢀ8.5, 7.0, 1.5 Hz, 1H, Ar-H), 7.06–6.98 (m, 2H, Ar-H), 6.92–
1H, PhNH-H), 7.86 (bs, 1H, EtNH-H), 7.24–7.11 (m, 5H, 6.89 (m, 2H, Ar-H), 6.62 (ddd, Jꢀ=ꢀ8.1, 7.0, 1.0 Hz, 1H, Ar-H),
Ar-H), 7.02 (dd, Jꢀ=ꢀ8.5, 1.0 Hz, 2H, Ar-H), 6.88 (tt, Jꢀ=ꢀ7.3, 3.53 (q, Jꢀ=ꢀ7.3 Hz, 2H, CH2-H), 1.27 (t, Jꢀ=ꢀ7.3 Hz, 3H, CH3-H)
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