3 f: Off-white solid; yield: 79% (based on 1); m.p. 241–2438C;
1H NMR (400 MHz, CDCl3): d=10.57 (s, 3H, N-CH-N), 8.89 (s, 3H, Im-
H), 7.49–7.45 (t, 3H, ArH), 7.25–7.23 (d, JH,H =8 Hz, 6H, ArH), 7.06 (s,
3H, Im-H) 6.19 (s, 6H, Mes-CH2-Im), 2.50 (s, 9H, Ar-CH3), 2.41–2.24
4d: White crystalline solid; yield: 73% (based on 3); m.p. 234–
2368C; H NMR (400 MHz, CDCl3): d=6.79–6.78 (d, JH,H =2.4 Hz, 3H,
1
Im-H), 6.25–6.24 (d, JH,H =2.4 Hz, 3H, Im-H), 5.97–5.90 (m, 3H, N-
CH2CHCH2), 5.31 (s, 6H, Mes-CH2-Im), 5.29–5.21 (m, 6H, N-
CH2CHCH2), 4.80–4.78 (d, JH,H =6.4 Hz, 6H, N-CH2CHCH2), 2.19 (s,
9H, Ar-CH3) ppm; 13C NMR (100 MHz, CDCl3): d=156.05 (C=Se),
139.98 (ArC), 131.42 (N-CH2CHCH2), 131.18 (ArC) 119.68 (N-
CH2CHCH2), 118.56 (Im-CH), 116.73 (Im-CH), 51.93 (N-CH2CHCH2),
48.98 (Mes-CH2-Im), 16.84 (Ar-CH3) ppm; FTIR (neat): n=3129 (w),
3087(w), 2962 (w), 2917 (w), 1563 (w), 1440 (m), 1396 (s), 1327 (w),
1260 (m), 1235 (s), 1217 (s), 1178 (w), 1090 (m), 1016 cmÀ1 (s); ele-
mental analysis calcd (%) for C30H36N6Se3 (717.53): C 50.22, H 5.06,
N 11.71; found: C 50.1, H 5.0, N 11.6.
(m, 6H, Ar-CH(CH3)2),1.20–1.10(dd,
JH,H =6.8 Hz, 36H, Ar-
CH(CH3)2) ppm; 13C NMR (100 MHz, CDCl3): d=144.99 (ArC), 142.28
(ArC), 137.55 (ArC), 131.59 (N-CH-N), 130.17 (ArC), 128.56 (ArC),
124.55 (ArC), 124.51 (Im-CH), 124.11 (Im-CH), 49.31 (Mes-CH2-Im),
28.65 (Ar-CH(CH3)2), 24.48 (Ar-CH(CH3)2), 24.40 (Ar-CH(CH3)2), 17.43
(Ar-CH3) ppm; FTIR (neat): n=3383 (w), 3111 (w), 3030 (w), 2961 (s),
2927 (m), 2868 (m), 2032 (w), 1623 (w), 1592 (w), 1540 (s), 1457 (s),
1418 (w), 1384 (w), 1364 cmÀ1 (m); elemental analysis calcd (%) for
C57H75N6Br3 (1084.36): C 63.16, H 6.97, N 7.75; found: C 63.3, H 7.0,
N 7.8.
4e: White crystalline solid; yield: 65% (based on 3); m.p. 296–
1
2988C; H NMR (400 MHz, CDCl3): d=7.32–7.28 (t, 3H, ArH), 7.20–
Synthesis and characterization of 3,3’,3’’-[(2,4,6-trimethylbenzene-
1,3,5-triyl)tris(methylene)]tris[1-(2,6-alkyl/aryl)-1H-imidazole-2(3H)-
selenone]s 4a–f: An oven-dried Schleck tube was charged with
compound 3a (or 3b--f) (0.25 mmol), potassium carbonate
(6 equiv.), and selenium powder (6 equiv.) under an inert atmos-
phere. MeOH (5 mL) was added, and the mixture was stirred until
all compounds were fully dissolved. The mixture was then heated
to 708C for 2–5 days. Upon completion of the reaction, as moni-
tored by TLC, the mixture was filtered through Celite and washed
with CH2Cl2 (45 mL). The combined organic phase was evaporat-
ed to obtain the crude solid, which was further washed with
CH2Cl2 and water to afford the analytically pure compound. Suita-
ble crystals for X-ray analysis were grown in CH2Cl2/MeCN (2:1) at
room temperature.
7.18 (d, JH,H =7.6 Hz, 6H, ArH), 6.80–6.79 (d, JH,H =2.4 Hz, 3H, Im-H),
6.50–6.49 (d, JH,H =2 Hz, 3H, Im-H), 5.46 (s, 6H, Mes-CH2-Im), 2.36 (s,
9H, Ar-CH3), 2.07 (s, 18H, Ar-CH3) ppm; 13C NMR (100 MHz, CDCl3):
d=156.84 (C=Se), 139.90 (ArC), 136.43 (ArC), 135.73 (ArC), 131.71
(ArC), 129.60 (ArC), 128.51 (ArC), 119.62 (Im-CH), 117.48 (Im-CH),
49.14 (Mes-CH2-Im), 18.15 (Ar-CH3), 16.96 (Ar-CH3) ppm; FTIR (neat):
n=3149 (w), 3118 (w), 3077 (w), 2963 (w), 2917 (w), 2855 (w), 1727
(w), 1553 (w), 1478 (m), 1443 (w), 1416 (w), 1375 (s), 1332 (m),
1260 (w), 1120 cmÀ1 (m); elemental analysis calcd (%) for
C45H52N6Se3O2 (945.81): C 57.14, H 5.54, N 8.89; found: C 57.1, H
5.4, N 8.7.
4 f: Off-white crystalline solid; yield: 78% (based on 3); m.p. 122–
1
1248C; H NMR (400 MHz, CDCl3): d=7.50–7.47 (t, 3H, ArH), 7.31–
7.29 (d, JH,H =7.6 Hz, 6H, ArH), 6.83–6.82 (d, JH,H =2 Hz, 3H, Im-H),
6.50–6.49 (d, JH,H =2.4 Hz, 3H, Im-H), 5.50 (s, 6H, Mes-CH2-Im), 2.50–
1
4a: White solid; yield: 68% (based on 3); m.p. 287–2888C; H NMR
(400 MHz, [D6]DMSO): d=7.304–7.299 (d, JH,H =2 Hz, 3H, Im-H),
6.64–6.63 (d, JH,H =4 Hz, 3H, Im-H), 5.17 (s, 6H, Mes-CH2 -Im), 3.59
(s, 9H, N-CH3), 2.12 (s, 9H, Ar-CH3) ppm; 13C NMR (100 MHz, CDCl3):
d=119.94 (Im-CH), 116.50 (Im-CH), 49.08 (Mes-CH2 -Im), 37.04 (N-
CH3), 16.85 (Ar-CH3), 140.05 (ArC), 131.19 (ArC), 156.21 (C=Se) ppm;
FTIR (neat): n=3150 (w), 3123 (w), 2975(w), 2910(w), 1668 (w),
1567 (w), 1486 (w), 1447 (m), 1385 (s), 1343 (m), 1311 (m), 1219 (s),
1194 (s), 1125 cmÀ1 (m).[52]
2.47 (m, 6H, Ar-CH(CH3)2), 2.39 (s, 9H, Ar-CH3) 1.33–1.32 (d, JH,H
=
6.8 Hz, 18H, Ar-CH(CH3)2), 1.11–1.09 (d, JH,H =6.8 Hz, 18H, Ar-
CH(CH3)2) ppm; 13C NMR (100 MHz, CDCl3): d=159.09 (C=Se),
146.09 (ArC), 139.87 (ArC), 133.83 (ArC), 131.91 (ArC), 130.34 (ArC),
124.25 (ArC), 121.18 (Im-CH), 116.96 (Im-CH), 49.27 (Mes-CH2-Im),
29.65 (Ar-CH(CH3)2), 24.46 (Ar-CH(CH3)2), 23.33 (Ar-CH(CH3)2), 16.95
(Ar-CH3) ppm; FTIR (neat): n=3162 (w), 3135 (w), 3073 (w), 2961
(m), 2924 (m), 2867 (m), 1560 (w), 1470 (m), 1416 (m), 1377 (m),
1349 (m), 1303 (w), 1260 (s), 1216 (m), 1088 (m), 1020 cmÀ1 (s); ele-
mental analysis calcd (%) for C57H72N6Se3 (1078.10): C 63.50, H 6.73,
N 7.80; found: C 63.5, H 6.6, N 7.8.
4b: White crystalline solid; yield: 74% (based on 3); m.p. 236–
2388C; H NMR (400 MHz, CDCl3): d=6.83–6.82 (d, JH,H =2.4 Hz, 3H,
1
Im-H), 6.25–6.24 (d, JH,H =2.4 Hz, 3H, Im-H), 5.29 (s, 6H, Mes-CH2-
Im), 5.25–5.22 (m, 3H, N-CH-(CH3)3), 2.18 (s, 9H, Ar-CH3), 1.39–1.38
(d, JH,H =6.8 Hz, 18H, N-CH(CH3)3) ppm; 13C NMR (100 MHz, CDCl3):
d=154.65 (C=Se), 139.95 (ArC), 131.22 (ArC), 116.95 (Im-CH), 115.04
(Im-CH), 50.88 (N-CH(CH3)2), 48.64 (Mes-CH2-Im), 21.92 (N-CH(CH3)2),
16.81 (Ar-CH3) ppm; FTIR (neat): n=3121 (w), 3082 (w), 2971 (w),
2924 (m), 2854 (w), 1561 (w), 1459 (w), 1425 (m), 1407 (s), 1366
(m), 1331 (m), 1293 (w), 1218 (m), 1196 cmÀ1 (m); elemental analy-
sis calcd (%) for C32H48N7Se3 (767.65): C 50.07, H 6.30, N 12.77;
found: C 50.1, H 6.2, N 12.8.
Acknowledgements
The authors would like to express their deep thanks to the “State
Key Laboratory of Advanced Technology for Materials Synthesis
and Processing” for financial support. F.V. acknowledges the Chi-
nese Central Government for an “Expert of the State” position in
the program of “Thousand Talents”. I.N. and J.C. express their
deep appreciation to the Chinese Scholarship Council (CSC) for fi-
nancial support of their PhD studies, grants 2014GXZ328 and
2014GXZ323, respectively.
4c: Brown crystalline solid; yield: 75% (based on 3); m.p. 212–
2148C; 1H NMR (400 MHz, CDCl3): d=7.69–7.63 (q, 3H, N-CHCH2),
7.08–7.07 (d, JH,H =2.4 Hz, 3H, Im-H), 6.30–6.29 (d, JH,H =4 Hz, 3H,
Im-H), 5.30 (s, 6H, Mes-CH2-Im), 5.25–5.02 (dd, JH,H =7.2 Hz, 6H, N-
CHCH2), 2.23 (s, 9H, Ar-CH3) ppm; 13C NMR (100 MHz, CDCl3): d=
157.53 (C=Se), 140.19 (ArC), 131.59 (N-CHCH2), 131.02 (ArC) 117.69
(Im-CH), 114.96 (Im-CH), 102.45 (N-CHCH2), 48.60 (Mes-CH2-Im),
16.96 (Ar-CH3) ppm; FTIR (neat): n=3161 (w), 3130 (w), 3086 (w),
2922 (w), 1692 (w), 1642 (s), 1564 (w), 1428 (s), 1325 (m), 1291 (w),
1225 (m), 1116 (w), 1042 cmÀ1 (w); elemental analysis calcd (%) for
C29H36N7Se3 (719.52): C 48.41, H 5.04, N 13.63; found: C 48.5, H 5.1,
N 13.5.
Conflict of Interest
The authors declare no conflict of interest.
Keywords: crystallinity · NMR spectroscopy · selenium
structure elucidation · X-ray diffraction
·
ChemistryOpen 2017, 6, 1 –8
6
ꢀ 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim