8
Z. Hassan et al. / Tetrahedron xxx (2012) 1e10
312 (17), 215 (24), 214 (100), 194 (20), 193 (27), 184 (17); HRMS (EI):
1593, 1455, 1407, 1343, 1343 (m), 1288 (s), 1214, 1184, 1120, 1059,
832, 817 (m), 799 (s), 723 (s), 646, 638 (m); lmax (log ε)¼254
(4.77), 324 (4.10): m/z (%)¼366 (Mþ, 100), 351 (14), 337 (45), 308
(41), 265 (25); HRMS (EI): calcd for C26H22O2 (Mþ) 366.1614, found
366.1619.
calcd for C30H16F4O2 [M]þ: m/z¼484.1080; found: 484.1077.
3.5.2. 2,3,5,6-Tetrakis(3,5-dimethylphenyl)cyclohexa-2,5-diene-1,4-
dione (3q). Starting from 5 (211 mg, 0.5 mmol), and 2q (300 mg,
2.0 mmol) following the general procedure D, 3q was obtained as
a yellow solid (192 mg, 73%), mp¼263e265 ꢀC; 1H NMR (300 MHz,
3.5.6. 2,3-Di(3-fluorophenyl)naphthoquinone (8b). Starting from 7
(316 mg, 1 mmol), and boronic acid 2l (2.0 mmol) following general
procedure A, 8b was obtained as a yellow solid (180 mg, 69%),
298 K, CDCl3):
H
d
¼2.09 (s, 24H, 8CH3), 6.63 (s, 8H, HAr), 6.76 (s, 4H,
Ar); 13C NMR (75 MHz, 298 K, CDCl3):
d
¼21.1 (CH3), 128.4, 129.7
(CHAr), 132.7, 136.7, 143.0 (CAr), 187.4 (C]O); IR (neat, cmꢂ1):
mp¼180e182 ꢀC; 1H NMR (CDCl3, 250 MHz):
¼6.75e6.78 (m, 4H),
d
~
v¼3267, 3002 (w), 2913 (m), 2860, 2734 (w), 1648 (s), 1601, 1462,
6.87e6.93 (m, 2H), 7.12e7.18 (m, 2H), 7.73e7.76 (m, 2H), 8.11e8.14
2
1376, 1332 (m), 1269 (w), 1239 (s), 1168 (w), 1099, 1037, 995, 937
(m), 878 (w), 840 (s), 781 (m), 692 (s), 601 (m) cmꢂ1. Under the
conditions of electronic ionization (EI), the compound was reduced
to dihydrobenzoquinone. GCeMS (EI, 70 eV): m/z (%) 527 (43,
Mþ1), 526 (Mþ,100), 524 (31), 510 (15), 509 (29), 496 (21), 468 (14),
263 (17), 234 (44), 219 (25), 203 (30), 202 (15), 191 (16), 189 (15), 91
(9); HRMS (EI): calcd for C38H36O6 [M]þ: m/z¼524.2709; found:
524.2706.
(m, 2H); 13C NMR (CDCl3, 63 MHz):
d
¼114.5 (d, JCeF¼20.8 Hz,
2
4
CHAr), 116.5 (d, JCeF¼23.0 Hz, CHAr), 125.1 (d, JCeF¼2.7 Hz, CHAr),
125.7 (CHAr), 128.4 (d, 3JCeF¼8.2 Hz, CHAr), 130.9 (CAr), 133.1 (CHAr),
3
4
133.9 (d, JCeF¼8.2 Hz, CAr), 143.9 (d, JCeF¼2.4 Hz, C]C), 161.1 (d,
1
JCeF¼246.6 Hz, CAr),183.1 (C]O); IR (ATR, cmꢂ1):
¼3307, 3095,
~
n
3070, 3038 (w), 1662 (s), 1596 (m), 1581 (s), 1557, 1479, 1434, 1339,
1327 (m), 1290 (s), 1279, 1267 (m), 1245 (s), 1223, 1181, 1169, 1149,
1108, 1077, 1057, 959, 949, 927, 885 (s), 872, 794 (m), 777, 759, 718
(s); lmax (log ε)¼212 (4.20), 252 (4.72), 303 (4.17): m/z (%)¼346 (Mþ,
100), 317 (26), 288 (10), 270 (41), 194 (22); HRMS (EI): calcd for
3.5.3. 2,3,5,6-Tetrakis(3,4-dimethylphenyl)cyclohexa-2,5-diene-1,4-
dione (3s). Starting from 5 (211 mg, 0.5 mmol), and 2r (300 mg,
2.0 mmol) following general procedure D, 3s was obtained as
a yellow solid (207 mg, 79%), mp¼224e226 ꢀC; 1H NMR (300 MHz,
C
22H12O2F2 (Mþ) 346.0799, found 346.0801.
3.5.7. 2,3-Di(3-trifluoromethylphenyl)naphthoquinone (8c). Starting
from 7 (316 mg,1 mmol), and boronic acid 2m (2.0 mmol) following
general procedure A, 8c was obtained as a yellow solid (243 mg,
298 K, CDCl3):
H
d
¼2.06, 2.10 (s, 24H, 8CH3), 6.69 (d, 4H, 3J¼7.8 Hz,
Ar), 6.85 (m, 8H, HAr); 13C NMR (75 MHz, 298 K, CDCl3):
d
¼19.6,
19.7 (CH3), 128.2 (CAr), 128.9 (CHAr), 130.5 (CAr), 132.1, 135.5 (CHAr),
83%), mp¼139e141 ꢀC; 1H NMR (CDCl3, 250 MHz):
¼7.19e7.21 (m,
d
136.6, 142.6 (CAr), 187.5 (C]O); IR (neat, cmꢂ1): v¼3260, 3019 (w),
4H), 7.33 (t, 3J¼8.3 Hz, 2H), 7.46 (d, 3J¼7.7 Hz, 2H), 7.76e7.79 (m,
~
2915 (m), 2728 (w), 1645 (s), 1607, 1557, 1495, 1446, 1379, 1313,
1223, 1177, 1111, 1068, 1019 (m), 958 (w), 896 (m), 814 (s), 758, 717,
659, 575 (m) cmꢂ1. Under the conditions of electronic ionization
(EI), the compound was reduced to dihydrobenzoquinone. GCeMS
(EI, 70 eV): m/z (%) 527 (45, Mþ1), 526 (Mþ, 100), 524 (15), 503 (12),
502 (36), 500 (37), 406 (13), 277 (13), 243 (15), 234 (18), 231 (19),
229 (12), 220 (11), 219 (21), 215 (14), 205 (15), 203 (21), 202 (23),
157 (16), 133 (17), 105 (14), 91 (25), 77 (21), 44 (19), 43 (23), 41 (13);
2H), 8.14e8.17 (m, 2H); 13C NMR (CDCl3, 63 MHz):
d
¼123.6 (q,
1JCeF¼272.5 Hz, CF3), 125.3 (q, 3JCeF¼3.7 Hz, CHAr), 126.9 (CH), 127.5
3
2
(q, JCeF¼4.0 Hz, CHAr), 128.4 (CHAr), 130.5 (q, JCeF¼32.8 Hz,
CeCF3), 131.9, 133.4 (CAr), 133.8, 134.3 (CHAr), 145.1 (C]C), 183.9
(C]O); IR (ATR, cmꢂ1):
¼3306, 3069, 3041 (w), 1664 (s), 1614 (w),
~
n
1595 (m), 1486, 1429 (w), 1331 (s), 1291, 1265, 1205 (m), 1166, 1115
(s), 1097, 1075, 1063, 1024, 917 (m), 793, 721, 698 (s), 653 (m).; lmax
(log ε)¼200 (4.27), 250 (4.75), 303 (4.23): m/z (%)¼466 (Mþ, 100),
417 (14), 397 (31), 377 (16), 349 (18), 320 (45); HRMS (EI): calcd for
HRMS (EI): calcd for
524.2711.
C
38H36O2 [M]þ: m/z¼524.2709; found:
C
24H12O2F6 (Mþ) 446.0736, found 446.0739.
3.5.4. 2,3,5,6-Tetrakis(4-tert-butylphenyl)cyclohexa-2,5-diene-1,4-
dione (3t). Starting from 5 (211 mg, 0.5 mmol), and 2t (356 mg,
2.0 mmol) following general procedure D, 3t was obtained as
a yellow solid (248 mg, 78%), mp¼253e255 ꢀC; 1H NMR (300 MHz,
3.5.8. 2,3-Di(3,5-dimethylphenyl)naphthoquinone (8d). Starting
from 7 (316 mg, 1 mmol), and boronic acid 2q (2.0 mmol) fol-
lowing general procedure A, 8d was obtained as a yellow solid
(290 mg, 79%), mp¼263e265 ꢀC; 1H NMR (CDCl3, 250 MHz):
298 K, CDCl3):
d
¼1.17 (s, 36H, 12CH3), 6.93 (d, 8H, 3J¼8.6 Hz, 8HAr),
d
¼2.12 (s, 12H, CH3), 6.61 (s, 4H, CHAr), 6.78 (s, 2H, CHAr),
7.12 (d, 8H, 3J¼8.6 Hz, 8HAr); 13C NMR (63 MHz, 298 K, CDCl3):
7.69e7.72 (m, 2H, CH), 8.09e8.12 (m, 2H, CH); 13C NMR (CDCl3,
d
¼31.1 (CH3), 34.5 (C), 124.3 (CHAr), 130.1 (CAr), 130.7 (CHAr), 142.8,
63 MHz):
d
¼20.4 (CH3), 125.3, 126.9, 128.6 (CH), 131.1, 131.9 (C),
151.1 (CAr), 187.2 (C]O); IR (neat, cmꢂ1): v¼3085 (w), 2958, 1650
(m), 1582 (w), 1502, 1393, 1304, 1197 (m), 1100 (s), 1015 (m), 965
(w), 820 (s), 723, 643 (m), 562 (s) cmꢂ1. Under the conditions of
electronic ionization (EI), the compound was reduced to dihy-
drobenzoquinone. Under the conditions of electronic ionization
(EI), the compound was reduced to dihydrobenzoquinone. GCeMS
(EI, 70 eV): m/z (%) 639 (49, Mþ1), 638 (Mþ,100), 608 (38), 304 (27),
129 (35), 111 (53), 97 (23), 85 (16), 83 (26), 71 (25), 57 (75), 43 (31);
HRMS (ESI-TOF): calcd for C46H53O2 [MþH]þ: m/z¼637.4045;
found: 637.4047.
132.5 (CH), 135.6 (C), 144.8 (C]C), 183.9 (C]O); IR (ATR, cmꢂ1):
~
~
n
¼3305, 3001, 2911, 2859 (w), 1660, 1651 (s), 1594, 1574 (m), 1463,
1455, 1374 (w), 1348, 1325, 1309 (m), 1274 (s), 1189, 1175 (m) 1083,
920 (w), 835, 793 (m), 719, 714 (s) 694, 681, 617 (m); UVevis
(CH2Cl2, nm): lmax (log ε)¼227 (4.50), 254 (4.62), 321 (3.9): m/z
(%)¼366 (Mþ, 100), 336 (8), 323 (36); HRMS (EI): calcd for
C
26H22O2 (Mþ) 366.1614, found 366.1612.
3.5.9. 2,3-Di(3-biphenyl)naphthoquinone (8e). Starting from
7
(316 mg, 1 mmol), and boronic acid 2w (2.0 mmol) following
general procedure A, 8e was obtained as a yellow solid (258 mg,
3.5.5. 2,3-Di(4-ethylphenyl)naphthoquinone (8a). Starting from 7
(316 mg, 1 mmol), and boronic acid 2c (2.0 mmol) following
general procedure A, 8a was obtained as a yellow solid (246 mg,
74%), mp¼186e188 ꢀC; 1H NMR (CDCl3, 250 MHz):
¼7.07e7.11
d
(m, 2H), 7.18e7.32 (m, 14H), 7.39e7.24 (m, 2H), 7.72e7.76 (m, 2H),
8.14e8.17 (m, 2H); 13C NMR (CDCl3, 63 MHz):
d
¼126.7, 127.2, 127.3,
67%), mp¼135e137 ꢀC; 1H NMR (CDCl3, 250 MHz):
d
¼1.13 (t,
127.4, 128.2, 128.7, 129.5, 129.9 (CH), 132.2, 133.7 (C), 133.9 (CH),
3J¼7.6 Hz, 6H, CH3), 2.53 (q, 3J¼7.6 Hz, 4H, CH2) 6.91e7.2 (m, 8H,
140.7, 140.9 (C), 145.9 (C]C), 184.7 (C]O); IR (ATR, cmꢂ1):
CHAr), 7.69e7.72 (m, 2H, CH), 8.10e8.13 (m, 2H, CH); 13C NMR
n
¼3304, 3062, 3033 (w), 1661, 1591 (m), 1472, 1450, 1406, 1323
~
(CDCl3, 63 MHz):
d
¼15.1 (CH3), 28.6 (CH2), 126.6, 127.1, 130.6 (CH),
(w), 1278 (s), 1255, 1195 (m), 1016 (w), 803, 791 (m), 753 (s), 738
(m), 714, 693 (s), 659, 595 (m); lmax (log ε)¼208 (4.58), 252 (5.04),
310 (4.09): m/z (%)¼462 (Mþ, 100), 433 (28), 357 (37), 327 (49),
132.3 (C), 133.7 (CH), 144.3 (C), 145.5 (C]C), 185.0 (C]O); IR (ATR,
cmꢂ1):
~
n
¼0.3295, 3082, 3023, 2966, 2930, 2872 (w), 1657 (s), 1609,