8
E.T. Akin et al. / Tetrahedron xxx (2017) 1e10
4.22. 6-Bromo-1,2,3,4-tetrafluoronaphthalene (15l)
J ¼ 251.8 Hz), 138.9 (bd, J ¼ 249.4 Hz), 129.2 (bdt, J ¼ 18.6, 2.9 Hz),
128.2 (bdt, J ¼ 18.1, 3.0 Hz), 42.4, 41.1. 19F NMR (376 MHz, CDCl3):
Yield (300 mg, 90%), white crystals from CH2Cl2/n-hexane (9:1),
mp 63e64 ꢀC (lit55 mp 63e64 ꢀC). 1H NMR (400 MHz, CDCl3):
d
¼ ꢁ151.0 (m), ꢁ151.3 (m), ꢁ164.31 (m), ꢁ164.5 (m). IR (KBr, cmꢁ1):
3600-3000, 2929, 2868, 1687, 1497, 1423, 1325, 1254, 1065, 976,
852, 748. HRMS (ESI-TOF): m/z [MþNa]þ calcd. for C13H6F4NaO2:
293.0202; found: 293.0216.
d
¼ 8.18 (bs, 1H), 7.90 (bd, J ¼ 9.0 Hz, 1H), 7.66 (bd, J ¼ 9.0 Hz, 1H).
13C NMR (100 MHz, CDCl3):
d
¼ 142.5 (bd, J ¼ 250.8 Hz),141.4 (dddd,
J ¼ 251.8, 10.7, 4.6, 2.4 Hz), 138.7 (dtd, J ¼ 254.2, 15.2, 3.1 Hz), 138.2
(dtd, J ¼ 253.4, 15.3, 3.0 Hz), 131.2, 122.6 (m), 122.2, 122.0 (m), 120.8
(dd, J ¼ 14.5, 4.0 Hz), 118.3 (dd, J ¼ 14.6, 3.8 Hz). 19F NMR (376 MHz,
4.27. 5,6,7,8-Tetrafluoro-2-naphthoic acid (15o)
Yield (75 mg, 83%), white solid, mp 173e175 ꢀC (lit56 mp
CDCl3):
d
¼ ꢁ149.9 (m), ꢁ150.5 (m), ꢁ157.0 (m), ꢁ158.3 (m). IR (KBr,
cmꢁ1): 1667, 1603, 1523, 1483, 1453, 1409, 1364, 1248, 1137, 1126,
1069, 1033, 962, 889, 879, 817, 717. Anal. calc. for C10H3BrF4: C
43.05, H 1.08; found: C 42.95, H 1.20%.
233e235 ꢀC). 1H NMR (400 MHz, MeOD-d4):
d
¼ 8.65 (s, 1H), 8.14
(bd, A part of AB system, J ¼ 8.9 Hz, 1H), 8.09 (bd, B part of AB
system, J ¼ 8.9 Hz, 1H). 13C NMR (100 MHz, MeOD-d4):
d
¼ 166.9,
150.3, 149.6, 142.7 (ddd, J ¼ 251.0, 10.4 Hz, 5.1 Hz), 141.0 (ddd, J ¼
249.6, J ¼ 10.6, 4.8 Hz),137.9 (td, J ¼ 253.6,15.5, 2.9 Hz),137.0 (td, J ¼
252.5, 5.5, 2.9 Hz), 122.3 (dd, J ¼ 6.7, 4.1 Hz), 120.3 (dd, J ¼ 6.5,
4.23. 1,2,3,4-Tetrafluoro-6-(phenylethynyl)naphthalene (15m)
Yield (85 mg, 92%), white solid, mp 120e124 ꢀC. 1H NMR
3.9 Hz), 130.3, 127.2. 19F NMR (376 MHz, CDCl3):
d
¼ ꢁ151.4 (t, J ¼
(400 MHz, CDCl3):
d
¼ 8.22 (bs, 1H), 8.03 (bd, A part of AB system,
16.8 Hz), ꢁ152.4 (t, J ¼ 17.1 Hz), ꢁ158.8 (t, J ¼ 17.1 Hz), ꢁ161.2 (t, J ¼
17.1 Hz). IR (KBr, cmꢁ1): 3600-3000 (b), 2533, 1688, 1662, 1518,
1500, 1462, 1412, 1307, 1249, 1142, 1113, 1041, 987, 915, 837, 770,
704.
J ¼ 8.8 Hz, 1H), 7.69 (bd, B part of AB system, J ¼ 8.8 Hz, 1H),
7.61e7.56 (m, 2H), 7.41e7.37 (m, 3H). 13C NMR (100 MHz, CDCl3):
d
¼ 142.4 (bd, J ¼ 250.3 Hz), 142.0 (bd, J ¼ 254.2 Hz), 138.5 (bd, J ¼
254.8 Hz, 2C), 132.0, 130.3, 129.1, 128.7, 123.4, 123.0, 122.8, 120.5,
119.8 (bd, J ¼ 14.9 Hz), 118.8 (bd, J ¼ 15.4 Hz), 91.9, 88.6. 19F NMR
4.28. 6-Bromo-1,2,3,4-tetrachloronaphthalene (15p)
(376 MHz, CDCl3):
d
¼ ꢁ150.0 (t, J ¼ 17.7 Hz), ꢁ150.4 (t, J ¼
17.7 Hz), ꢁ158.1 (t, J ¼ 17.7 Hz), ꢁ158.3 (t, J ¼ 17.7 Hz). IR (KBr,
cmꢁ1): 2957, 2951, 2924, 1664, 1660, 1513, 1482, 1450, 1362, 1033,
823. HRMS (ESI-TOF): m/z [MþH]þ calcd. for C18H9F4: 301.0640;
found: 301.0654.
Yield (250 mg, 89%), white crystals, mp 155e157 ꢀC. 1H NMR
(400 MHz, CDCl3):
d
¼ 8.37 (bd, J ¼ 1.5 Hz,1H), 8.07 (bd, A part of AB
system, J ¼ 9.0 Hz, 1H), 7.71 (bdd, B part of AB system, J ¼ 9.0,1.5 Hz,
1H). 13C NMR (100 MHz, CDCl3):
d
¼ 132.4, 131.4, 131.3, 130.7, 129.4,
128.9, 127.8, 127.4, 123.8 (2C). IR (KBr, cmꢁ1): 3600-3000 (b), 1546,
4.24. [1R(S),4R(S)]-5,6,7,8-tetrafluoro-1,4-dihydro-1,4-
ethenonaphthalene-2-carbonitrile (12n)
1468, 1289, 1250, 1177, 906, 864. HRMS (ESI-TOF): m/z [M]þ calcd.
79
for C
H
BrCl4: 341.8172; found: 341.8168, calcd. for C10H481BrCl4:
10
4
343.8143; found: 343.8142.
Yield (360 mg, 87%), white crystals, mp 84e86 ꢀC. 1H NMR
(400 MHz, CDCl3):
d
¼ 7.68 (dd, J ¼ 6.2, 1.5 Hz, 1H), 7.05e6.95 (m,
4.29. [1S(R),4R(S)]-5,6,7,8-tetrachloro-2-(phenylethynyl)-1,4-
dihydro-1,4-ethenonaphthalene (12q)
2H), 5.48e5.44 (m, 2H). 13C NMR (100 MHz, CDCl3):
d
¼ 155.0, 142.2
(m, J ¼ 241.2 Hz), 137.5 (dddd, J ¼ 244.2 Hz, J ¼ 17.4, 14.7, 6.9 Hz),
140.6, 139.6, 139.2, 127.7 (dt, J ¼ 15.3, 2.9 Hz), 127.4 (dt, J ¼ 19.1,
2.9 Hz). 125.9, 121.6, 116.1, 43.9, 42.2. 19F NMR (376 MHz, CDCl3):
Yield (0.5 g, 78%), white solid, mp 145e148 ꢀC. 1H NMR
(400 MHz, CDCl3):
d
¼ 7.38e7.33 (m, 2H), 7.26e7.20 (m, 3H), 7.01
d
¼ ꢁ147.1 (t, J ¼ 19.1 Hz), ꢁ147.5 (m), ꢁ159.2, ꢁ159.5 (m, 2F). HRMS
(dd, J ¼ 5.9, 1.5 Hz, 1H), 6.93 (td, J ¼ 5.9, 1.5 Hz, 1H), 6.86 (td, J ¼ 5.9,
1.5 Hz, 1H), 5.40 (td, J ¼ 5.9, 1.5 Hz, 1H), 5.36 (td, J ¼ 5.9, 1.5 Hz, 1H).
(ESI-TOF): m/z [MþH]þ calcd. for C13H6F4N: 252.0436; found:
252.0433.
13C NMR (100 MHz, CDCl3):
d
¼ 145.2, 144.9, 142.6, 139.3, 138.9,
135.5, 131.4, 128.6, 128.6, 128.5, 128.4, 126.8, 126.5, 122.9, 97.1, 85.3,
52.3, 47.1. IR (KBr, cmꢁ1): 3070, 3008, 2924, 2845, 2201, 1488, 1366,
1309, 1211, 1137, 914, 826, 755, 751. HRMS (ESI-TOF): m/z [MþNa]þ
calcd. for C20H10Cl4Na: 412.9434; found: 412.9418.
4.25. 5,6,7,8-Tetrafluoro-2-naphthonitrile (15n)
Yield (300 mg, 95%), white crystals from n-hexane/CH2Cl2 (1:9),
mp 71e73 ꢀC. 1H NMR (400 MHz, CDCl3):
d
¼ 8.45 (bs, 1H), 8.19 (bd,
A part of AB system, J ¼ 8.8 Hz,1H), 7.76 (bd, B part of AB system, J ¼
8.8 Hz, 1H). 13C NMR (100 MHz, CDCl3):
4.30. 1,2,3,4-Tetrachloro-6-(phenylethynyl)naphthalene (15q)
Yield (75 mg, 85%), white solid, mp 160e164 ꢀC. 1H NMR
d
¼ 141.3 (ddd, J ¼ 255.0,
10.5, 4.7 Hz), 139.4 (td, J ¼ 255.5, 15.0 Hz), 138.4 (td, J ¼ 255.5,
15.2 Hz), 128.3 (2C), 126.6 (dt, J ¼ 6.7, 2.8 Hz), 122.0 (dt, J ¼ 6.4,
2.5 Hz), 120.8 (m), 119.1 (m), 118.0, 111.9. 19F NMR (376 MHz, CDCl3):
(400 MHz, CDCl3):
d
¼ 8.45 (dd, J ¼ 1.6 Hz, 0.5 Hz, 1H), 8.25 (dd, A
part of AB system, J ¼ 8.8, 0.5 Hz, 1H), 7.69 (dd, B part of AB system,
d
¼ ꢁ147.2 (t, J ¼ 18.5 Hz), ꢁ148.1 (t, J ¼ 18.5 Hz), ꢁ152.3 (t, J ¼
J ¼ 8.8, 1.6 Hz, 1H), 7.63e7.58 (m, 2H), 7.42e7.37 (m, 3H). 13C NMR
20.0 Hz), ꢁ154.6 (t, J ¼ 20.0 Hz). IR (KBr, cmꢁ1): 2925, 2854, 2232,
1668, 1614, 1511, 1490, 1456, 1419, 1384, 1373, 1257, 1177, 1139, 1126,
1042, 991, 914, 836, 763. HRMS (ESI-TOF): m/z [MþNa]þ calcd. for
(100 MHz, CDCl3):
d
¼ 132.0, 131.5, 131.0, 130.7, 130.5, 130.2, 130.1,
129.5, 129.1, 128.7, 128.6, 125.9, 124.3, 122.8, 92.6, 88.7. IR (KBr,
cmꢁ1): 2921, 2851, 2207, 1610, 1552, 1493, 1298, 881, 819, 748.
HRMS (ESI-TOF): m/z [MþNa]þ calcd. for C18H8Cl4Na: 386.9278;
found: 386.9290.
C
11H3F4NNa: 248.0099; found: 248.0102.
4.26. [1S(R),4R(S)]-5,6,7,8-tetrafluoro-1,4-dihydro-1,4-
ethenonaphthalene-2-carboxylic acid (12o)
4.31. Trinaphthylene (15r)
Yield (124 mg, 14%), white crystals from CH2Cl2/n-hexane (9:1),
mp 186e189 ꢀC. 1H NMR (400 MHz, CDCl3):
d
¼ 7.88 (dd, J ¼ 6.2,
1.8 Hz, 1H), 7.03e6.91 (m, 2H), 5.80e5.76 (m, 1H), 5.44 (bt, J ¼
5.9 Hz, 1H). 13C NMR (100 MHz, CDCl3):
¼ 169.2, 152.7, 145.0, 142.5
(bd, J ¼ 249.2 Hz), 142.3 (bd, J ¼ 250.3 Hz), 140.5, 139.0, 138.0 (bd,
Yield (11.82 mg, 95%), white solid, mp >350 ꢀC (lit42 > 370 ꢀC),
1H NMR (400 MHz, CDCl3):
d
¼ 9.11 (s, 6H), 8.11e8.07 (m, AA0 part of
d
AA’BB0 system, 6H), 7.59e7.56 (m, BB0 part of AA’BB0 system, 6H).
13C NMR (100 MHz, CDCl3):
d
¼ 133.1, 129.2, 128.3, 126.6, 122.9.
Please cite this article in press as: Akin ET, et al., Access to polysubstituted naphthalenes and anthracenes via a retro-DielseAlder reaction,