D. Vuk et al. / Tetrahedron 68 (2012) 6873e6880
6879
ane¼7:3); colourless crystals; mp 105 ꢁC; UV (EtOH) lmax (log
3
)
4 . 3 . 7 . 4 . 3 . 7 19 - ( 1 - B e n z o t h i e n - 3 - yl ) - 9 - t h i a h e x a c y c l o
[9.7.1.02,10.02,18.03,8.012,17]nonadeca-3,5,7,12,14,16-hexaene
(12b). Yield 110 mg (44%); Rf 0.40 (petroleum ether/
dichloromethane¼7:3); colourless crystals; mp 95e97 ꢁC; UV
341 (4.32), 241 (4.18); 1H NMR (CDCl3; 600 MHz)
d
7.18 (dt, J¼7.3,
1.6 Hz, 1H, H-ar), 7.15 (dd, J¼7.3, 1.6 Hz, 1H, H-ar), 7.11 (dt, J¼7.3,
1.6 Hz, 1H, H-ar), 7.07 (d, J¼7.3 Hz, 1H, H-ar), 6.96 (d, J¼3.6 Hz, 1H,),
6.86 (s, 1H, H-A), 6.62 (dd, J¼3.6, 1.0 Hz, 1H), 6.53 (d, J¼3.4 Hz, 1H),
6.38 (dd, J¼3.4, 1.0 Hz, 1H), 4.28 (dd, JB,C¼7.1 Hz, JB,D¼1.6 Hz, 1H,
H-B), 3.44 (dd, JB,C¼7.1 Hz, JC,D¼15.6 Hz, 1H, H-C), 3.06 (dd,
JB,D¼1.6 Hz, JC,D¼15.6 Hz, 1H, H-D), 2.45 (d, J¼1.0 Hz, 3H, eCH3),
(EtOH) lmax (log
3
) 300 (3.77), 292 (3.72), 270 (3.85), 225 (4.62); 1H
NMR (CDCl3, 600 MHz)
d
7.86 (d, J¼8.0 Hz, 1H, H-ar), 7.71 (d,
J¼8.0 Hz, 1H, H-ar), 7.38 (dt, J¼8.0, 1.0 Hz, 1H, H-ar), 7.36 (d,
J¼7.5 Hz, 1H, H-ar), 7.28 (dt, J¼8.0, 1.0 Hz, 1H, H-ar), 7.23 (d,
J¼7.5 Hz, 1H, H-ar), 7.12 (dt, J¼7.5, 1.0 Hz, 1H, H-ar), 7.12 (dt, J¼7.5,
1.0 Hz, 1H, H-ar), 7.05 (dt, J¼7.5, 1.0 Hz, 1H, H-ar), 7.00 (dd, J¼7.5,
1.0 Hz, 1H, H-ar), 6.87 (dt, J¼7.5, 1.0 Hz, 1H, H-ar), 6.55 (d, J¼7.5 Hz,
1H, H-ar), 6.43 (d, J¼0.6 Hz, 1H, H-t), 4.72 (dd, J¼4.4, 2.9 Hz, 1H, H-
A), 4.10 (s, H-B), 3.80 (d, J¼4.4 Hz, 1H, H-C), 3.37 (d, J¼7.4 Hz, 1H, H-
D), 1.98 (ddd, J¼7.4, 2.9, 1.0 Hz, 1H, H-E); 13C NMR (CDCl3, 150 MHz)
2.28 (d, J¼1.0 Hz, 3H, eCH3); 13C NMR (CDCl3; 150 MHz)
d 143.1 (s),
142.2 (s), 139.3 (s), 137.7 (s), 134.9 (s), 133.9 (s), 132.6 (s), 128.3 (d),
127.3 (d),126.8 (d), 126.3 (d), 125.9 (d),124.4 (d), 124.1 (d), 123.9 (d),
122.0 (d, CA), 37.9 (d, CB), 37.1 (t, CC,D), 15.6 (q), 15.3 (q); IR 3067,
1433, 1225, 1030, 687 cmꢀ1. Anal. Calcd for C20H18S2: C, 74.49; H,
5.63. Found: C, 74.88; H, 5.88.
d
145.0 (s), 140.3 (s), 138.8 (s), 138.6 (s), 136.7 (s), 134.1 (s), 133.9 (s),
4.3.3. 2,20-(1,2-Dihydronaphthalene-2,3-diyl)bis(5-bromothiophene)
127.7 (d), 127.4 (d), 126.3 (d), 126.0 (d), 125.9 (d), 125.0 (d), 124.4 (d),
124.2 (d), 123.4 (d), 122.2 (d), 121.8 (d), 121.8 (d), 120.5 (d), 60.7 (d),
46.3 (d), 38.0 (d), 34.4 (d), 26.0 (d); IR 2957, 1443, 731 cmꢀ1; HRMS:
Mþ, found 394.0828.. C26H18S2 requires 394.0844.
(9c). Yield 15 mg (8%); Rf 0.79 (petroleum ether/dichlorometh
ane¼7:3); colourless crystals; mp 130 ꢁC; UV (EtOH) lmax (log
3 )
344 (3.96), 240 (3.85); 1H NMR (CDCl3, 600 MHz)
d
7.21 (d, J¼7.1 Hz,
1H, H-ar), 7.16e7.19 (m, 2H, H-ar), 7.08 (d, J¼7.3 Hz, 1H, H-ar), 6.93
(d, J3t,4t¼3.9 Hz, 1H, H-3t), 6.88 (s, 1H, H-0A), 6.87 (d, J3t,4t¼3.9 Hz,
4.4. Dehydrogenation of 9a with DDQ
0
0
0
0
1H, H-4t), 6.71 (d, J3t ,4t ¼3.8 Hz, 1H, H-3t ), 6.53 (d, J3t ,4t ¼3.8 Hz,
1H, H-4t0), 4.24 (dd, JB,C¼7.1 Hz, JB,D¼1.6 Hz, 1H, H-B), 3.50 (dd,
JC,D¼15.7 Hz, JB,C¼7.1 Hz, 1H, H-C), 3.04 (dd, JC,D¼15.7 Hz,
Benzene
solution
(8 mg,
3.4ꢂ10ꢀ3 M)
of
2,20-(1,2-
dihydronaphthalene-2,3-diyl)dithiophene (9a) was heated in the
presence of 6 mg 2,3-dichloro-5,6-dicyano-1,4-benzoquinone
(DDQ) for 7 h. The crude reaction mixture was purified by column
chromatography on a silica gel using petroleum ether as the eluent.
From the enriched first chromatographic fractions product 11 was
isolated.
JB,D¼1.6 Hz,1H, HD); 13C NMR (CDCl3, 150 MHz)
d 146.7 (s), 145.5 (s),
133.1 (s), 133.1 (s), 132.1 (s), 130.6 (d), 129.3 (d), 128.4 (d), 128.1 (d),
127.2 (d), 126.8 (d), 124.9 (d), 123.9 (d), 123.9 (d), 38.0 (d, CB), 36.9
(t, CC,D); IR 2920, 1514, 1022, 768 cmꢀ1. Anal. Calcd for C18H12Br2S2:
C, 47.81; H, 2.6. Found: C, 47.55; H, 2.59.
4.3.4. 2,20,200,2000-(1,2,2a,6b,7,8,8a,12b-Octahydrodibenzo[a,e]dicyclo-
buta[c,g]cyclooctene-1,2,7,8-tetrayl)tetrathiophene (10). Yield 30 mg
(25%); Rf 0.36 (petroleum ether/dichloromethane¼7:3); colourless
4.4.1. 2,3-(2,20-Dithienyl)naphthalene (11). Yield 5 mg (63%); Rf 0.74
(petroleum ether/dichloromethane¼7:3); colourless crystals with
spectroscopic data identical to compound 10 obtained previously.7
crystals; mp 294 ꢁC; UV (EtOH) lmax (log ): 231 (4.53); 1HNMR(CDCl3,
3
600 MHz)
d
7.19 (d, J¼8.9 Hz, 4H, H-ar), 7.15 (dd, J2t,3t¼5.0 Hz,
Acknowledgements
J2t,4t¼1.1 Hz, 4H, H-2t), 7.06 (d, J¼8.9 Hz, 4H, H-ar), 6.92 (dd,
J2t,3t¼5.0 Hz, J3t,4t¼3.5 Hz, 4H, H-3t), 6.90 (dd, J3t,4t¼3.5 Hz,
This work was supported by grants from the Ministry of Science,
Education and Sports of the Republic of Croatia (grant nos. 125-
0982933-2926, 098-0982929-2917, 098-1191344-2943).
J2t,4t¼1.1 Hz, 4H, H-4t), 4.66(d, J¼6.3 Hz, 4H), 4.61 (d, J¼6.3 Hz, 4H); 13
C
NMR (CDCl3, 150 MHz) d 143.1 (s), 137.5 (s), 126.2 (d), 126.0 (d), 124.7
(d), 124.6 (d), 123.7 (d), 47.7 (d), 41.4 (d); IR 2941, 1487, 1238, 1038,
685 cmꢀ1; HRMS: Mþ, found 588.1083. C36H28S4 requires 588.1079.
Supplementary data
4.3.5. 15-(3-Thienyl)-11-thiapentacyclo[7.5.1.02,14.03,8.010,14]penta-
deca-3,5,7,12-tetraene (12a). Yield 20 mg (13%); Rf 0.47 (petroleum
ether/dichloromethane¼7:3); colourless crystals; mp 69e71 ꢁC; UV
1H and 13C NMR spectra of compounds 7aec, 8a,b, 9aec, 10,
12a,b,13, UV spectra after irradiation of cis,cis-7a/8a, cis,trans-7a/8a
and trans,trans-7a/8a and crystal data and structure refinement of
9a and 12b. Supplementary crystallographic data for 9a and 12b
Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax: þ44 1223
contain the supplementary crystallographic data for this paper.
Supplementary data associated with this article can be found in the
data include MOL files and InChiKeys of the most important com-
pounds described in this article.
(EtOH) lmax (log
600 MHz)
3
) 245 (3.88), 228 (4.35); 1H NMR (CDCl3,
d
7.27 (d, J¼7.5 Hz, 1H, H-ar), 7.13 (dt, J¼7.5, 1.2 Hz, 1H, H-
ar), 6.96e7.00 (m, 2H), 6.77 (d, J¼7.5 Hz, 1H, H-ar), 6.50 (s and d,
J¼5.9 Hz, 2H), 6.33 (d, J¼5.9 Hz, 1H), 5.74 (d, J¼5.9 Hz, 1H), 4.40 (dd,
J¼4.9; 2.8 Hz, 1H, H-A), 3.90 (s, 1H, H-B), 3.55 (d, J¼4.9 Hz, 1H, H-C),
3.01 (d, J¼7.3 Hz,1H, H-D),1.89 (dd, J¼7.3, 2.8 Hz,1H, H-E); 13C NMR
(CDCl3,150 MHz) d 140.2 (s),136.2 (2s),133.4 (s),128.6 (d),126.9 (d),
126.4 (d),125.5 (d),125.3 (d),124.9 (d),123.8 (d),122.5 (d),120.1 (d),
60.3 (d), 46.7 (d), 39.2 (d), 30.6 (d), 27.0 (d); IR 2920, 1728, 1119,
719 cmꢀ1; HRMS: Mþ, found 294.0541. C18H14S2 requires 294.0531.
4.3.6. 3,30,300,3000-(1,2,2a,6b,7,8,8a,12b-Octahydrodibenzo[a,e]dicyclo-
buta[c,g]cyclooctene-1,2,7,8-tetrayl)tetrathiophene (13). Yield 46 mg
(31%); Rf 0,30 (petroleum ether/dichloromethane¼7:3); colourless
References and notes
crystals; mp 136e138 ꢁC; UV (EtOH) lmax (log
3
) 231 (4.27); 1H NMR
1. Vidakovic, D.; Skoric, I.; Horvat, M.; Marinic, Z.; Sindler-Kulyk, M. Tetrahedron
2008, 64, 3928e3934.
ꢀ
ꢀ
ꢀ
ꢁ
ꢁ
ꢁ
(CDCl3, 600 MHz)
d
7.20 (d, J¼8.9 Hz, 4H, H-ar), 7.18 (dd, J2t,5t¼5.0,
ꢀ
ꢀ
ꢀ
ꢁ
ꢁ
ꢁ
2. (a) Sindler-Kulyk, M.; Spoljaric, L.; Marinic, Z. Heterocycles 1989, 29, 679e682;
(b) Sindler-Kulyk, M.; Stiplosek, Z.; Vojnovic, D.; Metelko, B.; Marinic, Z. Het-
2.9 Hz, 4H, H-5t), 7.06 (d, J¼8.9 Hz, 4H, H-ar), 6.98 (dd, J2t,5t¼2.9 Hz,
J2t,4t¼1.2 Hz, 4H, H-2t), 6.86 (dd, J4t,5t¼5.0 Hz, J2t,4t¼1.2 Hz, 4H, H-
4t), 4.50 (d, 4H, J¼5.5 Hz), 4.48 (d, 4H, J¼5.5 Hz); 13C NMR (CDCl3,
ꢀ
ꢀ
ꢁ
ꢀ
ꢀ
erocycles 1991, 32, 2357e2363; (c) Sindler-Kulyk, M.; Kragol, G.; Piantanida, I.;
ꢀ
ꢁ
ꢀ ꢁ
ꢁ
Tomsic, S.; Vujkovic Cvijin, I.; Marinic, Z.; Metelko, B. Croat. Chem. Acta 1996, 69,
ꢀ
ꢀ
ꢀ
ꢁ
ꢀ ꢁ
ꢁ
ꢁ
ꢀ
1593e1602; (d) Sindler-Kulyk, M.; Skoric, I.; Tomsic, S.; Marinic, Z.; Mrvos-
150 MHz)
d 141.8 (s), 138.6 (s), 127.9 (d), 126.4 (d), 125.3 (d), 125.2
ꢀ
ꢀ
ꢀ
ꢁ
Sermek, D. Heterocycles 1999, 51, 1355e1369; (e) Skoric, I.; Marinic, Z.; Sindler-
Kulyk, M. Heterocycles 2000, 53, 55e68; (f) Skoric, I.; Basaric, N.; Marinic, Z.;
(d), 120.9 (d, C2t), 47.0 (d), 41.0 (d); IR 2914, 1483, 1080, 746 cmꢀ1
.
ꢀ
ꢀ
ꢁ
ꢁ
ꢁ