Eur. J. Org. Chem. 2008 · © WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2008 · ISSN 1434–193X

SUPPORTING INFORMATION

Title: Synthesis of Annulenes via Multiple Wittig Reactions; In-Situ Dimerization of 1,2;5,6-Dibenzocyclooctatetraene Author(s): Jan Bornhöft, Jan Siegwarth, Christian Näther, Rainer Herges* Ref. No.: O200701174

Physical and spectroscopic data for Tricyclo[11.4.0.04,9]hexadeca-2,4,6,8,10,12,14,16-octaene (1,2;5,6-Dibenzocyclooctatetraene) (3a) tr = 4.3 min. Yield: 298 mg (6 %). Colorless solid. M.p. 109 °C. 1H-NMR (600 MHz, CDCl3, 298 K, TMS): δ =

7.16-7.13 (m, 4 H, H-6, H-7, H-14, H-15), 7.07-7.04 (m, 4 H, H-5, H-8, H-13, H-16), 6.75 (s, 4 H, H-2, H-3, H-

10, H-11) ppm. 13C-NMR (150.9 MHz, CDCl3, 298 K, TMS): δ = 137.12 (C-1, C-4, C-9, C-12), 133.25 (C-2, C-

3, C-10, C-11), 129.11 (C-5, C-8, C-13, C-16), 126.83 (C-6, C-7, C-14, C-15) ppm. MS (EI, 70 eV): m/z (%)

[Frag.] = 204 (100) [M+], 176 (4), 101 (37). MS (CI, Isobutan): m/z (%) [Frag.] = 205 (55) [M+ + H], 191 (100).

EA: calcd. C16H12 (204.28): C: 94.08 %, H: 5.92 %; found: C: 93.94 %, H: 6.06 %

Physical and spectroscopic data for Octahydrotetrabenzo[16]annulene (7)

The hydrogenation product was purified on a silica gel column. Yield: 50 mg (99%). Colorless solid. M.p. 198-

199 °C (Lit.:[18] 198-201). 1H-NMR (500 MHz, CDCl3, 298 K, TMS): δ = 7.22-7.15 (m, 16 H, H-Ar), 2.89 (s, 16

H, H-CH2) ppm. 13C-NMR (125.8 MHz, CDCl3, 297 K, TMS): δ = 139.55 (Cquart.-Ar), 128.72, 126.33 (CH-Ar),

33.38 (CH2) ppm. MS (EI, 70 eV): m/z (%) [Frag.] = 416 (100) [M+], 311 (46), 219 (20), 209 (63), 207 (65), 193

(43), 178 (25), 149 (6), 129 (14), 119 (57), 105 (48). IR (KBr): = 3040 (w), 3002 (w), 2948 (m), 2931 (m), 2923

(m), 2853 (m), 1490 (m), 1452 (m), 1443 (m), 753 (s) cm-1. UV/Vis (dichloromethane): λmax (lg ε) = 265 nm

(3.18).

Atom numbering used for proton and carbon NMR-assignment

11

12

10

9

1 4

2 31615

1314

56

87

Compound 3a

11

1217

18

16

15

13

14

19 10

20

25

262423

2122

2

128

27

29

30

32

31

3

9

45

6

87

Compound all-trans-6

26

25

27

28

20

1

19

2 3

18

17

4

12

9

11

10

13

14

16

15

21

22

24

23

32

31

29

30

8

7

5

6 Compound 7

25

24

26

27

19

32

18

1 2

17

16

3

11

8

10

9

12

13

15

14

20

21

23

22

31

30

28

29

7

6

4

5

H H

H H

Compound 10a

25

24

26

27

19

32

18

1 2

17

16

3

11

8

10

9

12

13

15

14

20

21

23

22

31

30

28

29

7

6

4

5

H H

H H

Compound 10b

25

24

26

27

19

32

18

1 2

17

16

3

11

8

10

9

12

13

15

14

20

21

23

22

31

30

28

29

7

6

4

5

H H

H H

Compound 10c

25

24

26

27

19

32

18

1 2

17

16

3

11

8

10

9

12

13

15

14

20

21

23

22

31

30

28

29

7

6

4

5

H H

H H

Compound 11

NMR-Spectroscopy

Figure S1. 1H-NMR Spectrum (600 MHz, CDCl3, TMS, 298 K) of dibenzocyclooctatetraene 3a

Figure S2. 13C-NMR Spectrum (150.9 MHz, CDCl3, TMS, 298 K) of dibenzocyclooctatetraene 3a

Figure S3. 1H-NMR Spectrum (600 MHz, CDCl3, TMS, 298 K) of all-trans-tetrabenzo[16]annulene all-trans-6

Figure S4. 13C-NMR Spectrum (150.9 MHz, CDCl3, TMS, 298 K) of all-trans-tetrabenzo[16]annulene all-trans-6

Figure S5. 1H-NMR Spectrum (500 MHz, CDCl3, TMS, 298 K) of Octahydrotetrabenzo[16]annulene 7

Figure S6. 13C-NMR Spectrum (125.8 MHz, CDCl3, TMS, 298 K) of Octahydrotetrabenzo[16]annulene 7

Figure S7. 1H-NMR Spectrum (500 MHz, CDCl3, TMS, 298 K) of Dodecahydrohexabenzo[24]annulene 9

Figure S8. 13C-NMR Spectrum (125.8 MHz, CDCl3, TMS, 298 K) of Dodecahydrohexabenzo[24]annulene 9

Figure S9. 1H-NMR Spectrum (600 MHz, CDCl3, TMS, 298 K) of C1 symmetric dimer 10a

Figure S10. 13C-NMR Spectrum (150.9 MHz, CDCl3, TMS, 298 K) of C1 symmetric dimer 10a

Figure S11. 1H-NMR Spectrum (600 MHz, CDCl3, TMS, 298 K) of Ci symmetric dimer 10b

Figure S12.13C-NMR Spectrum (150.9 MHz, CDCl3, TMS, 298 K) of Ci symmetric dimer 10b

Figure S13. 1H-NMR Spectrum (600 MHz, CDCl3, TMS, 298 K) of D2 symmetric dimer 10c

Figure S14. 13C-NMR Spectrum (150.9 MHz, CDCl3, TMS, 298 K) of D2 symmetric dimer 10c

UV-Spectroscopy

250 300 350 400 450 500 550 600

10c 10b 10a 11

A (s

tand

ardi

zed)

λ in nm

Figure S15. UV-Spectra (recorded in dichloromethane solution) of compounds 10a-c and 11

250 300 350 400 450 500 550 600

all-trans-6 7

A (s

tand

ardi

zed)

λ in nm

Figure S16. UV-Spectra (recorded in dichloromethane solution) of compounds all-trans-6 and 7