G
Synthesis
P. Niermeier et al.
Paper
1
3
1
C{ H} NMR (125 MHz, CDCl ): δ = 182.6 (C=O), 138.4, 135.1 (C2/C7),
References
3
1
35.0, 132.9, 130.2, 126.7 (C4/C5), 61.8 (CHOH).
(
1) Examples for organic applications: (a) Toyota, S.; Goichi, M.;
Kotani, M. Angew. Chem. Int. Ed. 2004, 43, 2248; Angew. Chem.
2004, 116, 2298. (b) Tsuya, T.; Iritani, K.; Tahara, K.; Tobe, Y.;
Iwanaga, T.; Toyota, S. Chem. Eur. J. 2015, 21, 5520. (c) Fudickar,
W.; Linker, T. J. Am. Chem. Soc. 2012, 134, 15071. (d) Fudickar,
W.; Linker, T. J. Org. Chem. 2017, 82, 9258.
+
+
+
MS (EI, 70 eV): m/z = 278.1 [M] , 261.1 [M – OH] , 243.1 [M – Cl] .
+
HRMS (ESI, + ions): m/z calcd for C14H O Cl Na : 300.97936; mea-
8
2
2
sured: 300.9785; dev. [ppm]: 2.86, dev. [mmu]: 0.86.
9
,10:3′,4′ Photocyclomer of Bis(1,8-dichloroanthracen-10-yl)di-
methylsilane (12)
(2) Examples of organometallic applications, for example: (a) Katz,
H. E. J. Org. Chem. 1989, 54, 2179. (b) Li, Y.; Köse, M. E.; Schanze,
K. S. J. Phys. Chem. B 2013, 117, 9025. (c) Chmiel, J.; Neumann,
B.; Stammler, H.-G.; Mitzel, N. W. Chem. Eur. J. 2010, 16, 11906.
This compound was formed from bisanthracene 2 as described above
in the general procedure.
1
3
H NMR (500 MHz, CDCl ): δ = 8.15 (s, 1 H, H9 ), 7.72 (d, J = 8.2 Hz,
3
a
H,H
(
d) Lamm, J.-H.; Niermeier, P.; Mix, A.; Chmiel, J.; Neumann, B.;
Stammler, H.-G.; Mitzel, N. W. Angew. Chem. Int. Ed. 2014, 53,
938; Angew. Chem. 2014, 126, 8072.
3
3
1
H, H5 ), 7.50 (d, J = 7.4 Hz, 1 H, H7 ), 7.40 (t, J = 7.8 Hz, 1 H,
a H,H a H,H
3
3
4
H6 ), 7.28 (d, J = 7.1 Hz, 1 H, H4 ), 7.24 (dd, J = 8.1 Hz, J = 1.0
a
H,H
b
H,H
H,H
7
3
3
Hz, 1 H, H2 ), 7.13 (dd, J = 7.4, 8.0 Hz, 1 H, H3 ), 6.98 (dd, J = 8.1
b
H,H
b
H,H
(
3) (a) Bouas-Laurent, H.; Castellan, A.; Desvergne, J.-P. Pure Appl.
Chem. 1980, 52, 2633. (b) Desvergne, J.-P.; Bouas-Laurent, H.
J. Chem. Soc., Chem. Comm. 1978, 403.
4
3
Hz, JH,H = 0.8 Hz, 1 H, H7 ), 6.83 (d, JH,H = 7.6 Hz, 1 H, H5 ), 6.67 (t,
b
b
3
3
3
JH,H = 7.8 Hz, 1 H, H6 ), 6.21 (d, J = 4.0 Hz, 1 H, H2 ), 5.56 (d, J
=
=
b
H,H
a
H,H
3
3
2.5 Hz, 1 H, H9 ), 3.95 (d, JH,H = 12.0 Hz, 1 H, H4 ), 3.39 (ddd, JH,H
b a
(4) Lamm, J.-H.; Niermeier, P.; Körte, L. A.; Neumann, B.; Stammler,
H.-G.; Mitzel, N. W. Synthesis 2018, 50, 2009.
12.0, 4.0, 2.5 Hz, 1 H, H3 ), 1.24 (s, 3 H, CH ), 0.78 (s, 3 H, CH ).
a
3
3
13
1
C{ H} NMR (125 MHz, CDCl ): δ = 146.4, 146.2, 145.9, 142.2, 139.9,
3
(5) Becker, H.-D. Chem. Rev. 1993, 93, 145.
1
38.0 136.5, 133.7, 131.3, 131.0, 130.7, 130.4, 127.6, 127.3 (C3b),
(6) Lamm, J.-H.; Vishnevskiy, Yu. V.; Ziemann, E.; Kinder, T. A.;
Neumann, B.; Stammler, H.-G.; Mitzel, N. W. Eur. J. Inorg. Chem.
2014, 941.
(7) Cordero, B.; Gómez, V.; Platero-Prats, A. E.; Revés, M.;
Echeverría, J.; Cremades, E.; Barragán, F.; Alvarez, S. Dalton
Trans. 2008, 2832.
1
27.0 (C2 ), 126.8 (C2 ), 126.8 (C6 ), 126.7 (C6 ), 126.3 (C7 ), 126.2
a
b
a
b
b
(
C5 ), 126.1 (C7 ), 124.4 (C5 ), 123.2 (C4 ), 121.5 (C9 ), 53.9 (C10 ),
a a b b a b
4
4.8 (C4 ), 43.1 (C9 ), 41.2 (C3 ), 0.2 (CH ), –2.9 (CH ).
a b a 3 3
29
1
Si{ H} NMR (99 MHz, CDCl ): δ = 4.9.
3
+
+
MS (MALDI-TOF, + ions, DCTB): m/z = 548.0 [M] , 413.0 [M – Cl] .
HRMS (MALDI-TOF): m/z calcd for C29H16Cl4+: 548.00829; measured:
48.0074, dev. [ppm]: 1.62, dev. [mmu]: 0.89.
(
8) (a) Desvergne, J.-P.; Bitit, N.; Pillot, J.-P.; Bouas-Laurent, H.
J. Chem. Res. 1989, 146. (b) Felix, G.; Lapouyade, R.; Bouas-Lau-
rent, H.; Clin, B. Tetrahedron Lett. 1976, 26, 2277. (c) Desvergne,
J.-P.; Bitit, N.; Castellan, A.; Webb, M.; Bouas-Laurent, H. J. Chem.
Soc., Perkin Trans. 2 1988, 1885.
5
Crystal Structure Determination
Suitable crystals of compounds 2–5 and 7–12 were obtained by slow
evaporation of saturated solutions of n-pentane (5, 9 and 10), ben-
zene (3, 7 and 12), CH Cl (8) and CHCl (2, 4 and 11). They were se-
(9) Klaper, M.; Wessig, P.; Linker, T. Chem. Commun. 2016, 52, 1210.
(10) Karama, U.; Sultan, M. A.; Ghabour, H. A.; Fun, H. K.; Warad, I.
Kh. Z. Kristallogr. - New Cryst. Struct. 2013, 228, 405.
(11) Daney, M.; Vanucci, C.; Desvergne, J.-P.; Castellan, A.; Bouas-
Laurent, H. Tetrahedron Lett. 1985, 26, 1505.
(12) Becker, H.-D.; Skelton, B. W.; White, A. H. Aust. J. Chem. 1989, 42,
1869.
(13) Hine, J.; Brown, J. A.; Zalkow, L. H.; Gardner, W. E.; Hine, M.
J. Am. Chem. Soc. 1955, 77, 594.
2
2
3
lected, coated with paratone-N oil, mounted on a glass fibre and
transferred onto the goniometer of the diffractometer into a nitrogen
gas cold stream solidifying the oil. Data collection was performed on a
Rigaku SuperNova diffractometer. The structures were refined by full-
18
matrix least-squares cycles (program SHELXL). Crystal and refine-
19
ment details, as well as CCDC numbers are provided in Table S2 (SI).
(
14) (a) Chmiel, J.; Heesemann, I.; Mix, A.; Neumann, B.; Stammler,
H.-G.; Mitzel, N. W. Eur. J. Org. Chem. 2010, 3897. (b) Lamm, J.-
H.; Vishnevskiy, Yu. V.; Ziemann, E.; Neumann, B.; Stammler,
H.-G.; Mitzel, N. W. ChemistryOpen 2018, 7, 111.
Funding Information
This work was financially supported by Deutsche Forschungsgemein-
(15) Examples for 9,10:1′,2′-photocyclomers: (a) Becker, H.-D.;
Hansen, L.; Andersson, K. J. Org. Chem. 1986, 51, 2956.
schaft (DFG, grant no. MI 477/25-3, project no. 248859450).
D
e
ustch
e
F
orsch
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n
gsg
e
m
en
i
sch
a
tf
4(
7
7
2/5-1)
(b) Sakurai, H.; Sakamoto, K.; Nakamura, A.; Kira, M. Chem. Lett.
1985, 497. (c) Nishimae, Y.; Kurata, H.; Oda, M. Angew. Chem.
Acknowledgment
Int. Ed. 2004, 43, 4947; Angew. Chem. 2004, 116, 5055.
16) Becker, H.-D.; Skelton, B. W.; White, A. H. Aust. J. Chem. 1991, 44,
181.
(17) Toyama, H.; Nakamura, M.; Nakamura, M.; Matsumoto, Y.;
Nakagomi, M.; Hashimoto, Y. Bioorg. Med. Chem. 2014, 22, 1948.
(18) Sheldrick, G. M. Acta Crystallogr., Sect. C 2015, 71, 3.
(
The authors thank Sonja Fürst (laboratory assistant) for her help in
the lab, Dipl. Ing. Klaus-Peter Mester and Gerd Lipinski for recording
NMR spectra, as well as Dr. Jens Sproß and Heinz-Werner Patruck for
measuring mass spectra.
(
19) CCDC 1824699 (2), 1824700 (3), 1824701 (4), 1003188 (5),
824702 (7), 1824703 (8), 1003186 (9), 1003187 (10), 1003190
11), 1824704 (12) contain the supplementary crystallographic
1
(
Supporting Information
data for this paper. These data can be obtained free of charge
from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/getstructures.
Supporting information for this article is available online at
https://doi.org/10.1055/s-0037-1610128.
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©
Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–G