Progress Towards Double-Stranded Hydrocarbon Cycles
FULL PAPER
(125 MHz, CDCl3): δ = 171.02, 145.07, 137.97, 137.47, 137.38,
1.33 (m, 32 H, CH2(CH2)4CH3), 0.99 (m, 12 H, CH2(CH2)4CH3)
134.64, 131.55, 128.15, 122.29, 121.33, 116.82, 72.14, 49.76, 31.75, ppm. 13C NMR (75 MHz, C6D6): δ = 148.81, 146.09, 143.57, 142.
31.64, 29.73, 28.60, 22.73, 21.96, 14.17 ppm. HR MALDI MS:
76,139.74, 139. 27, 138. 38, 137.82, 137.39, 137.33, 136.93, 136.80,
135.94, 135.83, 134.96, 134.66, 134. 61, 134.41, 133.40, 133.09,
calcd. for C80H84O8 1172.6161; found 1172.6140 [M]+, 1114 [M –
(OCOCH3)]+, 1072 [M – (OCOCH3)–(COCH3)]+, 1054 [M – 2- 132.25, 131.42, 132.31, 130.03, 128.67, 121.66, 121.50, 120.95,
(OCOCH3)]+·, 995 [M – 3(OCOCH3)]+·.
120.67, 120.45, 120.39, 120.04, 119.49, 116.47, 116.32, 81. 48,
81.35, 72.36, 56.37, 53.54, 31.92, 31.87, 31.84, 31.81, 31.44, 31.08,
30.85, 29.97, 29.82, 29.67, 22.93, 22.80, 22.79, 14.13, 14.10, 14.07
ppm. HR MALDI MS: calcd. for C72H74O3 1986.5633; found
1986.5616 [M]+.
1,4,9,18-Tetrabromo-8,19,23,24-tetrahexyl-1,4,4a,9,9a,17b,18,22b-
octahydro-2,14:3,13-dimethenodiindeno[1,2,3-c,d:1Ј,2Ј,3Ј-cЈ,dЈ]-
benzo[2,3-j:5,6-jЈ]difluoranthene (15). Route A: To a solution of
compound 2 (0.200 g, 0.206 mmol) in dry CH2Cl2 (5 mL) was
added dropwise at room temp. BBr3 (1 solution in CH2Cl2,
1.1 mL, 1.3 mmol) over a period of 30 min, whereupon the colour
changed slowly to brown. After 4 h stirring at room temp., the reac-
tion was quenched with water (2 mL) whereupon a precipitate
formed. The precipitate was recovered by filtration, washed with
ethanol and dried in vacuo to give compound 15 as a yellow solid
(160 mg, 62% yield). If the precipitate was dissolved in CH2Cl2 and
washed with water, a mixture of compounds 2 and 16 was obtained.
Route B: A solution of 14 (10 mg) in CDCl3 (0.5 mL) was prepared
in an NMR tube, and a drop of PBr3 was added. The transforma-
tion of 14 into 15 was followed by NMR spectroscopy, which
showed that the reaction was complete within 3 h. 1H NMR
(300 MHz, CD2Cl2): δ = 7.70 (s, 4 H, H-7, H-12, H-15, H-20), 7.63
(d, 3J = 7.2 Hz, 4 H, H-6, H-11, H-16, H-21), 7.44 (d, 3J = 7.2 Hz,
4 H, H-5, H-10, H-17, H-22), 6.15 (s, 4 H, H-1, H-4, H-9, H-18),
5.05 (s, 4 H, H-4a, H-9a, H-17b, H-22b), 2.91 (m, 8 H, CH2-
(CH2)4CH3) 1.66–1.38 (m, 32 H, CH2(CH2)4CH3), 0.96 (m, 12 H,
CH2(CH2)4CH3) ppm. 1H NMR (500 MHz, [D8]THF): δ = 7.76 (s,
8,19,23,24-Tetrahexyl-9,9-dihydroxy-18-oxo-1,4,4a,9,9a,17b,18,22b-
octahydro-1,4-epoxy-2,14:3,13-dimethenodiindeno[1,2,3-c,d:1Ј,2Ј,3Ј-
cЈ,dЈ]benzo[2,3-j:5,6-jЈ]difluoranthene (18): A solution of 16 (3 mg)
in CD2Cl2 (0.5 mL) was prepared in an NMR tube, and pyridinium
chlorochromate (PCC, 15 mg) was added. After 1 h at room temp.,
the reaction mixture was washed through a short silica gel column
with CH2Cl2. 1H NMR: (700 MHz, CDCl3): δ = 7.83 (s, 1 H), 7.80
(d, 3J = 6.8 Hz, 1 H), 7.70 (s, 1 H), 7.69 (d, 3J = 6.9 Hz, 1 H), 7.66
(d, 3J = 2.0 Hz, 1 H), 7.64 (d, 3J = 1.9 Hz, 1 H), 7.62 (d, 3J =
6.9 Hz, 1 H), 7.61 (s, 1 H), 7.56 (d, 3J = 7.0 Hz, 1 H), 7.53 (s, 1
3
H), 7.40 (dd, 3J = 6.8 Hz, 3J = 1.1 Hz, 1 H), 7.39 (dd, J = 6.8 Hz,
3
3
3J = 1.1 Hz, 1 H), 6.35 (d, J = 8.4 Hz, 1 H, H-9a), 6.01 (d, J =
3
5.9 Hz, 1 H, H-1 or H-4), 5.98 (d, J = 5.9 Hz, 1 H, H-1 or H-4),
4.87 (m, 2 H, H-4a, H-22b), 4.79 (d, 3J = 8.2 Hz, 1 H, H-17b), 3.38
(m, 1 H, CH2(CH2)4CH3), 2.97 (m, 3 H, CH2(CH2)4CH3), 2.72 (m,
2 H, CH2(CH2)4CH3) 2.61 (m, 1 H, CH2(CH2)4CH3) 2.52 (m, 1 H,
CH2(CH2)4CH3) 1.67–1.28 (m, 32 H, CH2(CH2)4CH3), 0.91 (m, 12
H, CH2(CH2)4CH3) ppm. HR MALDI MS: calcd. for C72H72O4
1000.5430 [M]+ 998.5269; found 998.5263 [M – 2H]+, 999.5341
[M – H]+, 1000.5380 [M]+, 1021.521 [M – 2H + Na]+, 1021.521
[M – 2H + K]+.
3
4 H, H-7, H-12, H-15, H-20), 7.61 (d, J = 7.2 Hz, 4 H, H-6, H-
11, H-16, H-21), 7.55 (d, 3J = 7.2 Hz, 4 H, H-5, H-10, H-17, H-
22), 6.25 (s, 4 H, H-1, H-4, H-9, H-18), 4.97 (s, 4 H, H-4a, H-
9a, H-17b, H-22b), 2.99 (m, 4 H, CH2(CH2)4CH3), 2.90 (m, 4 H,
Supporting Information (see also the footnote on the first page of
this article): The original reaction scheme for the synthesis of com-
pound 1. Representative NMR spectra for all compounds. HR-
MALDI MS of a mixture of compounds 11, 12, and 13.
3
CH2(CH2)4CH3), 1.60–1.33 (m, 32 H, CH2(CH2)4CH3), 0.91 (t, J
= 6.6 Hz, 12 H, CH2(CH2)4CH3) ppm. 13C NMR (125 MHz,
CDCl3): δ = 165.18, 146.26, 138.09, 137.68, 134.96, 128.59, 122.36,
121.86, 116. 88, 53.67, 44.54, 39.09, 31.63, 30.77, 29.79, 28.06,
22.57, 14.10 ppm. HR MALDI MS: calcd. for C72H72Br4; found
1093.379 [M – Br–HBr]+, 1015.477 [M – 3Br]+, 936.5611
[M – 4Br]+, 851.4120 [M – 4Br–C6H13]+.
Acknowledgments
We thank Dr. W. Amrein and his crew, ETHZ, for countless mass
spectrometric analyses and helpful advice, Prof. H. Hartl, FU
Berlin, for taking the X-ray powder diffractogram of the black ma-
terial, Prof. H.-U. Reissig, FU Berlin, for helpful advice regarding
some transformations and M. Sc. D. Ban, on leave from UBB, Cluj
Napoca, for her engaged help with the scaling-up process. Prof. R.
Prins, ETHZ, is thanked for a sample of γ-Al2O3. We thank Prof.
A. Stanger, Technion, Israel, for his continued interest and input
in this research. This work was supported by the Swiss National
Science Foundation.
8,19,23,24-Tetrahexyl-9,18-dihydroxy-1,4,4a,9,9a,17b,18,22b-octa-
hydro-1,4-epoxy-2,14:3,13-dimethenodiindeno[1,2,3-c,d:1Ј,2Ј,3Ј-
cЈ,dЈ]benzo[2,3-j:5,6-jЈ]difluoranthene (16): To an ice-cooled solution
of compound 2 (0.130 g, 0.164 mmol) in dry CH2Cl2 (15 mL), BBr3
(1 solution in CH2Cl2, 0.402 mL, 0.402 mmol) was added drop-
wise. After the completed addition, a colour change from yellow
to brown was observed. Stirring was continued for 1 h under ice
cooling while the colour disappeared, and a yellow precipitate
formed. The reaction was allowed to stir for another 2 h at room
temp. and quenched with water (5 mL). Additional CH2Cl2 was
added until all the precipitate dissolved. The organic phase was
washed twice with water, dried with MgSO4, and the solvent was
removed. The residue was purified by column chromatography on
silica gel (CH2Cl2). After the first compound (2) had eluted, the
polarity of the solvent was increased by the addition of 10% ace-
tone, whereupon the second compound (6) eluted. The solvent was
removed, and compound 6 was obtained as a yellow solid (38 mg,
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28% yield). H NMR: (300 MHz, C6D6): δ = 7.98 (s, 2 H, H-7, H-
3
20), 7.89 (s, 2 H, H-12, H-15) 7.51 (d, J = 7.0 Hz, 2 H, H-11, H-
3
3
16), 7.46 (d, J = 7.0 Hz, 2 H, H-6, H-21), 7.14 (d, J = 7.1 Hz, 2
3
H, H-10, H-17), 7.10 (d, J = 7.1 Hz, 2 H, H-5, H-22) 5.94 (m, 2
H, H-1, H-4), 5.68 (s, 2 H, H-9, H-18), 4.72 (m, 42 H, H-4a, H-9a,
H-17b, H-22b), 3.13 (t, 3J = 7.4 Hz, 4 H, CH2(CH2)4CH3), 2.96
(m, 2 H, CH2(CH2)4CH3), 2.57 (m, 2 H, CH2(CH2)4CH3) 1.81–
Eur. J. Org. Chem. 2007, 88–100
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