A. R. Wartini, J. Valenzuela, H. A. Staab, F. A. Neugebauer
FULL PAPER
G/UV254, Macherey-Nagel. Ϫ 1H NMR: Bruker Physik WP-80, chloride (11.5 g, 0.1 mol) was heated under dry hydrogen chloride
AM 360 or AM 500 (internal reference tetramethylsilane, tempera- at 200°C for 20 min. After cooling the melt was dissolved in water
ture 303 K). Ϫ MS: Finnigan MAT 212 or Jeol JMS-SX 102A (50 ml), and sodium metaperiodate (3.25 g, 15 mmol) was added
(ionization potential 70 eV; only the most prominent peaks are
with stirring. The bright brown solution was then extracted with
listed, usually with Irel > 5%). Ϫ Cyclovoltammetry: All electro-
dichloromethane (4 ϫ 50 ml). The combined organic phases were
chemical studies were performed using an EG & G Princeton Ap- dried (MgSO
4
) and concentrated under reduced pressure. Flash
chromatography of the brown residue on silica gel using trichloro-
methane as eluent afforded compound 8 (168 mg, 47%; R ϭ 0.30,
trichloromethane) as yellow crystals from toluene/hexane, m.p.
plied Research 263 A potentiostat attached to an EG & G electro-
chemical microcell (K0264), which was equipped with a glassy car-
bon millielectrode (G0229, 2 mm diameter) as working electrode,
a standard Ag/AgCl reference electrode (K0265), and a platinum
f
1
3
180°C (dec.). Ϫ H NMR (500 MHz, CDCl ): δ ϭ 2.25Ϫ2.40 (m,
wire counter-electrode (K0264). The measurements were carried 2 H, 2,9-syn-H with regard to 5,8-H), 3.00Ϫ3.20 (m, 4 H, 1,1,10,10-
out on degassed anhydrous acetonitrile or dichloromethane solu- H), 3.20Ϫ3.30 (m, 2 H, 2,9-anti-H with regard to 5,8-H), 5.83 (s, 2
tions containing the sample (0.5Ϫ1 m) and tetrabutylammonium H, 5,8-H), 6.74 (dd, J ϭ 7.9 Hz, J ϭ 1.9 Hz, 2 H, 12,15- or 13,16-
3
4
3
4
hexafluorophosphate (0.1 ) as supporting electrolyte at 298 K. H), 6.86 (dd, J ϭ 7.9 Hz, J ϭ 1.9 Hz, 2 H, 13,16- or 12,15-H);
Cyclic voltammograms were scanned at a sweep rate of about 100 irradiation of the 5,8-H signal at δ ϭ 5.83 yielded a positive NOE
Ϫ1
Ϫ/0
mV s . Redox potentials are referred to ferrocene (FeCp
2
,
response for 2,9-syn-H at δ ϭ 2.25Ϫ2.40.
1,1,10,10,12,13,15,16-D ][2.2]Paracyclophane-4,7-dione
8a): Prepared as described above using 4,7-dimeth-
oxy[1,1,10,10,12,13,15,16-D ][2.2]paracyclophane : Yellow crys-
8
tals, m.p. 180 (dec.). The ether cleavage led to a partial (approxi-
mately 50%) reexchange of the deuterons in the 12,13,15,16 posi-
0
E
1
ϭ ϩ0.352 V) set to 0.00 V. Ϫ ESR and ENDOR: Bruker ESP
00 spectrometer equipped with the ER 252 (ENMR) ENDOR
[
8
3
(
system; g values were determined using an NMR gaussmeter and
a Hewlett-Packard 5342A microwave frequency counter; this was
calibrated with the perylene radical cation. Hyperfine coupling
constants measured in megahertz (ENDOR) were converted into
gauss using 1 MHz ϭ (0.7145/gex) G. The radical anions were gen-
erated by reduction of the parent compounds (about 1 mg) in di-
methoxyethane (DME) or in methyltetrahydrofuran (MTHF) (1Ϫ2
ml) with potassium under high-vacuum conditions in the presence
of kryptofix 222 Merck (1,10-diaza-4,7,13,16,21,24-hexaoxabicy-
clo[8.8.8]hexacosane; about 4 mg). The solvents were carefully
dried (potassium) and deoxygenated. Potassium was purified by
repeated vacuum distillation.
[4]
1
2
tions. Ϫ H NMR (500 MHz, CDCl
H, 2,9-syn-H with regard to 5,8-H), 3.22 (d, 2 H, 2,9-anti-H with
regard to 5,8-H), 5.82 (s, 2 H, 5,8-H), 6.7Ϫ6.8 (m, 1.3 H), 6.8Ϫ6.9
m, 1.1 H).
4.4]Paracyclophane-6,9-dione (9): To a solution of 6,9-dimeth-
3
): δ ϭ 2.30 (d, J ϭ 12.7 Hz,
2
(
[
[4]
oxy[4.4]paracyclophane (300 mg, 0.92 mmol) in anhydrous aceto-
nitrile (35 ml) under argon, iodotrimethylsilane (0.9 ml, 6.3 mmol)
was added with stirring, and the mixture was heated at 70°C for
further 2 h. Iodotrimethylsilane (0.9 ml, 6.3 mmol) was again then
added, and heating at 70°C was continued for a further 14 h. The
mixture was hydrolized with water (20 ml) and extracted with di-
ethyl ether (3 ϫ 50 ml). The combined extracts were shaken with
The compounds pseudogeminal- (1)[
2b][2c]
and pseudoortho-
, syn- (3) and anti-
[2a][2c]
[5]
[
[
2.2]paracyclophane-4,7,12,15-tetrone (2)
2.2](1,4)naphthalenophane-4,7,14,17-tetrone (4)[5], 2,3,9,10-tetra-
[6]
methyl-1,4,8,11-pentacenetetrone (5) , and 6,13-dihexyl-2,3,9,10-
tetramethyl-1,4,8,11-pentacenetetrone (6)[ were available in our
laboratory or were prepared as described in the literature.
2 4
a saturated aqueous sodium sulphite solution, dried (Na SO ), and
concentrated under reduced pressure. The residue was dissolved in
acetone (200 ml), silver oxide (1.24 g, 50 mmol) was added, and
6]
pseudoortho-4,7,13,16-Tetramethoxy[1,1,2,2,9,9,10,10-D
paracyclophane: Prepared from 1,4-bis(chloro[D ]methyl)-2,5-di-
]methyl)-2,5-dimeth-
oxybenzene following the procedures as described in the litera-
8
][2.2]- the mixture was stirred for 1 h. After separation of the precipitated
2
silver salts, the filtrate was evaporated under reduced pressure.
Crystallization of the residue from acetone afforded compound 9
[
4]
methoxybenzene
and 1,4-bis(mercapto[D
2
[
4]
(226 mg, 83%; R ϭ 0.30, dichloromethane) as yellow needles, m.p.
f
[2a][2c]
[18]
1
ture for the undeuterated compound
found for the undeuterated compound[
MHz, CDCl ): δ ϭ 3.65 (s, 12 H, OCH
H). Ϫ EI-MS; m/z (%): 336 (100) [M ]. Ϫ C20
calcd. C 71.39, H ϩ D 9.59; found C 71.41, H ϩ D 9.80.
pseudoortho-[1,1,2,2,9,9,10,10-D
tetrone (2a): mixture of pseudoortho-4,7,13,16-tetrameth-
oxy[1,1,2,2,9,9,10,10-D ][2.2]paracyclophane (1.51 g, 4.5 mmol)
and pyridine hydrochloride (17.5 g, 0.15 mol) was heated to 200°C
for 10 min. After cooling, the melt was dissolved in hot water (20
ml) and added to a solution of sodium metaperiodate (9.75 g, 45
mmol) in water (50 ml). After stirring for 1 h the precipitated prod-
uct was filtered and washed with water and methanol. Flash chro-
matography of the residue on silica gel using trichloromethane as
: m.p. 121Ϫ122°C as 221Ϫ222°C (ref. : m.p. 217Ϫ223°C). Ϫ H NMR (360 MHz,
2a][2c]
. Ϫ 1H NMR (360 CDCl ): δ ϭ 1.05Ϫ2.85 (m, 16 H, CH ), 6.13 (s, 2 H, 7,10-H),
3
2
3
3
ϩ
), 6.10 (s, 4 H, 5,8,12,16- 6.75Ϫ6.95 (m, 4 H, 16,17,19,20-H). Ϫ EI-MS; m/z (%): 295 (14),
•
•ϩ
H
16
D
O
8 4
(336.5): 294 (100) [M ], 163 (16), 143 (11), 136 (17), 131 (15), 130 (15),
129 (20), 117 (20),115 (11), 104 (16), 91 (19). Ϫ C H O (294.4):
2
0
22
2
][2.2]Paracyclophane-4,7,12,15- calcd. C 81.60, H 7.53; found C 81.53, H 7.80.
8
A
1
,4-Dimethoxy-5,8-dimethylnaphthalene: To a stirred solution of
[5]
8
1
,4-dimethoxy-5-hydroxymethyl-8-methylnaphthalene (1.90 g, 8.2
mmol) in dichloromethane (60 ml) were added zinc iodide (4.12 g,
2.9 mmol) and sodium cyanoborohydride (4.05 g, 64.5 mmol) in
1
small portions. Stirring at room temperature was continued for
further 24 h. The mixture was then hydrolized with water (10 ml),
and the separated organic phase was dried (MgSO ) and concen-
4
trated under reduced pressure. The dark residue dissolved in di-
chloromethane, was filtered through a short silica gel column. After
evaporation of the filtrate, the residue was distilled in a Büchi Ku-
the eluent afforded compound 2a (780 mg, 63%; R
chloromethane) as yellow crystals from methanol, m.p. 210°C
f
ϭ 0.45, tri-
2a][2c]
1
(
(
(
(
dec.) as found for the undeuterated compound[
360 MHz, CDCl ): δ ϭ 6.25 (s, 4 H, 5,8,12,16-H). Ϫ EI-MS; m/z
%): 277 (44), 276 (100) [M• ], 248 (34), 220 (56), 207 (70), 179
29), 151(23), 82 (28), 69 (63), 41 (95). Ϫ C16 (276.3): calcd.
. Ϫ H NMR
Ϫ2
gelrohr distillation apparatus at 150°C /2·10 bar to yield the
3
f
product (290 mg, 16%; R ϭ 0.69, dichloromethane) as colourless
ϩ
1
crystals, m.p. 64Ϫ65°C. Ϫ H NMR (360 MHz, CDCl
s, 6 H, CH ), 3.85 (s, 6 H, OCH ), 6.73 (s, 2 H, 2,3-H), 7.07 (s, 2
H, 6,7-H). Ϫ EI-MS; m/z (%): 216 (93) [M ], 201 (100) [M
CH ], 173 (12), 115 (6), 108 (5). Ϫ C14 (216.3): calcd. C
(402 mg, 15 mmol) in pyridine hydro- 77.75, H 7.46; found C 77.69, H 7.74.
3
): δ ϭ 2.83
4 8 4
H D O
(
3
3
C 69.54, H ϩ D 7.30; found C 69.58, H ϩ D 7.10.
2.2]Paracyclophane-4,7-dione (8)[16]: A mixture of 4,7-dimeth-
oxy[2.2]paracyclophane
•ϩ
16
•ϩ
Ϫ
[
3
H
O
2
[17]
226
Eur. J. Org. Chem. 1998, 221Ϫ227