4548
A. M. Christo® et al. / Tetrahedron 58 ꢀ2002) 4543±4549
under vacuum to give 5 as a white solid ꢀ0.79 g, 0.8 mmol,
4.1.8. 1,4,5,8-TetrakisꢀDABCO-N-methyl)-2,3,6,7-tetra-
methylnaphthalene tetrabromide ꢀ11). 1,4,5,8-Tetrakis-
ꢀbromomethyl)-2,3,6,7-tetramethylnaphthalene ꢀ10) ꢀ2.40 g,
4.3 mmol) was added to a solution of DABCO ꢀ2.45 g,
21.8 mmol) in acetonitrile ꢀ200 mL). The mixture was
stirred for 72 h. The solid formed was removed by ®ltration,
washed with acetonitrile, and dried under vacuum to give 11
1
9
4
8%); mp 281±2858C ꢀdec.); H NMR ꢀD O) d 8.00 ꢀs,
2
13
H,), 5.21 ꢀs, 8H,), 3.09 ꢀbr, 24H), 2.92 ꢀbr, 24H);
C
NMR ꢀD O) d 139.6, 128.0, 98.2, 71.2, 55.2, 46.8; IR
2
2
962, 2891, 2371, 1648, 1459, 1363 cm ; MS m/e 869
1
2
ꢀ
ꢀ
1
13, M2Br ), 755 ꢀ3), 675 ꢀ8), 483 ꢀ45), 371 ꢀ52), 259
23), 179 ꢀ52), 112 ꢀ100); C H Br N ´3H O requires
3
8
60
4
8
2
C, 45.52; H, 6.63; N, 11.18. Found: C, 45.39; H, 6.58; N,
1.07.
as a white solid ꢀ3.98 g, 3.6 mmol, 84%); mp 268±2708C
1
1
ꢀdec.); H NMR ꢀD O) d 5.48 ꢀd, J15.2 Hz, 4H), 4.93 ꢀd,
2
J15.2 Hz, 4H), 3.00 ꢀm, 12H), 2.85 ꢀm, 36H), 2.57 ꢀs,
1
.1.4. Pentamethylpyrrole ꢀ7). A mixture of 3,4-di-
5
13
12H); C NMR ꢀD O) d 147.5, 136.7, 123.8, 67.5, 55.3,
47.2, 22.6; IR 2960, 2884, 2074, 1636, 1459, 1358,
4
2
methyl-2,5-hexanedione ꢀ6) ꢀ20.00 g, 140.6 mmol), methyl-
amine ꢀ40% aqueous, 75 mL, 27.18 g, 875.1 mmol) and
benzene ꢀ300 mL) was re¯uxed for 6 h, water being
removed continuously with a Dean and Stark trap. The
2
1
1
1191 cm ; MS m/e 923 ꢀ5, M2Br ), 813 ꢀ2), 731 ꢀ7),
619 ꢀ13), 539 ꢀ28), 427 ꢀ37), 315 ꢀ17), 235 ꢀ38), 112
ꢀ100); C H Br N ´5H O requires C, 46.08; H, 7.18; N,
4
2
68
4
8
2
resulting solution was dried with anhydrous MgSO and
4
10.24. Found: C, 45.97; H, 7.08; N, 10.43.
the solvent removed under reduced pressure. The solid
residue was dried under vacuum to give 7 as yellow solid
4.2. Polyanions
ꢀ
16.98 g, 123.7 mmol, 88%) which was used immediately.
These were prepared from the corresponding acids by
treatment with sodium hydroxide followed by addition of
acetone, isolation and drying under vacuum.
1
5
4
.1.5. Nonamethyl-1,4-dihydronaphthalen-1,4-imine ꢀ8).
N-Butyllithium ꢀ1.6 M solution in hexane) ꢀ30 mL, 48 mmol)
was added dropwise over a period of 1 h to a suspension
of 1,2-dibromo-3,4,5,6-tetramethylbenzene ꢀ10.64 g, 36.4
mmol) and pentamethylpyrrole ꢀ7) ꢀ5.00 g, 36.4 mmol) in
anhydrous tetrahydrofuran ꢀ170 mL) at 2788C under nitro-
gen. After addition, the resulting mixture was kept at this
temperature for an additional hour and left for 20 h at room
temperature. Water ꢀ10 mL) and diethyl ether ꢀ20 mL) were
added slowly, the layers were separated, and the aqueous
layer was extracted with diethyl ether ꢀ20 mL). The
combined organic layers were dried with anhydrous MgSO4
and the solvent removed under reduced pressure. Petroleum
ether 40±608C ꢀ40 mL) was added to the residue, the solution
was ®ltered, and the solvent was removed by rotary evapo-
ration to give 8 as a yellow solid ꢀ9.66 g, 35.9 mmol, 99%);
4.3. Crystallisation with ferro- and ferricyanide
A half saturated solution of either the potassium ferro- or
ferricyanide was added to a dilute solution of the polycation
2
1
ꢀconcentration ca. 10 mg mL ) and, after standing, the
precipitate was removed by ®ltration.
For the competitive experiment, a solution was made from
equal volumes of saturated potassium ferricyanide and
saturated ferrocyanide and this was then added to a dilute
2
1
solution of the polycation ꢀconcentration ca. 10 mg mL ).
After standing, the precipitate was removed by ®ltration.
1
5
mp 90±928C, lit. 94±968C.
4.4. NMR titrations and Job plots
1
5
.1.6. Octamethylnaphthalene ꢀ9). A mixture of nona-
12
4
These were carried out as previously described.
methyl-1,4-dihydronaphthalen-1,4-imine ꢀ8) ꢀ9.00 g, 33.4
mmol), anhydrous sodium carbonate ꢀ3.60 g, 34.0 mmol),
m-chloroperoxybenzoic acid ꢀ57±86%, 11.22 g, 37.1
mmol) and benzene ꢀ200 mL) was heated under re¯ux for
4.5. X-Ray structure analyses
Crystals were mounted on a thin glass ®bre using a fast
setting epoxy resin and cooled on the diffractometer to
100 K using an Oxford Cryostream low temperature attach-
ment. A total of 90 oscillation frames each of width 28 in f
and of 30 s exposure time were recorded using a Nonius
KappaCCD diffractometer, with a detector to crystal
distance of 25 mm. Crystals were indexed from the ®rst
1
5 h. Water ꢀ100 mL) was added, the layers were separated
and the aqueous layer was extracted with chloroform
50 mL). The combined organic layers were dried with
ꢀ
anhydrous MgSO and the solvent removed under reduced
4
pressure. The solid residue was triturated with methanol
ꢀ
55 mL) and ®ltered to give 9 as white needles ꢀ4.67 g,
1
5
9.4 mmol, 58%); mp 180±1828C, lit. 181±1828C.
19
1
10 frames using the DENZO-SMN package and positional
data were re®ned along with diffractometer constants to give
the ®nal unit cell parameters. Integration and scaling
ꢀDENZO, Scalepack ) resulted in unique data sets
4
.1.7. 1,4,5,8-Tetrakisꢀbromomethyl)-2,3,6,7-tetramethyl-
1
6
19
naphthalene ꢀ10). A solution of bromine ꢀ3.84 mL,
1.98 g, 75.0 mmol) in dichloromethane ꢀ190 mL) was
added dropwise to a solution of octamethylnaphthalene ꢀ9)
4.50 g, 18.7 mmol) in dichloromethane ꢀ560 mL) at 08C.
1
corrected for Lorentz and polarisation effects and for the
effects of crystal decay and absorption by a combination
of averaging of equivalent re¯ections and an overall volume
and scaling correction. Structures were solved using
ꢀ
The resulting solution was left at room temperature for 2 h,
then was washed with saturated aqueous sodium carbonate
ꢀ3£600 mL) and dried with anhydrous MgSO . The solvent
was removed under reduced pressure and the solid residue
2
0
SHELXS-97 and developed via alternating least squares
cycles and difference Fourier synthesis ꢀSHELXL-972) with
4
2
1
the aid of the program XSeed. All non-hydrogen atoms
were modelled anisotropically, while hydrogen atoms are
assigned an isotropic thermal parameter 1.2 times that of
the parent atom ꢀ1.5 for terminal atoms) and allowed to ride.
was recrystallised from THF to give 10 as a white solid
6.79 g, 12.2 mmol, 65%); mp 178±1818C ꢀdec.), lit.
808C ꢀdec.).
1
6
ꢀ
1