Translational Isomerizations in [2]Catenanes
8.3 Hz, 1H), 6.73 (d, J ) 2.4 Hz, 1H), 6.51 (dd, J ) 8.3, 2.4 Hz,
1H), 5.38 (m, 2H), 5.33 (m, 2H), 4.71 (m, J ) 5.0 Hz, 4H), 2.41
(m, 2H), 1.33-1.23 (m, 2H), 1.21-1.09 (m, 6H), 0.73 (m, 3H);
MS (ESI) m/z 705.3 (MPF6+), 280.1 (M2+) (C36H40O2N42+ requires
560.7).
400 MHz) δ 9.34 (m, J ) 6.7 Hz, 2H), 9.28 (m, J ) 6.7 Hz, 2H),
9.14 (m, J ) 6.6 Hz, 2H), 9.07 (m, 2H), 8.44 (m, J ) 3.8 Hz, 2H),
8.36-8.06 (m, 2H), 8.01 (m, 1H), 7.94 (d, J ) 8.5 Hz, 2H), 7.66
(d, J ) 8.5 Hz, 2H), 7.15 (d, J ) 8.5 Hz, 1H), 6.77 (d, J ) 2.0 Hz,
1H), 6.65 (dd, J ) 8.4, 2.0 Hz, 1H), 6.26 (s, 2H), 6.23 (s, 2H),
5.74 (br s, 8H), 5.34 (m, 2H), 5.26 (m, 2H), 4.64-4.55 (m, 4H),
3.88-3.63 (m, 32H), 2.68-2.65 (m, 2H), 1.62 (m, 2H), 1.43 (s,
9H), 1.40-1.33 (m, 7H), 0.91 (m, J ) 6.9 Hz, 3H); MS (ESI)
666.4 (M2+), 492.9 (MPF63+), 333.2 (M4+) (C82H100N4O124+ requires
1333.69).
Purification of Catenanes. After stirring for 3-4 days, the
catenane solutions were purified and isolated according to the
following method. The dark red solid was dissolved in ap-
proximately 10 mL of CH3OH/EtOAc/CH3COCH3 (1:1:1) and
loaded onto a 2 mm PLC plate. After drying, the plate was eluted
twice with CH3OH/EtOAc (1:1) at 35 °C and finally with CH3-
OH/2 M NH4Cl/CH3NO2 (7:2:1) at room temperature. The product
was washed from the silica gel using the final eluant, and NH4PF6
(0.300 g) was added to the red solution. Solvents CH3OH and CH3-
NO2 were removed via rotary evaporator, leaving a red solid
suspended in water. This red product was filtered, washed with
distilled water, and allowed to dry. Impurities detected after the
first separation were removed by an additional purification using a
0.5 mm PLC plate and identical procedures.
Catenane 5. 1,3-Bis(2-(4,4′-dipyridinium)ethoxy)-4-chloroben-
zene dihexafluorophosphate (17) (0.128 g, 0.16 mmol) and
BPP34C10 (0.172 g, 0.320 mmol) were combined and dissolved
in CH3CN (15 mL). This solution was allowed to stir for 10 min
at which point R,R′-dibromo-m-xylene (0.051 g, 0.192 mmol) was
added and the reaction vessel sealed with a septa. This red solution
stirred 4 days under ambient conditions after which time the solvent
was removed in vacuo. The catenane was purified, and after drying,
55 mg (20%) of pure product was recovered: 1H NMR (CDCl3,
400 MHz) δ 9.25 (m, J ) 7.0 Hz, 2H), 9.17 (m, J ) 7.0, 4.05 Hz,
4H), 9.11 (m, J ) 6.7 Hz, 2H), 8.31 (m, J ) 6.6 Hz, 2H), 8.27 (m,
J ) 6.5 Hz, 2H), 8.23 (m, J ) 6.7 Hz, 2H), 8.15 (m, J ) 7.7, 6.9
Hz, 4H), 8.06 (t, J ) 1.6, Hz, 1H), 7.90 (t, J ) 7.8 Hz, 1H), 7.39
(d, J ) 8.9 Hz, 1H), 6.90 (d, J ) 2.7 Hz, 1H), 6.76 (dd, J ) 8.9,
2.7 Hz, 1H), 6.20 (s, 2H), 6.17 (s, 2H), 5.39 (s, 2H), 5.29 (s, 2H),
5.03 (br s, 8H), 4.68 (t, J ) 3.8 Hz, 4H), 3.91-3.51 (m, 32H); MS
Catenane 2. 1,3-Bis(2-(4,4′-dipyridinium)ethoxy)-4-chloroben-
zene dihexafluorophosphate (17) (0.128 g, 0.16 mmol) and
BPP34C10 (0.223 g, 0.416 mmol) were combined and dissolved
in CH3CN (15 mL). This solution was allowed to stir for 10 min
at which point 5-bis(bromomethyl)-4′-(1,1′-dimethylethyl)-1,1′-
biphenyl (0.0765 g, 0.192 mmol) was added and the reaction vessel
sealed with a septa. This red solution stirred 4 days under ambient
conditions after which time the solvent was removed in vacuo. The
catenane was purified, and after drying, 51 mg (17%) of pure
product was recovered: 1H NMR (CDCl3, 400 MHz) δ 9.34 (m, J
) 7.0 Hz, 2H), 9.27 (m, J ) 7.0 Hz, 2H), 9.13 (d, J ) 7.1 Hz,
1H), 9.11 (d, J ) 7.1 Hz, 1H), 8.44 (m, J ) 4.1, 1.6 Hz, 2H), 8.29
(d, J ) 4.8 Hz, 1H), 8.27 (d, J ) 4.8 Hz, 1H), 8.23 (m, J ) 7.0
Hz, 2H), 8.13 (m, J ) 7.0 Hz, 2H), 8.00 (t, J ) 1.4 Hz, 1H), 7.93
(m, J ) 8.6 Hz, 2H), 7.66 (m, J ) 8.6 Hz, 2H), 7.39 (d, J ) 8.9
Hz, 1H), 6.89 (d, J ) 2.7 Hz, 1H), 6.77 (dd, J ) 8.9, 2.7 Hz, 1H),
6.26 (s, 2H), 6.24 (s, 2H), 5.66 (br s, 8H), 5.38 (m, 2H), 5.29 (m,
2H), 4.68 (m, J ) 9.5, 5.0 Hz, 4H), 3.88-3.62 (m, 32H), 1.43 (s,
9H); MS (ESI) 786.3 (M2PF62+), 476.2 (MPF63+), 427.6 (M3+),
(ESI) 648.3 (M1PF62+), 432.2 (MPF63+), 383.5 (M3+), 288.2 (M4+
(C66H75ClN4O12 requires 1151.77).
)
4+
Catenane 6. 1,3-Bis(2-(4,4′-dipyridinium)ethoxy)-4-ethylbenzene
dihexafluorophosphate (18) (0.123 g, 0.16 mmol) and BPP34C10
(0.172 g, 0.32 mmol) were combined and dissolved in CH3CN (15
mL). This solution was allowed to stir for 10 min at which point
R,R′-dibromo-m-xylene (0.051 g, 0.192 mmol) was added and the
reaction vessel sealed with a septa. This red solution stirred 4 days
under ambient conditions after which time the solvent was removed
in vacuo. The catenane was purified, and after drying, 29 mg (11%)
of pure product was recovered: 1H NMR (CDCl3, 400 MHz) δ
9.25 (m, J ) 7.0 Hz, 2H), 9.15 (m, J ) 7.0 Hz, 4H), 9.09 (m, J )
7.0 Hz, 2H), 8.28 (m, J ) 7.0 Hz, 2H), 8.27-8.22 (m, 4H), 8.16
(dd, J ) 7.7, 1.2 Hz, 2H), 8.11 (m, J ) 7.0 Hz, 2H), 8.06 (t, J )
1.2, Hz, 1H), 7.89 (t, J ) 7.7 Hz, 1H), 7.16 (d, J ) 8.4 Hz, 1H),
6.76 (d, J ) 2.4 Hz, 1H), 6.65 (dd, J ) 8.4, 2.4 Hz, 1H), 6.19 (s,
2H), 6.16 (s, 2H), 5.72 (br s, 8H), 5.36 (m, J ) 4.9 Hz, 2H), 5.27
(m, J ) 4.8 Hz, 2H), 4.64 (m, J ) 4.9 Hz, 2H), 4.59 (m, J ) 4.8
Hz, 2H), 3.89-3.63 (m, 32H), 2.68 (q, J ) 7.7 Hz, 2H), 1.20 (t, J
) 7.7 Hz, 3H); MS (ESI) 717.3 (M2PF62+), 430.2 (MPF63+), 286.3
4+
320.7 (M4+) (C76H87ClN4O12 requires 1283.97).
Catenane 3. 1,3-Bis(2-(4,4′-dipyridinium)ethoxy)-4-ethylbenzene
dihexafluorophosphate (18) (0.123 g, 0.16 mmol) and BPP34C10
(0.223 g, 0.416 mmol) were combined and dissolved in CH3CN
(15 mL). This solution was allowed to stir for 10 min at which
point 5-bis(bromomethyl)-4′-(1,1′-dimethylethyl)-1,1′-biphenyl
(0.0.0765 g, 0.192 mmol) was added and the reaction vessel sealed
with a septa. This red solution stirred 4 days under ambient
conditions after which time the solvent was removed in vacuo. The
catenane was purified, and after drying, 48 mg (16%) of pure
product was recovered: 1H NMR (CDCl3, 400 MHz) δ 9.34 (m, J
) 6.6 Hz, 2H), 9.27 (m, J ) 6.6 Hz, 2H), 9.15 (m, J ) 7.0 Hz,
2H), 9.10 (m, J ) 7.0 Hz, 2H), 8.44 (m, J ) 6.6 Hz, 2H), 8.26 (m,
J ) 6.6, 7.0 Hz, 6H), 8.11 (m, J ) 7.0 Hz, 2H), 8.00 (t, J ) 1.5
Hz, 1H), 7.93 (m, J ) 8.5 Hz, 2H), 7.66 (m, J ) 8.5 Hz, 2H), 7.16
(d, J ) 8.4 Hz, 1H), 6.76 (d, J ) 2.4 Hz, 1H), 6.66 (dd, J ) 8.4,
2.4 Hz, 1H), 6.27 (s, 2H), 6.23 (s, 2H), 6.03-5.46 (m, 8H), 5.36
(m, 2H), 5.27 (m, 2H), 4.63 (m, 2H), 4.58 (m, 2H), 3.87-3.64 (m,
32H), 2.68 (q, J ) 7.5 Hz, 2H), 1.43 (s, 9H), 1.20 (t, J ) 7.5 Hz,
3H); MS (ESI) m/z 1718.6 (M3PF6+), 783.3 (M2PF62+), 473.9
(M4+) (C68H80N4O12 requires 1145.38).
4+
Catenane 7. 1,3-Bis(2-(4,4′-dipyridinium)ethoxy)-4-n-hexylben-
zene dihexafluorophosphate (19) (0.123 g, 0.16 mmol) and
BPP34C10 (0.223 g, 0.416 mmol) were combined and dissolved
in CH3CN (15 mL). This solution was allowed to stir for 10 min
at which point R,R′-dibromo-m-xylene (0.051 g, 0.192 mmol) was
added and the reaction vessel sealed with a septa. This red solution
stirred 4 days under ambient conditions after which time the solvent
was removed in vacuo. The catenane was purified, and after drying,
43 mg (15%) of pure product was recovered: 1H NMR (CDCl3,
400 MHz) δ 9.26 (m, J ) 6.9 Hz, 2H), 9.17 (m, J ) 6.9 Hz, 4H),
9.09 (m, J ) 6.9 Hz, 2H), 8.31-8.23 (m, 6H), 8.19-8.11 (m, 4H),
8.07-8.05 (m, 1H), 7.90 (t, J ) 7.7 Hz, 1H), 7.16 (d, J ) 8.4 Hz,
1H), 6.78 (d, J ) 2.4 Hz, 1H), 6.66 (dd, J ) 8.4, 2.4 Hz, 1H), 6.20
(s, 2H), 6.17 (s, 2H), 5.77 (br s, 8H), 5.36 (s, 2H), 5.28 (s, 2H),
4.61 (m, J ) 4.9 Hz, 4H), 3.90-3.62 (m, 32H), 2.08 (m, J ) 3.1
Hz, 2H), 1.68-1.56 (m, 2H), 1.43-1.29 (m, 6H), 0.91 (t, J ) 6.9
Hz, 3H); MS (ESI) 745.3 (M2PF62+), 672.8 (MPF62+), 600.5 (M2+),
448.6 (MPF63+), 400.2 (M3+), 300.2 (M4+) (C72H88N4O124+ requires
1201.49).
(MPF63+), 427.6 (M3+), 319.4 (M4+) (C78H92N4O12 requires
4+
1277.58).
Catenane 4. 1,3-Bis(2-(4,4′-dipyridinium)ethoxy)-4-n-hexylben-
zene dihexafluorophosphate (19) (0.123 g, 0.16 mmol) and
BPP34C10 (0.223 g, 0.416 mmol) were combined and dissolved
in CH3CN (15 mL). This solution was allowed to stir for 10 min
at which point R,R′-dibromo-p-xylene (0.051 g, 0.192 mmol) was
added and the reaction vessel sealed with a septa. This red solution
stirred 4 days under ambient conditions after which time the solvent
was removed in vacuo. The catenane was purified, and after drying,
17 mg (6%) of pure product was recovered: 1H NMR (CDCl3,
Catenane 8. 1,3-Bis(2-(4,4′-dipyridinium)ethoxy)-4-chloroben-
zene dihexafluorophosphate (17) (0.128 g, 0.16 mmol) and
BPP34C10 (0.223 g, 0.416 mmol) were combined and dissolved
J. Org. Chem, Vol. 72, No. 21, 2007 7847