A R T I C L E S
Bartholomew and Bazan
and fitted with a thermometer and placed under vaccuum. Excess
triethyl phosphite was removed under vacuum at 100 °C. The resulting
oil was washed with several portions of pentane and diethyl ether
affording a yellowish solid. The final yield was 98%. 1H NMR
(CDCl3): 6.459 (s, 4H), 3.895 (m, 16H), 3.482 (m, 4H), 3.072 (m,
4H), 2.770 (m, 8H), 1.175 (q, 24H). 13C (CDCl3): 140.142, 138.762,
134.191, 131.089, 62.307, 32.300, 31.514, 16.532. HRMS-EI: 809.3120,
∆ ) 1.0 ppm (for M + H)+.
mmol) of potassium t-butoxide dissolved in a minimal amount of dry
THF added again by syringe. The reaction was allowed to warm to
room temperature and to progress overnight. The reaction was quenched
with deionized water and extracted into 125 mL of CHCl3 and washed
with brine. The solvent was removed under vacuum, and the mixture
was separated using HPLC. The resulting yield was 23%. Alternatively,
reaction in DMF results in a 68% yield for the same procedure. The
regiochemistry was assigned by characteristic paracyclophane frag-
1
mentation during mass spectrometry. H NMR (CD2Cl2): 7.411 (d,
(4,7,12,15)-Tetra(4′-dihexylaminostyryl)[2.2]paracyclophane (1).
A 25 mL 14/20 round-bottom flask was charged with 153.4 mg (0.19
mmol) of 8, 275 mg (0.95 mmol) of 4-dihexylaminobenzaldehyde, a
Teflon-coated stirbar, and closed with a septum. Approximately 5 mL
of anhydrous DMF was added via syringe, and the mixture was stirred
under argon at 0 °C. Deprotonation of the phosphonate was achieved
with 96.5 mg (0.86 mmol) of potassium t-butoxide dissolved in a
minimal amount of dry DMF added again by syringe. The reaction
was allowed to warm to room temperature and stir overnight. The
resulting mixture was extracted with hexanes (250 mL) and washed
with three 250 mL portions of brine and then dried over MgSO4. After
filtration, the solvent was again reduced by rotary evaporation. Flash
chromatography eluting with 10% diethyl ether in hexanes produced
243 mg of the product as an orange powder for a yield of 95%.
Alternatively, the resulting orange oil from rotary evaporation was
recrystallized twice in hexanes and afforded orange cube-shaped crystals
of single-crystal X-ray diffraction quality for a final yield of 86% (214
mg). 1H NMR (CDCl3): 7.400 (d, 8H), 6.961 (m, 12H), 6.670 (d, 8H),
3.510 (m, 4H), 3.331 (t, 16H), 2.838 (m, 4H), 1.645 (m, 16H), 1.356
(m, 48H), 0.931 (m, 24H). 13C NMR (CDCl3): 147.774, 137.232,
136.781, 128.310, 128.106, 127.498, 125.641, 121.428, 111.872, 51.364,
33.316, 31.998, 27.574, 27.126, 22.945, 14.307. HRMS-FAB/NBA:
1349.1123, ∆ ) 3.3 ppm.
4-(4′-Dihexylaminostyryl)-7,12,15-tri(4′′-nitrostyryl)[2.2]-
paracyclophane (2). A 25 mL 14/20 round-bottom flask was charged
with 300 mg (0.37 mmol) of 8, 110 mg (0.37 mmol) of 4-dihexylami-
nobenzaldehyde, a Teflon-coated stirbar, and closed with a septum.
Approximately 5 mL of anhydrous DMF was added via syringe, and
the mixture was stirred under argon at 0 °C. Deprotonation of the
phosphonate was achieved with 45 mg (0.37 mmol) of potassium
t-butoxide dissolved in a minimal amount of dry DMF. The reaction
was allowed to warm to room temperature and stir overnight. Next,
170 mg (1.13 mmol) of 4-nitrobenzaldehyde in THF was added, and
the reaction was again cooled to 0 °C. Another 1.2 mmol of potassium
t-butoxide was added, and the reaction was allowed to proceed
overnight. The resulting mixture was extracted with CHCl3 (500 mL)
and washed with three 500 mL portions of brine and then dried over
MgSO4. After filtration, the solvent was again reduced by rotary
evaporation. Purification by HPLC afforded 235 mg of a black-metallic
solid for a yield of 68%. 1H NMR (CDCl3): 8.275 (m, 6H), 7.567 (m,
6H), 7.376 (m, 4H), 7.135 (s, 1H), 7.006 (m, 4H), 6.92-6.83 (bm,
4H), 6.691 (d, 3H), 3.652 (m, 4H), 3.364 (t, 4H), 2.920 (m, 4H), 1.646
(m, 4H), 1.357 (m, 12H), 0.941 (t, 6H). 13C NMR (CDCl3): 148.510,
147.02, 146.882, 144.304, 144.078, 143.976, 139.308, 138.911, 138.743,
137.145, 136.824, 134.494, 130.339, 130.004, 129.745, 129.446,
129.148, 128.966, 128.678, 128.365, 128.103, 128.487, 127.298,
126.974, 126.741, 125.419, 124.636, 124.461, 124.173, 119.574,
111.839, 51.328, 33.622, 33.429, 33.054, 31.987, 31.852, 29.922,
27.552, 27.322, 27.078, 26.933, 22.938, 22.861, 14.300. HRMS-FAB/
NBA: 934.4691, ∆ ) 2.3 ppm.
4H), 6.851 (m, 6H), 6.661 (d, 4H), 6.450 (s, 2H), 3.844 (m, 8H), 3.451
(m, 2H), 3.330 (m, 10H), 3.173 (m, 2H), 2.820 (m, 6H), 1.608 (t, 8H),
1.342 (m, 24H), 1.121 (m, 12H), 0.915 (m, 12H). 13C NMR (CD2Cl2):
148.423, 138.712, 138.067, 137.475, 135.101, 130.716, 128.804,
128.242, 127.423, 125.276, 121.141, 112.159, 62.474, 51.557, 33.046,
32.887, 32.310, 32.052, 27.804, 27.348, 23.267, 16.674, 14.390. HRMS-
ESI/TOF: 1079.71151, ∆ ) 1.2 ppm for M+4
.
(4,12)Bis(diethylphosphonatemethyl)-(7,15)bis(4′ -
dihexylaminostyryl)[2.2]paracyclophane (10). A 25 mL 14/20 round-
bottom flask was charged with 50 mg (0.06 mmol) of 8, 35 mg (0.12
mmol) of 4-dihexylaminobenzaldehyde, a Teflon-coated stirbar, and
closed with a septum. Approximately 2 mL of anhydrous THF was
added via syringe, and the mixture was stirred under argon at 0 °C.
Deprotonation of the phosphonate was achieved with 13.4 mg (0.12
mmol) of potassium t-butoxide dissolved in a minimal amount of dry
DMF added again by syringe. The reaction was allowed to warm to
room temperature and progress overnight. The reaction was quenched
with deionized water and extracted into 125 mL of CHCl3 washed with
brine. The solvent was removed under vacuum, and the mixture was
separated by HPLC. The resulting yield was 57% (37 mg). The
regiochemistry was assigned by characteristic paracyclophane frag-
mentation during mass spectrometry combined with 2D 1H NMR
(COSY). 1H NMR (CD2Cl2): 7.416 (d, 4H), 6.851 (m, 6H), 6.662 (d,
4H), 6.424 (d, 2H), 3.863 (m, 8H), 3.451 (m, 4H), 3.311 (t, 8H), 3.113
(m, 2H), 2.789 (m, 6H), 1.620 (m, 8H), 1.342 (m, 24H), 1.159 (m,
12H), 0.915 (t, 12H). 13C NMR (CD2Cl2): 148.461, 138.848, 138.120,
137.832, 135.245, 129.980, 129.873, 129.107, 128.258, 127.355,
125.193, 121.301, 112.151, 62.565, 62.497, 51.557, 33.008, 32.871,
32.318, 31.627, 27.804, 27.348, 23.267, 16.750, 16.689, 16.636, 14.390.
HRMS-ESI/TOF: 1079.71151, ∆ ) 1.8 ppm for M+4
.
4,7-Bis(4′-dihexylaminostyryl)-12,15-bis(4′′-nitrostyryl)[2.2]-
paracyclophane (3). A 25 mL 14/20 round-bottom flask was charged
with 0.5 mmol (540 mg) of 9, 2.2 mmol of 4-nitrobenzaldehyde, a
Teflon-coated stirbar, and was closed with a septum. Anhydrous DMF
was added, and the reaction was cooled to 0 °C. Potassium t-butoxide
(1.7 mmol) dissolved in a minimal amount of DMF was added via
syringe, and the reaction was allowed to proceed for 24 h, warming
slowly to room temperature. The resulting mixture was extracted with
CHCl3 (250 mL) and washed with three 250 mL portions of brine and
then dried over MgSO4. After filtration, the solvent was reduced by
rotary evaporation. Purification by HPLC afforded 453.4 mg of a
metallic-purple solid for a yield of 84%. 1H NMR (CDCl3): 8.252 (d,
4H), 7.589 (d, 4H), 7.363 (m, 6H), 7.121 (s, 2H), 7.001 (dd, 4H), 6.894
(s, 2H), 6.785 (d, 2H), 6.690 (d, 4H), 3.603 (m, 4H), 3.358 (t, 8H),
2.971 (m, 2H), 2.813 (m, 2H), 1.662 (m, 8H), 1.383 (m, 24H), 0.946
(t, 12H). 13C NMR (CDCl3): 147.892, 146.652, 144.136, 139.028,
136.753, 136.623, 136.530, 129.604, 128.439, 128.299, 127.814,
127.656, 127.003, 126.854, 124.496, 124.207, 120.143, 111.614, 51.102,
33.346, 32.954, 31.771, 27.325, 26.868, 22.720, 14.083. HRMS-EI:
1072.6818, ∆ ) 1.1 ppm.
(4,7)Bis(diethylphosphonatemethyl)-(12,15)bis(4′ -
dihexylaminostyryl)[2.2]paracyclophane (9). A 25 mL 14/20 round-
bottom flask was charged with 50 mg (0.06 mmol) of 8, 35 mg (0.12
mmol) of 4-dihexylaminobenzaldehyde, a Teflon-coated stirbar, and
closed with a septum. Approximately 2 mL of anhydrous THF was
added via syringe, and the mixture was stirred under argon at 0 °C.
Deprotonation of the phosphonate was achieved with 13.4 mg (0.12
4,7,12-Tribromo-15-formyl[2.2]paracyclophane (13). A 100 mL
24/40 round-bottom flask was charged with 500 mg (0.95 mmol) of
1226 and a Teflon-coated stirbar and fitted with a needle valve.
Approximately 50 mL of dry THF was transferred to the flask, and
the reaction mixture was cooled to -78 °C. To the flask was added 1
equiv of n-butyllithium (0.95 mmol) via syringe through the needle
9
5194 J. AM. CHEM. SOC. VOL. 124, NO. 18, 2002