1440 Bull. Chem. Soc. Jpn. Vol. 79, No. 9 (2006)
Guest Encapsulations in Cavitand-Porphyrins
matography (CH2Cl2–AcOEt = 2:1 v/v) to give 4 as a white solid
in 98% yield (467 mg, 461 mmol). The product was dried in vacuo
at 120 ꢆC for 3 h, prior to the next reaction.
chloroform washed with 1 M HCl, saturated solution of NaHCO3
in water, and brine. The organic layer was dried with Na2SO4, and
then evaporated, then purified by alumina-column chromatogra-
phy (CHCl3). The first and second fractions were collected. The
two fractions were combined and evaporated to give 7 as a purple
solid in 89% yield (131 mg, 203 mmol). The product was dried in
vacuo at 120 ꢆC for 3 h.
7: 1H NMR (400 MHz, CDCl3): ꢇ 8.89–8.86 (m, 8H, pyrrole ꢁ-
H), 8.21–8.19 (m, 4H, Ar–H), 8.01–7.96 (m, 2H, Ar–H), 7.81–
7.69 (m, 8H, Ar–H), 7.36–7.31 (m, 4H, Ar–H), 4.98 (brs, 2H,
OH), ꢃ2:75 (s, 2H, NH). HR-MS (C44H30N4O2): m=z = calcd
646.2369, found 646.2370.
4: mp 243–247 ꢆC. 1H NMR (400 MHz, CDCl3): ꢇ 7.23–7.15
(m, 24H, CHCH2CH2C6H5 + Ar–H meta to OCH2O), 6.57 (s, 2H,
Ar–H ortho to OCH2O), 5.94 (d, J ¼ 6:8 Hz, 1H, Hao of OCH2O),
5.84 (d, J ¼ 6:8 Hz, 2H, Hbo of OCH2O), 5.74 (d, J ¼ 7:2 Hz, 1H,
Hco of OCH2O), 4.90–4.86 (m, 4H, CHCH2CH2C6H5), 4.61–4.59
(s + d, 5H, J ¼ 6:8 Hz, ArCH2OH, Hai of OCH2O), 4.48 (d, J ¼
7:6 Hz, 2H, Hbi of OCH2O), 4.37 (d, J ¼ 7:2 Hz, 1H, Hci of
OCH2O), 2.70–2.52 (m, 16H, CHCH2CH2C6H5), 1.94 (t, J ¼
4:8 Hz, 2H, OH). HR-MS (C66H60O10): m=z = calcd 1012.4186,
found 1012.4189.
Cavitand–Porphyrin (H2cp) and Its Configurational Isomer
(8): 5 (400 mg, 381 mmol), 7 (255 mg, 394 mmol), and K2CO3
(1.0 g) were dried in vacuo at 120 ꢆC with CaCl2 for 3 h prior
to the reaction. The mixture of 5, 7, and K2CO3 in dry NMP
(80 mL) and dry THF (80 mL) was heated for 4 days at 120 ꢆC
in an autoclave. After cooled to room temperature, THF was
evaporated and the residue was extracted with CHCl3. The organic
layer was washed with 1 M HCl, water (ꢄ3), and brine, dried with
Na2SO4, and then evaporated. The residue was passed through an
activated alumina-column (CH2Cl2) and the eluate was evaporat-
ed. The residue was carefully purified by silica-gel column chro-
matography (benzene) to give a purple solid of H2cp (less polar
fraction) in 46% yield (286 mg, 176 mmol) and the configurational
isomer 8 as a purple solid (more polar fraction) in 14% yield
(87 mg, 54 mmol). The products were recrystallized ꢆfrom chloro-
form/methanol and dried in vacuo (0.1 torr) at 120 C for 6 h.
Bis(chloromethyl)cavitand (5; 7,11-Bis(chloromethyl)-2,3-
dihydro-1,21,23,25-tetrakis(2-phenylethyl)-2,20:3,19-dimetheno-
1H,21H,23H,25H-bis[1,3]dioxocino[5,4-i:50,40-i0]benzo[1,2-d:5,4-
d0]bis[1,3]benzodioxocin): To a suspension of N-chlorosuccin-
imide (500 mg, 3.74 mmol) in dry CH2Cl2 (20 mL) at ꢃ20 ꢆC un-
der N2 was quickly added dry Me2S (0.50 mL). Then, the solution
of 4 (626 mg, 618 mmol) in dry CH2Cl2 (100 mL) was added drop-
wise for 1 h. After completion of the addition, the reaction mixture
was warmed to 0 ꢆC and stirred for 2 h. It was then carefully
quenched with water and extracted by CH2Cl2. The organic layer
was washed with brine, dried with Na2SO4, and then evaporated.
The residue was purified by silica-gel column chromatography
(CH2Cl2) to give 5 as a white solid in 72% yield (466 mg, 444
mmol). The product was dried in vacuo at 120 ꢆC for 3 h.
5: mp 260–263 ꢆC. 1H NMR (400 MHz, CDCl3): ꢇ 7.24–7.12
(m, 24H, CHCH2CH2C6H5 + Ar–H meta to OCH2O), 6.59 (s, 2H,
Ar–H ortho to OCH2O), 6.00 (d, J ¼ 7:6 Hz, 1H, Hao of OCH2O),
5.83 (d, J ¼ 8:0 Hz, 2H, Hbo of OCH2O), 5.81 (d, J ¼ 7:2 Hz,
2H, Hco of OCH2O), 4.89–4.85 (m, 4H, CHCH2CH2C6H5), 4.73
(d, J ¼ 7:6 Hz, 1H, Hai of OCH2O), 4.65 (s, 4H, ArCH2Cl), 4.63
(d, J ¼ 7:2 Hz, 2H, Hbi of OCH2O), 4.52 (d, J ¼ 7:2 Hz, 1H,
Hci of OCH2O), 2.69–2.51 (m, 16H, CHCH2CH2C6H5). HR-MS
(C66H58Cl2O8): m=z = calcd 1048.3509, found 1048.3510.
meso-Bis(2-methoxyphenyl)diphenylporphyrin Stereoiso-
meric Mixture (6): To the solution of benzaldehyde (35 mL,
336 mmol), 2-methoxybenzaldehyde (45.8 g, 336 mmol), and pro-
pionic anhydride (40 mL) in refluxing propionic acid (2000 mL)
under aerobic conditions was slowly added pyrrole (44 mL,
640 mmol). The reaction mixture was stirred for 2 h and then
evaporated. The residue was washed by MeOH and then purified
by alumina-column chromatography (CHCl3) to give the mixture
of tetraarylporphyrins, which were further separated carefully by
silica-gel column chromatography (benzene). The fraction of di-
methoxy porphyrin, which was eluted at third and fourth, was col-
lected and evaporated to give 6 as a purple solid in 14.4% yield
based on the amount of pyrrole (15.5 g, 23.0 mmol). The product
was dried in vacuo at room temperature for 3 h prior to the next
reaction.
1
H2cp: mp ꢂ280 ꢆC (dec). H NMR (400 MHz, CDCl3): ꢇ 9.05
(s, 2H, pyrrole ꢁ-H), 8.91 (m, 4H, pyrrole ꢁ-H), 8.57 (s, 2H, pyr-
role ꢁ-H), 8.54 (s, 2H, Ar–H of porphyrin), 8.27 (d, J ¼ 6:4 Hz,
2H, Ar–H of porphyrin), 7.90–7.70 (m, 10H, Ar–H of porphyrin),
7.56 (d, J ¼ 8:0 Hz, 2H, Ar–H of porphyrin), 7.33 (t, J ¼ 7:4 Hz,
2H, Ar–H of porphyrin), 7.13–6.84 (m, 20H, CHCH2CH2C6H5),
6.57 (s, 2H, Ar–H), 6.25 (s, 2H, Ar–H), 5.86 (br, 1H, Hco of
OCH2O), 5.31 (br, 2H, Hbo of OCH2O), 5.12 (d, J ¼ 8:0 Hz, 2H,
bridge ArCH2OAr), 5.04 (d, J ¼ 8:4 Hz, 2H, bridge ArCH2OAr),
4.51 (br, 1H, CHCH2CH2C6H5), 4.27 (br, 4H, CHCH2CH2C6H5 +
Ar–H), 3.83 (br, 1H, CHCH2CH2C6H5), 3.18 (br, 1H, Hci of
OCH2O), 2.43–1.81 (m, 19H, CHCH2CH2C6H5 + Hao and Hbi of
OCH2O), ꢃ1:13 (br, 1H, Hai of OCH2O), ꢃ3:12 (s, 2H, NH). HR-
MS (C110H86N4O10): m=z = calcd 1622.6344, found 1622.6339.
Elemental analysis calcd for C110H86N4O10 H2O: C, 80.47; H,
ꢁ
5.40; N, 3.41%. Found: C, 80.74; H, 5.34; N, 3.64%.
Isomer 8: mp ꢂ290 ꢆC (dec). 1H NMR (400 MHz, CDCl3): ꢇ
9.03 (d, J ¼ 4:4 Hz, 2H, pyrrole ꢁ-H), 8.95 (d, J ¼ 5:2 Hz, 2H,
pyrrole ꢁ-H), 8.82 (s, 2H, pyrrole ꢁ-H), 8.57 (s, 2H, pyrrole ꢁ-H),
8.30 (d, J ¼ 7:4 Hz, 2H, Ar–H of porphyrin), 8.23 (d, J ¼ 7:5 Hz,
2H, Ar–H of porphyrin), 8.10–8.07 (m, 2H, Ar–H of porphyrin),
7.83–7.74 (m, 8H, Ar–H of porphyrin), 7.54 (d, J ¼ 7:5 Hz, 2H,
Ar–H of porphyrin), 7.50 (d, 2H, J ¼ 8:0 Hz, Ar–H of porphyrin),
7.18–6.90 (m, 20H, CHCH2CH2C6H5), 6.70–6.65 (m, 6H, Ar–H),
6.21 (d, J ¼ 6:8 Hz, 2H, Hbo of OCH2O), 5.85 (d, J ¼ 7:4 Hz, 1H,
Hao of OCH2O), 4.99 (d, J ¼ 7:2 Hz, 2H, Hbi of OCH2O), 4.83–
4.75 (m, 5H, Hai of OCH2O + CHCH2CH2C6H5), 4.51 (d, J ¼
8:8 Hz, 2H, bridge ArCH2OAr), 3.76 (d, J ¼ 8:4 Hz, 2H, bridge
ArCH2OAr), 2.63–2.29 (m, 16H, CHCH2CH2C6H5), 1.68 (d,
J ¼ 7:6 Hz, 1H, Hco of OCH2O), ꢃ0:37 (d, J ¼ 7:2 Hz, 1H, Hci
of OCH2O), ꢃ2:60 (s, 2H, NH). HR-MS (C110H86N4O10): m=z =
calcd 1622.6344, found 1622.6348. Elemental anlysis: calcd for
6: 1H NMR (400 MHz, CDCl3): ꢇ 8.80–8.76 (m, 8H, pyrrole ꢁ-
H), 8.22–8.18 (m, 4H, Ar–H), 8.02–7.97 (m, 2H, Ar–H), 7.77–
7.70 (m, 8H, Ar–H), 7.36–7.31 (m, 4H, Ar–H), 3.59–3.55 (m, 6H,
OCH3), ꢃ2:69 (s, 2H, NH). HR-MS (C46H34N4O2): m=z = calcd
674.2682, found 674.2671.
meso-Bis(2-hydroxyphenyl)diphenylporphyrin (7) (as a ster-
eoisomeric mixture): The mixture of 6 (153 mg, 227 mmol) and
an excess amount of pyridinium hydrochloride was heated for 3 h
at 240 ꢆC under N2. Pyridinium salt melted and refluxed at the
temperature. The reaction mixture was cooled to below 100 ꢆC,
and then treated with water. The residue was extracted with
C
79.75; H, 5.32; N, 3.35%.
110H86N4O10 2H2O: C, 79.59; H, 5.47; N, 3.38%. Found: C,
ꢁ