Tomohiro Higashino and Atsuhiro Osuka
À140.35 (d, J=20.7 Hz, 2F, ortho-F), À149.79 (t, J=20.7 Hz, 2F, para-F),
À151.17 (t, J=20.7 Hz, 2F, para-F), À152.90 (t, J=20.7 Hz, 2F, para-F),
À158.53 (brs, 2F, meta-F), À159.66 (td, J=20.7 Hz, J=6.9 Hz, 2F, meta-
F), À160.88 (m, 4F, meta-F), À161.28 (t, J=17.3 Hz, 2F, meta-F), and
Recrystallization from CH2Cl2 and n-hexane gave violet crystals of 7c
quantitatively. 1H NMR (600.17 MHz, CDCl3, 508C, Figure-of-eight): d=
10.75 (brs, 2H, NH), 10.47 (brs, 2H, NH), 7.04 (brs, 2H, b-H), 6.91 (brs,
2H, b-H), 5.31 (brs, 2H, b-H), and 4.93 ppm (brs, 2H, b-H); (CDCl3,
À408C, rectangle): d=8.63 (brs, 2H, outer-NH), 7.66 (brs, 2H, outer b-
H), 7.50 (brs, 2H, outer b-H), 5.33 (brs, 2H, inner-NH), 2.91 (brs, 2H,
inner b-H), and 2.32 ppm (brs, 2H, inner b-H); 19F NMR (564.73 MHz,
CDCl3, 258C): d=À137.24 (brs, 4F, ortho-F), À138.34 (brs, 4F, ortho-F),
À138.98 (brs, 4F, ortho-F), À149.89 (t, J=20.7 Hz, 2F, para-F), À150.15
(t, J=20.7 Hz, 2F, para-F), À150.26 (s, 2F, b-F), À151.69 (s, 2F, b-F),
À152.27 (t, J=20.7 Hz, 2F, para-F), À159.42 (brs, 4F, meta-F), À160.31 (t,
J=17.3 Hz, 4F, meta-F), and À161.24 ppm (m, 4F, meta-F); UV/Vis
(CH2Cl2): l (e, MÀ1 cmÀ1)=310 (34000), 378 (33000), 593 (160000), 766
(12000), 854 (7300), 885 (6300) and 1013 nm (1300); HRMS (ESI-TOF,
positive) calcd. for C66H13F34N6:1535.0653 [M+H]+; found 1535.0666.
À161.63 ppm (t, J=20.7 Hz, 2F, meta-F). UV/Vis (CH2Cl2):
l (e,
MÀ1 cmÀ1)=326 (34000), 375(sh) (24000), 545 (84000), 568 (83000),
743(sh) (6100) and 899 (1200) nm; HRMS (ESI-TOF, positive) calcd. for
C66H13Cl4F30N6:1600.9458 [M+H]+; found 1600.9438.
5,10,15,20,25,30-Hexakis(pentafluorophenyl)-2,3,17,18-
tetrachloro[26]hexaphyrin(1.1.1.1.1.1) (6b)
MnO2 (8.7 mg) was added to a solution of 7b (8.0 mg, 5 mmol) in CH2Cl2
(10 mL), and the resulting solution was stirred for 1 h. The mixture was
passed through a Celite pad and the solvent was removed. The crude
product was purified by column chromatography using CH2Cl2 to give 6b
as a blue fraction. Recrystallization from CH2Cl2 and n-hexane gave
violet crystals of 6b quantitatively. 1H NMR (600.17 MHz, CDCl3,
À608C) (conformer A): d=9.17 (d, J=4.8 Hz, 4H, b-H), 8.96 (d, J=
4.8 Hz, 4H, b-H) and 0.23 ppm (s, 2H, NH); (conformer B): d=9.26 (d,
J=3.5 Hz, 2H, outer b-H), 8.89 (d, J=3.5 Hz, 2H, outer b-H), À0.39 (s,
2H, inner b-H), À0.69 (s, 2H, NH) and À0.72 (s, 2H, inner b-H) ppm;
(conformer C): d=8.42 (brs, 2H, NH), 7.41 (brs, 2H, b-H), 7.17 (brs, 2H,
b-H), 5.69 (brs, 2H, b-H) and 4.68 ppm (brs, 2H, b-H); 19F NMR
(564.73 MHz, CDCl3, À608C) (conformer A): d=À136.06 (m, 4F, ortho-
F), À136.38 (d, J=20.7 Hz, 4F, ortho-F), À137.28 (m, 4F, ortho-F),
À148.48 (m, 2F, para-F), À149.61 (m, 4F, para-F), À159.50 (m, 4F, meta-
F), À161.19 (m, 4F, meta-F), and À162.13 ppm (m, 4F, meta-F); UV/Vis
(CH2Cl2): l (e, MÀ1 cmÀ1)=353 (40000), 578 (120000), 592(sh) (110000),
729 (11000), 786 (11000), and 1087 nm (6500); HRMS (ESI-TOF, posi-
tive) calcd. for C66H11Cl4F30N6: 1598.9301 [M+H]+; found 1598.9313.
5,10,15,20,25,30-Hexakis(pentafluorophenyl)-5-hydro-2,3,17,18-
tetrabromohexaphyrin(1.1.1.1.1.1) (8a)
NaBH4 (38 mg, 1.0 mmol) was added to a solution of 7a (8.7 mg, 5 mmol)
in CH2Cl2/MeOH (10 mL, 10:1), and the resulting solution was stirred at
room temperature for 1 h under N2 atmosphere. The reaction was
quenched by addition of water, and the product was extracted with
CH2Cl2. The combined organic layer was washed with water and brine,
and dried over Na2SO4. The crude product was purified by column chro-
matography using (CH2Cl2/n-hexane 1:2) to give a red fraction. Recrys-
tallization from CH2Cl2 and n-hexane gave violet crystals of 8a (3.7 mg,
42%). Single crystals suitable for X-ray crystallographic analysis were
obtained by vapor diffusion of n-hexane into a solution of 8a in CH2Cl2.
1H NMR (600.17 MHz, CDCl3, À608C) (two diastereomers): d=11.24 (s,
1H, NH), 10.68 (s, 1H, NH), 10.53 (s, 1H, NH), 10.41 (s, 1H, NH), 8.40
(s, 1H, NH), 8.08 (s, 1H, NH), 7.92 (s, 1H, NH), 7.89 (s, 1H, NH), 7.74
(s, 1H, NH), 7.65 (s, 1H, NH), 6.85 (m, 1H, b-H), 6.79 (m, 1H, b-H),
6.72 (m, 1H, b-H), 6.70 (m, 1H, b-H), 6.61 (m, 1H, b-H), 6.56 (m, 3H, b-
H), 6.44 (d, J=5.5 Hz, 1H, b-H), 6.40 (d, J=5.5 Hz, 1H, b-H), 6.22 (d,
J=5.5 hz, 1H, b-H), 6.15 (d, J=5.5 Hz, 1H, b-H), 6.07 (m, 1H, b-H),
5.82 (m, 1H, b-H), 5.62 (s, 1H, meso-H), 5.54 (m, 1H, b-H), and
5.47 ppm (m, 1H, b-H and meso-H); 19F NMR (564.73 MHz, CDCl3,
À608C) (two diastereomers): d=À135.43 (d, J=24.2 Hz, 1F, ortho-F),
À135.65 (d, J=24.2 Hz, 1F, ortho-F), À135.78 (d, J=24.2 Hz, 1F, ortho-
F), À135.95 (d, J=24.2 Hz, 1F, ortho-F), À136.46 (d, J=24.2 Hz, 1F,
ortho-F), À136.93 (d, J=24.2 Hz, 1F, ortho-F), À138.03 (d, J=20.7 Hz,
1F, ortho-F), À138.17 (d, J=24.2 Hz, 1F, ortho-F), À138.69 (m, 1F, ortho-
F), À138.84 (m, 1F, ortho-F), À139.23 (d, J=24.2 Hz, 1F, ortho-F),
À139.58 (d, J=24.2 Hz, 1F, ortho-F), À139.75 (d, J=24.2 Hz, 1F, ortho-
F), À140.22 (d, J=20.7 Hz, 1F, ortho-F), À140.20 (m, 2F, ortho-F),
À140.92 (m, 4F, ortho-F), À141.27 (m, 1F, ortho-F), À141.41 (m, 1F,
ortho-F), À141.66 (m, 1F, ortho-F), À145.23 (d, J=24.2 Hz, 1F, ortho-F),
À149.06 (m, 1F, para-F), À149.42 (m, 1F, para-F), À149.60 (m, 1F, para-
F), À149.84 (m, 1F, para-F), À151.38 (m, 1F, para-F), À151.67 (m, 3F,
para-F), À152.14 (m, 3F, para-F), À152.40 (m, 1F, para-F), À156.90 (m,
1F, meta-F), À157.96 (m, 2F, meta-F), À158.26 (m, 3F, meta-F), À158.89
(m, 1F, meta-F), À159.36 (m, 4F, para-F), À159.68 (m, 1F, meta-F),
À159.93 (m, 1F, meta-F), À160.49 (m, 1F, meta-F), and À160.64 to
À161.11 ppm (m, 10F, meta-F); UV/vis (CH2Cl2): l (e, MÀ1 cmÀ1)=385
(23000), 441 (40000), 516 (41000), 555 (44000), and 923 nm (13000);
HRMS (ESI-TOF, negative) calcd. for C66H13Br4F30N6: 1778.7434
[MÀH]À; found 1778.7437.
5,10,15,20,25,30-Hexakis(pentafluorophenyl)-2,3,17,18-
tetrafluoro[26]hexaphyrin(1.1.1.1.1.1) (6c)
A solution of nBu4NF in THF (1.0m, 0.42 mL, 0.42 mmol) was added to
a solution of 3c (100 mg, 0.38 mmol) in dry CH2Cl2 (38 mL). After 5 min,
the mixture was directly passed through a short Florisil column using
CH2Cl2 as eluent (20 mL). The resulting solution containing 3,4-difluoro-
pyrrole 4c was added to the solution of dicarbinol 5 (0.38 mmol) in dry
CH2Cl2 (10 mL). p-Toluenesulfonic acid monohydrate (36 mg, 0.19 mmol)
was added, and the mixture was stirred for 1 h under N2 atmosphere in
the dark at 08C. After addition of DDQ (259 mg, 1.14 mmol), the result-
ing mixture was stirred for 3 h. The reaction mixture was directly passed
through a short alumina column using CH2Cl2 as eluent, followed by
evaporation of the solvent. Subsequent purification by silica gel column
chromatography (CH2Cl2/n-hexane 3:2) provided 6c as a violet fraction.
Recrystallization from CH2Cl2 and n-hexane gave green crystals of 6c
(32 mg, 11%). Single crystals for preliminary X-ray crystallographic anal-
ysis were obtained by vapor diffusion of methanol into solution of 6c in
1
1,2-dichloroethane. H NMR (600.17 MHz, CDCl3, 258C): d=9.36 (d, J=
4.8 Hz, 4H, b-H), 9.09 (d, J=4.8 Hz, 4H, b-H), and À1.45 ppm (s, 2H,
NH); 19F NMR (564.73 MHz, CDCl3, 258C): d=À136.09 (dd, J=20.7 Hz,
J=6.9 Hz, 4F, ortho-F), À136.85 (d, J=17.3 Hz, 8F, ortho-F), À145.82 (s,
4F, b-F), À149.34 (t, J=20.7 Hz, 2F, para-F), À152.01 (t, J=17.3 Hz, 4F,
para-F), À159.97 (td, J=20.7 Hz, J=6.9 Hz, 4F, meta-F), and
À162.48 ppm (t, J=17.3 Hz, 8F, meta-F). UV/Vis (CH2Cl2):
l (e,
MÀ1 cmÀ1)=345 (23000), 567 (200000), 714 (21000), 773 (9900), 894
(5200), and 1021 nm (6600); HRMS (ESI-TOF, positive) calcd. for
C66H11F34N6: 1533.0497 [M+H]+; found 1533.0509.
5,10,15,20,25,30-Hexakis(pentafluorophenyl)-5-hydro-2,3,17,18-
tetrachlorohexaphyrin(1.1.1.1.1.1) (8b)
5,10,15,20,25,30-Hexakis(pentafluorophenyl)-2,3,17,18-
tetrafluoro[28]hexaphyrin(1.1.1.1.1.1) (7c)
NaBH4 (38 mg, 1.0 mmol) was added to a solution of 7b (8.0 mg, 5 mmol)
in CH2Cl2/MeOH, and the resulting solution was stirred at room temper-
ature for 1 h under N2 atmosphere. The reaction was quenched by addi-
tion of water, and the product was extracted with CH2Cl2. The combined
organic layer was washed with water and brine, and dried over Na2SO4.
The crude product was purified by column chromatography using
(CH2Cl2/n-hexane 1:2) to give a red fraction. Recrystallization from
CH2Cl2 and n-hexane gave violet crystals of 8a (3.6 mg, 45%). 1H NMR
(600.17 MHz, CDCl3, À608C) (diastereomer 1): d=11.08 (s, 1H, NH),
NaBH4 (4 mg, 0.1 mmol) was added to a solution of 6c (7.7 mg, 5 mmol)
in CH2Cl2/MeOH (10 mL, 10:1), and the resulting solution was stirred at
room temperature for 30 min under N2 atmosphere. The reaction was
quenched by addition of water, and the product was extracted with
CH2Cl2. The combined organic layer was washed with water and brine,
and dried over Na2SO4. The crude product was purified by column chro-
matography using (CH2Cl2/n-hexane 1:1) to give 7c as a blue fraction.
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Chem. Asian J. 2013, 00, 0 – 0
ꢀ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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