7732 J. Am. Chem. Soc., Vol. 119, No. 33, 1997
Wen et al.
of 100 s. X-ray photoelectron spectroscopy (XPS) was performed with
a Perkin-Elmer PHI5100 system employing a 10-360 precision energy
analyzer, and a Mg KR source. The takeoff angle for photoelectrons
was 75°, the base vacuum was better than 1 × 10-8 Torr, and pass
energies for elements were as follows: C1s, 17.9 eV; Cu2p, 44.75 eV;
N1s, 17.9 eV; S2p, 44.75 eV; Co2p, 44.75 eV. Polymer film thickness
was measured with a digital micrometer for films in the micrometer
range. Thinner films were measured by weighing them on a micro-
of KI in 20 mL of dry acetone was added 1.22 g (0.01 mol) of
4-hydroxybenzaldehyde dissolved in 20 mL of acetone dropwise, under
N2. The mixture was heated under reflux for 18 h. The solution was
poured into ice-water, and the precipitate filtered and then washed
with hexane. Yield: 2.02 g (71%). 1H NMR: δ 4.04 (t, 2, J ) 6 Hz,
-OCH2-), 6.99 (d, 2, J ) 9 Hz, H-3,5), 7.83 (d, 2, J ) 9 Hz, H-2,4),
9.88 (s, 1, CHO), 3.43 (t, 2, J ) 6 Hz, -CH2Br), 1.85 (m, 4, -OCCH2-
and -CH2CBr), 1.55 (m, 4, -OCCCH2- and -CH2CCBr).
5,10,15,20-Tetratolylporphyrin, 6.30 A 5.00 g (41.6 mmol) sample
of tolualdehyde and 100 mL of propionic acid was added to a 250 mL
flask. The solution was stirred and heated to reflux for 20 min. A
2.79 g (41.6 mmol) portion pyrrole was then added, and heating was
continued for another 30 min. The mixture was cooled to 4 °C and
filtered. The purple shiny crystals were washed with methanol three
times and dried under vacuum. Yield: 1.33 g (19.1%). 1H NMR: δ
2.66 (s, 12, -CH3), 7.41 (d, 8, J ) 8 Hz, H-3′,5′), 7.94 (d, 8, J ) 8
Hz, H-2′,4′), 8.66 (s, 8, pyrrolic â-H), -2.78 (s, 2, dNH). UV-vis
(in chloroform): λmax 420 nm (ꢀ 4.8 × 105 mol-1‚L‚cm-1), 516 (1.9 ×
104), 551 (9.7 × 103), 590 (5.7 × 103), 649 (6.2 × 103).
balance, determining their area, and assuming a density of 1.2 g cm-3
.
As-made films contained metal (e.g., Cu2+) ion. Demetalation was
performed by exposing films to aqueous solutions of mineral acids,
and films were metalated by heating under reflux in a solution of metal
actetate in 40:60 (v/v) methanol/chloroform.
Triplet-sensitized oxidation of thietane, as described by Clennan et
al.,27 was performed using films of poly-1 approximately 1 µm thick
and 4 cm in diameter, prepared as described below. Films were treated
with 10 M HCl in 1:1 water/acetone for 2 h at room temperature to
remove copper and then sequentially rinsed in water, 0.1 M NH4OH,
acetone, and chloroform. Photochemistry was carried out by irradiating
20 mL of a 1 wt % solution of thietane in chloroform under ambient
conditions. The light source was a 100 W xenon arc lamp (Varian
P-1505-71) filtered through 1 cm of 12 M NaNO2(aq). Reaction
products were determined at intervals using a Varian 3300 gas
chromatograph equipped with a DB-5MS (J&W Scientific) capillary
column and a flame ionization detector.
5,10,15,20-tetrakis(r-bromo-p-tolyl)porphyrin, 3.11 To 1.5 L of
chloroform were added 3.00 g (15 mmol) of R-bromo-p-tolualdehyde
and 1.05 g (15 mmol) of pyrrole. During stirring, 0.71 g (5.0 mmol)
of Et2O‚BF3 was added to the mixture. Stirring was continued for 1 h
more at room temperature followed by the addition of 0.61 g (6.0 mmol)
of triethylamine and 2.77 g (11.3 mmol) of TCBQ, and the temperature
was raised to reflux and kept under reflux for 1 h. The volume of the
mixture was then reduced to ca. 200 mL and filtered through silica gel
(neutral). After the filtrate was dried under reduced pressure, the purple
sediment was redissolved in toluene. The solution was passed over
silica gel, eluting with toluene. After the toluene was removed, the
sediment was washed with methanol again, giving shiny purple fine
crystals. The product was dried at 100 °C under vacuum. Yield: 2.23
g (60%). Anal. Found: C, 58.57; H, 3.51; N, 5.73; Br, 32.16.
Calcd: C, 58.44; H, 3.47; N, 5.68; Br, 32.40. 1H NMR: δ -2.8 (s, 2,
NH), 4.84 (s, 8, CH2Br), 7.82 (d, 8, J ) 8 Hz, H-3′,5′), 8.19 (d, 8, J
) 8 Hz, H-2′,6′), 8.85 (s, 8, â-pyrrolic H). IR (KBr): υ (cm-1) 3325
and 3308 (m, dNH), 3027 (m, CsH on phenyl and pyrroles), 1614,
1575, 1540 (m, CdC), 1221 (s, -CH2Br), 595 (s, -CBr). UV-vis
(CHCl3): λmax 420 nm (ꢀ 3.9 × 105 mol-1‚L‚cm-1), 516 (1.6 × 104),
551 (8.4 × 103), 589 (5.8 × 103), 646 (4.9 × 103).
r-Bromo-p-tolunitrile.28 p-tolunitrile (10.0 g, 85.4 mmol), n-
bromosuccinimide, (15.2 g, (85.5 mmol), and benzoyl peroxide (0.2
g) were added to 60 mL of CCl4. This mixture was heated under reflux
for 7 h, after which time all solids floated to the surface. The mixture
was filtered when hot, washed with hot and CCl4, and the solvent was
removed from the filtrate under reduced pressure. The product was
recrystallized twice from cyclohexane and dried under vacuum at 50
°C for 6 h. Yield: 8.05 g (48.1%). The product appeared as white
1
crystals. H NMR: δ 4.45 (s, 1, CH2Br), 7.48 (d, 1, J ) Hz, H-3,5),
7.64 (d, 1, J ) Hz, H-2,6). Mp: 113-116 °C (lit. 114-116 °C).28
Anal. Found: C, 49.02; H, 3.09; N, 7.14; Br, 40.77. Calcd: C, 48.98;
H, 3.06; N, 7.14; Br, 40.81.
R-Bromo-p-tolualdehyde.11 This was a modified version of Bookser
and Bruice’s method.11 Toluene was used as solvent instead of
chlorobenzene for easier workup. A 6.00 g (30.6 mmol) sample of
R-bromo-p-tolunitrile was dissolved in 60 mL of toluene and cooled
to 0 °C. A 40 mL (43.2 mmol) portion of 1.08 M DIBAL-H in hexane
was added dropwise under N2. The solution was stirred for another
hour at 0 °C. An 80 mL sample of chloroform was then added followed
by ca. 200 mL of 10% HCl, and the solution was stirred at room
temperature for 1 h. The organic layer was separated, washed with
distilled water, dried over anhydrous MgSO4, and filtered. The solvent
was almost completely removed from the filtrate under reduced
pressure, and the residue was cooled, filtered, washed with cold hexane,
and dried at 50 °C under vacuum. Yield: 5.21 g (85%). The product
appeared as white crystals. Mp: 97-100 °C (lit. 97-99 °C). Anal.
Found: C, 48.78; H, 3.58; N, 0, Br, 39.57. Calcd: C, 48.27; H, 3.54;
N, 0; Br, 40.14. IR: υ (cm-1) 1711 (s, CdO), 2745 and 2824 (m,
CHO), 1585 and 1610 (m, CdC). 1H NMR: δ 4.50 (s, 2, CH2Br), δ
7.55 (d, 2, J ) 8.2 Hz, H-3,5), 7.85 (d, 2, J ) 8.2 Hz, H-2,6), δ 10.04
(s, 1, CHO).
5,10,15,20-Tetrakis(r-bromo-m-tolyl)porphyrin. R-Bromo-m-
tolylaldehyde (2.80 g, 14.0 mmol) and pyrrole (0.98 g, 14.0 mmol)
were dissolved in 1500 mL of dry chloroform; after 0.71 g (5.0 mmol)
of Et2O‚BF3 was added, the mixture was stirred at room temperature
for 1 h. Triethylamine (0.61 g, 6.0 mmol) and TCBQ (2.80 g, 11.4
mmol) were then added and heated under reflux for 1 h. The volume
was reduced to 200 mL under vacuum and the solution filtered through
60 g of silica gel. The filtrate and the CH2Cl2 washing were combined
and dried under reduced pressure. The solid was washed with toluene
and methanol. The product was recrystallized from MeOH/CH2Cl2 and
dried under vacuum. Yield: 1.54 g (42%). 1H NMR: δ -2.8 (s, 2,
NH), 4.78 (s, 8, CH2Br), 7.74 (t, 4, J ) 7.6 Hz, H-5′), 7.82 (d, 4, J )
7.6 Hz, H-6′), 8.15(d, 4, J ) 7.6 Hz, H-4′), δ 8.25 (s, 4, H-2′), 8.88 (s,
8, â-pyrrolic H). IR (KBr): υ (cm-1) 3331 (w, dNH), 3037 (m, CsH
on phenyl and pyrroles), 1610, 1592, 1559 (m, CdC). UV-vis (in
chloroform): λmax 419 nm (ꢀ 2.4 × 105 mol-1‚L‚cm-1), 516 (1.1 ×
104), 551 (5.8 × 103), 590 (5.3 × 103), 666 (1.4 × 104).
R-Bromo-m-tolualdehyde. Procedures were similar to those for
R-bromo-p-tolualdehyde. A 5.00 g (25.5 mmol) sample of R-bromo-
m-tolunitrile was dissolved in 50 mL of chlorobenzene and cooled to
0 °C under N2. A 34 mL (36 mmol) portion of the DIBAL-H stock
solution was added dropwise. The reaction was completed and worked
up as for R-bromo-p-tolualdehyde. Yield: 3.80 g (75%). Mp: 45-
47 °C (lit. 46-49 °C). 1H NMR: δ 4.52 (s, 2, CH2Br), 7.53 (t, 1, J )
8 Hz, H-5), 7.65 (d, 1, J ) 8 Hz, H-4), 7.83 (d, 1, J ) 8 Hz, H-6),
7.91 (s, 1, H-2), 10.02 (s, 1, CHO). IR: υ (cm-1) 1712 (s, CdO),
2743 and 2822 (m, CHO), 1596 and 1608 (m, CdC).
5,10,15,20-Tetrakis[(ω-bromo-p-hexoxy)phenyl]porphyrin, 4. (ω-
Bromo-p-hexoxy)benzaldehyde, (3.00 g, 10.5 mmol), pyrrole (0.74 g,
10.5 mmol), and BF3 etherate (0.50 g) were mixed in 1100 mL of
chloroform. After the mixture was stirred at room temperature for 1
h, 0.43 g of triethylamine and 1.95 g of TCBQ were added, and the
resulting mixture was heated under reflux for 1 h. The product was
worked up the same way as for 3. Yield: 1.95 g (57%). Anal.
Found: C, 61.44; H, 5.45; N, 4.23; Br, 24.15. Calcd: C, 60.99; H,
6.17; N, 4.19; Br, 23.87. 1H NMR: δ -2.76 (s, 2, NH), 4.26 (t, 8, J
) 6 Hz, -OCH2-), 7.27 (d, 8, J ) 7.2 Hz, H-3′, 5′), 8.11 (d, 8, J )
7.2 Hz, H-2′,6′), 3.51(t, 8, J ) 6.6 Hz, -CH2Br), 2.01 (m, 16,
-OCCH2- and -CH2CBr), 1.67 (m, 16, -OCCCH2- and -CH2-
(ω-Bromo-p-hexoxyl)benzaldehyde.29 To a mixture of 7.32 g (0.03
mol) of Br(CH2)6Br, 1.4 g (0.01 mol) of K2CO3, and a catalytic amount
(28) Kalir, A. Organic Syntheses; Wiley: New York, 1973; Collect. Vol.
V, p 825.
(29) (a) Scho¨nberg, A.; Sina, A. J. Am. Chem. Soc. 1950, 72, 3396-
3399. (b) Ritchie, E.; Taylor, W. C. Tetrahedron Lett. 1964, 1431-1436.
(30) Adler, A. D.; Sklar, L.; Longo, J. D.; Finarelli, J. D.; Finarelli, M.
G. J. Heterocycl. Chem. 1968, 5, 669-678.