Preparation of meso-Tetraarylporphyrins Nitrated in Two Neighboring Aromatic Rings

Article abstract of DOI:10.1081/SCC-120026352

Selective nitration of tetraphenylporphyrin (TPP) and its derivatives is reported. The reaction of meso-aryl substituted porphyrins with fuming yellow nitric acid (d = 1.53) at the temperature 0-20°C results in the formation of 5,10-bis(4-nitroaryl)-15,20

Full text of DOI:10.1081/SCC-120026352

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Preparation of meso -Tetraarylporphyrins Nitrated in
Two Neighboring Aromatic Rings
Stanisław Ostrowski a b & Beata Łopuszyńska a
a Institute of Chemistry, University of Podlasie, Siedlce, Poland
b Institute of Organic Chemistry, Polish Academy of Sciences, Warszawa, Poland
Published online: 16 Aug 2006.
To cite this article: Stanisław Ostrowski & Beata Łopuszyńska (2003) Preparation of meso -Tetraarylporphyrins Nitrated in
Two Neighboring Aromatic Rings, Synthetic Communications: An International Journal for Rapid Communication of Synthetic
Organic Chemistry, 33:23, 4101-4110, DOI: 10.1081/SCC-120026352
To link to this article: http://dx.doi.org/10.1081/SCC-120026352
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SYNTHETIC COMMUNICATIONSÕ
Vol. 33, No. 23, pp. 4101–4110, 2003
Preparation of meso-Tetraarylporphyrins
Nitrated in Two Neighboring Aromatic Rings
1
Stanislaw Ostrowski1,2, and Beata Bopuszynska
*
´
1Institute of Chemistry, University of Podlasie,
Siedlce, Poland
2Institute of Organic Chemistry,
Polish Academy of Sciences, Warszawa, Poland
ABSTRACT
Selective nitration of tetraphenylporphyrin (TPP) and its derivatives
is reported. The reaction of meso-aryl substituted porphyrins with
fuming yellow nitric acid (d ¼ 1.53) at the temperature 0–20ꢀC results
in the formation of 5,10-bis(4-nitroaryl)-15,20-diarylporphyrins with
yields of 30–83%.
*Correspondence: Stanislaw Ostrowski, Institute of Chemistry, University of
Podlasie, ul. 3-Maja 54, PL-08-110 Siedlce, Poland; Fax: (þ48)-25-644-2045;
E-mail: stan@ap.siedlce.pl. Institute of Organic Chemistry, Polish Academy of
Sciences, ul. Kasprzaka 44/52, PL-01-224 Warszawa, Poland; Fax: (þ48)-22-632-
6681; E-mail: stan@icho.edu.pl.
4101
DOI: 10.1081/SCC-120026352
Copyright & 2003 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com

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4102
Ostrowski and Bopuszynska
Key Words: meso-Tetraarylporphyrins; 5-10-bis(4-Nitrophenyl)-15,
20-diphenylporphyrin and its derivatives; Nitration.
Selective functionalization of easily available TPP (and its derivatives)
is of significant importance due to their potential use as photosensitizers
in Photodynamic Therapy (PDT).[1] From this process, the hydrophobic
moieties can be transformed into the lipophilic compounds. The latter,
as such, being soluble in the physiological milieu, may be considered as
potential PDT agents. One of the most versatile substituents for this pur-
pose is a nitro group, lending the possibility for further transformations.[2]
Direct nitration of tetraarylporphyrins and their metal complexes
usually occurs in the b-positions in pyrrole units.[3] In 1989, Kruper
et al.[4] described the selective mono-nitration in position para- of one
phenyl ring of TPP. They investigated the possibility of the introduction
of an additional NO2 group to another phenyl ring; however, this
was practically limited to one case of an electron-enriched meta-tolyl
substituent only, with the use of inconvenient, expensive, and dangerous
red fuming nitric acid (containing 12–24% of N2O4). Moreover, they
unfortunately obtained a mixture of two different dinitro-compounds:
5,10-bis(3-methyl-4-nitrophenyl)-15,20-bis(3-methylphenyl)porphyrin
and 5,15-bis(3-methyl-4-nitrophenyl)-10,20-bis(3-methylphenyl)porphyrin.
On the other hand, the direct synthesis of porphyrins, substituted with
electrophilic aryl rings in positions meso-, by the Rothemund synthesis[5]
(and its cross-condensation modifications[6]), from the corresponding alde-
hyde(s) and pyrrole, is an extremely difficult task (yields <3%).[7] It is
improbable that the synthesis of porphyrins, substituted by the nitro
groups in two meso-aryl rings, can be effectively realized by this method.
Herein, we would like to present method for the selective nitration
of meso-tetraarylporphyrins in two neighboring aromatic rings. We
found that it could be realized with the use of fuming yellow nitric acid
(d ¼ 1.53) when the temperature is manipulated. First, the reaction is
carried-out at 0–5ꢀC until disappearance of the substrate, then the
temperature is raised slightly to room temperature and the reaction is
continued for completion (monitored by TLC).
We used for this purpose readily available TPP,[8] and other tetra-
arylporphyrins, with a variety of aromatic ring substituents, each contain-
ing different kinds of electron-drawing properties (e.g., hydrogen, methyl,
methoxy, and chlorine; both in the 2- and in 3-positions). In every above
reaction, the nitration occurred selectively in position 4- (for TPP and
3-substituted rings; probably in position 5- for 2-methoxy-substituted

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Preparation of meso-Tetraarylporphyrins
4103
Ar
Ar
NH
N
N
NH
N
HNO3 (d=1.53) / CHCl3
Ar
Ar
Ar
NO2
0 - 5 °C to r.t.
HN
N
HN
X
Ar
X
2a: X = H ;
42%
1
2b: X = m-Me ; 83%
2c: X = m-Cl ; 30%
2d: X = m-OMe; 37%
a: Ar = Ph
b: Ar = m-Tol
c: Ar = m-Cl-C6H4
d: Ar = m-OMe-C6H4
e: Ar = o-OMe-C6H4*
NO2
* in this case the dinitro product 5 was formed (see Fig. 1)
Scheme 1.
derivative 1e) to give the compounds 2a–d as main products with
satisfactory yields (30–83%).
For TPP, small amounts of the mono-nitration product, 3, were
observed (6%). In the case of the electron-withdrawing substituent, -Cl,
the nitration proved somewhat troublesome. Finally, the use of the large
excess HNO3 within a short interval (4 min) gave a mixture of nitro-
compounds from which 2c was isolated as the major product.
Moderate amounts of the mono-nitrated derivative, 4, were also found.
Prolonging the reaction time in this case allows for the exhaustive
conversion of the mono-nitrocompound into the desired product 2c;
however, it also led to the partial degradation of this product, decreasing
the overall yield.
The structures of the porphyrins obtained were confirmed by
1H NMR spectra. In this case the values of chemical shifts of the
Hb-pyrrole protons were the most diagnostic signals. It was easy to
Cl
Ph
O
Cl
O
NO2
NH
NH
N
N
N
NH
N
N
Ph
Ph
N
HN
HN
HN
Cl
O
O
Cl
NO2
NO2
NO2
3, 6%
4, 22%
5, ca 39%,
contaminated
Figure 1.

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Ostrowski and Bopuszynska
4104
assign correctly the structures due to different symmetry of the 5,10-
bis(4-nitroaryl)porphyrin derivatives vs. their 5,15-bis(4-nitroaryl)-
isomers.
The latter is more trivial problem and the compounds should give
two doublets for protons of pyrrole rings. Instead, in the first case, the
spectral pattern in the region 8.75–9.05 ppm, due to different symmetry of
the compounds, is more complicated and appears as the singlet–doublet–
doublet–singlet system (4 ꢁ 2H) with the coupling in the doublets
J ꢂ 5 Hz, typical for pyrrole ring. This was a case in all investigated
structures of the products obtained herein. Thus, it confirmed the correct
assignments in the porphyrin skeleton.
The examples presented in this article demonstrate the general
character of selective nitration in two neighboring aromatic rings of
meso-tetraarylporphyrins. Taking into account a wide range of synthetic
possibilities offered by the conversion of the NO2 group (reduction to NO
and NH2, further functionalization via diazotization, substitution of
hydrogen in position ortho-,[9] many types of cyclizations,[10] etc.) the
presented method probably can receive much attention in the area of
porphyrin skeleton modifications.
EXPERIMENTAL SECTION
1H NMR spectra were recorded with a Varian GEMINI-200
spectrometer operating at 200 MHz. Coupling constants J are expressed
in hertz [Hz]. Mass spectra were measured with an AMD 604 (AMD
Intectra GmbH, Germany) spectrometer (electron impact and LSIMS
methods) and MARINER (ESI-TOF) PerSeptive Biosystems spectrom-
eter (ESI method); m/z intensity values for peaks are given as a % of
relative intensity. UV–Vis spectra were measured with Beckman DU-68
spectrometer. TLC analysis was performed on aluminum foil plates pre-
coated with silica gel (60F 254, Merck). Silica gel, 200–300 mesh (Merck
AG), was used for column chromatography.
All of the meso-tetraarylporphyrins used were prepared from pyrrole
and the corresponding benzaldehyde derivatives by the method described
earlier in the literature for TPP[8]: 1a, 48%; 1b, 53%; 1c, 74%; 1d, 45%;
1e, ca 39%. Product 1e despite several attempts, could not be separated
from the contaminations via chromatography, ca 90% purity; this
compound, as such, was used in the nitration with HNO3.
Data for porphyrins 1a and 1b - see literature.[4] Data obtained for
porphyrins 1c–e are similar to that described previously.[11–13]

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Preparation of meso-Tetraarylporphyrins
4105
meso-Tetrakis(3-chlorophenyl)porphyrin (1c).[11] M.p.: >300ꢀC.
1H NMR (CDCl3, 200 MHz): 8.86 (s, 8H, Hb-pyrrole), 8.22 (s, 4H, H-2
of Ar-Cl), 8.10 (apparent d, J ¼ 7.3 Hz, 4H, H-4 of Ar-Cl), 7.84–7.65 (m,
8H, H-5 and H-6 of Ar-Cl), ꢃ2.88 (s, 2H, 2 ꢁ NH). UV–Vis (CHCl3),
ꢀmax (lge): 644.5 (3.60), 589 (3.91), 548 (3.93), 515 (4.38), 418 nm (5.67,
Soret). MS (EI), m/z (% rel. int.): 758 (3), 757 (7), 756 (13), 755 (19), 754
(47), 753 (47), 752 (84), 751 (35), and 750 (66) [isotopic MþE], 719 (9), 717
(14), 716 (11), 715 (13), 680 (3), 679 (3), 678 (4), 641 (6), 639 (6), 604 (9),
569 (5), 567 (5), 502 (10), 500 (10), [379 (7), 378 (15), 377 (13), 376 (13),
375 (7)-isotopic doubly charged ions M2þ], 340 (11), 305 (15), 190 (23), 89
(40), 77 (86), 44 (100). HR-MS (ESI) calcd. for C44H27N4Cl4 (M þ H):
751.0990, Found: 751.0971.
meso-Tetrakis(3-methoxyphenyl)porphyrin (1d).[12] M.p.: >300ꢀC.
1H NMR (CDCl3, 200 MHz): 8.88 (s, 8H, Hb-pyrrole), 7.81 (d,
J ¼ 7.4 Hz, 4H, H-6 of Ar-OCH3), 7.78 (d, J ¼ 2.4 Hz, 4H, H-2 of
Ar-OCH3), 7.64 (apparent t, J ¼ 7.8 Hz, 4H, H-5 of Ar-OCH3),
7.33 (ddd, J ¼ 8.2,2.3,1.0 Hz, 4H, H-4 of Ar-OCH3), 3.98 (s, 12H,
4 ꢁ OCH3), 2.81 (s, 2H, 2 ꢁ NH). UV–Vis (CHCl3), ꢀmax (lge): 643
(3.46), 589 (3.72), 550.5 (3.81), 515 (4.31), 419 nm (5.70, Soret). MS
(EI), m/z (% rel. int.): 738 (1), 737 (4), 736 (17), 735 (55), and 734
(100) [isotopic MþE], 719 (4), 703 (3), 675 (2), 627 (3), 597 (2), 569 (2),
[368 (9) and 367 (14)-isotopic doubly charged ions M2þ], 69 (21), 57 (29).
MS (ESI), m/z (% rel. int.): 737 (7), 736 (44), and 735 (100) [isotopic
M þ H]. HR-MS (ESI) calcd. for C48H39N4O4 (M þ H): 735.2971,
Found: 735.2970.
meso-Tetrakis(2-methoxyphenyl)porphyrin (1e).[12,13] Main product,
1
contaminated with other compounds, ca 90% purity. H NMR (CDCl3,
200 MHz): 8.72 (s, 8H, Hb-pyrrole), 8.09–7.91, 7.81–7.70, and 7.39–7.27
(3 ꢁ m, 16H, H-Ar(OCH3)), 3.61, 3.58, and 3.55 (3 lines, 12H, 4 ꢁ OCH3),
ꢃ2.62 (s, 2H, 2 ꢁ NH). UV–Vis (CHCl3), ꢀmax: 643.5, 589.5, 548,
513.5, 417.5 nm (Soret); as the product was not pure, the lge values are
not given herein. MS (EI), m/z (% rel. int.): 735 (M þ H, 44), 734 (MþE
,
81), 703 (4), 673 (3), 596 (2), 492 (17), 491 (33), [368 (16) and 367 (37)-
isotopic doubly charged ions M2þ], 201 (29), 200 (20), 121 (37), 77 (41),
44 (100). HR-MS (ESI) calcd. for C48H39N4O4 (M þ H): 735.2971,
Found: 735.2968.
Nitration of meso-Tetraarylporphyrins.
General Procedure and Modifications.
TPP (1a; 50 mg, 0.08 mmole) was dissolved in dry CHCl3 (15 mL),
and the solution was stirred under argon and cooled to ca 2ꢀC. To this

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Ostrowski and Bopuszynska
4106
mixture nitric acid (314 mg, 0.2 mL, d ¼ 1.53) was added via syringe.
After 2 h the next portion of HNO3 (0.2 mL) was added, the reaction
was continued for 1 h, and the mixture was allowed to warm to room
temperature. Then, the next portion of HNO3 (0.2 mL) was added and it
was left for 20 h (overnight) at room temperature. The reaction mixture
was washed with water (5 ꢁ 20 mL) and dried with MgSO4/Na2CO3. The
crude residue was chromatographed using a mixture of n-hexane/CHCl3
as eluent (from 1:1 to 1:4) to give: 5-(4-nitrophenyl)-10,15,20-triphenyl-
porphyrin (3)[4] (3 mg, 6%) and 5,10-bis(4-nitrophenyl)-15,20-diphenyl-
porphyrin (2a) (24 mg, 42%).
For 5,10,15,20-tetra(meta-tolyl)porphyrin (1b, 50 mg), 200 mg
(0.13 mL) of HNO3 was used at 0–2ꢀC and after 2 h–314 mg (0.2 mL);
then it was permitted to stir while equilibrating to room temperature
(ca 0.5 h; TLC monitoring of the reaction). Chromatography was per-
formed using a gradient mixture of n-hexane/CHCl3 (from 2:1 to 1:2,
then with CHCl3); yield of 5,10-bis(3-methyl-4-nitrophenyl)-15,20–
bis(3-methylphenyl) porphyrin (2b) - 47 mg (83%).
For 5,10,15,20-tetrakis(3-chlorophenyl)porphyrin (1c) 1.5 g of HNO3
(ca 1.0 mL) was added to 51 mg of 1c at room temperature and stirred for
4 min. Then, CHCl3 (10 mL) was added and it was poured onto ice water
(30 mL). After separation, the organic layer was washed with water
(5 ꢁ 10 mL). After drying over MgSO4/Na2CO3 it was chromatographed
(CHCl3/n-hexane; from 1:1 to 4:1, then with CHCl3) to give the starting
5,10,15,20-tetrakis(3-chlorophenyl)porphyrin 1c: 6 mg (12%); 5-(3-
chloro-4-nitrophenyl)-10,15,20-tris(3-chlorophenyl)porphyrin (4): 12 mg
(22%); and 5,10-bis(3-chloro-4-nitrophenyl)-15,20-bis(3-chlorophenyl)-
porphyrin (2c): 15 mg (26%; 30% for recovered 1c).
For 5,10,15,20-tetrakis(3-methoxyphenyl)porphyrin (1d) and 5,10,15,
20-(2-methoxyphenyl)porphyrin (1e) [48 mg, 0.065 mmole] 150 mg (0.10 mL)
of HNO3 was used at 0–2ꢀC and the mixture was stirred at this tempera-
ture for 1 h. Then, the next portion of HNO3 (150 mg, 0.10 mL) was
added and the reaction was continued for 10 min to 1 h (TLC monitor-
ing). After work-up, the crude mixture was chromatographed on pre-
parative TLC (eluent: CHCl3/n-hexane–1:1) to give respectively:
5,10-bis(3-methoxy-4-nitrophenyl)-15,20-bis(3-methoxyphenyl)porphyrin
(2d); 20 mg (37%) – from 1d.
or a mixture of bis-nitrated porphyrins in which compound 5 was the
major product; 21 mg (39%) – from 1e.
5-(4-Nitrophenyl)-10,15,20-triphenylporphyrin (3). For data – see
literature[4]; all spectral data in our hands were in agreement with those
described in Ref.[4]

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Preparation of meso-Tetraarylporphyrins
4107
5,10-Bis(4-nitrophenyl)-15,20-diphenylporphyrin (2a). M.p.: >300ꢀC.
1H NMR (CDCl3, 200 MHz): 8.92 (d, J ¼ 4.9 Hz, 2H, Hb-pyrrole), 8.89
(s, 2H, Hb-pyrrole), 8.79 (s, 2H, Hb-pyrrole), 8.75 (d, J ¼ 4.9 Hz, 2H,
Hb-pyrrole), 8.62 and 8.38 (AA0XX0, 8H, H-Ar(NO2)), 8.26–8.18 (m,
4H, H-Ar), 7.84–7.72 (m, 6H, H-Ar), ꢃ2.77 (s, 2H, 2 ꢁ NH). UV–Vis
(CHCl3), ꢀmax (lge): 646 (3.60), 591 (3.82), 553 (3.99), 517 (4.30), 420.5 nm
(5.48, Soret). MS (EI), m/z (% rel. int.): 707 (3), 706 (8), 705 (37), and 704
(72) [isotopic MþE], 675 (5), 674 (12), 659 (7), 658 (7), 644 (8), 612 (5), 536
(4), 535 (4), 505 (2), 429 (4), 352 (6, doubly charged ion M2þ), 281 (16),
207 (45), 77 (50), 57 (31), 55 (33), 44 (100). HR-MS (ESI) calcd. for
C44H29N6O4 (M þ H): 705.2250, Found: 705.2220.
5,10-Bis(3-methyl-4-nitrophenyl)-15,20-bis(3-methylphenyl)porphyrin (2b).
M.p.: >300ꢀC. 1H NMR (CDCl3, 200 MHz): 9.03 (d, J ¼ 4.7 Hz,
2H, Hb-pyrrole), 9.00 (s, 2H, Hb-pyrrole), 8.93 (s, 2H, Hb-pyrrole),
8.89 (d, J ¼ 4.7 Hz, 2H, Hb-pyrrole), 8.40 (part of AB, J ¼ 8.8 Hz, 2H,
H-Ar(NO2)), 8.30–8.18 (m, 4H), 8.09–8.00 (m, 4H), and 7.72–7.58 (m,
4H) [H-Ar], 2.91 (s, 6H, 2 ꢁ CH3), 2.66 (s, 6H, 2 ꢁ CH3), NH-undetected.
UV–Vis (CHCl3), ꢀmax (lge): 645.5 (3.71), 590.5 (3.92), 552 (4.08), 516
(4.41), 421 nm (5.66, Soret). MS (EI), m/z (% rel. int.): 762 (6), 761 (10),
and 760 (16) [isotopic MþE], 714 (2), 668 (2), 640 (2), 281 (7), 248 (9), 246
(10), 207 (43), 91 (36), 57 (75), 44 (100). MS (ESI), m/z (% rel. int.): 763
(19) and 762 (61) [isotopic Mþ and M þ H], 761 (M þ H, 100). HR-MS
(ESI) calcd. for C48H37N6O4 (M þ H): 761.2876, Found: 761.2991. Calcd.
for C48H36N6O4 (760.85): C, 75.77; H, 4.77; N, 11.05. Found: C, 76.23;
H, 4.70; N, 10.11.
5,10-Bis(3-chloro-4-nitrophenyl)-15,20-bis(3-chlorophenyl)porphyrin (2c).
M.p.: >300ꢀC. H NMR (CDCl3, 200 MHz): 8.93 (d, J ¼ 4.9 Hz, 2H,
1
Hb-pyrrole), 8.89 (s, 2H, Hb-pyrrole), 8.86 (s, 2H, Hb-pyrrole), 8.82 (d,
J ¼ 4.9 Hz, 2H, Hb-pyrrole), 8.43 (d, J ¼ 1.4 Hz, 2H, H-Ar(Cl)(NO2)),
8.32 (part of AB, J ¼ 8.4 Hz, 2H, H-Ar(Cl)(NO2)), 8.27 (part of AB
coupled with another proton, J ¼ 8.4,1.4 Hz, 2H, H-Ar(Cl)(NO2)),
8.23–8.06 (m, 4H, H-Ar), 7.87–7.67 (m, 4H, H-Ar), ꢃ2.90 (broad s,
2H, 2 ꢁ NH). UV–Vis (CHCl3), ꢀmax (lge): 646 (3.50), 590.5 (3.89),
549.5 (3.93), 515 (4.38), 420.5 nm (5.60, Soret). MS (EI), m/z (% rel.
int.): 848 (1), 847 (2), 846 (5), 845 (7), 844 (15), 843 (11), 842 (22), 841
(9), and 840 (17) [isotopic MþE], 796 (4), 795 (3), 794 (3), 759 (3), 714 (4),
305 (5), 304 (5), 107 (42), 89 (47), 77 (100), 44 (69). LSIMS (þ): m/z (%
rel. int.): 846 (<1), 845 (3), 844 (2), 843 (5), 842 (3), and 841 (3) [isotopic
M þ H]. HR-MS (ESI) calcd. for C44H25N6O4Cl4 (M þ H): 841.0691,
Found: 841.0635. Calcd. for C44H24N6O4Cl4 (842.52): C, 62.73; H,
2.87; N, 9.97. Found: C, 62.53; H, 2.88; N, 9.38.

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Ostrowski and Bopuszynska
5,10-Bis(3-methoxy-4-nitrophenyl)-15,20-bis(3-methoxyphenyl)porphy-
rin (2d). M.p.: >300ꢀC. 1H NMR (CDCl3, 200 MHz): 8.96 (d, J ¼ 5.0 Hz,
2 H, Hb-pyrrole), 8.92 (s, 2H, Hb-pyrrole), 8.89 (s, 2 H, Hb-pyrrole), 8.83
(d, J ¼ 5.0 Hz, 2H, Hb-pyrrole), 8.26 (d, J ¼ 8.2 Hz, 2H, H-5 of
Ar(OCH3)(NO2)), 7.96 (d, J ¼ 1.2 Hz, 2H, H-2 of Ar(OCH3)(NO2)),
7.90 (dd, J ¼ 8.2,1.4 Hz, 2H, H-6 of Ar(OCH3)(NO2)), 7.81 (d,
J ¼ 7.7 Hz, 2H, H-6 of Ar-OCH3), 7.78 (s, 2H, H-2 of Ar-OCH3), 7.67
(apparent t, J ¼ 7.6 Hz, 2H, H-5 of Ar-OCH3), 7.48–7.31 (m, 2H, H-4 of
Ar-OCH3), 4.07 (s, 6H, 2 ꢁ OCH3), 4.00 (s, 6H, 2 ꢁ OCH3), ꢃ2.74 and
ꢃ2.83 (2 ꢁ s, 2 H, 2 ꢁ NH). UV–Vis (CHCl3), ꢀmax (lge): 647.5 (3.58), 592
(3.85), 556 (3.97), 516 (4.24), 421 nm (5.52, Soret). MS (EI), m/z (% rel.
int.): 827 (2), 826 (5), 825 (16), 824 (32) [isotopic MþE and M þ H], 794
(3), 778 (4), 777 (3), 731 (2), 701 (2), 672 (1), 412 (2, doubly charged ion
M2þ), 355 (3), 341 (2), 281 (14), 207 (17), 44 (100). MS (ESI), m/z (% rel.
int.): 827 (12), 826 (48), 825 (100), 824 (32) [isotopic Mþ and M þ H].
HR-MS (ESI) calcd. for C48H37N6O8 (M þ H): 825.2673, Found:
825.2546. Calcd. for C48H36N6O8 (824.85): C, 69.89; H, 4.40; N, 10.19.
Found: C, 70.18; H, 4.16; N, 9.74.
5-(3-Chloro-4-nitrophenyl)-10,15,20-tris(3-chlorophenyl)porphyrin (4).
M.p.: >300ꢀC. 1H NMR (CDCl3, 200 MHz): 8.92 (d, J ¼ 4.9 Hz, 2H, Hb-
pyrrole), 8.88 (s, 4H, Hb-pyrrole), 8.81 (d, J ¼ 4.9 Hz, 2H, Hb-pyrrole),
8.44 (s, 1H, H-Ar(Cl)(NO2)), 8.30 and 8.26 (AB system, J ¼ 7.7 Hz, 2H,
H-Ar(Cl)(NO2)), 8.23 (s, 3H, H-Ar), 8.11 (d, J ¼ 7.3 Hz, 3H, H-Ar(Cl)),
7.86–7.66 (m, 6H, H-Ar(Cl)), ꢃ2.88 (s, 2H, 2 ꢁ NH). UV–Vis (CHCl3),
ꢀmax (lge): 645 (3.69), 589.5 (4.06), 550 (4.13), 515 (4.58), 419.5 nm (5.71,
Soret). MS (EI), m/z (% rel. int.): 803 (3), 802 (2), 801 (4), 800 (7), 799
(12), 798 (11), 797 (19), 796 (10), and 795 (15) [isotopic MþE], 752 (4), 751
(3), 749 (3), 716 (4), 714 (2), 107 (34), 89 (48), 77 (100), 44 (85). LSIMS
(þ), m/z (% rel. int.): 803 (3), 802 (6), 801 (7), 800 (19), 799 (24), 798 (28),
797 (30), 796 (28), and 795 (17) [isotopic Mþ and M þ H]; HR-LSIMS
calcd. for C44H25N5O2Cl4 (Mþ): 795.0762, Found: 795.0804. Calcd. for
C44H25N5O2Cl4 (797.53): C, 66.27; H, 3.16; N, 8.78. Found: C, 66.51; H,
3.17; N, 8.34.
5,10-Bis(2-methoxy-5-nitrophenyl)-15,20-bis(2-methoxyphenyl)porphy-
rin (5). In this case we postulated the structure 5 of the dinitro product
(see Fig.1) as the most probable structure due to steric and electronic
demands; the spontaneous decomposition of the product at all stages of
the synthesis and work-up was observed.
For contaminated product, 1H NMR, UV–Vis, and MS spectra were
recorded; the molecular mass was determined by LSIMS (þ) method.
1H NMR (CDCl3, 200 MHz; main isomer): 8.82–8.58 (m, 8 H, Hb-
pyrrole), 8.26–7.70 (m, 6H, H-Ar), 7.46–7.28 (m, 8H, H-Ar), 3.70 (s,

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Preparation of meso-Tetraarylporphyrins
4109
6H, 2 ꢁ OCH3), 3.59 (s, 6H, 2 ꢁ OCH3). ꢃ2.66 (s, 2H, 2 ꢁ NH). UV–Vis
(CHCl3), ꢀmax (lge): 642, 589, 549, 513, 420 nm (Soret); as the product
was not pure, the lge values are not given herein. MS (EI), m/z (% rel.
int.): 827 (1), 826 (3), 825 (5), and 824 (9) [isotopic Mþ], 794 (1), 614 (4).
LSIMS (þ): 825 (8%, M þ H). HR-LSIMS calcd. for C48H37N6O8
(M þ H): 825.2673, Found: 825.2704.
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©2003 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.
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Received in Poland May 10, 2003