Direct amination of meso-tetraarylporphyrin derivatives - Easy route to A3B-, A2BC-, and A2B2-type porphyrins bearing two nitrogen-containing substituents at the meso-positioned phenyl groups

Article abstract of DOI:10.1002/hlca.200790207

meso-Tetraarylporphyrinato complexes 1a-g (Zn¹¹, Cu ¹¹, and Ni¹¹) bearing one or two nitro-substituted aryl moieties react with 1,1,1-trimethylhydrazinium iodide in the presence of 'BuOK in THF at 0 - 5^c or in t

Full text of DOI:10.1002/hlca.200790207

2000
Helvetica Chimica Acta – Vol. 90 (2007)
Direct Amination of meso-Tetraarylporphyrin Derivatives – Easy Route to
A3B-, A2BC-, and A2B2-Type Porphyrins BearingTwo Nitrogen-Containing
Substituents at the meso-Positioned Phenyl Groups
by Stanisław Ostrowski*, Sebastian Grzyb, and Agnieszka Mikus
Institute of Chemistry, University of Podlasie, ul. 3 Maja 54, PL-08-110 Siedlce
(fax: þ 48-25-644-2045; e-mail: stan@ap.siedlce.pl)
meso-Tetraarylporphyrinato complexes 1a – g (ZnII, CuII, and NiII) bearing one or two nitro-
substituted aryl moieties react with 1,1,1-trimethylhydrazinium iodide in the presence of tBuOK in THF
at 0 – 58 or in the presence of KOH in DMSO at 60 – 708 according to a nucleophilic substitution of an H-
atom, thus affording porphyrins 2a – g and 3f,g with amino-functionalized meso-positioned aryl
substituents in yields up to 73% (Scheme 1 and Table). The products obtained are attractive
intermediates for further derivatization of porphyrins and may be of potential use as sensitizers in
photodynamic cancer therapy.
Introduction. – The selective derivatization of easily available meso-tetraarylpor-
phyrins (¼ 5,10,15,20-tetraaryl-21H,23H-porphines) is of significant importance due to
their potential use as photosensitizers in photodynamic therapy [1], molecular-based
multi-bit memory storage [2], bis-faced substituted building blocks [3], and electron-
donor parts in artificial photosynthetic models [4].
In the past decade, much attention has been focused on the preparation of well-
defined 5,10,15,20-tetraarylporphyrin derivatives, substituted by various aryl groups.
Finally, a fully controlled stepwise cyclocondensation process was achieved, and a large
spectrum of the desired porphyrins was synthesized, from the A4-type to the ABCD-
type (A,B,C,D ¼ different aryl groups) [5]. However, in some cases, a serious limitation
of this methodology is a low total yield of the final product.
An alternative route to this type of compounds is an easy straightforward synthesis
of symmetrical meso-tetraarylporphyrins followed by selective derivatization of their
aryl substituents. In this approach, the synthesis is usually limited to the introduction of
one type of substituent into either one or into all four meso-positioned aryl
substituents1). An additional possibility could be the manipulation of the already
existing groups by their transformation or replacement by other ones (e.g., via an
aromatic nucleophilic substitution (SNAr) [7]).
We have recently extended this latter methodology to the introduction, in a fully
controlled processes, of up to 10 various substituents in meso-positioned aryl groups
[8]. This allows the preparation of highly substituted Cl-, N-, O-, and C-substituted
synthetic porphyrins.
1
)
For nitration, see [6a – c]; for sulfonation, see [6d,e]; for chlorosulfonation, see [6f]; for deuteration,
see [6g]; for alkylation, see [6h].
ꢀ 2007 Verlag Helvetica Chimica Acta AG, Zürich

Helvetica Chimica Acta – Vol. 90 (2007)
2001
In continuation of our studies in this field, we were also planning to investigate the
introduction of the very attractive amino group. It is known from the recent literature
that the presence of a nitro group in an aromatic ring gives an opportunity for further
amination of the system by the so-called ꢁvicarious nucleophilic substitution of
hydrogenꢂ (VNS) [9] (for a review, see [9d]). The products of such a reaction in
porphyrin systems could be very versatile intermediates because porphyrins bearing
water-solubilizing groups, such as ÀNMeþ3 , exhibit increased photodynamic efficacy
[10]. On the other hand, nitro-substituted aromatic moieties have been found to be
effective electron-affinity radiosensitizers [11].
Results and Discussion. – We present herein a direct amination of meso-
tetraarylporphyrinato complexes (ZnII, CuII, NiII) bearing NO2-substituted aryl groups
by VNS with the use of 1,1,1-trimethylhydrazinium anion as nucleophilic amino species.
It was found that the reaction of [5-(4-nitrophenyl)-10,15,20-triphenylporphyrinato]-
t
zinc(II) complex 1a with 1,1,1-trimethylhydrazinium iodide (TMHI) in the BuOK/
THF system at 0 – 58 (Procedure A) led to the product 2a by nucleophilic substitution
of a H-atom in the yield of 45% (Scheme 1, Table). Similar results were obtained for
copper and nickel complexes (formation of 2b and 2c in 40 and 51% yield, resp.). The
main product in the reactions of the ZnII and CuII complexes 1a,b was accompanied by
Scheme 1. Direct Amination of meso-Tetraarylporphyrinato Chelates
þ
þ
t
a) Procedure A: 1. H2NÀNMe3 , BuOK, THF, 0 – 58, 6 – 8h; 2. H þ. b) Procedure B: 1. H2NÀNMe3 ,
KOH, DMSO, 60 – 708, 8 – 10 h; 2. Hþ.

2002
Helvetica Chimica Acta – Vol. 90 (2007)
Table. Products and Yields of the Amination of meso-Tetraarylporphyrin Derivatives
Starting porphyrin
Procedure
Products (yield [%])
Total yield [%]
2
3
Others
1a
1b
1c
1d
1e
1f
1g
A
B
A
B
A
B
A
B
A
B
A
B
A
B
2a (45)
2a (66)
2b (40)
2b (63)
2c (51)
2c (13)
2d (27)
2d (11)
2e (41)
2e (< 1)
2f (16)
2f (18)
2g (15)
2g (19)
4a (4)
49
66
56
63
51
13
46
33
41
< 1
33
73
15
68
4b (16)
8 (19)
8 (22)
3f (5)
3f (55)
9 (12)a)
b
)
3g (49)
a) Traces of 10 were detected. b) Traces of 11 were detected.
small amounts of a by-product, in which one phenyl group is substituted by a tert-
butoxy and an amino group. For these by-products, the structures 4a and 4b were
assigned (Figure).
Formation of compounds 4a,b can be explained by oxidative nucleophilic
t
substitution of a H-atom by the BuOÀ anion (! 5; ONSH process [12]) followed by
reduction of the nitro to the amino group (Scheme 2). It can take place as an
intramolecular or intermolecular red-ox process. In the latter, the sH-adduct 5 could be
oxidized by O2 or by the NO2 group of another molecule. The intramolecular
transformation is more likely in this case (Path A, Scheme 2) because we always
observed a tBuO-substituted product bearing concomitantly a NH2 group at the same
t
ring, and we never could isolate a corresponding BuO/NO2-substituted intermediate
from the post-reaction mixtures. The alternative reaction course (amination of 1a,b to
t
6, then SNAr substitution of the NO2 group by the BuOÀ anion) should lead to the
possible product 7 with the inverted substitution pattern of these groups. However, the
NH2 substituent strongly deactivates the ortho-position for SNAr replacement. Thus,
this pathway was a priori excluded from the consideration (Path C).
The heterogeneous KOH/DMSO system at 60 – 708 (Procedure B) was also
successfully applied to the amination process 1 ! 2 and gave, in most of the investigated
instances, higher yields of 2 and better selectivity (see Table). Thus we never observed
the ONSH by-products of type 4.
In the case of a 3-chloro-4-nitro-substituted aryl group of the porphyrin moiety
(substrate 1d), the reaction partially took a different course, and a considerable amount
of SNAr compound was isolated as a by-product. For the product obtained from 1d, on
the basis of the MS ([M þ H]þ at m/z 839; isotope pattern in accord with the expected
1
one) and H-NMR investigations, structure 8 was proposed (Fig). This mode of
reactivity can be rationalized by the strong NO2 activation of the ortho-Cl substituent

Helvetica Chimica Acta – Vol. 90 (2007)
2003
Figure. Other products
for an SNAr process (herein, substitution by the hydrazinium anion). However, the
subsequent conversion of the NHNMe3þ group into NH2 is rather a more complicated
process.
The dinitro-substituted porphyrins 1f and 1g can lead to mono-amination (!2f,g),
as well as to bis-amination (! 3f,g). However, the preferences for substitution in both
rings is more pronounced with the KOH/DMSO system at 60 – 708, thus affording the
dinitro diamino derivatives 3f,g.
t
On the other hand, with the BuOK/THF system at 0 – 58, in the reaction of [5,10-
bis(4-nitrophenyl)-15,20-diphenylporphyrinato]zinc(II) complex 1f, the formation of
small amounts of the ꢁONSH/reductionꢂ product 9 was observed (12%). Additionally,
traces of the disubstituted ꢁONSH/reductionꢂ compound 10 were identified in the post-
reaction mixture (ESI-MS: [M þ H]þ at m/z 851). Under the same reaction conditions,
1g yielded a small amount (< 5%) of compound 11 as by-product, which was observed
in the crude post-reaction mixture (MS: Mþ at m/z 909).

2004
Helvetica Chimica Acta – Vol. 90 (2007)
Scheme 2. Alternative Substitution – Reduction Pathways of 1a and 1b
Conclusions. – We have described a method for the direct amination of
tetraarylporphyrins in their nitro-substituted meso-positioned aryl groups. The type
of products obtained demonstrate the general character of the presented methodology.
It allows the synthesis of porphyrins bearing two N-substituents at the same aryl group,
which are potentially attractive and versatile intermediates for the further derivatiza-
tion of porphyrins designed as photosensitizers in photodynamic therapy.
Moreover, as the syntheses of A3B, A2BC, and A2B2-type meso-tetraarylporphyrins
(A,B,C ¼ different aryl groups) are possible the method may well receive future
attention in the area of porphyrin skeleton modifications.
Experimental Part
1. General. The nitroporphyrinato complexes 1a, 1b, and 1f were obtained in 89, 92, and 40% yield,
resp., from 5-(4-nitrophenyl)-10,15,20-triphenylporphyrin or 5,10-bis(4-nitrophenyl)-15,20-diphenylpor-
phyrin according to procedures described in [13]. The remaining nitroporphyrinato complexes were
prepared according to the above procedures with the corresponding inorganic salts (Zn(OAc)2 · 2 H2O,
Cu(OAc)2 · H2O, or Ni(OAc)2 · 4 H2O); i.e., [5-(4-nitrophenyl)-10,15,20-triphenylporphyrinato]nickel-
(II) 1c (40 h, reflux; 70%), [5-(3-chloro-4-nitrophenyl)-10,15,20-tris(3-chlorophenyl)porphyrinato]zinc-
(II) 1d (47%), [5-(3-chloro-4-nitrophenyl)-10,15,20-tris(3-chlorophenyl)porphyrinato]copper(II) 1e
(62%), and [5,10-bis(4-nitrophenyl)-15,20-diphenylporphyrinato]copper(II) 1g (39%). The 1,1,1-
trimethylhydrazinium iodide (TMHI) was prepared in 87% yield from commercially available 1,1-
dimethylhydrazine (Sigma-Aldrich) by alkylation with MeI in CH2Cl2. TLC: aluminium-foil plates pre-
coated with silica gel (60F 254, Merck). Column chromatography (CC): silica gel 230 – 400 mesh (Merck

Helvetica Chimica Acta – Vol. 90 (2007)
2005
1
AG). UV/VIS Spectra: Beckman DU-68 spectrophotometer; in lmax (log e). H-NMR Spectra: Varian
Gemini-2000BB spectrometer, at 200 MHz; chemical shifts d in ppm rel. to CHCl3 (¼ 7.26 ppm); coupling
constants J in Hz. MS: Mariner (PerSeptive Biosystems) spectrometer in the ESI-TOF mode; in m/z (rel.
int. %).
2. Data of 1c – g. [5-(4-Nitrophenyl)-10,15,20-triphenyl-21H,23H-porphinato(2À)-kN21,kN22,kN23,
kN24]nickel (1c). M.p. > 3008. UV/VIS (CHCl3): 529.0 (4.32), 414.0 (5.38, Soret band), 324.5 (4.13).
1H-NMR (200 MHz, CDCl3): 8.79 (d, J ¼ 5.0, 2 Hb (pyr)); 8.76 (s, 4 Hb (pyr)); 8.62 (d, J ¼ 5.0, 2 Hb
(pyr)); 8.56, 8.20 (AA’XX’, NO2C6H4); 8.05 – 7.96 (m, 6 arom. H); 7.78– 7.61 ( m, 9 arom. H). ESI-MS:
721 (4), 720 (5), 719 (10), 718(25), 717 (60), 716 (100), 715 (34) (isotope Mþ and [M þ H]þ). HR-ESI-
MS: 715.1541 (Mþ, C44H27N5NiOþ2 ; calc. 715.1518).
[5-(3-Chloro-4-nitrophenyl)-10,15,20-tris(3-chlorophenyl)-21H,23H-porphinato(2À)-kN21,kN22,kN23,
kN24]zinc (1d). M.p. > 3008. UV/VIS (CHCl3): 585.0 (3.56), 547.5 (4.45), 510.0 (3.63), 419.5 (5.67, Soret
band), 348.0 (4.16), 310.5 (4.29). 1H-NMR (200 MHz, CDCl3): 8.99 (d, J ¼ 4.7, 1 Hb (pyr)); 8.96 (s, 4 Hb
(pyr)); 8.95 – 8.81 (m, 2 Hb (pyr)); 8.88 (d, J ¼ 4.7, 1 Hb (pyr)); 8.43 (d, J ¼ 1.5, HÀC(2) of NO2C6H3(Cl));
8.31 (part of AB, J ¼ 8.1, HÀC(5) of NO2C6H3(Cl)); 8.27 (part of AB coupled with another proton, J ¼
8.1, 1.5, HÀC(6) of NO2C6H3(Cl)); 8.21 (br. s, HÀC(2) of 3 ClC6H4); 8.11 (d, J ¼ 7.1, 3 H of 3 ClC6H4);
7.86 – 7.63 (m, 6 H of 3 ClC6H4). ESI-MS: 868 (3), 867 (6), 866 (10), 865 (24), 864 (31), 863 (58), 862
(58), 861 (100), 860 (52), 859 (91), 858 (24), 857 (47) (isotope Mþ). HR-ESI-MS: 856.9875 (Mþ,
C44H23Cl4N5O2Znþ; calc. 856.9897).
[5-(3-Chloro-4-nitrophenyl)-10,15,20-tris(3-chlorophenyl)-21H,23H-porphinato(2À)-kN21,kN22,kN23,
kN24]copper (1e). M.p. > 3008. UV/VIS (CHCl3): 572.0 (3.31), 539.5 (4.20), 499.5 (3.39), 415.5 (5.48,
Soret band). ESI-MS: 865 (3), 864 (8), 863 (14), 862 (29), 861 (34), 860 (75), 859 (59), 858 (100), 857
(27), 856 (57) (isotope Mþ). HR-ESI-MS: 855.9925 (Mþ, C44H23Cl4CuN5Oþ2 ; calc. 855.9902).
[5,10-Bis(4-nitrophenyl)-15,20-diphenyl-21H,23H-porphinato(2À)-kN21,kN22,kN23,kN24]zinc (1f).
M.p. > 3008. UV/VIS (CHCl3): 588.0 (3.70), 548.5 (4.42), 511.0 (3.61), 421.0 (5.49, Soret band), 349.0
(4.12). 1H-NMR (200 MHz, CDCl3): 9.07 – 8.77 (m, 8 Hb (pyr)); ca. 8.65 and 8.41 (AA’XX’, 2 NO2C6H4);
8.28 – 8.10 (m, 4 arom. H); 7.88 – 7.66 (m, 6 arom. H). ESI-MS: 773 (5), 772 (11), 771 (30), 770 (51), 769
(49), 768(74), 767 (58), 766 (100) (isotope Mþ). HR-ESI-MS: 766.1296 (Mþ, C44H26N6O4Znþ; calc.
766.1307).
[5,10-Bis(4-nitrophenyl)-15,20-diphenyl-21H,23H-porphinato(2À)-kN21,kN22,kN23,kN24]copper
(1g). M.p. > 3008. UV/VIS (CHCl3): 576.0 (4.04), 540.5 (4.79), 501.5 (4.08), 418.5 (5.75, Soret band).
ESI-MS: 769 (13), 768(37), 767 (68), 766 (62), 765 (100) (isotope Mþ). HR-ESI-MS: 765.1275 (Mþ,
C44H26CuN6O4; calc. 765.1312).
3. Amination of Porphyrin Derivatives. Procedure A (tBuOK/THF system). To a stirred soln. of
tBuOK (16.8mg, 0.15 mmol) in anh. THF (0.5 ml), a soln. of 5,10,15,20 -tetraarylporphyrinato complex 1
(0.03 mmol) and 1,1,1-trimethylhydrazinium iodide (TMHI; 18.2 mg, 0.09 mmol) in THF (0.5 ml) was
added dropwise at 0 – 58 within 10 min, and the mixture was stirred under Ar in a light-shielded flask.
Upon addition of the reagents, the soln. immediately changed from red to deep-green (ZnII complexes)
t
or to red-orange (CuII and NiII complexes). After 2 h of stirring, new portions of BuOK (10.1 mg,
0.09 mmol) and TMHI (12.1 mg, 0.06 mmol) were added. After an additional 2 h of stirring, another
t
portion of BuOK (6.7 mg, 0.06 mmol) and TMHI (6.1 mg, 0.03 mmol) was added. The reaction was
continued for 2 – 4 h, and then the mixture was poured into 3% aq. HCl soln. containing ice (10 ml). The
acidified soln. was extracted with CHCl3 (5 ꢀ 10 ml), the combined org. layer washed with H2O (3 ꢀ
50 ml), dried (Na2SO4), and evaporated, and the residue subjected to CC (CHCl3/hexane 2 :1, then
3 :1, then CHCl3) to give the desired product (for yields, see Table).
Procedure B (KOH/DMSO system). To a vigorously stirred suspension of powdered KOH (77.3 mg,
1.38mmol) and porphyrinato complex 1 (0.069 mmol) in anh. DMSO (1 ml) in a light-shielded flask,
TMHI (42.4 mg, 0.21 mmol) was added at 60 – 708 under Ar. Upon addition of TMHI, the odor of Me3N
was noted. After 4 h of stirring at 60 – 708, additional portions of KOH (38.1 mg, 0.68 mmol) and TMHI
(14.1 mg, 0.07 mmol) were added. The reaction was continued for 4 – 6 h, and then the mixture was
poured into 3% aq. HCl soln. containing ice (30 ml) and worked up as described for Procedure A.
4. Data of Products. [5-(3-Amino-4-nitrophenyl)-10,15,20-triphenyl-21H,23H-porphinato(2À)-
kN21,kN22,kN23,kN24]zinc (2a). M.p. > 3008. 1H-NMR (200 MHz, CDCl3): 8.98, 8.96 (2s (atypical),

2006
Helvetica Chimica Acta – Vol. 90 (2007)
8 Hb (pyr)); 8.45 (d, J ¼ 8.7, HÀC(5) of NO2C6H3(NH2)); 8.26 – 8.17 (m, 6 arom. H); 7.82 – 7.72 (m, 9
arom. H); 7.62 (dd, J ¼ 8.7, 1.7, HÀC(6) of NO2C6H3(NH2)); 7.55 (d, J ¼ 1.7, HÀC(2) of NO2C6H3(NH2));
6.15 (br. s, NH2). 1H-NMR (200 MHz, (D6)DMSO): 8.95 (d, J ¼ 4.8(typical), 2 H b (pyr)); 8.80 (d, J ¼
b
4.8(typical), 2 H (pyr)); 8.79 (s (typical), 4 Hb (pyr)); 8.34 (d, J ¼ 8.7, HÀC(5) of NO2C6H3(NH2));
8.25 – 8.14 (m, 6 arom. H); 7.90 – 7.72 (m, HÀC(2) of NO2C6H3(NH2), 9 arom. H); 7.49 (dd, J ¼ 8.7, 1.7,
HÀC(6) of NO2C6H3(NH2)); NH2 undetected. For UV/VIS, MS, and HR-MS, see [14].
5-(3-Amino-4-nitrophenyl)-10,15,20-triphenyl-21H,23H-porphinato(2À)-kN21,kN22,kN23,kN24]cop-
per (2b). M.p. > 3008. UV/VIS (CHCl3): 572.0 (3.83), 540.0 (4.66), 501.5 (3.94), 423.5 (5.45, Soret band).
ESI-MS: 739 (4), 738(20), 737 (49), 736 (50), 735 (100) (isotope Mþ). HR-ESI-MS: 735.1592 (Mþ,
C44H28CuN6Oþ2 ; calc. 735.1570).
[5-(3-Amino-4-nitrophenyl)-10,15,20-triphenyl-21H,23H-porphinato(2À)-kN21,kN22,kN23,kN24]nick-
1
el (2c). M.p. > 3008. UV/VIS (CHCl3): 555.5 (3.85), 530.0 (4.32), 416.5 (5.35, Soret band). H-NMR
(200 MHz, CDCl3): 8.78 (s, 4 Hb (pyr)); 8.75 (s, 4 Hb (pyr)); 8.42 (d, J ¼ 8.6, HÀC(5) of NO2C6H3(NH2);
8.05 – 7.95 (m, 6 arom. H); 7.74 – 7.62 (m, 9 arom. H); 7.45 (dd, J ¼ 8.6, 1.8, HÀC(6) of NO2C6H3(NH2));
7.40 (d, J ¼ 1.8, HÀC(2) of NO2C6H3(NH2)); 6.28(br. s, NH2). ESI-MS: 737 (3), 736 (4), 735 (6), 734
(10), 733 (24), 732 (53), 731 (54), 730 (100) (isotope Mþ). HR-ESI-MS: 730.1641 (Mþ, C44H28N6NiO2þ ;
calc. 730.1627).
[5-(3-Amino-5-chloro-4-nitrophenyl)-10,15,20-tris(3-chlorophenyl)-21H,23H-porphinato(2 À)-
kN21,kN22,kN23,kN24]zinc (2d). M.p. > 3008. UV/VIS (CHCl3): 582.5 (3.67), 548.0 (4.60), 510.0 (3.77),
b
420.0 (5.83, Soret band), 347.5 (4.32), 311.0 (4.40). 1H-NMR (200 MHz, CDCl3): 9.02 – 8.81 (m, 8 H
(pyr)); 8.30 – 8.02, 7.86 – 7.61 (2m, 12 H of 3 ClC6H4, 2 H of NO2C6H2(Cl)(NH2)); 5.37 (br. s, NH2). ESI-
MS: 883 (5), 882 (7), 881 (15), 880 (30), 879 (34), 878 (63), 877 (62), 876 (100), 875 (67), 874 (95), 873
(35), 872 (50) (isotope Mþ). HR-ESI-MS: 872.0006 (Mþ, C44H24Cl4N6O2Znþ; calc. 872.0006).
[5-(3-Amino-5-chloro-4-nitrophenyl)-10,15,20-tris(3-chlorophenyl)-21H,23H-porphinato(2 À)-
kN21,kN22,kN23,kN24]copper (2e). M.p. > 3008. UV/VIS (CHCl3): 570.0 (3.66), 539.5 (4.50), 499.5 (3.75),
416.0 (5.84, Soret band), 309.0 (4.13). ESI-MS: 881 (2), 880 (4), 879 (6), 878 (12), 877 (27), 876 (34), 875
(83), 874 (54), 873 (100), 872 (29), 871 (47) (isotope Mþ). HR-ESI-MS: 871.0064 (Mþ,
C44H24Cl4CuN6Oþ2 ; calc. 871.0011).
5-(3-Amino-4-nitrophenyl)-10-(4-nitrophenyl)-15,20-diphenyl-21H,23H-porphinato(2À)-kN21,kN22,
kN23,kN24]zinc (2f). M.p. > 3008. UV/VIS (CHCl3): 587.0 (3.84), 549.0 (4.60), 513.0 (3.78), 421.5 (5.70,
Soret band), 350.0 (4.36). 1H-NMR (200 MHz, CDCl3): 9.00 (d, J ¼ 4.7, 1 Hb (pyr)); 8.98 – 8.93 (m, 3 Hb
(pyr)); 8.91 (d, J ¼ 4.9, 1 Hb (pyr)); 8.88 – 8.81 (m, 3 Hb (pyr)); 8.69 – 8.57 (m, 2 H of NO2C6H4); 8.47 –
8.35 (m, 2 H of NO2C6H4); 8.31 (d, J ¼ 8.8, HÀC(5) of NO2C6H3(NH2)); 8.28 – 8.12 (m, 4 arom. H);
7.86 – 7.69 ( m, HÀC(2) of NO2C6H3(NH2), 6 arom. H); 7.56 (dd, J ¼ 8.8, 1.7, HÀC(6) of
NO2C6H3(NH2)); 5.27 (br. s, NH2). ESI-MS: 788 (3), 787 (8), 786 (19), 785 (45), 784 (39), 783 (76),
782 (51), 781 (100) (isotope Mþ). HR-ESI-MS: 781.1409 (Mþ, C44H27N7O4Znþ; calc. 781.1416).
[5-(3-Amino-4-nitrophenyl)-10-(4-nitrophenyl)-15,20-diphenyl-21H,23H-porphinato(2À)-kN21,kN22,
kN23,kN24]copper (2g). M.p. > 3008. UV/VIS (CHCl3): 569.5 (3.94), 535.5 (4.72), 500.0 (3.99), 418.5
(5.48, Soret band). ESI-MS: 784 (8), 783 (32), 782 (54), 781 (58), 780 (100) (isotope Mþ). HR-ESI-MS:
780.1483 (Mþ, C44H27CuN7Oþ4 ; calc. 780.1421).
[5,10-Bis(3-amino-4-nitrophenyl)-15,20-diphenyl-21H,23H-porphinato(2À)-kN21,kN22,kN23,kN24]-
zinc (3f). M.p. > 3008. UV/VIS (CHCl3): 587.5 (3.76), 548.5 (4.52), 510.5 (3.71), 422.5 (5.64, Soret
1
band), 354.5 (4.33). H-NMR (200 MHz, CDCl3): 9.01 – 8.79 (m, 8 Hb (pyr)); 8.34 – 8.13 (m, HÀ(5) of
2 NO2C6H3(NH2), 4 arom. H); 7.85 – 7.67 (m, HÀC(2) of 2 NO2C6H3(NH2), 6 arom. H); 7.62 – 7.46 (m,
HÀC(6) of 2 NO2C6H3(NH2)); 5.24, 5.07 (2 br. s, 2 NH2 of atropisomers). ESI-MS: 802 (9), 801 (26), 800
(49), 799 (47), 798(79), 797 (65), 796 (100) (isotope Mþ). HR-ESI-MS: 796.1502 (Mþ, C44H28N8O4Zn;
calc. 796.1525).
[5,10-Bis(3-amino-4-nitrophenyl)-15,20-diphenyl-21H,23H-porphinato(2À)-kN21,kN22,kN23,kN24]-
copper (3g). M.p. > 3008. UV/VIS (CHCl3): 573.5 (3.42), 540.5 (4.27), 500.5 (3.53), 418.5 (5.40, Soret
band). ESI-MS: 800 (4), 799 (10), 798 (31), 797 (75), 796 (61), 795 (100) (isotope Mþ). HR-ESI-MS:
795.1583 (Mþ, C44H28CuN8Oþ4 ; calc. 795.1530).
{5-[4-Amino-3-(tert-butoxy)phenyl]-10,15,20-triphenyl-21H,23H-porphinato(2À)-kN21,kN22,kN23,
kN24}zinc (4a). M.p. > 3008. UV/VIS (CHCl3): 589.5 (3.48), 549.0 (4.14), 513.0 (3.49), 419.5 (5.42,

Helvetica Chimica Acta – Vol. 90 (2007)
2007
1
b
Soret band), 347.5 (3.94). H-NMR (200 MHz, CDCl3): 8.99, 8.96 (2s, 8 H (pyr)); 8.28 – 8.18 (m, 6
arom. H); 8.16 (d, J ¼ 8.2, HÀC(5) of tBuOC6H3(NH2)); 7.89 (d, J ¼ 1.6, HÀC(2) of tBuOC6H3(NH2));
t
t
7.85 – 7.72 ( m, 9 arom. H); 7.71 (dd, J ¼ 8 .2, 1.6, HÀC(6) of BuOC6H3(NH2)); 1.28( s, BuO); NH2
undetected. ESI-MS: 770 (1), 769 (6), 768(29), 767 (24), 766 (74), 765 (46), 764 (100) (isotope [ M þ
H]þ), 394 (2), 393 (21). HR-ESI-MS: 764.2395 ([M þ H]þ, C48H38N5OZnþ; calc. 764.2368).
{5-[4-Amino-3-(tert-butoxy)phenyl]-10,15,20-triphenyl-21H,23H-porphinato(2À)-kN21,kN22,kN23,
kN24}copper (4b). M.p. > 3008. UV/VIS (CHCl3): 578.0 (3.68), 541.0 (4.37), 414.0 (5.56, Soret band).
ESI-MS: 768(4), 767 (10), 766 (29), 765 (59), 764 (64), 763 (100) (isotope [ M þ H]þ), 394 (7), 393 (22),
309 (15). HR-ESI-MS: 763.2316 ([M þ H]þ, C48H38CuN5Oþ; calc. 763.2372).
{5-(3-Amino-4-nitrophenyl)-10,15,20-tris(3-chlorophenyl)porphinato(2À)-kN21,kN22,kN23,kN24}zinc
(8). M.p. > 3008. UV/VIS (CHCl3): 587.0 (3.26), 548.0 (4.10), 509.0 (3.27), 419.0 (5.33, Soret band),
350.0 (3.86), 309.5 (3.95). 1H-NMR (200 MHz, CDCl3): 8.97 (part of AB, J ¼ 4.7, 1 Hb (pyr)); 8.97 – 8.91
(m, 7 Hb (pyr)); 8.47 (d, J ¼ 8.5, HÀC(5) of NO2C6H3(NH2)); 8.22 (br. s, HÀC(2) of 3 ClC6H4); 8.11 (d,
J ¼ 7.3, 3 H of 3 ClC6H4); 7.99 (d, J ¼ 1.7, HÀC(2) of NO2C6H3(NH2)); 7.87 (dd, J ¼ 8.5, 1.7, HÀC(6) of
NO2C6H3(NH2)); 7.84 – 7.64 (m, 6 H of 3 ClC6H4); NH2 undetected. ESI-MS: 849 (6), 848 (10), 847 (18),
846 (25), 845 (45), 844 (47), 843 (82), 842 (56), 841 (100), 840 (28), 839 (41) (isotope [M þ H]þ). HR-
ESI-MS: 839.0439 ([M þ H]þ, C44H26Cl3N6O2Znþ; calc. 839.0474).
{5-[4-Amino-3-(tert-butoxy)phenyl]-10-(4-nitrophenyl)-15,20-diphenyl-21H,23H-porphinato(2À)-
kN21,kN22,kN23,kN24}zinc (9). M.p. > 3008. UV/VIS (CHCl3): 610.5 (3.31), 578.0 (3.72), 541.0 (4.47),
419.5 (5.33, Soret band). 1H-NMR (200 MHz, CDCl3): 9.03 – 8.81 (m, 8 Hb (pyr)); 8.69 – 8.58, 8.49 – 8.36
t
(2m, NO2C6H4); 8.26 – 8.08 (m, HÀC(5) of BuOC6H3(NH2), 4 arom. H); 7.85 – 7.51 (m, HÀC(2) and
HÀC(6) of tBuOC6H3(NH2), 6 arom. H); 5.34 (br. s, NH2); 1.25 (s, tBuO). ESI-MS: 816 (14), 815 (19),
814 (48), 813 (66), 812 (62), 811 (100), 810 (80), 809 (94) (isotope [M þ H]þ). HR-ESI-MS: 809.2280
([M þ H]þ, C48H37N6O3Znþ; calc. 809.2219).
{5,10-Bis[4-amino-3-(tert-butoxy)phenyl]-15,20-diphenyl-21H,23H-porphinato(2À)-kN21,kN22,kN23,
kN24}zinc (10). Identified in the crude post-reaction mixture by its ESI-MS: 851 (15, [M þ H]þ).
{5,10-Bis[3-(tert-butoxy)-4-nitrophenyl]-15,20-diphenyl-21H,23H-porphinato(2À)-kN21,kN22,kN23,
kN24}copper (11). Identified in the crude post-reaction mixture by its ESI-MS: 909 (73, Mþ).
REFERENCES
[1] L. Bourre, G. Simonneaux, Y. Ferrand, S. Thibaut, Y. Lajat, T. Patrice, J. Photochem. Photobiol., B
2003, 69, 179; E. S. Nyman, P. H. Hynninen, J. Photochem. Photobiol., B 2004, 73, 1.
[2] L. Wei, K. Padmaja, W. J. Youngblood, A. B. Lysenko, J. S. Lindsey, D. F. Bocian, J. Org. Chem. 2004,
69, 1461, and refs. cit. therein.
´
[3] C. Ruzie, D. Gueyrard, B. Boitrel, Tetrahedron Lett. 2004, 45, 1713, and refs. cit. therein.
[4] H. Imahori, K. Hagiwara, M. Aoki, T. Akiyama, S. Taniguchi, T. Okada, M. Shirakawa, Y. Sakata, J.
Am. Chem. Soc. 1996, 118, 11771; P. Cheng, S. R. Wilson, D. I. Schuster, Chem. Commun. 1999, 8 9;
G. Zheng, T. J. Dougherty, R. K. Pandey, Chem. Commun. 1999, 2469; J.-C. Lee, T.-Y. Kim, S. H.
Kang, Y. K. Shim, Bull. Korean Chem. Soc. 2001, 22, 257; S. Ostrowski, A. Mikus, Mol. Diversity
2003, 6, 315.
[5] P. D. Rao, S. Dhanalekshmi, B. J. Littler, J. S. Lindsey, J. Org. Chem. 2000, 65, 7323.
[6] a) W. J. Kruper Jr., T. A. Chamberlin, M. Kochanny, J. Org. Chem. 1989, 54, 2753; b) G. G. Meng,
B. R. James, K. A. Skov, M. Korbelik, Can. J. Chem. 1994, 72, 1894; c) R. Luguya, L. Jaquinod, F. R.
Fronczek, M. G. H. Vicente, K. M. Smith, Tetrahedron 2004, 60, 2757; d) E. B. Fleischer, J. M.
Palmer, T. S. Srivastava, A. Chatterjee, J. Am. Chem. Soc. 1971, 93, 3162; e) T. S. Srivastava, M.
Tsutsui, J. Org. Chem. 1973, 38, 2103; f) A. M. dꢂA. Rocha Gonsalves, R. A. W. Johnstone, M. M.
Pereira, A. M. P. de SantAna, A. C. Serra, A. J. F. N. Sobral, P. A. Stocks, Heterocycles 1996, 43, 829;
g) Z. Gross, L. Kaustov, Tetrahedron Lett. 1995, 36, 3735; h) I. Willner, Y. Degani, J. Chem. Soc.,
Chem. Commun. 1982, 1249.
[7] J.-H. Fuhrhop, in ꢁThe Porphyrinsꢂ, Ed. D. Dolphin, Academic Press, New York, 1978, Vol. 2,
p. 131 – 159; L. Jaquinod, in ꢁThe Porphyrin Handbookꢂ, Eds. K. M. Kadish, K. M. Smith, R. Guilard,
Academic Press, San Diego, 2000, Vol. 1, p. 213 – 215.

2008
Helvetica Chimica Acta – Vol. 90 (2007)
´
[8] S. Ostrowski, A. Mikus, B. Łopuszynska, Tetrahedron 2004, 60, 11951.
[9] a) A. R. Katritzky, K. S. Laurenzo, J. Org. Chem. 1988, 53, 3978; b) M. Ma˛kosza, M. Białecki, J. Org.
Chem. 1992, 57, 4784; c) M. Ma˛kosza, M. Białecki, J. Org. Chem. 1998, 63, 48 78 ; d) M. M˛kaosza, K.
Wojciechowski, Chem. Rev. 2004, 104, 2631.
[10] M. G. H. Vicente, Curr. Med. Chem. Anticancer Agents 2001, 1, 175; T. B. Amor, L. Bortolotto, G.
Jori, Photochem. Photobiol. 1998, 68, 314; D. Kessel, R. Luguya, M. G. H. Vicente, Photochem.
Photobiol. 2003, 78, 431.
[11] E. M. Lord, L. Harwell, C. J. Koch, Cancer Res. 1993, 53, 5721.
´
´
[12] M. Ma˛kosza, K. Stalinski, Tetrahedron 1998, 54, 8 797; M. M˛akosza, K. Stalinski, Pol. J. Chem. 1999,
73, 151.
[13] S. Ostrowski, A. Mikus, Y. K. Shim, J.-Ch. Lee, E.-Y. Seo, K.-I. Lee, M. Olejnik, Heterocycles 2002,
57, 1615.
[14] S. Ostrowski, S. Grzyb, Jordan J. Chem., in print.
Received February 2, 2007